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Solar Energy 113 (2015) 158170
www.elsevier.com/locate/solener

Concept analysis of an indirect particle-based redox

process for solar-driven H2O/CO2 splitting
Stefan Brendelberger , Christian Sattler
Deutsches Zentrum fur Luft- und Raumfahrt/German Aerospace Center DLR, Linder Hohe, 51147 Koln, Germany

Received 11 August 2014; received in revised form 21 December 2014; accepted 29 December 2014
Available online 22 January 2015

Communicated by: Associate Editor Michael Epstein

Abstract

The production of solar fuels by thermochemical redox cycles has gathered a lot of attention in the research community over the last
years. Still, several challenges are to be overcome to reach high eciencies with technically feasible process concepts. Critical barriers
have been identied for the development of receiverreactors because of conicting design and operation requirements for the processes
of solar absorption, heat and mass transfer, and the chemical reaction. In addition, thermodynamic studies have indicated the need of
solid phase heat recuperation in order to reach high process eciencies, which adds further complexity to the design. Balancing out the
multitude of constrains while respecting technical limitations is a very dicult but necessary task. This study addresses this challenge with
the development of a new process concept which includes a solid phase heat recovery approach. The concept is based on decoupling the
dierent process steps by using a particulate redox material in combination with a particulate heat transfer material. A model is intro-
duced to analyse the process performance of the proposed concept. The performance of the system is calculated and assessed for a range
of cases, with optimistic and more conservative assumptions for the boundary conditions. While the system reaches peak eciencies in
the range of 30% for optimistic boundary conditions, the peak eciency drops to just above 15% for the conservative case. Additionally,
the implementation of a multi-reactor approach to lower parasitic losses is presented and analysed. By extending the system to multiple
reactors working at optimized oxygen partial pressures signicant reductions of the vacuum pumping power demand are obtained,
resulting in a 20% system eciency increase. Besides the performance analysis of the concept, its specic challenges and advantages, like
the increased exibility for design and operation, are discussed.
2015 Elsevier Ltd. All rights reserved.

Keywords: Redox cycle; Solar fuel; Heat recovery; Heat transfer particle

1. Introduction renewable energy became more of a focus for technological

Thermochemical cycles were extensively investigated
during the 1970s oil crises. Initially, the main application
was predicted to be the coupling with high temperature
gas cooled nuclear reactors (Yalcin, 1989). Due to discus-
sions around climate change and energy security issues,
Corresponding author. Tel.: +49 2203 6012905; fax: +49 2203
6014072.
E-mail address: Stefan.Brendelberger@dlr.de (S. Brendelberger).
development and the provision of high temperature heat by
concentrated solar radiation for thermochemical cycles was
discussed (Fletcher and Moen, 1977; Nakamura, 1977;
Steinfeld, 2005). The theoretical eciencies of these cycles
have been shown to be above 60% (Kodama and Gokon,
2007) but the technical challenges are signicant due to
the rigorous process requirements.
Some of the most investigated thermochemical cycles for
the production of solar fuels utilise metal-oxides to split
water or carbon dioxide to produce hydrogen or carbon

http://dx.doi.org/10.1016/j.solener.2014.12.035
0038-092X/ 2015 Elsevier Ltd. All rights reserved.
 S. Brendelberger, C. Sattler / Solar Energy 113 (2015) 158170 159

Nomenclature

A area (m2) gGHR gas phase heat recovery eectiveness ()

C concentration factor () gSHR solid phase heat recovery eectiveness ()
DNI direct normal irradiance (W/m2) gsolar solar-to-fuel conversion eciency ()
f objective function gvacuum vacuum pumping eciency ()
HHV higher heating value (J/mol) gw2e waste heat to electricity eciency ()
HXC heat exchanger cooling the redox stream r StefanBoltzmann constant (W/m2/K4)
HXH heat exchanger pre-heating the redox stream
l loss factor () Subscripts
m_ mass ow rate (kg/s)
n_ molar ow rate (mol/s) 1 absorption particle stream
OR oxidation-reactor 2 redox particle stream
p pressure (Pa) 3 heat recovery particle stream
p O2 oxygen partial pressure (Pa) ai aperture intercept
P power (W) atm atmospheric
Q_ heat ow (W) cd cool-down
R gas constant (J/mol/K) m mirror
RE receiver max maximum
RR reduction-reactor ox oxidation-reactor
ST storage ph pre-heat
T temperature (K) red reduction
Tox temperature of oxidation step (K) rr reduction-reactor
d reduction extent () w window

monoxide respectively in a two-step process. Firstly, the
metal-oxide MO is reduced in an endothermic reaction
(1) where the high temperature heat is provided by concen-
trated solar radiation.
d
MO ! MO1d O2 1 strategy for the concept by Lapp et al. (2013) was numeri-
2 cally analysed and resulted in an recovery eciency of 30%
In a second exothermic reaction (2) the reduced metal-
oxide is used to split H2O or CO2, or a mixture of both,
returning the metal-oxide to the original state.
MO1d dH2 O ! MO dH2
MO1d dCO2 ! MO dCO 2 combined with a receiverreactor.
The reduction extent d implies that the reduction is often
non-stoichiometric, especially for non-volatile cycles and is
dependent on the temperature and partial pressure of oxy-
gen during the reduction; here the reduction extent is
increased with higher temperatures and lower partial pres-
sures of oxygen.
The reduction extent of ceria, as a frequently considered
redox material, is about 0.06 at 1500 C and 1 Pa oxygen
partial pressure (Panlener et al., 1975). As a result 94% of
the ceria remains unreacted during the cycle even at these
challenging temperatures and partial pressures. Further-
more, the processes are usually driven in a temperature
swing mode, where the temperatures of the two steps dier
by several hundred Kelvin. Therefore, the sensible heating
demand is typically several times higher than the endother-
mic energy required for the reduction reaction which
results in severe thermal energy losses if solid phase heat
recovery is not implemented.
Heat recovery strategies were proposed for dierent
receiverreactors (Diver et al., 2008; Lapp et al., 2013;
Ermanoski et al., 2013). The solid phase heat recovery
for a baseline case (Lapp and Lipinski, 2014). Still, an
experimental demonstration of signicant recovery rates
in the context of thermochemical cycles has not been yet
reported. Any such attempts face severe technical chal-
lenges due to the extreme process conditions, especially if
A reduction of the temperature dierence and optimiza-
tion of the process temperatures and pressures is discussed
in dierent publications (Bader et al., 2013; Ermanoski
et al., 2014; Hao et al., 2013; Muhich et al., 2013; Roeb
and Sattler, 2013). In this literature concerns about possi-
ble constraints by thermodynamics and kinetics of the
redox material and gas phase heat recovery were raised.
It is expected that further eorts in material develop-
ment will result in redox materials with more favourable
properties which will reduce the need for demanding pro-
cess requirements. Amongst others, potential material
improvements have been reported for dopants of ceria
(Call et al., 2013; Le Gal et al., 2013; Lee et al., 2013;
Miller et al., 2014) and types of perovskites (McDaniel
et al., 2013). These improvements refer mainly to an
increase of the reduction extent at given temperature and
oxygen partial pressure. But since this is only one of several
160 S. Brendelberger, C. Sattler / Solar Energy 113 (2015) 158170
physical and chemical material properties which have to be
considered in process level performance calculations, fur-
ther information is necessary to assess the system potential
of redox material improvements.
Another eciency challenge is the energy demand for
keeping low oxygen partial pressures during the reduction
step. Theoretical studies suggest that under the assumption
of perfect mixing of the released oxygen and sweep gas,
purging results in far higher energy demand than using vac-
uum pumping systems (Ermanoski et al., 2013). In a coun-
ter ow arrangement purging energy demands may be
signicantly reduced (Bader et al., 2013). However, this
has to be further investigated to understand the extent that
this assumption is relevant for an actual reactor design and
operation. Maintaining a low partial pressure during the
reduction is expected to be a signicant parasitic loss factor
which has to be considered appropriately in a process
concept.
A nal process challenge is how well the reaction can be
matched to the high heat ux environment of the com-
monly considered solar receiverreactor. Theoretical inves-
tigations have shown that it is very challenging to address
in a coherent manner the dierent requirements which limit
the reaction progress in a receiverreactor (Chueh et al.,
2010; Kaneko et al., 2011; Keene et al., 2013; Lapp et al.,
2013; Lapp and Lipinski, 2014; Miller et al., 2014). Possible
limiting factors are heat transfer, surface reaction, oxygen
diusion, and oxygen removal in the gas phase. In process
concepts with rotating redox structures, the rotational
speed relates the residence time of the redox material in
the receiverreactor to the residence time in the oxidation
reactor which adds further limitations to the operational
parameters (Diver et al., 2008; Kaneko et al., 2011; Lapp
et al., 2013). Ermanoski et al. (2013) proposed to decouple
the oxidation step from the reduction step by using a par-
ticulate redox material which is cycled between two sepa-
rate reactors. Still, some of the constrains for the coupled
absorption and reduction in the receiverreactor remain
for this concept.
Taking into account these challenges a new process con-
cept is proposed. The process concept considers a particu-
late redox material in combination with a second
particulate heat transfer material to extensively decouple
the process steps. Furthermore the concept considers a
quasi-counter ow solid phase heat exchanger, and the
use of multiple reactors with optimized partial pressures
for the minimization of the vacuum pumping power
demand.
2. Concept
2.1. Description
The schematic in Fig. 1 shows the basic principle of the
concept. It includes three particulate material cycles. In
the rst cycle, inert particles absorb the concentrated
solar radiation and provide high temperature heat for the
Fig. 1. Process scheme: the particulate redox material (stream 2) is cycled
between the reduction-reactor (RR) and the oxidation-reactor (OR). The
high temperature heat for the reduction is provided by the solar heated
particulate stream 1. The particulate stream 3 is used for heat recovery and
transfers heat from the reduced redox material to the redox material after
the oxidation step.
reduction reactor (RR). The actual redox material is cycled
as stream 2 between the reduction-reactor (RR Eq. (1))
and the oxidation-reactor (OR Eq. (2)). In two heat
recovery sections (Cooling Redox and Pre-Heating Redox)
heat is transferred from the reduced redox particles to the
oxidised redox particles after leaving the oxidation-reactor
(OR) by means of a third inert particle stream. The reduc-
tion-reactor (RR) as well as the single heat exchanger
stages (HX) have two streams entering which are mixed
in the units. The streams are again separated at the exit
of the units. More information on the heat exchanger units
is given in Brendelberger et al. (2014) and Felinks et al.
(2014).
The purpose of the rst cycle (stream 1 absorption) is
to use the solar radiation to heat particle stream 1 and
increase its thermal energy. Therefore, the particles are
irradiated in the receiver (RE) and then stored at the tem-
perature level T1,high in a storage unit (ST). Then the hot
particles are used as a high temperature heat source for
the reduction reaction of the redox material in the reduc-
tion-reactor (RR). As heat is provided to the reaction the
particles lose sensible energy and are fed back into the
receiver (RE) at the lower temperature level T1,low.
The second particulate material cycle (stream 2 redox)
illustrates the stream of the actual redox material. The
redox material is fed into the reduction-reactor (RR) at a
temperature T2,rr_in and reduction extent drr_in and mixed
with stream 1. The reduction-reactor (RR) is operated at
a xed oxygen partial pressure pO2 which is achieved using
a vacuum system. Through high temperature heat transfer
from stream 1 to stream 2 the temperature of stream 2 is
further increased and the redox material is reduced and it
 S. Brendelberger, C. Sattler / Solar Energy 113 (2015) 158170
leaves the reduction-reactor (RR) after separation from
stream 1 particles at a temperature T2,rr_out and a reduction
extent drr_out. Subsequently the hot, reduced redox stream
enters a heat recovery system to transfer sensible heat to
stream 3 while cooling. The reduced particles of stream 2
leave the cooling section at a temperature T2,cd_out and
the reduction extent drr_out. The stream has then to be fur-
ther cooled to the oxidation temperature Tox before it
enters the oxidation-reactor (OR). Here the reduced redox
material stream is used to split H2O, CO2 or a combination
of both. While in principle the process can be applied to all
three cases the following analysis considers only H2O for
reasons of simplicity. Exothermic heat generated during
the reaction is removed from the reactor. The redox stream
leaves the oxidation-reactor (OR) at the temperature Tox
and the reduction extent dox_out. Afterwards the redox
stream is fed into the second heat recovery section where
it is pre-heated by the high temperature heat of the particles
in stream 3. The redox particle stream leaves the pre-heat-
ing section at a temperature T2,ph_out which is equal to
T2,rr_in. In Fig. 1 two heat exchange stages per recovery sys-
tem are depicted HXC1 and HXC2 for the cooling of the
redox stream and HXH1 and HXH2 for pre-heating the
redox stream. The number of stages in each recovery sys-
tem should be optimized for a given set of boundary
parameters (Felinks et al., 2014).
The third stream consists of particles which are used as
solid heat transfer medium. Stream 3 cycles between the
two heat recovery sections. It enters the cooling redox sec-
tion at a temperature T3,cd_in and leaves it at a higher tem-
perature T3,cd_out. Its heat is then used in the pre-heating
redox section to heat the redox stream while lowering its
own temperature from T3,ph_in to T3,ph_out.
2.2. Process characteristics and challenges
An indirect concept has the inherent drawback that for
reaching the same temperature during the reduction reac-
tion as in a receiverreactor, the absorbing material has
to have a somewhat higher temperature. Therefore, higher
heat losses have to be expected. The impact of the higher
heat losses on the system performance will be analysed in
Section 3.
The concept has increased complexity due to the inte-
gration of additional material streams and additional pro-
cess elements. However, the indirect concept decouples the
solar integration from the reaction and hence separates the
requirements for the receiver and for the reduction reactor.
While the process schema becomes more complex, con-
strains on the single process units are reduced, increasing
the exibility for design and operation.
A specic challenge of this concept is to nd a compat-
ible combination of redox particles and inert particles
which are stable under the process conditions. Also the
handling of the particles is challenging and under further
investigation. In the reduction-reactor, and in the heat
exchange stages, particles of two streams are mixed to
161
provide high heat transfer rates between both particle
streams. Afterwards the particles of the two streams are
separated. In the case of particles with diering sizes, the
separation might be achieved by sieving. Other separation
methods are possible if the particles dier in other physical
properties like density or their magnetic state. An analysis
of the heat transfer between the particles in the particle mix
and the implications for the system can be found at
Brendelberger et al. (2014) and Felinks et al. (2014).
2.3. Concept advantages
In the following subsections the advantages of the con-
cept are described. To better understand the potential of
the concept some general prerequisites of solar-driven ther-
mochemical redox processes for the ecient production of
signicant amounts of solar fuel are briey outlined. The
framework of these requirements is given by the perfor-
mance of experimentally tested redox materials. Central
requirements are:
 Provision of high temperature heat
 Low partial pressures of oxygen during reduction
 Low auxiliary energy consumption
 High solid heat recovery rates
 Continuous use of solar radiation
 Reasonable performance during part load
 Scalability
Many proposed concepts in literature do not address at
least one of these requirements and it is not a simple task to
overcome these constraints at a later stage of development.
Instead it is recommended to consider all these aspects in
the early stages of the concept development to avoid unsat-
isfactory compromises being adopted later in the
development.
The herein proposed concept is an attempt to provide a
strategy to meaningfully account for the outlined require-
ments. The concept is considering the decoupling of several
process steps in order to maximize the design and opera-
tion exibility of the related technical units and to make
the process constrains manageable by dividing them to
the decoupled steps. The term decoupling is used to
describe a spatial and temporal separation of dierent
physical or chemical phenomena. Especially the decoupling
of the solar integration and the reduction reaction by use of
a heat transfer material has the potential to decrease tech-
nical challenges. These aspects will be discussed in further
detail in the following sections.
2.3.1. Decoupling
Most of the concepts for solar thermochemical cycles in
the literature propose processes where the solar integration
is coupled to the thermal reduction using so called receiver
reactors (Chueh et al., 2010; Diver et al., 2010; Ermanoski
et al., 2013; Furler et al., 2012; Gokon et al., 2009; Kaneko
et al., 2011; Lapp et al., 2013; Roeb et al., 2011). While
162 S. Brendelberger, C. Sattler / Solar Energy 113 (2015) 158170
often heat recovery is not considered in the design, some of
the concepts have an inherent heat recovery approach
(Diver et al., 2010; Ermanoski et al., 2013; Lapp et al.,
2013). To enable a continuous operation, concepts are pro-
posed where the redox material is positioned on a cylinder
and rotated from a receiverreactor section to an oxidation
reactor section (Diver et al., 2010; Kaneko et al., 2011;
Lapp et al., 2013). The residence time of the redox material
in each reactor zone is strongly linked to the rotation steed
and the reactor sizes. The exibility for choosing optimal
sizes for both reactors is limited by the circumference of
the rotating cylinder. This leads to compromises in the
selection of design and operational parameters (Lapp and
Lipinski, 2014) which may result in reduced system ecien-
cies especially during part load.
Ermanoski et al. (2013) pointed out the benet of decou-
pling the reduction step from the oxidation step to account
for the discrepancy in the characteristic times of the two
reactions. They therefore proposed to transport a particu-
late redox material through the cycle. With this approach,
the sizes of the reactors can be chosen independently giving
more freedom in the selection of the residence times. Still,
the concept considers a receiverreactor with coupled solar
integration and reduction reaction. In addition the pro-
posed heat recovery strategy is strongly linked to the recei-
verreactor resulting in challenges described above.
In the herein proposed new indirect concept the idea of
decoupling is further expanded so that the process steps
solar integration, thermal reduction, oxidation and heat
recovery are implemented in independent units with clearly
denable interfaces. This permits the design and optimiza-
tion of each unit to be undertaken somewhat
independently.
2.3.2. Heat transfer particles
The application of heat transfer particles has a great
potential for improving the system performance by
enabling new operational strategies. The rst clear benet
is the possibility to store the heat transfer particles and
make the operation of the redox cycle to a certain extent
independent of the current solar irradiation. This permits
that the redox cycle can be operated continuously near
design point eciency even during changing solar irradia-
tion conditions.
Due to the high specic surface of the particle streams,
high heat transfer rates can be realized. This applies to
the solar integration in the receiver as well as to the heat
transfer between the dierent kinds of particles in the reac-
tor and the heat recovery stages.
2.3.3. Receiver
So far, in most receiverreactor concepts proposed in lit-
erature the redox material is directly irradiated in a con-
trolled atmosphere with a low partial pressure of oxygen
(Chueh et al., 2010; Diver et al., 2010; Ermanoski et al.,
2013; Furler et al., 2012; Gokon et al., 2009; Kaneko
et al., 2011; Lapp et al., 2013; Roeb et al., 2011). This leads
to the requirement of a window. The window is often posi-
tioned close to the aperture to reduce the window size since
quartz glass windows of high quality are so far not avail-
able for larger dimensions. The high process temperatures
require high concentration factors to limit the re-radiation
losses. This results in high solar uxes at the level of the
windows. Extreme care has to be taken to avoid the soiling
of the windows in such an environment, especially if a par-
ticulate material is used in the receiverreactor. The size
limitations of these windows have also to be considered if
the scalability of the concept is discussed.
If particles are used in receiverreactors and long resi-
dence times are needed, often beam down congurations
are considered. Receiverreactors for beam down system
also have the advantage that a contact between the absorb-
ing particles and the window can be avoided more easily.
Nevertheless, beam down systems are in a less mature stage
of development and their complex optics are challenging
for the eciency and system costs (Segal and Epstein,
1999). Additional research eort has to be provided if beam
down congurations are considered.
In the herein proposed indirect concept there are less
constraints for the receiver. This is due to the combination
of its decoupling from the reactor, the use of particles, and
the assumed ecient solid phase heat recovery system. A
highly ecient heat recovery system signicantly reduces
the necessary temperature increase which has to be pro-
vided by solar irradiation. If heat recovery rates of 0.75
can be reached and similar particle mass ow rates of heat
transfer particles and redox particles are considered this
temperature dierence is in the order of 200 K. At the tar-
geted high heat uxes the residence times of the particles in
the receiver can be kept relatively short. Since no special
requirements on the atmosphere are to be met, a window
might be avoided but increased convection losses would
have to be considered. Convection losses can be limited
by declined apertures (Clausing 1981, 1983) and might be
compensated by a performance gain due to the absence
of reection losses of the window. Given the requirements
above, a free falling particle open cavity receiver on a tower
might be considered. Similar receiver types are currently
investigated (Roger et al., 2011; Siegel et al., 2010; Wu
et al., 2014, 2011) and are to be adapted to the process
requirements.
2.3.4. Materials
As described in Section 2.3.2, the introduction of heat
transfer particles comes with its own challenges. However,
it reduces the requirements of the redox material signi-
cantly due to the decoupling of the solar integration and
the thermal reduction. The coupled solar integration and
thermal reduction in a receiverreactor leads to demanding
requirements if reaction limitations by heat transfer, mass
transfer and reduction kinetics have to be avoided. As
described above the high process temperatures presuppose
high levels of solar concentration. Since the ratio of cavity
surface to aperture area is limited for scalable designs, also
 S. Brendelberger, C. Sattler / Solar Energy 113 (2015) 158170
the redox material at the level of the cavity walls is exposed
to high solar uxes. A perfect redox material would heat up
homogenously and reduce directly to the thermodynami-
cally described reduction extent. Due to limitations in heat
transfer, in oxygen diusion in the redox material, in sur-
face reaction and in oxygen removal in the gas phase, the
reaction propagation in a real reactor may be considerably
delayed, with an actual achieved reduction extent well
below that for the thermodynamic equilibrium. This is par-
ticularly the case due to the low thermal conductivities and
limited oxygen diusivities of typical redox material candi-
dates which leads to reduction extent gradients for thicker
structures. This eect was reported for receiverreactors
where the heat and mass transfer and the chemical reaction
were simulated (Kaneko et al., 2011; Lapp and Lipinski,
2014). Also Miller et al. (2014) address this point by analys-
ing diusion lengths for heat and mass transport of typical
redox material candidates.
In case of the indirect concept the eective surface area
for the heat exchange in the particle mix can be much larger
than in the receiver assuming a larger reactor volume with
longer residence times. Due to this, more time is available
for the reaction to progress and a reduction extent closer
to the thermodynamic limit may be obtained.
2.4. Methodology
For the analysis of the process concept a model was
built using MATLAB1. The physical and chemical interac-
tions in each step of the process are calculated considering
energy and mass conservation.
The incident power on the primary mirrors is dened as:
P solar DNI Acollector
with the collector area Acollector and the direct normal irra-
diance DNI. The power absorbed by the irradiated parti-
cles Pabsorption is determined by Eq. (4) considering the
mirror losses lm, the aperture intercept lai, the optional win-
dow lw, and the absorptivity a.
P absorption lm lai lw aP solar
The hot absorbing particles re-radiate energy out of the
aperture. This power loss Pre-radiation is a function of the
temperature T and the concentration factor C.
P re-radiation P absorption rT 4 =C DNI
The absorption and emission coecients are considered
being equal. The thermal power Pthermal provided by the
receiver is used to increase the temperature of the inert par-
ticles of stream 1.
P thermal P absorption  P re-radiation
In the reduction-reactor the heat of the inert particle
stream 1 is used to heat the redox particle stream 2 and
to reduce it in an atmosphere with dened oxygen partial
1
MATLAB (R2008b) www.mathworks.com.
163
pressure. Reduced oxygen partial pressures are maintained
by lowering the absolute pressure in the chamber using a
vacuum system. Purging with a sweep gas or a combination
of purging and reduction of the working pressure are also
options for maintaining a low oxygen partial pressure but
are likely to result in larger parasitic losses Ermanoski
et al. (2013), Lapp et al. (2012) and are therefore not dis-
cussed here.
This study focuses on the introduction of the new con-
cept and its process implications rather than on material
aspects. Therefore ceria is chosen because it is a well inves-
tigated reference redox material (Abanades and Flamant,
2006; Chueh and Haile, 2010; Lee et al., 2013; Panlener
et al., 1975) which has been considered in several previous
solar thermochemical redox concepts (Chueh et al., 2010;
Ermanoski et al., 2013; Lapp et al., 2013).
Material candidates for stream 1 and stream 3 are high
temperature materials like zirconia, alumina or silica but
also adequately doped ceria may be considered. In this
study a nonreactive material with the physical properties
of ceria is assumed. Again, this helps to keep the focus of
the analysis on the concept performance, rather than on
material aspects. Since the mass ow rates of the streams
can be selected independently, a material with diering heat
capacity is expected to result in a similar process perfor-
mance when the mass ow rates are adjusted accordingly.
The model of the reduction-reactor considers the condi-
tions of the particles of stream 1 and stream 2 as input
parameters. The oxygen partial pressure is set to a xed
value and is assumed to be maintained constant. The
reduction extent is calculated based on this oxygen partial
pressure and the temperature of the redox material of
stream 2 leaving the reactor. For this calculation the ther-
3
modynamic data of the redox material is used (Panlener
et al., 1975), assuming that the residence time in the reduc-
tion-reactor is long enough for the thermodynamic equilib-
rium reduction extent to be reached. For redox material
with fast reaction kinetics like ceria and small particle sizes,
this assumption seems reasonable (Schee et al., 2014).
4 The oxidation-reactor is operated with steam at ambient
pressure and at a xed oxidation temperature. The exother-
mic heat of the oxidation is made available for auxiliary
processes. A gas-phase heat recovery system is considered.
The reduction extent after oxidation is calculated with the
5 above described thermodynamics of the redox material and
the operational parameters. Excess ratios of steam to
hydrogen are calculated assuming a counter ow arrange-
ment of steam and redox material (Bader et al., 2013).
For the recuperation of the sensible heat of the redox
particles the heat of the hot reduced redox particles is
6 transferred to the particles of stream 3. Afterwards the
stream 3 particles are used to heat the redox particle stream
after leaving the oxidation-reactor. Using one mixing and
separation unit results in a co-current heat exchanger. By
using multiple units a quasi-counter-current heat transfer
system is realized (Brendelberger et al., 2014; Felinks
et al., 2014).
164 S. Brendelberger, C. Sattler / Solar Energy 113 (2015) 158170

The auxiliary electrical power demand is calculated for Table 1

the elevation of the particles between the dierent process Process parameters for performance calculation of base case and
conservative cases.
units and for the vacuum pumping system. In addition
the necessary auxiliary heat to provide the required steam Parameters Label Valuea base case
(conservative case)
ow rate at the oxidation temperature is calculated
considering a gas phase heat recovery system with an Concentration factor C 5000 (3000)
Direct normal irradiance DNI 1 kW/m2
eectiveness gGHR. Maximum temperature in receiver T1,max 1805 K
The power demand of the vacuum system is obtained by Maximum redox temperature T2,max 1773 K
calculated the work related to an isothermal change of Oxidation temperature Tox 1373 K
pressure. Waste heat to electrical energy eciency gw2e 0.4 (0.1)
Particle lift eciency glift 0.4
1 p Solid phase heat recovery eectiveness gSHR 0.8 (0.7)
P vacuum n_ O R T ln atm 7 Gas phase heat recovery eectiveness gGHR 0.95 (0.85)
gvacuum 2 p O2
Particle lifting height htotal 20 m
So far in literature the pumping eciency gvacuum has Emissivity, absorptivity e 0.9
a
been considered constant (Ermanoski et al., 2013). An Where applicable the parameters of Ermanoski et al. (2013) were used
analysis of pumping eciencies of commercial systems sug- for model comparison.
gests rather, that the pumping eciency decreases at lower
pressure. While the eciency of an analysed commercial the waste heat ow surpasses the heat ow demand, the
multi stage pump arrangement for pumping the released remaining waste heat ow is considered as lost to the envi-
mass ow rates of oxygen at 1000 Pa stays well above ronment. If the heat ow demand cannot be compensated
15%, a pump conguration for the same mass ow rates by the waste heat ow, an additional heat ow Q_ additional
at 1 Pa falls below 1%. Larger losses are due to increased has to be provided for the process. The heat ow of the
backows at low pressures and higher friction losses at lar- oxygen stream leaving the system is considered as lost to
ger volumetric ow rates. In between the pump stages the the environment.
compressed gas has to be cooled considerably. Further
1
details of the pumping eciency analysis will be published Q_ additional P vacuum P lift Q_ steam  Q_ sensible  Q_ ox 10
elsewhere. Since the analysed pumping arrangements were gw2e
not optimized with respect to energy consumption, a more
optimistic semi-empirical pressure dependent pumping e- 2.4.1. Optimization method
ciency is dened: The performance of the system is calculated in an itera-
  tive manner considering the heat and mass ows within the
p
gvacuum p 0:07 log 0:4 8 system, incoming and outgoing uxes and the chemical
patm
reactions based on thermodynamic considerations. Besides
In the assumption the pumping eciency gvacuum drops the process parameters given in Table 1 a set of mass ow
from 40% at 100 kPa to 5% at 1 Pa. This semi-empirical rates for the considered particle streams is selected. The
formulation is limited to pressures between 1 Pa and system converges after about 500 iterations to a constant
100 kPa. state (see Fig. 2). The values of the variables reached after
An ecient transportation method for the particles is a 500 iterations dier by less than 0.1% relative to the once
requirement for the proposed concept. In addition to the achieved after 2000 iterations.
redox material, the particles of stream 1 and stream 3 have
to be transported between dierent steps of the process.
The power related to the lifting of the particles is calculated
for the sum of the particle streams with an assumed total
lifting height htotal and a lifting eciency glift (see Table 1).
m_ 1 m_ 2 m_ 3 g htotal
P lift 9
glift

The auxiliary electrical power demand is converted into

an equivalent auxiliary heat ow demand with a factor of
1/gw2e. The sum of this equivalent heat ow demand and
the heat ow demand for the provision of steam at the oxi-
dation temperature is compensated by the waste heat ow
of the process. The waste heat ow comprises of the non-
recovered sensible heat ow of the redox stream 2:
Q_ sensible 1  gHR m_ 2 c2 T 2;rr out  T ox and the heat ow Fig. 2. Convergence of the process after about 500 iterations to a
of the exothermal oxidation reaction: Q_ ox DdDH n_ 2 . If stationary state.
 S. Brendelberger, C. Sattler / Solar Energy 113 (2015) 158170
The converged solution is characterised by the tempera-
tures of the particle streams and the reduction extent of the
redox material at all steps, and the incoming and outgoing
mass and energy ows. Based on this converged solution
the performance of the system is analysed considering the
resulting hydrogen production rate and the power con-
sumption of the system. The solar-to-fuel conversion e-
ciency shortly called solar eciency of the process is
dened as:
n_ H2 HHV H2
gsolar
DNI ACollector Q_ additional
The denominator comprises the solar input at the collec-
tor eld area ACollector and the additionally required heat
ow Q_ additional for the non-compensated auxiliary power
demand.
Dierent cases are assessed by varying the oxygen par-
tial pressure while the other process parameters are kept
constant. For any given set of process parameters a nonlin-
ear multivariable optimization routine is applied to nd
mass ow rates of the dierent particle streams which result
in the highest solar-to-fuel conversion eciency respecting
maximum temperature limits for the dierent particle
streams. These optimized eciency values are depicted in
the following gures as function of the oxygen partial
pressure.
3. Performance analysis
3.1. Base case
The introduced model is used to calculate the
performance of the proposed indirect particle based
process concept for dierent process parameters. For
the validation of the process model methodology the
performance results are compared to the direct particle
based system presented by Ermanoski et al. (2013). For
this purpose a receiverreactor is included in the model
description. Assuming the same boundary conditions,
the calculated system performance agrees well with
the reference.
Firstly, the indirect concept is compared to the direct
concept to assess the eciency penalty resulting from the
indirect approach. A concentration factor value of
C = 5000 and a reduction reactor operation temperature
of 1773 K are assumed. The heat recovery eectiveness is
set to 0.8 for both systems. For the heat recovery system
presented in this paper, this requires an arrangement of
10 units with an eectiveness of 0.9 per unit (Felinks
et al., 2014)). Further process parameters are given in
Table 1.
The performance of the direct system is shown in
Fig. 3. For oxygen partial pressures above 100 Pa
the system performance is similar to the results pre-
sented by Ermanoski et al. (2013). For lower partial
pressures the pressure depended vacuum pumping
165
eciency (Eq. (8)) plays an increasing role for the
overall performance and the solar eciency drops
signicantly.
The second calculated performance shows the indirect
system with the same boundary conditions like in the direct
case. The maximum temperature limits of the particles in
stream 1, 2 and 3 are set to 1773 K respectively. The e-
ciency of the indirect concept is on average 2 percentage
points lower compared to the eciency of the direct con-
cept. Even though the redox material can in theory reach
11 1773 K, this would require an innitely large mass ow rate
of stream 1. As discussed in Section 2.4.1 an increase in the
mass ow rate of stream 1 is related to a larger auxiliary
power demand for particle transportation, limiting the
maximum redox temperature during the optimization. At
reduced redox material temperatures lower reduction
extents are obtained which result in the observed eciency
discrepancy between the direct and indirect concept.
Even though the temperature of a redox material may be
limited to a certain maximum value due to stability and
volatilisation issues, the particles used for the absorption
in the receiver may in principle not have the same limita-
tions and may therefore be operated at a higher tempera-
ture. With an increased maximum temperature limit of
stream 1 particles the redox material can reach a tempera-
ture of 1773 K at a nite stream 1 mass ow rate. Higher
temperatures of stream 1 particles lead to higher heat
losses. On the other hand, higher temperatures also
increase the reduction extent and thus the thermal to chem-
ical eciency. The system is analysed at dierent oxygen
partial pressures as a function of the temperature limit
for stream 1 particles in the receiver. In Fig. 4 the solar e-
ciency of an indirect system relative to a direct system at a
reduction temperature of 1773 K is given as a function of
the stream 1 temperature limit T1,max for several oxygen
partial pressures. By increasing the temperature limit, the
Fig. 3. Solar eciency as function of oxygen partial pressure. The
maximum temperature of the particles in stream 1 is varied. For
comparison the solar eciency of a direct system with a heat recovery
rate of 0.8 is included. Further parameters for the calculation are given in
Table 1.
166 S. Brendelberger, C. Sattler / Solar Energy 113 (2015) 158170
dierence between the indirect and the direct system
becomes less signicant. The higher thermal to chemical
eciency overcompensates the increased heat losses and
the solar to chemical eciency approaches the performance
of a direct system. For pressures between 10 Pa and
10,000 Pa the relative eciency grelative reaches 0.99 at
about T1,max = 1805 K. For 1 Pa the relative eciency is
minimally aected by a change in T1,max and stays at
around 0.975. For 100,000 Pa the relative eciency grows
rapidly with increasing T1,max but stays slightly below
0.975 for T1,max = 1810 K. For a temperature limit of
1805 K the relative eciency losses of the indirect system,
for all considered cases, remain below 5% and, in most
cases, under 1%. In the following discussion a stream 1
temperature limit of T1,max = 1805 K will be assumed. It
is to be noted, that even though the maximum temperature
limit for the optimization routine is increased, the actual
obtained maximum temperature of the optimized solution
might be lower than this value.
In Fig. 3 the performance of an indirect system with a
stream 1 temperature limit T1,max = 1805 K is depicted.
In this case, the eciencies are only slightly lower
compared to the direct case for oxygen partial pressures
down to 30 Pa. Since the vacuum pumping power
demand increases with decreasing pressures the available
excess waste heat for the lifting of the particles gets
reduced at lower pressures. As a result the optimized
eciency values drop under the values of the direct
system and approach the values of the indirect system
with a stream 1 temperature limit of T1,max = 1773 K.
This analysis shows that the increased re-radiation losses
are not a critical eciency drawback of an indirect system
under the given boundary conditions. The maximum
temperatures will be rather dened by technical and
material limitations. The indirect system with T1,max =
1805 K at C = 5000 will be considered as the base case
in the following analysis.
Fig. 4. Relative solar eciency of a indirect system compared to a direct
system at 1773 K as a function of the temperature limit for stream 1 heat
transfer particles.
3.2. Conservative case
The base case scenario, shown in Fig. 5, considers rather
optimistic assumptions for the boundary conditions (see
Table 1). In the following analysis, for several boundary
conditions more conservative values are assumed and the
changes in system performance are discussed. The conser-
vative values accumulate from case to case so that in the
nal case conservative values are considered for all dis-
cussed boundary conditions.
Starting from the base case scenario the concentration
factor is reduced from C = 5000 to C = 3000 which is a
more realistic but still challenging value for a tower cong-
uration. The solar eciency values in this scenario are
smaller than in the base case especially at the peak of the
eciency curve. Here the two cases dier by about 2.5 per-
centage points which seems reasonable considering a 40%
lower concentration factor.
For the next case also the number of heat recovery
stages is reduced from 10 to 6 which results in a reduced
solid phase heat recovery eectiveness of gSHR = 0.7 com-
pared to the previous value of gSHR = 0.8. This reduction
of the heat recovery eectiveness of 12.5% results in
another solar eciency shift of a similar magnitude like
in the last case. Also here the dierence in the eciencies
diminishes for the lower and upper limits of the considered
oxygen partial pressure range and reaches a maximum
value of about 5.5 percentage points compared to the base
case at the peak eciency. This emphasises the importance
of a solid phase heat recovery system for the process.
In the next case the conversion eciency of waste heat
to electricity is reduced form gw2e = 0.4 to gw2e = 0.1
accounting for higher non-recoverable heat losses. With
this assumption the quality of the eciency curve changes
signicantly, shifting the peak eciency to a higher oxygen
partial pressures of about 100 Pa and reducing it to 17.8%
compared to a peak eciency of the base case of about
29.5%. Compared to the last case the reduced conversion
Fig. 5. Comparison of dierent parameter sets demonstrating the eects
of more conservative boundary conditions.
 S. Brendelberger, C. Sattler / Solar Energy 113 (2015) 158170
eciency mainly aects the performance at low oxygen
partial pressure levels. The main consumer of auxiliary
power at these pressures is the vacuum system. This again
shows that the vacuum system eciency is an important
factor limiting the minimum operational partial pressure
of the reduction reaction.
In the last scenario, in addition to the conservative val-
ues of the previous cases, the gas phase heat recovery eec-
tiveness is reduced from gGHR = 0.95 to gGHR = 0.85. This
change is aecting the eciency mainly at higher partial
pressures since here larger excess steam rates result in con-
siderable auxiliary heat requirements. The peak eciency is
reduced by another percentage point resulting in an abso-
lute peak solar eciency value of 16.5%.
Low oxygen partial pressure during the reduction are
very important to reach high reduction extents which
are essential for high process eciencies. On the other
hand the auxiliary power consumption for maintaining
reduced partial pressures is increasing signicantly at
lower pressures especially below 100 Pa which limits the
operational minimum pressure and achievable peak e-
ciency. Therefore it is crucial to further reduce the auxil-
iary power consumption of the vacuum system. One
possible solution is the utilization of multiple reactors
operated at optimized pressures. This concept will be dis-
cussed in the next section.
3.3. Multi reactor system
As seen in the previous analysis the auxiliary power
demand limits the maximum solar eciency particularly
at low oxygen partial pressures. This eect is observed in
the base case scenario and further more pronounced in
the conservative scenarios. One possibility to reduce the
auxiliary power demand is by using a multi reduction reac-
tor arrangement. Here the pO2-level in the reactors is grad-
ually decreased allowing to remove a share of the released
oxygen at higher pO2-levels. Since the pumping power
demand (Eq. (7)) and the pumping eciency (Eq. (8))
depend on the partial pressures at which the oxygen is
released, the total pumping power eort can be reduced
by optimizing the pressures in the dierent reactors
(Brendelberger et al., 2014). In addition to a reduced power
demand, the distribution of the oxygen removal also
reduces the required volumetric ows and by this the sizes
of the pumps. While the analysis here is focused on a vac-
uum system the approach can also be applied if purge gas
or a combination of both is considered.
The theoretical pumping power saving potential is sig-
nicant. Already for a 3 reduction reactor system with opti-
mized pressures and a nal pressure of 100 Pa the pumping
power demand is reduced by more than 40% compared to a
one reactor system (Brendelberger et al., 2014). Fig. 6
shows the optimized pressures of the reactors for a 3
reduction reactor system for dierent nal oxygen partial
pressures. While the pressure of reactor 3 is given by
the selected nal pressure, the pressures in reactor 1 and
167
Fig. 6. Optimized oxygen partial pressures for a 3 reactor system. Reactor
3 has a xed nal oxygen partial pressure while the pressures of the other
two reactors are optimized for minimum total pumping power.
reactor 2 are obtained by minimizing the total pumping
power demand.
The model is extended to include multiple reduction
reactors. The mass ow rates of the stream 1 particles
entering the dierent reduction reactors are independently
optimized. The partial pressures in the single reduction
reactors are dened accordingly to the values obtained by
minimizing the pumping power demand as function of
the nal pressure and the number of reactors (see the exam-
ple of a 3 reactor case in Fig. 6). The pO2 value in the last
reduction reactor is set to a xed value which is changed in
a parametric study. The schematic of a process with a three
reduction reactor arrangement and the particle ows is
shown in Fig. 7. The single reduction reactors are labelled
with RR1 to RR3. The RR3 is operated at the lowest
pO2-level.
The performance of a 2 reactor and a 3 reactor system
are simulated using the same boundary conditions as in
the last conservative case discussed in Section 3.2. The
resulting solar eciencies can be seen in Fig. 8. Also the
eciency of the 1 reduction reactor system is shown for
comparison.
As can be seen, the dierent systems show a similar per-
formance at the upper limit of the considered oxygen par-
tial pressure range. For smaller oxygen partial pressures
the systems reach higher solar eciencies with an increas-
ing number of reactor units. The peak of the eciencies
are slightly shifted towards lower partial pressures. The
peak eciency of the 3 units system is about 20% higher
than a 1 unit system. While the peak eciency increases
by about 2.2 percentage points when two reactor units
are used instead of one, the third unit only adds another
1.0 percentage points, indicating a shrinking performance
gain with an increasing number of reactor units. If one fur-
ther considers the increase in system complexity a reason-
able number of reactor units is likely to be less than 4.
While the analysis gives an estimate on the potential e-
ciency benet, the actual trade-o between the dierent
168 S. Brendelberger, C. Sattler / Solar Energy 113 (2015) 158170
Fig. 7. Schematic of the process layout for a system with 3 reduction reactors.
Fig. 8. Increasing solar eciency with increasing number of reduction
reactors at low oxygen partial pressures.
options has to be based on a more sophisticated process
model considering the reactors in more detail.
4. Conclusions
A new indirect particle-based concept for solar-driven
thermochemical redox cycles is proposed. The potential
benets of the indirect concept on the design and opera-
tional exibility are numerous. This is mainly due to the
decoupling of the process steps and the resulting partition-
ing of the requirements on the separate step. The residence
time in the dierent stages of the process can be chosen
independently to a large extent. By this, the dierent steps
of the process can be separately optimized avoiding low
performing design and operation compromises. Further-
more, the interfaces between the single process steps can
be clearly dened and the implementation of the process
steps can be independently developed and optimized. For
example, the receiver layout can focus on heating inert par-
ticles and therefore can be kept relatively simple. Designs
already being developed in the eld of open particle receiv-
ers may be adapted. In addition, the use of heat transfer
particles permits the storage of high temperature heat
and the continuous operation of the redox cycle even dur-
ing uctuations of the solar radiation.
A numerical model description of a particle based pro-
cess with heat recovery is presented to evaluate the perfor-
mance of the new concept. Firstly, the model is used to
compare the performance of the indirect system with the
performance of a direct system. In an indirect system the
temperature in the receiver is larger than the temperature
of the redox material in the reactor. This higher receiver
temperate results in higher re-radiation losses compared
to a direct system. Nonetheless, by increasing the receiver
temperature by about 35 K compared to the receiverreac-
tor temperature of a direct system, while keeping the max-
imum temperature in the reactor constant, similar solar
eciency values are reached compared to the direct case.
This shows that higher re-radiation losses of the indirect
system are at an acceptable level.
The concept is analysed for cases with dierent bound-
ary conditions. Starting from an optimistic base case, sub-
sequently the concentration factor, the solid phase heat
recovery, the conversion eectiveness from waste heat to
electricity, and the gas phase heat recovery eciency are
lowered. While the gas phase heat recovery eectiveness
plays a more important role at higher oxygen partial pres-
sures, the concentration factor and the solid phase heat
recovery eectiveness impact the eciency over a wide
pressure range. The waste heat electricity conversion
eectiveness has the largest eect at low partial pressures.
This is mainly due to the increasing electrical power
consumption of the vacuum system at low partial pres-
sures. In contrast to other studies, a pressure dependent
 S. Brendelberger, C. Sattler / Solar Energy 113 (2015) 158170
vacuum pumping eciency is considered in the process
simulation. As a consequence the peak eciencies are
reduced and shifted to higher oxygen partial pressures
compared to reported performances in literature with an
assumed constant pumping eciency. This shows that the
parasitic power consumption of the vacuum system is likely
to limit the reasonable operational pressure to more than
10 Pa. Since low oxygen partial pressures are essential for
reaching high reduction extents, a reduction of the auxil-
iary vacuum power consumption is crucial for increasing
the peak solar eciencies.
One option to reduce the auxiliary power consumption
of the vacuum system is dividing the reduction by using a
sequence of reduction reactors operated at optimized pO2-
levels. The solar eciencies of a two and a three reactor
system are calculated and compared with a one reactor sys-
tem. A gain in peak solar eciency of about 20% is
obtained for a three reactor system. The additional perfor-
mance gain shrinks with increasing number of reactors
while the system complexity increases. So the denition
of an optimal number of reactors will require a more
sophisticated model, considering the implications of multi-
ple reactors in more detail and accounting for increased
system complexity.
As experimental studies in the last years have demon-
strated, an ecient transformation of solar radiation into
chemical energy by thermochemical redox cycles has pro-
ven to be technically extremely challenging. The concept
presented here oers an alternative approach that gives
more freedom for the design and for the choice of opera-
tional parameters. While the concept has specic challenges
with respect to material issues, particle handling and
increased system complexity, the authors expect it to allow
more practicable and realistic implementation solutions,
which adequately address the dierent process
requirements.
Acknowledgements
This work was supported by the Federal Ministry of
Education and Research of Germany (BMBF).
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