Solar Water Splitting For Hydrogen Production With Monolithic Reactors
Solar Water Splitting For Hydrogen Production With Monolithic Reactors
www.elsevier.com/locate/solener
Chemical Process Engineering Research Institute, Center for Research and TechnologyHellas (CERTH/CPERI),
P.O. Box 361, 57001 Thermi-Thessaloniki, Greece
b
Deutsches Zentrum fur Luft- und Raumfahrt e.V. (DLR), Institut fur Technische Thermodynamik, Solarforschung,
D-51170 Koln, Germany
c
Stobbe Tech Ceramics (STC), Vejlemosevej 60, DK-2840, Holte, Denmark
d
Johnson Matthey Fuel Cells Centre, Sonning Common, RG4 9NH Reading, UK
Received 21 July 2004; received in revised form 12 November 2004; accepted 23 February 2005
Available online 4 June 2005
Communicated by: Associate Editor Sixto Malato-Rodrguez
Abstract
The present work proposes the exploitation of solar energy for the dissociation of water and production of hydrogen
via an integrated thermo-chemical reactor/receiver system. The basic idea is the use of multi-channelled honeycomb
ceramic supports coated with active redox reagent powders, in a conguration similar to that encountered in automobile exhaust catalytic aftertreatment.
Iron-oxide-based redox materials were synthesized, capable to operate under a complete redox cycle: they could take
oxygen from water producing pure hydrogen at reasonably low temperatures (800 C) and could be regenerated at temperatures below 1300 C. Ceramic honeycombs capable of achieving temperatures in that range when heated by concentrated solar radiation were manufactured and incorporated in a dedicated solar receiver/reactor. The operating
conditions of the solar reactor were optimised to achieve adjustable, uniform temperatures up to 1300 C throughout
the honeycomb, making thus feasible the operation of the complete cycle by a single solar energy converter.
2005 Elsevier Ltd. All rights reserved.
Keywords: Water-splitting; Solar; Redox materials; Iron oxide; Honeycomb reactors; Hydrogen
1. Introduction
0038-092X/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.solener.2005.02.026
410
During the second step the oxidized state of the reagent is reduced, to be used again (re-generation), delivering some of the oxygen of its lattice according to the
reaction:
MOox ! MOred 12O2
The disadvantage is that a two-step process is required, consisting of a water splitting and a regeneration
(oxygen release) step. The advantage is the production
of pure hydrogen and the removal of oxygen in separate
steps, avoiding the need for high-temperature separation
and the chance of explosive mixtures formation.
Current research eorts have focused on thermochemical cycles based on various types of ferrites (Tamaura et al., 1995, 1998a,b, 1999, 2001; Kaneko et al.,
2001, 2002a,b; Kojima et al., 1996; Kodama et al.,
2003), iron oxide (Weidenka et al., 1997; Ehrensberger
et al., 1995, 1996), manganese oxide (Sturzenegger and
Nuesch, 1999), zinc oxide (Steinfeld, 2002) and combinations of the above (Steinfeld et al., 1998, 1999). It
has been suggested that the only feasible two-cycle redox
pairs are ZnO/Zn and Fe3O4/FeO (Steinfeld et al., 1999).
The concept has been proven experimentally: with the
most active of these materials, water splitting has reportedly taken place at temperatures as low as 627 C (Tamaura et al., 1998b; Steinfeld et al., 1999), however the
regeneration temperatures are still high (>1300 C), a
most important problem since it can cause signicant
411
droplets and subsequently passed through a high-temperature tube furnace where it transforms within a very
short time to the desired powder (Lorentzou et al.,
2004). The two latter methods provide an alternative
way for synthesis of materials with high defects concentration due to their common characteristic of very short
synthesis times and extremely high cooling rates; in addition they can also take place within reactors that can
provide for controlled oxygen partial pressure, therefore
tuning further the products oxygen vacancies
concentration.
Redox material powders synthesized via the methods
above were subsequently laboratory-tested with respect
to water-splitting activity and regeneration capability
in the form of powders as described below. These series
of experiments were focussed on determining the most
promising material compositions, to be thereafter synthesized in larger quantities and used for the coating
of SiC honeycombs for the eventual solar testing. In parallel, the dedicated solar reactor was designed, built and
tested in a solar furnace facility, in order to minimise
temperature gradients within the volume of the honeycomb absorber and develop the proper solar test programme. A detailed description of the experimental
procedure follows.
2.1. Powder synthesis
2.1.1. Solid-state synthesis (SSS)
For the reasons argued above the targeted redox
materials were MnZn- or NiZn-doped ferrites crystallized in the spinel structure. They were synthesized
by the typical mixed oxide route, which includes
powder mixing of component oxides, prering, milling,
spray drying and calcination at high temperatures
(1250 C) according to the scheme (MnZn ferrites):
Fe2 O3 x=3Mn3 O4 1 xZnO
! Mnx Zn1x Fe2 O4
2. Experimental
In this work, three routes were employed for the synthesis of iron-oxide-based redox materials: in the rst,
the mixed oxides were prepared with conventional
solid-state synthesis via sintering of the respective oxides
in a controlled-atmosphere sintering furnace; after the
calcination step the materials were cooled under controllable oxygen partial pressure so that materials with controllable defect chemistry were obtained (Tsakaloudi et
al., 2004). The second route involved the so-called selfpropagating high-temperature synthesis (SHS or combustion synthesis) reactions between iron metal powder
and oxygen in the presence of the dopant metal oxides
(Agraotis and Zaspalis, 2004). The third route selected
was Aerosol Spray Pyrolysis where a liquid solution of
the metal precursor salts is atomized in a spray of ne
412
is decomposed by pulling away some of the redox reagents lattice oxygen. This treatment (activation) reduces the reagent and results in solids very active
towards water splitting. Three dierent types of carbon
containing species were employed: tylose, diesel fuel
and wood chips. Compared to hydrogen or CO reductive means, these are low- or zero-cost waste streams
of typically low organics concentration. The reduction
process was not found sensitive to the activator type.
The rst set of experiments indicated that by adding less
than 10 wt.% of reductant, reduction was not ecient
and only very small quantities of hydrogen were produced; thus subsequent experiments reported below,
were performed with 10 wt.% of reductant. Both activated and non-activated samples were comparatively
evaluated.
2.3. Reagents characterization with respect to
water-splitting
The materials tested were Mn/(Ni)ZnFeO systems
of spinel (Mnx/(Ni)xZn1xFe2O4) and of wustite (Mnx/
(Ni)xZnyFe1xyO) structure as well as the component
oxides Mn3O4, NiO, ZnO and Fe2O3. A special laboratory unit has been set-up for the evaluation of the redox
reagents, described in detail in Nalbandian et al. (2004).
The basic component of the unit is a U-shaped reactor
placed in a temperature programmable furnace. All the
materials were tested for the water splitting reaction by
successive injections of water in a stream of Ar owing
continuously over the heated sample at temperatures
ranging from 750 to 1100 C. At preselected temperatures, known quantities of high purity water were injected to the reactor by using a microliter syringe. The
euent from the reactor was monitored through a mass
spectrometer (MS) detector (Balzers, Omnistar). The
sensitivity of the MS detector to hydrogen was calibrated by injecting a series of at least 10 constant volume
loops of a 2 mol% H2/Ar mixture. The quantities of
unconverted water and of produced hydrogen were calculated, based on the areas of the corresponding MS
injection peaks.
2.4. Regeneration under inert atmosphere
413
Fig. 1. (a) Front view of receiver-reactor for solar water splitting, (b) extruded reSiC honeycombs (carriers) and cast parts (housing
vessel), (c) position of thermocouples in the absorber.
414
415
416
SHS - (Mn0.5Zn0.5)FeO
600
SHS - (Ni0.5Zn0.5)FeO
SHS - (Mn0.5Zn0.5)Fe2O4+Activator
500
SHS - (Mn0.5Zn0.5)Fe2O4
Mn3O4 + Activator
NiO+Activator
400
300
200
100
500
SSS - (Ni0.66Zn0.33)Fe2O4+Activator
SSS - (Mn0.75Zn0.16)Fe2O4+Activator
SSS - (Mn0.75Zn0.16)Fe2O4
400
SSS - (Ni0.66Zn0.33)Fe2O4
300
200
100
0
0
1000
2000
3000
4000
5000
6000
1000
2000
3000
4000
5000
6000
3000
2000
1000
ASP - Mn0.5Zn0.5Fe2O4
ASP - Ni0.2Zn0.8Fe2O4
ASP - ZnFe2O4
0
0
10000
20000
30000
40000
50000
60000
Fig. 2. Total micromoles of hydrogen produced/g solid versus total micromoles of water injected/g solid for representative samples.
417
Table 1
Final comparison of the most representative materials tested with respect to water splitting
Material
SHS (Mn0.5Zn0.5)FeO
SHS (Ni0.5Zn0.5)FeO
SHS (Mn0.5Zn0.5)Fe2O4
ASP (Mn0.5Zn0.5)Fe2O4
ASP (Ni0.2Zn0.8)Fe2O4
ASP ZnFe2O4
SHS (Mn0.5Zn0.5)Fe2O4 + activator
3
SSS Mn0.75 Zn0.16 Fe2
0.09 Fe2 O4
2
SSS Mn0.75 Zn0.16 Fe0.09 Fe3
2 O4 activator
SSS (Ni0.66Zn0.33)Fe2O4
SSS (Ni0.66Zn0.33)Fe2O4 + activator
Fe2O3(A) + activator
Fe2O3(B) + activator
NiO + activator
Mn3O4 + activatora
28 3
22 3
0
30 3
80 10
65 8
7.5 2
0.75 0.2
11 2
0
10.5 2
34 3
26 3
1.1 0.3
66 8
100.8
1400
Argon flush
Argon flush
100.6
100.4
1000
100.2
O2 mixture
Introduction
Temperature (C)
] Weight (%)
1200
800
100.0
O2 mixture
Introduction
99.8
600
40
80
120
160
200
240
Time (min)
Table 2
Regeneration comparison of the most representative materials tested
Material
Temperature
range (C)
Peak
(C)
Temperature
range (C)
Peak
(C)
SHS (Mn0.5Zn0.5)FeO
SHS (Mn0.5Zn0.5)Fe2O4
SSS MnZn ferrite
Fe2O3(A)
Fe2O3(B)
Fe2O3(A) + 10% activator
1.59 0.1
1.19 0.1
0.68 0.1
3.32 0.2
3.31 0.2
3.09 0.2 (3.33 0.2
based on Fe2O3(A))
10.90 0.1
1.20 0.1
8001250
8001210
8001300
12001300
12001300
12001300
1065
1045
1075
1286
1290
1286
8001210
8001210
8001210
11201295
10801300
11101295
1060
1055
1090
1285
1280
1285
8001270
8001285
1260
1005
1.12 0.1
0.79 0.1
0.79 0.1
3.36 0.2
3.35 0.2
3.02 0.2 (3.37 0.2
based on Fe2O3(A))
9.1 0.1
2.07 0.1
8001275
8001285
1280
1095
ASP (Mn0.5Zn0.5)Fe2O4
ASP ZnFe2O4
418
1200
Temperature (C)
1000
T(centre)
800
T(edge)
600
400
0
10
12
14
Position (cm)
Fig. 5. Axial temperature distribution in the irradiated honeycomb (sealed reactor, near to thermal equilibrium, errormax(T) =
15 C: resolution limit of data acquisition hardware).
419
4. Conclusions
A new promising method for performing solar heated
thermo-chemical process applying two-step water splitting operating at a moderate temperature level of about
8001200 C has been presented. It includes the combination of a support structure capable of achieving high
temperatures when heated by concentrated solar radiation, with an iron-oxide-based redox system suitable
for the performance of water dissociation and subsequent regeneration at these temperatures. To the
authors knowledge this is the rst time that such a solar
reactor concept based on monolithic honeycombs is
being proposed and tested.
A wide variety of iron-oxide-based redox pair systems was synthesized, characterized and comparatively
evaluated with respect to water splitting and regeneration capability. The proposed concept has been proved:
the synthesized catalyst systems are able to split water
and generate hydrogen as the only product, at temperatures as low as 800 C with conversions reaching 80% in
terms of water (amount of water converted/total amount
of water). From the regeneration experiments, it became
obvious that several of these materials could be reduced
under inert atmospheres at temperatures well below
1300 C and that the reductionoxidation cycle could
be repeated at least two times, indicating high potential
for their integration in a two-step water splitting process
within a solar system. Hydrogen yields more than 90%
of the maximum possible were achieved from at least
one catalyst system synthesized.
A dedicated solar chemical receiver/reactor suitable
to carry out the described two-step thermo-chemical
cycle has been designed, constructed, and qualied. A
test programme has been developed. The temperature
420
Acknowledgments
The work has been funded by the European Commission within the Project Catalytic monolith reactor for
Hydrogen generation from solar water splittingHYDROSOL (ENK6-CT-2002-00629), under the Energy, environment and sustainable development (part b:
Energy) Programme (19982002).
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