Stephan Mller Solar thermal Hydrogen Production via Reforming and ThermoChemicalCycles

FVS Workshop 2007

Solar thermal Hydrogen Production

via Reforming and
ThermoChemicalCycles
Produced from renewable energy, hydrogen is
looked upon as a future secondary energy
carrier, which has the potential to become an
important substitute for fossil fuels for the next
generations. If water and renewable energy,
such as solar radiation, can be used for hydro
gen production, then it is sustainable.

Apart from the still very costly procedure of

electrolysing water by means of renewable elec
tricity, the technologies needed for producing
sustainable hydrogen are not yet ready for use.
Researchers at DLR therefore dedicate their
efforts on developing new ways of producing
renewable hydrogen. Together with its Euro
pean partners, DLR is involved in a number of
very promising R&D projects, such as the solar
powered steam reforming of methane and the
solardriven thermochemical splitting of water.

S. Mller
DLR Stuttgart
stephan.moeller@dlr.de

Ch. Sattler
M. Roeb
DLR Kln

Solar Thermal
Processes for
Hydrogen Production

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FVS Workshop 2007

Solar Thermal
Processes for
Hydrogen Production

Projects coordinated
by DLR or involved as
a partner

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Stephan Mller Solar thermal Hydrogen Production via Reforming and ThermoChemicalCycles

Stephan Mller Solar thermal Hydrogen Production via Reforming and ThermoChemicalCycles

FVS Workshop 2007

Scheme of a plant for

solar thermal H2
production

Heliostat field

Transition pathway
merging fossil fuels
with solar thermal
energy

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Stephan Mller Solar thermal Hydrogen Production via Reforming and ThermoChemicalCycles

Solar Steam
Reforming Different
Routes

Reformer is externally
heated. (700 bis 850C)

Reformer wall is irradiated Catalytically active

(up to 850C)
absorber is directly

irradiated

Heat storage operation is Approx. 70 % Reformer

possible
Approx. 90 % Reformer
Ongoing research at
e.g. project Asterix (DLR,
CSIRO in Australia and in High flux densities
late eighties, begin nine
Japan; research in
Projects coord. by DLR:
ties)
Germany and at WIS in
(SCR, SOLASYS, SOLREF);
Israel in the eighties and
further research in Israel
nineties
and Japan

Solar Steam Reforming

Today approx. 95% of the produced hydrogen
is made from carbonaceous raw materials,
mainly from natural gas via processes based on
steam reforming and partial oxidation respecti
vely. A transition to a hydrogen economy would
have to start with these applicable technologies
that means with hydrogen produced from fossil
fuels. In a next step the conventional processes
must be substituted successively by renewable
technologies. The first step could be the use of
solar energy to provide the necessary heat for
the steam reforming of methane.

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By covering the heat demand of that process by

solar energy the demand for fossil fuels and the
refore CO2emissions can be reduced by up to
40% compared to the conventional steam
reforming processes. The product is at first syn
thesis gas, a mixture of H2 and CO, which can
be further transformed to hydrogen and carbon
dioxide by the catalytic watergas shift reaction
using additional steam. The solar steam refor
ming was successfully demonstrated at the solar

field of the Weizmann Institute of Science/Israel

within the scope of the ECfunded project
SOLASYS. Significant advancements will be
achieved in the ongoing followup project
SOLREF. A pressurized volumetric receiver
reactor at a few hundred kW level developed by
DLR represents the core of the plant.
An economic study shows that hydrogen could
be produced at cost below 5 ct /kWhLHV by
solar steam reforming of natural gas in a 50
MW plant. This is only 20% more expensive
than the conventional production today. The
solar driven process could reach profitability
when the todays price of natural gas increases
by a factor of about two. Therefore, the applica
tion of the solar driven reforming process opens
the gate to the Hydrogen economy with less
CO2 emissions at an acceptable price.

Stephan Mller Solar thermal Hydrogen Production via Reforming and ThermoChemicalCycles

FVS Workshop 2007

Some examples of
Solar Reformers

Process schematic

Inside receiver

2050 kWth reformer

Tubular concept
The catalyst is packed in between the inner and outer tubes; the inner tube is
purely for countercurrent heating of the feed water stream
Ongoing research at CSIRO, Australia

10 kWth reformer (DIAPRRef)

Some examples of
Solar Reformers

Integrated concept
Ongoing research at WIS, Israel

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SOLREF

Solar Reformer

Solar steam
reforming: project
SOLREF
Improvements

Stephan Mller Solar thermal Hydrogen Production via Reforming and ThermoChemicalCycles

The catalytically active absorber is

directly heated by concentrated solar
energy. Efficiencies above 90% can be
achieved. (increase of sensible and
chemical power of the gas mixture
divided by the incoming solar power).

New construction of the

reformer
Enhanced catalysts
Enhanced absorber (Material/
construction)
Enhanced frontflange holding
the window
Reduced cost
Solar power input: 400 kWth
Reforming temperature:
800900C
Operation pressure, optimal:
10 bar.
Study on a 1 MW testplant and
on an industrial 50 MW plant.

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Stephan Mller Solar thermal Hydrogen Production via Reforming and ThermoChemicalCycles

FVS Workshop 2007

Future Production
of renewable H2 from
H2O

Long term necessary for the

decarbonised H2 society
Benchmark: Renewable
electricity + electrolysis
Challenging technologies

Hydrogen Production
by Thermochemical
Cycles

Solar thermal water splitting

H2O H2 + O2 (> 2200C)
Problems:
High temperatures
Materials
Separation of the products
Solution:
TCCycles
Temperature decrease
To achieve good h the number
of steps should be low (<4).
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Stephan Mller Solar thermal Hydrogen Production via Reforming and ThermoChemicalCycles

Solar Thermochemical Cycles

By using water as feedstock and by applying
solar energy as the driving energy for its
decomposition, the production of hydrogen
becomes free of emissions and free of the con
sumption of fossil fuels. A mature technology in
that respect is the alkaline electrolysis of water,
which is environmentally benign if renewable
electricity is used, for example from photovol
taic and solar thermal power plants. A major
disadvantage of this technology is the impact
of high electricity/electrolyser costs.
The direct use of solar generated heat to split
water has the potential to be less expensive.
Direct thermal splitting of water is technologi
cally difficult. Operating temperatures required
to shift the equilibrium to the hydrogen side are
far above 2.500C posing high demands on
materials and process conditions. To reduce the
technical problems associated with those condi
tions the reaction can be replaced by two or
multistep thermochemical cycles enabling the
reduction of the maximum process tempera
ture. In these cycles all the deployed chemicals
apart from water that is converted into hydro
gen and oxygen are regained and recycled.
A promising twostep water splitting process is
investigated in the project HYDROSOL2. Multi
valence metal oxide redox materials are used to
split the water in a temperature range between
700 1.200C. These temperatures can be
technically achieved by concentrated solar
radiation.
The reaction is carried out as follows: during the
first step a metal oxide (MO) is reduced by
releasing oxygen. In the second step the redu
ced and therefore activated redox material is
oxidized by taking the oxygen from water and
releasing hydrogen.

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Mixed iron oxides doped with zinc, nickel or

manganese have proven to be suitable for this
process. A solar thermal reactor was developed
for operation in the Solar Furnace of DLR in
Cologne. Hydrogen and oxygen production
take place alternating at different temperature
levels. An important breakthrough was
achieved. For the first time water was thermally

split by concentrated sunlight producing solar

hydrogen. Also the regeneration step the
release of oxygen was successfully demonstra
ted and repeated several times.
Three or more step thermochemical cycles
have been developed mainly under the aspect
of a potential coupling with a high temperature
nuclear reactor working in a temperature range
of 850900C.
The IodineSulphur (IS) cycle and the Westing
house cycle are both sulphur based cycles. They
have been developed in the US in the 1970s
and 1980s turned out to be two of the most
promising. The former comprises only thermo
chemical process steps. The latter combines a
thermochemical and an electrolytic reaction
step to split water offering the possibility to
simplify the cycle.
In the project Hydrogen Thermochemical
Cycles HYTHEC both of these cycles are inve
stigated with respect to solar and nuclear
energy sources. The input of solar energy allows
higher operation temperatures and therefore,
the efficiency might be improved. The technical
and economic feasibility is investigated by expe
rimental methods using the DLR solar furnace in
Cologne as well as by simulation and process
design methods.
DLR has developed a solar test reactor which
directly absorbs concentrated sunlight to use it
as process heat for the decomposition of sulp
huric acid. The higher temperatures allow split
ting of sulphuric acid even without any catalyst.
HYTHEC and HYDROSOL are both accomplished
with cooperation of different European partners
and funded by the European Commission
within the scope of research into sustainable
energy systems.
The integration of concentrating solar radiation
in reaction systems able to split water might
provoke an important impact on the energy
economy worldwide. The mentioned projects
concern key technologies for using solar heat to
provide large amounts of sustainable hydrogen
on the road to commercialization in the future.

Stephan Mller Solar thermal Hydrogen Production via Reforming and ThermoChemicalCycles

Several hundred TCCs were invented during the last 40 years

FVS Workshop 2007

Hydrogen Production
by Thermochemical
Cycles

Originally developed to use nuclear heat and power for fuel production
(General Atomics, Westinghouse, )
Today very much in the focus again because:
CO2 free
No dependency on fossil fuels
Today research on renewable TCCs (D, CH, USA, F, E, I, ) and nuclear TCCs
(F, JPN, USA )
Most promising today:
Metal/Metaloxide: Fe, Zn, Mn, Ce (?)
Salts: UT3, CuCl, (?)
Sulfur: Westinghouse, SulfurIodine (General Atomics)
Carbon (CO/CO2)

HYTHEC Hydrogen
Production by
Thermochemical
Cycles

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FVS Workshop 2007

HYTHEC:
SulphurIodine Process

HYTHEC:
Comparison of
catalyst behaviour

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Stephan Mller Solar thermal Hydrogen Production via Reforming and ThermoChemicalCycles

Stephan Mller Solar thermal Hydrogen Production via Reforming and ThermoChemicalCycles

FVS Workshop 2007

HYTHEC:
Efficiency depending
on total volume flow

HYDROSOL:
2Step redox cycle
with mixed iron oxides
Principle of
Operation

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Stephan Mller Solar thermal Hydrogen Production via Reforming and ThermoChemicalCycles

HYDROSOL:
Continously operating
reactor during
exposure to sunlight

HYDROSOL:
Longterm test

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Hydrogen generation for 53 cycles performed with one sample

Stephan Mller Solar thermal Hydrogen Production via Reforming and ThermoChemicalCycles

FVS Workshop 2007

HYDROSOL: Start of
installation at the PSA

Scaleup from solar furnacescale

of few kW to 100kW thermal
energy input

For the EU H2 is the Energy carrier of the future especially for mobile applications

Conclusion and
Outlook

Thermal H2 production is besides electrolysis the technology for bulk production

of H2
The market introduction in Europe is planned to be done by carbon containing
processes.
In the USA only carbon free processes will be developed (solar, nuclear, biomass)
The solar research of DLR will continue its work on reforming und cracking
because of the medium term chances of these technologies
Thermochemical cycles are for long term use
Three main problems have to be solved:
Heat provision
Material properties of components and reactants
Product separation
The aim is to produce renewable hydrogen under ecologically and economically
reasonable conditions
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Stephan Mller Solar thermal Hydrogen Production via Reforming and ThermoChemicalCycles

Acknowledgement

The Projects
HYDROSOL, HYDROSOL II; HYTHEC,
SCR, SOLASYS, SOLREF, Hi2H2, and
INNOHYPCA
have been cofunded by the European
Commission.

HYDROSOL was awarded

Eco Tech Award Expo 2005, Tokyo
IPHE Technical Achievement Award
2006
Descartes Research Price 2006

Forschungsbedarf im
Bereich solarer
Reformierung

Pilotanlagen und Demonstration (Langzeittests)

Entwicklung von Regelungsstrategien und Prozeduren fr den Betrieb von
optimierten SolarReformierungsanlagen
Neuentwicklung von Solarreformern fr die H2Erzeugung
Fertigung und Qualifizierung von Prototypen (Receiver, Spaltreaktoren,
Separatoren, Wrmebertrager)
Materialentwicklung und tests fr Hochtemperaturanwendungen und
korrosive Medien
Prozessdesign und Simulation
Modellierung von Schlsselkomponenten

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Stephan Mller Solar thermal Hydrogen Production via Reforming and ThermoChemicalCycles

FVS Workshop 2007

Forschungsbedarf im

Bereich solarer TCC

Fertigung und Qualifizierung von Prototypen (Receiver, Spaltreaktoren,

Separatoren, Wrmebertrager)
Materialentwicklung und tests fr Hochtemperaturanwendungen und
korrosive Medien
Hardware fr Hochtemperaturwrmetransport
Prozessdesign und Simulation
Ausbeuteoptimierung, Optimierung von Reaktionsgeschwindigkeiten,
Katalysatorentwicklung
Grundsatzuntersuchungen zu Mechanismen der H2OSpaltung an
Metalloxiden
Entwicklung von Regelungsstrategien und Prozeduren fr solche
solarchemischen Prozesse
Modellierung von Schlsselkomponenten
Pilotanlagen und Demonstration!!!

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