US DOE Nuclear H2 R&D Plan

Nuclear Hydrogen
R&D Plan

March 2004

Nuclear Hydrogen

R&D Plan

March 2004
Department Of Energy

Office of Nuclear Energy, Science and Technology

CONTENTS

1. Hydrogen and The Role of Nuclear Energy ................................................................................. 11
1.1 The DOE Hydrogen Program ........................................................................................... 12
1.2 Energy Sources for Hydrogen – The Nuclear Connection ............................................... 14
1.3 Nuclear Hydrogen Initiative (NHI) .................................................................................. 15
2. Nuclear Hydrogen Development Strategy.................................................................................... 21
2.1 Objective .......................................................................................................................... 21
2.2 Approach .......................................................................................................................... 21
2.2.1 Thermochemical Cycles ....................................................................................... 21
2.2.2 HighTemperature Electrolysis ............................................................................ 22
2.2.3 Other Production Methods ................................................................................... 22
2.2.4 Systems Interface ................................................................................................. 22
2.3 Technology Assessment ................................................................................................... 22
2.3.1 General Evaluation Criteria.................................................................................. 22
2.3.2 Production Process Prioritization ......................................................................... 23
2.4 Process Demonstration Strategy....................................................................................... 24
3. Thermochemical Cycles ............................................................................................................... 31
3.1 Objective .......................................................................................................................... 31
3.2 Approach .......................................................................................................................... 31
3.3 Thermochemical Cycle Assessment................................................................................. 31
3.3.1 Summary of Previous Studies .............................................................................. 32
3.3.2 Conclusions from Previous Studies ..................................................................... 33
3.4 Thermochemical Cycle R&D Needs ................................................................................ 33
3.4.1 SulfurBased Cycles ............................................................................................. 36
3.4.2 Calcium Bromide Cycles ..................................................................................... 37
3.4.3 Alternative Thermochemical Cycles .................................................................... 38
3.5 Thermochemical Cycle R&D Program ............................................................................ 39
3.6 Thermochemical R&D Activities .................................................................................. 310
4. HighTemperature Electrolysis .................................................................................................... 41
Nuclear Hydrogen R&D Plan March 2004
ii
4.1 Objective .......................................................................................................................... 41
4.2 Approach .......................................................................................................................... 41
4.3 High Temperature Electrolysis Assessment ..................................................................... 41
4.3.1 HTE Energy Efficiency ........................................................................................ 42
4.3.2 HTE Production Plant Features............................................................................ 43
4.4 High Temperature Electrolysis R&D Needs .................................................................... 43
4.4.1 System Design and Trade Studies ........................................................................ 43
4.4.2 HTE Cell / Module Optimization......................................................................... 44
4.5 High Temperature Electrolysis R&D Program ................................................................ 46
4.6 HTE Milestones ............................................................................................................... 46
5. Systems Interfaces and Balance of Plant ...................................................................................... 51
5.1 Objective .......................................................................................................................... 51
5.2 Approach .......................................................................................................................... 51
5.3 Systems Interface and BalanceofPlant Assessment ....................................................... 51
5.4 Systems Interface and Balance of Plant R&D Needs....................................................... 53
5.4.1 Nuclear Hydrogen System Design Studies........................................................... 53
5.4.2 Heat Exchanger Design Studies ........................................................................... 53
5.4.3 Intermediate Heat Transfer Loop ......................................................................... 54
5.4.4 Supporting Systems Scoping Studies ................................................................... 54
5.5 Systems Interface and Balance of Plant R&D Program ................................................... 55
6. Nuclear Hydrogen R&D Plan Summary ...................................................................................... 61
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Nuclear Hydrogen R&D Plan

1. HYDROGEN AND THE ROLE OF NUCLEAR ENERGY
In November 2002, the U.S. Department of Energy scale supporting infrastructure—and building
(DOE) issued its National Hydrogen Energy one will require major investment. Although
Roadmap. The purpose of the Roadmap was to hydrogen production, storage, and delivery
identify the activities required to realize hydrogen’s technologies are currently in commercial use
potential to address U.S. energy security, diversity, by the chemical and refining industries,
and environmental needs. The Roadmap concluded existing hydrogen storage and conversion
that: technologies are still too costly for
widespread use in energy applications.
“Expanded use of hydrogen as an energy Finally, existing energy policies do not
carrier for America could help address promote consideration of the external
concerns about energy security, global environmental and security costs of energy
climate change, and air quality. Hydrogen that would encourage wider use of
can be derived from a variety of domestically hydrogen.”
available primary sources, including fossil
The Administration has proposed a research and
fuels, renewables, and nuclear power.
development (R&D) program to accelerate the
Another key benefit is that the byproducts of
development of hydrogen technology. Successful
conversion are generally benign for human
implementation of the DOE Hydrogen Program will
health and the environment.
enable industry to make an investment decision by
“Despite these compelling benefits, 2015 regarding the commercial viability of hydrogen
realization of a hydrogen economy faces for fuel cell vehicles. The transition to a hydrogen
multiple challenges. Unlike gasoline and economy involves several phases, which are
natural gas, hydrogen has no existing, large summarized in Figure 11.
Figure 11. Phases in the development of the hydrogen economy.

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1.1 The DOE Hydrogen Program Figure 12. These offices are now working together

synergistically to accomplish the overall program
One of the advantages of hydrogen is that it can goals. The immediate focus is on distributed
utilize a variety of feedstocks and a variety of production to meet shortterm needs most cost
production technologies. Feedstock options include effectively. To meet longerterm needs, there is
fossil resources, such as coal and natural gas, and significant effort to provide competitive renewable
renewable resources, such as biomass and water. feedstocks and energy sources, to develop centralized
Production technologies include thermochemical, production from coal with sequestration, and to
biological, electrolytic, and photolytic processes. develop hightemperature processes using advanced
Energy needed for these processes can be supplied nuclear reactors.
through fossil, renewable, or nuclear sources.
Ultimately, a spectrum of feedstocks and technologies While R&D on production technologies are carried
for hydrogen production will be necessary to address out within various DOE offices, the DOE uses three
energy security and climate change concerns. criteria for all feedstocks and production technologies
Therefore, the DOE Hydrogen Program will address in determining which to develop. All production
multiple feedstock and technology options to provide options must:
effective and efficient hydrogen production for both
the short and long term. • Be produced from domestic resources
The DOE Hydrogen Program is contained within the • Avoid the production of greenhouse gases
Offices of Nuclear Energy, Science and Technology
(NE), Fossil Energy (FE), and Energy Efficiency and • Be costcompetitive with gasoline in the
Renewable Energy (EE), which has the lead implementation timeframe.
organizational role for the DOE as shown in

Figure 12. DOE proposed organizational structure for hydrogen program.

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These technical challenges and the investment DOE has undertaken major research programs to
required to achieve these primary goals are address the full range of hydrogen production,
significant. To address the multiple challenges that distribution, storage, and utilization issues that were
face the widespread use of hydrogen, the DOE identified in the National Hydrogen Energy Roadmap.
Hydrogen Program must: Hydrogen production technologies that are being
addressed by FE, EE, and NE will have some
• Produce hydrogen economically. Largescale, technology issues in common, which will require an
costeffective hydrogen production methods integrated approach to ensure that the issues are
that make the cost of hydrogen competitive efficiently addressed. Solid oxide materials, anode
with gasoline must be developed. A and cathode materials, and sealing technologies being
significant component of this production must developed for fuel cells are relevant to high
ultimately come from sources that are not temperature electrolyzers. Thermochemical methods
dependent on fossil fuels or do not produce and basic data, and engineering materials being
carbon emission. developed for other programs are also relevant to the
nuclear hydrogen processes. Technology working
• Develop storage methods for hydrogen to groups will be formed around common research
provide an adequate capacity for the next opportunities to facilitate efficient interoffice
generation of vehicles. communications for these common technology areas.
Figure 13 illustrates the flow of technology and
• Develop technologies that use hydrogen information between DOE programs for the hydrogen
efficiently for the wide range of industrial and production technologies being developed within the
transportation applications (e.g., fuel cells, Nuclear Hydrogen Initiative (NHI).
internal combustion engines).
• Develop the delivery infrastructure to enable
routine hydrogen use for transportation.
Figure 13. DOE hydrogen program elements/structure.

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1.2 Energy Sources for Hydrogen • Very high temperatures or highefficiency

electricity is required to drive the most
– The Nuclear Connection promising hydrogen production processes.
Advanced nuclear systems must be developed
Hydrogen is abundant in nature but occurs primarily
that provide the necessary high heat to enable
in stable compounds that require significant energy to
these processes. The DOE Generation IV
produce hydrogen for use as a fuel. Hydrogen is an
Nuclear Systems Initiative (Generation IV) is
energy carrier, much like electricity, that requires a
developing options to address this need with
primary energy source to produce. Domestic energy
international collaboration. The focus of this
sources that do not generate greenhouse gases and
effort is the Very High Temperature Reactor
have the potential to produce hydrogen at costs
(VHTR), which would provide the advanced
competitive with gasoline will be essential
nuclear heat source for demonstrating nuclear
components of the longterm energy supply. The
hydrogen and electricity production.
DOE Hydrogen Program is investigating the potential
for all of the practical energy sources for hydrogen
The DOE Office of Nuclear Energy, Science, and
production, including:
Technology (NE) is considering a major
demonstration project, which would demonstrate the
• Fossil sources with carbon sequestration (coal
commercial potential of hydrogen production from
and natural gas)
nuclear energy at a 50 megawatt thermal (MWth)
scale by 2017 and provide a basis for industry
• Renewable energy sources (solar, wind, and
investment decisions. The Next Generation Nuclear
hydroelectric)
Plant (NGNP) project would develop and demonstrate
the VHTR with the most promising hydrogen
• Biological methods (biomass and biological)
production processes developed by the Nuclear
Hydrogen Initiative.
• Nuclear energy.
For hydrogen production from nuclear energy to be
In the long term, economics and national policy will
sustainable, the technology and policy questions that
determine the mix of energy sources that are
have limited nuclear energy’s contribution to the
implemented, and the technologies initially
energy supply must also be addressed. Advanced
implemented may differ from those ultimately
reactor systems that are passively safe, more efficient,
selected for longterm deployment. In any scenario,
and demonstrably cost effective are essential to the
domestically based, emissionfree energy sources will
wider public acceptance of the nuclear role. The
be high priority candidates for further development.
advantage of more efficient fuel cycles that minimize
Among these primary energy sources, nuclear energy waste volumes, toxicity, and proliferation concerns
offers great potential for the largescale production of must be considered. The DOE Advanced Fuel Cycle
hydrogen that is virtually emissionfree and generated Initiative (AFCI) has initiated development of
from domestic resources. The production of hydrogen advanced fuel, separations, and transmutation
represents a new mission for nuclear energy that is technologies to address these issues.
potentially larger than the current mission of
The relationship of these nuclear energy programs to
emissionfree electrical production. To accomplish
the overall DOE Hydrogen Program is illustrated in
this goal:
Figure 14. The relative sizes and positions
represented in the diagram are not intended to signify
• Efficient, largescale production methods
program importance. The NHI and Generation IV
suitable for use with advanced nuclear
programs together will provide the technologies
reactors must be demonstrated. The most
needed for emissionfree transportation fuels from
promising production methods are in the early
nuclear energy.
stages of development. The NHI will develop
and demonstrate these hydrogen production
methods.
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Figure 14. The Nuclear Hydrogen Initiative is part of an integrated DOE program to develop technologies for
nuclear hydrogen production.
1.3 Nuclear Hydrogen Initiative hydrogen production technologies needs to be

understood as a baseline for nuclear hydrogen
The NHI will focus on hydrogen production economics. Since these technologies are currently in
technologies best suited for use with advanced nuclear commercial use, they do not require significant
systems. Although there are already significant process R&D to assess the nuclear hydrogen potential.
quantities of hydrogen produced in the United States, When nuclear energy replaces fossil fuel in the
it is primarily produced by steam reforming of natural reforming or gasification process, the environmental
gas, which is already a highquality fuel (see benefit of nuclear energy is significantly reduced
Appendix 11). Reforming one highquality fuel to since carbon emissions are still generated. As such,
another is economically justified because of the value the NHI will only address these conventional
of hydrogen to the petrochemical industry for use in production options in system studies and economic
refining lowergrade crude oil to produce gasoline, assessments for comparison with advanced
and to the agricultural industry for use in fertilizer technologies.
production. The current production level in the
United States would be equivalent to about 100 GWth The most attractive hydrogen production options for
of nuclear or fossil power, assuming 50% efficiency nuclear energy are those that utilize high temperatures
for hydrogen production. Other fossil fuel production or efficient electricity from a VHTR to produce
options based on coal, such as coal gasification, are hydrogen from nonfossil resources (i.e., water) and
also being developed. These production methods and will, therefore, be the focus of the NHI. These NHI
the necessary carbon sequestration technologies are production processes will have materials and systems
being pursued by FE. technology issues in common with the hydrogen
production research being performed by EE, FE, and
Nuclear energy can be used to provide thermal energy SC, and will be closely coordinated through the DOE
for steam reformation, replacing approximately 25 to Hydrogen Program. The NHI will collaborate,
30% of the natural gas requirement (or electricity augment, and complement ongoing DOE research
equivalent for conventional electrolysis). The efforts, where appropriate, or initiate needed R&D in
application of nuclear energy to these existing nuclearspecific areas to accomplish NHI program
goals.
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The NHI research effort will focus on: comparison of cost and performance for
alternative processes. More comprehensive
• Nuclear Hydrogen Production Process R&D systems analyses that examine the
for production processes that most efficiently implications (e.g., economic, environmental,
couple to advanced hightemperature reactors social/political) of nuclear hydrogen
to produce cost effective hydrogen from technology choices and implementation
nuclear energy. These processes include a strategies will provide the necessary
range of thermochemical cycles and high perspective to inform technology and policy
temperature electrolysis (HTE). decisions.
• Nuclear Hydrogen Systems Interface R&D to • NHI Program Interfaces to support program
address the essential hightemperature direction and maintain essential interfaces
thermal transport, heat exchanger, and with related hydrogen programs. These
materials issues to couple the high include the necessary international and
temperature reactor to the process plant. industry interfaces to conduct the most
costeffective research. Collaboration with
The NHI will also require independent analysis countries performing related research (e.g.,
capabilities to support the assessment and evaluation Japan, France, European Community) will
of technology options and scaling decisions. expand available resources and improve the
Effective interfaces with other U.S. and international potential for success. An early, effective
hydrogen research must also be established to ensure interface with both the chemical and nuclear
effective collaboration and integration. These NHI industries will be essential to assessing the
program functions include the following: technical and economic viability of nuclear
hydrogen options since both process
• Nuclear Hydrogen System Studies for development and implementation stages
independent analyses to support comparative should have strong chemical and nuclear
technology assessments, and more industry components.
comprehensive systems analyses to provide
programmatic perspective on technology These major NHI elements are summarized in
choices and implications. Independent Figure 15.
analyses will provide a consistent basis for
Figure 15. Nuclear Hydrogen Initiative program and technology development elements.

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2. NUCLEAR HYDROGEN DEVELOPMENT STRATEGY

The first step in developing a nuclear hydrogen were evaluated using general evaluation criteria based
capability is the development of a coordinated on performance potential and demonstrated technical
research plan to define the necessary R&D and viability. These criteria are also part of the ongoing
evaluation criteria to guide technology decisions. systematic reevaluation of process potential based on
This Nuclear Hydrogen R&D Plan constitutes that R&D results.
first step and defines the path to develop the
technologies necessary to demonstrate hydrogen 2.2.1 Thermochemical Cycles
production using nuclear energy.
Thermochemical cycles produce hydrogen through a
2.1 Objective series of chemical reactions where the net result is the
production of hydrogen and oxygen from water at
The purpose of this R&D plan is to identify the much lower temperatures than direct thermal
candidate advanced hydrogen production technologies decomposition. Energy is supplied as heat in the
most suitable for nuclear energy, assess their viability, temperature range necessary to drive the endothermic
and prioritize the needed R&D to enable the reactions, generally 750 to 1000°C or higher. All
demonstration of nuclear hydrogen production. This process chemicals in the system are fully recycled.
plan outlines the process and systems interface Thermochemical cycles were widely investigated
information that must be available to guide NHI R&D from the late 1960’s through the mid1980s. The
investment decisions. advantages of thermochemical cycles are generally
considered to be high projected efficiencies, on the
order of 50% or more, and attractive scaling
2.2 Approach characteristics for largescale applications. However,
of the more than 200 cycles that have been identified
The NHI will focus on the nonfossilbased
in the literature, many have been found to be
production processes that couple efficiently to high
unworkable, have low efficiency, or require excessive
temperature nuclear reactors. Most of these
temperatures.
production methods split water molecules using
thermal or electrical energy. This decomposition of
Thermochemical cycle technology is at a relatively
water takes significant energy; assuming no ohmic
early stage, and only a few cycles have been
losses, about 123 megajoules (MJ) is required to
demonstrated at the laboratoryscale. Although there
produce one kilogram (kg) of hydrogen. (The energy
is greater uncertainty in the outcome of R&D, there is
content of 1 kg of hydrogen is approximately equal to
also potential for significant process improvement
one gallon of gasoline). To accomplish this with heat
based on more recent advances in materials and
(thermolysis) alone requires extreme temperatures of
chemical technology over the past two decades.
2500°C or more. Furthermore, current technology to
Based on the information that is available, (i.e.,
produce hydrogen using radiolysis (the chemical
performance potential and demonstrated technical
decomposition of water by the action of radiation)
viability) promising cycles have been identified for
does not meet minimum efficiency requirements for
further investigation. Several “families” of
largescale applications.
thermochemical cycles emerged as the most
promising options. The various cycles within these
Although research is being conducted on techniques
families were further evaluated and prioritized by
to reduce the temperature required for thermolysis and
factors such as theoretically achievable efficiencies,
other possible production approaches, the most
technical risk, and technical maturity. Key R&D
promising methods using nuclear energy are based on
needs for these families of cycles were developed,
electrolytic or thermochemical processes. To identify
along with preliminary recommendations regarding
the most promising hydrogen production options,
decision points in cycle development.
available information on thermochemical cycles, high
temperature electrolysis, and other possible
Thermochemical cycles described in the literature
production methods was reviewed, and limited
indicate potential for higherefficiency, lower
confirmatory analyses were performed. Processes
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temperature operation or other attractive cycle current demonstration schedule. Process
characteristics but are not sufficiently developed to improvements for commercial technologies, such as
make a clear determination. These highrisk, but conventional electrolysis or steam reforming of
potentially highpayoff, cycles are listed as alternative methane process improvements, are supported by
cycles and should be analyzed further at a lower other elements of DOE and are not addressed as part
priority. Several cycles were identified, and others of the NHI (see Appendix 11). Finally, while the
may be added as more detailed evaluations are transportation, storage, and use of hydrogen are
completed. necessary components of a hydrogen energy system,
these technologies are being developed by EE and are
2.2.2 Hightemperature Electrolysis not addressed in this R&D plan.
Electrolysis is the most straightforward approach 2.2.4 Systems Interface

currently available to produce hydrogen directly from
water. Conventional electrolyzers are available with Both thermochemical and HTE processes introduce
electric to hydrogen conversion efficiencies of 70% at new considerations into the design, licensing, and
a cost of about $400/kWe installed. This gives an operation of combined nuclearchemical plants that
overall hydrogen production efficiency of 23 to 28% must also be considered in the technology selection
if electricity generation is 33 to 40% efficient. High process. These balanceofplant and systems interface
temperature electrolysis (HTE), or steam electrolysis, issues are identified as important components in the
has the potential for higher efficiency. Thermal R&D program for nuclear hydrogen. R&D needs that
energy is used to produce hightemperature steam, address the essential hightemperature thermal
which results in a reduction of the electrical energy transport, heat exchanger, and materials issues to
required for electrolysis. couple the hightemperature reactor to the process
plant were identified. Many supporting systems will
Electrolysis requires lowcost, efficient electricity and be common to both the nuclear and hydrogen plants,
an energy source that provides the highest possible while the hightemperature heat exchanger and the
temperatures consistent with materials capabilities. materials associated with thermal transfer will be
The temperature range currently being considered is specific to each production process.
nominally up to 950°C. HTE has the potential for
higher efficiency than conventional electrolysis and 2.3 Technology Assessment
can be accomplished using similar materials and
technology to those used in solidoxide fuel cells Since all nuclear hydrogen production approaches
(SOFC). Specific technologies used in the HTE being considered in the NHI avoid the production of
process are being developed by other DOE offices. greenhouse gases and can be based primarily on
Therefore, the assessment of the nuclear application domestic resources, the primary issue for nuclear
will integrate these results and focus on developing a hydrogen is the development of costeffective systems
conceptual design for an HTE system coupled to an that produce hydrogen at a cost that is competitive
advanced hightemperature reactor. with gasoline. Projecting costs for technologies at this
early stage of development is highly uncertain for any
Largescale applications would be composed of many of the approaches being considered. The criteria to be
smaller electrolyzer modules. The cost effectiveness used to evaluate the benefits of the various hydrogen
of scaling the modular electrolysis process as production methods in relation to these cost objectives
compared with the scaling of thermochemical include the system and performance characteristics
methods needs to be evaluated. that drive costs, and the uncertainty of the projected
costs.
2.2.3 Other Production Methods
2.3.1 General Evaluation Criteria
Additional alternative technologies or enhancements
were also considered. Some of these potentially General evaluation criteria were based on process
promising concepts (including thermallyassisted performance potential and development maturity.
membrane hydrogen production and directcontact Laboratory demonstration of a process may not ensure
methods) were not considered consistent with the
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cost effectiveness; however, the performance and cost safety concerns pose a different type of
uncertainties can be reduced. None of the processes developmental risk that must also be included
reviewed have been demonstrated on a scale that in future implementation decisions.
would be necessary for reliable cost estimates.
2.3.2 Production Process Prioritization
• Costs – Capital cost recovery is considered to
be the dominant component of nuclear Performance and viability information on candidate
hydrogen costs. Although early studies hydrogen production processes will be needed in
suggest that the capital cost of the hydrogen 2009 to provide the basis for pilot plant decisions.
production process will be less than the Integrated demonstrations of those cycles under
nuclear heat source, the projected capital cost consideration must be sufficiently complete by that
of the process plant is a key selection time to assess performance and cost implications. To
criterion. The most direct indicator of ensure that the necessary information is available for
process costs is process efficiency since critical scaleup decisions, it is essential to establish a
higher efficiency processes leverage both prioritization process that ensures that information on
hydrogen and nuclear plant capital costs. the highpriority processes is available for this
Hydrogen production efficiency is defined as decision, while not overlooking other potentially
the lower heating value of hydrogen (~123 higher performance alternatives. The NHI will pursue
MJ/kg) divided by the total energy required to a twotier approach as described below.
produce the hydrogen, including net reaction
energies and energy loss mechanisms. Processes identified as having the highest probability
Processes with potential for efficiencies in the of achieving program goals in the planned schedule
range of 50% were considered promising. and budget will have the highest priority. The goal of
Other factors considered as cost indicators the R&D for these baseline processes will be to
were process complexity (number of complete an integrated, laboratoryscale experiment
reactions, separations), materials (high by 2009 to provide a basis for pilot plant process
temperature compatibility requirements, selection. Initial process priorities will be
corrosion, toxicity), level of industrial safety systematically reevaluated as R&D progresses. At the
concern, and operational modes and same time, however, it is recognized that alternative
flexibility. processes, those posing higher risk but with
potentially higher gain, should also be evaluated
• Uncertainty/Risk – Assessing the probability further to ensure that potentially important options are
that a particular hydrogen production option not overlooked. These analyses will be lower priority
will meet expectations for performance and but in parallel with baseline process development.
cost involves significant uncertainty at this This demonstration strategy is designed to ensure that
stage of development. Processes a 2017 engineeringscale demonstration is fully
demonstrated at a laboratory scale allow more supported while minimizing risk and allowing
reliable estimates of performance and cost. flexibility by exploring potentially more efficient, yet
Promising processes that have not been currently immature, processes.
demonstrated may still deserve further
evaluation, but not as a nearterm priority 2.3.2.1 Baseline Processes. Two families of
until additional confirmatory analyses are thermochemical processes were identified as baseline
available. To be considered as a baseline methods. These processes have potential for high
process, all individual chemical reactions or efficiencies (~50%), have process steps that have been
physical process steps should have been demonstrated to show feasibility, and can be
demonstrated in laboratory experiments. An developed by 2017. Hightemperature electrolysis
integrated process demonstration is necessary was also identified as a baseline process. Cost
before a process can be selected for a pilot uncertainties remain, but preliminary projections were
plant demonstration. Demonstrations at the available to support the potential for making hydrogen
pilot plant or engineeringscale have not been at a cost competitive with gasoline.
completed for any process. Unique industrial
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• The first priority baseline thermochemical 2.4 Process Demonstration

cycles are the sulfurbased family of cycles.
The sulfuriodine, sulfurbromine hybrid, and
Strategy
hybrid sulfur cycles are sulfurbased
Demonstrating nuclear hydrogen production by 2017
variations that have demonstrated high
will require a systematic approach to develop the
performance and are the focus of ongoing
required information for each candidate process
research in the United States, Japan, and
necessary to provide an adequate basis for decisions
France. The sulfurbased cycles are first
on the next stage of demonstration. Such a systematic
priority because they are projected to have
demonstration strategy has been developed to allow
high efficiencies at NGNP temperatures, are
the maximum amount of flexibility to reassess the
the most developed and supported, and much
promise of process technologies while still ensuring
of the R&D is potentially applicable to
that the overall goal is met. The production process
multiple cycle variations, thus reducing
options identified in this Nuclear Hydrogen R&D
overall risk.
Plan are currently in different stages of development.
Baseline processes are closer to demonstration than
• The second priority thermochemical baseline
the alternative processes. However, all highpriority
cycles are the calciumbromine family. The
processes will develop in a similar sequence,
calciumbromine cycle (UT3 and Star)
beginning with the demonstration of viability on a
involves lower peak temperatures and solid
laboratoryscale. The current demonstration strategy
gas reactions, and all process steps have been
is as follows.
demonstrated. The calciumbromine family is
identified as second priority because it is
• Consistent thermodynamic or systems
projected to have a lower overall efficiency
analyses will be performed on all candidate
potential than the sulfur cycles and does not
processes to confirm performance and process
have significant ongoing research support at
viability. Once analyses have confirmed
this time.
sufficient performance potential and process
viability, decisions can be made as to whether
• Hightemperature electrolysis, based on
laboratoryscale experiments should be
SOFC technology, is also a baseline process.
performed.
HTE is also projected to reach 50% overall
efficiencies at NGNP temperatures, and all
• Integrated laboratoryscale demonstrations
physical processes have been demonstrated.
will be performed to confirm technical
Much of the basic technology work is
feasibility of the closed loop process.
supported by other areas of DOE. NHI
Laboratoryscale demonstrations of selected
research will focus on system design and cost
processes need to be complete by 2009 to
assessment.
support pilot plant decisions. Pilot plant
conceptual designs and system interface
2.3.2.2 Alternative Processes. Several
technology requirements will also be
promising alternative cycles were identified (either
considerations in process selection. Although
because of greater efficiency, lower temperature
work on candidate processes must be
requirements, or reduced complexity) as deserving
substantially complete by 2009 to support
further study. Sufficient information was available to
pilot plant decisions, process improvement
identify their potential, but not to merit significant
R&D may proceed in parallel with pilot plant
early investment. The initial list of alternative cycles
construction. Processes that have not been
will be reevaluated as analysis results become
demonstrated by 2009 may also be tested at a
available.
pilot plantscale later if there is sufficient NHI
program interest.
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• Processes successfully demonstrated in demonstration. It is planned that the pilot
integrated laboratoryscale tests can then be plantscale experiments will be nominally one
considered for demonstration at a pilot plant tenth the size of the engineeringscale
scale to confirm engineering approaches and demonstration.
performance. Pilot plants on the order of 1
MW would be prototypic with regard to • The results of pilot plant operations provide
process technology and operating conditions, the engineering and performance basis for
but would not require nuclear heating. selecting production process(es) for the
Design and construction of the initial pilot NGNP engineeringscale demonstration. An
plant configuration is planned to begin in engineering demonstration, nominally 50
2009. Hightemperature heat exchanger and MW, will be designed, constructed, and
materials R&D must be sufficiently advanced operated to confirm economics and
to demonstrate viable engineering approaches commercial feasibility of the selected
for the reactorhydrogen interface. Pilot plant production process(s).
operations for one or more of the processes
provide the engineering and performance The sequence and schedule are summarized in
basis to select the production process for the Figure 21 for the major R&D areas that are identified
NGNP demonstration. Results from in the R&D plan leading to a nuclearheated
operations are needed by the end of 2011 to engineering demonstration in 2017.
impact final design of the NGNP engineering
Figure 21. Summary of Nuclear Hydrogen R&D Plan activities and sequence.

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3. THERMOCHEMICAL CYCLES

Thermochemical cycles produce hydrogen by a series information on cycle performance and cost needed to
of chemical reactions where the net result is the support the selection in 2009 of the production
decomposition or splitting of water, H2O-H2+½O2, process for a pilot plant. The target costs for
at much lower temperatures than can be done with hydrogen production are $2.50/kg in 2011, and
heat alone (thermolysis). A pure thermochemical $2.00/kg in 2017. These projected hydrogen cost
cycle involves a series of chemical reactions that are targets assume that pilot plant operations in 2011 and
driven only by thermal energy. The net result of the the engineeringscale demonstration in 2017 provide
input of heat and water is the production of hydrogen performance and cost information that allow
and oxygen. All other process chemicals in these projection to commercialscale production with these
systems are fully recycled. Hybrid thermochemical costs.
cycles include both chemical reaction steps and an
electrolysis step of some chemical compound (not 3.2 Approach
water) that usually produces hydrogen. Both thermal
and electrical energy are required to complete the Performance and technical viability information on
hybrid cycle. However, the energy requirements for candidate processes will be needed in 2009 to provide
the electrolysis step are much less than the the basis for pilot plant decisions. R&D activities to
requirements for electrolysis of water. The support this scaling decision will focus on laboratory
temperatures required to drive the endothermic demonstration of the most promising baseline cycles
reactions for most thermochemical cycles are identified as having the highest probability of
challenging – generally from 750 to 1000°C or higher. achieving program goals. These integrated baseline
systems must be substantially demonstrated by 2009.
Thermochemical cycles are considered promising
options for hydrogen production because of the The NHI research program will also address
potential for high efficiencies and scaling to large alternative thermochemical processes that have been
capacities. Thermochemical cycles are generally identified as having potential for high performance
considered to have potential for lower costs than but are considered to have high technical risk due to
conventional electrolysis of water because the lack of sufficient analyses and development. These
production of hydrogen by electrolysis requires cycles will be evaluated further to ensure that
conversion of heat to electricity prior to hydrogen potentially important options are not overlooked.
production, whereas thermochemical cycles produce These analyses will proceed in parallel with baseline
hydrogen directly from thermal energy. Chemical process development. This demonstration strategy is
plant economicsofscale (such as thermochemical designed to ensure that the 2017 NGNP
processes) have historically been favorable compared demonstration plant is fully supported, while
to the more modular electrolysis processes. Finally, minimizing risk and allowing the flexibility to explore
the status of thermochemical cycle technology is potentially more efficient, yet currently immature,
relatively immature (see Appendix 31), but there is a processes.
greater potential for improvement compared with
conventional electrolysis. Hightemperature (or 3.3 Thermochemical Cycle
steam) electrolysis is a variation of conventional Assessment
electrolysis that has potential for increased efficiency
(see Section 4). The energy crisis of the 1970s initiated a major effort
to develop thermochemical processes in Europe and
3.1 Objective the United States. Except for a limited amount of
work in Japan, this work ended by the early 1980s.
The objective of the thermochemical cycle research More than 200 cycles have been identified in the
effort is to develop and demonstrate thermochemical literature. The most comprehensive sources of
processes to produce hydrogen cost effectively using information were the extensive review studies that
nuclear energy. Based on analyses and laboratory have been published, which in some cases included
scale experiments, research will develop the necessary evaluation and selection criteria.
32
3.3.1 Summary of Previous Studies because the chemical reactions were too slow,

unwanted chemical reaction products were produced,
The first major program was at the European or no efficient methods were found to separate
Community Joint Research Center (ISPRA), chemical reaction products. New developments in
beginning in the late 1960s and continuing through catalysts or separations techniques could make some
1983. The goal of this work was to identify of these processes viable. The second conclusion was
thermochemical cycles to couple to the high that there are very large differences between
temperature, gascooled reactor. The threephase theoretical efficiencies and efficiencies based on
program investigated 24 cycles. In Phase I, initial process flow sheets; thus, processes that have
thermochemical cycles were developed based on the high theoretical efficiencies may not work in practice.
chemistries of mercury, manganese, and vanadium. The conclusion of this work was that relatively few of
In Phase II, nine cycles based on iron chloride the cycles investigated were promising for further
chemistry were investigated. The iron chloride cycles development. The three that were most highly ranked
were abandoned because of the difficulties with the were hybrid sulfur, sulfur iodine, and hybrid copper
thermal decomposition of ferric chloride. Later, the sulfate.
Gas Research Institute identified a proprietary
procedure that may have resolved these issues. Phase The largest singleprocess development effort was
III focused on multiple sulfurbased cycles with a conducted by Westinghouse Corporation to develop
laboratory demonstration of the sulfurbromine hybrid the hybrid sulfur process. This effort progressed
process. Associated with these laboratory efforts were through a laboratory demonstration with the final
parallel activities involving corrosion testing, design product being a conceptual design report for a pilot
of largerscale equipment, and development of plant. Two conclusions are derived from this work:
industrial flowsheets. The duration (1.5 yrs) of the first, the hybrid sulfur process with 1970s
sulfurbromine hybrid laboratory test is the most technologies could be made to work and second, there
extensive demonstration of any thermochemical cycle were many options to improve efficiency, given
to date. sufficient R&D resources. Process efficiencies above
40% were calculated for these hybrid sulfur
In the United States, the Gas Research Institute (now experiments; however, potential improvements were
known as the Gas Technology Institute) funded a also identified that could significantly increase
longterm program that systematically examined efficiency. With the decrease in energy prices in the
thermochemical cycles. Over the nineyear program, late 1970s, all of these efforts (except for a small
200 distinct thermochemical cycles were examined, effort in Japan) were abandoned.
about 125 cycles were considered feasible based on
thermodynamic considerations, 80 of the most More recently (1999), based on the renewed interest
promising cycles were tested in the laboratory, 15 of in hydrogen production, General Atomics, Sandia
these cycles were found to be operable using batch National Laboratories, and the University of Kentucky
techniques with reagentgrade chemicals, and eight jointly conducted a literature evaluation of
cycles were operated successfully with recycled thermochemical processes. The Nuclear Energy
materials to achieve proofofprinciple. This work is Research Initiative (NERI) study reviewed available
the single most comprehensive source of information information for 115 cycles, which were ranked by
on thermochemical cycles. The heat source for these complexity (reactions, separations, elements, and
cycles was to be either a nuclear reactor or a solar corrosiveness), development maturity (demonstration
system, and cycles covering a wide range of level and publications), and performance (efficiency
temperatures were considered. and cost). The four leading processes were hybrid
sulfur, sulfurbromide hybrid, UT3 (calcium
Several conclusions were drawn from the Gas bromine), and sulfur iodine. The new process was the
Research Institute work. The most important UT3 process developed by the University of Tokyo
conclusion was that experimental verification is since the 1970s. The work on this new cycle was
required to determine if a thermochemical cycle is initiated to provide a lowertemperature process that
viable. Analyses alone are not sufficient. Most would be compatible with lowertemperature heat
proposed cycles were eliminated in the laboratory sources.
33
3.3.2 Conclusions from Previous Studies 3.4 Thermochemical Cycle R&D

The general conclusion of these studies is that there Needs
are currently only a small number of processes that
can currently be considered as candidates for large The NHI R&D Plan assessment examined this
scale development. Given the scope of research in the distilled group of candidate cycles in light of the
1970s, it is judged relatively unlikely that a significant general evaluation criteria for NHI described in
number of new cycles with more promising chemistry Section 2 to define initial priorities for NHI research.
will be identified in the near term. It is recognized These general evaluation criteria focused on the
that new technologies (catalysts and separations projected cost of hydrogen produced by that cycle and
techniques) may make previously unattractive the technical and development risk (i.e., Can the cycle
thermochemical cycles viable. Although many cycles be made to work and meet performance expectations
should be reevaluated in light of these new in the NHI time frame?). For the thermochemical
technologies, they cannot yet be considered cycles, the most useful indicators of hydrogen
candidates for nearterm development. Therefore, the production cost are the cycle efficiency and
cycles that were examined in the previous efforts and complexity (number of reactions and separations).
that survived the laboratory confirmation process The indicator of acceptable technical risk was that all
formed the starting point for prioritizing these cycles cycle reactions and physical processes have been
for the NHI. Collectively, these studies identified demonstrated in the laboratory. Cost and technical
several cycles, or groups of cycles, that had promising risk perception is also influenced by other factors
performance and were confirmed as viable after (e.g., excessive temperature or pressure requirements,
laboratory experiments. Relatively few of the more highly toxic or corrosive materials). The potential for
than 200 cycles met these basic requirements. performance improvement, although not easily
quantifiable, was also considered as a factor in
The sulfurbased cycles were commonly identified in prioritizing these cycles for NHI. In cycles where
all studies: sulfuriodine, hybrid sulfur, and sulfur performance improvements had been suggested based
bromine hybrid. Theses cycles were demonstrated to on new technologies (i.e., membranes and catalysts;
have high efficiencies and were among the least see Appendices 32 and 33), the return on research
complex. They have also been extensively investment could be increased, such as in the recent
demonstrated at a laboratoryscale to confirm sulfur cycle membrane and catalyst proposals. This
performance characteristics. A calciumbromine (Ca trend should increase as visibility and interest in
Br) cycle (UT3), developed later in Japan, has also hydrogen production increases.
been demonstrated and appears as a promising cycle.
Researchers demonstrated high efficiencies at lower Based on the preliminary list of cycles derived from
temperatures than the sulfurbased cycles. The gas the literature on thermochemical cycles and on the
solid reactions involved in this cycle present both NHI general evaluation criteria, a short list of cycles
substantial technical challenges and some potential was identified that met the NHI efficiency and cycle
advantages. Recent Argonne National Laboratory characteristics criteria and had been experimentally
(ANL) work has proposed an alternative version of demonstrated in the laboratory. These cycles are
this cycle. listed in Table 31 and grouped in order of priority for
the NHI (see Appendix 31). Of the laboratory
These studies also identified many other cycles that demonstrated processes, four (sulfuriodine, hybrid
had potentially promising features (higher efficiency, sulfur, sulfurbromine hybrid, and calciumbromine
lower temperature, less complex configurations) that cycles) have been tested in small, laboratoryscale,
either had not been or could not be demonstrated as integrated experiments with fully developed
workable at the time. In most cases, there is a process flowsheets. The other cycles are promising but at an
step that makes the process noncompetitive with the earlier state of development with significant
leading sulfur processes. Examples of these uncertainties associated with the flowsheets and
potentially promising but highrisk cycles include: the estimated efficiencies. Definitive calculations of
hybrid copper sulfate cycles and the ironbased and efficiency exist only for the four demonstrated
copperbased cycles (with lower temperature and less baseline processes. Confirmatory analyses for the two
toxic materials). leading sulfur processes, hybrid sulfur and sulfur
34
iodine, were performed to confirm earlier results Ccalciumbromine cycles also have potential for high
using modern flowsheet analysis methods. performance, with lower temperature requirements
than the sulfurbased cycles, and the cycle
The sulfurbased cycles (sulfurhybrid, sulfuriodine, configuration has potential for further simplification.
and sulfurbromine hybrid) are the highest priority High performance has been demonstrated in a
candidates for NHI. These cycles have the highest continuous operation, and there is recent R&D
calculated efficiencies (>40%) of demonstrated interest in Japan and the United States. It is
cycles, and improvements have been proposed that considered a lower priority due to lower potential
could result in significant improvements in cycle efficiency and issues with integrity of the solidgas
efficiencies, projected to be as high as 60%. The reaction beds.
hybrid sulfur cycle is among the least complex
process of any thermochemical cycle. The high Other cycles were identified that should be pursued
temperature sulfuric acid decomposition reaction (see due to the promise of higher efficiency, lower
Section 3.4.1) and the associated materials temperatures, or better cycle characteristics.
requirements are common to all cycles in the family. Examples of these cycles are listed in Table 31 as
Thermochemical research programs worldwide have alternative cycles that should be analyzed further
increasingly emphasized sulfur cycles as work has before significant work is implemented. As interest
progressed, and R&D on these cycles is ongoing in and activity in thermochemical research increases,
the United States, Japan, and France. other cycles could be added to these examples.
35
Table 3.1. Prioritized thermochemical cycles for hydrogen production.

Peak Number Reported Cycle Status Advantages Key Issues

Temp of Flowsheet
(°°C) Reactions Efficiency %*
Sulfur Cycles
Sulfuriodine 827 4 4251 Continuous Projected >60% Hydrogeniodine distillation
900 Demo 48 hr efficiency
High temp materials
All thermal (no
Iodine hazard and cost
electrolysis step)
International R&D
ongoing
Hybrid sulfur Not 3 4153 Continuous Projected >60% Economic scaling of hybrid
Given Demo 200 hr efficiency processes
Depends on

cell voltage No halogens High temp materials
Conceptual
Plant Design Least complex Higher efficiency electrolysis
sulfur cycle
Sulfurbromine Not 4 39 Continuous Longest duration Economic scaling of hybrid
hybrid Given Demo 1.5 y demonstration processes
No major High temp materials
instabilities
Higher efficiency electrolysis
Bromine hazard and cost
CaBr Cycles
UT3 750 4 4050 Continuous Lower maximum Durability of the solid
Demo 10 hr temperature chemicals through multiple
cycles
Gassolid reactions
CaBrStar 750 3 44 Variant of UT3 Not fully demonstrated
(ANL) with fewer steps
Promising
Alternatives
Copper 550 4 46 (Est.) Rxn Demo Low peak Higher efficiency electrolysis
chlorine hybrid temperature
Ironchlorine 650 3 4749 Rxn Demo Low peak Need to suppress competing
temperature chemical reactions8
(Est.)
Copper –sulfur 827 5 6873 Rxn Demo Potential for high Economics of scaling hybrid
efficiency processes
hybrid (Est.)
Higher efficiency electrolysis
Vanadium 925 5 40.542.5 Rxn Demo Potential for Veryhigh temperature
chlorine improvement
O2 membrane
(O2 membrane)
Conflicting data on one
reaction
* Reported efficiencies and peak temperatures have been obtained from literature from the 1970s to 2003 using a range of assumptions
and methods. See Appendix 31 (table and accompanying references) for details on the efficiency calculations. Cycles defined as
promising alternatives are those that were not sufficiently developed in the past but may merit further investigation based on estimated
performance and improvements from incorporation of that new technologies may that may significantly improve performance.

36
3.4.1 SulfurBased Cycles family of cycles is shown in Figure 32. Note that the

common hightemperature reaction shown on the left
The sulfurbased thermochemical cycles have been can be used with any of the three lower temperature
sufficiently developed to extrapolate with reasonable reactions shown on the right.
confidence that, given sufficient resources, the
processes would be technically viable. No other cycle The decomposition of sulfuric acid is common to all
or group of cycles was identified that had the of these sulfurbased cycles. The sulfuriodine and
combination of performance potential, technical sulfurbromine hybrid cycles involve primary
maturity, and demonstrated viability. These cycles reactions that produce hydrogeniodine (HI) or
have the highest probability of success for NHI and hydrogenbromine (HBr) in solution, which must be
will be the focus of the NHI thermochemical R&D separated and decomposed to produce hydrogen.
program. An integrated program will be pursued that Hydrogen is produced in the sulfuriodine cycle by
explicitly recognizes common R&D areas. Similarly, thermal decomposition of hydrogeniodine, while the
pilot plant facilities will be designed to test the family hybrid sulfur and sulfurbromine hybrid cycles
of cycles. A schematic representation of the sulfur produce hydrogen in an electrolytic step.
Figure 32. Sulfur family of thermochemical cycles.

37
3.4.1.1 Common R&D Areas. The sulfur the use of electrodialysis and membrane

based thermochemical processes have a common reactors as alternative technologies.
oxygengenerating, hightemperature step (the
dissociation of sulfur trioxide into sulfur dioxide and • Hybrid Sulfur (also called Westinghouse, GA
oxygen at temperatures in the 850 to 1000°C range). 22, and ISPRA Mark 11) – This allfluids
Therefore, the hightemperature materials and heat cycle involves a single thermochemical step
exchanger (HX) designs required to interface the and a single electrolytic step. Westinghouse
sulfur cycles with the hightemperature reactor is Electric Corporation demonstrated this
common to all sulfur family cycles. The materials process on a scale of 150 l/h in 1976, and a
issues are challenging and different in the boiling and conceptual plant design has been developed.
decomposition regimes. R&D requirements for this As a twostep process, it is the simplest
stage include longterm materials tests and innovative process that has been demonstrated, involving
heat exchanger design studies, which are described in only sulfur compounds, water, hydrogen, and
Section 5. The incorporation of a hightemperature oxygen. The unique R&D needs for the
(inorganic) membrane in this common stage of the hybrid sulfur cycle focus on the electrolytic
sulfur cycles has the potential to increase efficiency or cell design and optimization. Reducing the
lower heat requirements by enhancing the electrical losses and requirements in the
decomposition reaction. This could significantly electrolysis step and designing improvements
reduce the engineering challenges or improve process to allow cost effective scale up are the highest
efficiency. R&D to evaluate the potential of high initial priorities. Anode, cathode, and
temperature inorganic membranes should be membrane materials need to be reevaluated in
performed early to determine the potential impact on light of the extensive R&D in those areas
sulfurbased cycle design. over the last several decades (electrical
consumption of these cells is small in
The R&D necessary to perform an integrated comparison with traditional water
laboratoryscale demonstration of sulfuriodine and electrolysis).
hybrid sulfur will be the highest priority for NHI. The
sulfurbromine hybrid cycle benefits from much of • Sulfur Bromine Hybrid –This allfluids cycle
this research, but due to lower projected performance involves two thermochemical steps and one
potential, processspecific work on sulfurbromine electrolysis step. It was demonstrated in a
hybrid will be initially limited to confirmatory laboratoryscale experiment operated in
analyses. The processspecific R&D areas for sulfur ISPRA for 1.5 years producing 100 l/h.
iodine and hybrid sulfur are summarized as follows. However, the projected efficiencies are
slightly lower than the hybrid sulfur cycle.
• Sulfur Iodine – This allfluidsandgases cycle The hybrid sulfur cycle is chosen relative to
involves three primary thermochemical steps. this cycle because the process is more
Unique technical issues associated with this efficient, primarily because the electrolytic
specific cycle include efficient separation of cell power consumption is less (0.6 vs. 0.8V),
hydrogen iodide, minimizing the recycle rates and it is a simpler process. Reduction of
of chemicals within the process per unit of energy requirements for the electrolytic step is
hydrogen produced, and reducing the the most important R&D area. Initial work
inventories of iodine within the process, on the sulfur bromine hybrid cycle will focus
which, although not consumed, is expensive on updated flowsheet analyses.
and toxic. Multiple alternative technical
solutions (primarily using membranes) have 3.4.2 Calcium Bromide Cycles
been proposed to address these challenges.
The distillation of hydrogeniodine from The calciumbromine cycle has been demonstrated at
solution is the most difficult process issue for 1 l/h for ~100 h. The primary incentive to develop
this cycle. The NHI work will examine both this cycle is that the peak temperature is lower than
reactive and extractive (H3PO4) distillation for the sulfur cycles, typically 750°C. Efficiencies
and investigate recent Japanese proposals for have been estimated between 40 to 50%. Major work
38
has been done in Europe and Japan, with continuing to develop stable reaction beds or alternative reaction
work in Japan and in the United States under the stages will be the focus of the initial NHI research on
NERI program. The key R&D areas that must be this process.
addressed for this cycle are associated with the solid
gas reactions that characterize the cycle. The CaO, 3.4.3 Alternative Thermochemical Cycles
CaBr2, and Fe3O4, and FeBr2 reactants in fixed beds
or other configurations undergo volume changes in In addition to these sulfur and calciumbromine
each reaction of the cycle. Research efforts to date families of baseline thermochemical cycles, several
have not been able to demonstrate the integrity of other cycles were identified as being promising due
these reaction beds after many cycles. While either to lower temperature requirements, high
industrial processes have been commercialized with advertised efficiencies, or other positive cycle
this characteristic, such processes present a significant characteristics. Examples of these cycles are given in
engineering challenge because of multiple Table 31 (copper chloride, iron chloride, and copper
degradation mechanisms (fines formation, slow sulfur). Additional analysis of these cycles will be
chemical reactions, etc.). performed at an early stage to assess the potential of
these cycles to provide a more cost effective process.
A schematic representation of the calciumbromine Because almost three decades have passed since there
UT3 cycle is shown in Figure 33. The UT3 cycles has been significant work in this field, there are
reactions occur in pairs of solid reaction beds. One multiple new technologies that may enable
pair contains calciumbromide and calciumoxide and improvements in previously considered
the other pair contains ironoxide and ironbromide. thermochemical cycles. These cycles have not been
The initial reaction steps form hydrogenbromine fully demonstrated in the laboratory. In most cases,
from a hightemperature steam reaction with the there is insufficient documentation to determine
calciumbromide bed and hydrogen from the iron whether a cycle has potential or whether a fatal flaw
bromide bed. A second (lower) series of reactions in the process was discovered. The lack of a common
regenerates the calcium and ironbromide reactants. database has resulted in significant duplication of
When the initial reaction beds are fully converted, the work and has hindered progress.
flows are switched in each pair of beds and the same
reactions occur in the opposite flow direction. Work Evaluation of alternative cycles will initially focus on
at ANL has identified a variation of this cycle that performing consistent thermochemical flowsheet
eliminates the iron reaction beds and introduces an analyses to improve estimates of efficiency and
alternative electrolytic or cold plasma step for complexity and provide a basis for assessing the
hydrogen generation from hydrogenbromine. R&D potential for an economic cycle. If these analyses
Figure 33. Schematic of CaBr thermochemical cycle (UT3).

39
confirm cycle potential above baseline cycles, integral part of heat exchanger
decisions will then be made whether to test key design.
reactions in the laboratory. Laboratory results
demonstrate the effects of chemical kinetics and – Sulfuriodine reactions – These
provide data that are essential to the final assessment. reactions consist primarily of prime
The evaluation of experimental data and a preliminary (Bunsen) reaction and hydrogen
flowsheet will provide the basis for a decision on iodine distillation. R&D will address
further development. This evaluation and the reduction of recycle volume in the
systematic documentation of the results could be done prime reaction and determination of
effectively in cooperation with universities, industry, optimum technique for hydrogen
and international partners. iodine distillation (reactive, extractive
[H3PO4], and electrolysis options) to
3.5 Thermochemical Cycle R&D maximize efficiency.
Program – Hybrid sulfur – Hybrid sulfur
involves an electrolytic step for
The R&D program for thermochemical cycles will hydrogen production. Research
develop the necessary information on candidate focuses on improved anodecathode
thermochemical processes to support pilot plant materials and fabrication methods
decisions in 2009. The decision to demonstrate a and on improved models of cell
thermochemical cycle at a pilot plantlevel (500 kWth operation (voltage, acid
to 1 MWth) requires that the candidate processes be concentration, and temperature
demonstrated in integrated, laboratoryscale characteristics) to optimize the cell
experiments that successfully confirmed technical design. Improved membrane options
viability and projected cost estimates. The objective will be developed based on recent
of the NHI thermochemical research is to complete membrane research results.
integrated, laboratoryscale demonstrations for the
baseline cycles to provide the technical basis for pilot – Flowsheet and thermochemical data
plant decisions in 2009. The research will also development will be performed to
provide sufficient information on alternative support the sulfurbased cycle R&D
thermochemical cycles to confirm that promising program.
options have not been overlooked. The
thermochemical R&D program priorities will focus • Calciumbromine cycle – Flowsheet analyses
on: and system design studies will be performed
to assess performance and cost. The initial
• Integrated laboratoryscale demonstration of focus will be on analyses, materials, and
sulfuriodine and hybrid sulfur baseline thermodynamic data experiments. Integrated
cycles – Both of these cycles are sufficiently demonstration decisions will be made after
well defined to proceed to integrated testing. key reaction bed or electrolytic issues have
These demonstrations will utilize engineering been addressed.
materials and be performed under prototypic
pressure and temperature conditions. The – R&D on calcium and iron reaction
component reactions that must be bed materials integrity, (materials
demonstrated to support these integrated tests and coating technology) – R&D will
are: focus on developing thermodynamic
property and kinetics data to support
– H2SO4 decomposition – H2SO4 flowsheet analyses.
decomposition is common to all
sulfurbased cycles. R&D will focus – Electrolytic step (STAR variation) –
on hightemperature materials Cell design and materials assessment
compatibility, heat exchanger design, for the hydrogenbromine electrolytic
and incorporation of catalysts as an step will be performed. Models of
310
hydrogenbromine dissociation and demonstrations of the highpriority sulfuriodine and
cell processes will also be developed hybrid sulfur in 2007.
to support improved performance
studies. Integrated demonstrations provide performance
confirmation and a basis for cost projections that
• Alternative thermochemical cycles – Initial support pilot plant decisions in 2009. Pilot plant
focus will be on consistent flowsheet analyses preliminary design activities will be performed as
of promising cycles to confirm potential. R&D progresses and provides a basis for comparative
Studies will examine membrane and catalyst cost estimates for scaling between hybrid and pure
options to resolve key issues in selected thermochemical cycles. This development strategy is
alternative cycles. summarized in Figure 35.
The proposed organization of the R&D for the 3.6 Thermochemical R&D

thermochemical cycles is shown in Figure 34. These
assessments will identify if calciumbromine or an
Activities
alternative cycle should be considered a higher
Major thermochemical R&D activities for sulfur,
priority in 2005. The demonstration of all component
calciumbromine, and alternative cycles are
reactions in 2006 supports the start of integrated
summarized in Table 3.2.
Figure 34. R&D program structure for the development of thermochemical processes for NHI.

311
Figure 35. Thermochemical cycle major research areas and R&D sequence.

312

Table 3.2. Thermochemical R&D milestones.

Year Sulfur Cycles CaBr Cycles Alternative Cycles
FY2004 Complete comparative analysis of SI cycle based on Complete preliminary flowsheet analysis for candidate
recommended NHI methodology CaBr cycle approaches, estimate performance potential
Complete final component reaction section flowsheets and identify the most promising approaches for the
incorporating alternative HI and H2SO4 flowsheet results CaBr thermochemical cycle
Complete final design for the SI thermochemical Define lab scale demonstration approach for the
laboratoryscale system selected CaBr cycle approach
FY2005 Construct SI component reaction systems Complete flowsheet analysis for UT3 and Star versions Flowsheet analyses of

Assess high temp membrane for H2SO4 decomposition of CaBr Cu and Fe cycles
Hightemperature materials test assessment
Complete cost/performance assessment Catalyst assessment
Hybrid sulfur system concept definition. Star approach evaluation
FY2006 Complete demonstration of SI component reactions Initiate component reaction experiments Flowsheet and economic

Construct SI integrated loop Design integrated demonstration loop analyses of alternative
cycles
Hybrid electrolyzer tests UT3 and Star experiments
Design labscale
High temp HX tests for H2SO4 experiments
FY2007 Start SI integrated demo (100 l/hr) Ca Br scaling scaling decision Labscale experiments
Start hybrid S integrated demo (100 l/hr) Construct Ca Br demo loop for CaBr cycle
for alternative cycles
Engineering HX tests Initiate integrated lab scale exps

Conceptual pilot plant designs for SI, hybrid
FY2008 Integrated SI, demonstration tests Perform CaBr integrated lab scale tests Labscale experiments

Integrated hybrid S demonstration tests Conceptual Ca Br pilot plant design
on alternative cycles
Preliminary pilot plant designs for SI and/or hybrid cycles

FY2009 S based cycle pilot plant decision Ca Br pilot plant design Integrated demonstration
Design sulfur cycle pilot plant
for alternative cycles
Process improvement R&D

FY2010 Construct sulfur cycle pilot plant CaBr pilot plant construction Conceptual pilot plant
Conceptual design for engineering demo design for alternative
cycles
41
4. HIGHTEMPERATURE ELECTROLYSIS

Electrolysis is the most straightforward approach requires the development of an HTE system design
currently available to produce hydrogen directly from and the demonstration of improved efficiency and
water. Conventional electrolyzers are available with projected costs. Advanced hightemperature reactors
electricaltohydrogen efficiencies of around 70% at a can provide both the hightemperatures needed for
cost of about $400/kilowatt electric (kWe) installed. superheated steam and the efficient electricity
For electrical conversion efficiencies of 33 to 40%, required for electrolysis. The projected target costs
the overall energy efficiency of hydrogen production for hydrogen production are $2.50/kg in 2011, and
is 23 to 28%. Conventional electrolysis allows $2.00/kg in 2017. These projected hydrogen cost
distributed production of hydrogen in limited targets mean that hightemperature electrolysis will be
amounts. Since conventional electrolyzers are demonstrated at a scale and efficiency that allows
generally limited by membrane characteristics to projection to a commercial facility with these
relatively small outputs (kW to MW range), a large production costs.
scale production application would be composed of
many electrolyzer modules. Although production 4.2 Approach
efficiencies for large quantities of cells can lead to
reduced costs per cell, the cost effectiveness of the Since electrolysis and related SOFC materials and
modular scaling for electrolysis in comparison with technology are being developed in other parts of the
the scaling of thermochemical methods is one of the DOE Hydrogen Program, the scope of the NHI R&D
issues to be evaluated. activity is to develop an HTE system design optimized
for use with a hightemperature reactor and to
Hightemperature electrolysis (HTE), or steam demonstrate cell and module performance. The
electrolysis, has the potential for higher overall primary tasks for HTE development are as follows:
efficiency. Thermal energy is used to produce high
temperature steam, which results in a reduction of the • Develop a conceptual design for an HTE
electrical energy required for electrolysis and, system coupled to an advanced high
therefore, a reduction in the total energy required for temperature reactor to provide a basis for cost
hydrogen generation. HTE can be accomplished and performance assessment.
using materials and technology similar to those used
in solid oxide fuel cells (SOFCs). Electrolysis • Demonstrate promising cell and module
approaches allow the use of offpeak electricity for approaches in a series of scaling experiments
hydrogen production, and the economic analysis of to confirm performance for conditions
the HTE approach will consider the potential for a relevant to an advanced hightemperature
dualuse plant based on the hightemperature fuel nuclear reactor.
cell/electrolyzer. This potential cost advantage can be
negated if the hightemperature cell remains too costly The research performed in the NHI will be closely
for largescale application. Conventional electrolysis coordinated with EE and FE to identify interfaces
(a commercially available technology) serves as a with ongoing research relevant to HTE development.
baseline for the evaluation of the cost and benefit of
advanced electrolysis methods. Hightemperature 4.3 Hightemperature Electrolysis
methods are expected to result in lower hydrogen Assessment
costs than conventional electrolysis.
Hightemperature electrolysis uses a combination of
4.1 Objective thermal energy and electricity to split water in a
device very similar to an SOFC. Fundamentally, the
The objective of HTE research is to assess the electrolytic cell consists of a solid oxide electrolyte
potential of an HTE production plant coupled to a (usually yttriastabilized zirconia) with conducting
hightemperature nuclear heat source for the large electrodes deposited on either side of the electrolyte,
scale production of hydrogen. This assessment as illustrated in Figure 41 (see Appendix 41 for
42
Figure 41. Typical hightemperature electrolysis cell configuration.

details). A nominally 50:50 (volume percent) mixture 4.3.1 High Temperature Electrolysis

of steam and hydrogen at 750950°C is supplied to Energy Efficiency
the anode side of the electrolyte. Oxygen ions are
drawn through the electrolyte by the electrical To be an attractive option, the potential for increased
potential and combine to oxygen on the cathode side. overall efficiency of HTE over conventional
The steamhydrogen mixture exits at about 25:75 electrolysis must offset any increases in capital costs
volume ratio, and the water and hydrogen gas mixture that might be incurred due to the more complex, high
is passed through a separator to separate hydrogen. temperature, electrolytic cell configuration. The
While present experiments and fuel cells operate near improved efficiency is achieved through the
atmospheric pressures, future cells may operate at substitution of thermal energy for electrical energy. A
pressures up to 5 MPa. less efficient electrical generation process results in a
greater overall benefit of using thermal energy
Because of shrinkage during sintering in current directly. The magnitude of the potential efficiency
manufacturing processes, the size of individual cells is improvement is illustrated in Figure 42 as a function
limited to about 15 cm2. Therefore, a high of steam temperature and a range of electrical
temperature electrolysis plant powered by a reactor conversion efficiency assumptions. The plotted lines
would consist of an array of relatively small modules show the efficiency of the electrical generation
connected together with the necessary high process supplied to the cell. The largest efficiency
temperature gas manifolding, electrical, and control improvements occur for the lowest electrical
connections. Costs for SOFCs are currently high conversion efficiencies. For current light water
(~$10k/kWe), primarily due to smallscale reactor electrical efficiencies (33%), the improvement
manufacture. Ongoing SOFC research is is on the order of 20%. This efficiency improvement
investigating approaches to reduce both materials and is potentially significant since it reduces not only the
manufacturing costs. Current estimates are that large size and capital cost of the hydrogen plant, but also
scale manufacturing could potentially reduce costs by reduces the size and cost of the nuclear plant required
an order of magnitude. to produce a given amount of hydrogen.
43
Figure 42. Efficiency improvement for high temperature electrolysis as a function of steam temperature.

4.3.2 Hightemperature Electrolysis solid oxide electrolysis cells (SOECs) for nuclear

Production Plant Features application. The NHI will coordinate with ongoing
research in the SECA program and other DOE SOFC
A schematic diagram of a nuclear hydrogen plant programs.
using HTE is shown in Figure 43 (see Appendix
42). The reactor (in this case an HTGR) supplies 4.4 Hightemperature Electrolysis
both electricity and steam to the electrolytic cell. The
steam generator supplies superheated steam to the
R&D Needs
cells at a temperature of 750 to 950°C, and at a
The primary categories of nuclearspecific HTE R&D
pressure of 1 to 5 MPa. The input gas contains both
that must be addressed are as follows:
steam and hydrogen to maintain reducing conditions.
A scoping system design that defines initial system
• System design studies to support cost and
parameters for an HTE plant is summarized in
performance assessment for HTE nuclear
Appendix 42.
plants
In addition to hightemperature electrolyzer
• HTE cell and module optimization to support
technology, the development of a costeffective HTE
technology demonstration.
process poses challenges for heat exchangers and
materials (750 to 950°C steam), thermal distribution
4.4.1 System Design and Trade Studies
and recovery systems (manifolds and heat loss), and
cell engineering (materials and sealing). The The most pressing research need for HTE is the
development of HTE units for use with nuclear development of a conceptual design to identify the
reactors will make use of the materials and component needs specific to nuclear applications of
configurations of SOFCs. The development of the technology. The NHI design study will identify
SOFCs has been supported by FE through the Solid the changes in present SOFC materials,
State Energy Conversion Alliance (SECA), an configurations, and operating modes necessary for
industryDOE collaboration. The NHI research needs HTE. For example, the tubular SOFC design is the
identified for hightemperature electrolysis are those
issues specific to the development and integration of
44
Figure 43. Major components of a conceptual nuclear hightemperature electrolysis plant.

most developed of the SOFC designs to date. separators, and flowcontrol devices are needed to
However, the tubular configuration requires optimize overall plant performance.
approximately ten times more hot volume than a
planar configuration for the same hydrogen The costs of power electronics are an important output
production rate. of these trade studies. Rectifiers for the conversion of
alternating current to direct current are a major cost in
Trade studies are needed to determine the economic the overall HTE plant. Proper choices of stack
and engineering impacts of the cell configuration, voltage and current and the use of standard
arrangement of the steam generator, need for components may substantially reduce the cost of
reheating the steam and/or heating the oxygen carrier power conditioning and control.
gas, methods for steamhydrogen separations, and the
choice of operating pressure. The overall design of 4.4.2 Hightemperature Electrolysis Cell /
the HTE plant can be optimized in relation to the Module Optimization
electrical grid requirements, peak power management,
and grid stability. Although the development effort for solid oxide
materials for hightemperature fuel cells has been
Models of HTE processes and systems performance substantial, the engineering and optimization of
are also required to support the conceptual design and SOFCs are at an early stage. Several engineering
assess HTE cell performance. These analyses include issues must be addressed as part of the development
cell and module thermal and structural models. These of the cell/module for an HTE hydrogen production
models address the behavior of the electrodes, plant.
electrolyte, interconnection, and seals in the face of
thermal and chemical challenges. Electrochemical • Interconnections – The use of metallic
models are also needed to describe materials flows interconnection between planar cells would
through the individual cells. These analyses will result in lower ohmic losses, improved
define temperature and current distributions, resistance to thermal and mechanical shock,
particularly in response to changes in materials and reduced manufacturing costs. The choice
properties. Thermal models of the HTE system and of interconnection material is closely related
reactor interface, including heat exchangers, to the choice of electrolyte, since the ionic
45
Table 41. Summary table of hightemperature electrolysis research needs.

R&D Area Technical Issues HTE Ongoing Needed
Requirement Research Research
System HTE System Configuration 100 – 300 MW Hydrogen NE Lead Design and trade studies for
Design Plant Design Trade Studies Engineering, Economics materials and component
Studies selection.
HTE Process Models Reheat of Steam
Celllevel and plantlevel
Power Electronics Costs Rectifiers AC to DC modeling necessary.
Material Demands HTE Large Materials Req’s
Cell / Stack Interconnections Thermal Cycling FE Lead Monitor FE research.
Optimization Cell Sealing Compressive or Steam Sealing
Electrolyte Performance YSZ Satisfactory at High Temps
Cathode Material HTE Less Challenging
Anode Materials Oxygen Diluent
Cell/Stack Performance for NHI Temp, Technology Demo by 2006 NE Lead Test program for candidate
Demonstratio Pressure Conditions HTE options.
n

• resistivity of the electrolyte is temperature maintain reducing conditions. Cathode
dependent, dropping by a factor of two conditions are less challenging for HTE than
between 750 and 850°C. Metallic for SOFC conditions, for which these cathode
interconnections would have to operate at materials have been developed. Issues in the
lower temperatures than present day ceramic use of nickel with coal combustion gases pose
interconnections. more difficult problems due to the presence of
sulfur and other contaminants.
• Cell Sealing – Sealing between SOFC cells is
a major issue in the choice of tubular versus • Anode Materials – Lanthanum strontium
planar configurations. The sealant must manganite (LSM) has been the most
withstand both the oxidizing environment of frequently used material in SOFCs, both
the anode and the reducing conditions of the tubular and planar. Perovskitestructured
cathode. Tubular designs allow separation ceramics have been developed for
the oxidizing and reducing environments, applications at lower temperatures. The
while edge sealing in a planar configuration is consensus of experts is that initial
more difficult. Design studies and laboratory demonstrations of HTE could rely on LSM.
tests are needed to address these issues.
• Materials costs – The operation of the SOFCs
• Electrolyte Performance – Research in the at high temperatures requires the use of
electrolyte material is seeking higher expensive alloys through the balance of plant.
conductivity materials with comparable cost Therefore, the development of materials for
and chemical advantages. Advanced lower temperature operation may result in
materials (e.g., scandium doped zirconia and overall reduction in the hydrogen cost due to
lanthanum gallate with strontium doping) are a reduced capital investment in the plant. The
being developed and will be examined for impact of reduced materials costs is a central
this application. consideration in the trade studies described
above.
• Cathode Materials – The use of nickelnickel
oxide or nickel zirconia cermets will be The R&D needs for the development of the nuclear
satisfactory as long as a steamhydrogen HTE system are summarized in Table 41.
mixture (rather than pure steam) is used to
46
4.5 Hightemperature Electrolysis effectiveness, the NHI research effort will focus on

the demonstration of HTE cell performance based on
R&D Program the most promising materials and technology available
The sequence and interaction of the major HTE areas from the FE program. The cell engineering efforts
are summarized in Figure 44. The planning will support the demonstration of SOFC modules in
assumptions for HTE include early testing of FY 20052006, while the NHI technology
candidate cells (button) based on materials being demonstrations will provide the basis for pilot plant
developed in the DOE fuel cell program. The NHI decisions in FY 2009. The EE and FE technology
activities will focus on cell/stack testing to provide research and the NHI system design and cell
performance information for pilot plant decisions. demonstration activity will be closely coordinated to
The design and operation of a pilot plant at the ensure the most efficient use of R&D investments
nominal 200kWe level could be initiated at a smaller from all DOE offices.
power level and expanded as improved materials and
electrolyzer cells become available. 4.6 Hightemperature Electrolysis
Milestones
The highest priority for nuclear HTE development is
to complete a conceptual design that can be used to The major R&D milestones associated with HTE are
support cost and performance assessments in summarized in Table 4.2
FY 2004. With confirmation of performance and cost
Figure 44. Hightemperature electrolysis R&D plan.

47
Table 42. Hightemperature electrolysis R&D milestones.

Year HTE Systems Analysis Cell Optimization
FY2004 Perform engineering analysis to support the Construct the HTE cell stack testing capability to
conceptual design of HTE scaling demonstration evaluate electrolyzer characteristics and performance
experiments, including electrolyzer cell and module Complete single (button) cell experiments on candidate
configurations, and steam distribution systems electrolyte materials for HTE
Complete a conceptual system design for a high
temperature electrolysis system coupled to a high
temperature reactor
Complete preliminary designs for HTE scaling
experiments at pilot and engineering scales
FY2005 Complete HTE preconceptual design Establish technology interface on materials, cell
Complete HTE system cost assessment (with EE) engineering and design options (with FE, EE)
Develop engineering model for HTE system Define HTE cell/module options, and develop cell and
performance evaluation (thermal, structural, module test plan (FY0507)
thermoelectric process) Button cell experiments (with EE)
FY2006 Complete thermal/structural analyses of module/stack HTE cell testing for highest priority cell options
and manifold options Construct stack /module arrays, initiate testing
Develop conceptual HTE pilot plant design Develop conceptual pilot plant module design
Design integrated labscale HTE demo
FY2007 HTE pilot plant preliminary design Complete HTE cell testing
Conduct integrated labscale demo experiments Conduct HTE stack / module tests
Candidate pilot plant module tests
FY2008 Conduct integrated labscale demo experiments Complete HTE stack / module tests
Implement cell/module technology improvements
FY2009 Pilot plant decision Cell technology support
HTE pilot plant final design
Pilot plant operation
FY2010 Conceptual design for Engineering demo
Pilot plant construction
48
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51
5. SYSTEMS INTERFACES AND BALANCE OF PLANT

Hydrogen production systems coupled with a high requirements at the production process interface and
temperature nuclear reactor introduce new the more general supporting systems and safety issues
considerations and requirements into the design of a that are associated with the coupled nuclear hydrogen
combined nuclear hydrogen plant. Both high plant.
temperature electrolysis and thermochemical systems
must be colocated with the nuclear heat source. The It is recognized that significant R&D activities are
interface between the reactor and hydrogen being pursued in other DOE offices, government
production system involves potentially long heat agencies, and industry. These systems interface
transfer paths at elevated temperatures, heat activities will complement or collaborate with other
exchangers that are subject to both elevated ongoing DOE or industrial system research efforts to
temperature and corrosive chemical environments, avoid any potential duplication. Therefore, this report
new safety and regulatory issues, and supporting will focus on the R&D issues unique to nuclear
systems for chemical processes and hydrogen and hydrogen production that are not currently being
oxygen transfer and storage. Although some of these planned or pursued under other programs.
issues will be common to any nuclear hydrogen plant,
many will depend on the specific hydrogen 5.3 Systems Interface and
production process selected. BalanceofPlant Assessment
5.1 Objective The primary balanceofplant systems and interfaces
are shown schematically in Figure 51. The high
The objective of the systems interface and balanceof temperature reactor provides nuclear process heat to
plant research effort is to develop the high the hydrogen plant through an intermediate heat
temperature interface components and materials transfer loop. The intermediate loop working fluid
required to couple the thermochemical or high and materials of construction are important
temperature electrolysis system to the high engineering issues at these elevated temperatures.
temperature heat source. Interface requirements are Physical isolation, either separation distance or an
defined by the characteristics of the thermochemical acceptable physical barrier, must be sufficient to
and HTE processes, and these activities are focused eliminate the propagation of accident consequences
on developing the components needed to demonstrate from one plant to the other. Additionally, numerous
selected processes. supporting systems are required for gas handling,
storage, and process support. Hightemperature heat
5.2 Approach exchangers that are required to transfer heat from the
reactor primary systems to the hydrogen process are
The NHI systems interface research will focus on the critical elements for efficient coupling of the nuclear
heat exchanger and materials required for the high hydrogen plant.
temperature components and materials needed for the
baseline processes, namely, the sulfur and calcium The major balanceofplant/plant interface systems are
bromine thermochemical cycles and hightemperature summarized in Table 51 along with the key issues to
electrolysis. Development of technology for the be addressed in the design phase of the project.
sulfur cycles will be the initial focus, but priorities Appendix 51 provides additional information on
will track the production process research priorities. major system interfaces and balanceofplant
R&D will also address the intermediate loop technology status.
52
Figure 51. Schematic of the major reactorhydrogen interfaces and balanceofplant systems.

Table 51. Major hydrogen plant interfaces and balanceofplant systems.
Systems/Components Design /Interface Considerations
Hightemperature Heat HX interface to production process, HX design options, operational conditions
Exchangers (temperature and pressure)
Hightemperature materials compatible with heat transfer medium and production process
chemical species
Intermediate Loop
Heat Transfer Medium Heat transfer conditions – temperature, pressure, pumping power, heat loss requirements,
working fluids
Hightemperature Transfer Isolation configuration, materials, operating conditions (temperature, pressure, and fluids),
Lines insulation, seals, auxiliary heating
Support Systems
Oxygen Recovery/Disposal Oxygen inventory, recovery, or disposal approach, storage, safety issues
Oxygen Safety Systems Oxygen hazards (combustion and health), materials corrosion, ventilation, fire systems,
diagnostics, environmental control
Hydrogen Safety Systems H2 diagnostics, storage, combustion, ventilation systems, explosive hazards,
Hydrogen Transfer Transfer system to interface with pipeline, storage systems
Chemical Support Systems Chemical feed, storage, purification, diagnostics, process controls
Instrumentation and Control H2 process diagnostics and controls, interface with reactor systems,
Electrical Hybrid process, grid, station power systems
Alternative Heat Source Interim process heat requirements for testing or production
53
5.4 Systems Interface and impact system design and preliminary

definition of accident categories may be
BalanceofPlant R&D Needs important in process evaluation. The tasks
that should be addressed include assessment
The primary systems interface and balanceofplant
of regulatory requirements, definition of
research areas are as follows:
separation and isolation criteria, and
preliminary plant safety studies.
• Nuclear hydrogen system design studies to
define configurations and component
• Applicable code assessment – Numerous
requirements
codes, standards, and guidelines are
applicable to hydrogen and oxygen, but no
• Hightemperature heat exchanger design and
definitive compilation was identified. The
materials
R&D effort should include a compilation of
applicable codes, standards, and guidelines
• Intermediate heat transfer loop and materials
for the nuclear plant and the hydrogen
production processes of interest, and identify
• Hydrogen plant support systems.
any issues.
5.4.1 Nuclear Hydrogen System Design
• BOP interface with hydrogen production
Studies
process and NGNP – Definition of design
System design studies for the system interface and and performance requirements determined by
balanceofplant areas address plant configuration hydrogen production process characteristics
options for both thermochemical and high and hightemperature reactor capabilities will
temperature electrolysis systems, safety and isolation be required to establish conditions for
issues for the coupled plants, and assessment of balanceofplant systems.
applicable codes and standards. Since these studies
define fundamental options for the nuclear hydrogen 5.4.2 Heat Exchanger Design Studies
plant configuration and nuclear interface, they must
Hightemperature heat exchangers that transfer
be addressed early in the FY 2004 to 2006 time
thermal energy to chemical processes or steam at
frame.
elevated temperature are critical components.
• Hydrogen plant configuration studies define Operational conditions for the interface heat
configuration options and the operational exchangers are challenging. The heat exchanger for
conditions and requirements for the hydrogen the sulfuriodine and hybrid sulfur processes require
plant subsystems. The isolation approach for decomposition of sulfuric acid at more than 900°C
nuclear and hydrogen production systems, and up to several megaPascals (MPa). Heat
both thermochemical and electrolytic exchangers for the hightemperature electrolysis
processes, has performance and economic process will actually be steam generators producing
implications that need to be addressed at the steam at up to 950°C and up to 5 MPa. The primary
earliest possible stage. These studies define R&D areas that must be addressed include:
options and tradeoffs for the optimum
coupling of the nuclear and chemical systems. • Thermal analyses between intermediate loop
and process conditions to define operational
• System interaction studies define safety and requirements for heat exchangers for the
isolation issues arising from system level range of candidate cycles to support heat
considerations and from functional and exchanger design studies.
physical coupling of the nuclear and
hydrogen plants. Nuclear hydrogen • Heat exchanger design studies to explore
production systems will require a new or innovative heat exchanger design approaches
modified framework for regulation. that could potentially mitigate temperature or
Identification of information on combined lifetime requirements. A range of heat
plant operational requirements that could exchanger design approaches can be
54
considered (tube/shell and printed circuit) that meet the hightemperature and lowpressure
involve differing materials and fabrication requirements, and their viscosities are close to
issues. Heat exchanger viability is an water at the temperatures being considered,
essential consideration in the selection of a which translates to relatively low pumping
pilot plant hydrogen process. costs. Helium is also a logical heat transfer
medium, but the gas heat capacity results in
• Hightemperature materials test programs extremely large volumes of medium needed
are required to demonstrate performance and to transfer heat, resulting in large line sizes
lifetime under prototypic conditions. Based and high blower operating costs. Liquid
on the operating conditions and requirements metals can also meet the temperature and
for processspecific heat exchangers, this task pressure range with different material
will identify and initiate materials testing compatibility issues. Liquid metals are also
programs for the candidate cycles. This potentially expensive systems, have purity
activity also addresses fabrication issues for and pumping component issues, and have
heat exchanger designs and will require high densities and viscosities that will result
industrial participation in their design and in higher pumping costs over long distances.
fabrication. Scaled demonstration testing is
required for selected heat exchanger systems. • Hightemperature Transfer Lines – The
Although no current material has primary R&D activities for the intermediate
demonstrated capabilities in the full heat transfer loop transfer lines focus on
temperature and composition ranges being thermal analyses and materials development.
considered for hydrogen production Materials development will be required for
processes, considerable information is piping and seals, circulator (pumps or
available on materials that have potential and blowers), valves, and structural materials (900
have been demonstrated for most conditions. to 1000°C range). Materials for molten salt
structural materials, pumps, and valves have a
5.4.3 Intermediate Heat Transfer Loop technology gap between previously
demonstrated use at approximately 700°C and
Intermediate loop studies will define the interface the required range of 900 to 1000°C. The
with the reactor heat source, including operational technology gaps for use of helium involve
conditions, materials, and controls. The selection of equipment sizes and blower operating costs.
the heat transfer medium and transfer line The technology gaps in the use of liquid
configuration and materials are key technologies that metals, which include pumping, high
impact both reactor and process design choices. temperature valve development, and
potentially material compatibility issues, lie
• Heat Transfer Medium Materials – The between 450°C and the required range of 900
selection of the medium/fluid for the
to 1000°C.
intermediate heat transfer loop impacts plant
configuration, separation distance decisions, 5.4.4 Supporting Systems Scoping
heat exchanger design, and materials Studies
selection. The medium must be compatible
with temperatures of approximately 1000°C, Preliminary design studies of the supporting
pressures of several MPa, and reasonable subsystems for hydrogen, oxygen, and chemical
pumping/circulating requirements, as well as systems are required for the hydrogen production
chemical compatibility with heat transfer loop process and preliminary designs that support pilot
materials. plant decisions. Operational conditions and
requirements for the range of NHI production options
Molten salts, helium, and liquid metal are will be defined, and scoping studies of the
potential candidates for the heat transfer engineering configuration and associated costs will be
medium. The commonly used fluoride salts developed.
55
5.5 Systems Interface and The heat exchanger design and materials testing

activities must be sequenced to support production
BalanceofPlant R&D Program process R&D and pilot plant design and construction.
A summary level diagram of the major elements and
Systems and balanceofplant activities are directly
interactions of the balanceofplant program is shown
coupled to the development and schedule of the
in Figure 52.
hydrogen production processes. Hightemperature
materials and heat exchanger development and A summary of the major systems interfaces and BOP
demonstration are essential to a successful milestones that will be accomplished in support of the
demonstration of hydrogen production processes. production process demonstrations is shown in
Table 5.2.
Figure 52. Systems interface and BOP R&D activities.

56
Table 52. Summary of major systems interface and BOP milestones.

Intermediate Supporting System
Year Systems Studies Hightemperature HX Loop Design
FY2004 Complete initial Identify key technical issues Evaluate candidate Complete high level
configuration studies to for intermediate loop coolants and infrastructure and facilities
define balance of plant candidate designs and develop develop requirements assessment
components and systems research requirements and conceptual designs for pilot scale experiments
for thermochemical or priorities for promising
hightemperature approaches
electrolysis systems.
FY2005 Develop H2 plant Develop process specific HX Perform thermal, Assess external (to nuclear
configuration options for requirements for baseline flow analyses for hydrogen plant) interface
baseline processes processes intermediate loop requirements
Perform initial isolation Develop conceptual design options
assessment options for high H2SO4
Compile applicable codes decomposition HXs
and standards Initiate materials testing for
Sulfur cycles
FY2006 Complete preliminary H2 Initiate materials testing for Intermediate loop Conceptual design for H2
system cost studies for CaBr or alternative cycles preliminary design system components and
baseline processes Scaled HX design and subsystems (pilot plant
fabrication for Sulfur cycles scale)
and HTE
FY2007 Interface and BOP design Longterm materials tests Intermediate loop Component development
for pilot plant Pilot plant HX design materials testing for pilot plant processes
Thermal, structural, flow
for baseline pilot plant
designs
FY2008 Pilot plant systems Long term materials tests Pilot plant construction
support Hightemp HX demo tests support
Hightemp HX tests
FY2009 Pilot plant systems Pilot plant support
support
FY2010 Conceptual design for Engineering demo HX design Engineering demo
baseline engineering Pilot plant support conceptual design
demo

61
6. NUCLEAR HYDROGEN R&D PLAN SUMMARY

This Nuclear Hydrogen R&D Plan defines the those processes with promise but whose viability is
research necessary to develop hydrogen production uncertain. This approach will provide a more
options for the demonstration of hydrogen production consistent and complete assessment upon which to
from nuclear energy by 2017. The technical base future R&D funding and scaling decisions. NHI
challenges to the development of largescale, cost research will follow a systematic approach to
effective production options are significant, but developing the required information for the sequence
promising approaches have been identified, all of of scaling decisions. Confirmation of performance
which meet the DOE objectives of emissionsfree potential based on consistent thermodynamic analyses
production based on domestic resources. The of candidate cycles will be confirmed in laboratory
fundamental challenge is to focus finite research scale tests to support pilot plant scaling decisions.
resources on processes that have the highest Pilot plant demonstrations of the selected processes
probability of producing hydrogen at costs that are confirm engineering viability and establish a basis for
competitive with gasoline. Both thermochemical process cost estimates. Pilot plant performance and
cycles and hightemperature electrolysis methods have cost information provides a basis for selecting the
been identified as having the potential to achieve this NGNP nuclearheated engineering demonstration.
objective.
Both thermochemical cycles and HTE processes
Though early in the development stage of these challenge current capabilities for hightemperature
promising methods (none have been demonstrated at a heat exchangers and materials. R&D for the nuclear
pilot plantscale), this Nuclear Hydrogen R&D Plan and hydrogen systems interface and balanceofplant
identifies baseline processes that meet NHI systems and components will be required to provide
performance criteria and are sufficiently demonstrated viable engineering options for the range of processes
to provide reasonable confidence that the processes being evaluated.
would be technically viable in a large plant. Two
thermochemical cycles (sulfur family and calcium The NHI program office will establish the capability
bromine) and HTE (based on fuel cell technology) to provide consistent and independent analyses of
were identified as the highest priority production performance and costs to support the comparative
processes for further development. The recognition of assessments required for technology selection and
several common R&D issues applicable to more than scaling decisions. The magnitude of the nuclear
a single cycle further leverages the research hydrogen research effort also suggests that the NHI
investment. program office establish effective interfaces with
industry and international partners to take advantage
Initially, a broader research effort is required. The of the significant expertise in hydrogen production.
planned R&D effort will include laboratoryscale
demonstrations, where justified by the available This nuclear hydrogen R&D strategy is summarized
information, in addition to analytical evaluations of in Figure 61.
62
Figure 61. Summary of NHI R&D plan for the development and demonstration of a nuclear hydrogen
production capability by 2017.

A1
APPENDICES

[THE APPENDICES ARE NOT INTENDED TO BE PRINTED AND BOUND
WITH THE R&D PLAN, BUT WILL BE ATTACHED AS A CD FOR SELECTED
DISTRIBUTION, AND AVAILABLE TO ALL OTHERS UPON REQUEST]
Appendix for Chapters 1 and 2 – Introductory Chapters
Appendix 11. Current Hydrogen Production Processes: Steam Methane Reforming
Appendices for Chapter 3 – Thermochemical Cycles
Appendix 31. Thermochemical Process Descriptions and Status

Appendix 32. Membrane Applications for Hydrogen Production Using Nuclear Energy

Appendix 33. Catalyst Requirements for SI

Appendices for Chapter 4 – Hightemperature Electrolysis
Appendix 41. Hydrogen Production through Hightemperature Electrolysis in a Solid Oxide Cell
Appendix 42. Conceptual Design of a Hightemperature Electrolysis Plant
Appendix for Chapter 5 – Systems Interface and BalanceofPlant
Appendix 51. System Interfaces and BalanceofPlant


US DOE Nuclear H2 R&D Plan

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1.1 The DOE Hydrogen Program ........................................................................................... 1­2

1.2 Energy Sources for Hydrogen – The Nuclear Connection ............................................... 1­4

1.3 Nuclear Hydrogen Initiative (NHI) .................................................................................. 1­5

2. Nuclear Hydrogen Development Strategy.................................................................................... 2­1

2.1 Objective .......................................................................................................................... 2­1

2.2 Approach .......................................................................................................................... 2­1

2.2.1 Thermochemical Cycles ....................................................................................... 2­1

2.2.2 High­Temperature Electrolysis ............................................................................ 2­2

2.2.3 Other Production Methods ................................................................................... 2­2

2.2.4 Systems Interface ................................................................................................. 2­2

2.3 Technology Assessment ................................................................................................... 2­2

2.3.1 General Evaluation Criteria.................................................................................. 2­2

2.3.2 Production Process Prioritization ......................................................................... 2­3

2.4 Process Demonstration Strategy....................................................................................... 2­4

3. Thermochemical Cycles ............................................................................................................... 3­1

3.1 Objective .......................................................................................................................... 3­1

3.2 Approach .......................................................................................................................... 3­1

3.3 Thermochemical Cycle Assessment................................................................................. 3­1

3.3.1 Summary of Previous Studies .............................................................................. 3­2

3.3.2 Conclusions from Previous Studies ..................................................................... 3­3

3.4 Thermochemical Cycle R&D Needs ................................................................................ 3­3

3.4.1 Sulfur­Based Cycles ............................................................................................. 3­6

3.4.2 Calcium Bromide Cycles ..................................................................................... 3­7

3.4.3 Alternative Thermochemical Cycles .................................................................... 3­8

3.5 Thermochemical Cycle R&D Program ............................................................................ 3­9

3.6 Thermochemical R&D Activities .................................................................................. 3­10

4. High­Temperature Electrolysis .................................................................................................... 4­1

4.1 Objective .......................................................................................................................... 4­1

4.2 Approach .......................................................................................................................... 4­1

4.3 High Temperature Electrolysis Assessment ..................................................................... 4­1

4.3.1 HTE Energy Efficiency ........................................................................................ 4­2

4.3.2 HTE Production Plant Features............................................................................ 4­3

4.4 High Temperature Electrolysis R&D Needs .................................................................... 4­3

4.4.1 System Design and Trade Studies ........................................................................ 4­3

4.4.2 HTE Cell / Module Optimization......................................................................... 4­4

4.5 High Temperature Electrolysis R&D Program ................................................................ 4­6

4.6 HTE Milestones ............................................................................................................... 4­6

5. Systems Interfaces and Balance of Plant ...................................................................................... 5­1

5.1 Objective .......................................................................................................................... 5­1

5.2 Approach .......................................................................................................................... 5­1

5.3 Systems Interface and Balance­of­Plant Assessment ....................................................... 5­1

5.4 Systems Interface and Balance of Plant R&D Needs....................................................... 5­3

5.4.1 Nuclear Hydrogen System Design Studies........................................................... 5­3

5.4.2 Heat Exchanger Design Studies ........................................................................... 5­3

5.4.3 Intermediate Heat Transfer Loop ......................................................................... 5­4

5.4.4 Supporting Systems Scoping Studies ................................................................... 5­4

5.5 Systems Interface and Balance of Plant R&D Program ................................................... 5­5

6. Nuclear Hydrogen R&D Plan Summary ...................................................................................... 6­1

1.1 The DOE Hydrogen Program Figure 1­2. These offices are now working together

1.2 Energy Sources for Hydrogen • Very high temperatures or high­efficiency

1.3 Nuclear Hydrogen Initiative hydrogen production technologies needs to be

Electrolysis is the most straightforward approach 2.2.4 Systems Interface

• The first priority baseline thermochemical 2.4 Process Demonstration

3.3.1 Summary of Previous Studies because the chemical reactions were too slow,

3.3.2 Conclusions from Previous Studies 3.4 Thermochemical Cycle R&D

Peak Number Reported Cycle Status Advantages Key Issues

3.4.1 Sulfur­Based Cycles family of cycles is shown in Figure 3­2. Note that the

3.4.1.1 Common R&D Areas. The sulfur­ the use of electrodialysis and membrane

The proposed organization of the R&D for the 3.6 Thermochemical R&D

FY2005 Construct S­I component reaction systems Complete flowsheet analysis for UT­3 and Star versions Flowsheet analyses of

FY2006 Complete demonstration of S­I component reactions Initiate component reaction experiments Flowsheet and economic

FY2008 Integrated S­I, demonstration tests Perform Ca­Br integrated lab scale tests Lab­scale experiments

details). A nominally 50:50 (volume percent) mixture 4.3.1 High Temperature Electrolysis

1.1 The DOE Hydrogen Program ........................................................................................... 12

1.2 Energy Sources for Hydrogen – The Nuclear Connection ............................................... 14

1.3 Nuclear Hydrogen Initiative (NHI) .................................................................................. 15

2. Nuclear Hydrogen Development Strategy.................................................................................... 21

2.1 Objective .......................................................................................................................... 21

2.2 Approach .......................................................................................................................... 21

2.2.1 Thermochemical Cycles ....................................................................................... 21

2.2.2 HighTemperature Electrolysis ............................................................................ 22

2.2.3 Other Production Methods ................................................................................... 22

2.2.4 Systems Interface ................................................................................................. 22

2.3 Technology Assessment ................................................................................................... 22

2.3.1 General Evaluation Criteria.................................................................................. 22

2.3.2 Production Process Prioritization ......................................................................... 23

2.4 Process Demonstration Strategy....................................................................................... 24

3. Thermochemical Cycles ............................................................................................................... 31

3.1 Objective .......................................................................................................................... 31

3.2 Approach .......................................................................................................................... 31

3.3 Thermochemical Cycle Assessment................................................................................. 31

3.3.1 Summary of Previous Studies .............................................................................. 32

3.3.2 Conclusions from Previous Studies ..................................................................... 33

3.4 Thermochemical Cycle R&D Needs ................................................................................ 33

3.4.1 SulfurBased Cycles ............................................................................................. 36

3.4.2 Calcium Bromide Cycles ..................................................................................... 37

3.4.3 Alternative Thermochemical Cycles .................................................................... 38

3.5 Thermochemical Cycle R&D Program ............................................................................ 39

3.6 Thermochemical R&D Activities .................................................................................. 310

4. HighTemperature Electrolysis .................................................................................................... 41

4.1 Objective .......................................................................................................................... 41

4.2 Approach .......................................................................................................................... 41

4.3 High Temperature Electrolysis Assessment ..................................................................... 41

4.3.1 HTE Energy Efficiency ........................................................................................ 42

4.3.2 HTE Production Plant Features............................................................................ 43

4.4 High Temperature Electrolysis R&D Needs .................................................................... 43

4.4.1 System Design and Trade Studies ........................................................................ 43

4.4.2 HTE Cell / Module Optimization......................................................................... 44

4.5 High Temperature Electrolysis R&D Program ................................................................ 46

4.6 HTE Milestones ............................................................................................................... 46

5. Systems Interfaces and Balance of Plant ...................................................................................... 51

5.1 Objective .......................................................................................................................... 51

5.2 Approach .......................................................................................................................... 51

5.3 Systems Interface and BalanceofPlant Assessment ....................................................... 51

5.4 Systems Interface and Balance of Plant R&D Needs....................................................... 53

5.4.1 Nuclear Hydrogen System Design Studies........................................................... 53

5.4.2 Heat Exchanger Design Studies ........................................................................... 53

5.4.3 Intermediate Heat Transfer Loop ......................................................................... 54

5.4.4 Supporting Systems Scoping Studies ................................................................... 54

5.5 Systems Interface and Balance of Plant R&D Program ................................................... 55

6. Nuclear Hydrogen R&D Plan Summary ...................................................................................... 61

1.1 The DOE Hydrogen Program Figure 12. These offices are now working together

1.2 Energy Sources for Hydrogen • Very high temperatures or highefficiency

3.4.1 SulfurBased Cycles family of cycles is shown in Figure 32. Note that the

3.4.1.1 Common R&D Areas. The sulfur the use of electrodialysis and membrane

FY2005 Construct SI component reaction systems Complete flowsheet analysis for UT3 and Star versions Flowsheet analyses of

FY2006 Complete demonstration of SI component reactions Initiate component reaction experiments Flowsheet and economic

FY2008 Integrated SI, demonstration tests Perform CaBr integrated lab scale tests Labscale experiments

4.3.2 Hightemperature Electrolysis solid oxide electrolysis cells (SOECs) for nuclear

4.5 Hightemperature Electrolysis effectiveness, the NHI research effort will focus on