Solar Thermochemical

SANDIA REPORT
SAND2011-3622
Unlimited Release
Printed May 2011
Solar Thermochemical Hydrogen

Production Research (STCH)
Thermochemical Cycle Selection and
Investment Priority
Robert Perret
Prepared by
Sandia National Laboratories
Albuquerque, New Mexico 87185 and Livermore, California 94550
Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia

Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of
Energys National Nuclear Security Administration under contract DE-AC04-94AL85000.
Approved for public release; further dissemination unlimited.
Issued by Sandia National Laboratories, operated for the United States Department of Energy
by Sandia Corporation.
NOTICE: This report was prepared as an account of work sponsored by an agency of the
United States Government. Neither the United States Government, nor any agency thereof, nor
any of their employees, nor any of their contractors, subcontractors, or their employees, make
any warranty, express or implied, or assume any legal liability or responsibility for the
accuracy, completeness, or usefulness of any information, apparatus, product, or process
disclosed, or represent that its use would not infringe privately owned rights. Reference herein
to any specific commercial product, process, or service by trade name, trademark,
manufacturer, or otherwise, does not necessarily constitute or imply its endorsement,
recommendation, or favoring by the United States Government, any agency thereof, or any of
their contractors or subcontractors. The views and opinions expressed herein do not
necessarily state or reflect those of the United States Government, any agency thereof, or any
of their contractors.
Printed in the United States of America. This report has been reproduced directly from the best
available copy.
Available to DOE and DOE contractors from
U.S. Department of Energy
Office of Scientific and Technical Information
P.O. Box 62
Oak Ridge, TN 37831
Telephone:
Facsimile:
E-Mail:
Online ordering:
(865) 576-8401
(865) 576-5728
reports@adonis.osti.gov
http://www.osti.gov/bridge
Available to the public from

U.S. Department of Commerce
National Technical Information Service
5285 Port Royal Rd.
Springfield, VA 22161
Telephone:
Facsimile:
E-Mail:
Online order:
(800) 553-6847
(703) 605-6900
orders@ntis.fedworld.gov
http://www.ntis.gov/help/ordermethods.asp?loc=7-4-0#online
SAND2011-3622
Unlimited Release
Printed May 2011
Solar Thermochemical Hydrogen

Production Research (STCH)
Thermochemical Cycle Selection and
Investment Priority
Robert Perret
The DOEEERE Fuel Cell Technologies Program
Sandia National Laboratories
P.O. Box 969
Livermore, CA. 94551-0969
Abstract
Eight cycles in a coordinated set of projects for Solar Thermochemical Cycles for Hydrogen
production (STCH) were self-evaluated for the DOE-EERE Fuel Cell Technologies Program at a
Working Group Meeting on October 8 and 9, 2008. This document reports the initial selection
process for development investment in STCH projects, the evaluation process meant to reduce
the number of projects as a means to focus resources on development of a few most-likely-tosucceed efforts, the obstacles encountered in project inventory reduction and the outcomes of the
evaluation process. Summary technical status of the projects under evaluation is reported and
recommendations identified to improve future project planning and selection activities.
Acknowledgements
This report is made possible in whole due to the excellent work undertaken by the STCH Team
comprised of scientists and engineers from Sandia National Laboratories, Argonne National
Laboratory, Savannah River National Laboratory, the National Renewable Energy Laboratory,
TIAX, LLC, the University of Colorado, the University of Nevada, Las Vegas, General Atomics
Corporation and its collaborators from the Weizmann Institute, and SAIC and its subcontractors
from the Florida Solar Energy Center and Electrosynthesis, Inc. Data and analysis representing
efforts by these team members will be found throughout this report. Support by the DOE-EERE
Fuel Cell Technologies Program is gratefully acknowledged. Sandia National Laboratories has
been generous in its technical support of drafting the document and its excellent
recommendations for improving the document are gratefully acknowledged. The same gratitude
is extended to staff members of the DOE-EERE Fuel Cell Technologies Program who ably
assisted this author in navigating the complex stream of propriety associated with multiple
sponsorship and Congressional authority.
Contents
1
3
4
Introduction....................................................................................................................... 11
1.1 STCH Basis ............................................................................................................... 11
1.2 STCH Historical Summary......................................................................................... 13
1.3 STCH Decision Framework ....................................................................................... 14
Cycle Inventory Development and Initial Selection ......................................................... 17
2.1 Economic Consideration ............................................................................................ 18
2.2 Solar Collector/Receiver Consideration ...................................................................... 19
2.3 Previous Level of Effort for Candidate Cycle ............................................................. 19
2.4 Safety and Environmental Consideration .................................................................... 20
Formal Cycle Evaluation and Research Prioritization .................................................... 28
Cycle Status Summaries and Path Forward Recommendations ..................................... 42
4.1 Sulfur Iodine .............................................................................................................. 42
4.2 Hybrid Sulfur ............................................................................................................. 50
4.3 Photolytic Sulfur Ammonia ........................................................................................ 55
4.4 Zinc Oxide ................................................................................................................. 59
4.5 Cadmium Oxide ......................................................................................................... 64
4.6 Sodium Manganese Cycle .......................................................................................... 71
4.7 Sodium Manganate .................................................................................................... 76
4.8 ALD Ferrite ............................................................................................................... 77
4.9 Hybrid Copper Chloride ............................................................................................. 80
Summary Remarks ........................................................................................................... 84
5.1 General Observations ................................................................................................. 84
5.2 Evaluation Outcomes ................................................................................................. 85
5.2.1 Sulfur Iodine ........................................................................................................ 86
5.2.2 Hybrid Sulfur ....................................................................................................... 86
5.2.3 Photolytic Sulfur Ammonia .................................................................................. 87
5.2.4 Zinc Oxide ........................................................................................................... 87
5.2.5 Cadmium Oxide ................................................................................................... 87
5.2.6 Sodium Manganese .............................................................................................. 88
5.2.7 Sodium Manganate .............................................................................................. 88
5.2.8 ALD Ferrite ......................................................................................................... 89
5.2.9 Hybrid Copper Chloride ....................................................................................... 89
Appendix A: Cycle Inventory Changes after the Evaluation ................................................ 98

Appendix B: Criteria Scores Established for the Four Solar Technologies ........................ 100
Figures
Figure 1.1. Thermochemical cycle class examples. ..................................................................13
Figure 4.1.1. Sulfur Iodine three-step cycle. ............................................................................42
Figure 4.1.2. Bayonet decomposition reactor designed by Sandia National Laboratories. ......... 43
Figure 4.1.3. Bayonet decomposition reactor manifold designed by Sandia National
Laboratories. ........................................................................................................44
Figure 4.1.4. Schematic solar interface with the solid particle receiver with intermediate
heat exchanger providing heated He gas to drive the decomposition reactor. ........ 45
Figure 4.1.5. Bunsen reaction flowsheet (section 1). ................................................................47
Figure 4.1.6. Acid decomposition flowsheet (section 2). ..........................................................48
Figure 4.1.7. HI decomposition flow sheet (section 3). ............................................................49
Figure 4.2.1. The Hybrid Sulfur cycle. .....................................................................................51
Figure 4.2.2. Schematic of PEM membrane in the Hy-Sulfur electrolysis step. ........................51
Figure 4.2.3. Hybrid Sulfur flowsheet. .....................................................................................53
Figure 4.2.4. H2A hydrogen cost estimates for Hybrid Sulfur. .................................................55
Figure 4.3.1. Photolytic Sulfur Ammonia schematic process....................................................56
Figure 4.3.2. Process chemistry for Photolytic Sulfur Ammonia. .............................................56
Figure 4.3.3. AspenPlusTM flow sheet for Sulfur Ammonia cycle...........................................58
Figure 4.4.1. Zinc Oxide cycle chemistry. ...............................................................................60
Figure 4.4.2. Zinc Oxide cycle flowsheet (CU Final Report)....................................................62
Figure 4.4.3. Plant cost allocation for the 2015 case study. ......................................................63
Figure 4.4.4. Plant cost allocation for the 2025 case study. ......................................................64
Figure 4.5.1. Chemical steps of the Cadmium Oxide cycle. .....................................................64
Figure 4.5.2. Process flow for a diurnal solar cadmium oxide hydrogen cycle. .........................65
Figure 4.5.3. Conceptual rotating kiln counter flow hydrolysis reactor with tungsten
carbide balls to enhance steam/Cd interaction. ......................................................66
Figure 4.5.4. Beam down collector integrated with fluidized bed decomposition
receiver/reactor.....................................................................................................67
Figure 4.5.5. CdO cycle flowsheet, AIChE Meeting, Salt Lake City, November 7, 2007. ........ 68
Figure 4.6.1. Schematic steps for the Sodium Manganese cycle. ..............................................71
Figure 4.6.2. Mixed metal oxide steps for the Sodium Manganese cycle. .................................72
Figure 4.6.3. Schematic flowsheet for analysis of the Mx-Sodium Manganese cycle. .............. 74
Figure 4.6.4. System layout with a single chemical plant for the Mx-Sodium Manganese
cycle. ....................................................................................................................75
Figure 4.6.5. Estimated capital cost distribution for the mixed metal oxide realization of
the Sodium Manganese cycle. ...............................................................................76
Figure 4.7.1. Reaction path for the preliminary Sodium Manganate cycle. ...............................77
Figure 4.8.1.
Figure 4.8.2.
Figure 4.9.1.
Figure 4.9.2.
Schematic chemistry of a water-splitting ferrite cycle. ........................................78

Atomic Layer Deposition of uniform thin layer of cobalt ferrite. .........................79
Hybrid Copper Chloride chemistry. ....................................................................80
Hy-CuCl conceptual block flow chart. ................................................................82
Tables
Table 1.1. DOE Performance Targets. .....................................................................................15
Table 2.1. Relative importance of criteria to plant development and operation. ........................22
Table 2.2. Solar-device criteria weighting factors. ...................................................................23
Table 2.3. Criteria scoring scheme. ..........................................................................................24
Table 2.4. Listing of non-zero efficiencies for top-scoring cycles.............................................26
Table 2.5. Cycles that could move to Phase 3 detailed theoretical and experimental study. ...... 27
Table 3.1. Cycles considered in the formal evaluation process. ................................................29
Table 3.2. Cycle feasibility assessments...................................................................................34
Table 3.3. Conceptual system design issues. ............................................................................35
Table 3.4. DOE performance targets issues. .............................................................................36
Table 3.5. Summary of evaluation outcomes. ...........................................................................40
Table 4.1.1. Sulfur-Iodine cycle advantages and challenges. ....................................................46
Table 4.2.1. Hybrid Sulfur advantages and challenges. ............................................................52
Table 4.3.1. Advantages and challenges for Photolytic Sulfur Ammonia. .................................57
Table 4.4.1. Advantages and challenges for Zinc Oxide. ..........................................................61
Table 4.5.1. Advantages and challenges for the Cadmium Oxide cycle. ...................................68
Table 4.5.2. Component capital costs cited for CdO cycle at the time of the evaluation. ........... 69
Table 4.5.3. CdO operating costs cited at the time of the evaluation. ........................................70
Table 4.5.4. Assumptions for 2015 case study cost analysis. ....................................................70
Table 4.5.5. CdO cost estimates with some sensitivity estimates. .............................................71
Table 4.6.1. Advantages and challenges for Mx-Sodium Manganese. ......................................73
Table 4.6.2. Component uncertainties for the Mx-Sodium Manganese cycle. ...........................75
Table 4.9.1. Advantages and challenges for Hy-CuCL. ............................................................81
Table 4.9.2. Hy-CuCl system performance sensitivity to electrolyzer performance. .................81
Table 4.9.3. H2A analysis results for Hy-CuCL. ......................................................................83
Table 5.1. Summary of evaluation outcomes. ...........................................................................85
This page intentionally left blank.
Executive Summary
Eight cycles in a coordinated set of projects for Solar Thermochemical Cycles for Hydrogen
production (STCH) were self-evaluated for the DOE-EERE Fuel Cell Technologies Program at a
Working Group Meeting on October 8 and 9, 2008. This document reports the initial selection
process for development investment in STCH projects, the evaluation process meant to reduce
the number of projects as a means to focus resources on development of a few most-likely-tosucceed efforts, the obstacles encountered in project inventory reduction and the outcomes of the
evaluation process. Summary technical status of the projects under evaluation is reported and
recommendations identified to improve future project planning and selection activities.
The initial selection process reduced more than 350 possible cycles to 14 cycles in 5 reaction
classes. Of these 14 cycles, 2 were under separate funding and management authority, 3 were
quickly abandoned after preliminary laboratory study showed them to be unworkable and
another 3 were never engaged actively because of obvious disadvantages. The remaining 8
cycles were actively pursued (2 under the Office of Nuclear Energy) and an Office of Energy
Efficiency and Renewable Energy solicitation added another cycle later. One of the original
cycles transformed to a different process that used the same materials. A second original cycle
was replaced by a similar but simpler cycle. Each of these is counted as a single R&D enterprise
so that a total of 9 thermochemical cycles participated in the evaluation.
None of the cycles under evaluation could demonstrate substantively that they would meet
published performance targets. Performance targets were under revision at the time of the
evaluation and a compelling case to terminate efforts for lack of performance was not made.
Cycle development maturity was widely disparate, with periods of study ranging from less than a
year to more than 30 years. Consequently, an equitable framework for comparative assessment
of achievement was impossible and comparisons would necessarily be based on a mix of
achievement and projected performance. Finally, nearly all cycles under development reported
single-point failure challenges whose successful prosecution would be necessary for the cycle to
promise competitive performance.
Decision-making for focused resource investment turned away from cycle termination to focused
investment in resolution of those critical path obstacles to competitive potential. Critical path
challenges for each cycle were identified and R&D teams were directed to pursue these with top
priority to assist in resource investment decisions in the near future.
10
1 Introduction
A Working Group Meeting of the participants in Solar Thermochemical Hydrogen Production
(STCH) research and development (R&D) was held at the University of Colorado in Boulder,
CO on October 8 and 9, 2008. Working Group participants represented institutions funded
(either directly or via subcontracts) by the DOE-EERE Fuel Cell Technologies Program.
Participating institutions were
1. Department of Energy
2. Nevada Technical Services, LLC
3. Sandia National Laboratories
4. Argonne National Laboratory
5. Savannah River National Laboratory
6. National Renewable Energy Laboratory
7. Science Applications International Corporation
8. General Atomics Corporation
9. The University of Colorado
10. The University of Nevada, Las Vegas
11. Florida Solar Energy Center
STCH participants provided status reports on accomplishments and obstacles along with
projected performance metrics for the purpose determining if any project elements should be
terminated so that available resources could be more effectively applied to continuing R&D
efforts. The Working Group Meeting also identified and addressed key R&D items whose
resolution was deemed critical to overcoming obstacles to realization of the DOE program goals.
This report addresses the evolution of STCH, technical status and projected performance at the
time of the Working Group Meeting and actions recommended on the basis of information
provided at the Working Group Meeting.
1.1 STCH Basis

The Department of Energy (DOE) Office of Energy Efficiency and Renewable Energy (EERE)
Fuel Cell Technologies Program (FCT) Solar Thermochemical Hydrogen Production R&D
portfolio focuses on solar-powered thermochemical water splitting to produce hydrogen using
water and solar thermal energy as the only feedstock. Thermochemical hydrogen production has
been under study at one level or another for many years. Most recently, renewable sources of
thermal energy, like solar and nuclear reactor sources, have been emphasized. Nuclear power
represents a high energy density source that is restricted in operating temperature range because
of the materials of construction needed to contain nuclear material. Solar power represents a low
energy density source that can attain far higher temperatures through solar concentration, but is
still restricted in operating temperature because of materials of construction needed to contain
11
the thermochemical reaction. Nevertheless, feasible operating temperatures for a solar cycle are
much higher than those for a nuclear cycle. As a consequence, the inventory of possible solarpowered thermochemical reactions to produce hydrogen from water is quite large.
A simple two-step thermochemical water-splitting reaction to produce hydrogen generally
requires very high temperature heat for endothermic metal oxide reduction to release oxygen,
and a lower temperature exothermic reaction of water with the metal, increasing the oxidation
state of the metal and releasing hydrogen. In most two-step cycles of this sort, the reduction
temperature exceeds the vaporization temperature of the metal and this class is called the
Volatile Metal Oxide class. Several two-step metal oxide cycles have been investigated in which
mixed oxides, usually ferrite compounds, undergo reduction and oxidation without volatilization
and these and other non-volatile multi-step reactions were assigned to a Non-Volatile Metal
Oxide class. All of the reactions in these two classes rely on very high temperatures (>1400 oC).
Thermal reduction of some more complex chemicals can be achieved at lower temperatures
because the oxygen bonds are weaker than for simple metal oxides. An intermediate reaction is
necessary to release hydrogen and another reaction (sometimes more than one) is required to
restore the oxidation state of the initial compound. Most lower temperature cycles either employ
intermediates for oxidation, complicating the cycle chemistry, or use electrolysis to release
hydrogen and restore the original oxidation state of the cycle. A sulfuric acid cycle is one of very
few low temperature pure thermochemical cycles that operate at a moderate temperature
(~850oC), but it is a multi-step cycle with an intermediate compound required to close the cycle.
Another sulfuric acid cycle is simplified to a two-step cycle by using an electrolytic step to close
the cycle. Electrolytic cycles are assigned to a Hybrid Reaction class.
Examples of these reaction classes from the inventory of thermochemical cycles that were
actively studied under STCH are shown in Fig. 1.1. The Sulfuric Acid class was studied
primarily under the auspices of the DOE Office of Nuclear Energy (NE), but these are included
here since STCH supported integration of this class with a solar power interface in lieu of a
nuclear power interface.
12
Volatile Metal Oxide:

CdO(s)
Cd(g) + O2(g)
Cd(l,s) + H2O CdO(s) + H2(g)
Non-Volatile Metal Oxide:
Ferrite:
NiMnFe4O6(s)+ O2(g)
NiMnFe4O8(s)
NiMnFe4O6(s) + H2O(g) NiMnFe4O8(s)+ H2(g)
Multi-step cycle:
2a-NaMnO2(s)+ H2O(l) Mn2O3(s)+ 2NaOH(a)
4MnO(s)+ O2(g)
2Mn2O3(s)
2MnO(s) + 2NaOH
2a-NaMnO2(s)+ H2(g)
(1450C)
(25-450C)
(~1800oC)
(~800oC)
(~100oC)
(~1560oC)
(~630oC)
Sulfuric Acid:
2H2SO4(g)
2SO2(g) + 2H2O(g) + O2(g)
I2 + SO2(a) + 2H2O 2HI(a) + H2SO4(a)
2HI
I2(g) + H2(g)
(~850oC)
(~100oC)
(~300oC)
Hybrid Copper Chloride:

2CuCl2 + H2O Cu2OCl2 + 2HCl
2Cu2OCl2
O2 + 4CuCl
e2CuCl + 2HCl 2CuCl2 + H2
(~400oC)
(~500oC)
(~100oC)
Figure 1.1. Thermochemical cycle class examples.
1.2 STCH Historical Summary

The Solar Thermochemical Hydrogen Production Research Project (STCH) originated under
Congressional direction to produce hydrogen in a closed chemical cycle using only solar thermal
energy and water as feedstocks. STCH was initiated in 2003 through funding provided by the
DOE-EERE and integrated work performed by the University of Nevada, Las Vegas (UNLV),
the University of Colorado (CU), the General Atomics Corporation (GA), the National
Renewable Energy Laboratory (NREL), Sandia National Laboratories (SNL) and the Argonne
National Laboratory (ANL) under administration and management by the UNLV Research
Foundation. Later, STCH became Solar Hydrogen Generation Research (SHGR) when
photoelectrochemical hydrogen production (PEC) was added to the project by request of the
DOE. This report deals only with thermochemical processes and the acronym STCH will be used
to reflect that part of SHGR managed for DOE-EERE by the UNLV Research Foundation and
subsequently by the DOE-EERE FCT Program.
The UNLV Research Foundation announced its intention to terminate its technical management
responsibilities during the period 2007-2008 and the DOE decided to continue the effort initiated
in 2003. Several new projects under grants managed by DOEs Golden Field Office (GO) were
added to the inventory of active thermochemical cycle R&D with management transition to
13
DOE-EERE FCT Program. Some work continued to be managed by the UNLV Research
Foundation through 2009 under no-cost extension decisions by DOE-EERE. Therefore, some of
the work was managed under awards administered by the DOE GO, some was managed by the
UNLV Research Foundation and some was managed by SNL through subcontracts funded under
Sandias Annual Operating Plan (AOP) approved by DOE Headquarters (DOE/HQ) in
Washington DC. Coordinating this distributed effort was implemented via a consulting contract
with Robert Perret issued by the GO with concurrence by DOE/HQ and with the cooperation of
the UNLV Research Foundation. Following transition to DOE management, the STCH portfolio
expanded to include SAIC in San Diego, CA and TIAX, LLC in Cambridge, MA. All other
participants identified earlier continued under STCH until research priorities were formalized
through a DOE selection process in 2008. The EERE FCT Program currently manages all DOE
funded STCH R&D.
1.3 STCH Decision Framework

The STCH project was founded as an applied research and development effort to identify the
most promising cycle or cycles and develop a pilot plant design (or designs) for construction,
operation and evaluation. The effort was organized into three investigative phases. It was known
from the outset that there are many closed thermochemical cycles capable of splitting water and
releasing hydrogen, so the Phase 1 objective was to document the known candidate cycles
(>350) and then select a smaller number (~50) of promising candidates for somewhat more
detailed investigation (2003-2004). Phase 2 applied HSC Chemistry modeling to establish
reaction temperatures necessary for completion of each cycle step and simplified flow charts for
the chemical process were developed to estimate the cycle thermodynamic efficiency (2004). A
base line efficiency was chosen and cycles with efficiencies exceeding the baseline were selected
to move into Phase 3 (2004-present). Quantitative performance data from this smaller set would
then be used to provide high-confidence comparative evaluation from which to select the cycle
or cycles for which pilot plant designs would be developed.
The ultimate objective of STCH was to provide a basis for commercial development and largescale hydrogen production in support of fuel cell technology for early market and transportation
applications. Accordingly, the prime metrics for transition to pilot plant design are those
embraced by industry.
The DOE, with industrial participation, applied considerable effort to develop guidelines that
would assist in determining the commercial viability of thermochemical hydrogen production.
These guidelines have changed over time and are even undergoing revision at the time of this
writing. However, the production targets for central plant designs have proven useful in
supporting comparative assessments for the cycles under study. The two principal metrics are
cost of hydrogen per gallon-of-gas-equivalent (gge) at the plant gate and process efficiency,
variously interpreted, but meaningfully defined as conversion efficiency of solar energy to
hydrogen energy. STCH efficiency is the efficiency of conversion of solar-derived thermal
energy to lower heating value (LHV) hydrogen energy. This efficiency definition is different
from Solar-to-Hydrogen efficiency used by some other solar-powered hydrogen production
programs. The original target schedules for high-temperature thermochemical production were
14
changing during the period of evaluation and the progression (circa 2003 to 2008) is shown
below (Table 1.1):
Table 1.1. DOE Performance Targets.
2012 2017
2017 2020
Cost target ($/gge)
Process efficiency (%)
30
>35
Target schedule transition
Phase 1 and Phase 2 selection processes are discussed in Section 2. The process for selection of
candidates from Phase 3 cycles is discussed in Section 3. Technical status of the evaluated cycles
along with path-forward recommendations or conditions that might lead to resumption of effort
are summarized in Section 4. Summary discussion of the evaluation process, key challenges and
recommendations are provided in Section 5. Appendix A describes changes in the STCH
inventory of cycles that occurred after the evaluation. Appendix B lists criteria scores selected
for the Phase 1 cycle selection process.
15
16
2 Cycle Inventory Development and Initial Selection

Many hydrogen producing thermochemical cycles have been proposed over the last 40 years. A
literature search was performed to identify all published cycles1-58. These were added to an
existing database that had been compiled earlier to identify cycles suitable for nuclear hydrogen
production56. Other cycles were provided by other researchers, particularly by Claude Royr
(private communication). Assessments of electrochemical processes for the two primary hybrid
cycles (Hybrid Sulfur and Hybrid Copper Chloride) were published at the same time as the initial
analyses of the developing inventory of hydrogen-producing thermochemical cycles.59,60 A
summary review assessed the proximity of deployment for some cycles.61 A smaller scale survey
was carried out by scientists at Centre Etude Atomique (CEA)62. All of these cycles had already
been included in the developed inventory. More than 350 distinct cycles were identified and new
ones were added as appropriate. Each cycle was assigned a process identification number (PID)
and a process name for use in a database developed by the STCH project. Cycle elements and
cycle chemicals were listed under cycle information to assist in database queries.
Initial screening was designed to restrict the number of cycles that qualified for detailed
evaluation. The Phase 1 (screening) objective was not to identify the best cycle but to eliminate
from consideration those processes that likely would not be worth the effort of a detailed
evaluation.
The approach established screening criteria to discriminate against unlikely processes. Sixteen
measurable criteria were devised for use in measuring the practicability of a cycle. The
methodology defined a numeric metric for each criterion in the range of 0 to 10 for each cycle.
Every attempt was made to make the criteria objective, which was possible in most cases. For
example, toxicity rankings were taken from EPA and NIOSH publications. When a chemical is
not listed in these compilations, an experienced chemist assigned a ranking for the chemical.
This ranking was then used for the chemical for any cycle in which it is present. Whenever there
was not a published ranking for a criterion, one was established based on the experience and
expertise of the contributing members. Corrosiveness ranking was derived from the rate of
chemical attack on common engineering materials used in chemical plant construction.
Criteria could be weighted to emphasize competitive features like capital and O&M cost,
development risk, environmental risk and sensitivity to unavoidable intermittency in solar
energy. Additional criteria weighting was used to account for cycle compatibility with different
solar energy collectors: trough, tower and dish technologies. This along with a weighted average
of the scores of the individual criterion would generate a composite score for the cycle.
The criteria used to screen the practicability of a thermochemical cycle can be broken down into
four different general categories: i) economic considerations, ii) applicability to solar power
system, iii) level of previous effort and iv) environmental and safety issues. The criteria are as
follows:
17
2.1 Economic Consideration

Criterion 1. Number of chemical reactions
As number of reactions increases, complexity, required separations and number of reactors
increases.
Criterion 2. Number of separation steps
solid-solid separations
solid-liquid separations
liquid-liquid separations
gas-gas separations
aqueous/non-aqueous
Gas-liquid and gas-solid separations were considered easy and were not included in the tally
for the total separation step within each cycle.
Criterion 3. Number of chemical elements
The number of chemicals in a cycle indirectly reflects the complexity of the process as a greater
number of species are involved and normally results in a more complex process.
Criterion 4. Abundance of chemical elements
Favorable cycles are those that employ common chemicals and elements since these would
usually be less expensive and readily available in large quantities.
Criterion 5. Corrosiveness of chemicals
Chemicals were classified from least to most corrosive, based on their corrosiveness on common
metallic materials of construction.
Criterion 6. Solids transport
Solids transport usually requires specifically designed machinery. Slurry suspensions are more
readily moved with available hardware and is scored as liquid transport.
18
2.2 Solar Collector/Receiver Consideration

Criterion 7. Use of radiant heat transfer to solids
The rate of radiant heat transfer to and from solids is higher than for liquids and solids for the
same driving potential, so cycles with very high temperature solids are favored. This criterion
uses variable scale for temperature ranges from below 900C to above 1800C.
Criterion 8. Temperature of high temperature endothermic step
The highest temperature of a cycle was compared to the optimal temperature range for a solar
thermal system82. If the highest cycle temperature was near the optimal temperature then a high
point score was assigned to the cycle when paired with this device. The further away the
temperature was from the optimal temperature, the lower the point score. Our screening analysis
considered the applicability of four solar collectors:
a. Trough optimal temperature 375oC
b. Standard tower optimal temperature 525oC
c. Advanced tower optimal temperature 875oC
d. Dish optimal temperature 1125oC
Cycles that were not well matched to a solar device received 0 points on this particular criterion
and were excluded from further assessment even though they had high scores from the other
criteria.
Criterion 9. Compatible with thermal transients and/or diurnal storage
Determined on a case-by-case basis and depends strongly on required storage of intermediates or
thermal energy.
2.3 Previous Level of Effort for Candidate Cycle

Criterion 10. Number of literature papers
A higher number of papers published on a cycle indicates higher maturity of understanding than
for cycles that have not been studied, suggesting that problems associated with it might have
already been addressed.
Criterion 11. Scale of testing
Favorable cycles that have attracted support for larger scale testing like integrated lab scale,
demonstration testing and pilot plant testing are likely to have improved chance of commercial
success.
19
Criterion 12. Energy efficiency and cost

Evidence of cost and efficiency studies is indicative of greater levels of effort and maturity of
development.
2.4 Safety and Environmental Consideration

Criterion 13. Acute toxicity to humans
This criterion considered the most dangerous chemical in a cycle, as determined for acute
human exposure. Points were assigned to the IDLH (Immediate Danger to Life and Health)
values found in the NIOSH (National Institute of Occupational Safety and Health) Pocket Guide
to Chemical Hazards.
Criterion 14. Long-term toxicity to humans
This criterion considered the most dangerous chemical in a cycle, as determined by chronic
long term human exposure. Points were assigned based on the REL (Recommended Exposure
Limits) values taken from the NIOSH Pocket Guide to Chemical Hazards.
Criterion 15. Environmental toxicity
This criterion examined the most dangerous chemical in a cycle, as determined for
environmental exposure, from EPA categories of reportable quantities discharged to the
environment. These values were found in 40 CFR1, table 302.4 and Appendix A of part 355, and
points were assigned accordingly.
Criterion 16. Reactivity with air or water
A chemical may be inert in an enclosed setting but may become very hazardous with an
accidental exposure to air or water. This criterion took the sum of the NFPA (National Fire
Protection Association) hazard ratings for flammability and reactivity with air & water, for each
chemical in a cycle, and assigned points based on the highest sum.
The scoring scheme of each criterion, other than those derived from published ranking, was
established after careful deliberation among the group members based on their technical
expertise and practical experience. Therefore, some criteria scores are based on expert opinion.
An archived list of criteria scores associated with the various solar technologies and used for
cycle scoring was maintained in the database developed by STCH. Those criteria scores are
listed in Appendix B.
The development and operations weighting factor was derived in two steps using a six-sigma
methodology. First, 5 operational factors were identified which were essential in the
development and operation of a solar thermal hydrogen production plant and they are i) capital
cost, ii) operation and management, iii) development risk, iv) diurnal cycle and v) environmental
risk. A multiplication factor (mp) between 1-5 was assigned to each of them based on their
20
perceived importance to the development and implementation of a central production plant.

Next, the relative importance of each of the 16 criteria with respect to the 5 operational factors
was determined. A relevance value of 0, 1, 3 or 9 was assigned to each criterion according to its
significance to the factor. The relevance value range and distribution were chosen to amplify
numeric differences among selection criteria. The raw weighting factor for each criterion
provides a measure of the criterions importance to a plant scale solar hydrogen production
system. Table 2.1 lists the multiplication factor for capital cost, operations and management,
development risk, variable and diurnal insolation and environmental risk along with the
relevance of each criterion for these factors. The raw weighting factor, indicative of the
importance of each criterion to plant development and operation is obtained by the sum of the
products of the relevance factor and the multiplication factor.
21
Table 2.1. Relative importance of criteria to plant development and operation.
Maximum temperature, use of hazardous materials, use of corrosive chemicals, the number of
reactions and the number of separations were found to be the most important criteria.
22
Table 2.2. Solar-device criteria weighting factors.
23
A set of weighting factors specific to each criterion and for each solar device were assigned on
the basis of concurrence and expert opinion. Based on the raw weighting factors and the
expertise of the team members, weighting factors between 1- 10 were generated and assigned to
each criterion for each solar device. Table 2.2 lists the solar-specific criteria weights.
The score multiplier was chosen to cast all scores in the range 0-100. It is obtained by assuming
a maximum score of 10 for each criterion and summing the product of the solar device weighting
factor and the maximum criterion score of 10. The score multiplier is 100 over the sum of
products. Cycles with scores less than the cutoff score were not included in the inventory of
possible cycles for that solar collector technology.
Table 2.3. Criteria scoring scheme.
Table 2.3 describes the criteria score assignment scheme. Criterion 8 scores reflect proximity of
the maximum cycle temperature to the sweet spot temperature of the selected solar device.
Cycle scores were obtained for each solar device by the sum of products of the device weighting
factor and the consensus criteria score, multiplied by the score multiplier. Based on this method,
360 cycles were evaluated and 67 thermochemical cycles with the highest scores were selected
for study under Phase 2.
24
One question that must be addressed was how well this type of process eliminates from the study
those cycles with a low probability of success. Stepwise regression and rank correlation methods
were applied to answer this question by staff at the Sandia National Laboratories. The results of
this study showed that (1) the selected cycles were not highly dependent on criteria weights so
that the results are expected to be unchanged under different subjective weighting schemes, (2)
the screening process was robust and (3) was generally accurate in determining the most
promising cycles for further analysis.
The 67 cycles with highest scores moved to Phase 2 in which the thermal efficiency of each
cycle was estimated. Phase 2 work included application of HSC Chemistry Database to
determine thermodynamic state variables consistent with phase equilibrium for each reaction
step in a cycle. A simplified flow chart was then developed for each cycle that included mass and
energy balance and non-optimal heat recuperation. Aspen PlusTM software was used where
necessary. The cycle thermal efficiency () was calculated early in the project using High
Heating Value for hydrogen. Subsequently, Low Heating Value was used throughout to be
consistent with DOE requirements.
= -H25C(H2O())/[Qsolar + (Ws + GT + RT ln(apnp/arnr) + nFEov)/e]
(Eqn.2.1)
where
H25C(H2O(l)) is the standard enthalpy of formation of liquid water,
Qsolar is the net solar heat determined from the mass and energy balance,
Ws is the amount of shaft work required, primarily compression work,
GT is the standard free energy of any electrochemical step,
R is the universal gas constant
T is the temperature of the electrochemical step,
ap are the activities of the products of the electrochemical step,
np are the stoichiometric coefficients of the electrochemical reactants,
n is the number of charges transferred in the electrochemical step,
F is Faradays constant,
Eov is the over-voltage of the electrochemical step, taken as 0.2 volts if no membrane is
required and 0.4 volts if a membrane is needed,
e is the efficiency of electrical generation, optimistically taken as 0.5.
25
The 67 top-scoring cycles were evaluated in this manner. Table 2.4 lists cycles and their
estimated efficiencies that resulted from the Phase 2 evaluation. Table 2.4 does not include
cycles whose efficiencies were estimated to be zero.
A cut-off efficiency of about 35% was chosen to keep the number of cycles moving to Phase 3
within a manageable number. Table 2.6 lists the cycles that met the 35% cut-off efficiency63. Of
the cycles in Table 2.5, Multivalent Sulfur was not investigated because of the number of
difficult gas separations. Hybrid Cadmium was not investigated because it required an
electrolysis step in addition to managing a volatile hazardous material. Iron Oxide was not
investigated because either batch processing or solids flow management would be required.
Metal Sulfate Cycles were investigated but hydrogen release could not be demonstrated and
these cycles were abandoned64. Cadmium Carbonate showed extremely poor kinetics in the
hydrolysis reaction and was abandoned in favor of a Cadmium Oxide cycle. DOE - NE
undertook Phase 3-like study of Sulfur Iodine and Hybrid Sulfur so that the original STCH
Project invested detailed theoretical and experimental effort in 6 cycles.
Table 2.4. Listing of non-zero efficiencies for top-scoring cycles.
PID
Cycle Name
Eff. (LHV)
PID
Cycle Name
Eff. (LHV)
110
Sodium-Mn-3
50.0
184
Hybrid Antimony-Br
30.6
106
High T Electrolysis
49.1
134
Cobalt Sulfate
29.9
147
Cadmium Sulfate
46.5
56
Cu Chloride
29.2
Hybrid Cd
45.1
114
Hybrid N-I
28.2
Zinc Oxide
45.0
62
Iron Bromide
27.7
Cadmium Carbonate
44.3
23
Mn-Chloride-1
26.6
Ni-Mn Ferrite
44.0
51
K-Peroxide
23.5
194
Zn-Mn Ferrite
44.0
61
Sodium-Iron
22.8
67
Hybrid Sulfur
43.1
185
Hybrid Cobalt Br-2
21.7
Iron Oxide
42.3
53
Hybrid Chlorine
21.6
191
Hybrid Copper
Chloride
41.6
160
Arsenic-Iodine
21.2
149
Ba-Mo-Sulfate
39.5
152
Iron-Zinc
19.9
Sulfur-Iodine
38.1
103
Cerium Chloride
18.0
193
Multivalent Sulfur-3
35.5
26
Cu-Mg Chloride
17.4
131
Mn Sulfate
35.4
199
Iron Chloride-11
16.9
72
Ca-Fe-Br-2
33.8
200
Iron Chloride-12
16.9
70
Hybrid S-Br
33.4
104
Mg-Ce-Chloride
15.1
24
Hybrid Li-NO3
32.8
132
Ferrous Sulfate-3
14.4
201
Carbon Oxides
31.4
68
As-Ammonium-I
6.7
22
Fe-Chloride-4
31.0
129
Mg Sulfate
5.1
182
26
Table 2.5. Cycles that could move to Phase 3 detailed theoretical and experimental study.
Cycle
PID
Efficiency %
Estimated Max T
Hybrid Sulfur
67
43
900
Sulfur Iodine
45
900
193
42
1570
Cadmium Sulfate
147
55
1200
Barium Sulfate
149
47
1200
Manganese Sulfate
131
42
1200
53
2200
52: 59
1600: 1450
53
1600
50
2200
110
59
1560
52
1800
194
52
1800
191
49
550
Sulfuric Acid Cycles
Multivalent Sulfur
Metal Sulfate Cycles
Volatile Metal Oxides

Zinc Oxide
Cadmium Carbonate: Cadmium Oxide
182: 213
Hybrid Cadmium
Non-volatile Metal Oxides
Iron Oxide
Mised Metal Sodium Manganese; Sodium
Mangante
Nickel Manganese Ferrite
Zinc Manganese Ferrite
Hybrid Cycles
Hybrid Copper Chloride
27
3 Formal Cycle Evaluation and Research

Prioritization
Scheduling and planning efforts were continuous throughout the original STCH project. The
earliest schedule called for pilot plan design(s) to be completed in FY 2008. As funding levels
failed to meet their targets, and as more understanding accompanied detailed study of the six
Phase 3 STCH cycles, it became apparent that the original schedule would not be met. In a series
of meetings with DOE representatives, both DOE and the initial STCH participants agreed upon
a new schedule. This new schedule called for selection of the best cycle or cycles in FY 2009, to
be accompanied by increased focus of resources on cycle particulars and implementation of onsun demonstration in FY 2012. Data from focused research and development of a few cycles and
from on-sun demonstration would be adequate to complete a pilot plant design.
It was during this period that the UNLV Research Foundation decided to terminate its
management and administration responsibilities and the STCH research and development effort
transitioned to DOE for all its management and administration. A decision to retain the schedule
for selection of a few cycles for focused attention accompanied this transition. At the same time,
there was another and serious interruption in planned funding. FY 2008 was funded essentially
with carryover from allocations made in FY 2007 and the FY 2009 allocation was less than onehalf the FY 2007 allocation. Consequently, work essential to a balanced comparative analysis of
the STCH cycles was not completed.
Additional changes in the STCH cycle inventory accompanied the transition to DOE
management and administration. The original Sodium Manganese cycle encountered
unacceptable levels of water to recover aqueous NaOH and close the cycle. Moreover, 80% or
less of NaOH was recovered experimentally in the hydrolysis step and the consequence of
carryover was not known. However, DOE-EERE provided funds to explore direct thermal
dissociation of NaMnO2, a process that is consistent with the Non-volatile Metal Oxide Cycles
although vaporized oxides of Na metal might be present. This cycle has been called the Sodium
Manganate cycle. Another cycle, the Photolytic Sulfur Ammonia cycle, was selected through a
competitive DOE-EERE solicitation in 2007. This cycle is similar to the Hybrid Cycles and
became a part of the STCH inventory without participating in the initial cycle selection process.
Finally, through the SNL-directed STCH effort, a ferrite process was introduced in which the
ferrite material is synthesized using atomic layer deposition (ALD). This cycle became the ALD
Ferrite cycle and is consistent with the Non-volatile Metal Oxide Cycles. Table 3.1 lists the
cycles being considered in the DOE-directed evaluation process that was implemented in a
STCH Working Group Meeting on October 8-9, 2008.
28
Table 3.1. Cycles considered in the formal evaluation process.

Class
Sulfuric Acid Cycles
Volatile Metal Oxide Cycles
Non-volatile Metal Oxide

Cycles
Hybrid Cycles
Cycle
Lead Organization
Sulfur Iodine
General Atomics, Sandia

National Labs, CEA
Hybrid Sulfur
Savannah River National

Laboratory
Zinc Oxide
University of Colorado
Cadmium Oxide
General Atomics
Sodium Manganese and Sodium

Manganate
Reactive Ferrite
Sandia National
Laboratories
ALD Ferrite
Argonne National Laboratory
Photolytic Sulfur Ammonia
SAIC
Nickel Manganese Ferrite did not participate fully in the evaluation and prioritization process
because work on this cycle was funded by Laboratory Directed Research and Development at
Sandia National Laboratories. Whereas a watching brief was maintained through cooperation
of SNL, decisions regarding continuation and priority were reserved to SNL. As mentioned
earlier, the DOE-NE managed and administered thermochemical work on Sulfur Iodine and
Hybrid Sulfur. However, DOE-EERE, through Savannah River National Laboratory (SRNL) and
SNL provided support to integrate these cycles with a solar energy source and both cycles
participated fully in the evaluation process.
Virtually all of the cycles listed in Table 3.1 were at different stages of R&D maturity at the time
of the evaluation.
Sulfur Iodine had progressed to implementation of an Integrated Lab Scale (ILS) test
that was meant to demonstrate all steps with cycle closure using a lab thermal source
instead of nuclear or solar. The ILS was never operated successfully. No reviewed
H2A analysis of product cost had been completed at the time of the evaluation.
Hybrid Sulfur had progressed to demonstration of an electrolytic step that nonetheless

suffered from sulfur crossover and contamination and degradation of the membrane.
29
No integrated process demonstration had been performed. H2A cost analysis was in
review but not completed at the time of the evaluation.
Photolytic Sulfur Ammonia had reached the point of preliminary demonstration of all
steps, but non-precious catalyst material had not been discovered for the photolysis
step and thermal efficiency had not been established principally because conceptual
system design issues remained unresolved. The same deficiency prevented
completion of reviewed H2A analysis.
Zinc Oxide had progressed in step-wise fashion (no closed or integrated cycle
demonstration) to a point where a termination recommendation was made by the
development team.
Cadmium Oxide had progressed to demonstration of hydrolysis and CdO

decomposition. The quench reaction was conceptually designed to minimize
recombination but not demonstrated. No reviewed H2A had been completed at the
time of the evaluation.
Sodium Manganese had progressed in step-wise fashion to a point where a

termination recommendation could be made on grounds of efficiency losses due to
aqueous NaOH distillation. Work on a simplified sodium manganese cycle, although
promising, was in its early stages. H2A analysis was performed but was not reviewed
at the time of the evaluation.
Nickel Manganese Ferrite did not participate fully in the process, but active material
degradation was identified as an obstacle.
Preliminary experimental work on the ALD Ferrite material suggested durability

under thermochemical cycling, but kinetics and optimal operating temperatures were
yet to be determined. Ferrite costs were estimated but not confirmed and active
material durability was unknown for extended thermochemical cycling. H2A results
were not reviewed.
Hybrid Copper Chloride had not yet demonstrated an electrolysis cell design that did
not degrade due to copper crossover. All other steps had been demonstrated but not
optimized. H2A analysis continued to undergo revision and review.
Nonuniform state of progress among the cycles made the establishment of an objective and
rigorous comparative framework unlikely. Objective metrics, like cost and system efficiency, for
the majority of cycles would be based on assumptions and cycle proponents, violating objectivity
in the process. Whereas these assumptions could be (and were) discussed and criticized in the
evaluation process, the critics would necessarily have been proponents of alternative cycles and
objectivity would once again be violated. Rigor in the comparative assessment would require that
metrics be developed for the same performance characteristics for all cycles. Since the cycles
varied so significantly in their development, it was difficult to establish rigorous performance
metrics that would apply equally to all.
These obstacles to a rigorous and objective comparison suggested a subjective and qualitative
framework designed to assess
30
schedule and likelihood of demonstrating cycle technical feasibility
likelihood that the cycle would (or would potentially) meet DOE cost and efficiency
targets
obstacles and proposed resolutions for the above two issues
An informal ranking process was proposed to develop consensus priority ranking of the
candidate cycles according to
projected performance in terms of DOE targets
likelihood of overcoming R&D obstacles
likelihood of meeting system/engineering requirements
As these criteria are essentially qualitative and judgmental in nature, it was decided to seek
Working Group consensus for each assessment topic for each thermochemical cycle.. Essential
information necessary to undertake the assessment was provided in the form of a white paper for
each cycle that was distributed to the entire project team to assure all had the opportunity to
engage technical and judgmental issues well before the evaluation meeting. Points in the white
papers were to be addressed in more detail in a formal presentation delivered during the
evaluation meeting during which members of other projects could bring up issues and questions.
Specific evaluation elements were described for inclusion in the white papers and the
presentations. Discussion points associated with each of the required elements were identified
and provided to the authors, presenters and participants. The elements and associated discussion
points are listed below:
a. Cycle description in summary form with a block diagram describing the R&D pathway
and milestones to meeting DOE targets.
i. Are technological strengths and weaknesses of the cycle comprehensive?
ii. Does the block diagram include all chemical reactions?
iii. Is there theoretical and/or experimental demonstration of cycle closure?
iv. Are side reactions and reaction yields for each step addressed?
v. Are effects of recycled chemicals from reactions that do not go to completion
addressed?
vi. Is the R&D pathway comprehensive in describing all the development and testing
necessary to assert cycle feasibility?
vii. Is the milestone list comprehensive?
b. Listing of proven and unproven pathway elements
i.
Is the listing of proven and unproven pathway elements comprehensive?
ii. Are the proven pathway elements supported by data or literature citations?
iii. Are potential side reactions identified and demonstrated to be inconsequential?
31
c. Listing of materials and component challenges accompanying a laboratory scale

integrated demonstration
i.
Have all materials and components requirements been addressed?
ii. Are all raw materials readily available?

d. Summary of economic analysis using H2A with identified assumptions and uncertainties
i.
Are the assumptions reasonable?
ii. Are all assumptions identified?

iii. Are the parametric ranges of uncertainties reasonable?
iv. Has the analysis package been reviewed and approved by TIAX, LLC?
v. What are the significant issues requiring resolution in the H2A analysis?
vi. Do projected hydrogen gate costs meet DOE targets ($3/gge by 2017)?
e. Cycle proponent recommendation to terminate or proceed
f. If proceed, detailed research plan with workforce and budget requirements and
schedule to resolve cycle performance and technology barriers necessary for integrated
laboratory scale demonstration
i.
Does the R&D plan address all issues relevant to integrated cycle demonstration?
ii.
Are there critical elements of cycle performance whose resolution is high risk?
iii. Are workforce and budget requirements consistent with the R&D plan?
iv. Is the R&D team in place to complete the plan?
v.
Is the schedule consistent with stated workforce and budget requirements?
vi. Is the schedule consistent with the DOE Program Plan?

vii. Are new facilities or capital equipment required for a integrated demonstration?
viii. Do resources exist at other sites for a laboratory scale integrated demonstration?
g. For transition to on-sun demonstration:
i.
What new facilities are required for integrated on-sun demonstration?
ii. What existing appropriate resources are available at other sites for integrated cycle
on-sun demonstration?
There are too many discussion points to address in this report. Instead of going through the
discussion points individually, several are called out to address the most important issues that
pertain to all cycles:
Technical feasibility issues
theoretical and demonstrated cycle closure
side and incomplete reaction effects on efficiency or feasibility
32
Integrated system concept design issues

effective materials of construction
component availability
DOE performance target issues

cost projections for 2015 and 2025
thermal efficiency estimates for 2015 and 2025
principal uncertainties in projections/estimates
Table 3.2 (feasibility), Table 3.3 (concept design) and Table 3.4 (DOE target) list the principal
respective issues for each STCH cycle identified from the submitted white papers and the
presentations at the evaluation meeting. The evaluation process made it very clear that
comparative assessment of the cycles under study could not be done with any level of certainty,
mostly because of the different states of progress reflected in the submitted materials. This was
not surprising since Photolytic Sulfur Ammonia R&D had been pursued for only about a year,
compared with >5 years for Sulfur Iodine, Hybrid Sulfur, Hybrid Copper Chloride and Zinc
Oxide; reactive ferrite had been under study for more than 5 years while ALD Ferrite had been
active for less than a year. Sodium Manganese and Cadmium Oxide cycles had been under active
investigation for about 3 years. In lieu of performing a comparative assessment accompanied by
decisions to discontinue cycles, it was decided instead to redirect the R&D efforts for all cycles
on those issues whose solutions would be essential to a continuation decision.
The Zinc Oxide and Sodium Manganese proponent concluded on the basis of R&D and analysis
results that these cycles were very unlikely to meet DOE targets even with continued support. It
was recommended that these cycles complete necessary work to document their achievements
and then to terminate further research and development. Issues pertaining to feasibility, concept
design and performance that were common within a cycle are color coded to help with
identification of the critical path items called out for emphasized R&D.
33
Table 3.2. Cycle feasibility assessments.
Closure
Cycle
Theory
Experiment
(stepwise)
Theoretical
Efficiency
metallic sulfur
possible; HI
decomposition
Tech
Feasibility
Experimental
Efficiency
Tech
Feasibility
no sig. effect
non-ideal
reactions; more
data necessary
feasibility
probably not
affected but no
demonstration
depends on
successful
electrolyzer
design
S crossover
solution might
increase bias or
reduce current
density
depends on
successful
electrolyzer
design
Sulfur Iodine
yes
yes
Hybrid Sulfur
yes
yes
Photolytic
Sulfur
Ammonia
yes
yes
possible
catalyst
deactivation
unknown
photolysis
efficiency
unknown
unknown
Zinc Oxide
yes
yes but
incomplete Zn
recovery
none
none
reduction yield
loss by
recombination
depends on
adequate Zn
metal recovery
Cadmium
Oxide
yes
yes but
incomplete Cd
recovery
none
none
reduction yield
loss by
recombination
depends on
molten Cd
quench
effectiveness
Sodium
Manganese
yes
yes but
incomplete Na
recovery
mixed oxide
kinetics/compo
sition unknown
side reactions
might affect
complete Na
recovery
hydrolysis and
reduction
incomplete
carryover
effects not
demonstrated
ALD Ferrite
yes
yes
none
none
back reaction
effects
unknown
Durability under
TCH cycling
Hybrid Copper
Chloride
yes
yes
prevention of
Cu crossover
depends on
successful
electrolyzer
design
spent anolyte
composition;
Crystallizer
performance
unknown
depends on
successful
electrolyzer
design
34
Table 3.3. Conceptual system design issues.

Cycle
Block system
TM
Aspen Plus
Materials
Components
Sulfur Iodine
complete
yes
sulfuric acid
concentrator heat
exchanger
counter current
Bunsen reactor;
reactive distillation
reactor; SPR heat
exchanger
Hybrid Sulfur
complete
yes
sulfuric acid
concentrator
electrolyzer; SPR
heat exchanger
Photolytic Sulfur
Ammonia
solar field and

mirror choice
no
non-precious
photocatalyst
beam-splitting
optics; hot mirrors
Zinc Oxide
complete
yes
high temperature
reactor materials
fluid wall reactor
Cadmium Oxide
solar system
preliminary
yes
hydrogen
separation
membrane
fluidized bed
decomposition
reactor w/ quench;
hight temp H2
transport
membrane
Sodium
Manganese
complete
yes
Na and Mx
volatility could
lead to deposits
on and corrosion
of reactor vessel
material
oxygen transport
membrane; hot
particle heat
exchanger;
pneumatic particle
transport system
ALD Ferrite
complete, but
choice remains
between fluidized
bed, moving bed
or stationary thin
film reactor
no; might not be

necessary
reactor materials
of design; reactant
material cycling
stability
fluidized bed
reactor or moving
bed reactor
Hybrid Copper
Chloride
complete
yes but not

converged
hydrolysis and
oxychloride
decomposition
reactors
electrolyzer;
spent anolyte
separator
35
Table 3.4. DOE performance targets issues.

Cost ($/gge)
Cycle
Efficiency (%)
Uncertainty
2015
2025
2015/2025
Sulfur Iodine
4.78 (2005)
5.77 (2015)
35/35
HI decomposition not
demonstrated; sulfuric acid
concentrator; efficiency
Hybrid Sulfur
4.80
3.19
33/33
Electrolyzer costs; sulfuric acid

concentrator materials of
construction; efficiency
Photolytic
Sulfur
Ammonia
5.73
NA
29/29
Cycle definition at the time of

evaluation too uncertain for
substantive analysis
Zinc Oxide
5.58
4.14
45/45 (from
initial Phase 2
estimate; not
reported in
white paper)
Cadmium
Oxide
3.94 (2005)
4.75 (2015)
40/40
Receiver cost and materials;

quench feasibility and
effectiveness;
Sodium
Manganese
5.22
4.40
38/38
Oxygen transport membrane;

recuperation from quench;
particle heat exchanger
materials; Na recovery
ALD Ferrite
3.45
2.91
(material cost
estimated)
19/19
Ferrite cost and durability;

process and component
uncertainties; recycling rate
Hybrid
Copper
Chloride
4.50
3.45
39/41
Electrolyzer cost and

effectiveness; reactor materials
of construction; spent anolyte
separation process
Assumed 70% decomposition

yield vs. 18% demonstrated;
reactor materials of construction;
oxygen transport membrane
None of the cycles could present reviewed H2A analyses so that uncertainty persists for the cost
estimates presented. Information about H2A Analysis can be found on the Department of Energy
Website (URL: http://www.hydrogen.energy.gov/h2a_analysis.html). Flowsheets for the multi-
36
step processes were still undergoing optimization so that AspenPlusTM analyses of mass and
energy flow balances were not finalized. Consequently some degree of uncertainty persists for
the cost and thermal efficiency figures cited. It is noted that substantial progress in H2A analyses
appears in Cost Analyses on Solar-Driven High Temperature Thermochemical Water-Splitting
Cycles, TIAX, Final Report to Department of Energy, Order DE-DT0000951, February, 2011.
The evaluation process made it very clear that comparative assessment of the cycles under study
could not be done with any level of certainty, mostly because of the different states of progress
reflected in the submitted materials. This was not surprising since Photolytic Sulfur Ammonia
R&D had been pursued for only about a year, compared with >5 years for Sulfur Iodine, Hybrid
Sulfur, Hybrid Copper Chloride and Zinc Oxide; reactive ferrites had been under study for more
than 5 years while ALD Ferrite had been active for less than a year. Sodium Manganese and
Cadmium Oxide cycles had been under active investigation for about 3 years. In lieu of
performing a comparative assessment accompanied by decisions to discontinue cycles, it was
decided instead to redirect the R&D efforts for all cycles to those issues whose resolution would
be essential for a continuation decision. Technical success in these identified topics would not in
and of itself warrant continuation, but absent such success, the cycles would be either technically
infeasible or economically uncompetitive. The Zinc Oxide and Sodium Manganese proponent
concluded on the basis of R&D and analysis results that these cycles were very unlikely to meet
DOE targets even with continued support. It was decided for these cycles that necessary work to
document their achievements would be completed and no further research and development
would be pursued, at least until additional information warranted resumption of effort.
It is evident from Tables 3.2-3.4 that the Nuclear Hydrogen Initiative would manage many of the
unresolved issues for the Sulfur Iodine and Hybrid Sulfur cycles. These were not called out for
prioritization by the formal evaluation. However, the integration of both cycles with a solar
source was not defined with sufficient detail. Since both cycles planned to use the Solid Particle
Receiver (SPR) under development by Sandia National Laboratories, effort under DOE/EERE
support was directed to focus on integration of these cycles with the SPR. Additionally, the
Sulfur Iodine, Hybrid Sulfur and Hybrid Copper Chloride teams were asked to collaborate in an
effort to achieve commonality in their component and capital costing methodologies.
Photolytic Sulfur Ammonia had not yet achieved sufficient maturity to settle on a conceptual
design since a choice between beam-splitting mirrors or dual solar fields had not been made.
Serious uncertainty in the cost and effectiveness of beam splitting optics was generally evident
during the evaluation. The proposed alternative was dual solar fields, with one to provide thermal
energy for ammonium sulfate reduction to produce ammonia and sulfur dioxide and the other to
provide shorter wavelength radiation to drive photolytic oxidation of ammonium sulfite and
produce hydrogen and ammonium sulfate. Accordingly, the Photolytic Sulfur Ammonia team
was directed to acquire firm performance information and costs for beam-splitting optics and
develop a design and cost estimates for a dual solar field architecture. Simultaneously, the team
was directed to undertake preliminary investigation of a hybrid approach, replacing photolysis
with electrolysis.
Zinc Oxide would be documented and further effort deferred until new information might arise
that would argue for resumption of research and development. Economical means to suppress
37
recombination during the quench of the ZnO decomposition step, possibly through use of a high
temperature oxygen transport membrane, and identification of reactor materials capable of
enduring thermal shock and operation at extremely high temperatures would be necessary for
this cycle to become economically competitive. Additionally, demonstration of the proposed
fluid wall reactor to prevent Zn loss by condensation on reactor surfaces would be necessary for
cycle closure while demonstrated avoidance of sintering or other growth mechanisms affecting
the size distribution of aerosolized Zn particles would be necessary to retain hydrolysis
efficiency under cycling.
The Cadmium Oxide cycle suffers from recombination during quench of the CdO thermal
decomposition step in ways very similar to the difficulties experienced by the Zinc Oxide cycle.
Apart form the materials, the essential difference between the zinc and cadmium decomposition
steps is that the zinc vapor quench is taken to solid zinc while the cadmium vapor quench is
taken to molten cadmium, the material used in the hydrolysis step. Demonstration of the quench
step for the Cadmium Oxide cycle had not been performed at the time of the evaluation so it was
not possible to quantify the fraction of initial molten cadmium that would be re-cycled in the
hydrolysis step. The process proposed for cadmium vapor quench was a rapid quench using
either cold gas like carbon dioxide or molten cadmium spray as the quench medium. A cold
gas quench is expected to nucleate homogeneously molten cadmium droplets, which then
become condensation sites to reduce cadmium vapor concentrations. Here, the number density of
condensation sites can be crucial to effectiveness since higher number density generates higher
surface to volume ratio causing greater surface recombination fraction. Molten cadmium droplet
quench could be effective in reducing the number density of condensation sites but quench rate
might be limited by thermal diffusion, causing significant recombination in the gas phase. The
critical path issue for Cadmium Oxide was determined to be modeling the quench process to
identify the optimum path and then demonstrate performance in laboratory scale experiments. A
second issue in this cycle is the relatively slow hydrolysis process whose kinetics, if not
improved significantly by hydrolysis reactor design, could require much greater quantities of
molten cadmium to be recycled in hydrolysis reactors to match throughput of the cadmium oxide
decomposition step.
The mixed oxide sodium manganese cycle would be terminated after completion of work
necessary to document achievements. This cycle suffered from a number of significant
uncertainties, chief among which is economic recovery of sodium to close the cycle. Whereas
incorporation of mixed metal ingredients like Zn-Mn and Zn-Fe improved sodium recovery
without inordinate addition of water, the reaction did not go to completion, probably due to
diffusion of Na and O into the MnO matrix. Moreover, side reactions like volatilization of NaOH
or formation of other stable Na compounds introduced additional difficulty in assuring cycle
closure. Na deposit was found on the apparatus so this volatility problem would have to be
resolved to move the cycle forward. The plant design incorporated significant transport of stored
hot reactant solids and the cost of pneumatic transport over the ~25 km distance for solids (both
hot and cold) instilled considerable uncertainty in plant capital and operating costs. These
uncertainties when coupled with the projected hydrogen gate cost argued for termination of this
cycle. An alternative cycle, direct thermal dissociation of NaMnO2 (Sodium Manganate cycle)
was proposed as a mixed volatility oxide cycle in which sodium manganate would be
decomposed to MnO and vapor phase of NaxOy. The kinetics of the decomposition step is the
38
primary barrier to operation of this cycle although there are several other obstacles, including
performance of a fluid wall reactor and uncertainty regarding affinity of oxygen for sodium
compounds relative to manganese. The project team was directed to evaluate the kinetics of the
decomposition step preparatory for a later decision to continue or terminate.
The ALD Ferrite cycle was relatively immature at the time of the evaluation but is sufficiently
simple that closure could be readily demonstrated in spite of residual uncertainty regarding back
reaction extent that could affect performance sufficiently to prevent economic operation.
However, performance would hinge crucially on the ability of the active materials to withstand
repeated thermochemical cycling. If material characteristics are not stable under cycling, then the
cycle might be abandoned, or it might be made more complex if a means could be found to
restore initial active material characteristics. The team was directed to focus its attention on
active material stability and durability preparatory to a subsequent decision to continue or
terminate.
Hybrid Copper Chloride has material issues for the hydrolysis and crystallizer reactors, likely
resolvable at the appropriate time. Demonstration of material transfer from the crystallizer
remains to be done, again likely to be successful. More importantly, quantitative composition of
spent anolyte from the electrolysis process has not been determined and this step must precede
the choice of membrane separation material for final processing of spent anolyte (aqueous CuCl
and CuCl2). However, until a satisfactory electrolyzer membrane and process have been
established, anolyte composition cannot be determined with any confidence. Electrolytic
processing of fresh aqueous HCl with fresh aqueous CuCl produces hydrogen at the cathode and
CuCl2 in the anolyte. At the time of the evaluation, electrolysis membrane tests showed
degradation by transport and deposition of metallic copper. This causes degradation in
performance and ultimately destruction of the membrane. Discovery of effective and durable
membrane along with electrolysis cell design were identified as critical issues for resolution
before a decision for continuation or termination could be made.
Table 3.5 provides a summary of identified issues resulting from presentations and discussions at
the meeting. The tabulation of critical path items in table 3.5 is labeled STCH critical path
focus to emphasize that recommended R&D paths should apply only to effort under
sponsorship of the DOE-EERE FCT Program.
39
Table 3.5. Summary of evaluation outcomes.

Cycle
Issues
STCH critical path focus
Sulfur Iodine
HI decomposition; acid
concentrator heat exchanger;
non-ideal chemistries; SPR
SPR integration
Hybrid Sulfur
acid concentrator; electrolysis

membrane and cell design; SPR
SPR integration
Concept design; photolysis

catalyst;
Beam splitting optics vs dual

solar field; electrolysis option
Zinc Oxide
Recombination; reactor
materials; fluid wall reactor; size
distribution of metallic zinc
Document progress; terminate

cycle R&D
Cadmium Oxide
Recombination; high
temperature hydrogen transport
membrane; beam down reactor
cost
Quench
modeling/demonstration; beam
down reactor design and
demonstration
Sodium Manganese
Na recovery; incomplete
hydrolysis; reactant volatility;
Document progress; terminate

cycle R&D
Mixed Volatility Sodium

Manganate
Decomposition kinetics;
effectiveness of fluid wall
reactor; extent of back reaction;
Measure decomposition kinetics

and back reaction
ALD Ferrite
Ferrite stability under extended

thermochemical cycling; active
material cost; back reaction
effects
Evaluate ferrite stability under

thermochemical cycling
Electrolysis cell component

materials and design; hydrolysis
and crystallizer materials of
construction; spent anolyte
composition and separation
membrane
Develop and demonstrate

effective electrolysis membrane
40
41
4 Cycle Status Summaries and Path Forward

Recommendations
Status of the evaluated cycles at the time of the October 2008 evaluation is reported here and
reflects information reported in submitted white papers and presentations by cycle R&D teams.
The summaries are not uniform in content due to contrast in cycle maturity and documents
submitted by R&D teams.
4.1 Sulfur Iodine

The Sulfur Iodine Cycle is a three-step cycle (Fig. 4.1.1) that has been under development since
~19732,7,40,45,54,56,57,59. DOE NE under its Nuclear Hydrogen Initiative has sponsored research and
development of this cycle and Sulfur Iodine was selected for solar integration because its
maximum temperature requirement is consistent with an advanced solar power tower. Each of
the steps was demonstrated at laboratory scale but not all steps were optimized and an integrated
lab-scale (ILS) demonstration was not successfully operated before termination. A week-long
demonstration of the complete cycle was conducted in Japan but this was not a closed-loop
demonstration, leaving open the question of reaction completion and effects of re-cycled reaction
products.
Figure 4.1.1. Sulfur Iodine three-step cycle.
42
Concentrated sulfuric acid is reduced in the thermal decomposition reactor. Oxygen gas is
released and aqueous SO2 is reacted with iodine in the Bunsen reaction to produce sulfuric acid
and hydriotic acid (HI) whose specific gravities are sufficiently distinct to permit gravimetric
separation. Sulfuric acid is concentrated and recycled to the decomposition reactor while HI is
distilled to release hydrogen and the iodine is recycled for reuse.
Extractive distillation using phosphoric acid has been demonstrated but the process is slow and
inefficient, requiring extended distillation column residence or recycling for recovery of
expensive iodine. A reactive distillation step has been proposed that is anticipated to be more
efficient but the process was not described in detail and had not achieved full laboratory
demonstration so iodine recovery remains an issue. The Bunsen reaction does not appear to go to
completion, giving rise to recirculated SO2 whose consequence is unknown. A counter-flow
reactor has been designed but not quantitatively demonstrated so the Bunsen reaction also
remains problematic. Sulfuric acid concentration remains a materials challenge and the
decomposition reactor (shown in Figure 4.1.2), while demonstrated, relies on multiple units
(Figure 4.1.3) with a noble metal catalyst whose activity degrades with use and must be either
cleaned or replaced, causing operational difficulty and expense.
Figure 4.1.2. Bayonet decomposition reactor

designed by Sandia National Laboratories.
43
Figure 4.1.3. Bayonet decomposition reactor manifold designed by

Sandia National Laboratories.
A solid particle receiver was chosen to provide solar thermal heat for integration with the Sulfur
Iodine cycle65,66,67,68. The conceptual design called for particulate thermal medium to be heated
by direct solar flux to about 1000oC and stored for use in the thermal decomposition reactor. The
unknown consequence of hot particles impinging on the decomposition reactor led to
implementation of an intermediate heat exchanger to provide either air or helium at 1000oC for
heating the decomposition reactor. The particle medium is heated in the receiver section, stored
in a hot storage vessel, used to heat the intermediate thermal medium and is then collected in a
cold storage vessel. The particles are transported back to the solar receiver section by a bucket or
auger system before recycling through the receiver and back to the hot storage vessel. This
design concept has not been demonstrated and possibly serious difficulty could exist with
durability of the particle thermal media and durability of an intermediate heat exchanger. The
proposed solar interface schematic design is shown in Figure 4.1.4.
44
Figure 4.1.4. Schematic solar interface with the solid particle receiver with intermediate
heat exchanger providing heated He gas to drive the decomposition reactor.
45
Primary advantages and obstacles for the Sulfur-Iodine cycle are listed in Table 4.1.1.
Table 4.1.1. Sulfur-Iodine cycle advantages and challenges.
Advantages
Challenges
Sulfur cheap and abundant
Iodine scarce and expensive
Liquid/gas stream; continuous flow process;

separations are relatively easy
Corrosive chemicals
Thermal heat well-matched to advanced power

tower
Non-ideal solutions prevent theoretical prediction

of equilibrium states
Thermal storage concept is simple
Heat exchangers for solid particle thermal medium

not demonstrated
A detailed flowsheet for the Sulfur Iodine thermochemical process was developed for the nuclear
option. The thermochemical flowsheet for the solar option is identical. Simultaneous display of
the entire flowsheet is not practical, so the process is divided into 3 sections (see Figures 4.1.5
4.1.7):
1. Bunsen reaction section: I2 + SO2 + 2H2O 2HI + H2SO4
(T ~ 120C)
2. Acid decomposition section: H2SO4
SO2 + H2O + O2
(T > 800C)
3. HI decomposition section: 2HI
I2 + H2
(T > 350C)
Sections 2 and 3 were optimized using AspenPlusTM software but lack of data and departure
from ideal behavior of solutions in section 1 required a different model approach. Stream
compositions and states were determined for each stream in the combined flowsheets and energy
and mass balance calculations resulted in calculated process efficiency of ~ 0.35 to 0.39,
depending on the heat exchanger medium, but the data from which these numbers were derived
were not listed. No provision for solar integration is evident other than the presence of the He
heat exchanger that could be coupled to an intermediate heat exchanger at the SPR.
46
Figure 4.1.5. Bunsen reaction flowsheet (section 1).
47
Figure 4.1.6. Acid decomposition flowsheet (section 2).
48
Figure 4.1.7. HI decomposition flow sheet (section 3).
Apparently, there was insufficient time to do serious cost analysis for the solar-powered Sulfur
Iodine process so no reviewed H2A was available for comparison. The costs and efficiencies
cited in Table 3.4 might change. Substantial progress is reported in a recent report82.
The path forward for the Sulfur Iodine cycle presented at the evaluation meeting engaged only
the solar interface because NE was responsible for all other aspects of this cycle. Nevertheless,
the issues identified above must all be resolved before the cycle can be considered for further
49
development. The HI decomposition process is perhaps the most important issue because
inefficiency in this step would likely increase cost beyond acceptable levels. The second most
important issue is developing understanding of the equilibrium in the Bunsen reaction, unless it
can be demonstrated that SO2 carryover raises no obstacles to a closed cycle. Third, discovery of
heat exchanger materials that can withstand the abrasive environment of a solid particle receiver
is essential to either direct or indirect provision of thermal energy to the process. Finally, it is
essential to demonstrate operation of a solid particle receiver using an adequate thermal medium
at the required temperatures and at scale sufficient to assure further scale-up.
4.2 Hybrid Sulfur

Hybrid Sulfur is a two-step cycle that uses high temperature heat (~900oC) to reduce sulfuric
acid and an electrolysis step to oxidize SO2 and restore the original oxidation state of the cycle.
The Hybrid Sulfur cycle has been under development since before 1975 when the Westinghouse
Corporation was issued a patent. Westinghouse demonstrated closed-loop operation in 1978
using an electrolysis cell designed and fabricated at Westinghouse so that both steps have been
demonstrated but additional refinement remains necessary to optimize the cycle. The R&D was
discontinued in 1983 but was resumed under the Nuclear Hydrogen
Initiative1,2,4,5,10,15,16,18,19,26,30,43,59. Fig. 4.2.1, taken from the team White Paper, illustrates the
cycle. Research and development of this cycle has been sponsored by
DOE NE under its Nuclear Hydrogen Initiative and it was selected for solar integration because
it is a thermochemical process and its required temperature is consistent with the optimal
temperature of an advanced solar power tower. Oxygen gas is separated from the sulfuric acid
decomposition products and aqueous sulfur dioxide is oxidized in the electrolyzer to release
hydrogen gas and form sulfuric acid for recycle to the decomposition step. In practice, only
about 40% of the SO2 is electrolyzed and residuals are recycled through the electrolyzer with
continuous feed of aqueous SO2 from the thermal decomposition reactor. Dilute (~50 wt%)
sulfuric acid from the electrolyzer is concentrated to about 75 wt% for feed to the thermal
decomposition reactor.
50
Figure 4.2.1. The Hybrid Sulfur cycle.
Figure 4.2.2. Schematic of PEM membrane in the Hy-Sulfur electrolysis step.
51
The solar interface schematic for Hybrid Sulfur is the same as shown for Sulfur Iodine in Figure
4.1.3 and the decomposition reactor shown in Figs. 4.1.1 and 4.1.3 is also identical. Oxidation,
however is accomplished electrolytically as shown in Figure 4.2.2.
The electrolysis cell has been demonstrated, but membrane permeability allows SO2 diffusion to
the cathode where reduced sulfur is deposited, degrading electrolyzer performance and,
ultimately, destroying the membrane. This has been a key technical issue and no solution had
been found at the time of the evaluation.
Hybrid Sulfur has the same advantages as Sulfur Iodine but has additional advantage owing to its
simplicity. The obstacles are, however, somewhat different.
Table 4.2.1. Hybrid Sulfur advantages and challenges.
Advantages
Challenges
Sulfur cheap and abundant
Corrosive chemicals
Continuous flow process; easy separations
Efficient cell design without sulfur deposition
Thermal heat well-matched to solar
Grid or solar electric power is required
Thermal storage concept is simple
Heat exchangers not demonstrated
Simple 2-step process
Solid particle receiver and sand
The Hybrid Sulfur flowsheet, shown in Figure 4.2.3, was designed to optimize integration
between the decomposition reactor and the electrolysis cell and achieve maximum efficiency.
More work could be invested to optimize the flowsheet to achieve minimum hydrogen cost to
provide tradeoff analysis between cost and efficiency. SO2 is dissolved in 43 wt% sulfuric acid
and fed to the anode of the electrolysis cell. Approximately 40% of the SO2 is reacted, producing
H2SO4 at 50 wt% after electrolysis. H2SO4 is then concentrated to 75 wt% by two flashes in
series (operating at 1 and 0.3 bar) and a vacuum column (at 0.13 bar). Oxygen separation is
required before being extracted as byproduct.
The process efficiency was calculated with material and energy balances for the flowsheet in
Figure 4.2.3 under the assumptions:
Maximum process temperature
920C
Maximum process pressure
40 bar
H2SO4 decomposition inlet concentration
75 wt%
H2SO4 SDE inlet concentration
43 wt%
Electrolysis cell temperature
100oC
Electrolysis cell pressure
21 bar
Electrolysis cell avg cell voltage
600 mV
52
Figure 4.2.3. Hybrid Sulfur flowsheet.
Calculated values for efficiency evaluation as reported in the process white paper are reported
below:
Input:
High temperature H2SO4 decomposition thermal power: 358 kJ/molSO2 at about 950
C, which represents some 82% of the total thermal power needed to sustain the
thermochemical process
53
Low temperature thermal power for H2SO4 concentration: 75.5 kJ/molSO2 at about
130 C, which is some 18% of the total external thermal power needed to sustain the
HyS process
Electric power for SO2 oxidation: 115.7 kJe/molSO2, which is almost 97% of the
overall electricity needed for the HyS plant
Electric power for HyS auxiliaries: 4.1 kJe/molSO2, which is about 3% of the
electricity needed for the thermochemical plant
Output:
H2 production (LHV = 242 kJ/molH2) at 21 bar and 100oC
O2 as byproduct
The process efficiency is calculated on the basis of H2 LHV and assuming a thermal- electric
efficiency of 0.4 (H2A guidelines):
Cost analysis of the Hybrid Sulfur cycle was done for 2015 and 2025 in accord with assumptions
and guidelines of the H2A analysis process. The plant was sized to produce annual average 100
tonne H2/day with plant capacity of 0.75. An intermediate heat exchanger, used in the 2015 case,
was replaced with direct heating of the decomposition reactor for the 2025 case. Helium
transport allowed two heliostat fields and two towers to service a single process system in the
2015 case whereas direct heating of the decomposition reactor in the 2025 case required a single
operational heliostat field and tower because transport of particulate thermal medium is difficult.
The plant was equipped with hot storage providing 13 hours operation when off-sun. The H2A
production costs for the two cases are shown in Figure 4.2.4 with primary differences in
decomposition reactor heating, heliostat cost reduction and electrolysis cell cost and performance
improvements from 2015 to 2025. Much improved cost analysis is reported in a recent report82.
The path forward for Hybrid Sulfur includes work that would be sponsored by both NE and
EERE. Under the Office of Nuclear Energy the primary obstacle for successful operation was
discovery of an electrolysis process and materials that would prevent SO2 crossover and sulphur
deposit at the cathode. Under EERE, as for Sulfur Iodine, discovery of heat exchanger materials
that can withstand the abrasive environment of a solid particle receiver is essential to either
direct or indirect provision of thermal energy to the process. Finally, demonstration of operation
of a solid particle receiver using an adequate thermal medium at the required temperatures and at
scale sufficient to assure further scale-up is necessary.
54
2015 Case $4.80/kg H2
2025 Case $3.19/kg H2
Figure 4.2.4. H2A hydrogen cost estimates for Hybrid Sulfur.
4.3 Photolytic Sulfur Ammonia

The Photolytic Sulfur Ammonia cycle was presented as a four-step hybrid thermochemical cycle
designed to make selective use of the solar spectrum with long wavelength spectral composition
used to drive thermal processes and short wavelength spectral composition used to drive the
hydrogen producing oxidation step using photolysis9. The cycle invoked intermediate
thermochemical reduction steps to release oxygen. Figure 4.3.1 (taken from the team white
paper) shows a schematic representation of the process in which it is evident that spectral beam
splitting or dual solar fields would be required to power the process.
55
Figure 4.3.1. Photolytic Sulfur Ammonia schematic process.
SO2(g) + 2NH3(g) + H2O(l)
(NH4)2SO3(aq)
120oC
(NH4)2SO3(aq) + H2O(l) + h (NH4)2SO4(aq) + H2
80oC
(NH4)2SO4(s) + ZnO(s)
2NH3(g) + ZnSO4(s) + H2O
ZnSO4(s)
SO2(g) + ZnO(s) + O2
500oC
870-1000oC
Figure 4.3.2. Process chemistry for Photolytic Sulfur Ammonia.
The cycle chemistry at the time of the evaluation is shown in Figure 4.3.2. The cycle team
reported in their white paper that all steps had been demonstrated, all reactions went to
completion and that there were no side reactions or unreacted products that carried over to the
next step. The photolysis was carried out in the presence of a cadmium sulfide photocatalyst
doped (or alloyed) with about 0.5 wt% Pt/Pd/Ru co-catalyst. The reported photolysis efficiency
was about 0.29 as defined by the ratio of LHV H2 generated to the energy of incident photons
with wavelength less than 520 nm. These assertions apply only to laboratory experiments and the
project plan shows continued work in all these areas. The issue of cost associated with noble
metal catalysts was identified as a challenge, but not resolved. Difficulties, such as the solidsolid reaction of ammonium sulfate with zinc oxide to form ammonia and zinc sulfate, as well as
transport of solids (zinc sulfate and zinc oxide) were identified as challenges, but design
concepts had not progressed to the point that analysis and testing could be implemented.
Similarly, options for solar field designs were offered (beam spectral splitting or dual solar
56
fields) but specific designs were not developed at the time of the evaluation. As a consequence of
these deficiencies, doubtless due at least in part to the short period of R&D before the evaluation,
system efficiency calculations and estimates of hydrogen gate costs were without substance at
the time of the evaluation and these are therefore not reported here.
Table 4.3.1 lists advantages and challenges for this cycle. Entries are taken liberally from
evaluation materials submitted by the research team.
Table 4.3.1. Advantages and challenges for Photolytic Sulfur Ammonia.
Advantages
Challenges
Separations are simple
Solids transport required
Ultra-high temperature not required
Coordinated operation of two reactors
Solar thermal spectrum applied to

thermochemical steps; solar photolytic spectrum
applied to photolysis step
Spectral splitting or dual solar field; either

expensive or obviates photolytic advantage
Low cost photolytic reactor
Photocatalyst cost effectiveness
Figure 4.3.3 reproduces a flowsheet provided for the evaluation and description of its operation
is also liberally taken from the cycle white paper. AspenPlusTM analysis was underway at the
time of the evaluation but not completed.
57
Figure 4.3.3. AspenPlusTM flow sheet for Sulfur Ammonia cycle.
Hydrogen is produced at a rate of 11,199 kg/hr based on 12 hr/day operation in the PHOTOCAT
reactor. In the photoreactor, ammonium sulfite (NH4)2SO3 and water react to produce H2 and
ammonium sulfate in the presence of a visible light activated photocatalyst. Hydrogen gas is
separated from the aqueous ammonium sulfate (NH4)2SO4 solution by venting it from the
photoreactor (represented by the flash separation tank (FL-H2)). Aqueous ammonium sulfate
solution is then pumped through a series of heat exchangers that preheat the brine before it is fed
into the first solar thermolytic reactor LOTEMRXN to release ammonia and form zinc sulfate.
Hot product gases from this reaction (NH3 and H2O) are easily separated from solid zinc sulfate
and allowed to expand in a turbine (TURBINE1) to generate electricity. The exit stream from
TURBINE1 is sent to the heat exchanger HX-9 while the solid product ZnSO4 is decomposed in
HITEMRXN to release oxygen and form zinc oxide and sulfur dioxide. Hot gases SO2 and O2
enter heat exchanger HX-2 and are cooled by the ammonium sulfate stream entering
LOTEMRXN.
58
SO2/O2 and NH3/H2O streams are reacted in SFIT-GEN producing aqueous ammonium sulfite
and a moist gaseous oxygen stream. The aqueous products are collected in an above-ground tank
(STORAGE) and allowed to cool down during the night - to be used later as a feedstock for
replenishing the photocatalytic reactor. The oxygen stream O2-EX is further cooled in a heat
exchanger HX-1 and cooling tower (TOWER). The moist oxygen leaving the cooling tower
enters into a flash evaporator (FL-O2) which recovers condensed water and releases the oxygen
into the ambient air.
Water H2ORECY collected in FL-O2 is combined with the makeup water and ammonia stream
exiting HX-9 and sent to TOWER2 where it is condensed and fed into the sulfite synthesis
reactor SFIT-GEN. The LOTEMRXN and HITEMRXN reactions will most likely be carried out
in a single solar receiver reactor the design of which is still being worked on. The reaction in
the photoreactor PHTOTOCAT will be conducted in a simple shallow (less than 1"), Kynar (or
other suitable UV-VIS transparent material) covered flat bed unit illuminated by sunlight. The
photolyte is continuously pumped in and out of the photoreactor(s). LOTEMRXN, HITEMRXN
and SFIT-GEN have been simulated using Rgibbs model. In the present flow sheet, PHOTOCAT
is simulated using a stoichiometric reactor model. A ratio of about 10 moles of H2O per mole of
(NH4)2SO3 has been assumed in the simulation.
The cycle white paper cited tower and heliostat cost at about 48% of capital cost whereas
virtually all other cycles find the solar system comprising about 70% of capital cost. Since either
specialized heliostats or dual soar fields would be required, it is difficult to reconcile the quoted
solar costs in the white paper. Accordingly, the H2A results are assumed to be so preliminary
that they will not be reported here.
The prime rationale for the photolytic process was founded on more efficient use of solar power
by applying the shorter wavelength spectral component to photolysis and the longer wavelength
component to thermal processes. The only way to realize this benefit is to split intercepted solar
radiation into these components and direct the split beams to their respective tasks. A dual field
realization does not use intercepted radiation more efficiently since the thermal component will
be useless for the photolysis process and the photoactive component will not add materially to
thermal processes. Consequently, discovery of a cost effective means of spectral beam splitting
is mandatory for the Photolytic Sulfur Ammonia cycle to be continued.
4.4 Zinc Oxide

The Zinc Oxide cycle is a two-step volatile metal oxide cycle that has been under development
since before 2003. In its simplest form, the metal oxide is reduced at a high temperature of about
2000oC, quenched to zinc particles and oxygen is released. The zinc is recycled and exposed to
water vapor at about 425oC to release hydrogen and form ZnO51,52,61,62,69,70,71,72,73,74.
59
2 ZnO
2 Zn + O2
~1800oC
Zn + H2O ZnO + H2
Figure 4.4.1. Zinc Oxide cycle chemistry.
Four issues have driven the cycle development. First, the reduction step temperature generates
serious difficulty in finding reactor materials of construction that are durable under operation. It
was found that introduction of an inert gas, argon in experiments, would reduce the operating
temperature to about 1750oC, but separation of argon from the oxygen is problematic since even
a high temperature oxygen permeable membrane would suffer from either condensation or
physical deposition of zinc particles in the pores.
Second, the zinc oxide decomposition step is limited in efficiency because quench is
accompanied by significant recombination. Only 18% of zinc metal has been recovered under
rapid quench whereas up to 70% and 85% recovery have been cited in analytic studies. It is
speculated that recovery could be improved by quenching with fine zinc metal particles, but this
approach would likely lead to larger zinc particles, reducing the effectiveness of the hydrolysis
step. At this time, no process other than rapid quench has been found to reduce significantly
recombination and thereby improve metal recovery. However, rapid quench reduces sensible
heat recuperation for the cycle, thereby decreasing cycle efficiency.
Third, the oxidation (hydrolysis) step is limited by surface area of zinc metal since formation of
the metal oxide on the surface inhibits further oxidation of the underlying metal. The higher the
particle surface to volume ratio, the higher the efficiency of the hydrolysis process so that submicrometer zinc particles are necessary. Rapid quenching of the reduction step does produce
very small particles, but efficient recovery has not been demonstrated and a closed cycle
demonstration has not been attempted.
Finally, a porous flow-through wall was proposed to counter loss of zinc metal to condensation
and particle deposition on reactor walls. The fluid wall concept has been used in other chemical
processes but has not been demonstrated for the zinc cycle. A fluid wall reactor would require
additional gas separation and would doubtless increase costs.
60
Table 4.4.1. Advantages and challenges for Zinc Oxide.

Advantages
Challenges
Extremely high temperature limits materials

choice
Reactant materials abundant, safe and

relatively cheap
Recombination limits efficiency
Continuous operation through Zn metal

storage
Particle size limits hydrolysis efficiency
Variable insolation easily managed by

oxide feed to reactor
Zn deposition on reactor walls and

components
High temperature oxygen transport
membrane
The process flowsheet for a plant sized to produce annual average 100 tonne H2/day with
capacity factor 0.75 is shown in Figure 4.4.2. For the 2015 H2A case study, a 3:1 molar flow rate
of Argon:ZnO was assumed, ZnO decomposition was assumed to proceed at ~1750oC to 70%
conversion, hydrolysis was assumed to be 100% efficient, and a 3-stage vacuum swing absorber
(VSA) was used for Ar/O2 separation. Quench sensible heat between 1800oC and 900oC is
consumed and it is assumed that sensible heat between 900oC and a recovery temperature is
recuperated. A dual multi-tube aerosol transport reactor75 of siliconized graphite was configured
with porous wall to maintain flowing Ar between Zn and ZnO gases and the reactor walls. The
2015 reaction was executed at atmospheric pressure so that compression is required to provide
H2 at 300 psig at the plant gate.
61
Figure 4.4.2. Zinc Oxide cycle flowsheet (CU Final Report).
The 2025 H2A case study assumed a single pressurized (300 psig) multi-tube reactor, 85%
conversion efficiency for the decomposition step and a single stage VSA.
Three heliostat fields illuminated a 250 m tower and 13 hours of thermal storage (Zn metal)
were maintained to allow continuous operation (weather permitting). The 2015 case required 15
towers to provide annual average production of 100 tonne H2/day, while the 2025 case required
14 towers. Each heliostat field for both case studies contained 358 heliostats in about 3 acres and
delivered 123 MWth to three secondary concentrators on each tower. The secondary
concentrators delivered 112 MWth to each receiver.
The team calculated efficiency of solar energy to Lower Heating Value hydrogen energy so that
the calculated ZnO efficiency values will be lower than the differently defined efficiencies
requested by the program office. The 2015 efficiency was 17.2% while the 2025 efficiency was
calculated to be 20.7%. The main causes of efficiency increase are increased decomposition
62
yield (85% for 2025 and 70% for 2015), operation at gate pressure of 300 psig for 2025 instead
of atmospheric pressure for 2015, and reduced argon inert gas use in 2025 so that a single stage
VSA could be used instead of the 3-stage VSA used in the 2015 case study.
Capital cost allocations are shown for case studies 2015 and 2025 in Figures 4.4.3 and 4.4.4. The
baseline gate cost for hydrogen in 2015 was $5.58 /gge H2 and could conceivably reduce to
$4.47 /gge H2 with aggressive reduction in heliostat and tower costs accompanied by reduced
cost for the receiver/reactor. 2025 baseline cost was found to be $4.14 /gge H2 and with similar
aggressive component cost reductions could conceivably reduce to about $3.46 /gge H2 . Since
these cost figures did not appear to be reducible to meet the projected cost targets, the Zinc
Oxide cycle was not recommended for continued development. A recent report provides
substantially improved cost analysis but does not change the recommendation.
The Zinc Oxide cycle development is unlikely to be continued without discovery of reactor
materials capable of withstanding thermal shock and fatigue. Moreover, product cost is unlikely
to meet targets without significant reduction in heliostat and tower costs well beyond those
projected for the foreseeable future. Efficiency improvements are unlikely in the absence of
methods for recuperating the sensible heat lost to rapid quench, and demonstration of ZnO
decomposition yield of zinc metal near 70% is necessary to seriously consider resumption of
development.
Figure 4.4.3. Plant cost allocation for the 2015 case study.
63
Figure 4.4.4. Plant cost allocation for the 2025 case study.
4.5 Cadmium Oxide

The Cadmium Oxide cycle is a simple two-step volatile metal oxide cycle21,24,29 with many
similarities to the Zinc Oxide cycle. Primary differences are that the decomposition temperature
is significantly lower for CdO, ~1450oC, the quench process proceeds to molten Cd instead of
the solid metal product for ZnO, the proposed rapid quench is facilitated by use of molten Cd
droplets as opposed to expansion through a cooled orifice as used by ZnO and the chemical plant
is operated on the surface under a beam down solar collector design. Other important differences
are the use of hazardous Cd as opposed to nonhazardous zinc in the two processes. The
Cadmium Oxide cycle chemical steps and conditions are shown in Figure 4.5.1.
CdO(s)
Cd(g) + O2(g)
Cd(l) + H2O(g) CdO(s) + H2(g)
1450oC
450oC
Figure 4.5.1. Chemical steps of the Cadmium Oxide cycle.
As in the Zinc Oxide cycle, a third non-chemical step, quenching the decomposition products
rapidly, is necessary to reduce recombination or back-reaction that reduces cadmium yield and
recycles CdO to the hydrolysis step. A conceptual flow diagram for a process designed to operate
24 hours per day was developed and is shown in Figure 4.5.2.
64
Figure 4.5.2. Process flow for a diurnal solar cadmium oxide hydrogen cycle.
Thermal storage and power generation are options included in the conceptual design. A third
option reduces the decomposition temperature by incorporating inert gas flow with CdO in the
decomposition reactor. O2 and the inert gas can be separated readily from the quenched product
but the inert gas would require separation for recycling. Replacing the inert gas with air is
possible, but increase in O2 partial pressure would likely make the quench less effective. Inert
gas use has not been analyzed to determine if the temperature reduction is worth the additional
separation required. Analysis of the CdO cycle without inert gas provided a thermal efficiency
estimate of 59% (LHV).
Whereas the thermal efficiency of the CdO cycle is among the highest of all cycles considered,
there remain difficult obstacles in the chemistry as well as in plant operations. Just as with the
zinc cycle, recombination will limit the effectiveness unless it can be shown that rapid quench
either with or without molten cadmium nucleating sites provides high yield of Cd metal for
recycling to the hydrolysis step. Moreover, hydrolysis of molten cadmium is rate limited due
both to chemical kinetics and to accumulation of CdO on the molten Cd surface. A rotating kiln
counter flow hydrolysis reactor was designed for increasing the hydrolysis yield through mixing
and residence time selected (through kiln dimension and orientation) to react all molten
cadmium.
65
Figure 4.5.3. Conceptual rotating kiln counter flow hydrolysis reactor

with tungsten carbide balls to enhance steam/Cd interaction.
Operationally, the cycle suffers from the need to manage solids transport along with liquids and
gases, but most separations are easy unless an inert gas is used to reduce recombination in the
decomposition step. In the case of the hydrolysis reactor, operation at elevated pressure is
proposed in response to counter elevated Cd vapor pressure at hydrolysis operating temperature.
A high temperature/high pressure separation of hydrogen from steam will be required but design
concepts were not available at the time of the evaluation. Alternatively, the steam could be
condensed, allowing easy separation of hydrogen, but plant efficiency would diminish
significantly. Finally, even with inherent thermal storage in solid CdO, plant shutdown could
raise serious difficulties without incorporation of auxiliary heating to prevent solidification of
molten cadmium in vessels and pipes.
Both of the primary chemical reactions have been demonstrated in laboratory studies, but neither
has been implemented in operational component designs to allow evaluation of feasibility of
closed cycle operation. Data necessary for establishing reaction yields and downstream product
concentrations did not exist at the time of the evaluation.
66
Figure 4.5.4. Beam down collector integrated with

fluidized bed decomposition receiver/reactor.
Integration with solar power was proposed using a beam down collector design illuminating a
cavity receiver on the ground. (Figure 4.5.4) Preliminary beam down design work performed by
the Weizmann Institute called for 10 towers, each surrounded by a graded density nearly circular
heliostat field of approximately 700 m diameter providing about 72 MWth to a fluidized bed
decomposition receiver/reactor. A beam down solar collector system at the necessary power
levels has not been demonstrated. 10 towers with reactor/receivers were required to meet
production targets of annual average 100 tonne H2/day and chemical plants were sized to meet
production with two plants serviced by the 10 towers and decomposition reactors.
The proposed molten cadmium quench process has not been demonstrated. Preliminary modeling
was underway at the time of the evaluation to allow assessment of the fraction of Cd vapor that
would condense on the quench droplets and the rate of condensation removing Cd from
participation in gas-phase recombination. Since some recombination will necessarily occur at the
vapor-liquid interface, a lower surface/volume ratio of molten Cd will reduce the recombination
fraction and increase the Cd metal yield for recycle to the hydrolysis section. On the other hand,
longer residence time in the gas phase increases gas-phase recombination and reduces the Cd
metal yield for recycling. Rapid quench is desirable, but Cd supersaturation must be kept below
the threshold for homogenous nucleation since the surface/volume ratio under homogeneous
nucleation is exceedingly high and Cd metal yield will diminish sharply. Determining molten Cd
quench feasibility and optimizing quench conditions was not done at the time of the evaluation.
67
Table 4.5.1. Advantages and challenges for the Cadmium Oxide cycle.
Advantages
Challenges
Cd hazardous material management
Materials abundant and relatively cheap
Molten Cd quench
High thermal efficiency
High temperature/high pressure H2 separation
Thermal storage
Solids transport over significant distance
Chemical processes are ground-based
Plant shutdown management
A detailed flow sheet for the CdO cycle was not presented at the evaluation meeting. However,
an earlier presentation by the team included a flowsheet that predated the evaluation by about
10 months. That flowsheet is presented here in Figure 4.5.5 with the caveat that it should not be
interpreted as reflecting the process at the time of the evaluation.
Figure 4.5.5. CdO cycle flowsheet, AIChE Meeting, Salt Lake City, November 7, 2007.
68
Since the process changed significantly after this flowsheet was developed, Aspen PlusTM
analysis and optimization will not be addressed. Preliminary H2A analysis for a 2015 case study
was presented at the evaluation but documentation was not thorough and the analysis had not
been reviewed prior to the evaluation. The cost figures presented at the evaluation are included
here for historical purposes and the hydrogen production cost cited by the team is shown but
should not be relied upon for comparative purposes.
Table 4.5.2. Component capital costs cited for CdO cycle
at the time of the evaluation.
Component
Cost
10 beam down solar collector

receiver systems
$352.8 M
10 CdO decomposition reactor

vessels
$72 M
Heat exchangers/hydrolysis
reactors
$33.4 M
H2/H2O membrane separation

units
$8 M
Vertical vessels/separators
$13 M
Turbines and pumps
$29.8 M
Solids transport
$7.7 M
H2 compressors
$15.5 M
Total Capital
$532.2 M
69
Table 4.5.3. CdO operating costs cited at the time of the evaluation.
Item
Cost
Electricity
$0.0682/kW-hr
Purified water
$0.00132/liter
Cooling water
$0.0000509/liter
78 eng/tech staff members
$6.9 M/yr
Maintenance
$8.7 M/yr
Total O&M
$32.8 M/yr
Table 4.5.4. Assumptions for 2015 case study cost analysis.

Assumptions
Startup Year
2015
Hydrogen Production, kg/yr (Peak)

Capacity Factor
133,333
75%
Hydrogen Production, kg/yr (Average)
100,000
Cost of Electricity, $/kW-hr
0.0682
Cost of Cooling Water, $/gal

Inflation, %/year
Cost of Heliostats, $/m
0.000079
1.9
$127
Table 4.5.5 presents cost estimates and sensitivity effects for the CdO cycle under the
assumptions in table 4.5.4 and using the capital and operating cost estimates shown in Tables
4.5.2 and 4.5.3. The H2A analysis was unreviewed at the time of the evaluation and no projected
costs for improvements for the 2025 case were presented.
70
Table 4.5.5. CdO cost estimates with some sensitivity estimates.

Results
Baseline Hydrogen Cost,
$(2005)/kg
$3.94
Baseline Hydrogen Cost,

$(2015)/kg
$4.75
Sensitivity Factors
Low/High
Hydrogen Cost, $/kg
Cost of Electricity, $/kW-hr
0.04/0.097
$3.92/$3.95
Capital Cost of Hydrogen Plant
-25%/+50%
$3.77/$4.28
70%/80%
$4.21/$3.69
120/160
$3.86/$4.31
40/59.6
$5.83/$3.94
Capacity Factor
Cost of Heliostats, $/m
Hydrogen Plant Efficiency, %

(LHV)
The Cadmium Oxide cycle shows promise primarily through its high thermal efficiency, but
overall efficiency could suffer significantly as the challenges listed in Table 4.5.1 are addressed.
Whereas cycle simplicity remains a plus, that simplicity is somewhat offset by the volatile and
hazardous primary material. The highest priority issue to be resolved is establishing and
demonstrating an effective quench process. Without that, everything else is speculative. It was
agreed that molten Cd quench feasibility should first be addressed via modeling and simulation
before attempting to demonstrate the process in the laboratory. That work was proceeding after
the evaluation meeting. Scaled performance modeling of the beam down solar system might have
been done, but definitive results and description of the process were not made available. If not
done, such modeling is essential to confident estimates of solar system cost.
4.6 Sodium Manganese Cycle

The original Sodium Manganese cycle is a non-volatile metal oxide and is attractive both
because its thermal efficiency is among the highest of the cycles studied (along with the
Cadmium Oxide cycle) and because its reactants are both abundant and nonhazardous76,77. The
cycle steps are shown in schematic form in Figure 4.6.1.
2Mn2O3
4MnO + O2
1500oC
2MnO + 2NaOH 2NaMnO2 + H2
700oC
2NaMnO2 + H2O Mn2O3 + 2NaOH
100oC
Figure 4.6.1. Schematic steps for the Sodium Manganese cycle.
71
The straightforward cyclic process in Figure 4.6.1 requires considerable excess of water in the
hydrolysis step to recover Mn2O3 and form aqueous NaOH. The aqueous solution must be
concentrated by vaporizing the water to provide NaOH for the hydrogen production step. The
excess water removal reduces cycle thermal efficiency so a secondary metal, Zn, was added to
improve the hydrolysis step and reduce the required excess water and aid in Na recovery. Figure
4.6.2 shows the operational chemical steps for 3:1 Mn:Zn stoichiometry48,50,76,77.
2 Zn0.33MnO1.33 + O2
1500oC
2 Zn0.33MnO1.33 + 2 NaOH H2 + Na2Zn0.66Mn2O4.66
700oC
Na2Zn0.66Mn2O4.66 + H2O Zn0.66Mn2O3.66 + 2 NaOH
100oC
Zn0.66Mn2O3.66
Figure 4.6.2. Mixed metal oxide steps for the Sodium Manganese cycle.
Both zinc and iron were tested for hydrolysis improvement and zinc showed significantly better
performance, reducing the amount of water required by about a factor of 3. Even so, about
10 moles of water were required for production of 1 mol H2. The secondary metal appears to
prevent, or at least inhibit the formation of a sodium/manganese birnessite that does not
participate in the hydrolysis reaction and would be carried through the high temperature step.
The consequence of this side reaction is not known. If the birnessite does not decompose, then
birnessite would likely accumulate and the reaction could not be closed. If it does decompose, it
will likely reduce cycle efficiency, possibly to the point that economics are not competitive.
Laboratory experiments demonstrate recovery of only about 80% of the sodium although closed
cycle would require recovery of 100% unless the birnessite decomposes in the high temperature
step and the sodium is made available once again for hydrolysis. This would change the reaction
class from a nonvolatile metal oxide to a mixed volatile/nonvolatile metal oxide since the sodium
would vaporize in the high temperature process.
The reduction step was demonstrated in both thermogravimetric analysis (TGA) and flowing
aerosol experiments. Reducing oxygen partial pressure with simultaneous inert gas flow
minimized the effects of recombination. A closed system design would require oxygen/inert gas
separation. Conversion efficiency was greater than 80% when a fluidized bed of Mn2O3 was
reduced to MnO but component design for continuous (as opposed to batch) operation of a
fluidized bed was not described. The team noted that residual sodium from incomplete
hydrolysis as well as the secondary metal used to reduce the amount of NaOH leach water could
undergo volatilization in the reduction chamber with consequent loss through wall condensation.
Apart from possible corrosion effects, such loss of reagent would prevent cycle closure absent
some recovery process. These obstacles were not evaluated in the experiments and not addressed
in the system model used for analysis.
Release of hydrogen by mixing MnO with NaOH at ~700oC is complicated by the mixing of
liquid NaOH with solid MnO and Zn-Mn-O compounds. Nearly 100% reaction has been
reported for NaOH and pure MnO but those earlier results could not be repeated with the mixed
72
metal oxide used for improved sodium recovery. Some evidence was found that indicated that
NaOH was vaporized and lost to the reaction. No such effect was observed for the pure
MnO/NaOH reaction. The team speculated that sodium and oxygen could be trapped in the MnO
structure but it remains unclear why this would occur in the mixed metal oxide process and not
in the pure MnO process. Many issues remain unresolved for the hydrogen release process so
that closed cycle feasibility remains uncertain.
Table 4.6.1. Advantages and challenges for Mx-Sodium Manganese.
Advantages
Challenges
High thermodynamic efficiency
Excessive leach water for Na recovery
Materials are abundant and non-toxic
Hydrolysis side reactions inhibit closure
Alumina useable in high temperature step
Possible Na volatility: loss and corrosion
Back reaction repressed by reactant state
Low pressure H2 formation at 0.1 atm
Figure 4.6.3 shows the process flowsheet used for cost and performance analysis of a 3:1 Zn:Mn
oxide process. The analysis assumed that no Zn or Na was lost due to volatility. The reduction
step was assumed to be 80% efficient, the hydrolysis step was assumed to be 100% efficient and
NaOH recovery was assumed to be 80% efficient. The analysis assumes cyclic processing for all
materials so that no side reactions to accumulate passive materials from cycle to cycle existed.
The Mn2O3 high temperature reaction is carried out at 1500 oC in aerosol flow reactors mounted
on six towers. The Mn2O3/NaMnO2/ZnO precursor is transported from a storage tank with a
pneumatic transport system to an aerosol feeder system after passing through a heat exchanger to
recover sensible heat from the reaction product. The feeder disperses the powder in a preheated
inert argon stream to further minimize the thermal load of the reactor prior to entering the solar
furnace. The effluent of the reactor is rapidly quenched to 800 oC with a cool argon/oxide feed
stream to minimize recombination of the reduced metal oxide and oxygen. The cooled aerosol
stream passes through a metal filter at ~800 oC that removes the solid reaction product from the
oxygen containing argon stream for storage and further processing. The argon/oxygen stream is
heated to ~1000 oC and passes through a membrane module equipped with a ceramic oxygen
transport membrane. The purified argon is then recycled into the process.
The reduced oxides produced during the daytime operation of the high temperature reduction
(formally a mixture of MnO/Mn2O3/NaMnO2/ZnO) are stored at 800 oC in insulated tanks for
24/7 production of hydrogen. The powders are mixed with a concentrated solution of NaOH. The
residual water is vaporized in a dryer and the heat of vaporization is supplied by the latent heat of
the hot oxides. The solid NaOH/oxide mixture is then reheated in a furnace to >650 oC to form
hydrogen. It is assumed that the process is carried out continuously but the need for 0.1 atm
vacuum might require several smaller batch reactors.
73
Figure 4.6.3. Schematic flowsheet for analysis of the Mx-Sodium Manganese cycle.
The product from the hydrogen reaction (formally NaMnO2/ZnO/Mn2O3) is hydrolyzed with
excess water at 80-100 oC. The hydrolysis product is a mixture of solid oxides and an aqueous
NaOH solution. A multi-effect evaporator system concentrates the NaOH solution that is about
5-10 molar to saturation (~25 molar) for recycling into the hydrogen formation reaction. The
water is recovered as a liquid to be recycled into the hydrolysis reaction. The energy required for
the high temperature on-sun reaction is supplied to eight 221 m high towers that are irradiated by
24 heliostat fields with 934 heliostats each (111 m2 /heliostat) for a total area of 2.5x106 m2. The
supplemental energy required for hydrogen formation and to recycle NaOH after hydrolysis is
obtained from a solid particle receiver/sand storage system. The particle receivers are mounted
on three 181 m high towers and utilize an inorganic storage material that is heated to 1000 oC
during daylight operation. Solar thermal energy is collected by 12 heliostat fields with 934
heliostats each (90 m2/heliostat) for a total heliostat area of 1.03 million m2. The heated sand is
stored in holding tanks for the 24/7 low temperature hydrogen formation and sodium recovery
steps. The thermal efficiency for the LHV of H2 based on the energy delivered to the reactor is
estimated to >38%. This calculation is optimistic since it does not account for heat losses during
transport and storage of the hot materials. Figure 4.6.4 shows schematically the proposed plant
layout with a single chemical plant serviced by 8 high temperature towers and 3 moderate
temperature solid particle receivers.
74
Figure 4.6.4. System layout with a single chemical plant for the Mx-Sodium Manganese cycle.
H2A analysis was presented but details were provided only for a 2015 case study even though
estimated product costs were given for both 2015 and 2025. The documented difference between
the 2015 and 2025 case studies was heliostat cost of $126.50/m2 in 2015 and $90/m2 in 2025.
Significant uncertainty in process cost persisted largely because assessment of side reaction
effects remained to be done and, for example, recuperation of energy from the rapid quench
process. Uncertainties in component costs were cited and these appeared sufficiently significant
that listing estimates for these costs would be pointless. These uncertainties are shown in
Table 4.6.2.
Table 4.6.2. Component uncertainties for the Mx-Sodium Manganese cycle.
Component
Issue
Ar/O2 separation
VSA too expensive; membrane does not exist
SPR heat exchangers
Not designed/tested
Solids transport
Not designed/tested
Hot storage for oxide
Not designed/tested
Hot storage for sand
Not designed/tested
75
Figure 4.6.5. Estimated capital cost distribution for the mixed metal oxide
realization of the Sodium Manganese cycle.
Figure 4.6.5 shows the estimated installed capital cost allocation for 2015 of $668 M. No similar
figures were available for the 2025 case study although H2 gate costs were estimated for 2015 $5.22/kg H2 - and for 2025 - $4.22/kg H2.
The R&D team concluded that resolution of the remaining issues for this cycle would be unlikely
to reduce the product cost sufficiently to meet the program cost targets and recommended that
further work on the cycle be terminated. A sine qua non for this cycle is discovery of a means of
sodium recovery without inordinate water addition that does not excite side reactions so that
cycle closure is assured.
4.7 Sodium Manganate

The failure of the standard Sodium Manganese cycle suggested a modification of the process
whereby sodium would be re-circulated to the high temperature reaction. TGA measurements at
1500oC confirmed that the reduction of NaMnO2 to pure MnO and vapor phase NaxOy proceeds
slowly to completion. The reaction will be feasible if it can be confirmed that the complete
vaporization of Na is not necessary for the reduction of Mn((III) to Mn(II) or that the reaction
proceeds sufficiently fast in an aerosol with small particle sizes. Vaporized sodium compounds
will likely re-condense on the MnO particles as the product mix is cooled to lower temperature
since the particles will provide a large number of nucleation sites. Thermodynamic predictions
indicate that sodium will be recovered after the reaction in the form of either Na metal, Na2O, or
Na2O2. Any of these species will easily hydrolyze to NaOH in the presence of liquid water or
steam which then can be reduced with MnO to hydrogen and NaMnO2 at temperatures above
650oC similar to the original manganese cycle. In addition, the high affinity of sodium for
oxygen might minimize recombination with Mn since gas phase oxygen will more likely react
with vaporized sodium and form one of the oxide species. A fluid wall reactor for the high
76
temperature step might be necessary to prevent deposition of sodium compounds. The cycle is
shown in more detail in Figure 4.7.1.
4NaMnO2
4MnO + 2Na2O + O2
2MnO + Na2O + H2O 2MnO + 2NaOH

2MnO + 2NaOH
2NaMnO2 + H2
1500oC
300oC
700oC
Figure 4.7.1. Reaction path for the preliminary Sodium Manganate cycle.
A preliminary H2A estimate suggests that this cycle might yield H2 costs in the range of $3/kg
since the large excess energy requirements for sodium recovery as well as the additional sensible
heat for the inert component in the mixed oxide cycle are avoided. In addition, both reaction
steps are endothermic and therefore, the need for heat integration is minimized.
At the time of the evaluation, insufficient work had been performed on this concept to warrant
further details in this report. Work that had been done found that the reduction step was slow and
the team was directed to focus its study on kinetics of the reduction. Additional work would be
required to assess the role of vapor phase Na and its corrosion effects on container materials.
4.8 ALD Ferrite

Ferrite material used as a water oxidation/reduction agent to generate hydrogen from water has
been under study for a number of years55,58. Virtually all ferrite materials produced as coprecipitates have suffered from very similar drawbacks. Conversion efficiency is low for the
reduction step, oxidation using water is slow and the active material performance degrades under
cyclic operation. Most previous ferrite work studied co-precipitated ferrite material from solution
onto (and sometimes into) a substrate. The resulting active material is essentially heterogeneous
in distribution and composition and characteristics continue to change under the severe cyclic
thermal environments. The chemistry is schematically shown in Figure 4.8.1.
77
Figure 4.8.1. Schematic chemistry of a water-splitting ferrite cycle.
In applying methods of Atomic Layer Deposition (ALD), it is possible uniformly to deposit

virtually identical layers of material interspersed with other material itself uniformly deposited in
virtually identical layers. Using this technique, a highly uniform and thin layer of CoFe2O4 can
be formed on a substrate as illustrated in Figure 4.8.2. Alternating layers of CoO and Fe2O3 are
deposited using ALD and then the layers and substrate are calcined resulting in a highly uniform
and thin layer of cobalt ferrite. Heating the layer to between 1200oC and 1500oC gives rise to
thermal reduction with the cobalt ferrite converting possibly to an alloy of CoO and 2FeO and
release of oxygen. Exposure of the alloy to steam at a temperature of about 1000oC releases
hydrogen and restores the original composition of the layer. X-ray dispersive (XRD) analysis of
the ALD layer showed no crystallinity change after thermal reduction. No data was shown for
layer characteristics after water oxidation.
Preliminary experiments showed that the ALD ferrite (Fe3O4) reacted much more quickly than
the co-precipitated cobalt ferrite (CoFe2O3) but the cobalt ferrite provided measurably higher
conversion efficiency. In another experiment, co-precipitated cobalt ferrite was compared with
ALD cobalt ferrite. Here, the ALD sample showed both faster response and higher conversion
efficiency than the co-precipitated sample.
78
Figure 4.8.2. Atomic Layer Deposition of uniform thin layer of cobalt ferrite.
Another set of experiments examined the effect of substrate by comparing ALD cobalt ferrite
performance when deposited on zirconia and on alumina. A number of observations are
noteworthy. First, thermal reduction of cobalt ferrite on alumina substrate initiates at much lower
temperature (~900oC) than for zirconia substrate (~1200oC). Second, since the response time is
roughly the same for both substrates, the conversion efficiency is higher for alumina than for
zirconia. The third observation is that cobalt ferrite reduction on alumina forms hercynite
(FeAl2O4) which appears to persist from cycle to cycle. Finally, response times and conversion
efficiency for the hercynite material appear to be stable over multiple cycles.
These promising observations provided basis for recommending that ALD ferrite materials
continue under investigation even though none of the requirements for the evaluation process
had been met. The primary uncertainty for ALD ferrite systems was determined to be its physical
durability and chemical stability under repetitive thermochemical cycling and this feature was
called out as the critical path item for focused study. In spite of this recommendation, a great
deal of work remains to be done before this cycle could assume serious competitive stature.
Cycle thermodynamic performance needs to be quantified and its potential thermal efficiency
evaluated. An operational concept needs to be developed that shows consistency with whatever
form of active material is selected for cycling. Given that form, the conversion efficiency and
kinetics (or residence time) need to be quantified and a means of heat recuperation must be
identified and designed in order to maintain an acceptable level of cycle thermal efficiency.
Moreover, since the active material is fabricated, the cost of material and fabrication must be
established. Satisfaction of these requirements should permit assessment of capital and
operational costs from which to estimate product cost in a way consistent with the assumptions
and guidelines imposed on the other thermochemical cycles.
79
4.9 Hybrid Copper Chloride

The Hybrid Copper Chloride cycle is a 3-step process requiring relatively low temperature but
also requiring an electrolysis step to release hydrogen and convert CuCl to the original CuCl2 for
the hydrolysis reaction. Research and development of this cycle is relatively mature with all
reactions verified in the laboratory but discovery of a durable membrane and electrolysis
conditions preventing copper crossover had not been achieved at the time of the
evaluation60,78,79,80,81. The process is described by hydrolysis of CuCl2 to form copper
oxychloride (Cu2OCl2) and HCl. Cu2OCl2 is decomposed in the high temperature step to form
CuCl and release oxygen. The CuCl and HCl are electrolyzed to release hydrogen and form
CuCl2. Figure 4.9.1 shows the hybrid thermochemical process.
2CuCl2(s) + H2O(g) Cu2OCl2(s) + 2HCl(g)

Cu2OCl2(s)
O2(g) + 2CuCl(s)
2CuCl(s) + 2HCl(g)e- 2CuCl2 + H2(g)
340-400C
450-530C
100C
Figure 4.9.1. Hybrid Copper Chloride chemistry.
The Hybrid Copper Chloride team includes Argonne National Laboratory (ANL), Atomic
Energy of Canada, Ltd., Pennsylvania State University, the University of South Carolina, Tulane
University, and the universities associated with the Ontario Research Foundation. The team
reflected a relatively loose federation except for Pennsylvania State University and the
University of South Carolina which ultimately executed subcontracts with Argonne to undertake
specific tasks in support of the Argonne project.
Laboratory work demonstrated proof of concepts assuring cycle closure. Chlorine gas was
thought to be a possible side reaction product of Cu2OCl2 decomposition but experiments at
NREL and CEA showed no Cl2 presence. Further experiments must be done to resolve the
contrast between the ANL , NREL and CEA results but this side reaction is not expected to be an
issue. Reaction yields were good for the hydrolysis and decomposition tests and reactor designs
have been developed but not fully fabricated and tested. A decomposition temperature of 550oC
gave 100% O2 recovery in laboratory testing. This result suggests complete reaction of the
decomposition step in light of the NREL and CEA negative tests for chlorine gas. Indirect
evidence for performance of the hydrolysis reaction rests on heat and mass transfer
measurements using an ultrasonic nebulizer.
Table 4.9.1 lists advantages and challenges for the Hybrid Copper Chloride cycle as interpreted
by the R&D team.
80
Table 4.9.1. Advantages and challenges for Hy-CuCL.

Advantages
Challenges
Lowest high temperature for STCH
Copper crossover in electrolyzer
System efficiency meets target
500 mA/cm at 0.63 V
Active materials cheap and abundant
Separation of spent anolyte
Cycle has long history of development
Excess water or low pressure for hydrolysis
Chemistry components commercially used
Possible Cl2 gas from decomposition step
Materials of construction identified
Amount and effect of carryover reagents
Chemistry and system modeling difficult
Cycle efficiency and product cost parameters are sensitive to the electrolyzer performance for the
targeted current density of 500 mA/cm2. Table 4.9.2 shows this dependence for the system
design concept at the time of the evaluation. Whereas demonstrated electrolyzer performance at
the time of the evaluation was 429 mA/cm2 at 0.9 V, there are engineering solutions that should
improve the performance like higher operating temperature and electrolyte stirring. Nevertheless,
engineering solutions will not supplant the need to discover a membrane material and operating
conditions that prevent copper crossover and cathode deposition since initial performance will
degrade by such behavior.
Table 4.9.2. Hy-CuCl system performance sensitivity to electrolyzer performance.
Cell emf at 500 mA/cm2
System efficiency (LHV)
Product cost ($/kg H2)
0.7 V
39%
4.53
0.63V
41%
3.48
Figure 4.9.2 shows a conceptual block flow chart for the process and is useful in discussing cycle
challenges. Technical issues for the electrolyzer cell were discussed above. Chemical and
materials challenges remain in the crystallizer and hydrolysis sections. For example, it is not
practical to maintain a continuous flow process and drive the electrolysis reaction to completion.
That means that an aqueous mixture of CuCl2 and CuCl will flow as spent anolyte to the
crystallizer. CuCl must be separated and recycled to the electrolyzer as complement to fresh
anolyte while the CuCl2 is directed to the hydrolysis reactor to form copper oxychloride for feed
to the high temperature decomposition reactor. Spent anolyte separation has not been
81
demonstrated although membrane distillation or electrodialysis have been identified as possible

methods.
Reactor components suitable for testing and scale-up have not been fabricated and tested and
materials of construction have not been selected although glass-lined components are mentioned
as routine for other applications with similar reagents. The amounts and effects of recycled
reagents have not been demonstrated.
Figure 4.9.2. Hy-CuCl conceptual block flow chart.
A detailed flowsheet was not presented for the evaluation, but AspenPlusTM analysis has been
underway for some time. Inadequate data and the complexity of the process prevented
convergent optimization at the time of the evaluation. The solar collector/receiver concept was
not described, reportedly because of teaming with a commercial collaborator whose information
was proprietary. Nevertheless, H2A analysis was presented and is repeated here.
82
Table 4.9.3. H2A analysis results for Hy-CuCL.

Case
Solar/Chemical
Capital ($M)
Cell EMF
V
Elect Cost
$/kW-hr
Product cost
$/kg H2
Sensitivity
Efficiency
% (LHV)
2015
208.3/136
0.7
0.068
4.53
3.78-5.31
39
2025
168.5-106.6
0.63
0.048
3.48
2.91-4.11
41
Capital cost reductions in this unreviewed H2A analysis were due to
Heliostat cost reduction from $127/m2 to $90/m2 (~$40M savings)
Reduced hydrolysis reactor residence time
Reduced decomposition reactor size (~$30M savings)
Reduced electrolyzer costs by use of Pd instead of Pt, increased efficiency and

durability (~$2M savings)
The path forward for Hy-CuCl depends on discovery of materials and operating procedures that
permit durable electrolyzer performance at ~500 mA/cm2 and ~0.63 V without copper crossover
and deposition on the cathode. Such performance must be achieved in order for the cycle to meet
efficiency and product cost targets.
Additional development is necessary to manage hydrolysis reactor performance. Presently, either
excess water or low pressure reactor operation is required to achieve satisfactory hydrolysis yield
of copper oxychloride. The first option entails water removal from the product stream and the
second requires compression work. The tradeoff between these two options is not clear, nor is it
evident that consideration has been given to other hydrolysis processes like a mix of excess
water and lower pressure operation. Detailed Cu2OCl2 decomposition testing is necessary to
resolve fully the issue of chlorine gas release. Recovery of released chlorine is possible but
would add to the complexity and cost of the system. Corrosive activity of molten CuCl needs to
be determined to permit optimal selection of construction materials. Finally, considerable
laboratory work is needed to acquire necessary data to support component modeling and
AspenPlusTM analysis.
83
5 Summary Remarks
5.1 General Observations
The selection of projects for termination engages the problem of determining if future benefit is
balanced by earlier investment and necessary resources for continuation. The process is
facilitated by the identification of quantitative performance metrics and, at the same time, made
difficult by the assessment of work still in progress so that performance is projected and not
assured. No easy solution to this conundrum exists because investment expense necessary to
assure performance prediction usually exceeds what is available and/or reasonable. A
competitive process, pitting one idea against another, can be used to make decisions for work-inprogress, but the process is complicated by contrast in project maturity. It is self-evident why
middle-school players are not fielded against university-level players and roughly the same
rationale applies to projects in widely different stages of R&D. It is difficult to make
comparative assessments of potential when some teams have had significantly more opportunity
than others to survey options, perform tests and make path-forward decisions.
These issues would be irrelevant if one or more cycles showed clear dominance in terms of
meeting the established quantitative performance metrics. However, none of the STCH projects
could clearly and definitively demonstrate performance in line with the DOE targets at the time
of the evaluation. In fact, it is rather surprising that projected performance metrics generally were
close to the targets, but still outside desired levels. It is possible that cycles selected for
investigation reflect best of show and that thermochemical processes are simply unable to meet
target performance metrics. It is also possible that more R&D is needed to establish better cost
and performance projections.
None of the evaluated cycles projected performance consistent with DOE targets. Moreover,
there was no cycle under consideration whose inferred potential warranted certain favor over all
the other cycles. R&D maturity of cycles under evaluation showed remarkable range with several
cycles having experienced about a year of development effort while several others had
development history that exceeded 30 years, although such extended period did not refect
continuous R&D effort. Finally every cycle under consideration reported technical obstacles
whose resolution was essential to serious consideration for development to pilot plant design.
These features of the cycles under evaluation led to the conclusion that no substantive decision
could be made to terminate R&D of any specific cycle unless the cycle proponent declared that
targets could not be achieved in the absence of progress that in the proponents opinion was
unlikely.
The evaluation and selection effort was conceived to facilitate focus of available resources on
continued development and realization of cycles most likely to transition from R&D through
pilot plant to commercial deployment. The absence of discriminating features adequate to focus
resources on a few cycles led to an outcome that was different from intended but arguably as
useful. The existence for all cycles of performance-critical obstacles permitted focus of resources
84
on resolution of those obstacles and successful prosecution of such resolution would be

necessary for R&D continuation.
5.2 Evaluation Outcomes

The following summarizes R&D priority on critical path obstacles derived from the evaluation
process for each cycle under consideration. Successful resolution of critical path items does not
assure cycle success, but failure to resolve critical path obstacles assures the cycle cannot be
competitive. For those cycles whose R&D was terminated by recommendation of the cycle
proponent, necessary progress is described in those areas that could lead to its restoration to
active R&D status.
Table 3.5 is repeated here to provide a consolidated summary of the observations in Sections
5.2.1 through 5.2.9. It is relabled here as Table 5.1 but is identical in all respects to Table 3.5.
Table 5.1. Summary of evaluation outcomes.
Cycle
Issues
STCH critical path focus
Sulfur Iodine
HI decomposition; acid concentrator

heat exchanger;
non-ideal chemistries; SPR
SPR integration
Hybrid Sulfur
acid concentrator; electrolysis

membrane and cell design; SPR
SPR integration
Concept design; photolysis catalyst;
Beam splitting optics vs dual solar

field; electrolysis option
Zinc Oxide
Recombination; reactor materials;

fluid wall reactor; size distribution of
metallic zinc
Document progress; terminate cycle

R&D
Cadmium Oxide
Recombination; high temperature

Quench modeling/demonstration;
hydrogen transport membrane; beam beam down reactor design and
down reactor cost
demonstration
Sodium Manganese
Na recovery; incomplete hydrolysis;

reactant volatility;
Mixed Volatility Sodium Manganate
Decomposition kinetics; effectiveness Measure decomposition kinetics and

of fluid wall reactor; extent of back
back reaction
reaction;
ALD Ferrite
Ferrite stability under extended

thermochemical cycling; active
material cost; back reaction effects
Electrolysis cell component materials Develop and demonstrate effective

and design; hydrolysis and
electrolysis membrane
crystallizer materials of construction;
spent anolyte composition and
separation membrane
85
Document progress; terminate cycle

R&D
Evaluate ferrite stability under

thermochemical cycling
5.2.1 Sulfur Iodine

R&D for this cycle is under management by the DOE-NE. Critical path obstacles are not subject
to mandate by the DOE-EERE . Consequently, the critical path obstacle is an observation, not a
direction. Findings are:
Hydrolysis (Bunsen) reaction unreliable and may not go to completion
Hydriotic acid decomposition step not demonstrated adequately to support system

analysis
Amount and effects of carryover reagents unknown
Sulfuric acid decomposition reactor component lifetimes unknown
Solar thermal integration not designed or tested
The STCH critical path obstacle for the Sulfur Iodine cycle was identified to be solar thermal
integration with the Solid Particle Receiver (SPR). Resolution of this obstacle is complicated by
absence of STCH funding for SPR development, but includes:
Identification and testing SPR thermal medium to verify durability and absence of
sintering73
Design and test heat exchangers for thermal coupling of SPR to thermochemical
process
Design and test scaleable SPR
5.2.2 Hybrid Sulfur

R&D for this cycle is under management by the DOE-NE. Critical path obstacles are not subject
to mandate by the DOE-EERE. Consequently, the critical path obstacle is an observation, not a
direction. Findings are:
Electrolyzer membrane performance limited by sulfur crossover and deposition
Sulfuric acid decomposition reactor component lifetimes unknown
Solar thermal integration not designed or tested
The STCH critical path obstacle for the Hybrid Sulfur cycle was identified to be solar thermal
integration with the Solid Particle Receiver (SPR). Resolution of this obstacle is complicated by
absence of STCH funding for SPR development, but includes:
Identification and testing SPR thermal medium to verify durability and absence of
sintering73
Design and test heat exchangers for thermal coupling of SPR to thermochemical
process
Design and test scaleable SPR
86
5.2.3 Photolytic Sulfur Ammonia

R&D for this cycle was in a very early stage at the time of the evaluation, having been active for
less than a year. Nevertheless, the rationale for this cycle was founded on more efficient use of
solar radiation by spectral beam splitting and distribution of spectral components to photoactive
and thermal steps. The R&D team proposed either spectral beam splitting using a single solar
field or using dual solar fields with one dedicated to the photoactive process and the other
dedicated to thermal processes. It is argued that the dual field approach does not use solar
radiation more efficiently but the team was directed to evaluate cost and effectiveness of both the
dual field approach and the beam splitting approach to resolve general concept design issues
before proceeding. Evident skepticism resulted in an additional recommendation to evaluate the
feasibility and value of replacing the photolysis step with an electrolysis process.
5.2.4 Zinc Oxide
The Zinc Oxide cycle was thoroughly studied and the proponent recommended termination
largely because no path appeared to be feasible that would bring product costs in line with
targets. Findings are:
discovery of reactor materials capable of withstanding thermal shock and operating

durably in the necessarily extreme temperature environment and in the presence of
oxygen is extremely challenging
experiments were unable to demonstrate more than 18% zinc recovery in quench of
the reduction step because of recombination and product costs are projected to
significantly exceeded target levels even assuming 85% zinc recovery
feeding relatively large zinc particles in the quench stream would reduce
recombination losses by unknown amount but would generate larger particles for
feed to hydrolysis, adversely affecting hydrolysis efficiency
use of a high temperature oxygen transport membrane or flowing inert gas with
the quench stream could reduce recombination but both approaches would entail a
high temperature gas separation that was not designed
loss of zinc to reactor walls might be avoided by use of a fluid wall design but would
entail a gas separation process
A means of recovering at least 70% zinc metal while retaining hydrolysis efficiency would be
necessary to warrant investment in materials discovery for fabrication of an effective reduction
reactor and continued cycle development.
5.2.5 Cadmium Oxide
The Cadmium Oxide cycle has very high thermal efficiency but entails use of volatile hazardous
material and the team concluded the thermochemical processing would be safer if performed at
ground level instead of on a tower. A beam down receiver/reactor was selected for this purpose.
It was not made clear that such a system has ever been tested at the necessary power levels and
the solar field capital costs were not made clear during the evaluation. Initial laboratory
87
measurements found that molten cadmium hydrolysis proceeded very slowly and excessive
residence time in the hydrolysis reactor was needed to obtain satisfactory CdO yield. However,
an effective design that was tested at laboratory scale appeared to resolve the slow kinetics and
surface passivation found in the hydrolysis step. TGA measurements confirmed that
recombination in the thermal reduction step would need to be mitigated and avoidance of
excessive recombination was identified as a critical path issue requiring resolution. The team
proposed a rapid quench assisted by inclusion of finely dispersed molten cadmium to promote
condensation without initiating homogeneous nucleation that would cause excessive
recombination in a rapid quench of pure Cd vapor. The exact details of this quench process
require careful analysis of quench droplet temperature, size and number density effects on the
rate of Cd vapor condensation in order to assure absence of homogeneous nucleation and to
estimate the recovery efficiency of recycled cadmium metal. Modeling a molten cadmium
quench process was identified as the top priority effort for this cycle. The team was encouraged
to continue working with the Weizmann Institute in Israel to establish firm design and cost of the
beam down solar system.
5.2.6 Sodium Manganese
Sodium Manganese shows very high thermal efficiency and uses abundant and cheap reagent
materials. The high temperature reduction step is amenable to operation in standard materials
like alumina and the reduction back reaction is suppressed in this nonvolatile process. The first
obstacle encountered was the need for excess water in the hydrolysis step to permit leach
recovery of NaOH. Managing excess water increases product cost so a mixed metal oxide
process with zinc was used to reduce water molality. Even so, water molality remained high
although about a factor of 3 less than with the pure Mn2O2 and experiments were able to
demonstrate only about 80% NaOH recovery. It is speculated that some of the sodium might
volatilize and be condensed on reactor walls (indeed some evidence of this was found). It is also
thought that sodium ions and oxygen might be incorporated in the manganese oxide matrix.
Whatever the cause, recovery of NaOH is essential to cycle closure and the team was unable to
identify an effective process. The R&D team recommended termination of the mixed metal
Sodium Manganese cycle in favor of exploring a sodium manganate thermal cycle. Restoration
of the mixed metal Sodium Manganese cycle to active R&D status would require the discovery
of a means of sodium recovery without the need for excess water and unaccompanied by side
reactions that could remove Na from the active cycle.
5.2.7 Sodium Manganate
This cycle was conceived upon perceptible failure of the mixed metal Sodium Manganese cycle
and appeared attractive because sodium would be recycled to the high temperature step as a
mixed oxide of NaxOy which is easily hydrolyzed to NaOH closing the cycle. In effect, the
hydrolysis and oxidation steps do not have to go to completion in order to close the cycle. Since
sodium is cheap and abundant, an excess of sodium required by incomplete reactions is of no
consequence to cycle economics. Appearance of this concept so late in the project prevented
performance of significant work to define and resolve obstacles. However, assuming no
irreconcilable obstacles, product cost estimates fell within the DOE targets. One observation is
that the reduction step proceeds slowly but completely at about 1500oC but it was not confirmed
88
if the NaxOy would have to be vaporized to complete the conversion of Mn(III) to Mn(II). So
volatilization and possible corrosion and/or loss to reactor walls remain issues for closure of this
cycle. Because the reduction step that was tested in a TGA is slow, it is possible that residence
times in the high temperature reduction reactor would not be conducive to operation as a
continuous flow aerosol process. Whereas a fluidized bed approach could manage residence
time, a continuous process design (as opposed to batch processing) had not been developed at the
time of the evaluation. The R&D team was directed to focus its attention on kinetics of the
reduction reaction to determine the feasibility of a continuously flowing aerosol process.
5.2.8 ALD Ferrite
ALD Ferrite is another cycle whose investigation began only shortly before the evaluation.
Primary findings of the early investigations were that ALD cobalt ferrite mixtures were both
more efficient and faster responding than co-precipitated samples of the same materials. When
ALD ferrite is reduced on alumina, hercynite (FeAl2O4) is formed and this material showed onset
of reduction at much lower temperature (900oC) than ALD ferrite reduced on zirconia (1200oC).
Because response times are about the same for both substrate materials, it was conjectured that
the reduction efficiency of hercynite is higher than that of ALD ferrite and both perform better
than co-precipitated ferrite materials. Finally, some cycling experiments were performed that
appeared to show physical and chemical material stability. All other ferrite materials tested have
consistently degraded in both form and activity so this fact, if borne out by further study, would
be a breakthrough in non-volatile metal oxide cycle performance. The ALD Ferrite team was
directed to focus effort on establishing the veracity of hercynite stability under repetitive
thermochemical cycling. At the same time, the behavior of thin films or small particles would
need to be assessed in order to arrive at a conceptual design for a hydrogen production system,
but this was not included in the priority task assigned to this cycle. Given active material
stability, conversion efficiency and kinetics (or residence time) still need to be quantified and a
means of heat recuperation would need to be identified to maintain an acceptable level of cycle
thermal efficiency.
5.2.9 Hybrid Copper Chloride
Hy-CuCl is a high thermal efficiency cycle whose thermal reduction temperature is the lowest of
all the STCH cycles under active investigation. This is a three-step cycle that requires
electrolysis to release hydrogen and close the cycle. Hy-CuCl has been under study by various
institutions since the 1970s although R&D experienced a lengthy hiatus before serious work
resumed in the early 2000s. Active materials in the cycle are cheap and abundant, the reactor
components are similar to others used in common commercial applications and materials of
construction have been identified but not optimized. Three difficult obstacles remain to be
resolved. First, the use of excess hydrolyzer water can be mitigated by low pressure operation of
the reactor, but both options require process energy to manage. Second, spent anolyte containing
an aqueous mixture of CuCl and CuCl2 must be processed to separate these species to direct the
CuCl back through the electrolysis step and to direct the CuCl2 through the crystallizer to the
hydrolysis reactor. Several separation options have been identified, but none tested. Finally,
electrolyzer membranes at the time of the evaluation showed copper crossover to the cathode
where deposited metallic copper degrades the electrolyzer performance. Competitive
89
performance of his cycle requires electrolyzer current density of about 500 mA/cm2 with cell emf
of about 0.63 V. The best performance at the time of the evaluation was about 429 mA/cm2 at
about 0.9 V and the design experienced copper crossover. Whereas engineering solutions for
higher current density at lower bias were proposed, the overwhelming obstacle for this cycle
remains the discovery of electrolyzer membrane material and associated electrolysis processes
that prevent copper crossover. This was a priority task for the Hy-CuCl team.
90
91
Reference Materials
12. Dorner, S. and Schnurr, W. Hydrogen production from water by reactor heat Nucl. Sci.
Abstr. 30(1) (1974).
13. Porter, J. T. II and Russell, J. L. Jr Production of Hydrogen from Water General
Atomics Report GA-A12889 (1974).
14. Sato, S. and Nakajima, H. New class of thermochemical hydrogen production
processes Journal of Nuclear Science and Technology 12(10) (1975).
15. Bamberger, C. and Richardson, D. Hydrogen production from water by thermochemical
cycles Cryogenics 16(4) (1976).
16. Brecher, L. E. , Spewok, S. and Warde, C. J. The Westinghouse Sulfur Cycle for the
thermochemical decomposition of water Conf. Proc. - World Hydrogen Energy Conf. 1
(1976).
17. Cremer, H. , Steinborn, G. and Knoche, K. F. A thermochemical process for hydrogen
production Int.J. of Hydrogen Energy 1 (1976).
18. DeGraaf, J. , Halvers, L. , Porter, J. T. II and Russell, J. L. Jr Engineering Design of a
Thermochemical Water-Splitting Cycle Final Report General Atomics Report GAA13726 (1976).
19. Kittle, P. A., Mahoney, D. and Schuler, J. A low temperature, three-step water splitting
process Conf. Proc. - World Hydrogen Energy Conf., 1(3A) (1976).
20. Ohta, T., Kamiya, N., Yamaguchi, M., Gotoh, N., Otagawa, T. and Asakura, S. Watersplitting-system synthesized by photochemical and thermoelectric utilizations of solar
energy Conf. Proc. - World Hydrogen Energy Conf. 1(3A), 19-30. Publisher: Univ.
Miami, Coral Gables, Fla (1976).
21. Brecher, L. E. , Spewok, S. and Warde, C. J. Westinghouse sulfur cycle for the
thermochemical decomposition of water Int. J. Hydrogen Energy 21 (1977).
22. Knoche, K. F. Status of hydrogen production with nuclear process heat Chem.-Ing.Tech. 493 (1977).
23. Bamberger, C. E. Hydrogen production from water by thermochemical cycles; a 1977
update Cryogenics 18(3) (1978).
24. Dafler, J. R., Foh, S. and Schreiber, J. Assessment of thermochemical hydrogen
production Inst. Gas Technol., Chicago,IL,USA. (1978).
25. Chuang, M. C. A study on utilizing solar energy for hydrogen production AIChE Symp.
Ser. 75(189) (1979).
26. Farbman, G. and Fiebelmann, P. The Westinghouse sulfur cycle hydrogen production
process: program status Hydrogen Energy Syst., 5 2485-2504 (1979).
92
27. Fiebelmann, P., Flamm, J., Lalonde, D., Langenkamp, H., Schuetz, G. and Van Velzen,
D. Development, design and operation of a continuous laboratory-scale plant for
hydrogen production by the Mark-13 cycle Hydrogen Energy Syst., 2 649-665 (1979).
28. Liu, F., Kondo, W. , Kumagai, T. , Oosawa, Y. , Takemori, Y. and Mizuta, S. The
magnesium-iodine cycle for the thermochemical decomposition of water Hydrogen
Energy Syst., 2 (1979).
29. Boltersdorf, D., Gehrmann, J., Junginger, R. and Struck, B. D. Anodic oxidation of
sulfur dioxide in the sulfuric acid hybrid cycle Int. J. Hydrogen Energy 55 (1980).
30. Carty, R. H. and Conger, W. L. Heat penalty and economic analysis of the hybrid
sulfuric acid process Int.J. of Hydrogen Energy 51 (1980).
31. Ducarroir, M., Tmar, M. and Bernard, C. Possibilities of solar energy storage using
sulfates Revue de Physique Appliquee 15(3) (1980).
32. Pangborn, J. "Experimental Work on a CdO based Solar Cycle for Water Splitting,
Proceed. of the STTFUA, 28(11) (1980).
33. Williams, L.O. "Hydrogen Power: An Introduction to Hydrogen Energy and Its
Applications, Pergamon Press, (1980).
34. Bilgen, E. and Bilgen, C. "Solar Synthetic Fuel Production, Int. J. Hydrogen Energy,
6(4) (1981).
35. Remick, R. , Schreiber, J. and Foh, S. A cadmium-cadmium hydroxide thermochemical
water-splitting cycle Advances in Hydrogen Energy 2 (1981).
36. Knoche, K. F. High-temperature process heat for thermochemical splitting of water
VGB Kraftwerkstech. 62(12) (1982).
37. Langenkamp, H. and Van Velzen, D. Status report on the operation of the bench-scale
plant for hydrogen production by the Mark-13 process Int. J. Hydrogen Energy 7(8)
(1982).
38. Bremen, J., Hartmann, H. and Von Wolfersdorff, W. Separation of sulfur dioxide and
oxygen by absorption Int. J. Hydrogen Energy 8(2) (1983).
39. Pierre, J. and Yannopoulous, L. N. Hydrogen production process: High temperaturestable catalysts for the conversion of SO3 to SO2 Int. J. Hydrogen Energy 9(5) (1984).
40. Ambriz, J.J. "Hydrogen Production from Cd/CdO Thermochemical Cycle Using a Solar
Furnace" H2 Produced from Renewable Energy (2nd Int Symp) (1985).
41. Bilgen, E. and Joels, R. K. An assessment of solar hydrogen production using the Mark
13 hybrid process Int. J. Hydrogen Energy 10(3) (1985).
42. Upadhyay "Thermodynamic Investigation of a Thermochemical Cycle of Fe-Cl Family
for the Production of H2, 1 (1985).
43. Hakajima, H. , Ikezoe, Y. , Onuki, K. , Sato, S. and Shimizu, S. Studies on the Ni-I-S
Process for Hydrogen Production Int. J. Hydrogen Energy 11(9) (1986).
44. Kumagi, T. and Mizuta, S. Continuous Flow Demonstration of the Mg-S-I Cycle for
Thermochemical Hydrogen Production Chem. Lett. (1986).
93
45. Liao, X. A new hybrid thermochemical cycle for production of hydrogen from water
Scientia Sinica, Series B: Chemical, Biological, Agricultural, Medical & Earth Sciences
29(7) (1986).
46. Engels, H., Funk, J., Hesselmann, K. and Knoche, K. F. Thermochemical Hydrogen
Production Int. J. Hydrogen Energy 12(5) (1987).
47. Pretzel, C.W. "The Developmental Status of Solar Thermochemical Hydrogen
Production, SAND86-8056, (1987).
48. De Bruin, D. and Onstott, E. I. Thermochemical Hydrogen Production with the Sulfur
Dioxide-Iodine Cycle by Utilization of Dipraseodymium dioxymonosulate as a Recycle
Reagent Int. J. Hydrogen Energy 13(1) (1988).
49. Hayashi, H., Mitate, T. and Takehara, Z. Hybrid process for hydrogen production by the
use of hydrobromic acid electrolysis in lithium bromide-potassium bromide melts Int. J.
Hydrogen Energy 12(5) (1988).
50. Ikenoya, A., Kumagai, N., Liao, X., Tanno, K. and Yashiro, H. Studies on the KNO3-I2
Hybrid Cycle for Hydrogen Production Int. J. Hydrogen Energy 13(5) (1988).
51. Knoche, K. F. and Roth, M. Thermochemical Water Splitting Through Direct HIDecomposition from H2O/HI/I2 Int. J. Hydrogen Energy 14 (1989).
52. Yalcin, S. A Review of Nuclear Hydrogen Production Int. J. Hydrogen Energy 14
(1989).
53. Kumagi, T. and Mizuta, S. Continuous Flow System Demonstration and Evaluation of
Thermal Efficiency for the Magnesium-Sulfur-Iodine Thermochemical Water-Splitting
Cycle Ind. Eng. Chem. Res. 29 (1990).
54. Wendt, H. "Electrochemical Hydrogen Technologies, Elsevier, (1990).
55. Lundberg, M. Model calculations on some feasible two-step water splitting processes
Int. J. Hydrogen Energy 18 (1993).
56. Berndhauser, C. and Knoche, K. F. Experimental Investigations of Thermal HI
Decomposition from H2O-HI-I2 Solutions Int. J. Hydrogen Energy 19 (1994).
57. Tamaura, Y. "Production of Solar Hydrogen by a Novel, 2-Step, Water Splitting
thermochemical Cycle, Energy, 20(4) (1995).
58. Tamaura, Y., Yoshida, S., Kawabe, M., Hosokawa, Y. and Tsuji, M. Conversion of
Solar Energy to Chemical Energy of H2 Gas: H2 Production Cycle Using 2-Step WaterSplitting in the Na-Fe-O System Nippon Kagakkai Koen Yokoshu 74(1) (1998).
59. Ganz, J. , Nuesch, P. , Schelling, T. and Sturzenegger, M. Solar hydrogen from a
manganese oxide based thermochemical cycle Journal de Physique IV 9 (1999).
60. Hasegawa, N. , Matsunami, J. , Nezuka, M. , Sano, T. , Tamaura, Y. , Tsuji, M. , Ueda,
Y. Solar Hydrogen Production by Using Ferrites Solar Energy 65(1) (1999).
61. Nuesch, P. and Sturzenegger, M. Efficiency analysis for a manganese-oxide-based
thermochemical cycle Conference Proceedings: Energy (Oxford) 24 (1999).
94
62. Berman, A. and Epstein, M. Kinetics of hydrogen production in the oxidation of liquid
zinc with water vapor Int. J. Hydrogen Energy 25(10) (2000).
63. Weidenkaff, A. , Reller, A. W. , Wokaun, A. and Steinfeld, A. Thermogravimetric
analysis of the ZnO/Zn water splitting cycle Thermochimica Acta 359 (2000).
64. Gokon, N., Inoue, M., Hasegawa, N., Kaneko, H., Tamaura, Y., Uehara, R. and Kojima,
N Stoichiometric studies of H2 generation reaction for H2O/Zn/Fe3O4 system Int. J.
Hydrogen Energy 26(9) (2001).
65. Kurata, Y., Akino, N., Sakurai, M., Onuki, K., Nakajima, H., Shimizu, S., Ioka, I.,
Futakawa, M., Hwang, G., Ishiyama S., Kubo, S. and Higashi, Shun'I'chi A study on the
thermo-chemical IS process Nuclear Production of Hydrogen, Information Exchange
Meeting, 1st, Paris, France, Oct. 2-3, 2000 (2001), Meeting Date 2000, 129-136.
Publisher: OECD Publications and Information Center, Washington, D. C (2001).
66. Gokon, N., Inoue, M., Hasegawa, N., Kaneko, H., Tamaura, Y. and Uehara, R. XPS
Analysis in Hydrogen Generation Reaction of Two-step Water Splitting Using Zn-ferrite
Kotai no Hannosei Toronkai Koen Yokoshu 13 (2002).
67. Brown LC, Besenbruch GE, Lentsch RD, Schultz KR, Funk JF and Pickard PS High
Efficiency Generation of Hydrogen Fuels Using Nuclear Power General Atomics Report
GA-A24285. Prepared under the Nuclear Energy Research Initiative Program for the US
Department of Energy, Dec. (2003).
68. Pierrard, P., Goldstein, S., Borgard, J., Powers, D., Pickard, P., Brown, L., Funk, J.,
Schultz, K. and Besenbruch, G. An international laboratory-scale demonstration of the
sulfur-iodine thermochemical water-splitting cycle American Institute of Chemical
Engineers, [Spring National Meeting], New Orleans, LA, United States, Mar. 30-Apr. 3,
(2003).
69. Kodama, T., Yamamoto, R., Kondo, Y. and Shimizu, K. Thermochemical watersplitting by reactive ceramic materials (1) Two-step cycle by using ZrO2-supported
ferrite Nippon Kagakkai Koen Yokoshu 83(1) (2003).
70. Fujiwara, S., Ikenoya, K., Onuki, K., Onuki, K., Nakajima, H., Nakajima, H., Shimizu,
S., Futakawa, M., Kasahara, S., Hwang, G., Choi, H., Nomura, M., Ishiyama S., Kubo,
S., Kubo, S. and Higashi, S. Application of an electrochemical membrane reactor to the
thermochemical water splitting IS process for hydrogen production Journal of
Membrane Science 240 (2004).
71. M. Serban, M.A. Lewis MA, J.K. Basco, Kinetic study for the hydrogen and oxygen
production reactions in the copper-chlorine thermochemical cycle Conference
Proceedings, 2004 AIChE Spring National Meeting, pp. 2690-2698 (2004).
72. Perkins, C. and A.W. Weimer, Likely Near Term Solar-thermal Water Splitting
Technologies, Int. J. Hydrogen Energy 29 (15), 1587-1599 (2004).
73. Abanades, S., Charvin, P., Flamant, G. and Pierre Neveu Screening of water-splitting
thermochemical cycles potentially attractive for hydrogen production by concentrated
solar energy Energy, 31(14) 2805-2822 (2006).
95
74. Wong, B., Lloyd C. Brown, Gottfried E Besenbruch, Yitung Chen, Richard Diver, B.
Earl, Sean H. T. Hsieh, K. Kwan, Barry W. McQuillan, C. Perkins, P. Phol, Roger
Rennels, N. Siegel and Alan Weimer Evaluation of Water-Splitting Cycles Applicable
to Solar Thermal Systems, Proceedings of the 13th International Symposium on
Concentrated Solar Power and Chemical Energy Technology (SolarPACES), Seville,
Spain, June 20-23 (2006).
75. McQuillan, B., Gottfried E. Besenbruch, Lloyd C. Brown, Roger A. Rennels and Bunsen
Y. Wong Metal Sulfate Water-Splitting Thermochemical Hydrogen Production Cycles,
Proceedings of the 16th World Hydrogen Energy Conference, Lyon, France, June 13-16
(2006).
76. Kolb, G. J., R. Diver and N. Siegel, Central Station Solar Hydrogen Power Plant
Journal of Solar Energy Engineering, American Society of Mechanical Engineers, May
(2007).
77. Siegel, N.P., et al., Solid particle receiver flow characterization studies, ASME
Proceedings of Energy Sustainability 2007, ES2007-36118, (2007).
78. Huajun Chen, Yitung Chen, and Hsuan-Tsung Hsieh, Computational Fluid Dynamics
Modeling of Gas-Particle Flow within a Solid-Particle Solar Receiver, Journal of Solar
Energy Engineering-Transactions of the ASME, 129 pp. 160-170, (2007).
79. Vijayarangan, B.R., Moujaes, S., Flores, M., Particle Attrition Analysis in a High
Temperature Rotating Drum, Proceedings of the Nineteenth Annual Conference On
Systems Engineering, pp. 512-518 (2008).
80. Perkins, C. and A.W. Weimer, Computational Fluid Dynamics Simulation of a Tubular
Aeorosol Reactor for Solar-thermal ZnO Decomposition, Journal of Solar Energy
Engineering, 129, 391-404 (2007).
81. Perkins, C., P.R. Lichty, and A.W. Weimer, Determination of Aerosol Kinetics of
Thermal ZnO Dissociation by Thermogravimetry, Chemical Engineering Science 62,
5952-962 (2007).
82. Perkins, C., P.R. Lichty, C. Bingham, and A.W. Weimer, Effectiveness of a Fluid-wall
for Preventing Oxidation in Solar-thermal Dissociation of ZnO, AIChE Journal, 53(7),
1830 (2007).
83. Perkins, C., P.R. Lichty, and A.W. Weimer, Thermal ZnO Dissociation in a Rapid
Aerosol Reactor as part of a Solar Hydrogen Production Cycle, Int.J. of Hydrogen
Energy, 33(2), 499-510 (2008).
84. Funke, H.H., H. Diaz, X. Liang, C.S. Carney, and A.W. Weimer, Hydrogen Generation
by Hydrolysis of Zinc Powder Aerosol, Int. J. of Hydrogen Energy, 33, 1127 1134
(2008).
85. Perkins, C. and A.W. Weimer, Solar-thermal Production of Renewable Hydrogen,
AIChE Journal 55(2), 286-293(2009).
86. Haussener, S., D. Hirsch, C. Perkins, A.W. Weimer, A. Lewandowski, A. Steinfeld,
Modeling a Multitube High-temperature Solar Thermochemical Reactor for Hydrogen
Production, Journal of Solar Energy Engineering, 131, 024503 (2009).
96
87. Francis, T., Casey S. Carney, Paul R. Lichty, Roger Rennels, and Alan W. Weimer, The
Rapid Dissociation Of Manganese Oxide To Produce Solar Hydrogen, Annual Meeting
of the American Institute of Chemical Engineers, Salt Lake City, UT Nov (2007).
88. Kilbury, O., Casey S. Carney, Hans Funke and Alan W. Weimer, "Improving Sodium
Recovery in the Hydrolysis Step of a Manganese-Oxide Thermochemical Cycle for
Hydrogen Production," Annual Meeting of the American Institute of Chemical
Engineers, Salt Lake City, UT Nov (2007).
89. M. Ferrandon, M. Lewis, D. Tatterson, A. Gross, D. Doizi, L. Croiz, V. Dauvois, J.L.
Roujou, Y. Zanella, P. Carles, Hydrogen Production by the Cu-Cl Thermochemical
Cycle: Investigation of the Key Step of Hydrolyzing CuCl2 to Cu2OCl2 and HCl Using A
Spray Reactor, to be published in International Journal of Hydrogen Energy.
90. M. A. Lewis and J. G. Masin, P.A.OHare Evaluation of alternative thermochemical
cycles. Part I: The methodology Int. J. Hydrogen Energy. 34 4115-4124 (2009).
91. M. A. Lewis and J. G. Masin, The evaluation of alternative thermochemical cycles
Part II: The down-selection process Int. J. Hydrogen Energy 34, 4125-4135 (2009).
92. M.A. Lewis, M.S. Ferrandon, D.F. Tatterson, P. Mathias, Evaluation of alternative
thermochemical cycles Part III further development of the CuCl cycle Int. J.
Hydrogen Energy 34, 4136-4145 (2009).
93. Cost Analyses on Solar-Driven High Temperature Thermochemical Water-Splitting
Cycles, TIAX, Final Report to Department of Energy, Order DE-DT0000951, February,
2011
97
Appendix A: Cycle Inventory Changes after

the Evaluation
A number of important events after the evaluation and prioritization actions affected the STCH
cycle inventory. Some of these were driven by fiscal decisions, some by external decisions, some
by end-of-contract/award events and some by prosecution of the critical path tasks identified in
the evaluation. Listed below, by cycle name, are significant changes in the STCH program.
Sulfur Iodine and Hybrid Sulfur

Immediately prior to the termination of the Nuclear Hydrogen Initiative in the Office of Nuclear
Energy, a formal advisory panel conducted a competitive evaluation of the nuclear cycles Hybrid
Sulfur, Sulfur Iodine and High Temperature Electrolysis (HTE). Panel deliberations were not
made public in accord with Federal law, but recommendation was made to terminate both Hybrid
Sulfur and Sulfur Iodine in favor of emphasis on THE investment. Research and development of
these thermochemical cycles has terminated. No planning has been forthcoming for continuation
of solar energy integration and analysis of performance of the Hy-Sulfur and Sulfur Iodine
cycles.

Evaluation of cost and effectiveness of a spectrum-splitting mirror and cost analysis of a dual
solar field design concluded that the photolysis concept would not be cost effective. The Sulfur
Ammonia cycle continues as a hybrid-electrolysis concept. The intermediate ZnO/ZnSO4 steps
were replaced with intermediate K2SO4/K2S2O7 steps. It is noted that the most recent quarterly
report reverted to the ZnO/ZnSO4 subcycles without clarification.
Zinc Oxide
Research and development of the ZnO cycle has been terminated. Grounds for renewing
investment in this cycle are discussed in Sections 4.4 and 5.2.4 .
Cadmium Oxide
The critical issue for the CdO cycle was determined to be managing recombination in the quench
step to assure adequate supply of metallic molten Cd for hydrolysis in a closed system. Priority
was given to developing a model of a molten Cd spray quench that would perform this step
effectively. Some progress in an equilibrium spreadsheet quench model without fluid dynamics
was reported but not verified. Fiscal restraint on the overall program resulted in loss of funding
to continue research and development of this cycle. Should funds become available for
resumption of work the priority tasks discussed in Sections 4.5 and 5.2.5 remain unchanged.
98
Sodium Manganese and Sodium Manganate

Sodium recovery remains the critical issue for these high thermal efficiency cycles. Funding and
period-of-performance of the efforts have been expended and no research and development work
is proceeding presently. Discovery of a sodium-selective ion transfer membrane has renewed
interest in the Sodium Manganese cycle but new work awaits a new Department solicitation or
funding from some other source.
Current STCH Cycle Inventory

The STCH cycle inventory current with this report consists of
Hybrid Sulfur Ammonia
ALD Ferrite
Other Nonvolatile Metal Oxide research may be proceeding under STCH, but these have not
been reported to the author.
99
Appendix B: Criteria Scores Established for the Four

Solar Technologies
The tables listed on the following pages contain criteria scores as determined by the STCH
project group for initial scoring of cycles. The scores are tabulated according to the Process
Identification number (PID). The correlation of the thermochemical cycle with the PID is
tabulated in a second set of tables in this Appendix B.
The tabulated criteria scores include the various solar technologies scores as multiple
Criterion 8 entries. These are in order (left to right) Trough Technology, Standard Tower
Technology, Advanced Tower Technology and Dish Technology.
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
Distribution
1
8360
Jay Keller
9052
2
1
9018
0899
Central Technical Files

Technical Library
8944
4536
Robert Perret
Nevada Technical Services, LLC
PO Box 531
Red Lodge, MT 59068
117

Solar Thermochemical

Uploaded by

Copyright:

Available Formats

Solar Thermochemical

Uploaded by

Document Information

Original Description:

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Solar Thermochemical

Uploaded by

Copyright:

Available Formats

SANDIA REPORT

Solar Thermochemical Hydrogen

Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia

Approved for public release; further dissemination unlimited.

Available to the public from

Solar Thermochemical Hydrogen

Appendix A: Cycle Inventory Changes after the Evaluation ................................................ 98

Schematic chemistry of a water-splitting ferrite cycle. ........................................78

This page intentionally left blank.

This page intentionally left blank.

1.1 STCH Basis

Volatile Metal Oxide:

Hybrid Copper Chloride:

Figure 1.1. Thermochemical cycle class examples.

1.2 STCH Historical Summary

1.3 STCH Decision Framework

Cost target ($/gge)

Process efficiency (%)

Target schedule transition

This page intentionally left blank.

2 Cycle Inventory Development and Initial Selection

2.1 Economic Consideration

2.2 Solar Collector/Receiver Consideration

2.3 Previous Level of Effort for Candidate Cycle

Criterion 12. Energy efficiency and cost

2.4 Safety and Environmental Consideration

perceived importance to the development and implementation of a central production plant.

Table 2.1. Relative importance of criteria to plant development and operation.

Table 2.2. Solar-device criteria weighting factors.

Hybrid Cobalt Br-2

Sulfuric Acid Cycles

Volatile Metal Oxides

3 Formal Cycle Evaluation and Research

Table 3.1. Cycles considered in the formal evaluation process.

Volatile Metal Oxide Cycles

Non-volatile Metal Oxide

General Atomics, Sandia

Savannah River National

Sodium Manganese and Sodium

Hybrid Copper Chloride

Argonne National Laboratory

Photolytic Sulfur Ammonia

Hybrid Sulfur had progressed to demonstration of an electrolytic step that nonetheless

Cadmium Oxide had progressed to demonstration of hydrolysis and CdO

Sodium Manganese had progressed in step-wise fashion to a point where a

Preliminary experimental work on the ALD Ferrite material suggested durability

schedule and likelihood of demonstrating cycle technical feasibility

obstacles and proposed resolutions for the above two issues

projected performance in terms of DOE targets

likelihood of overcoming R&D obstacles

likelihood of meeting system/engineering requirements

Is the listing of proven and unproven pathway elements comprehensive?

c. Listing of materials and component challenges accompanying a laboratory scale

Have all materials and components requirements been addressed?

ii. Are all raw materials readily available?

Are the assumptions reasonable?

ii. Are all assumptions identified?

Is the schedule consistent with stated workforce and budget requirements?

vi. Is the schedule consistent with the DOE Program Plan?