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Appendix C
Interim Report
255
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257
APPENDIX C
Waste Forms Technology and Performance
INTERIM REPORT
Committee on Waste Forms Technology and Performance
Nuclear and Radiation Studies Board
Division on Earth and Life Studies
THE NATIONAL ACADEMIES PRESS
Washington, D.C.
www.nap.edu
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258 APPENDIX C
THE NATIONAL ACADEMIES PRESS 500 Fifth Street, N.W. Washington, DC 20001
NOTICE: The project that is the subject of this report was approved by the Governing Board of
the National Research Council, whose members are drawn from the councils of the National
Academy of Sciences, the National Academy of Engineering, and the Institute of Medicine. The
members of the committee responsible for the report were chosen for their special competences
and with regard for appropriate balance.
This study was supported by Contract No. DE-FC01-04EW07022 between the National
Academy of Sciences and the U.S. Department of Energy. Any opinions, findings, conclusions,
or recommendations expressed in this publication are those of the author(s) and do not
necessarily reflect the views of the organizations or agencies that provided support for the
project.
This report is available online at www.nap.edu.
Copyright 2010 by the National Academy of Sciences. All rights reserved.
Printed in the United States of America
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APPENDIX C
The National Academy of Sciences is a private, nonprofit, self-perpetuating society of
distinguished scholars engaged in scientific and engineering research, dedicated to the
furtherance of science and technology and to their use for the general welfare. Upon the
authority of the charter granted to it by the Congress in 1863, the Academy has a
mandate that requires it to advise the federal government on scientific and technical
matters. Dr. Ralph J. Cicerone is president of the National Academy of Sciences.
The National Academy of Engineering was established in 1964, under the charter of
the National Academy of Sciences, as a parallel organization of outstanding engineers.
It is autonomous in its administration and in the selection of its members, sharing with
the National Academy of Sciences the responsibility for advising the federal government.
The National Academy of Engineering also sponsors engineering programs aimed at
meeting national needs, encourages education and research, and recognizes the
superior achievements of engineers. Dr. Charles M. Vest is president of the National
Academy of Engineering.
The Institute of Medicine was established in 1970 by the National Academy of
Sciences to secure the services of eminent members of appropriate professions in the
examination of policy matters pertaining to the health of the public. The Institute acts
under the responsibility given to the National Academy of Sciences by its congressional
charter to be an adviser to the federal government and, upon its own initiative, to identify
issues of medical care, research, and education. Dr. Harvey V. Fineberg is president of
the Institute of Medicine.
The National Research Council was organized by the National Academy of Sciences
in 1916 to associate the broad community of science and technology with the Academy’s
purposes of furthering knowledge and advising the federal government. Functioning in
accordance with general policies determined by the Academy, the Council has become
the principal operating agency of both the National Academy of Sciences and the
National Academy of Engineering in providing services to the government, the public,
and the scientific and engineering communities. The Council is administered jointly by
both Academies and the Institute of Medicine. Dr. Ralph J. Cicerone and Dr. Charles M.
Vest are chair and vice chair, respectively, of the National Research Council.
www.national-academies.org
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260 APPENDIX C
Nuclear and Radiation Studies Board 500 Fifth Street, NW
Washington, DC 20001
Phone: 202 334-3066
Fax: 202 334-3077
www.nationalacademies.org
June 15, 2010
Yvette Collazo
Deputy Assistant Secretary for Technology
Innovation and Development
Office of Environmental Management
U.S. Department of Energy
Washington, DC 20585
Subject: Interim Report on Waste Form Technology and Performance
Dear Ms. Collazo:
The Committee on Waste Forms Technology and Performance (Attachment B)
was appointed by the National Research Council in May 2009 to examine requirements
for waste form (Box 1) technology and performance in the context of the disposal system
in which the waste will be emplaced. The complete statement of task for this study is
given in Box 2.
The Department of Energy, Office of Environmental Management (DOE-EM)
requested this interim report to provide timely information for fiscal year 2011 technology
development planning. The committee has focused this interim report on
opportunities associated with selected aspects of the last three bullets of its
statement of task (Box 2). These tasks are:
The state-of-the-art tests and models of waste forms used to predict their
performance for time periods appropriate to their disposal system. 1
Potential modifications of waste form production methods that may lead to
more efficient production of waste forms that meet their performance
requirements.
Potential new waste forms that may offer enhanced performance or lead to
more efficient production.
The committee judges that the opportunities identified in this report are sufficiently
mature to justify consideration by DOE-EM as it plans its fiscal year 2011 technology
development program.
1
The focus of this interim report is primarily on tests and models for assessing waste form
durability (see Footnote 6). The final report will provide a more detailed discussion of waste form
performance over time periods of concern for disposal.
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Box 1: Waste Forms
The International Atomic Energy Agency defines waste immobilization as the
conversion of a waste into a waste form by solidification, embedding, or encapsulation.
The waste form can be produced by chemical incorporation of the waste species into the
structure of a suitable matrix (typically a glass or ceramic) so that the radioactive species
are atomistically bound in the structure. Chemical incorporation is typical for high-level
radioactive waste. Encapsulation of waste, on the other hand, is achieved by physically
surrounding it in materials (typically bitumen, grout, or cement) so it is isolated and
radionuclides are retained. Encapsulation is typically used for low-level or intermediate-
level waste and may include some chemical incorporation.
The primary role of a waste form is to immobilize radioactive and/or hazardous
constituents in a stable, solid matrix for storage and eventual disposal. In a well-designed
disposal system, the waste forms and disposal facility into which they are emplaced work
together to sequester radioactive and hazardous constituents. The near-field environment
of the disposal site and other engineered barriers, if present, establish the physical and
chemical bounds within which the waste form performs its sequestering function. This
promotes the maintenance of waste form integrity over extended periods, which helps to
slow the release of radioactive and other hazardous constituents from the waste form and
the transport of these constituents out of the disposal facility.
In addressing these charges, the committee has focused primarily, but not
exclusively, on high-level radioactive waste (HLW) cleanup, which is the longest
schedule, highest cost, highest risk, and arguably DOE-EM’s most difficult technical
cleanup challenge (see, for example, DOE, 1998, 2010a; NRC, 2001, 2006). At present,
tank waste retrieval and closure are limited by schedules for treating and immobilizing
HLW in the Defense Waste Processing Facility, which is currently operating at the
Savannah River Site; the Waste Treatment Plant, which is under construction at the
Hanford Site; and a facility to be designed and constructed at the Idaho Site.
Accelerating schedules for treating and immobilizing HLW by introducing new and/or
improved waste forms and processing technologies could also accelerate tank waste
retrieval and closure schedules.
The committee used its expert judgment to identify the opportunities described in
this report. This judgment was informed through a series of briefings, site visits, and a
scientific workshop. The committee received briefings on DOE’s current programs and
future plans for waste processing, storage, and disposal from DOE-EM, national
laboratory, and contractor staff, including information on comparable international
programs. The committee visited the Hanford Site (Washington), Idaho Site, Savannah
River Site (South Carolina), and their associated national laboratories (Pacific Northwest
National Laboratory, Idaho National Laboratory, and Savannah River National
Laboratory, respectively) to observe DOE’s waste processing and waste form production
programs and to hold technical discussions with site and laboratory staff. The committee
also organized a workshop to discuss scientific advances in waste form development
and processing. This workshop, which was held in Washington, D.C., on November 4,
2009, featured presentations from researchers in the United States, Russia, Europe, and
Australia. The workshop agenda is provided in Attachment C.
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Box 2: Statement of Task
The National Academies will examine the requirements for waste form technology and
performance in the context of the disposal system in which the waste form will be
emplaced. Findings and recommendations will be developed to assist DOE in making
decisions for improving current methods for processing radioactive wastes and for
selecting and fabricating waste forms for disposal. The study will identify and describe:
Essential characteristics of waste forms that will govern their performance
within relevant disposal systems. This study will focus on disposal systems
associated with high-cost waste streams such as high-level tank waste and
calcine but include some consideration of low-level and transuranic waste
disposal.
Scientific, technical, regulatory, and legal factors that underpin requirements
for waste form performance.
The state-of-the-art tests and models of waste forms used to predict their
performance for time periods appropriate to their disposal system.
Potential modifications of waste form production methods that may lead to
more efficient production of waste forms that meet their performance
requirements.
Potential new waste forms that may offer enhanced performance or lead to
more efficient production.
The committee will not make recommendations on applications of particular
production methods or waste forms to specific EM waste streams.
A major focus of the DOE-EM cleanup program is on retrieving legacy wastes
resulting from nuclear weapons production and testing and processing them into waste
forms suitable for disposal in onsite or offsite facilities. Some waste requires minimal
processing to make it suitable for disposal; for example, lightly contaminated solid waste
generated during facility decommissioning may be suitable for disposal in near-surface
engineered facilities with little or no processing. Other waste will require more extensive
processing to make it suitable for disposal; for example, HLW, liquid wastes from facility
decontamination, contaminated resins from groundwater cleanup, and radioactive
sources and other nuclear materials used in civilian and defense applications may
require processing to destroy organic components; to remove components that are
incompatible with the processing method or final waste form or that are not acceptable
for disposal; and to immobilize radioactive and other hazardous components. DOE-EM
is using a variety of waste forms to immobilize these components.
The committee observes that the DOE-EM cleanup program is successfully
processing waste and producing waste forms at several sites. For example, DOE
has completed HLW vitrification at the West Valley, New York, site. DOE is also
retrieving HLW from tanks at the Savannah River Site, separating it into high-activity and
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low-activity waste streams, and processing these waste streams into high-activity waste
glass for disposal in a future geologic repository and low-activity waste saltstone for
near-surface onsite disposal. However, DOE-EM’s cleanup program is not expected to
be completed for at least another four decades. Consequently, as this program
continues, DOE-EM will have opportunities to incorporate emerging developments in
science and technology on waste forms and waste form production technologies into its
baseline approaches to increase program efficiencies, reduce lifecycle costs and risks,
and advance scientific understanding of and stakeholder confidence in waste form
behavior in different disposal environments. In short, scientific advances, both now and
in the future, will offer the potential for better solutions to DOE-EM’s waste management
challenges. It may be important for DOE-EM to maintain sufficient flexibility in its cleanup
program to take advantage of these advances.
Based on an analysis of the information it has gathered, the committee
observes that waste form science and technology have advanced significantly
over the past three decades. The committee judges that there are opportunities to
apply these advances in the DOE-EM cleanup program, both now and in the
future, to reduce schedules, costs, and risks. The committee offers several
observations about potential opportunities in this interim report. Detailed findings and
recommendations will be provided in the committee’s final report.
Waste form-relevant science and technology are advancing rapidly along several
fronts—for example, chemical and materials processing in industry, waste management
in advanced nuclear fuel cycle programs, and management of special nuclear materials
in national security applications. There have been numerous recent reports on the
development of waste forms and processing technologies for advanced nuclear fuel
cycles; some examples are given in Attachment D. Examples of these technologies
include:
Waste form materials designed for significantly higher waste loadings or for
improved performance in specific disposal environments.
Waste processing technologies that can handle large volumes of highly
radioactive wastes or that produce highly uniform waste form products.
Advanced analytical and computational techniques that can be used to
understand and quantitatively model interactions between waste forms and
near-field 2 environments of disposal facilities.
Many of these technologies are potentially applicable to DOE-EM waste streams.
However, not all are ready for full-scale implementation.
This interim report and the committee’s final report provide only snapshots of
these advances. To take full advantage of future scientific and technological
2
The near-field environment is generally taken to include the engineered barriers in a disposal
system (e.g., waste canisters) as well as the host geologic media in contact with or near these
barriers whose properties have been affected by the presence of the repository. The far-field
environment is generally taken to include areas beyond the near field, including the biosphere
(e.g., OECD-NEA, 2003).
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advances, DOE-EM will need to identify, develop where needed, and incorporate
where appropriate state-of-the-art science and technology on waste forms and
waste form production processes, especially for high-cost, high-risk, and/or
orphan 3 waste streams. DOE-EM can become cognizant of scientific and technological
advances by collaborating with appropriate governmental, scientific, and technical
organizations to identify waste forms and waste form production technologies that are
potentially applicable to DOE-EM waste streams. For example, collaborations can be
established with other DOE offices, 4 especially the Office of Science and Office of
Nuclear Energy; other government agencies (e.g., Department of Defense); scientific,
academic, and industrial organizations; and especially other nations’ radioactive waste
management programs.
DOE-EM is operating its cleanup program under various regulatory requirements
and legal agreements with states and the U.S. Environmental Protection Agency.
Modifications of existing requirements or agreements might be necessary before DOE-
EM could implement the technologies identified in this report. However, it is outside of
the committee’s scope to consider how the use of the technologies identified in this
report might impact those requirements and agreements.
WASTE FORM AND PROCESSING OPPORTUNITIES
The committee has identified four opportunities consistent with its statement of
task (Box 2):
Production of crystalline ceramic 5 waste forms using fluidized bed steam
reforming
Production of glass, glass composite, and crystalline ceramic waste forms
using cold crucible induction melters
Production of glass, glass composite, and crystalline ceramic waste forms
using hot isostatic pressing
Evaluation of the long-term durability of new waste form materials using
experimental studies, laboratory tests, and model development
3
A waste stream is referred to as orphan when it has no clear-cut disposition pathway. The DOE-
EM cleanup program has identified several orphan waste streams including, for example, actinide
targets, beryllium reflectors, certain radioactive wastes produced outside of the nuclear fuel cycle,
and sealed radiation sources. Many of these orphan waste streams are volumetrically small
compared to the inventories of high-level waste, transuranic waste, and low-level waste that exist
at DOE sites.
4
See, for example, the basic research needs reports that are listed in Attachment D.
5
A crystalline material has a well-defined, periodic-ordering of its atomic structure. Crystalline
ceramic materials can consist of one or more crystalline phases. In contrast, a glass is aperiodic
and lacks long-range atomic-scale ordering. Glass composite materials consist of a mixture of
both glass and crystalline phases.
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The first three opportunities involve new applications of existing technologies to
DOE-EM waste streams. These waste form production technologies are being used
commercially and appear to be applicable for processing and immobilizing a range of
DOE-EM waste streams, especially HLW streams. DOE-EM is already planning to apply
these technologies to some of its waste streams, as discussed in the following sections.
The committee concurs with DOE-EM about the applicability of these technologies and
offers observations in this interim report on the wider application of these technologies in
the cleanup program.
The fourth opportunity involves extending the application of experiments, tests,
and model development for evaluating the durability 6 of new waste form materials over
time periods for concern for disposal (typically 103-106 years). This would provide DOE-
EM with future flexibility to use new waste forms in its cleanup program and enhance the
long-term safety of disposal.
Fluidized Bed Steam Reforming Technology
Fluidized Bed Steam Reforming (FBSR; see Attachment E for a brief technology
description) is a robust technology for processing wastes. Its primary advantages are
high throughput and ability to accommodate a wide range of feeds and additives,
including feeds containing anionic sulfur and nitrogen species, halides, and organics that
are incompatible with some other types of waste forms and waste form production
processes.
FBSR is based on fluidized bed technology, which was invented in the 19th
century and found widespread use in the refining and chemical industries starting around
World War II. Applications of fluidized bed technology in nuclear fuel production, fuel
recovery, and waste processing date back to late 1950s and early 1960s. For example,
fluidization was used for the reduction and hydrofluorination of uranium concentrates
and calcination of high-level radioactive waste. Two calcination facilities were
successfully operated at the Idaho National Engineering Laboratory (now Idaho National
Laboratory) from 1963 to 1981 and from 1981 to 2000 to immobilize HLW.
The FBSR process is already being used commercially for processing nuclear
waste. A commercial facility to continuously process organic radioactive wastes at
moderate temperatures in a hydrothermal steam environment was built by Studsvik in
Erwin, Tennessee, in 1999. The Erwin facility uses a steam reforming technology,
referred to as THermal Organic Reduction (THOR®), to pyrolyze organic resins loaded
with Cs-137 and Co-60 from commercial nuclear facilities. The Erwin facility has the
current capability to process a wide variety of solid and liquid streams including ion
exchange resins, charcoal, graphite, sludge, oils, solvents, and cleaning solutions at
radiation levels of up to 400R/hr (Mason et al., 1999).
6
Durability is a measure of the resistance of a waste form to physical and chemical alteration and
the associated release of contained radioactive or hazardous constituents.
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Attachment A: References
ASME (American Society of Mechanical Engineers). 1985. The Evolution of HIP:
Commemorating the First Hot and Cold Isostatic Processing Vessels. ASME
Landmarks Program. Available at
http://files.asme.org/ASMEORG/Communities/History/Landmarks/5569.pdf
Clarke, D.R. 1981. Preferential dissolution of an intergranular amorphous phase in a
nuclear waste ceramic. J. Am. Ceram. Soc 64, C89-90.
Cooper, J.A., Cousens, D.R., Hanna, J.A., Lewis, R.A., Myhra, S., Segall, R.L., Smart,
R. St.C., Turner, P.S., and T.J. White, 1986. Intergranular films and pore
surfaces in Synroc C: Structure, Composition, and Dissolution characteristics, J.
Am. Ceram. Soc, 69(4), 347-352.
DOE (U.S. Department of Energy). 1998. Accelerating Cleanup: Paths to Closure.
DOE/EM-0362. Washington, D.C.: Office of Environmental Management.
DOE. 2010a. Technical Evaluation of Strategies for Transforming the Tank Waste
System: Tank Waste System Integrated Project Team Final Report. Washington,
D.C.: U.S. Department of Energy.
DOE. 2010b. Amended Record of Decision: Idaho High-Level Waste and Facilities
Disposition Final Environmental Impact Statement Revised by State 12/21/09.
Federal Register 75(1), 137-140. Available at
http://edocket.access.gpo.gov/2010/pdf/E9-31151.pdf.
Elliott, M.L. 1996. Letter report: Cold Crucible Melter Assessment. PNNL-11018.
Richland, Wash.: Pacific Northwest National Laboratory.
IPET [Independent Project Evaluation Team]. 2003. Technical Evaluation of Hanford
HLW Vitrification Process Alternatives: Report of the Independent Project
Evaluation Team. U.S. Department of Energy.
Jantzen, C.M. 2004. Disposition of Tank 48H Organics by Fluidized Bed Steam
Reforming (FBSR). WSRC-TR-2003-00352, Rev. 1. Aiken, S.C.: Westinghouse
Savannah River Co.
Jantzen, C.M. 2006. Fluidized Bed Steam Reformer (FBSR) Product: Monolith
Formation and Characterization. WSRC-STI-2006-00033. Aiken, S.C.:
Westinghouse Savannah River Co..
Jantzen, C.M. and M.R. Williams. 2008. Fluidized bed steam reforming (FBSR)
mineralization for high organic and nitrate waste streams for the Global Nuclear
Energy Partnership (GNEP), Waste Management ‘08, Paper #8314.
Marshall, D.W., Soelberg, N.R., and K.M. Shaber. 2003. THORsm Bench-Scale Steam
Reforming Demonstration. INEEL/EXT-03-00437. Idaho Falls: Idaho National
Engineering & Environmental Laboratory.
Mason, J.B., Oliver, T.W., Carson, M.P., and G.M. Hill. 1999. Studsvik Processing
Facility Pyrolysis/Steam Reforming Technology for Volume and Weight
Reduction and Stabilization of LLRW and Mixed Wastes, Waste Management
‘99.
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NRC [National Research Council]. 2001. Research Needs for High-Level Waste Stored
in Tanks and Bins at U.S. Department of Energy Sites. Washington, D.C.:
National Academy Press.
NRC. 2006. Tank Waste Retrieval, Processing, and On-Site Disposal at Three
Department of Energy Sites. Washington, D.C.: National Academy Press.
OECD-NEA [Organisation for Economic Co-Operation and Development, Nuclear
Energy Agency]. 2003. Engineered Barrier Systems and the Safety of Deep
Geological Repositories: State-of-the-art Report. Paris, France: OECD. 76 pp.
Steefel, C.I., DePaolo, D.J., and P. C. Lichtner. 2005. Reactive transport modeling: An
essential tool and a new research approach for the Earth sciences. Earth and
Planetary Science Letters 240, 539-558.
Vernaz, E.Y., and C. Poinssot. 2008. Overview of the CEA French Research Program
on Nuclear Waste. Mater. Res. Soc. Symp. Proc. 1107.
Vernaz, E.Y. 2009. (editor) Nuclear Waste Conditioning. Paris, France: Commissariat à
l'Énergie Atomique.
Zhang Z., and M.L. Carter. 2010. An X-ray photoelectron spectroscopy investigation of
highly soluble grain-boundary impurity films in hollandite. J. Am. Ceram. Soc.
93(3), 894-899.
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Attachment B: Committee on Waste Forms Technology and Performance
MILTON LEVENSON, Chair, Bechtel International (retired), Menlo Park, California
RODNEY C. EWING, Vice Chair, University of Michigan, Ann Arbor
JOONHONG AHN, University of California, Berkeley
MICHAEL J. APTED, INTERRA, Inc., Denver, Colorado
PETER C. BURNS, University of Notre Dame, Notre Dame, Indiana
MANUK COLAKYAN, Dow Chemical Company (retired), South Charleston, West Virginia
JUNE FABRYKA-MARTIN, Los Alamos National Laboratory, Los Alamos, New Mexico
CAROL M. JANTZEN, Savannah River National Laboratory, Aiken, South Carolina
DAVID W. JOHNSON, JR, Bells Labs (retired), Bedminster, New Jersey
KENNETH L. NASH, Washington State University, Pullman
TINA M. NENOFF, Sandia National Laboratories, Albuquerque, New Mexico
Staff
KEVIN D. CROWLEY, Study Director
DANIELA STRICKLIN, Study Director (Through February 12, 2010)
SARAH CASE, Staff Officer
TONI GREENLEAF, Administrative and Financial Associate
SHAUNTEÉ WHETSTONE, Senior Program Assistant
JAMES YATES, JR., Office Assistant
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Attachment C: Workshop Agenda
Workshop on Waste Form Technology and Performance
The Lecture Room
The National Academy of Sciences (NAS) Building
2101 Constitution Avenue, NW, Washington, DC 20418
Wednesday, November 4, 2009
Welcome and Introduction
8:15-8:30 am
Milt Levenson and Rod Ewing
Session I: International Perspectives
Glass and spent fuel corrosion, coupling of waste forms to the
8:30–9:00 am
near field, and long-term models of performance
Berndt Grambow, Laboratoire De Physique Subatomique Et Des
Technologies Associees (SUBATECH), France
Cementatious waste forms and barriers
9:00–9:30 am
Fred Glasser, University of Aberdeen, UK
Combined inert matrix fuels and related waste forms
9:30-10:00 am
Claude Degueldre, Paul Sheerer Institute, Switzerland
Break
10:00-10:30 am
Ceramic and phosphate glass waste forms and cold crucible
10:30-11:00 pm
technology
Sergey Stefanovsky, SIA Radon, Russia
Overview of CEA’s and French initiatives related to waste forms
11:00-11:30 pm
Etienne Vernaz, Commissariat à l'Énergie Atomique, France
Overview of Australia/ANSTO initiatives related to waste forms
11:30-12:00 pm
Kath Smith and Bruce Begg, Australian Nuclear Science and
Technology Organisation (ANSTO), Australia
Lunch
12:00-1:00 pm
Session II: Select Domestic Issues
Computational methods applied to the design and evaluation of
1:00–1:30 am
waste forms
Bill Weber, Pacific Northwest National Laboratory
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Overview of waste forms and near-field interactions in a
1:30-2:00 pm
performance assessment perspective
Carl Steefel, Lawrence Berkeley National Laboratory
Matching waste forms to waste processing strategies
2:00-2:30 pm
Mark Peters, Argonne National Laboratory
Impact of waste forms on overall repository performance
2:30-3:00 pm
assessment
Peter Swift, Sandia National Laboratories
Break
3:00-3:15 pm
Overview of the Vitreous State Laboratory and geopolymer
3:15-3:45 pm
development
Ian Pegg and Werner Lutze, Catholic University of America
Cementitious Barriers Partnership
3:45-4:15 pm
David Kosson, Vanderbilt University
Industry perspectives on potential waste forms from recycling
4:15-4:45 pm
Rod McCullum, Nuclear Energy Institute
Panel discussion
4:45-5:15 pm
All participants
Adjourn
5:15 pm
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Attachment D: Selected Recent Reports on Science and Technology
for Waste Immobilization
Summary Report of the Nuclear Energy Research Initiative Workshop, April 23-25, 1998
(see the report of working group #4). Available at
http://www.ne.doe.gov/pdfFiles/nerachWorkshop.pdf.
Basic Research Needs for Advanced Nuclear Energy Systems, July 31- August 3, 2006
(see the panel #5 report on advanced waste forms). Available at
http://www.er.doe.gov/bes/reports/files/ANES_rpt.pdf.
Basic Research Needs for Geosciences: Facilitating 21st Century Energy Systems,
February 21-23, 2007 (see sections related to subsurface geologic storage and
modeling/simulation of geologic systems). Available at
http://www.er.doe.gov/bes/reports/files/GEO_rpt.pdf.
Basic Research Needs for Materials under Extreme Environments, June 11-13, 2007
(see section on nuclear energy). Available at
http://www.er.doe.gov/bes/reports/files/MUEE_rpt.pdf.
Global Nuclear Energy Partnership Integrated Waste Management Strategy Waste
Treatment Baseline Study. GNEP-WAST-AI-RT-2007-00034. 2007 (see vol. 1
sections on processing and stabilization with different types of waste forms).
Directing Matter and Energy: Five Challenges for Science and the Imagination, A Report
from the Basic Energy Sciences Advisory Committee, 2007 (see chapter 7 on
designing new materials). Available at
http://www.er.doe.gov/bes/reports/files/GC_rpt.pdf.
Advice on the Department of Energy’s Cleanup Technology Roadmap: Gaps and
Bridges. 2009. National Academies Press. Available at
http://www.nap.edu/openbook.php?record_id=12603&page=1.
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Attachment E: Fluidized Bed Steam Reforming
A bed of granular material can be made to exhibit fluid-like properties by passing
a liquid or gas through it. This process is referred to as fluidization, and the apparatus
that supports this process is referred to as a fluidized bed. Fluidization came to age
during World War II, when the urgent demand for aviation gasoline led to the
development and construction of the first fluid bed catalytic cracker. In addition to
gasoline production, fluidization technology is broadly used in coal gasification and
combustion, mineral processing, food processing, pharmaceuticals, soil washing,
manufacturing of polymers, waste treatment, and environmental remediation. Its
applications include several unit operations such as drying, heating/cooling, particle
coating, and chemical reactions.
The Fluidized Bed Steam Reforming (FBSR) of nuclear waste is a relatively new
technology, though the fluidization phenomenon and steam reforming are well
established in the chemical engineering field. Steam reforming is a method for
generating hydrogen by reacting fossil fuels with water. For example, for natural gas:
CH4(g) + H2O(g) CO(g) + 3H2(g)
If coal is used as a carbon source, it first undergoes pyrolysis or devolatilization then the
char (C) reacts with steam according to the following reaction:
C(s) + H2O(g) CO(g) + H2(g)
The H2 is combined with O2 so that no excess H2 exists in the system at any one time.
This combination is exothermic and provides energy in the form of heat for the
autocatalytic operation of the FBSR.
The FBSR consists of two fluidized beds. The first one operates in a reducing
environment and its function is to evaporate the liquid nuclear waste stream; destroy
organics; reduce nitrates, nitrites, and nitric acid to nitrogen gas; and form a stable solid
waste product. The first stage fluidized bed of the FBSR process is referred to as the
Denitration and Mineralization Reformer, or DMR. The DMR uses superheated steam as
the fluidizing media. The bed material consists of granular solid additives and co-
reactant(s), such as carbon, clay, silica, and/or catalysts. Liquid waste is directly fed to
the fluidized bed after minor pre-treatment (e.g., to concentrate or dilute solubles) except
the addition of clay.
By analogy to the above steam reforming chemistry, the carbon fed to FBSR
(coal in this instance) produces H2 and CO. For organic compounds in the waste stream
which undergo pyrolysis to form various hydrocarbons, the reducing environment is
generated by the following reaction:
CnHm(g) + nH2O(g) nCO(g) + (n + m/2)H2(g)
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Similarly, the nitrates contained in the liquid waste are reduced to
2NaNO3(g) + 3C(s) 2NO(g) + 3CO(g) + Na2O(s)
In the steam environment, the sodium oxide is transferred to sodium hydroxide:
Na2O(s) + H2O(g) 2NaOH(s,l)
yielding the overall reaction
2NaNO3(g) + 3C(s) + H2O(g) 2NO(g) + 3CO(g) + 2NaOH(s,l)
2NaNO3(g) + 2C(s) + H2O(g) 2NO2(g) + 2CO(g) + 2NaOH(l,s)
The NO and NO2 are further reduced to nitrogen gas by the reaction of CO, C, or
H2 generated from the reaction of the organic material with steam as shown above. The
nitrates can also be reduced by the addition of a catalyst or a metal. For example:
2NaNO3(g) + 5Fe(s) + H2O(g) N2(g) + 5FeO(s) + 2NaOH(s,l)
The second fluidized bed of the FBSR process operates in an oxidizing
environment and is referred to as the Carbon Reduction Reformer, or CRR. The
fluidizing gases are the off-gas from the first stage and added oxygen. Its function is to
gasify carbon fines carried over in the process gases from the DMR, oxidize CO and H2
to CO2 and water, and convert trace acid gases to stable alkali compounds by reacting
these acids with the bed media consisting of calcium carbonate and/or calcium silicate
particles.
The addition of bulk aluminosilicates to the fluidized bed results in the production
of anhydrous feldspathoid phases such as sodalite. The sodalite family of minerals
(including nosean) are unique because they have cage-like structures formed of
aluminosilicate tetrahedra. The remaining feldspathoid minerals, such as nepheline,
have a silica “stuffed derivative” ring type structure. The cage structures are typical of
sodalite and/or nosean phases where leach testing has indicated that the cavities in the
cage structure retain anions and/or radionuclides which are ionically bonded to the
aluminosilicate tetrahedra and to sodium cation.
Sodalite has the formula Na8[Al6Si6O24](Cl2). In sodalites and analogues with
sodalite topologies, the cage is occupied by two sodium and two chlorine ions. When the
2NaCl are replaced by Na2SO4, the mineral phase is known as nosean,
(Na6[Al6Si6O24](Na2SO4)). Since the Cl, SO4, and/or S2, are chemically bonded and
physically restricted inside the sodalite cage structure, these species do not readily leach
out of the respective FBSR waste form mineral phases. Thus, FBSR waste forms can be
useful for immobilizing these species to prevent their leaching into groundwater.
Other minerals in the sodalite family, namely hauyne and lazurite which are also
cage structured minerals, can accommodate either (SO4=) or (S=) depending on the
REDOX of the sulfur during the steam reforming process. Sodalite minerals are known
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to accommodate Be in place of Al and S2 in the cage structure along with Fe, Mn, and
Zn, e.g., helvite (Mn4[Be3Si3O12]S), danalite (Fe4[Be3Si3O12]S), and genthelvite
(Zn4[Be3Si3O12]S). These cage-structured sodalites were minor phases in HLW
supercalcine waste forms and were found to retain Cs, Sr, and Mo into the cage-like
structure, e.g., Mo as Na6[Al6Si6O24](NaMoO4)2. In addition, sodalite structures are
known to retain B, Ge, I, and Br in the cage-like structures. Indeed, waste stabilization at
Idaho National Laboratory currently uses a glass-bonded sodalite ceramic waste form
(CWF) for disposal of electrorefiner wastes for sodium-bonded metallic spent nuclear
fuel from the EBR II fast breeder reactor.
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Attachment F: Joule Heated Melters
The DOE-EM program for immobilizing high-level waste currently utilizes Joule-
heated melters (JHMs) to produce high-level waste waste glass. In Joule heating an
electric current is passed through a material, in this case glass. The internal resistance
of the material causes the electric currents to be dissipated as heat. A JHM is usually
lined with refractory, and the glass is Joule heated by electricity transferred through the
melt between nickel-chromium alloy electrodes, usually Inconel. The nominal melt
temperature in JHMs is 1150°C, which is only 200°C lower than the melting point of the
Inconel electrodes. These melters can be calcine fed or slurry fed and vitrification is a
continuous or semi-continuous process.
JHM’s have been used for waste glass production in the United States, France,
and Japan because of the high production rate and high glass quality. The size of these
systems is limited only by the replacement crane capacity since all the structural support
is provided by a stainless steel shell which contains the refractory. The Defense Waste
Process Facility at Savannah River Site is the largest production melter of this type ever
built. A larger one is under construction for use at the Waste Treatment Plant at the
Hanford Site and replacement of this system (due to its size) is by rail instead of by
crane.
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Attachment G: Reviewer Acknowledgments
This report has been reviewed in draft form by individuals chosen for their
diverse perspectives and technical expertise, in accordance with procedures approved
by the National Research Council Report Review Committee. The purpose of this
independent review is to provide candid and critical comments that will assist the
institution in making the published report as sound as possible and to ensure that the
report meets institutional standards for objectivity, evidence, and responsiveness to the
study charge. The content of the review comments and draft manuscript remains
confidential to protect the integrity of the deliberative process. We wish to thank the
following individuals for their participation in the review of this report:
Patricia Culligan, Columbia University
George Keller (NAE), Mid-Atlantic Technology, Research and Innovation Center
Alexandra Navrotsky (NAS), University of California, Davis
Alfred Sattelberger, Argonne National Laboratory
Carl Steefel, Lawrence Berkeley National Laboratory
Etienne Vernaz, CEA, Nuclear Energy Division, Marcoule
Raymond Wymer, Oak Ridge National Laboratory (retired)
Although the reviewers listed above have provided many constructive comments
and suggestions, they were not asked to endorse the conclusions or recommendations,
nor did they see the final draft of the report before its release. The review of this report
was overseen by Ed Przybylowicz, appointed by the National Research Council, who
was responsible for making certain that an independent examination of this report was
carried out in accordance with institutional procedures and that all review comments
were carefully considered. Responsibility for the final content of this report rests entirely
with the authoring committee and the National Research Council.
