Chemical Technology Division 1991

256 Pages·2004·7.37 MB·English

ANL-92/15
Chemical Technology Division
Annual Technical Report
1991
Argonne National Laboratory
Or,.- fhr U S Df-prKt merit of im^tvy Line lor ConiMc I W^l Mt -
Cover
Description
The electrorefinei in this
photograph will be used in the
1. EBR-lTFuel Cycle Facility to
demonstrate the reprocessing
of spent fuel fiom an Integral
Fast Reactor
Reseatcher is preparing canister
for gas analysis as part of the
Waste Isolation Pilot Plant
project the objective of which
is to demonstrate the safe
disposal of defense-generated
iadioactive waste
2. 3. Samples are being analyzed to
investigate the geochemistry
and evolution of the hydro-
thermal system shown in this
photograph - Mammoth Hot
Springs (Minerva Terrace),
Yellowstone National Park.
Wyoming.
Researcher is pointing to
peripheral seal ring developed
for bipolar lithium/sulfide cell
4. 5. to be used in electric-vehicle
and other energy-storage
applications.
5. Micrograph shows ceramic
fibers formed by new electrode
fabrication process developed
for molten carbonate fuel cells.
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General, Miscellaneous, and Progress
Reports (Nuclear) (UC-500)
ANL-92/15 ANL—92/15
DE92 014059
ARGONNE NATIONAL LABORATORY
9700 South Cass Avenue
Argonne, IL 60439
CHEMICAL TECHNOLOGY DIVISION
ANNUAL TECHNICAL REPORT
1991
M. J. Steindler Division Director
P. A. Nelson Deputy Division Director
J. E. Battles Associate Division Director
D. W. Green Associate Division Director
March 1992
Previous reports in this series
ANL-91/18 January-December 1990
ANL-90/11 January-December 1989
RpQTrp
ANL-89/15 January-December 1988
ANL-88-19 January-December 1987
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TABLE OF CONTENTS
Page
ABSTRACT 1
SUMMARY 1
I. ELECTROCHEMICAL TECHNOLOGY 18
A. U.S. Advanced Battery Consortium 18
B. Advanced Battery Research and Development 19
1. Lithium/Iron Sulfide System 19
2. Sodium/Metal Chloride System 24
C. Analysis and Diagnostics Laboratory 29
1. Performance and Life Evaluations 29
2. Post-Test Analyses 33
D. Fuel Cell Research and Development : 35
1. Solid Oxide Fuel Cell 35
2. Molten Carbonate Fuel Cell 42
E. Development of Fuel Cell Systems for
Transportation Applications 46
1. Fuel Ceil/Battery Powered Bus System 46
2. Proton Exchange Membrane Fuel Cell 48
3. Fuel Reforming Technology 48
II. FOSSIL FUEL RESEARCH 51
A. Fluidized-Bed Combustion Studies 51
1. Metal Wastage in Fluidized-Bed Combustors 51
2. Atmospheric Fluidized-Bed Cogeneration Air Heater
Experiment 54
3. Development of Regenerable Activated-Bauxite
Sorbent Alkali Monitor 55
4. Parametric Study of N O Emissions from FBC 57
2
5. Evaluation of Illinois Limestones for Reducing SO and
2
HC1 Emissions 58
B. Magnetohydrodynamic Studies 60
in
TABLE OF CONTENTS (contd)
Page
III. HAZARDOUS WASTE RESEARCH 64
A. Aqueous Biphase Process for Actinide Recovery
from Solid Wastes 64
B. Microwave-Assisted Detoxification 68
C. New Initiatives 70
1. Electrokinetic Processes 70
2. Combined Physical and Biochemical Treatment
of Uranium-Contaminated Soils 71
3. Chemically Bonded Ceramic Waste Forms 71
IV NUCLEAR WASTE PROGRAMS 72
A. Glass Testing Program for Environmental
Restoration and Waste Management 72
1. Critical Review 72
2. Long-Term Testing of Radioactive Glasses 73
3. Effects of Radiation 75
4. Effects of SA/V Ratio 76
5. Formation and Characterization of Colloids 79
6. Natural Analogues 81
7. Analytical Support 82
B. Yucca Mountain Site Characterization Project 82
1. Unsaturated Glass Testing 82
2. Spent Fuel Testing 86
3. Radiation Effects Studies 87
C. Actinide Speciation Studies 90
D. Radiation Effects Studies for Waste
Isolation Pilot Plant 91
V. SEPARATION SCIENCE AND TECHNOLOGY 94
A. TRUEX Technology-Base Development 94
1. Improvements to Generic TRUEX Model 94
2. Development of Data Base and Modeling Capability 96
3. Monitoring and Control of TRUEX Processes 99
4. Centrifugal Contactor Development 103
TABLE OF CONTENTS (contd)
Page
B. Treatment of Plutonium Waste Solution
by TRUEX Process 104
C. Treatment of Rocky Flats Plant Waste
by TRUEX Process 108
D. Decontamination of Groundwaters
Containing Volatile Organic Compounds 111
E. Advanced Evaporator Technology 113
VI. INTEGRAL FAST REACTOR PYROCHEMICAL PROCESS 114
A. Process Flowsheet and Chemistry Studies 114
B. Process Development Studies 116
1. Zirconium Behavior Studies 116
2. Laboratory-Scale Electrorefiner 119
C. Engineering-Scale Process Development 119
1. Dissolution of Spent Fuel 120
2. Electrotransport to Solid Cathode 120
3. Electrotransport to Liquid Cadmium Cathode 120
4. Experiments with Pulsed Liquid Cadmium Cathode 122
5. Cover-Gas Treatment System 123
6. Equipment Testing 124
7. Zirconium Behavior in the Engineering-Scale
Electrorefiner 125
D. Waste Treatment Processes 128
1. Salt Extraction 128
2. Salt Stripping 129
3. Salt Immobilization 130
4. Metal Waste Handling 132
5. Waste Form Assessment 133
VII. ACTINIDE RECOVERY 134
A. Flowsheet Development 134
B. Materials Development 135
C. Laboratory-Scale Testing 136
TABLE OF CONTENTS (conM)
Page
D. Development of Calcium/Salt Recovery Method 137
E. Engineering-Scale Testing 138
VDI. APPLIED PHYSICAL CHEMISTRY 140
A. Liquidus-Solidus Temperatures and
Viscosities of Core-Concrete Mixtures 140
1. Differential Thermal Analysis Experiments 141
2. Viscosity Experiments 144
B. Metal Fuel Property Studies 145
1. Phase Studies of U-Fe-Zr System 145
2. Thermal Conductivity Studies 146
3. Behavior of Actinide and Lanthanide Alloys 147
C. Fusion-Related Research 149
1. Temperature-Programmed Desorption from LiA10 150
2
2. Lithium Vaporization Behavior of Lithium Ceramics 153
3. Tritium Release Studies 155
D. Support Studies for New Production Reactor 158
IX BASIC CHEMISTRY RESEARCH 162
A. Fluid Catalysis 162
1. Catalytic Chemistry in Supercritical Media 162
2. Hydrocarbon Activation Chemistry 168
B. Materials Chemistry 170
1. Studies of High-T Superconductors 170
c
2. Quantum Chemical Studies 173
C. Interfacial and Corrosion Science 175
1. Interface Structure and Dynamics 175
2. Research on Molecular Sieve Materials 179
3. Preparation of High-T Films by Alloy Oxidation 182
c
D. Geochemistry 183
1. Radium Geochemistry and Isotopy of Thermal
Waters in Yellowstone National Park, Wyoming , 184
VI
TABLE OF CONTENTS (contd)
Page
2. Origin and History of Petroleum:
Compound-Specific Isotopic Evidence 186
3. New Facilities 187
X. ANALYTICAL CHEMISTRY LABORATORY 188
XI. R&D PROGRAM COORDINATION OFFICE 205
A. Private-Sector Contracts 205
B. Hazardous Substance Research Centers 208
XII. COMPUTER APPLICATIONS 210
XIU. ADDENDUM. CHEMICAL TECHNOLOGY DIVISION
PUBLICATIONS — 1991 213
Vll
CHEMICAL TECHNOLOGY DIVISION
ANNUAL TECHNICAL REPORT
1991
ABSTRACT
Highlights of the Chemical Technology (CMT) Division's activities during
1991 are presented. In this period, CMT conducted research and development in
the following areas: (1) electrochemical technology, including advanced batteries
and fuel cells; (2) technology for fluidized-bed combustion and coal-fired
magnetohydrodynamics; (3) methods for treatment of hazardous and mixed
hazardous/radioactive waste; (4) the reaction of nuclear waste glass and spent fuel
under conditions expected for an unsaturated repository; (5) processes for
separating and recovering transuranic elements from nuclear waste streams;
(6) recovery processes for discharged fuel and the uranium blanket in the Integral
Fast Reactor (IFR); (7) processes for removal of actinides in spent fuel from
commercial water-cooled nuclear reactors and burnup in IFRs; and (8) physical
chemistry of selected materials in environments simulating those of fission and
fusion energy systems. The Division also conducts basic research in catalytic
chemistry associated with molecular energy resources; chemistry of
superconducting oxides and other materials of interest with technological
application; interfacial processes of importance to corrosion science, catalysis, and
high-temperature superconductivity; and the geochemical processes involved in
water-rock interactions occurring in active hydrothermal systems. In addition, the
Analytical Chemistry Laboratory in CMT provides a. broad range of analytical
chemistry support services to the technical programs at Argonne National
Laboratory (ANL).
SUMMARY
Current programs within CMT are briefly summarized below. These programs are
discussed in greater detail in the remainder of the report.
1. Electrochemical Technology
The CMT Division is engaged in a variety of activities related to the development of
advanced batteries for vehicle propulsion, utility load-leveling, and other energy storage
applications. These activities include research, performance and lifetime testing, post-test
examinations, modeling, technology transfer, and technical management of industrial contracts
from the Department of Energy (DOE). Work is also being conducted on advanced fuel cells for
power plant and transportation applications.
During 1991, DOE's battery R&D program underwent a major restructuring because
a partnership among the three major U.S. automakers was formed with the objective of
accelerating the development of advanced battery systems for electric-vehicle applications. This
new partnership-designated the U.S. Advanced Battery Consortium (USABC)--has pooled its
financial resources with the Electric Power Research Institute (EPRI) and DOE. Several
briefings were given by CMT staff to members of the US ABC regarding the relative capabilities
and limitations of various advanced battery systems, as well as the capabilities of CMT to
provide R&D support to future USABC-sponsored programs.
Over the past 19 years, CMT has been conducting in-house R&D on lithium/iron
sulfide batteries, which have a molten-salt electrolyte and operate at high temperature (375-
425 °C). In 1990, DOE signed an industrial R&D contract with SAFT America, Inc., to develop
lithium/iron sulfide batteries for electric-van applications. The contract specifies delivery of
three full-size Li/FeS batteries for testing in the third year of the contract. In support of this
project, CMT provided technology transfer to SAFT, technical management for DOE, and R&D
on critical technical issues. Full-size EV cells (prismatic design) built by SAFT are undergoing
evaluation in performance and lifetime tests at SAFT and CMT.
In the past year, CMT undertook performance modeling studies for lithium/sulfide
batteries with various designs. The performance projections indicated that the "bipolar" Li/FeS
2
battery (i.e., cylindrical cells stacked so that the positive and negative electrodes of adjacent cells
have a common current collector) has the best prospects of meeting the USABC long-term
performance objectives (specific power of 400 W/kg and specific energy of 200 Wh/kg).
Our in-house research program on the lithium/iron sulfide system has been
concentrated on further improving the bipolar design. A critical component in the bipolar battery
is the hermetic seal formed at the cell periphery. We have developed sealant materials that are
electronic insulators and bond tenaciously to metals and ceramics in the molten-salt cell
environment. This seal was successfully tested in a stack of four small-scale (3-cm dia) bipolar
cells, which operated for >500 cycles with >98% coulombic efficiency. Effort in the past year
was concentrated on scaling up the bipolar cell from the small-scale electrode diameter of 3 cm
to a battery prototype size of 13 cm. To that end, prototype FeS and FeS bipolar cells with our
2
new sealant technology were fabricated and tested. These prototype cells have exhibited
approximately 30% increased specific energy and doubled specific power compared with the
earlier prismatic cells. Testing is continuing.
In-house research is also being conducted on the sodium/nickel chloride battery,
which normally operates at 260°C. Recent efforts have focused on improving the performance
of the Ni/NiCl positive electrode, which limits the cell performance in the present construction.
2
As a result of this work, we achieved a significant breakthrough by development of a
"synergistic" Ni/NiCl electrode in which the usable capacity was increased by four times and
2
the area-specific impedance was reduced to one-third that of a baseline Ni/NiCl electrode. This
2
significant performance improvement was achieved by the use of additives and a modified
morphology in the Ni/NiCl electrode. For exact measurements of usable capacity and area-
2
specific impedance in these studies, we designed and operated small research cells with 0.6-
1.8 Ah capacity. These cells simulate the components and operational conditions of a full-size