CONTENTS xi
Chapter 14 Uranium Isotope Separation Introduction Isotopic
Content of Uranium Uranium Enrichment Projects Gaseous Diffusion
The Gas Centrifuge Aerodynamic Processes Mass Diffusion Thermal
Diffusion Laser Isotope Separation Nomenclature References
Problems
Appendixes A Fundamental Physical Constants B Conversion Factors
C Properties of the Nuclides D Radioactivity Concentration Limits
for Selected
Radionuclides
812 812 813 815 818 847 876 895 906 914 922 925 929
933
933 935 937
979
Index 983
Front MatterPrefaceTable of Contents1. Chemical Engineering
Aspects of Nuclear Power1.1 Introduction1.2 Nuclear Fission1.3
Nuclear Fuels1.4 Nuclear Reactor Types1.5 Fuel Processing Flow
Sheets1.5.1 Uranium Fuel1.5.2 Thorium Fuel
1.6 Fuel-Cycle Operations1.7 Fuel Reprocessing1.8 Isotope
Separation1.9 Nuclear FusionReferencesProblems
2. Nuclear Reactions2.1 Nuclides2.1.1 Make-up of Nuclides2.1.2
Balancing Nuclear Reactions
2.2 Radioactivity2.2.1 Types2.2.2 Rate of Radioactive Decay2.2.3
Alpha Radioactivity2.2.4 Beta Radioactivity2.2.5 Gamma
Radioactivity2.2.6 Positron Emission2.2.7 Electron Capture2.2.8
Spontaneous Fission
2.3 Decay Chains2.3.1 Batch Decay2.3.2 Continuous
Production2.3.3 Continuous Production and Shutdown
2.4 Neutron Reactions2.4.1 Capture Reactions2.4.2 Fission
Reactions2.4.3 Reaction Rates2.4.4 Cross Sections2.4.5 Neutron
Speeds in Reactors2.4.6 Neutron Flux2.4.7 Effective Cross
Sections2.4.8 Half-life for Neutron Reactions
2.5 The Fission Process2.5.1 Fissile Materials2.5.2 Fission
Products2.5.3 Energy Release in Fission
2.6 Growth and Decay of Nuclides with Simultaneous Radioactive
Decay, Neutron Absorption, and Continuous Processing2.6.1 Batch
Operation2.6.2 Continuous Production2.6.3 135 Xe Fission-Product
Poisoning2.6.4 135 Xe Transient after Reactor Shutdown2.6.5 149 Sm
Chain
2.7 Derivation of the Bateman Equation (2.17) by Laplace
Transforms2.7.1 Properties of Laplace Transforms2.7.2 Derivation of
the Bateman Equation (2.17)
NomenclatureReferencesProblems
3. Fuel Cycles for Nuclear Reactors3.1 Nuclear Fuels3.2 Effects
of Irradiation on Nuclear Fuels3.3 Fuel and Poison Management3.3.1
Objectives3.3.2 Drawbacks of Batch Irradiation of Uniform Fuel and
Poison3.3.3 Idealized Methods of Fuel and Poison Management3.3.4
Reactivity-limited Burnup in PWR with Modified Scatter Fueling
3.4 Fuel Management in a Large Pressurized-Water Reactor3.4.1
Reactor Construction3.4.2 Reactor Performance, Cycle 13.4.3 Reactor
Performance, Cycle 23.4.4 Reactor Performance, Cycle 33.4.5
Approach to Steady State
3.5 Fuel-Cycle Costs3.5.1 Procedure for Calculating Fuel-Cycle
Costs3.5.2 Steady-State Fuel-Cycle Costs
3.6 Hand Calculation of Fuel-Cycle Performance3.6.1 Neutron
Energy Cycle3.6.2 Neutron Balance for Reference Design3.6.3 Neutron
Balance for Operating Reactor3.6.4 Reactor Example3.6.5 Change of
Composition with Flux Time3.6.6 Composition Changes in PWR3.6.7
Reactivity Changes in PWR3.6.8 Effect of Fuel Management Method on
Burnup
3.7 Fuel-Cycle Material Flow Sheets3.7.1 LWR Fueled with
Slightly Enriched Uranium3.7.2 LWR Fueled with Plutonium and
Natural Uranium3.7.3 The HTGR3.7.4 The LMFBR
NomenclatureReferencesProblems
4. Solvent Extraction of Metals4.1 Applications4.2 Extractable
Metal-Organic Complexes4.3 Solvent Extraction Principles4.4
Distribution Coefficients4.4.1 Element Being Extracted4.4.2
Oxidation-Reduction Potential4.4.3 Nature of Solvent4.4.4
Complexing Agents4.4.5 Concentration of Salting Agent4.4.6
Correlation of Equilibrium Extraction Data4.4.7 Presence of Other
Extractable Species4.4.8 Hydrogen Ion Concentration
4.5 Solvent Requirements4.6 Theory of Countercurrent Equilibrium
Extraction4.6.1 Extracting Cascade4.6.2 Extracting Cascade with
Constant Distribution Coefficients4.6.3 The Extracting-scrubbing
Cascade4.6.4 Limiting Flow Ratios for the Extracting-scrubbing
Cascade4.6.5 Extracting-scrubbing Cascade with Constant
Distribution Coefficients4.6.6 Extracting-scrubbing Cascade:
Numerical Procedure for Use with Variable Distribution
Coefficients
4.7 Solvent Extraction Equipment4.7.1 Requirements4.7.2 Types of
Equipment4.7.3 Mixer-Settlers4.7.4 Centrifugal Contactor4.7.5
Rotary Annular Contactor4.7.6 Rotating Disk Contactor4.7.7 Spray
Column4.7.8 Packed Columns4.7.9 Pulse Columns
NomenclatureReferencesProblems
5. Uranium5.1 Uranium Isotopes5.1.1 Natural Uranium5.1.2 232 U
and 233 U5.1.3 236 U and 237 U5.1.4 239 U
5.2 Uranium Radioactive Decay Series5.2.1 238 U Decay
Series5.2.2 235 U Decay Series5.2.3 Radioactive Decay of 237 U, 237
Np, and 233 U5.2.4 Radioactivity in Uranium Mines and
Refineries
5.3 Metallic Uranium5.3.1 Uses5.3.2 Phases of Uranium5.3.3
Density and Thermal Expansion5.3.4 Chemical Reactivity
5.4 Uranium Compounds5.4.1 Uranium Valence States4.4.2 Uranium
Oxides5.4.3 Uranium Carbides5.4.4 Uranium Nitride5.4.5 Uranium
Hydride5.4.6 Uranium Halides5.4.7 Uranium Hexafluoride
5.5 Uranium Solution Chemistry5.5.1 Oxidation States of Uranium
in Aqueous Solution5.5.2 Uranium(IV) Solutions5.5.3 Uranyl
Solutions5.5.4 Solvent Extraction of Uranyl Compounds
5.6 Sources of Uranium5.6.1 Principal Uranium-containing
Minerals5.6.2 Low-Grade Sources of Uranium
5.7 Uranium Resource Estimates5.7.1 World Resources5.7.2 United
States
5.8 Concentration of Uranium5.8.1 Steps in Producing Refined
Uranium Compounds5.8.2 Concentration Methods5.8.3 U.S. Uranium
Mills5.8.4 Uranium Concentration by Carbonate Leaching5.8.5 Acid
Leaching of Uranium Ores5.8.6 Solvent Extraction of Uranium from
Leach Liquors5.8.7 Uranium Concentration by Anion Exchange5.8.8
Uranium from Seawater5.8.9 Radioactive Effluents from Uranium
Mills
5.9 Uranium Refining5.9.1 Uranium Refineries5.9.2 Purification
of Uranium Concentrates5.9.3 Conversion of UNH to UO 35.9.4
Reduction of UO 3 to UO 25.9.5 Hydrofluorination of UO 2 to UF
45.9.6 Fluorination of UF 4 to UF 65.9.7 Allied Chemical Process
for Converting Uranium Concentrates to UF 65.9.8 Conversion of UF 6
to UF 4 and UO 2
5.10 Production of Uranium Metal5.10.1 Difficulties5.10.2
Alternative Methods5.10.3 Heat Balances in Uranium Metal
Production5.10.4 Production of Uranium Metal by Reduction of UF 4
with Magnesium
ReferencesProblems
6. Thorium6.1 Uses of Thorium6.2 Thorium Isotopes6.2.1 Naturally
Occurring Thorium Isotopes6.2.2 Synthetic Thorium Isotopes
6.3 Thorium Radioactivity6.4 Metallic Thorium6.4.1 Uses6.4.2
Phases6.4.3 Density and Thermal Expansion6.4.4 Thermodynamic
Properties6.4.5 Thermal and Electrical Conductivity6.4.6 Chemical
Reactivity
6.5 Thorium Compounds6.5.1 Thorium Valence States6.5.2 Thorium
Dioxide6.5.3 Thorium Carbides6.5.4 Thorium Nitrides6.5.5 Thorium
Hydrides [M2]6.5.6 Thorium Halides
6.6 Thorium Solution Chemistry6.6.1 Solubility of Thorium
Compounds in Aqueous Solution6.6.2 Solvent Extraction of Thorium
Compounds
6.7 Thorium Resources6.7.1 Principal Thorium-containing
Minerals6.7.2 World Thorium Resources6.7.3 U.S. Thorium
Resources6.7.4 Thorium Production6.7.5 Thorium Requirements
6.8 Concentration and Extraction of Thorium6.8.1 Concentration
of Monazite6.8.2 Composition of Monazite6.8.3 Processes for Opening
Up Monazite6.8.4 Caustic Soda Process6.8.5 Sulfuric Acid
Processes6.8.6 Separation of Thorium, Rare Earths, and Uranium from
Monazite by Solvent Extraction6.8.7 Separation of Thorium from
Other Minerals by Solvent Extraction
6.9 Purification of Thorium6.10 Conversion of Thorium Nitrate to
Oxide, Fluoride, Chloride, or Metal6.10.1 Conversion of Thorium
Nitrate to ThO 26.10.2 Production of ThF 46.10.3 Production of ThCl
46.10.4 Production of Thorium Metal
ReferencesProblems
7. Zirconium and Hafnium7.1 Uses of Zirconium and Hafnium7.2
Natural Occurrence7.3 Production and Price7.4 Zirconium and Hafnium
Metal and Alloys7.4.1 Phases7.4.2 Density and Thermal
Expansion7.4.3 Thermodynamic Properties7.4.4 Thermal and Electrical
Conductivity7.4.5 Chemical Reactivity7.4.6 Zirconium Alloys
7.5 Zirconium and Hafnium Compounds7.5.1 Valence States7.5.2
Zirconium Dioxide7.5.3 Zirconium Carbide7.5.4 Zirconium
Nitride7.5.5 Zirconium Hydrides7.5.6 Zirconium Halides7.5.7
Compounds of Hafnium7.5.8 Aqueous Chemistry of Zirconium and
Hafnium
7.6 Extraction of Zirconium and Hafnium from Zircon7.6.1
Composition of Zircon7.6.2 Zircon Extraction Processes7.6.3
Chlorination of Zircon7.6.4 Alkali Fusion7.6.5 Fluosilicate
Fusion
7.7 Separation of Zirconium and Hafnium7.7.1 Methods7.7.2
Fractional Crystallization7.7.3 Solvent Extraction of
Thiocyanates7.7.4 Solvent Extraction with TBP7.7.5 Selective
Reduction of Double Fluorides by Aluminum
7.8 Production of Metallic Zirconium and Hafnium7.8.1
Difficulties7.8.2 Available Processes7.8.3 Kroll Process7.8.4 The
Hot-Wire Process7.8.5 Electrolysis of Fused Salts
7.9 Alternatives for Producing Hafnium-Free Zirconium from
ZirconReferencesProblems
8. Properties of Irradiated Fuel and Other Reactor Materials8.1
Fission-Product Radioactivity8.1.1 Activity in Irradiated Fuel8.1.2
Chemical Composition of Fission Products8.1.3 Neutron Absorption by
Long-lived Fission Products8.1.4 Toxicity of Inhaled or Ingested
Fission Products8.1.5 Effects of Fuel-Cycle Alternatives on Fission
Products in Irradiated Fuel
8.2 Radioactivity of the Actinides8.2.1 Actinide Radioactivity
in Uranium and Uranium-Plutonium Fuel8.2.2 Preprocessing Storage
Time for Irradiated Uranium Fuel8.2.3 Radioactive Decay of Recycled
Plutonium8.2.4 Long-term Radioactivity of Actinides from
Uranium-Plutonium Fuel8.2.5 Actinide Reactions in Thorium Fuel8.2.6
Growth of 232 U in Irradiated Uranium-Thorium Fuel8.2.7 Growth of
228 Th and Gamma Activity in Separated Uranium8.2.8 234 Th in
Separated Thorium8.2.9 228 Th in Irradiated Thorium
8.3 Effect of Fuel-Cycle Alternatives on Properties of
Irradiated Fuel8.4 Radioactivity from Neutron Activation8.4.1
Tritium from Neutron Activation8.4.2 14 C8.4.3 35 S, 33 P, and 36
Cl in HTGR Fuel8.4.4 Nonvolatile Radionuclides Activated in
Fuel-Element Structure
8.5 Neutron Activity in Recycled Fuel8.5.1 Light-Element (, n)
Reactions8.5.2 Neutrons from Spontaneous Fission
NomenclatureReferencesProblems
9. Plutonium and Other Actinide Elements9.1 General Chemical
Properties of the Actinides9.1.1 Electronic Configurations9.1.2
Hydrolytic Behavior9.1.3 Complex Formation9.1.4 Oxidation-Reduction
Reactions in Aqueous Solutions9.1.5 Summary
9.2 Properties of Protactinium9.2.1 Protactinium Isotopes9.2.2
Metallic Protactinium9.2.3 Protactinium Compounds9.2.4 Protactinium
Solution Chemistry
9.3 Properties of Neptunium9.3.1 Neptunium Isotopes9.3.2
Metallic Neptunium9.3.3 Neptunium Compounds9.3.4 Neptunium Solution
Chemistry
9.4 Properties of Plutonium9.4.1 Plutonium Isotopes9.4.2
Plutonium Radioactivity9.4.3 Plutonium Electronic Structure9.4.4
Plutonium Metal9.4.5 Plutonium Compounds9.4.6 Plutonium Solution
Chemistry9.4.7 Plutonium Conversion9.4.8 Production of Plutonium
Metal
9.5 Properties of Americium9.5.1 Americium Isotopes9.5.2
Metallic Americium9.5.3 Americium Compounds9.5.4 Americium Solution
Chemistry
9.6 Properties of Curium9.6.1 Curium Isotopes9.6.2 Metallic
Curium9.6.3 Curium Compounds9.6.4 Curium Solution Chemistry
ReferencesProblems
10. Fuel Reprocessing10.1 Objectives of Reprocessing10.2
Composition of Irradiated Fuel10.3 History of Reprocessing10.3.1
Bismuth Phosphate Process10.3.2 Redox Process10.3.3 Trigly
Process10.3.4 Butex Process10.3.5 Purex Process10.3.6 Thorex
Process10.3.7 Other Aqueous Processes10.3.8 Nonaqueous
Processes10.3.9 Pyrometallurgical Processes10.3.10 Pyrochemical
Processes10.3.11 Fluoride Volatility Processes
10.4 The Purex Process10.4.1 Steps in Purex Process10.4.2
Principal Reprocessing Plants10.4.3 Decladding10.4.4
Dissolution10.4.5 No x Absorption10.4.6 Off-gas Treatment10.4.7
Primary Decontamination10.4.8 Plutonium Partitioning10.4.9 Uranium
Purification10.4.10 Plutonium Purification10.4.11 Solvent
Reuse10.4.12 Aqueous Waste Processing10.4.13 Nitric Acid
Recovery10.4.14 Barnwell Nuclear Fuel Plant10.4.15 Distribution
Equilibria in Purex Systems10.4.16 Example of Use of Purex
Equilibrium Data10.4.17 Physical Properties of TBP and Its Mixtures
with Hydrocarbons, Water, and Nitric Acid10.4.18 Degradation of
TBP-Hydrocarbon Mixtures
10.5 Reprocessing Thorium-Based Fuels10.5.1 History10.5.2
Decladding Thorium-based Fuels10.5.3 Dissolution of ThO 2 -UO 2
Fuel10.5.4 Feed Pretreatment10.5.5 Thorex Solvent Extraction at
Hanford10.5.6 Two-Stage Acid Thorex Process for High Burnup
Fuel10.5.7 JUPITER Pilot Plant10.5.8 Phase Equilibria in Thorex
Systems
10.6 Reprocessing LMFBR Fuels10.6.1 Differences from LWR
Fuels10.6.2 Principal Steps in Reprocessing LMFBR Fuel10.6.3
Problem Areas10.6.4 Decay Heat Removal10.6.5 Deactivation of
Sodium10.6.6 Voloxidation10.6.7 Retention of Iodine10.6.8
Dissolution10.6.9 Purex Process for LMFBR Fuel
10.7 Neptunium Recovery in Reprocessing10.7.1 Use of
Neptunium10.7.2 Sources of Neptunium10.7.3 Oxidation-Reduction
Equilibria in Neptunium Recovery10.7.4 Distribution Coefficients in
Neptunium Recovery10.7.5 Kinetics of Neptunium Oxidation and
Reduction10.7.6 Neptunium Recovery Examples10.7.7 Neptunium
Recovery Process
10.8 Prevention of Criticality in Reprocessing Plants10.8.1
Factors Affecting Criticality Safety10.8.2 Single-Parameter Limits
for Fissile Nuclides10.8.3 Multiparameter, Concentration-dependent
Limits for Criticality Control
ReferencesProblems
11. Radioactive Waste Management11.1 Introduction11.1.1
Definition11.1.2 Classification11.1.3 Sources
11.2 High-Level Waste11.2.1 Characterization of Liquid HLW11.2.2
Projections of HLW Generation11.2.3 Alternatives for Commercial HLW
Management11.2.4 Tank Storage11.2.5 Solidification Products11.2.6
Solidification Processes11.2.7 Actinide Partitioning
11.3 Non-High-Level Waste11.3.1 Volume Reduction11.3.2 Recovery
of Transuranium Elements11.3.3 Immobilization
11.4 Special Radioactive Waste11.4.1 Tritium11.4.2 129 I11.4.3
85 Kr
11.5 Disposal of Radioactive Waste11.5.1 Basic Considerations on
Geologic Disposal11.5.2 Design of Repositories in Salt
Formations11.5.3 Other Disposal Techniques
11.6 Assessment of Long-Term Safety11.6.1 Evaluation of Barriers
between Waste and People11.6.2 Significant Period of the Hazard
ReferencesProblems
12. Stable Isotopes: Uses, Separation Methods, and Separation
Principles12.1 Uses of Stable Isotopes12.1.1 235 U12.1.2
Deuterium12.1.3 Lithium Isotopes12.1.4 10 B12.1.5 13 C12.1.6 15
N12.1.7 Oxygen Isotopes
12.2 Isotope Separation Methods12.2.1 235 U12.2.2
Deuterium12.2.3 Lithium Isotopes12.2.4 10 B12.2.5 13 C12.2.6 15
N12.2.7 Heavy Oxygen Isotopes12.2.8 Recapitulation of Separation
Methods
12.3 Terminology12.3.1 Separating Unit, Stage, and Cascade12.3.2
Measures of Composition
12.4 Stage Properties12.4.1 Terminology12.4.2 Separation
Factors12.4.3 Differential Stage Separation
12.5 Types of Cascade12.6 The Simple Cascade12.7 The Recycle
Cascade12.7.1 Material-Balance Relations12.7.2 Number of Ideal
Stages12.7.3 Minimum Number of Stages: Constant Separation
Factor12.7.4 Minimum Reflux Ratio12.7.5 Practical Reflux Ratio
12.8 The Ideal Cascade12.8.1 Heads Separation Factor12.8.2
Number of Stages12.8.3 Reflux Ratio12.8.4 Shape of Ideal
Cascade12.8.5 Total Flow Rates
12.9 Close-Separation Cascade12.10 Separative Capacity,
Separative Work, and Separation Potential12.10.1 Definitions12.10.2
Applications of Sparative Capacity and Separative Work12.10.3 Costs
from Separative Work12.10.4 Toll Enrichment Charges12.10.5 Cost of
Enriched Uranium12.10.6 Optimum Tails Composition
12.11 Differential Equation for Separation Potential12.12
Equilibrium Time for Isotope Separation Plants12.12.1 Operating
Procedure during Start-up12.12.2 Relation between Equilibrium Time
and Inventory12.12.3 Inventory of Ideal Cascade12.12.4 Relation
between Equilibrium Time and Separative Work12.12.5 Inventory
Functions12.12.6 Equilibrium Time Example
12.13 Squared-off Cascade12.14 Generalized Ideal Cascade12.14.1
Separation Factor12.14.2 Cut12.14.3 Separative Capacity12.14.4
Special Cases12.14.5 Separative Capacity of Low-Enrichment, Two-Up,
One-Down Ideal Cascade
12.15 Three-Component Isotope Separation12.15.1 Separation
Factors12.15.2 Three-Component Value Function12.15.3
Three-Component Separation Example12.15.4 Number of Stages
NomenclatureReferencesProblems
13. Separation of Isotopes of Hydrogen and Other Light
Elements13.1 Sources of Deuterium13.2 Deuterium Production
Processes and Plants13.3 Separation Factors in Distillation13.3.1
Terminology13.3.2 Relation of Separation Factor to Vapor
Pressures13.3.3 Separation Factors
13.4 Distillation of Hydrogen13.5 Distillation of Water13.5.1
Primary Concentration of Deuterium13.5.2 Final Concentration of
Deuterium by Distillation of Water13.5.3 Separation of 18 O by
Distillation of Water
13.6 Electrolysis13.6.1 Electrolysis of Water13.6.2 Analysis of
Electrolysis
13.7 Electrolysis and Steam-Hydrogen Exchange13.7.1 Principle of
Process13.7.2 History13.7.3 Trail Plant13.7.4 Recovery of Deuterium
from Electrolytic Hydrogen by Exchange with Liquid Water Under
Pressure
13.8 Separation Factors in Deuterium Exchange Processes13.9
Number of Theoretical Stages in Exchange Columns13.10 Monothermal
Exchange Processes13.10.1 Monothermal Ammonia-Hydrogen
Exchange13.10.2 Monothermal Water-Hydrogen Sulfide Exchange
13.11 Dual-Temperature Water-Hydrogen Sulfide Exchange
Process13.11.1 Principle of Process13.11.2 History13.11.3
Simplified Analysis of Process13.11.4 Detailed Process Flow Sheet
for GS Plant13.11.5 Materials of Construction13.11.6
Economics13.11.7 Detailed Analysis of Process13.11.8 Improved GS
Flow Sheets
13.12 Dual-Temperature Ammonia-Hydrogen Exchange Process13.13
Methylamine-Hydrogen Exchange Processes13.14 Dual-Temperature
Water-Hydrogen Exchange Processes13.15 Exchange Processes for
Separation of Lithium Isotopes13.16 Exchange Processes for Other
Elements13.16.1 Separation Factors13.16.2 Separation of Nitrogen
Isotopes
NomenclatureReferencesProblems
14. Uranium Isotope Separation14.1 Introduction14.2 Isotopic
Content of Uranium14.3 Uranium Enrichment Projects14.3.1 Processes
Developed by Manhattan Project14.3.2 Current Industrial Uranium
Enrichment Projects14.3.3 Processes Under Development
14.4 Gaseous Diffusion14.4.1 Principle14.4.2 History14.4.3 U.S.
Process Equipment14.4.4 French Process Equipment14.4.5 Flow of
Gases through Diffusion Barrier14.4.6 Mixing Efficiency14.4.7 Stage
Characteristics14.4.8 Minimum Power Requirement of Gaseous
Diffusion Process
14.5 The Gas Centrifuge14.5.1 Principle14.5.2 History14.5.3
Description of Centrifuges14.5.4 Mechanical Performance of
Centrifuges14.5.5 Separation Performance of Gas Centrifuge
14.6 Aerodynamic Processes14.6.1 Introduction14.6.2 The
Separation Nozzle Process14.6.3 The South African UCOR Process
14.7 Mass Diffusion14.7.1 Mass Diffusion Stage14.7.2 Mass
Diffusion Column14.7.3 Sweep Diffusion14.7.4 Separation of Uranium
Isotopes by Cascade of Mass Diffusion Stages
14.8 Thermal Diffusion14.8.1 General Description14.8.2 Partial
Separation of Uranium Isotopes14.8.3 Theory of Thermal Diffusion
Separation
14.9 Laser Isotope Separation14.9.1 Introduction14.9.2 Laser
Isotope Separation of Uranium Metal Vapor14.9.3 Laser Isotope
Separation of UF 6
NomenclatureReferencesProblems
AppendixesIndex
