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OCR for page R1
Alternative Technologies for the Destruction of Chemical Agents and Munitions
Alternative Technologies for the Destruction of Chemical Agents and Munitions
COMMITTEE ON ALTERNATIVE CHEMICAL DEMILITARIZATION TECHNOLOGIES
BOARD ON ARMY SCIENCE AND TECHNOLOGY
COMMISSION ON ENGINEERING AND TECHNICAL SYSTEMS
NATIONAL RESEARCH COUNCIL
National Academy Press
Washington, D.C.
1993
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Alternative Technologies for the Destruction of Chemical Agents and Munitions
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 competencies and with regard for appropriate balance.
This report has been reviewed by a group other than the authors according to procedures approved by a Report Review Committee consisting of members of the National Academy of Sciences, the National Academy of Engineering, and the Institute of Medicine.
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. Frank Press 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. Robert M. White 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. Kenneth I. Shine 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. Frank Press and Dr. Robert White are chairman and vice chairman, respectively, of the National Research Council.
This is a report of work supported by Contract DAAL03-90-C-0035 (CLIN 001) between the U.S. Department of the Army and the National Academy of Sciences.
Library of Congress Catalog Card Number 93-84706
International Standard Book Number 0-309-04946-6
Copies available from:
National Academy Press
2101 Constitution Avenue, N.W. Box 284 Washington, D.C. 20418 1-800-24-6242 (202) 334-3313 (in the Washington Metropolitan area)
B-170
Copyright 1993 by the National Academy of Sciences. All rights reserved.
Printed in the United States of America
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Alternative Technologies for the Destruction of Chemical Agents and Munitions
COMMITTEE ON ALTERNATIVE CHEMICAL DEMILITARIZATION TECHNOLOGIES
JOHN P. LONGWELL (Chairman),
Massachusetts Institute of Technology, Cambridge
GEORGE APOSTOLAKIS,
University of California, Los Angeles
JOSEPH F. BUNNETT,
University of California, Santa Cruz
PETER S. DALEY,
Waste Management International, London, England
GENE H. DYER, Consultant,
San Raphael, California
DAVID S. KOSSON,
Rutgers, The State University of New Jersey, Piscataway
WALTER G. MAY,
University of Illinois, Urbana
MATTHEW MESELSON,
Harvard University, Cambridge, Massachusetts
HENRY SHAW,
New Jersey Institute of Technology, Newark
THOMAS O. TIERNAN,
Wright State University, Dayton, Ohio
BARRY M. TROST,
Stanford University, Stanford, California
JAMES R. WILD,
Texas A&M University, College Station
Staff
DONALD L. SIEBENALER, Study Director
JAMES J. ZUCCHETTO, Co-Study Director
MARGO L. FRANESCO, Senior Program Assistant
ALLISON P. KNIGHT, Administrative Secretary
ANN COVALT, Consulting Editor
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Alternative Technologies for the Destruction of Chemical Agents and Munitions
BOARD ON ARMY SCIENCE AND TECHNOLOGY
PHILIP A. ODEEN (Chairman),
BDM International, Inc., McLean, Virginia
LAWRENCE J. DELANEY (Vice Chairman),
Montgomery and Associates, Washington, D.C.
ROBERT A. BEAUDET,
University of Southern California, Los Angeles
WILLIAM K. BREHM,
Systems Research Applications Corporation, Arlington, Virginia
WILLIAM H. EVERS, JR.,
W. J. Schafer Associates, Inc., Arlington, Virginia
JAMES L. FLANAGAN,
Center for Computer Aids in Industrial Productivity, Piscataway, New Jersey
CHRISTOPHER C. GREEN,
General Motors Research Laboratories, Warren, Michigan
THOMAS MCNAUGHER,
The Brookings Institution, Washington, D.C.
GENERAL GLENN K. OTIS (Retired, U.S. Army),
Coleman Research Corporation, Fairfax, Virginia
NORMAN F. PARKER,
Varian Associates (Retired), Cardiff by the Sea, California
HARVEY W. SCHADLER,
General Electric Company, Schenectady, New York
F. STAN SETTLES,
Office of Science and Technology, Washington, D.C.
JOYCE L. SHIELDS,
Hay Systems, Inc., Arlington, Virginia
DANIEL C. TSUI,
Princeton University, Princeton
Staff
BRUCE A. BRAUN, Director,
Board on Army Science and Technology
DONALD L. SIEBENALER, Senior Program Officer
JAMES J. ZUCCHETTO, Senior Program Officer
HELEN D. JOHNSON, Staff Associate
ANN M. STARK, Program Officer
MARGO L. FRANCESCO, Senior Program Assistant
ALLISON P. KNIGHT, Administrative Secretary
KELLY NORSINGLE, Administrative Secretary (until 4/16/93)
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Alternative Technologies for the Destruction of Chemical Agents and Munitions
Preface
The unitary chemical warfare agents and munitions that are the focus of this study have not been manufactured in the United States since 1968. Some agent and munitions have been destroyed, but approximately 25,000 tons of agent remain in thousands of tons of munitions and bulk containers in the U.S. stockpile. In 1978 the U.S. Army began to test various large-scale disposal methods at the Tooele Army Depot, Utah, where over 42 percent of the stockpile is located. These methods included several techniques to handle and disassemble munitions to gain access to the agent therein. Techniques tested for agent destruction included chemical treatment and incineration.
At the request of the Army, the National Research Council (NRC) studied the overall disposal program and endorsed the Army's choice of incineration of agents and thermal treatment of energetics, metal parts, and containers in a 1984 report. A pioneer plant constructed at Johnston Island in the Pacific Ocean in the late 1980s recently completed Operational Verification Testing of a baseline technology involving incineration. At Tooele, construction of a larger, continental facility is nearing completion. Construction of similar but smaller facilities is proposed by the Army for seven additional storage sites in the continental United States.
As a result of growing interest in alternatives to the baseline technology, in 1992 Congress instructed the Army to recommend disposal technologies for all sites by December 31, 1993. These recommendations are to be based on two NRC studies. The first by the Committee on Alternative Chemical Demilitarization Technologies is reported here. The second, by the Committee on Review and Evaluation of the Army Chemical Stockpile Disposal Program, will use the information and analyses provided here to formulate recommendations for the Army to use in developing its own recommendations to Congress. Thus, this report is the first step in a three-part national advisory process.
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Alternative Technologies for the Destruction of Chemical Agents and Munitions
On January 13-15, 1993, an important step was taken when 132 countries signed the International Convention on Prohibition of the Development, Production, Stockpiling, and Use of Chemical Weapons and on their Destruction, known as the Chemical Weapons Convention. This convention specifies that stockpiled chemical warfare agents be destroyed in an "essentially irreversible manner" and that the weapons to apply them be rendered unusable. These demilitarization goals are to be met by December 31, 2004, with some possibility of schedule extension. The disposal technology to be used is not specified; however, within the United States the waste streams created by the chemical demilitarization system must be environmentally acceptable. Any gas stream from combustion-based processes is of particular concern to the public. Consequently, technologies to ensure environmental and public acceptability of this waste stream are also considered in this report.
This study was initiated with the first meeting of the committee in March 1992, followed by a workshop in June 1992. The workshop included presentations on proposed alternative technologies, with time for commentary by interested observers. Subsequent discussions and written submissions were additional important sources of information. The committee ended its data collection efforts in February 1993. More recent data may be available, especially for those technologies that have substantial development programs. The workshop was followed by three additional meetings, in September, October, and November 1992. Specific recommendations are not made in this report, but it is hoped that the information and discussion presented will provide a basis for more specific recommendations to be developed by the NRC and the Army.
The rapid pace of this study, the large number of contributions made to it, and the complexity of the subject offered substantial organizational and editorial challenges. The NRC staff, especially Margo Francesco, Allison Knight, Donald Siebenaler, and James Zucchetto, deserve special thanks and recognition for their essential roles in this study.
John P. Longwell, Chairman
Committee on Alternative Chemical Demilitarization Technologies
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Alternative Technologies for the Destruction of Chemical Agents and Munitions
Contents
EXECUTIVE SUMMARY
1
1
INTRODUCTION
22
The U.S. Chemical Stockpile Disposal Program
22
Risk and Community Concerns
27
Alternative Demilitarization Systems
29
Transportation of Untreated Weapons and Agents
31
Primary Goals and Strategies for Demilitarization
31
Scope and Organization of the Study
34
2
THE U.S. CHEMICAL WEAPONS STOCKPILE
37
Description of the Agents
37
Description of the Munitions
42
Geographical Distribution of the Stockpile
49
Summary
53
3
U.S. AND FOREIGN EXPERIENCE WITH CHEMICAL WEAPONS DESTRUCTION
54
U.S. Chemical Demilitarization Experience
54
Chemical Warfare Agent Destruction in Other Countries
62
Summary
74
4
REQUIREMENTS AND CONSIDERATIONS FOR CHEMICAL DEMILITARIZATION TECHNOLOGIES
75
Chemical Composition of Agents and Their Breakdown Products
76
Waste Streams in Chemical Weapons Destruction
77
Processing Rates
78
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Alternative Technologies for the Destruction of Chemical Agents and Munitions
Performance Standards
81
Worker Standards
81
Air Quality Standards
81
Liquid Wastes
81
Solid Wastes
82
General Considerations in Assessing Untested Alternative Technologies
83
Decontamination Standards
84
Chlorinated Dioxins
85
Monitoring
86
Effluent Retention Time Requirements
88
Time Required for Technology Development and Demonstration
89
Technology Development and Demonstration Costs
91
Assessment Criteria for Alternative Technologies
92
5
THERMAL TREATMENT AND PREPROCESSING THE POSTPROCESSING OPERATIONS
94
Preprocessing Operations
95
Cryoprocessing
95
Mechanical Disassembly of Explosives Propellants and Solidified Agent
96
Thermal Treatment
97
Postprocessing Operations
98
Solid Wastes
98
Control of Nitrogen Oxides
101
Water Recycle
101
Reduction of Waste Gas Volume
102
Waste Gas Storage Requirement
103
Storage and Retention Technologies
105
Activated-Carbon (Charcoal) Adsorption Systems
106
6
LOW-TEMPERATURE, LIQUID-PHASE PROCESSES
109
Chemical Detoxification Processes
110
GB (Satin)
112
VX
116
H (Mustard)
118
Reduction Methods Conceivably Applicable to GB, VX, and H
121
Detoxication with Ionizing Radiation
122
Low-Temperature and Low-Pressure Oxidation Processes
123
Chemical Oxidation
123
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Alternative Technologies for the Destruction of Chemical Agents and Munitions
Electrochemical Oxidation
124
Oxidizing Agents Plus UV Light
125
Biological Processes
126
Introduction and Overview
126
Direct Destruction of GB and VX
128
Biodegradation of the Reaction Products from the Chemical Processing of GB and VX
131
Chemical Hydrolysis and Bioremediation of Mustard
132
Bioremediation of Explosives and Energetics
132
Engineering Prospects
132
Summary of the Potential Application of Biological Processes
136
7
PROCESSES AT MEDIUM AND HIGH TEMPERATURES
137
Moderate-Temperature, High-Pressure Processes
138
Wet Air Oxidation
138
Supercritical Water Oxidation
146
High-Temperature, Low-Pressure Pyrolysis
152
Molten Metal Pyrolysis
152
Plasma Arc Processes
156
Gasification Processes
160
Synthetica Detoxifier
163
High-Temperature, Low-Pressure Oxidation
169
Catalytic Fluidized-Bed Oxidation
169
Molten Salt Oxidation
171
Catalytic Oxidation
174
Other Processes
176
Hydrogenation Processes
176
The Adams Process—Reaction with Sulfur
180
8
APPLICATION OF ALTERNATIVE TECHNOLOGIES TO THE DESTRUCTION OF THE U.S. CHEMICAL WEAPONS STOCKPILE
185
Destruction Technologies
185
Low-Temperature, Low-Pressure, Liquid-Phase, Detoxification
186
Low-Temperature, Low-Pressure, Liquid-Phase Oxidation
190
Moderate-Temperature, High-Pressure Oxidation
190
High-Temperature, Low-Pressure Pyrolysis
191
High-Temperature, Low-Pressure Oxidation
192
Waste Stream Handling Processes
193
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Alternative Technologies for the Destruction of Chemical Agents and Munitions
Solid Waste
193
Gas Waste Streams
194
Liquid Wastes
196
Goals, Strategies, and Systems for Chemical Demilitarization
196
Program Goals
196
Strategies for Disposal
197
System Considerations
200
General Observations
205
APPENDICES
209
Appendix A,
Statement of Task
209
Appendix B,
Letter from James R. Ambrose, Dated October 21, 1987
210
Appendix C,
Letter from Charles Baronian, Dated August 7, 1992
213
Appendix D,
Biographical Sketches
237
Appendix E,
Technology Developers That Supplied Information
244
Appendix F,
Committee Meetings and Activities
250
Appendix G,
Technology Status Worksheet
259
Appendix H,
Excerpt From the U.S. Army's 5X Decontamination Review
262
Appendix I,
Ionizing Radiation
271
Appendix J,
Electrochemical Oxidation
274
Appendix K,
Additional Data and Material Balances for Wet Air Oxidation, Supercritical Water Oxidation, and the Synthetica Detoxifier
279
REFERENCES
292
INDEX
311
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Alternative Technologies for the Destruction of Chemical Agents and Munitions
Figures
1-1
Schematic of the baseline technology.
25
2-1
Principal Chemical warfare agents in the U.S. stockpile.
38
2-2
M55 rocket and M23 land mine.
43
2-3
105-ram, 155-ram, 8-inch, and 4.2-inch projectiles.
44
2-4
Bomb, spray tank, and ton container.
45
2-5
Physical envelopes of chemical munitions.
50
2-6
Types of agent and munitions and percentage of total agent stockpile (by weight of agent) at each storage site.
50
4-1
JACADS Demilitarization process.
79
7-1
WAO flow diagram.
140
7-2
SCWO flow sheet (MODAR type).
147
7-3
The Molten Metal Technology.
154
7-4
Process flow sheet of the Elkem Multipurpose Furnace and associated equipment.
155
7-5
The Westinghouse plasma system.
158
7-6
The Electro-Pyrolysis, Inc. (EPI) furnace design.
159
7-7
Lurgi gasifier.
162
7-8
Schematic flow sheet for the Synthetica Steam Detoxifier.
164
7-9
Molten salt oxidation system.
172
7-10
Block flow diagram of the UOP HyChlor conversion process.
177
7-11
A process flow sheet for the Adams process as presented by CHEMLOOP, L.P.
181
8-1
Unit processes in demilitarization Strategy 1: disassembly and agent detoxification, with storage or transportation of residue.
198
8-2
Unit processes for demilitarization Strategy 2: mineralization.
199
K-1
Apparent first-order arrhenius plot for oxidation of model compounds in supercritical water at 24.6 MPa.
286
K-2
Heat and Material Balances for the Synthetica System.
289
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Alternative Technologies for the Destruction of Chemical Agents and Munitions
Tables
1-1
Schedule for the Construction and Operation of Chemical Stockpile Disposal Facilities
27
2-1
Physical Properties of Chemical Warfare Agents
39
2-2
Composition of Munitions in the U.S. Chemical Stockpile
47
2-3
Composition of Selected Chemical Munition Types, by Weight
48
2-4
Chemical Munitions Stored in the Continental United States
51
2-5
Approximate Amounts of Metals, Energetics and Agent Contained in the Chemical Weapons Stockpile (tons), by Site
52
3-1
U.S. Army Experience with Destruction of H (Mustard) by Incineration
55
3-2
U.S. Army Experience with Destruction of GB (Sarin) by Neutralization
56
3-3
U.S. Army Experience with Destruction of GB (Sarin) by Incineration, at CAMDS
57
3-4
U.S. Army Experience with Destruction of GB (Satin) by Incineration, at JACADS
58
3-5
U.S. Army Experience with Destruction of VX by Incineration, at CAMDS
59
3-6
U.S. Army Experience with Destruction of VX by Incineration, at JACADS
60
3-7
U.S. Army Experience with Destruction of HD by Incineration, at JACADS
61
3-8
Canadian Experience with Mustard Agent Destruction (1974 to 1976)
63
3-9
Canadian Experience with Mustard Destruction in 1990 to 1991
64
3-10
Canadian Experience with Nerve Agent Destruction
65
3-11
German Experience with Mustard Agent Destruction
66
3-12
Former Soviet Union Experience with Agent Destruction
67
3-13
Former Soviet Union Experience with VX Destruction
68
3-14
U.K Experience with Destruction of Mustard and World War I Gases
69
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Alternative Technologies for the Destruction of Chemical Agents and Munitions
3-15
U.K. Experience with GB Destruction
70
3-16
U.K. Experience with Mustard Destruction
71
3-17
U.N. Experience with Destruction of Mustard in Iraq
72
3-18
U.N. Experience with Destruction of Nerve Agents in Iraq
73
4-1
Permissible Agent Hazard Concentrations in Air and Lethal Doses
82
4-2
Time Estimates for Development and Demonstration of Alternative Technologies
91
5-1
Salt Formation from GB Oxidation Products
100
6-1
Oxidation Potential of Different Chemical Species
126
6-2
Enzymes Capable of Degrading Organophosphorus Neurotoxins
129
7-1
Recommended WAO Operating Temperatures and Saturation Pressures for Destruction of Chemical Warfare Agents and Propellants
142
7-2
Estimated Effluent Gas Composition for Two-Step Destruction of GB, Hydrolysis Followed by WAO (Using Air)
145
7-3
Some Characteristics of Gasifiers
161
8-1
Summary of Process Capabilities and Status
187
8-2
Low-and Moderate-Temperature Agent Detoxification Processes
201
8-3
Agent Mineralization Processes
202
8-4
Processes for Treatment of Energetics and Metal Parts and Containers
204
K-1
Chemicals Successfully Treated by Supercritical Water Oxidation and Typical Destruction Efficiencies
282
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Alternative Technologies for the Destruction of Chemical Agents and Munitions
Acronyms and Abbreviations
ACAMS
Automatic Chemical Agent Monitoring System
AChe
Acetylcholine
AChE
Acetylcholinesterase
ANAD
Anniston Army Depot
APG
Aberdeen Proving Ground
ARPA
Advanced Research Projects Agency
ASC
Allowable Stack Concentration
BOD
Biological oxygen demand
BRA
Brine Reduction Area
CAMDS
Chemical Agent Munitions Disposal System
CIS
Commonwealth of Independent States, formerly the Soviet Union
COD
Chemical oxygen demand
CRDEC
Chemical Research, Development and Engineering Center
CS
Riot control agent
CSDP
Chemical Stockpile Disposal Program
DAAMS
Depot Area Air Monitoring System
DMSO
Dimethyl sulfoxide
DOD
U.S. Department of Defense
DOE
U.S. Department of Energy
DPE
Demilitarization Protective Ensemble
DRE
Destruction and Removal Efficiency
DRMO
Defense Reutilization and Marketing Office
EIS
Environmental Impact Statement
EPA
Environmental Protection Agency
FRP
Fiberglass Reinforced Plastic
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Alternative Technologies for the Destruction of Chemical Agents and Munitions
GA
Tabun
GB
Satin
GPL
General Population Levels
H, HD, and HT
Blister or mustard agents
HLE
High Level Exposure
IARC
International Agency for Research on Cancer
IDLH
Immediately Dangerous to Life and Health
IUPAC
International Union of Pure and Applied Chemistry
JACADS
Johnston Atoll Chemical Agent Disposal System
L
Lewisite
LBAD
Lexington Blue Grass Army Depot
MBE
Moving bed evaporator
MDL
Minimum Detection Limits
MEO
Mediated electrochemical oxidation
MMT
Molten Metal Technology
MPF
Metal Parts Furnace
NAAP
Newport Army Ammunition Plant
NAS
National Academy of Sciences
NEPA
National Environmental Policy Act
NESHAP
National Emission Standards for Hazardous Waste Pollutants
NRC
National Research Council
OTA
Office of Technology Assessment
OVT
Operational verification testing
PBA
Pine Bluff Arsenal
PCB
Polychlorinated biphenyl
PCP
Pentachlorophenol
PEIS
Programmatic Environmental Impact Statement
PL
Public Law
PUDA
Pueblo Army Depot
R&D
Research and development
RCRA
Resource Conservation and Recovery Act
RDEC
Research, Development and Engineering Center
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Alternative Technologies for the Destruction of Chemical Agents and Munitions
SANA
Scientists Against Nuclear Arms
SCWO
Supercritical water oxidation
SNG
Synthetic natural gas
SRI
Southwest Research Institute
TCDD
Tetrachlorodibenzodioxin
TCDF
Tetrachlorodibenzofuran
TEAD
Tooele Army Depot
TNT
Trinitrotoluene
TSCA
Toxic Substances Control Act
TSDF
Treatment, Storage, and Disposal Facilities
TWA
Time Weighted Average
UMDA
Umatilla Army Depot
USATHAMA
U.S. Army Toxic and Hazardous Materials Agency
UV
Ultraviolet
VX
Organophosphate nerve agent
WAO
Wet air oxidation
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Alternative Technologies for the Destruction of Chemical Agents and Munitions
ALTERNATIVE TECHNOLOGIES FOR THE DESTRUCTION OF CHEMICAL AGENTS AND MUNITIONS
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Alternative Technologies for the Destruction of Chemical Agents and Munitions
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