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



The National Academies | 500 Fifth St. N.W. | Washington, D.C. 20001
Copyright © National Academy of Sciences. All rights reserved.
Terms of Use and Privacy Statement



Below are the first 10 and last 10 pages of uncorrected machine-read text (when available) of this chapter, followed by the top 30 algorithmically extracted key phrases from the chapter as a whole.
Intended to provide our own search engines and external engines with highly rich, chapter-representative searchable text on the opening pages of each chapter. Because it is UNCORRECTED material, please consider the following text as a useful but insufficient proxy for the authoritative book pages.

Do not use for reproduction, copying, pasting, or reading; exclusively for search engines.

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

OCR for page R1
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

OCR for page R1
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

OCR for page R1
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)

OCR for page R1
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.

OCR for page R1
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

OCR for page R1
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

OCR for page R1
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

OCR for page R1
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

OCR for page R1
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

OCR for page R1
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

OCR for page R1
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

OCR for page R1
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

OCR for page R1
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

OCR for page R1
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

OCR for page R1
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

OCR for page R1
Alternative Technologies for the Destruction of Chemical Agents and Munitions ALTERNATIVE TECHNOLOGIES FOR THE DESTRUCTION OF CHEMICAL AGENTS AND MUNITIONS

OCR for page R1
Alternative Technologies for the Destruction of Chemical Agents and Munitions This page in the original is blank.