Using Supercritical Water Oxidation to Treat Hydrolysate from VX Neutralization

Committee on Review and Evaluation of the Army Chemical Stockpile Disposal Program

Board on Army Science and Technology

Commission on Engineering and Technical Systems

National Research Council

NATIONAL ACADEMY PRESS
Washington, D.C.
1998



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Using Supercritical Water Oxidation to Treat Hydrolysate from VX Neutralization Using Supercritical Water Oxidation to Treat Hydrolysate from VX Neutralization Committee on Review and Evaluation of the Army Chemical Stockpile Disposal Program Board on Army Science and Technology Commission on Engineering and Technical Systems National Research Council NATIONAL ACADEMY PRESS Washington, D.C. 1998

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Using Supercritical Water Oxidation to Treat Hydrolysate from VX Neutralization 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. 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. Bruce Alberts 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. William A. Wulf is interim 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. Bruce M. Alberts and Dr. William A. Wulf are chairman and vice chairman, respectively, of the National Research Council. This is a report of work supported by Contract DAAG55-98-C-0021 between the U.S. Army and the National Academy of Sciences. Any opinions, findings, conclusions, or recommendations expressed in this publication are those of the author(s) and do not necessarily reflect the view of the organizations or agencies that provided support for the project. International Standard Book Number 0-309-06043-5 Limited copies are available from: Board on Army Science and Technology National Research Council 2101 Constitution Avenue, N.W. Washington, DC 20418 (202) 334-3118 Copies are available for sale from: National Academy Press 2101 Constitution Avenue, N.W. Washington, DC 20418 800-624-6242 or 202-334-3313 Copyright 1998 by the National Academy of Sciences. All rights reserved. Printed in the United States of America.

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Using Supercritical Water Oxidation to Treat Hydrolysate from VX Neutralization COMMITTEE ON REVIEW AND EVALUATION OF THE ARMY CHEMICAL STOCKPILE DISPOSAL PROGRAM RICHARD S. MAGEE, chair, New Jersey Institute of Technology, Newark ELISABETH M. DRAKE, vice chair, Massachusetts Institute of Technology, Cambridge DENNIS C. BLEY, Buttonwood Consulting, Inc., Oakton, Virginia J. ROBERT GIBSON, DuPont Agricultural Products, Wilmington, Delaware MICHAEL R. GREENBERG, Rutgers, The State University of New Jersey, New Brunswick KATHRYN E. KELLY, Delta Toxicology, Crystal Bay, Nevada CHARLES E. KOLB, Aerodyne Research, Inc., Billerica, Massachusetts DAVID S. KOSSON, Rutgers, The State University of New Jersey, New Brunswick JAMES F. MATHIS, Exxon Corporation (retired), Summit, New Jersey WALTER G. MAY, University of Illinois, Urbana ALVIN H. MUSHKATEL, Arizona State University, Tempe GEORGE W. PARSHALL, DuPont Company (retired), Wilmington, Delaware H. GREGOR RIGO, Rigo & Rigo Associates, Inc., Berea, Ohio ARNOLD F. STANCELL, Georgia Institute of Technology, Atlanta WILLIAM TUMAS, Los Alamos National Laboratory, Los Alamos, New Mexico Board on Army Science and Technology Liaison RICHARD A. CONWAY, R.A. Conway Associates, Charleston, West Virginia Staff BRUCE A. BRAUN, Director, Division of Military Science and Technology DONALD L. SIEBENALER, Study Director HARRISON T. PANNELLA, Consultant SHIREL R. SMITH, Senior Project Assistant

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Using Supercritical Water Oxidation to Treat Hydrolysate from VX Neutralization BOARD ON ARMY SCIENCE AND TECHNOLOGY CHRISTOPHER C. GREEN, chair, General Motors Corporation, Warren, Michigan WILLIAM H. FORSTER, vice chair, Northrop Grumman Corporation, Baltimore, Maryland GARY L. BORMAN, University of Wisconsin, Madison RICHARD A. CONWAY, Union Carbide Corporation, Charleston, West Virginia GILBERT F. DECKER, Consultant, Los Gatos, California LAWRENCE J. DELANEY, Delaney Group, Potomac, Maryland MARYE ANNE FOX, University of Texas, Austin ROBERT J. HEASTON, Guidance and Control Information Analysis Center (retired), Naperville, Illinois ELVIN R. HEIBERG, III, Heiberg Associates, Inc., Mason Neck, Virginia GERALD J. IAFRATE, University of Notre Dame, Indiana KATHRYN V. LOGAN, Georgia Institute of Technology, Atlanta THOMAS L. MCNAUGHER, RAND Corporation, Washington, D.C. JOHN H. MOXLEY, III, Korn/Ferry International, Los Angeles, California STEWART D. PERSONICK, Bell Communications Research, Inc., Morristown, New Jersey MILLARD F. ROSE, Auburn University, Auburn, Alabama CLARENCE G. THORNTON, Army Research Laboratories (retired), Colts Neck, New Jersey JOHN D. VENABLES, Venables and Associates, Towson, Maryland JOSEPH J. VERVIER, ENSCO, Inc., Melbourne, Florida ALLEN C. WARD, Ward Synthesis, Inc., Ann Arbor, Michigan Staff BRUCE A. BRAUN, Director MARGO L. FRANCESCO, Staff Associate ALVERA GIRCYS, Financial Associate DEANNA SPARGER, Project Assistant

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Using Supercritical Water Oxidation to Treat Hydrolysate from VX Neutralization Preface The United States has maintained a stockpile of highly toxic chemical agents and munitions for more than half a century. In 1985, Public Law 99-145 mandated an “expedited” effort to dispose of M55 rockets containing unitary chemical warfare agents because of their potential for self-ignition. This program soon expanded into the Army Chemical Stockpile Disposal Program (CSDP), whose mission was to eliminate the entire stockpile of unitary chemical weapons. The CSDP developed the current baseline incineration system for that purpose. Since 1987, the National Research Council (NRC), through its Committee on Review and Evaluation of the Army Chemical Stockpile Disposal Program (Stockpile Committee), has overseen the Army's disposal program and has endorsed the baseline incineration system as an adequate technology for destroying the stockpile. In 1992, after setting several intermediate goals and dates, Congress enacted Public Law 102-484, which directed the Army to dispose of the entire stockpile of unitary chemical warfare agents and munitions by December 31, 2004. In response to growing public concerns about, and opposition to, incineration, the Army has been investigating alternatives. In 1993-1994, the Stockpile Committee reviewed an earlier NRC study of alternative technologies and recommended that the Army continue research on four alternative technology combinations for agent destruction, all based on neutralization (chemical hydrolysis). The committee was concerned, however, that neutralization alone might not be sufficient to meet destruction and disposal requirements and recommended that the Army consider four different post-neutralization treatment options: biodegradation; incineration; wet air oxidation followed by biological oxidation; and supercritical water oxidation. The Army decided that it could pursue only two options within its funding and time constraints: neutralization; and neutralization followed by biological treatment. In 1995, at the request of the assistant secretary of the Army for research, development and acquisition, the NRC established the Panel on Review and Evaluation of Alternative Disposal Technologies (AltTech Panel) to reexamine the status of a limited number of maturing alternative chemical disposal technologies (including the two neutralization-based processes on which the Army was then conducting research) for possible implementation at the two bulk-storage sites at Aberdeen Proving Ground, Maryland, and the Newport Chemical Activity, Indiana. The AltTech Panel's NRC report recommended that the Army pilot-test VX neutralization with sodium hydroxide solution at Newport. The report also recommended that, if on-site disposal of the VX hydrolysate (from the neutralization process) was preferable to shipping it off site for treatment, existing commercial processes other than biodegradation should be considered because research on existing biodegradation processes has shown that they do not achieve adequate destruction. In 1997, after reviewing several secondary treatment options, the Army selected supercritical water oxidation (SCWO) as the most promising technology for treating the VX hydrolysate. SCWO technology has developed from bench-scale testing to a few pilot-scale demonstrations, as well as one current and several pending full-scale operations to treat hazardous wastes. The Army recognized that further development and testing would be necessary before a full-scale SCWO treatment system could be designed, installed, and operated and requested that the NRC evaluate whether SCWO would be an effective and appropriate method for treating VX hydrolysate for ultimate disposition. The NRC was not asked to conduct an in-depth analysis of the entire VX bulk agent destruction and disposal process for the Newport Chemical Agent Disposal Facility. When the facility design is being finalized (March 1999–April 2000), the NRC may be asked to assess all aspects of the facility design, including monitoring, containment, process control, and redundancy, as well as the quantitative risk assessment (QRA). This report has been reviewed by individuals chosen for their diverse perspectives and technical expertise, in accordance with procedures approved by the NRC's

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Using Supercritical Water Oxidation to Treat Hydrolysate from VX Neutralization Report Review Committee. The purpose of this independent review is to provide candid and critical comments that will assist the authors and the NRC 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 remain 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: Thomas Barton Brill, University of Delaware Steven Joseph Buelow, Los Alamos National Laboratory Emily A. Carter, University of California, Los Angeles Robert E. Connick, University of California, Berkeley Ruth M. Davis, Pymatuning Group, Inc. Gene H. Dyer, Bechtel (retired) Henry J. Hatch, Fluor Daniel Hanford, Inc. (U.S. Army, retired) Keith Paul Johnston, University of Texas Michael Klein, University of Delaware John P. Longwell, Massachusetts Institute of Technology Alexander MacLachlan, E.I. duPont de Nemours & Company (retired) Barry M. Trost, Stanford University While the individuals listed above have provided many constructive comments and suggestions, responsibility for the final content of this report rests solely with the authoring committee and the NRC. The committee greatly appreciates the support and assistance of National Research Council staff members Donald L. Siebenaler, Shirel R. Smith, Margo L. Francesco, and Carol R. Arenberg, as well as NRC consultant Harrison T. Pannella, in the production of this report. Richard S. Magee, chair Elisabeth M. Drake, vice chair Committee on Review and Evaluation of the Army Chemical Stockpile Disposal Program

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Using Supercritical Water Oxidation to Treat Hydrolysate from VX Neutralization Contents     EXECUTIVE SUMMARY   1  1   INTRODUCTION AND BACKGROUND   7      Selection of Neutralization Followed by Supercritical Water Oxidation for Stockpile Disposal at Newport, Indiana,   7      VX Storage at Newport, Indiana,   7      Neutralization of VX,   8  2   PROCESS DESCRIPTION AND SCIENTIFIC PRINCIPLES   11      Process Overview,   11      Scientific Principles,   12      Kinetics,   13      Phase Behavior,   14  3   TECHNOLOGY STATUS   15      Previous Applications of Supercritical Water Oxidation Technology,   15      Development Program for Application to VX Hydrolysate,   20      Laboratory-Scale Tests to Establish Methylphosphonic Acid DREs,   21      Pilot-Scale Testing with Surrogates and VX Hydrolysate,   22      Toxicity of the Liquid Effluent,   28      Summary of Solids Management and System Performance,   29      Status of Evaporator Technology,   32  4   SCALE-UP, STABILITY, AND RELIABILITY   35      Process Scale-Up,   35      Salt Management and Reactor Design,   35      Higher Pressure Systems,   37      Dissolution in Molten Sodium Hydroxide,   37      Catalyzed Oxidation,   37      Transpiring Wall Reactor,   37      Engineering Control,   37      Conclusion,   37      Choice of Oxidant, Mixing, and Heat Balance,   38      Corrosion and the Materials of Construction,   38      Pressure Let-Down Systems,   39      Summary,   39

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Using Supercritical Water Oxidation to Treat Hydrolysate from VX Neutralization  5   FULL-SCALE PROCESS DESIGN   41      Process Description,   41      Process Start-Up and Shutdown,   43      Process Mass and Energy Balances,   43      Process Monitoring and Control,   45      Managing Upsets and Maintenance,   46      Process Safety,   47      Process Effluent Requirements,   48      Technology Implementation Timeline,   49      Environmental Permit Requirements,   50  6   FINDINGS AND RECOMMENDATIONS   52      Findings,   52      Recommendations,   53     REFERENCES   55     APPENDICES       A  Process Flow Diagrams for the Supercritical Water Oxidation and Evaporation Process Steps   61     B  Mass Balance for the Newport Chemical Agent Disposal Facility (NECDF) Process   65

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Using Supercritical Water Oxidation to Treat Hydrolysate from VX Neutralization List of Figures and Tables Figures  ES-1   Overview of the disposal process for VX ton containers,   2  2-1   Block diagram of the overall neutralization and SCWO treatment process,   11  3-1   Schematic diagram of a transpiring wall reactor,   16  3-2   MPA DRE without sodium hydroxide and at 200 percent stoichiometric oxygen and 27.6 MPa as a function of temperature and residence time,   21  3-3   Simplified SCWO process flow diagram for pilot-scale testing with salt simulants and VX hydrolysate treatability studies (August 1996),   22  3-4   Normalized salt transport through the reactor during the pilot-scale treatability testing with salt simulants and with VX hydrolysate (August 1996),   25  3-5   Reactor wall temperature, pressure, and sampling history during the eight-hour hydrolysate test,   27  3-6   Internal reactor temperature for the uppermost region (feed end) of the reactor,   28  3-7   Liquid effluent pH and salt balance during the VX hydrolysate test campaign,   29  5-1   Overview of the disposal process for VX ton containers,   41  A-1   Process flow diagram for the SCWO process step (design basis),   63  A-2   Process flow diagram for the evaporation process step (design basis),   64  B-1   Process flow diagram for the integrated NECDF process,   67 Tables  1-1   Composition of Hydrolysate from Neutralization of VX,   9  3-1   Summary and Comparison of the Newport Chemical Agent Disposal Facility (NECDF) with Pilot Testing and Full-Scale Operation of SCWO Treatment Processes to Date,   17  3-2   Summary and Comparison of Full-Scale SCWO Treatment Processes Planned or under Construction as of December 1997,   19  3-3   Liquid Effluent Concentrations of VX Hydrolysate Constituents and DREs Observed during Pilot-Scale Treatability Testing (August 13, 1996),   24  3-4   Composition of Off-Gas Produced during Pilot-Scale Treatability Testing (August 13, 1996),   24  3-5   Analyses of Feed and Liquid Effluent for Specific Hydrolysate Constituents, TOC, and COD,   30  3-6   Analytical Precision and Accuracy Testing Results for TOC, MPA, and VX Thiol,   31

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Using Supercritical Water Oxidation to Treat Hydrolysate from VX Neutralization  3-7   Calculated DREs Based on Liquid Effluent Samples,   32  3-8   Composition of Effluent Gas,   33  3-9   Summary of Evaporator Installations Similar to the Design Specifications for NECDF,   33  4-1   Comparison of Full-Scale Design with Pilot-Scale Design Tested with VX Hydrolysate (February 1997),   36  5-1   Composition of the Post-Treatment SCWO Aqueous Effluent and the Solid Salt Streams,   44  5-2   Technology Implementation Timeline at NECDF (as of February 5, 1998),   50  B-1   NECDF Inputs for Process Mass Balance,   68  B-2   NECDF Outputs for Process Mass Balance,   69  B-3   Water Formation Resulting from the Neutralization of VX and Oxidation of the Hydrolysate during the NECDF Process,   70

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Using Supercritical Water Oxidation to Treat Hydrolysate from VX Neutralization Acronyms COD chemical oxygen demand CSDP Chemical Stockpile Disposal Program CWC Chemical Weapons Convention DMMP dimethyl methylphosphonate DRE destruction removal efficiency EFFDRUM effluent drum EMPA ethyl methylphosphonic acid EPA Environmental Protection Agency HEPA high-efficiency particulate air µmhos/cm micro siemens/centimeter (unit of conductance equal to the reciprocal of the ohm) MPA methylphosphonic acid NECDF Newport Chemical Agent Disposal Facility NEPA National Environmental Policy Act NMR nuclear magnetic resonance NRC National Research Council PPE personal protective equipment QRA quantitative risk assessment RCRA Resource Conservation and Recovery Act SCWO supercritical water oxidation SIP State Implementation Plan TC ton container TCC ton container cleanout TDS total dissolved solids TOC total organic carbon TSDF treatment, storage, and disposal facility VOC volatile organic compound VX a specific type of nerve agent

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