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Board on Army Science and Technology Mailing Address: 500 Fifth Street, NW Washington, DC 20001 www.nationalacademies.org July 3, 2006 Mr. Michael A. Parker Director Chemical Materials Agency 5183 Blackhawk Road Edgewood Area Aberdeen Proving Ground, MD 21010-5424 Re: Review and Assessment of the Proposals for Design and Operation of Designated Chemical Agent Destruction Pilot Plants (DCAPPBlue Grass) Dear Mr. Parker: As requested by the Program Manager, Assembled Chemical Weapons Alternatives (PMACWA), the National Research Council (NRC) of the National Academies has established two committees to review and assess proposals related to two different chemical agent destruction pilot plants. The first committee, the Committee to Review and Assess the Proposals for Design and Operation of Designated Chemical Agent Destruction Pilot Plants (DCAPPBlue Grass), now provides this letter report on the intermediate design for the supercritical water oxidation (SCWO) process design at the Blue Grass Chemical Agent Destruction Pilot Plant (BGCAPP) in Richmond, Kentucky (see Attachment A for the statement of task). A second committee will address the modified design of the Pueblo Chemical Agent Destruction Pilot Plant in Pueblo, Colorado. This study was initiated on April 3, 2006, and had to be completed within 60 days to support the sponsor's accelerated Defense Acquisition Board process. In view of the short study schedule and the detailed nature of the task, the NRC selected committee members with extensive past experience in SCWO, the treatment of secondary wastes, and the destruction of chemical weapons. The DCAPPBlue Grass Committee (see Attachment B for committee composition and expertise) has reviewed and assessed the proposal submitted by the Bechtel Parsons Blue Grass Team (BPBGT) and General Atomics Advanced Process Systems (GA) for the design and operation of the SCWO process at the BGCAPP (see Attachment C for references). The committee's findings are set forth in this letter. Attachment D contains the full assessment, which is not accessible to the public under the provisions of Subsection 15(b)(3) of the Federal Advisory Committee Act, 5 U.S.C. App., as amended by the Federal Advisory

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Committee Act Amendments of 1997, P.L. 105-153, December 17, 1997, 111 Stat. 2689. The National Research Council has determined that release of this information to the public would disclose information described in 5 U.S.C. 552(b). BACKGROUND In 2003, the Army issued a request for a proposal to design, build, operate, and close a full-scale pilot plant facility for the destruction of chemical weapons at the Blue Grass Army Depot (BGAD). A system contract was awarded to the BPBGT, a joint venture formed by Bechtel Corporation and Parsons Corporation. The teaming subcontractors are Battelle, General Physics Corporation, General Atomics Advanced Process Systems (GA), and the Washington Demilitarization Company. Because the life-cycle cost estimate was high, several efforts have been made to identify alternative design configurations and life-cycle cost options that would reduce the costs of the Blue Grass facility. Thus, the contractor has proposed a modified design to comply with DOD's instructions. This letter report focuses only on the technical aspects, maturity, and schedule of the proposed modified SCWO process design for BGCAPP, the overall design of which will be considered by the Defense Acquisition Board in August. The munitions stored at the BGAD contain the nerve agents GB (C4H10FO2P) and VX (C11H26NO2PS), or Levinstein mustard agent (H) (C4H8Cl2S). After removal from the weapons, the chemical agents and the energetic materials will be destroyed by neutralization (hydrolysis)1 with a hot caustic (NaOH) solution for GB, VX, and the energetics, and hot water for H. All of these reactions produce a multicomponent waste stream called hydrolysate, a hazardous material that must (1) undergo further treatment prior to being released into the environment or (2) be sent to a disposal facility. The system contractor, BGCAPP, proposes treating it by SCWO. A block diagram of the entire BGCAPP design is shown in Figure 1-1. 1"Neutralization," as used here, is the Army's term for the chemical destruction of agent. The scientific term "neutralization" refers to adjustment of pH to a value of 7. The term is used in both senses in various places in the report. 2

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1 Agent and Energetics Contaminated Rocket Motors, Drained 3 Access, Rocket Warheads, Bursters from the H Projectiles Energetics Separation Treatment (RCM, RSM, PMD, (EBH, ENR, OTE) EBH solids MWS) Energetics 2 Hydrolysate GB / VX / H Agent 5a Neutralization Aluminum Precipitation Munition Bodies (ANS) and Solid Debris & Filtration 4 Energetics Hydrolysate Metal Parts Agent Treatment Hydrolysate 5b SCWO and Water (MPT, OTM) Recovery Aluminum 6 (SCWO, RO) Solids Filtercake Waste Disposal Non-Contaminated Motors*, Dunnage. RO Reject (Brine) RCM Rocket Cutter Machine MPT Metal Parts Treater RSM Rocket Shear Machine OTM Offgas Treatment System for MPT PMD Projectile Mortar Disassembly OTE Offgas Treatment System for EBH MWS Munitions Washout System SCWO Supercritical Water Oxidation EBH Energetics Batch Hydrolyzer RO Reverse Osmosis ENR Energetics Neutralization Reactor * - non contaminated rocket motor ANS Agent Neutralization System (NCRM) disposition still under review FIGURE 1-1 Simplified block diagram of the BGCAPP process. SOURCE: Adapted from a briefing by the BPBGT to the Blue Grass Chemical Destruction Community Advisory Board on March 15, 2006. SCWO uses water at a temperature and pressure above its critical point of 374C (705F) and 221 bar (3,205 psi). A SCWO unit operates over a range of temperatures depending on a variety of factors that include flow rate and composition. The design operating conditions for the BGCAPP SCWO units are T = 600-650C (1112-1202F) and 234 bar (3,400 psi). Under these conditions, the density of supercritical water is about one-tenth that of the normal liquid. The associated increase in the intermolecular distances produces a great attenuation of the hydrogen bonding that is so characteristic of water under normal conditions. Thus, organic materials that are immiscible in water under normal conditions are miscible in supercritical water, but inorganic salts that normally dissolve in water do not dissolve in supercritical water. Air or oxygen is introduced into the SCWO reactor with the wastes to be treated. A fuel is added if the waste has inadequate energy content. Organic feed streams are oxidized to form carbon dioxide and water. Sulfur, halogens, and phosphorus in the feed streams are oxidized to sulfates, halides, or phosphates, respectively, because SCWO products containing halogens, phosphorus, or sulfur could rapidly corrode the reactor walls. After oxidation, the reaction 3

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products must be brought back to atmospheric pressure through a pressure letdown system before being released for further processing or disposal. Historically, SCWO technology has had only limited application in industry, primarily on organic-rich streams with low concentrations of salt-forming elements. Problems, including extensive corrosion of the reactor walls and components, plugging by the insoluble salts formed in the oxidation, and hydriding of replaceable liners, have hampered the development of SCWO technology for treating feed streams with high salt content. SCOPE AND METHODOLOGY The committee was directed to assess the technical aspects of the SCWO system configuration, its maturity, and its ability to meet the proposed schedule2 for BGCAPP. The design proposed for the SCWO processing system is an integral part of the overall Blue Grass design, which is being reviewed separately. For the purpose of this report, it is assumed that the other elements of the design will adequately support the planned operation of the SCWO system. This report evaluates only the SCWO process design for PMACWA. The committee received, reviewed, and assessed numerous documents and their supporting material. These documents are exempt from public disclosure under Subsection 15(b)(3) of the Federal Advisory Committee Act, 5 U.S.C. App., as cited on page 2. Documents reviewed include, but are not limited to, the following: System design descriptions for the supercritical water oxidation system, the aluminum precipitation system, and the aluminum filtration system. Engineering Design Studies Final Test Report, Volumes II (Supercritical Water Oxidation) and III (Supercritical Water Oxidation Appendices). Throughput and Availability Analysis for the Blue Grass Chemical Agent Destruction Pilot Plant (BGCAPP) Project. Process flow diagrams for the supercritical water oxidation system, the aluminum precipitation system, and the aluminum filtration system. Briefings of the BGCAPP SCWO Intermediate Design Review. Mass and energy balance documents for the SCWO, the aluminum precipitation system, and the aluminum filtration system. Preliminary hazard analyses of the SCWO and the aluminum systems. Aluminum Filtration System Aluminum Filtration Selection white paper. Technical risk reduction reports on supercritical water oxidation accelerated blended feed tests and blended feed performance tests. 2 Schedule, as normally defined, does not apply to the SCWO process because SCWO is the final unit in the process and it is only required to treat the hydrolysate at the rate it is generated. In order to comply with the statement of task, the committee has used the throughput rate in place of schedule. 4

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Summary of General Atomics Engineering Design Studies I Energetics Rotary Hydrolyzer (ERH) and Supercritical Water Oxidation (SCWO) Process Testing (Hydrolysates of GB, VX, and Comp B/M28), Final Technical Report, Volume 1 of 2. Summary of General Atomics Engineering Design Study I Supercritical Water Oxidation (SCWO) Testing, H and Tetrytol Campaigns, Final Technical Report. An evaluation of alternative SCWO configurations. An Assessment of the Supercritical Water Oxidation (SCWO) Engineering-Scale Test (EST). A PMACWA Summary of General Atomics ACWA Engineering Design Studies Testing. Materials handling, mechanical multipurpose, architectural drawings, and 3-D renderings. Piping and instrument diagrams. Two committee meetings were held. During the first, oral presentations by the PMACWA, the system contractor (BGBPT), and the subcontractor GA were heard, and considerable discussion took place between the committee and the subject-matter experts. Follow-on exchanges with the contractor took place electronically in response to additional questions from the committee. The second meeting was focused on finalizing the written proposal review. The committee's evaluation is based on all the design and testing results that were presented and is focused on the known issues associated with SCWO technology. The committee members' judgments were based on their combined experience and expertise in SCWO applications, chemical processing, and risk assessment and safety, and on their participation as committee members in past NRC evaluations.3 In this regard, the committee focused on the following topics: Corrosion, hydriding, and salt transport, Feed definition, Use of simulants for hydrolysate testing, Scale-up, Availability and maintainability, Safety, and Understanding of the chemical and physical processes. 3Analysis of Engineering Design Studies for Demilitarization of Assembled Chemical Weapons at Blue Grass Army Depot (2002); Update on the Engineering Design Studies Evaluated in the NRC Report, Analysis of Engineering Design Studies for Demilitarization of Assembled Chemical Weapons at Blue Grass Army Depot: Letter Report (2002); Review and Assessment Program Options for Agent Destruction Pilot Plants at Blue Grass: Letter Report (2005); Interim Design Assessment for the Blue Grass Chemical Agent Destruction Pilot Plant (2005). All of these reports were published in Washington, D.C., by the National Academies Press. 5

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FINDINGS These general findings summarize the conclusions of the committee regarding the design proposal. The supporting narrative for these findings is given in the body of the report. Finding 1. The committee believes that although the SCWO technology being designed for the Blue Grass Chemical Agent Destruction Pilot Plant is not technically mature, it can be used in the proposed application if adequate testing is performed. Finding 2. The committee believes that, at the proposed flow rates, the full-size SCWO unit could have an unacceptably high level of technical risk because there is no mechanistic understanding of corrosion, hydriding, salt flow, and, in particular, the effect of fluid velocity in the reaction zone. The committee believes the level of technical risk would be acceptable for the near-full-scale SCWO unit at the flow rates demonstrated during testing. Finding 3. The technical risk for the proposed full-size SCWO unit at the proposed flow rates could become acceptable if adequate additional testing is performed before the unit is used. Such testing could be performed at the proposed full-scale velocity in existing General Atomics reactors. Finding 4. Whether or not the proposed full-scale SCWO design can meet the schedule for the Blue Grass Chemical Agent Destruction Pilot Plant depends on obtaining satisfactory results in testing at higher flow rates. This assumes that the other elements of the BGCAPP processes operate as planned. Finding 5. Although the experimental evidence presented to the committee for assessment of the SCWO unit design for the Blue Grass Chemical Agent Destruction Pilot Plant is persuasive, there is a lack of basic understanding of the physical and chemical processes involved in achieving tolerable corrosion rates and in the corrosion process itself. 6

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Sincerely, Robert A. Beaudet, Chair Committee to Review and Assess the Proposals for Design and Operation of Designated Chemical Agent Destruction Pilot Plants (DCAPP BlueGrass) Attachments: A, Statement of Task B, Committee Membership--Roster and Biographies C, References D, Assessment (source selection information; not available to the public) E, Acknowledgment of Reviewers 7

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Attachment A Statement of Task Contractual Statement of Task The NRC will establish an ad hoc Committee to Review and Assess the Proposals for Design and Operation of Designated Chemical Agent Destruction Pilot Plants (DCAPP Committee). This new committee will receive, review, and assess the proposals submitted by the Bechtel National, Inc. for the Pueblo Chemical Agent Destruction Pilot Plant in Pueblo, Colorado, and the Blue Grass Chemical Agent Destruction Pilot Plant in Richmond, Kentucky, to consider the technical aspects of systems configurations, maturity, and schedule. The committee will provide a review to the Army of these proposals to advise them in their procurement decisions regarding award of the task order. Plan of Action To accomplish the statement of task, the NRC formed two separate committees to review the proposals for the chemical destruction plants at the Blue Grass Army Depot, Kentucky, and at Pueblo Army Depot, Colorado. The first committee's first task was to review the supercritical oxidation process at Blue Grass, which is the subject of this letter report. The committee will then be augmented to review the remainder of the Blue Grass plant design in a second letter report. A second committee was created to review the Pueblo plant design, and that committee will provide its assessment in still another letter report. 8

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Attachment B Roster and Biographies ROBERT A. BEAUDET, Chair, University of Southern California, Pasadena JOAN B. BERKOWITZ, Farkas Berkowitz & Company, Washington, D.C. WILLARD C. GEKLER, Consultant, PLG, Inc., Los Alamitos, California MARTIN GOLLIN, Carmagen Engineering, Inc., St. Davids, Pennsylvania KENNETH A. SMITH, NAE, Massachusetts Institute of Technology, Cambridge Staff BRUCE A. BRAUN, Director, Board on Army Science and Technology MARGARET N. NOVACK, Study Director JAMES C. MYSKA, Research Associate LAVONNE WILLIS, Senior Program Assistant BIOGRAPHIES Robert A. Beaudet received his Ph.D. in physical chemistry from Harvard University in 1962. From 1961 to 1962, he was a U.S. Army officer and served at the Jet Propulsion Laboratory as a research scientist. He joined the faculty of the University of Southern California in 1962 and has served continuously in the Department of Chemistry since that time. He also has served on Department of Defense committees addressing both offensive and defensive considerations surrounding chemical warfare agents. He was chair of an Army Science Board committee that addressed chemical detection and trace gas analysis. He also was the chair of an Air Force technical conference on chemical warfare decontamination and protection. He has participated in two NRC studies on chemical and biological sensor technologies and energetic materials and technologies. Most of his career has been devoted to research in molecular structure and molecular spectroscopy. Currently, Dr. Beaudet is chair of the Committee on Assembled Chemical Weapons Alternative Program. Previously, Dr. Beaudet served as a member of the NRC's Board on Army Science and Technology (BAST), as a member of the NRC Committee on Review of the Non-Stockpile Chemical Materiel Disposal Program, and as a BAST liaison to the Committee on Review and Evaluation of the Army Chemical Stockpile Disposal Program (Stockpile Committee). Joan B. Berkowitz is currently managing director of Farkas Berkowitz & Company. She graduated from the University of Illinois with a Ph.D. in physical chemistry. Dr. Berkowitz has extensive experience in the area of environmental and hazardous waste management, a knowledge of the technologies available for the cleanup of contaminated soils and groundwater, and a background in physical and electrochemistry. She has contributed to several of the Environmental Protection Agency studies, been a consultant on remediation techniques, and 9

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assessed various destruction technologies. Dr. Berkowitz is the author of numerous publications on hazardous waste treatment and environmental subjects. Willard C. Gekler is currently an independent consultant working for his previous employer, ABS Consulting, Inc. He graduated from the Colorado School of Mines with a B.S. in petroleum refining engineering and pursued graduate study in nuclear engineering at the University of California at Los Angeles. His extensive experience includes membership on NRC's ACWA committee and on the Mitretek Systems expert panel reviewing the quantitative risk assessments and safety analyses of hazardous materials handling, storage, and waste treatment systems for the Army's Anniston, Umatilla, Pine Bluff, and Aberdeen chemical agent disposal facilities. He also participated in a consequence screening assessment for the Newport Chemical Disposal Facility. Previously he was project engineer for various nuclear test facility designs and for development of facility design criteria for the Johnston Atoll chemical agent disposal system. His expertise is in hazard evaluation, quantitative risk analysis, reliability assessment, and database development for risk and reliability. Mr. Gekler is a certified reliability engineer and a member of the Society for Risk Analysis, the American Institute of Chemical Engineers (AIChE), and the American Nuclear Society (ANS). Martin Gollin graduated from Loughborough University of Technology in England with a B.S. and an M.S. in chemical engineering. He is currently a consultant affiliated with Carmagen Engineering, Inc. He has worked for an engineering contractor (Davy McKee), an R&D company (Dynatech), and an operating company (ARCO Chemical). He has extensive experience in process engineering, capital projects, commissioning, process safety, environmental processes, relief system design, and heat transfer. He has held positions in engineering design and engineering management. He was the EH&S manager for a $1 billion grass-roots project in the Netherlands and was a member of the panel that wrote the CCPS book "LOPA--Layer of Protection Analysis." He is a member of the NRC's Non-stockpile Committee and has also been a member of several other NAS committees. He consulted on projects for the CDC, petrochemical companies, and pharmaceutical companies and has presented two courses ("LOPA" and "Process Design for Safe Operations") for the AIChE. Kenneth A. Smith, NAE, is currently Edwin R. Gilliland Professor of Chemical Engineering at Massachusetts Institute of Technology. He received an Sc.D., an S.B., and an S.M. in chemical engineering from MIT and was a postdoctoral fellow at Cavendish Laboratory, University of Cambridge. He was elected to the National Academy of Engineering on the basis of his diverse, creative, and fundamental research in fluid mechanics and rheology, heat and mass transfer, and for professional and educational leadership. Dr. Smith's research interests are in application of the principles of fluid mechanics, thermodynamics, heat transfer, and mass transfer to important engineering problems. Specific applications have included desalination, hemodialysis, atherogensis, liquefied natural gas, aerosols in the atmosphere, and supercritical water oxidation. He has particular expertise in supercritical water oxidation. 10

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Attachment C References Bergman, A.G., A.M. Gasanaliev, and A.S. Trunin. 1969. The ternary system NaCl, SO4, PO3. Russian Journal of Inorganic Chemistry 14: 1675-1676. BPBGT (Bechtel Parsons Blue Grass Team). 2005a. System Design Description for Supercritical Water Oxidation System, Blue Grass Chemical Agent Destruction Pilot Plant (BGCAPP) Project, Revision E, October 29. Aberdeen Proving Ground, Md.: Program Manager for Assembled Chemical Weapons Alternatives. BPBGT. 2005b. Technical Risk Reduction Project 07 and 09: Report on Supercritical Water Oxidation Blended Feed Performance Tests, Revision 0, April. Aberdeen Proving Ground, Md.: Program Manager for Assembled Chemical Weapons Alternatives. BPBGT. 2005c. Technical Risk Reduction Project (TRRP) 07 and 08: Report on Supercritical Water Oxidation Accelerated Blended Feed Tests, Revision 0, January. Aberdeen Proving Ground, Md.: Program Manager for Assembled Chemical Weapons Alternatives. BPBGT. 2005d. Preliminary Hazard Analysis of Supercritical Water Oxidation System: Blue Grass Chemical Agent Destruction Pilot Plant (BGCAPP) Project, Revision C, October 31. Aberdeen Proving Ground, Md.: Program Manager for Assembled Chemical Weapons Alternatives. BPBGT. 2006. Evaluation of ACWA EDS SCWO System Availability and Application of Data to Full-Scale BGCAPP SCWO System, March 30. Aberdeen Proving Ground, Md.: Program Manager for Assembled Chemical Weapons Alternatives. Hodes, M., P.A. Marrone, G.T. Hong, K.A. Smith, and J.W. Tester. 2004. Salt precipitation and scale control in supercritical water oxidation--Part A: Fundamentals and research. The Journal of Supercritical Fluids 29(3): 265-288. Marrone, P.A., M. Hodes, K.A. Smith, and J.W. Tester. 2004. Salt precipitation and scale control in supercritical water oxidation--Part B: Commercial/full-scale applications. The Journal of Supercritical Fluids 29(3): 289-312. 11

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Attachment D Assessment The assessments contained in this attachment are not open to the public under Subsection 15(b)(3) of the Federal Advisory Committee Act, 5 U.S.C. App., as amended by the Federal Advisory Committee Act Amendments of 1997, P.L. 105-153, December 17, 1997, 111 Stat. 2689. The National Research Council has determined that to release this information to the public would disclose information described in 5 U.S.C. 552(b). 12

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Attachment E Acknowledgment of Reviewers This report has been reviewed in draft form by individuals chosen for their diverse perspectives and technical expertise, in accordance with procedures approved by the National Research Council's (NRC's) Report Review Committee. The purpose of this independent review is to provide candid and critical comments that will assist the institution in making its 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 review comments and draft manuscript remain confidential to protect the integrity of the deliberative process. We wish to thank the following individuals for their review of this report: Joan F. Brennecke, University of Notre Dame Peter Lederman, Hazardous Substance Management Research Center (retired) Richard S. Magee, Carmagen Engineering, Inc. James Mathis, NAE, ExxonMobil Corporation (retired) Robert B. Puyear, Independent Consultant Stanley I. Sandler, NAE, University of Delaware Although the reviewers listed above have provided many constructive comments and suggestions, they were not asked to endorse the conclusions or recommendations, nor did they see the final draft of the report before its release. The review of this report was overseen by Hyla Napadensky, Retired, Napadensky Energetics, Inc. Appointed by the NRC, she was responsible for making certain that an independent examination of this report was carried out in accordance with institutional procedures and that all review comments were carefully considered. Responsibility for the final content of this report rests entirely with the authoring committee and the institution. 13