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Evaluation of Demonstration Test Results of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: A Supplemental Review for Demonstration II Executive Summary By direction of Congress, the U.S. Department of Defense’s (DoD’s) program manager for the Assembled Chemical Weapons Assessment (PMACWA) asked the National Research Council (NRC) Committee on Review and Evaluation of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: Phase II (the ACW II committee) to conduct an independent scientific and technical assessment of three alternative technologies (referred to as Demo II) under consideration for the destruction of assembled chemical weapons at U.S. chemical weapons storage sites. The three technologies are AEA Technologies Corporation’s (AEA’s) electrochemical oxidation process; the transpiring-wall supercritical water oxidation and gasphase chemical reduction processes of Foster Wheeler/Eco Logic/Kvaerner (FW/EL/K); and Teledyne-Commodore’s solvated electron process. Each of these technologies represents an alternative to incineration for the complete destruction of chemical agents and associated energetic materials. The demonstration tests were approved by the PMACWA after an initial assessment of each technology. The results of that initial assessment were reviewed by an earlier NRC committee, the Committee on Review and Evaluation of Alternative Technologies for Demilitarization of Assembled Chemical Weapons (the ACW I committee) (NRC, 1999). For the present review, the committee conducted an indepth examination of each technology provider’s data, analyses, and demonstration test results for the critical components tested. This review report supplements the ACW I report and considers the demonstration performance of the Demo II candidate technologies and their readiness for advancement to pilot-scale implementation. Because testing in these areas is ongoing, the committee decided to cut short its fact-finding efforts for input to this report as of March 30, 2001. This cutoff was necessary in order to provide the sponsor with the needed information in a timely fashion. In 1996 the U.S. Congress enacted two laws, Public Law 104–201 (authorization legislation) and Public Law 104–208 (appropriation legislation), mandating that DoD assess alternative technologies to the baseline incineration process for the demilitarization of assembled chemical munitions. In December 1996 the deputy to the commander of the Soldier Biological Chemical Command was appointed as the PMACWA. Subsequently, seven technologies designed for the complete destruction of assembled chemical weapons were evaluated (ACW I report), and on July 29, 1998, three of them were selected for the Demonstration I (Demo I) phase of the ACWA program. The PMACWA requested that the NRC perform an independent evaluation of the seven technology packages that had been selected originally during earlier phases of the Assembled Chemical Weapons Assessment (ACWA) program and deliver a report by September 1, 1999. However, to meet that deadline, the NRC ACW I committee had to terminate its data-gathering activities on March 15, 1999, before the demonstration tests had been completed (NRC, 1999). In September 1999, the PMACWA asked the ACW I committee to examine the results of tests demonstrating the operations of three of the original seven alternative technologies and to determine if they had changed the committee’s original findings, recommendations, and comments. Accordingly, the NRC published a supplemental report in March 2000 (NRC, 2000), at which time the ACW I committee was disbanded. In 1999, Congress passed Public Law 105–261, mandating as follows: The program manager for the Assembled Chemical Weapons Assessment shall continue to manage the development and testing (including demonstration and pilot-scale testing) of technologies for the destruction of lethal chemical munitions that are potential or demonstrated alternatives to the baseline incineration program. In performing such management, the program manager shall act independently of the program manager for Chemical Demilitarization and shall report to the Under Secretary of Defense for Acquisition and Technology.
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Evaluation of Demonstration Test Results of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: A Supplemental Review for Demonstration II The Army was also directed to continue its coordination with the NRC. Congress extended the PMACWA’s task through Public Law 106–79 by mandating that he “conduct evaluations of [the] three additional alternative technologies under the ACWA program, …proceed under the same guidelines as contained in Public Law 104–208 and continue to use the Dialogue process and Citizens’ Advisory Technical Team and their consultants.” In response, the PMACWA initiated a new test program, commonly referred to as Demo II, to investigate whether three of the alternative technologies remaining from the original testing were ready to proceed to an engineering design phase.1 The remaining technologies were from AEA, FW/EL/K, and Teledyne-Commodore. The seventh of the original technologies had been judged to be too immature for further testing during the original multitiered selection process. In response to Congress, a second NRC committee, the Committee on Review and Evaluation of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: Phase II (ACW II committee), was formed and tasked to produce three reports: (1) an evaluation of the Demo II tests (Task 1), (2) an evaluation of two engineering design studies (EDSs) and tests for use at the Pueblo, Colorado, storage site (Task 2), and (3) an evaluation of EDS packages and tests for the Blue Grass, Kentucky, site (Task 3). The statement of task for Task 1 is as follows: At the request of the DoD’s Program Manager for Assembled Chemical Weapons Assessment (PMACWA), the NRC Committee on Review and Evaluation of Alternative Technologies for Demilitarization of Assembled Chemical Weapons will provide independent scientific and technical assessment of the Assembled Chemical Weapons Assessment (ACWA) program. This effort will be divided into three tasks. In each case, the NRC was asked to perform a technical assessment that did not include programmatic (cost and schedule) considerations. Task 1 To accomplish the first task, the NRC will review and evaluate the results of demonstrations for three alternative technologies for destruction of assembled chemical weapons located at U.S. chemical weapons storage sites. The alternative technologies to undergo demonstration testing are: the AEA Technologies electrochemical oxidation technology, the Teledyne Commodore solvated electron technology, and the Foster Wheeler and Eco Logic transpiring wall supercritical water oxidation and gas phase chemical reduction technology. The demonstrations will be performed in the June through September 2000 timeframe. Based on receipt of the appropriate information, including: (a) the PMACWA-approved Demonstration Study Plans, (b) the demonstration test reports produced by the ACWA technology providers and the associated required responses of the providers to questions from the PMACWA, and (c) the PMACWA’s demonstration testing results database, the committee will: Perform an in-depth review of the data, analyses, and results of the unit operation demonstration tests contained in the above and update as necessary the 1999 NRC report, Review and Evaluation of Alternative Technologies for Demilitarization of Assembled Chemical Weapons (the ACW report). Determine if any of the AEA Technologies, Teledyne Commodore, and Foster Wheeler/Eco Logic technologies have reached a technology readiness level sufficient to proceed with implementation of a pilot-scale program. Produce a report for delivery to the PMACWA by July 2001 provided the demonstration test reports are made available by November 2000. (An NRC report delivered in March 2000 covered the initial three technologies selected for demonstration phase testing.) In this current supplemental review, which responds to Task 1, the ACW II committee provides an extensive review of the data, analyses, and demonstration test results for critical components of the demilitarization processes of AEA, FW/EL/K, and Teledyne-Commodore. Like the first supplemental review (NRC, 2000), this review evaluates the effects of the new test results on the findings and recommendations in the original ACW I committee report (NRC, 1999) and assesses the level of maturity attained by each technology for proceeding to the engineering design phase of development. A separate chapter is devoted to each technology, and the chapters are organized as follows: descriptions of the demonstrated unit operations; descriptions of the tests used in the study, including committee commentary; a discussion of the effects of the demonstration results on previous findings; and, finally, new findings derived from this supplemental review. Chapter 5 considers the earlier general findings and recommendations and presents new ones in light of the demonstration test results. In general, very few of the original findings and recommendations were changed as a result of the new tests. In some cases, the original findings and recommendations were confirmed. The new findings and recommendations are presented below by technology. The level of development of unit operation processes from the candidate technologies is summarized in Table ES–1. General findings and recommendations are also presented below. 1 The AEA, Eco Logic, and General Atomics technology packages were chosen by the PMACWA to undergo engineering design studies for the destruction of the assembled chemical weapons at the Blue Grass Army depot. This decision was made by the PMACWA prior to the issuance of this NRC report.
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Evaluation of Demonstration Test Results of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: A Supplemental Review for Demonstration II TABLE ES-1 Summary Evaluation of the Maturity of Demo II Unit Operations and Processes Hydrolysates Agent Munitions Technology Provider/Unit Operation or Process VX/GB HD Energetics VX/GB HD Energetics Other AEA SILVER II™a C C C Solid/liquid waste treatment C C C Gaseous waste treatment D D D Foster Wheeler/Eco Logic/Kvaerner TW-SCWO B B C GPCR™ B B B Bb,c Teledyne-Commodore Ammonia fluid jet cutting and washout system D D E SET™ D D D Cb Persulfate oxidation (agent) D D D Peroxide oxidation (energetics) D D D Metals parts and dunnage shredding Ab,c NOTE: Environmental and safety issues were considered in assigning maturity categorizations. Schedule and cost issues were not considered. The letter designations are defined as follows (a blank space indicates that categorization was not applicable for that material): A, demonstration provides sufficient information to justify moving forward to full-scale design with reasonable probability of success; B, demonstration provides sufficient information to justify moving forward to the pilot stage with reasonable probability of success; C, demonstration indicates that unit operation or process requires additional refinement and additional demonstration before moving forward to pilot stage; D, not demonstrated, and more R&D is required; and E, demonstrated unit operation or process is inappropriate for treatment. aIncludes integrated gas polishing system to support demonstration. bDunnage. cMetal parts. SUPPLEMENTAL FINDINGS AND RECOMMENDATIONS AEA Demonstration Test Finding DII AEA-1. The overall process flow has been further complicated by major design changes in response to the Demo II testing. These changes include the addition of the impurities removal system (IRS), catalytic oxidation (CATOX) units, and a flow return circuit from the catholyte to the anolyte circuit. All three changes require small-scale and pilot-scale testing. Such modifications further complicate the interfaces between process units, which increases the time required for development, start-up, and commissioning of the full-scale system. Integration of the operating units will make achievement of a viable total solution very difficult. Finding DII AEA-2. The discovery of organic material migration across the electrochemical cell membrane will require major modifications in design and operation, such as recycling of the catholyte material to the anolyte circuit and the addition of hydrocyclones in the catholyte circuit. Finding DII AEA-3. The formation of intermediate oxidation by-products raises operational issues, including slower processing rates and reduced electrochemical efficiency. During the testing with tetrytol in the 12 kW unit, the problems were severe enough to cause the runs to be extended well beyond the planned processing times. Finding DII AEA-4. The generation of new energetic compounds trinitrobenzoic acid, picric acid, and trinitrobenzene (TNBA, PA, and TNB) in the course of processing increases the complexity and hazards of the SILVER II™ process. Although the explosion hazard is reduced as the energetic feed is consumed, it is not completely eliminated until all energetic intermediates are destroyed. Finding DII AEA-5. During the treatment of M28 in the Demo II test, lead oxide and other materials accumulated on cell anodes. The committee believes that a maintenance procedure for routine cleaning of the anodes will be required. Finding DII AEA-6. Low steady-state electrochemical efficiencies (20 to 30 percent) were observed during treatment
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Evaluation of Demonstration Test Results of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: A Supplemental Review for Demonstration II of tetrytol. These low efficiencies will decrease the throughput per cell and increase processing time and energy consumption. Finding DII AEA-7. Volatile organic compounds (VOCs) were detected in the off-gas of the AEA process technology. AEA has now included a CATOX unit in the preliminary design. The committee believes that the introduction of this additional unit operation will further complicate the scaleup and integration. Finding DII AEA-8. The IRS for removing salts (sulfates, phosphates, silver fluoride), excess water, and any metals that may be present requires extensive development and integration. The IRS has not yet been described in sufficient detail to allow for a meaningful assessment. Recommendation DII AEA-1. The possible formation of lead picrate when mixed energetic feeds are treated must be investigated before any processing of lead-containing propellant, TNT-based energetics, or tetryl is undertaken. Recommendation DII AEA-2. The IRS, the CATOX units, the return flow, and all other major modifications to the system must be tested and proven during the EDS design phase. Recommendation DII AEA-3. AEA must validate complete destruction of all energetic intermediates during the EDS design phase. Recommendation DII AEA-4. AEA must conduct additional tests to identify suitable materials of construction to overcome corrosion problems encountered owing to the formation of hydrofluoric acid (HF) in the treatment of GB. Foster Wheeler/Eco Logic/Kvaerner Demonstration Tests Finding DII FEK-1. The proposed full-scale TW-SCWO system has design and operating conditions significantly different from those tested in Demo II. These include the temperature of the transpiration water at the inlet; pH of the feed; turbulence in the reactor; and use of pure oxygen, not air, as the oxidant. Finding DII FEK-2. The proposed full-scale design for the TW-SCWO system involves a scale-up in reactor crosssectional area by a factor of 2 from the Demo II test unit and an increase in reactor throughput by a factor of 35. Performance under these full-scale design conditions has not been demonstrated. Finding DII FEK-3. Aluminum present in the hydrolysates, which could lead to the formation of slurries and plugging, could be a problem. The proposed changes for mitigating this problem (e.g., changing operating conditions and/or removing aluminum during weapon disassembly) must be tested. Finding DII FEK-4. Demo II tests confirmed that firing tubes and other solids could be treated to a 5X condition by the GPCR™ process. Finding DII FEK-5. All waste streams have been or can be characterized sufficiently for engineering design to proceed. Finding DII FEK-6. The current sampling and monitoring systems for agent in gaseous streams have not been certified or validated for use with the GPCR™ process off-gas. Finding DII FEK-7. The product gas from the GPCR™ process does not meet the EPA syngas requirements because of high benzene and polyaromatic hydrocarbon content. Finding DII FEK-8. While no agent was detected in the scrubbing solutions and scrubber filters, the ability of the GPCR™ process to destroy HD in mortars and neat GB could not be confirmed because sampling and analysis problems hampered the gathering of gas-phase data. Finding DII FEK-9. Little evidence of soot formation was indicated when the GPCR™ unit was tested separately with PCP-spiked wood, HD mortars, M55 rocket firing tubes, and neat GB. Finding DII FEK-10. The full-scale SCWO reactor design has not been tested and is different in size and in the flow rates of the feed streams from those used in the Demo II tests. The full-scale design treats hydrolysate at a rate per unit volume of reactor that is almost 10 times higher than that used during the Demo II tests. In addition, the ratio of the flow rates of all other streams to the flow rate of hydrolysate in the full-scale unit has decreased by approximately a factor of 10 from those used during the Demo II tests. These changes in hydrolysate processing per unit of reactor volume and the reduction of other feed streams relative to the hydrolysate may reduce the efficacy of the SCWO reactor and may be expected to exacerbate problems of corrosion and plugging. Finding DII FEK-11. The experience of multiple shutdowns during Demo II testing of the TW-SCWO and the resulting thermal stresses and crack generation in the liner indicate a potential reliability issue, which must be significantly reduced or eliminated. Recommendation DII FEK-1. Since the hydrolysate/total feed ratio and flow velocity used in Demo II testing are so different from those of the proposed design, the TW-SCWO reactor must be tested at a hydrolysate/total feed ratio and flow velocities close to the proposed design conditions.
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Evaluation of Demonstration Test Results of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: A Supplemental Review for Demonstration II Recommendation DIIFEK-2. Long-term testing of appropriately designed SCWO reactor liners under the new operating conditions for the proposed full-scale operation will be necessary to prove the reliability and effectiveness of the TW-SCWO unit. Recommendation DII FEK-3. Long-term testing of the TW-SCWO should include feeds containing chlorine, phosphorus, and sulfur and be at residence times and flow velocities close to the proposed design conditions. Recommendation DII FEK-4. The Army or the technology provider must develop analytical methods to determine the quantities of agent in the gas streams containing hydrogen. Teledyne-Commodore Demonstration Tests Finding DII TC 1. Demo II tests were delayed and could not be completed for the Teledyne-Commodore process because of incidents in which the immaturity of the process became apparent. For example, an exothermic reaction between ammonia vapor and M28 propellant led to an ignition incident. At another time, Composition B, dissolved in liquid ammonia, leaked through flanges into valves and piping that were intended to transfer the material from the ammonia fluid jet-cutting vessel to the SET™ reactor. These incidents revealed serious safety problems associated with the Teledyne-Commodore process. SUPPLEMENTAL GENERAL FINDINGS General Finding DII 1. The demonstration tests were not operated long enough to show reliability in long-term operation. The PMACWA’s Demo II tests were required to be of the same duration as the Demo I tests. The technology providers had neither the time nor the resources for extensive systemization (preoperational testing) in Demo II. Consequently, these tests were simply proof-of-concept demonstrations that indicate whether or not a particular unit operation (with more development) might be applicable to the disposal of assembled chemical munitions. General Finding DII 2. The AEA technology package is a very complex, immature chemical processing system. Several new unit operations required to address problems revealed in the Demo II tests will significantly increase the complexity of an integrated processing system and extend the time required for its development. General Finding DII 3. The demonstrated components of the FW/EL/K technology package are ready to progress to the EDS phase. However, certain key units were not tested (or the results were inconclusive). Additional testing will be needed to verify the ability of the transpiring-wall technology to minimize corrosion; the testing should be carried out in parallel with development of an engineering design. General Finding DII 4. Because of fire and safety problems, the basic process for the Teledyne-Commodore technology was not tested in Demo II. The Army decided against going forward because the Demo II goals could not be met in time. As a result, the committee had no technical basis on which to evaluate the process any further. General Finding DII 5. As was true for Demo I, none of the unit operations tested in Demo II has been integrated into a complete system. The lack of integration is a major concern and a significant obstacle to full-scale implementation. SUPPLEMENTAL GENERAL RECOMMENDATIONS General Recommendation DII 1. Further development of the Teledyne-Commodore technology package for the destruction of assembled chemical weapons should not be pursued under the ACWA program. General Recommendation DII 2. Before the AEA technology proceeds to the EDS phase, extensive testing should be performed on the SILVER II™ process, including all the new unit operations that are being proposed to address the shortcomings identified in Demo II results. General Recommendation DII 3. For the FW/EL/K technology package, additional testing should be performed in the EDS phase to complete GPCR™ off-gas characterization and demonstrate long-term operation of the modified TW-SWCO unit.
Representative terms from entire chapter: