4
Teledyne-Commodore Solvated Electron Technology Process

The Teledyne-Commodore process uses ammonia fluid jet cutting and washout for the disassembly of munitions and separation of agent, energetics, and metal parts. The agent and energetics are then destroyed by solvated electron technology (SET™), a process that reduces contaminants with a solution of metallic sodium in anhydrous liquid ammonia at ambient temperature and pressures of 110 to 167 pounds per square inch gauge (psig). The sodium ammonia reagent is prepared as it is used. The solid and liquid residuals from the SET™ process are first hydrolyzed with water to destroy the excess sodium. The hydrolysate is then oxidized with sodium persulfate or hydrogen peroxide to form environmentally more benign effluents. Metal parts are shredded and treated to 3X condition with SET™ solution in a tumbler. Dunnage is shredded and treated with SET™ solution in a rotary plow mixer. A schematic diagram of the process is shown in Figure 4–1.

The following unit operations were selected for Demo II testing:

  • ammonia fluid jet cutting and washout

  • SET™ destruction of energetics

  • chemical oxidation of energetics hydrolysates

  • SET™ destruction of agents

  • chemical oxidation of agent hydrolysates

  • shredding of metal parts and dunnage

  • SET™ treatment of shredded metal parts and dunnage

The testing was terminated by the PMACWA after two incidents occurred: (1) energetic ignition of M28 propellant and (2) a sulfuric acid spill during equipment servicing for the demonstrations of SET™ with agents.1 As a result of cost overruns and schedule constraints attributed to these incidents, the following tests were not conducted:

  • SET™ destruction of energetics

  • chemical oxidation of energetics hydrolysates

  • SET™ destruction of agents

  • chemical oxidation of agent hydrolysates

AMMONIA FLUID JET CUTTING AND WASHOUT

The objectives of the tests of fluid jet cutting and washout were as follows:

  • Demonstrate the ability to prepare a suitable feed to the SET™ and oxidation reactors.

  • Demonstrate the separation of the burster and propellant from the rockets.

  • Demonstrate the accuracy and precision with which the fluid jet cutting system can position and cut the rockets using manual placement of the rockets.

  • Determine the impact of operations on components in the SET™ chamber (e.g., integrity of the chamber seals).

The test plans called for validation runs on 15 inert M60 rockets that contained neither energetics nor agent and on three M61 rockets containing Composition B and M28 but no agent. The M60 tests were completed accurately and precisely. Visual examination showed no damage or degradation of chamber components.

No validation runs were completed on M61 rockets because the energetics ignited in the second workup (practice) run. At that point, all testing was stopped. A report of an investigation concluded that the most probable cause of the ignition was an exothermic reaction between ammonia vapor and M28 propellant. Ammonia vapor ignited after the propellant burn. Teledyne-Commodore subsequently deter-

1  

Teledyne-Commodore installed a sulfuric acid scrubber to capture ammonia vapor. The spill was caused by the failure of a check valve in the scrubber system.



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OCR for page 31
Evaluation of Demonstration Test Results of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: A Supplemental Review for Demonstration II 4 Teledyne-Commodore Solvated Electron Technology Process The Teledyne-Commodore process uses ammonia fluid jet cutting and washout for the disassembly of munitions and separation of agent, energetics, and metal parts. The agent and energetics are then destroyed by solvated electron technology (SET™), a process that reduces contaminants with a solution of metallic sodium in anhydrous liquid ammonia at ambient temperature and pressures of 110 to 167 pounds per square inch gauge (psig). The sodium ammonia reagent is prepared as it is used. The solid and liquid residuals from the SET™ process are first hydrolyzed with water to destroy the excess sodium. The hydrolysate is then oxidized with sodium persulfate or hydrogen peroxide to form environmentally more benign effluents. Metal parts are shredded and treated to 3X condition with SET™ solution in a tumbler. Dunnage is shredded and treated with SET™ solution in a rotary plow mixer. A schematic diagram of the process is shown in Figure 4–1. The following unit operations were selected for Demo II testing: ammonia fluid jet cutting and washout SET™ destruction of energetics chemical oxidation of energetics hydrolysates SET™ destruction of agents chemical oxidation of agent hydrolysates shredding of metal parts and dunnage SET™ treatment of shredded metal parts and dunnage The testing was terminated by the PMACWA after two incidents occurred: (1) energetic ignition of M28 propellant and (2) a sulfuric acid spill during equipment servicing for the demonstrations of SET™ with agents.1 As a result of cost overruns and schedule constraints attributed to these incidents, the following tests were not conducted: SET™ destruction of energetics chemical oxidation of energetics hydrolysates SET™ destruction of agents chemical oxidation of agent hydrolysates AMMONIA FLUID JET CUTTING AND WASHOUT The objectives of the tests of fluid jet cutting and washout were as follows: Demonstrate the ability to prepare a suitable feed to the SET™ and oxidation reactors. Demonstrate the separation of the burster and propellant from the rockets. Demonstrate the accuracy and precision with which the fluid jet cutting system can position and cut the rockets using manual placement of the rockets. Determine the impact of operations on components in the SET™ chamber (e.g., integrity of the chamber seals). The test plans called for validation runs on 15 inert M60 rockets that contained neither energetics nor agent and on three M61 rockets containing Composition B and M28 but no agent. The M60 tests were completed accurately and precisely. Visual examination showed no damage or degradation of chamber components. No validation runs were completed on M61 rockets because the energetics ignited in the second workup (practice) run. At that point, all testing was stopped. A report of an investigation concluded that the most probable cause of the ignition was an exothermic reaction between ammonia vapor and M28 propellant. Ammonia vapor ignited after the propellant burn. Teledyne-Commodore subsequently deter- 1   Teledyne-Commodore installed a sulfuric acid scrubber to capture ammonia vapor. The spill was caused by the failure of a check valve in the scrubber system.

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Evaluation of Demonstration Test Results of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: A Supplemental Review for Demonstration II FIGURE 4–1 Schematic diagram of the Teledyne-Commodore SET™ process. Solid boxes represent unit operations for demonstration. SOURCE: PMACWA (2001). mined that M28 propellant is chemically incompatible with ammonia vapor (Kumar, 2000). The investigation report also documented another potential safety issue. Investigators found that Composition B dissolved in liquid ammonia had leaked through flanges into the valves and piping transferring the material from the ammonia fluid jet-cutting vessel to the SET™ reactor. The investigators were unable to disassemble the piping and valves during the investigation because dissembling parts contaminated with Composition B would have posed a hazard. SHREDDING OF METAL PARTS AND DUNNAGE The objectives of the shredding demonstrations were as follows: Validate that the shredder can adequately prepare the dunnage and metal parts for downstream processing in the SET™/dunnage reactor. Demonstrate the safe, effective handling and feeding of shredded dunnage and metal parts into the SET™/dunnage reactor. Validation runs were conducted as planned on DPE/butyl bags (518 lb); wood pallets (52 lb) and pentachlorophenol; fiberglass firing tubes (54 lb); and M42A1 4.2-inch mortars (362 lb). The runs were carried out at a commercial facility, and all feed types were successfully size-reduced for subsequent processing in the SET™/dunnage reactor. Five pounds of each shredded material, spiked with simulant, were fed successfully into the SET™/dunnage reactor. SET™ TREATMENT OF SHREDDED METAL PARTS AND DUNNAGE The objectives of the tests of SET™ treatment of shredded metal parts and dunnage were as follows: Validate that the SET™/dunnage reactor could meet a 3X condition for agent simulants, metal parts, and dunnage. Relate the characterization of SET™/dunnage reactor off-gas to produce a total facility gas effluent that meets either the EPA syngas or BIF requirements. Characterize gas, liquid, and solid process streams from the SET™ process for selected chemical constituents and physical parameters and the presence or absence of hazardous and toxic compounds, including residual agent simulants.

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Evaluation of Demonstration Test Results of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: A Supplemental Review for Demonstration II Validation tests were conducted as planned on 5-lb aliquots of shredded DPE/butyl bags spiked with simulant, shredded wood pallets spiked with simulant and PCP, carbon spiked with simulant (shredding not required), shredded fiberglass firing tubes spiked with simulant, and shredded M42A1 4.2-inch mortars spiked with simulant. All five dunnage feeds were processed as planned, and all necessary validation data were collected. However, the data did not validate that the SET™/dunnage reactor could meet a 3X condition for all feeds. The criterion for 3X is that agent concentration in the headspace above the treated solids does not exceed 3.0 µg per cubic meter of air for HD, 0.01 µg per cubic meter of air for VX, and 0.1 µg per cubic meter of air for GB. The sampling and analysis procedures used for the simulants (1,4-dichlorobutane for HD and GB and malathion for VX) yielded detection limits in the range of 100 to 200 µg per cubic meter of air, too high to validate 3X decontamination of dunnage materials (Teledyne-Commodore, 2000). The major test objective was not met. In any case, 1,4-dichlorobutane is probably not a very good simulant for mustard and GB. REEVALUATION OF STEPS REQUIRED FOR IMPLEMENTATION The steps required for implementation from the ACW I committee’s report are reiterated below, along with a summary of the status as a result of the Demo II testing (NRC, 1999). Verify products of SET™/hydrolysis of agents through experimentation. This was not verified because testing was suspended. Establish optimum conditions for SET™/hydrolysis of agents through laboratory tests, followed by pilot-plant demonstration. This was not established because testing was suspended. Identify the unknown precipitates of SET™ energetics reactions. This was not identified because testing was suspended. Establish optimum conditions for the oxidation of residuals from SET™/hydrolysis of both agents and energetics through laboratory tests, followed by pilot-plant demonstration. This was not established because testing was suspended. Test waste disposal methods. This was not tested. Conduct pilot tests of methods of decontaminating metal parts and dunnage. The tests for this were inconclusive. Revise the preliminary design for the hypothetical system, especially the interfaces between the unit processes and operations, and demonstrate the revised design at pilot-scale. The data obtained from the demonstration tests of unit processes and operations were insufficient for meaningful redesign. REEVALUATION OF FINDINGS FROM ACW I REPORT Finding TC-1. The use of ammonia jet cutting in the munitions disassembly process could solve some of the problems encountered in baseline disassembly. However, the process must be thoroughly tested to address reliability and maintenance issues. The ignition that occurred during the workup run on M61 rockets calls into question the reliability of the system for the intended application. Finding TC-2. Conditions for SET™ destruction of agents have been reasonably well established but demonstrated only on a small scale. Finding TC-3. Conditions for SET™ destruction of energetics have not yet been determined. Moreover, energetics have not been completely deactivated in laboratory tests, which raises concerns about explosions or other upsets. Finding TC-4. The reaction chemistry is not yet fully understood for either SET™ destruction of agents or SET™ deactivation of energetics. Finding TC-5. The products of SET™/hydrolysis of agent and energetics have not been adequately characterized. Thus, the technology provider cannot be certain that all of the SET™/hydrolysis products can be oxidized by the persulfate step. Furthermore, the products of oxidation of the SET™/ hydrolysis products have not been adequately characterized. Finding TC-6. The solid wastes produced by the overall process have not been characterized well enough to establish whether they are suitable for safe disposal by existing methods, such as landfill, or whether pretreatment methods (i.e., stabilization) to convert them to an acceptable form for disposal will be necessary. Finding TC-7. The use of cleaned off-gas as a boiler fuel poses unique permitting challenges. Any process demonstration must characterize this stream to ensure that this off-gas can be permitted as boiler fuel. Because no agents or energetics were tested, findings TC-2, TC-3, TC-4, TC-5, TC-6, and TC-7 remain valid. Finding TC-8. The full scale system for hydrolysis of the SET™ products will differ significantly from the systems used in the reduced scale tests. Because further chemical reactions occur during hydrolysis, the components of the full scale system must be tested. The Demo II test was designed to test some of the components of a full-scale system. The only components for

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Evaluation of Demonstration Test Results of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: A Supplemental Review for Demonstration II which tests were completed, however, were the dunnage and metal shredders. SUPPLEMENTAL FINDING 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.