Munitions Processing Flowsheet for the Pueblo Chemical Agent Destruction Pilot Plant (PCAPP)

Craig A. Myler, Chief Engineer, Process, Bechtel National, Inc. August Benz, Bechtel Fellow, Bechtel National, Inc. Scott Susman, Project Engineer, U.S. Department of Defense Assembled Chemical Weapons Alternatives (ACWA) Program Gary Anderson, U.S. Department of Defense ACWA Site Project Manager, PCAPP Abstract
The Pueblo Chemical Agent-Destruction Pilot Plant, or PCAPP, will be built to destroysafely and efficientlythe stockpile of chemical weapons stored at the U.S. Army Pueblo Chemical Depot since the 1950s. The PCAPP is designed to destroy more than 2,600 tons of mustard agent in over 780,000 munitions to eliminate the risk from continued storage. The process involves five steps: 1. 2. 3. 4. 5. Removal and treatment of the energetic items Removing the mustard agent Neutralizing the mustard agent Post treatment of neutralized mustard agent (hydrolysate) Treatment of the metal parts

This paper will discuss the flowsheet and expectations for the above 5 steps. Full scale testing results will be presented for the Projectile Mortar Disassembly (PMD) machine, the Munitions Washout Station (MWS) and the Munitions Treatment Unit (MTU).

1. Background. The U.S. Army Pueblo Chemical Depot, located near Pueblo, Colo., was originally constructed as the Pueblo Ordnance Depot in 1942. Through many years and changing

missions, the depot is currently responsible for safe and secure storage of 2600 tons of mustard agent in projectiles and mortars. The weapons have been stored at the 23,000-acre depot since the 1950s. The Department of Defense Assembled Chemical Weapons Alternatives (ACWA) Program, the depot and the

community worked in partnership to recommend that the technology known as neutralization followed by biotreatment be used to destroy the chemical weapons. Neutralization followed by biotreatment uses hot water to neutralize the chemical agent, effectively destroying the mustard agent molecules. The follow-on process, biotreatment, utilizes microbes to digest and break down the neutralization byproduct, which is called hydrolysate. In 2002, Bechtel was selected as the systems contractor to design, construct, systemize, pilot test, operate and close the Pueblo Chemical Agent-Destruction Pilot Plant. The Bechtel Pueblo Team is made up of Bechtel National, Inc., and its partners, including Washington Demilitarization Company, Parsons, Battelle Memorial Institute, General Atomics and General Physics.1

Figure 1: Chemical Weapons in Storage

The Pueblo stockpile consists entirely of projectiles and mortars, all of which contain either distilled mustard (HD) or agent HT. The total number of munitions is over 780,000. It is apparent from the number of munitions to be destroyed at the PCAPP that the processing flowsheet must consider plant throughput as a critical design requirement. As the agent makeup of the munition items in the Pueblo Stockpile are all blister agent, retooling of the plant for each munition type (called changeover) requires only minor changes to the mechanical systems. With this in mind, and the overall requirement for neutralization followed by biological treatment of the chemical agent, the PCAPP process flowsheet was established. 2. Process Flowsheet.

EMICAL
1

Taken from ACWA Program Fact Sheet on Chemical Weapons Destruction at U.S. Army Pueblo Chemical Depot, http://www.pmacwa.army.mil/co/ip/dl/acwa_pueblo_overvie w.pdf

The overall process flowsheet for the PCAPP is shown in Figure 2. The main process operations described in this paper are highlighted in Figure 3.

2.1 Removing Energetics The munitions in the Pueblo Stockpile contain energetic materials including propellants and explosives. Only a portion of the 105 mm and all of the 4.2 inch mortars contain propelling energetics. These propellents will be safely removed manually, using procedures proven previously at other stockpile locations. The explosive components, which include fuses, boosters, and bursting charges will be removed using a robotic machine called the Linear Projectile Mortar Disassembly machine (LPMD). Existing U.S. baseline plants use a
MUNITIONS STORAGE (G-BLOCK) MUNITIONS SERVICE MAGAZINE MUNITIONS
HVA C VEN T ENERGETICS/ PROPELLANTS

turntable-based PMD machine to move projectiles and mortars from station to station for reverse assembly and energetics removal. Using advanced robotic technology, the LPMD moves projectiles and mortars between individual reverse assembly stations in a linear array, allowing for greater flexibility in both control and configuration. A significant improvement is the ability to easily replace individual LPMD component assemblies, thereby reducing maintenance, changeover, and closure complexity. After removal, all uncontaminated propellants and explosives are shipped off-site for commercial disposal. The LPMD is shown in Figure 4.
DUNNAGE/METAL PARTS

OFF-SITE SHIPMENT

ENHANCED RECONFIGURED MUNITIONS

BASELINE AND ENHANCED RECONFIGURATION

ENERGETICS SERVICE MAGAZINE

STORAGE IGLOO (H-BLOCK)

VENT TO ATMOSPHERE CLEAN WASTE

CONTAMINATED ENERGETICS, LEAKERS, AND REJECTS VENT VENT

EXPLOSIVE DESTRUCTION TECHNOLOGY (EDT)

25% NaOH VENT FROM SDU/AUTOCLAV E

OFF-SITE SHIPMENT

DEMIN WATER

OFF-GAS TREATMENT SYSTEM (OTS)

VENT

AGENT FILTER AREA

BUFFER STORAGE

MUNITIONS WASHOUT SYSTEM (MWS)

EMPTY MUNITIONS

MUNITIONS TREATMENT UNIT (MTU)

CLEAN MUNITIONS

OFF-SITE SHIPMENT
VENT TO ATMOSPHERE

VENT 25% NaOH 5% NaOH STEAM WASHED AGENT HYDROLYSAT E 25% NaOH VENT SOLID RESIDUE 25% NaOH 93% H2SO4 STEAM

BTA OTS
VENT TO ATMOS.

DECON SYSTEM

SPENT DECON

AGENT COLLECTION & NEUTRALIZATION

HOT PROCESS WATER

BIOTREATMENT

WATER RECOVERY SYSTEM (WRS)

BRS OTS
VENT SOLID RESIDU E

RECOVERED WATER TO USERS

PROCESS WATER SYSTEM

CONDENSAT E

BRINE REDUCTION SYSTEM (BRS)

OFF-SITE SHIPMENT

CLEAN DUNNAGE/ SECONDARY WASTE

VENT TO OTS

OFF-SITE SHIPMENT

CONTAMINATED DUNNAGE/ SECONDARY WASTE

SDU/AUTOCLAVE
RAW SANITARY WASTE

COOLING TOWER MAKEUP

25% NaOH

BULK CHEM STORAGE

25% NaOH TO USERS

SANITARY WASTE TREATMENT

TREATED SANITARY WASTE

Figure 2: PCAPP Process Flowsheet

MUNITIONS STORAGE (G-BLOCK)

MUNITIONS SERVICE MAGAZINE

MUNITIONS

DUNNAGE/METAL PARTS

OFF-SITE SHIPMENT

ENHANCED RECONFIGURED MUNITIONS

BASELINE AND ENHANCED RECONFIGURATION

HVA C VEN T

ENERGETICS/ PROPELLANTS

ENERGETICS SERVICE MAGAZINE

STORAGE IGLOO (H-BLOCK)

VENT TO ATMOSPHERE CLEAN WASTE

CONTAMINATED ENERGETICS, LEAKERS, AND REJECTS VENT VENT

EXPLOSIVE DESTRUCTION TECHNOLOGY (EDT)

25% NaOH VENT FROM SDU/AUTOCLAV E

OFF-SITE SHIPMENT

DEMIN WATER

OFF-GAS TREATMENT SYSTEM (OTS)

VENT

AGENT FILTER AREA

BUFFER STORAGE

MUNITIONS WASHOUT SYSTEM (MWS)

EMPTY MUNITIONS

MUNITIONS TREATMENT UNIT (MTU)

CLEAN MUNITIONS

OFF-SITE SHIPMENT
VENT TO ATMOSPHERE

VENT 25% NaOH 5% NaOH STEAM WASHED AGENT HYDROLYSAT E 25% NaOH VENT SOLID RESIDUE 25% NaOH 93% H2SO4 STEAM

BTA OTS WATER RECOVERY SYSTEM (WRS)

VENT TO ATMOS.

DECON SYSTEM

SPENT DECON

AGENT COLLECTION & NEUTRALIZATION

HOT PROCESS WATER

BIOTREATMENT

BRS OTS
VENT SOLID RESIDU E

RECOVERED WATER TO USERS

PROCESS WATER SYSTEM

CONDENSAT E

BRINE REDUCTION SYSTEM (BRS)

OFF-SITE SHIPMENT

CLEAN DUNNAGE/ SECONDARY WASTE

VENT TO OTS

OFF-SITE SHIPMENT

CONTAMINATED DUNNAGE/ SECONDARY WASTE

SDU/AUTOCLAVE
RAW SANITARY WASTE

COOLING TOWER MAKEUP

25% NaOH

BULK CHEM STORAGE

25% NaOH TO USERS

SANITARY WASTE TREATMENT

TREATED SANITARY WASTE

Figure 3: PCAPP Process Flowsheet Highlighting Main Process Operations a separate building for agent processing. The projectiles and mortars are at this point essentially heavy walled containers with a press fit burster well seal. In U.S. baseline incineration plants, the burster well is mechanically pulled out of the munition body and the chemical agent drawn out by vacuum. At the PCAPP, an innovative approach will be used to remove the chemical agent. The approach is different for the projectiles and the mortars so they will be discussed separately. 2.2.1 Munitions Washout System (MWS) for Projectiles. A unique system called a Munitions Washout System (MWS) will be used to remove the agent from projectiles and rinse residual agent material from the inside of the munition body. The system

Figure 4: Linear Projectile Mortar Disassembly Machine 2.2 Removing the Mustard Agent Once the energetic components have been removed, the projectile or mortar body containing the mustard agent fill is transferred to

consists of a robotic munitions handling system (using the same robot model as used in the LPMD) and a number of Cavity Access Machines (CAM). For projectiles (105 and 155 mm), the CAM operates by hydraulically pushing the burster well into the munition, fracturing the adapter, and creating an opening for the agent to drain from the munition. This operation is conducted with the projectile oriented vertically, ojive down. Once the adapter is fractured and the burster well crushed, agent drains into a receiving cup. Once drained, the projectile is rinsed with high pressure water to remove residual agent material. A schematic of the MWS is shown in Figure 5. The agent and rinse water from the MWS is recovered in tanks for subsequent processing in the Agent Neutralization System (ANS). 2.2.2 Munitions Washout System (MWS) for 4.2 inch Mortars As the 4.2 inch mortar has relatively thin walls and contains an internal baffle, hydraulic crushing of the burster well is not conducted. Instead, the CAM for 4.2 inch mortars incorporates a cutting wheel to remove the base of the mortar allowing agent to drain. The cutting is done in an enclosed space within the CAM to reduce overall contamination. Following removal of the mortar base, high pressure water is again used to rinse residual agent material from the mortar body and the removed mortar base. The MWS for 4.2 inch mortar processing is shown in Figure 6. As in the projectile MWS, agent and rinse

water from the mortar processing is collected in tanks and then fed to the ANS. 2.3 Neutralizing the Mustard Agent Hot water hydrolysis of distilled mustard was successfully proven out at the Aberdeen Chemical Agent Destruction Facility (ABCDF) at an industrial scale. Using experience gained at the ABCDF, the PCAPP ANS includes two turbine mixer equipped reactors with recirculation through static mixers which are equivalent in throughput to the four reactors used at the ABCDF. As HT has not previously been treated using this process, laboratory studies were conducted to confirm the feasibility of neutralization of HT. These studies demonstrated that HT reacts very similarly to HD, and analytical methods have been developed to confirm the destruction of HT.

Projectile

Burster Well

Cup

Hydraulic Ram And Spray

Figure 6: MWS for 4.2 in Mortar Processing

Projectile Placed in Cup Bursterwell Hydraulically Crushed

2.4 Biotreatment of the Mustard Agent HD mustard hydrolysates contain thiodiglycol (a similar diglycol is produced from the T in HT), salt, NaOH and water. The organic diglycols can be effectively treated biologically. The biotreatment of mustard hydrolysate was demonstrated at the ABCDF using a large, off-site, commercial treatment facility. To treat hydrolysates on-site, the PCAPP design includes the use of twentyfour Immobilized Cell Bioreactors (ICB) segregated into six modules of four ICBs. Each ICB contains three treatment cells where air is passed through a proprietary packing material. Biological treatment occurs at the surface of the packing and within the liquid in each ICB cell. Most of the treatment occurs in the first cell. Treatment in the second cell effectively completes the treatment with the third cell acting as a polishing treatment step. The effluent water from the ICBs is treated and returned to the process. Figure 7 shows the design of an ICB module.

Step 1

Step 2

Agent Drain

High Pressure Water Spray

Step 3

Step 4

Figure 5: MWS Schematic for Projectile Processing Another innovation at PCAPP is the elimination of the heating jacket for the reactors. The PCAPP reactors will use direct steam injection for heating. This will reduce the capital cost of equipment and provide for shorter heating times in what is the aqueous reactor system.

Figure 7: Immobilized Cell Bioreactor (ICB) Module 2.5 Disposing of the Metal Parts Another unique element of the PCAPP which supports the processing of large numbers of munitions is the method for treating the projectile and mortar bodies after washout in the MWS. After washout, the projectile and mortar bodies (metal parts) may contain small yet measurable quantities of chemical agent. Batch thermal treatment processes require some form of staging area before and after the process. Additionally, batch thermal processes produce a maximum vapor emission load associated with a batch of multiple metal parts thermally desorbing at roughly the same time. To avoid these two situations, the PCAPP will utilize a continuous thermal processor to treat the metal parts from the MWS. The treatment unit operation is called a Muntions Treatment Unit (MTU). The unit consists of an electrically heated, continuous belt muffle oven. Contaminated munitions from the MWS are placed on the chain belt

and are conveyed through the oven. Six resistance heating zones provide the positive control to heat the projectile and mortar bodies to at least 1000 oF (538 oC) for a minimum of 15 minutes thereby destroying any residual chemical agent. Clean air enters the unit at the discharge end and passes through the muffle counter-current to the metal parts. The volume of air is maintained above the capture velocity to assure that no chemical agent can be released from the clean end of the unit. Treated munitions exit the unit to bins outside of the processing facility. The steel from the projectile and mortar bodies will be reclaimed by smelting at an off-site facility. As the muffle contains both the metal parts and the ventilation air, there is never contact by chemical agent outside the muffle of the MTU. A cross-section of the MTU is shown in Figure 8.

Insulation

Muffle

Munition

Heating Elements

Belt

Figure 8: Munitions Treatment Unit (MTU) Cross-Sectional Diagram 2.6 Secondary Waste Treatment As chemical weapons are processed through the PCAPP, contamination of miscellaneous other materials will occur which require some form of treatment.

These materials include gloves, protective suits and masks, containers, hoses, pallets, and other items which may come in contact with chemical agent. This material is considered secondary waste. Two novel systems will be used to treat secondary wastes at PCAPP. The Supplemental Decontamination Unit (SDU) is a low temperature oven which treats waste in mesh trays in circulating hot air (typically 200-400F) in order to volatilize and/or decompose agent without combusting the waste itself. The Autoclave is the other waste treatment system at PCAPP, and is a standard commercial vacuum cycle steam autoclave unit. A version of SDU was successfully utilized at the ABCDF. Laboratory data collected on HD and HT show that with appropriate temperature and time, the range of potential secondary wastes expected at PCAPP can be effectively treated for disposal in these units. A list of the items tested is shown in Table 1. 3. Conclusion The process flowsheet for the Pueblo Chemical Agent Destruction Pilot Plant has been developed to safely destroy over 780,000 chemical weapons stored at the Pueblo Chemical Depot. A number of novel unit operations have been selected to remove energetics from the munitions, access the chemical agent contained in the munitions, chemically neutralize both HD and HT, biologically treat the agent hydrolysate, thermally treat the drained and rinsed projectile and mortar bodies, and treat the contaminated secondary wastes

from the process. The overall reliability and throughput of the PCAPP has been carefully evaluated in order to establish the number of parallel treatment systems required, as shown in Table 2.

Table 1: Secondary Wastes Tested in SDU and Autoclave for HD and HT Treatment Material Steel Leather PTFE LDPE Butyl Rubber Wood (Oak) Wood (Pine) HEPA Filter Activated Charcoal Fiber Container PPE Material Encapsulated HT SDU Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Autocla ve Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes No

Table 2: Unit Operations of the PCAPP Process Flowsheet Unit Operation Number of Parallel Treatment Systems 3

Linear Projectile Mortar Disassembly (LPMD) Munitions Washout Stations (MWS) Agent Neutralization System (ANS) Immobilized Cell

2 1 (consisting of 2 reactors) 24 ICBs in 6

Bioreactor (ICB) Munitions Treatment Unit (MTU) Supplemental Decontaminatio n Unit (SDU) Autoclave

Modules of 4 2 1 1