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OCR for page 102
7
Lockheed Martin Integrated
Demilitarization System
INTRODUCTION AND OVERVIEW
The Lockheed Martin Integrated Demilitarization
System (LMIDS) was designed by a project team of
Lockheed Martin and seven other companies (see Table
1-3~. The LMIDS includes four primary technologies.
First, the chemical agent, the energetic materials, and
the metal parts are separated via a modified version of
the Army's baseline disassembly process. Second,
caustic hydrolysis is used to decompose the chemical
agent, break down the energetic materials, and decom-
pose agent on metal parts and dunnage. Third, the hy
drolysates from the hydrolysis processes are further
treated using SCWO (supercritical water oxidation).
Finally, gas-phase chemical reduction (GPCR) is used
to decontaminate the metal parts and dunnage to a 5X
level and to treat gaseous effluents from the hydrolysis
processes. Table 7-1 describes how these four technolo-
gies are used to perform the six primary demilitariza-
tion operations described in Chapter 1.
The LMIDS segregates the four technologies, as-
signing a separate process area for each. Figure 7-1
illustrates how the technologies are linked and shows
the basic process flow. The four process areas are:
· munitions access and energetic deactivation (Area
100)
· caustic make-up and hydrolysis (Area 200)
· SCWO (Area 300)
· GPRC (Area 400)
Each of these areas is described in detail in the next
section.
The technology provider addressed the processing
102
of rockets, projectiles, and mortars but did not explic-
itly address the processing of land mines. However, the
proposal and the data-gap report included statements
that LMIDS could accommodate land mines with mi-
nor modifications.
DESCRIPTION OF THE TECHNOLOGY PACKAGE
Access to Munitions and the Deactivation
of Energetics (Area 100)
In area 100, the munitions are disassembled, and the
chemical agent and energetic components are separated
using equipment adapted from the baseline process (see
Appendix C). Energetic materials are initially deacti-
vated via hydrolysis and metal parts decontaminated
with caustic.
Rocket Disassembly
The delivery of the M55 rockets to Area 100 is iden-
tical to the baseline process. Once there, the rockets are
unpacked from their pallets and, still enclosed in their
shipping/firing tubes, are loaded one at a time nose first
through an entry airlock into the rocket demilitariza-
tion chamber. Inside this chamber, a hole is punched in
the firing tube and rocket, and the agent is drained as in
the baseline process. The agent is then pumped into an
agent weigh tank to verify the amount drained, and the
rocket is sheared into pieces. During the shearing op-
eration, the following modification is made to the
baseline process: when a shear cut first exposes the
propellant, a low-pressure hot-water jet is used to break
OCR for page 103
LOCKHEED MARTIN INTEGRATED DEMILITARIZATION SYSTEM
TABLE 7-1 Summary of the LMIDS Approach
103
Major Demilitarization Operation
Approach(es)
Disassembly of munitions Modified baseline disassembly (multiple lines, modified layout, new drain and wash).
Treatment of chemical agent Hydrolysis with caustic; SCWO of hydrolysate; GPCR of off-gas.
Treatment of energetics Hydrolysis with caustic; SCWO of hydrolysate; GPCR of off-gas.
Treatment of metal parts Wash in caustic; treatment in thermal reactor to SX; GPCR of volatilized materials.
Treatment of dunnage Wash in caustic; treatment in thermal reactor to SX; GPCR of volatilized materials.
Disposal of waste Solids. Decontaminated metal parts to recycling facility; decontaminated solid residue from GPCR to
landfill; salts from GPCR to treatment, storage, and disposal facility (TSDF); solids from SCWO to
TSDF; uncontaminated packing materials to landfill.
Liquids. None
Gases. Gas from GPCR burned in boiler; gas from SCWO released to atmosphere through carbon
filters.
up and remove the propellant from the interior of the
rocket motor casing.
Initia/ Deactivation of Rocket Energetics
The sheared metal parts, bursters, fuzes, and frag-
mented propellant are transported (via gravity feed)
into wire baskets in the rocket hydrolysis vessel. The
baskets move gradually from the vessel feed point to
the discharge point. A 20-percent NaOH solution (caus-
tic) at 90°C enters near the basket discharge point and
flows countercurrent to the basket motion. The caustic
is circulated to ensure mixing between the caustic solu-
tion and the rocket parts. The caustic dissolves the alu
Munitions
access and
energetic
deactivation
Area 100)
Liquid i
Caustic
make-up
· Neutralize and
agent , hydrolysis
· Deactivate ~ Area 200
energetics
Off-gas
·1
Metal Darts
Off-gas , ~
FIGURE 7-1 Process flow for the LMIDS.
minum fuze, exposing the energetic materials. The el-
evated temperature causes the energetic materials to
melt, and these materials are then rendered inert via
hydrolysis (see Appendix E for a discussion of the
chemistry of energetic hydrolysis). The residence time
is set to ensure that when a basket reaches the exit sta-
tion, the aluminum in the fuzes has dissolved, and the
energetic material has been completely removed from
the remaining parts. In the exit station, a gas sample
from the vapor space over the basket is analyzed to
verify that the agent concentration is below an accept-
able level. Isotopic neutron spectroscopy is also used
to confirm that no significant amounts of energetics are
present. If the results are acceptable, the basket is
Carbon filter/vent
to atmosphere
Water /|~
Super
critical
water
oxidation
(Area 300
Hydrolysate
Water
.
I Gas-phase Sa
chemical
reduction 5X solids to Landfill
process recycle/landfill
~~ I (Area 400) Gas
hold/test/release
To steam
boiler as fuel
OCR for page 104
104
ALTERNATIVE TECHNOLOGIES FOR DEMILITARIZATION OF ASSEMBLED CHEMICAL WEAPONS
moved to the thermal-reduction batch processor in Area
400 for thermal decontamination of the metal parts.
Baskets that do not pass this test are returned to the
rocket hydrolysis vessel for additional washing.
Projecti/e/Mortar Disassembly
Mortars and projectiles are delivered to Area 100 in
the same manner as they are delivered in the baseline
process (see Appendix C). The nose closure, miscella-
neous parts, and burster are separated, also according
to the baseline process. From this point on, the process
differs from the baseline process. Bursters are fed into
one of the burster hydrolysis vessels, while fuzes and
supplemental charges (if present) are fed into the nose-
closure hydrolysis vessel, and nonenergetic nose clo-
sures and other miscellaneous parts are collected in
baskets for delivery to the thermal-reduction batch pro-
cessor in Area 400. The treatment of the energetics is
described in the next section.
Once the energetic components have been removed,
the projectile/mortar is transported out of the explo-
sion-containment room and loaded into a special tray.
Once the tray is full, it is conveyed into the projectile
hydrolysis chamber where the burster wells are re-
moved using the baseline approach (although the ma-
chine has been significantly redesigned). When the
burster wells from all munitions have been removed,
the tray is conveyed into the projectile hydrolysis vessel.
All operations in the projectile hydrolysis vessel are
new. Agent is drained from the projectile bodies by
inverting the tray. The drained projectile bodies then
undergo initial decontamination by flushing with 90°C
sodium hydroxide solution to loosen any heels or crys-
talline material that may have formed during storage.
After flushing, the vapor space is monitored to ensure
that the agent concentration is below the level for the
3X standard. If the monitoring produces acceptable re-
sults, the tray is sent to the thermal reduction continu-
ous processor in Area 400 for further processing. Oth-
erwise the flush cycle is repeated.
Initia/ Deactivation of Energetics from Projectiles/
Mortars
The energetics from the projectiles/mortars include
bursters, fuzes, and supplemental charges. The bursters
enter the buster hydrolysis vessel from the explosion-
containment room via a gravity feed and are contained
in a wire basket. A slightly pressurized caustic solution
at 135°C is constantly pumped through the vessel to
facilitate melting, dissolution, and hydrolysis of the
energetic material. Multiple bursters can be processed
simultaneously, and the basket remains in the caustic
solution long enough to ensure that all of the energetic
material has dissolved completely. The basket is then
raised, allowed to drain, and passed into an airlock
where the headspace is tested for agent. Isotopic neu-
tron spectroscopy is also used to ensure that no signifi-
cant amounts of energetics remain. If the agent concen-
tration and neutron spectroscopy results are acceptable,
the basket is transported to the thermal-reduction batch
processor in Area 400; if not, the basket is returned to
the buster hydrolysis vessel.
The fuzes and supplemental charges are treated in
the nose-closure hydrolysis vessel in the same manner
as bursters. The caustic dissolves the aluminum por-
tions of the fuzes and exposes the energetic materials.
Caustic Make-Up and Hydrolysis (Area 200)
In Area 200, chemical agent and energetics are de-
activated, separately, by hydrolysis with hot caustic
solution in one of several hydrolysis vessels.
Hydro/ysis of Drained Chemica/ Agent
The chemical agent drained from the munitions in
Area 100 is pumped to an agent neutralization reactor
in Area 200. The agent neutralization reactor is a
400-gallon, baffled reactor filled with aqueous sodium
hydroxide solution (20 percent) heated to 90°C. Agent
is introduced at a measured rate until the specified agent
loading is reached. Agent feed is then switched to an-
other reactor. Each agent neutralization reactor is oper-
ated in a batch mode and is continuously agitated with
two high-efficiency impellers to facilitate the complete
hydrolysis of agent. The details of the agent hydrolysis
reactions are presented in Appendix D.
The hydrolysis reaction mixture is kept at a pH
greater than 13 with excess NaOH solution at all times.
The batch loading and retention times vary with the
type and composition of the materials being neutral-
ized. The technology provider's test results for a GB
OCR for page 105
LOCKHEED MARTIN INTEGRATED DEMILITARIZATION SYSTEM
loading of about 16.3 wt. percent Produced a destruc
. ,,. .
lion err~c~ency greater than 99.9999 percent with a re-
tention time of two hours, and a destruction efficiency
of 99.97 percent for VX after 30 minutes of reaction
time, with reactants consisting of mixtures of VX,
Comp B. blended propellant powder, and aluminum
alloy 6061 T6. (This feed mixture was generated to
simulate the feed from M55 rockets.)
The agent neutralization reactors and all other
neutralization (hydrolysis) reactors are blanketed
with nitrogen, and an induced draft fan draws a
slight vacuum on the reactor headspace. Off-gases
evolved during the hydrolysis process are drawn by
the fan through a reflux condenser to condense water
vapor and other condensable vapors. The condensate
~ . . . . .. .
flows neck Into the reactor, and the noncondensible
gases flow continuously to the GPCR reactor Area 400
for further treatment.
At the end of the processing period, the reactor's
liquid contents are transferred to a holding tank and
sampled to ensure that the agent concentration is below
the established threshold. If so, the hydrolysate is trans-
ferred to a feed tank for SCWO treatment in Area 300.
If not, the hydrolysate is recycled to one of the agent
neutralization reactors for additional processing.
Because GB has been shown to reform at pH below
13 (see Appendix D), excess caustic is used throughout
the hydrolysis process to prevent the reformation of
agent. Excess caustic is also necessary for the SCWO
treatment of hydrolysate to neutralize the acids formed
by heteroatoms (e.g., F and C1) during the oxidation
process. In the LMIDS, all batch neutralization reac-
tors are operated in a staged sequence. While one reac-
tor is receiving agent, the second is in the reaction
mode, and a third is either being emptied into a hy-
drolysate holding tank or being refilled with the caustic
decontamination solution. At the end of the neutraliza-
tion process, the reaction product (i.e., hydrolysate) is
discharged to a holding tank where agent analysis is
conducted to ensure that agent concentration require-
ments have been met. Agent destruction efficiencies of
99.99 percent are expected for VX by the technology
provider, and 99.9999 percent for GB, HD, H and HT.
(Note that neutralization followed by SCWO treatment
is expected to result in agent destruction to 99.9999
percent and concentration below detection limits.)
105
Hydrolysis of Energetics
The caustic solutions from the rocket, burster, and
nose closure hydrolysis vessels in Area 100 are con-
tinuously fed to an energetics deactivation reactor in
Area 200 to ensure that the hydrolysis reactions are
driven to completion. (See Appendix E for a detailed
discussion of the hydrolysis of energetics.) The ener-
getics deactivation reactor is a 9,200-gallon vessel
filled with aqueous sodium hydroxide solution (20 per-
cent) heated to 90°C. The energetics deactivation reac-
tor operates in the same way as the agent neutralization
reactor. The off-gases are passed through a reflux
condenser before being sent to the GPCR reactor in
Area 400 for further treatment.
The liquid solution is held in the energetics deacti-
vation reactor for a specified period of time (to be de-
termined). A sample is then taken and tested for agent
and energetic residue. If neither agent nor energetic is
detected above the target level, the hydrolysate is fed
into the feed tank in Area 300 for mixing with agent
hydrolysate and treatment by SCWO. If agent or ener-
getic is detected above the target level, further reaction
time is allowed, and another sample is then taken.
Supercritical Water Oxidation of Hydrolysates
of Agent and Energetics (Area 300)
The LMIDS uses SCWO for the final destruction of
the hydrolysis products of both agent and energetics.
(The basics of SCWO are described in Appendix F.)
The SCWO process in the LMIDS uses a transpiring
platelet wall reactor developed and patented by
GenCorp/Aerojet and Foster Wheeler. The inner wall
of the reactor is formed of layers of porous platelets
that allow the continuous transpiration of deionized
water at 315°C (600°F) through the inside wall of the
reactor during the SCWO reaction. This inner transpir-
ing wall is contained within a conventional outer wall.
The injection of transpiration water during opera-
tion is claimed to separate the SCWO working fluid,
which will be at 780°C (1,436°F) and 3,500 psi (238 atm),
from the inside surface of the reactor, which is kept at
the transpiration water temperature of 315°C (599°F).
This reactor technology is purported to have the fol-
lowing advantages over conventional-wall SCWO
reactors:
OCR for page 106
106
ALTERNATIVE TECHNOLOGIES FOR DEMILITARIZATION OF ASSEMBLED CHEMICAL WEAPONS
· Contact between the working fluid and the reactor
wall is reduced, thereby minimizing or corrosion.
· Deposition of salt on the reactor wall is essentially
eliminated.
· The cooled reactor wall allows higher working-
fluid reaction temperatures, reducing the residence
time necessary for complete oxidation.
The cooler transpiration water (315°C versus 780°C
for the working fluid) is intended to dissolve any inor-
ganic salts that reach the reactor wall and carry them to
the bottom of the reactor, where, together with the other
reactor contents, the reaction mixture is quenched and
collected. This design is intended to prevent the depo-
sition of inorganic salts and plugging. A schematic dia-
gram of the transpiring wall platelet liner is shown in
Figure 7-2.
Manifold (plenum)
At:
Hydrolysate
(center of annulus)
Transpired
platelet liner
(a) Detailed view of transpired platelet liner
Transpiration
water
315°C
Transpiration
water
315°C
1 1
Cooling
water
1 1
r I Plenum | ~
~ll~lr~lr~ll
~ Heat-up Operating zone Coo~-down \
2~1/ ~ ~ zone (6 0-78 C) zone Ant
. 1~11~l ~p>~p>~ 345°CV
~1 1
(b) Schematic drawing of reactor
FIGURE 7-2 Transpiring-wall platelet liner.
Prior to injection into the SCWO reactor, the agent
and energetic hydrolysates are mixed in the SCWO
feed tank, heated, and stirred to maintain a uniform
solution at 85°C. The mixed hydrolysate from the feed
tank is pumped up to the operating pressure of the tran-
spiring-wall SCWO reactor and mixed with supple-
mental fuel (kerosene or isopropyl alcohol) to ensure a
high temperature. The hydrolysate/fuel mixture is then
heated to 260°C by heat exchange with the SCWO re-
actor effluent in the hydrolysate feed/effluent heat ex-
changer, and the mixture is fed into the SCWO reactor.
Compressed oxygen is preheated to 205 °C and fed con-
currently to the reactor as the oxidant.
The proposed full-scale SCWO reactor is a 12-ft-
long, vertical down-flow, cylindrical reactor that pro-
cesses about 1,200 lb of hydrolysate per hour. The hy-
drolysate/fuel oxidation reaction begins at the reactor
inlet at 510°C. The oxidation reaction results in tem-
peratures of 780°C at the top of the reactor and about
620°C at the bottom. The reactor is designed to have a
total residence time of about 10 seconds. This tempera-
ture-residence time combination is believed by the
technology provider to be sufficient to oxidize all hy-
drolysate organics to the desired destruction level. The
oxidation products are quenched at the reactor bottom
with a water spray to about 345°C. The heteroatoms
(C1, F. N. S. and P) in the hydrolysate react with the
excess sodium hydroxide to form sodium salts. De-
struction efficiencies of 99.9999 percent are claimed
by the technology provider for all agent and energetic
hydrolysates.
The effluent from the SCWO reactor, consisting of
gases and liquid with dissolved salts, is cooled in heat
exchangers and then Repressurized through a let-down
valve to atmospheric pressure for separation of the
gases from the liquid brine. The liquid brine is sent to an
evaporator for drying. The evaporator steam is condensed
and the water recycled as process water. The dried salts,
which are sampled and analyzed for hazardous con-
stituents in accordance with RCRA requirements, are
stabilized off site and disposed of in a landfill.
The technology provider claims that the effluent gas
stream contains only nonregulated gases, mainly car-
bon dioxide, excess oxygen, and a small amount of ni-
trous oxide. Small amounts of carbon monoxide and
low molecular weight hydrocarbons may also be
present. The gas stream is dried and passed through
OCR for page 107
LOCKHEED MARTIN INTEGRATED DEMILITARIZATION SYSTEM
carbon bed filters to remove traces of volatile organics,
and the final gas effluent is monitored and analyzed for
regulated constituents as it is vented to the atmosphere.
Gas Phase Chemical Reduction Process
(Area 400)
The GPCR process developed and patented by ELI
Eco Logic is used to eliminate organic chemicals on
decontaminated metal parts and dunnage (from Area
100) or in gaseous process wastes or off-gases from the
neutralization reactors in Area 200.
The GPCR (Area 400) process block consists of
three parts: a thermal-reduction batch processor; a ther-
mal-reduction continuous processor, where applicable;
and a GPCR reactor. The thermal-reduction batch pro-
cessor is a large vessel that will be loaded with poten-
tially contaminated metal parts (such as pieces of
sheared M55 rockets and projectile/mortar casings that
were not dissolved in the hydrolysis step), other metal
parts, and dunnage. The inlet door is opened, and bins
containing the solids are conveyed into the thermal-
reduction batch processor chamber. After the inlet door
is sealed, nitrogen is introduced to purge oxygen. This
nitrogen purge gas is vented through carbon filters. The
chamber is then heated until the lowest temperature
recorded on the load is 538°C (1,000°F) for at least
15 minutes to ensure 5X treatment. The main process
in this chamber is the thermal desorption of organic
matter. Gases from the thermal-reduction batch pro-
cessor are swept to the GPCR reactor. After a batch has
been treated, the chamber is purged and cooled with
steam, purged with nitrogen, and unloaded.
Dunnage that is (or might be) agent-contaminated is
washed and immersed in 20 percent caustic solution,
loaded into bins similar to those used for processing
metal parts, and placed in the thermal-reduction batch
processor, which serves as a pyrolysis reactor. The
products are hydrocarbon gases, hydrocarbon liquids,
silica residue, and carbon soot. The gases are fed into
the GPCR reactor, where they are partially converted
into reformer gas (a mixture of hydrogen, methane,
carbon monoxide, carbon dioxide, and steam). Accord-
ing to the technology provider, approximately 10 per-
cent of the carbon feed may remain as soot that will
require off-site disposal. Other hydrocarbons, such as
tars and phenolic compounds, may also be present.
107
At munition depots where processing results in a
large quantity of metal parts of a consistent size and
shape (for example, projectile parts), a second type of
thermal desorption reactor, the thermal-reduction con-
tinuous processor, is used. This unit has three cham-
bers and operates continuously with a residence time
of one to two hours. The first (preheat) chamber has a
nitrogen purge to remove oxygen, and the second (pri-
mary treatment) chamber operates at 750°C with a re-
ducing hydrogen atmosphere. The third (exit) chamber
is also purged with nitrogen. All three chambers have
airlocks. Metal parts, which have been treated to 5X,
are quenched to room temperature and disposed of off
site.
The gaseous effluent from the thermal-reduction
batch processor and thermal-reduction continuous pro-
cessor, together with the off-gases from the initial mu-
nitions access and energetic deactivation step and from
the caustic hydrolysis step, are sent to the GPCR reac-
tor, the third part of Area 400. In the GPCR reactor, a
hydrogen-rich atmosphere is maintained, and organic
chemicals are reduced to methane and water. Hydro-
gen chloride, hydrogen fluoride, and hydrogen sulfide
are also produced when mustard, GB, and VX/mustard
are processed. In addition, the nitrogen from the treat-
ment of VX forms nitrogen gas and perhaps some am-
monia, while the phosphorus forms phosphorus acids.
The GPCR reactor operates at a temperature of 850°C
or above, and the technology provider claims that a
residence time of seconds is sufficient for the complete
reduction of all organic matter.
Catalytic steam reformers supply hydrogen gas to
the GPCR reactor by steam reforming of natural gas.
Vertical radiant tube heaters with internal electric heat-
ing elements heat the inside of the reactor. The gases
enter the top of the GPCR reactor, and their tempera-
ture exceeds 870°C when they reach the bottom. When
the gases leave the reactor, they pass through primary
and secondary caustic scrubbers to remove acid gases,
water, and fine Articulates. Hydroclones are used to
remove solids from the caustic scrubbing fluid. The
gas stream exiting the secondary scrubber, which is
saturated with water at 38°C, is a mixture of hydrogen,
methane, carbon monoxide, carbon dioxide, nitrogen,
and trace light hydrocarbons. To ensure that no agent is
present, this gas is stored in a series of tanks, where it is
sampled and tested. If the agent concentration is below
OCR for page 108
108
ALTERNATIVE TECHNOLOGIES FOR DEMILITARIZATION OF ASSEMBLED CHEMICAL WEAPONS
the allowable stack concentration (ASC), the gas is
used as an auxiliary fuel for the steam boiler.
Process Instrumentation, Monitoring,
and Control
Conventional monitoring and control of the pro-
cesses are used for the proposed system. The process
materials (with the exception of agents and energetics),
temperatures, and pressures in this technology package
are common in other industrial applications where they
are routinely monitored and controlled. The usual col-
lection of equipment for monitoring temperature, pres-
sure, level control, flow, and other parameters normally
measured in a chemical plant is used together with the
ACAMS and DAAMS equipment developed by the
Army. To prevent plugging in the SCWO reactor, the
flow of transpiration water, other flow rates, pressure
drops, and reactor operating conditions are closely
monitored.
Feed Streams
The teed streams entering the LMIDS are listed by
area in Table 7-2. With the exception of the chemical
munitions, the materials listed are routinely used in
large-scale chemical processes. The LMIDS proposal
includes the mass balances for five campaigns a base
case and two demilitarization campaigns each for the
Blue Grass and Pueblo arsenals. For the purposes of
illustration, only the Blue Grass VX base case is con-
sidered here. The feed streams will change for the other
weapons campaigns at Blue Grass and for the demilita-
rization campaigns at Pueblo. In Table 7-2, Areas 100
and 200 have been combined because it was impos-
sible from the flow diagrams to determine the split for
the use of caustic and decontamination solutions be-
tween these two areas.
Waste Streams
The waste streams for the LMIDS are listed by area
in Table 7-3. All solid wastes (other than the metal parts
which have been treated to 5X condition) are treated
and then disposed of in a hazardous-waste landfill.
Ventilation air from contained process areas is passed
through carbon filters and monitored for agent before
TABLE 7-2 Process Inflow Streams (lb/hr) from
Outside the Process for Blue Grass VX Base Case
Campaign (14 M55 rockets/hr and 14 M121A1
projectiles/hr)
Component
Amount
AREA 100a + AREA 200b
NaOH
Decontamination solution
NaOH
Water
NaOC1
Total
M55 rockets
VX
Steel
Aluminum
Comp B
Nitrocellulose
Nitroglycerine
Dunnage
Total
M121A1 projectiles
VX
Steel
Comp B
TNT
Dunnage
Total
Nitrogen
Total areas 100 + 200
AREA 300C
Kerosene
Oxygen
Waste Oils
Total area 300
AREA 400d
Natural gas
Steam
Hydrogen
Nitrogen
Other dunnage
Total area 400
Total plant inflow
741
7
126
7
140
140
172
171
45
189
81
308
1,106
84
1,262
34
4
74
1,458
652
4,203
114
1,074
14
1,202
472
557
s
25
151
1,210
6,615
amunitions access and energetics deactivation
bcaustic makeup and hydrolysis
Csupercritical water oxidation
dgas phase chemical reduction
Source: Lockheed Martin, 1998.
release. There are no liquid effluents other than rainfall
runoff and cooling water (which will not be in contact
with hazardous materials). The six waste streams pro-
duced by the process are listed below:
OCR for page 109
LOCKHEED MARTIN INTEGRATED DEMILITARIZATION SYSTEM
TABLE 7-3 Process Outflow Streams (lb/hr) to the
Environment for the Blue Grass VX Base Case Campaign
(14 M55 Rockets/hr and 14 M121A1 projectiles/hr)
Component
Amount
AREA 100a
AREA 200b
AREA 300C
Vent gas
Treated solids to landfill
Total Area 300
AREA 400d
Treated metals
Steel
Other
Clean solids to landfill
Product gas to boiler
Total Area 400
Total plant outflow
o
o
1,107
1,559
2,666
1,421
11
313
2,183
3,928
6,594
amunitions access and energetics deactivation
bcaustic makeup and hydrolysis
Csupercritical water oxidation
dgas phase chemical reduction
Source: Lockheed Martin, 1998.
.
The SCWO off-gas is continuously monitored,
passed through carbon filter beds, and then re-
leased to the atmosphere. This gas stream is ex
. . . . .
a,
pectea oy tne technology provider to contain
mainly carbon dioxide, oxygen, nitrogen, small
amounts of water vapor, and trace amounts of ni-
trous oxide and light hydrocarbons.
· Treated ventilation air from the process contain-
ment areas is passed through carbon filter beds.
· Decontaminated metal parts that have not dis-
solved in the hydrolysis reactors are processed to
a 5X condition in the GPCR reactor.
Sodium salts produced from elements in agent and
energetics hydrolysates (fluoride, chloride, sul-
fate, nitrate, nitrite, and some phosphate salts) are
fed to the SCWO reactor. Tests show that the salts
contain up to 10 ppm of organic materials, princi-
pally acetone and acetic acid. According to the
technology provider, the salts will be free of agent
and contain no CWC Schedule 2 compounds.
Chemical agents will yield a large amount of salt
(VX will yield salt equal to about 150 percent of
its original mass). The yield of solid salts from the
.
109
energetics will vary with the energetic but will be
approximately equal to the weight of the energetic.
Salts from the SCWO process will be sent off site
~ . .. . . . .
for stao~zat~on ana placement In a hazardous
waste landfill.
Residues of carbon (e.g. char and soot) and silica
will contain traces of hydrocarbons from GPCR
processing of dunnage, fiberglass shipping and fir-
ing tubes, DPE suits, etc. are shipped off site for
disposal in an approximately permitted landfill.
· GPCR off-gases that contain low molecular
weight hydrocarbons (methane and ethylene) and
small amounts of hydrogen chloride and hydrogen
sulfide are passed through an activated carbon fil-
ter and a caustic scrubber and then burned in the
facility boiler after passing through a hold-test-
release cycle.
Noncontaminated dunnage, such as the wood and
wood pallets used to package munitions, will be trans-
ported off site for reclamation or disposal.
Start-up anti Shutdown
The LMIDS uses both batch and continuous pro-
cesses operating in series (i.e., feeding one another).
Standard chemical-industry practices (operation, in-
strumentation, and control) can be used to implement
normal start-ups and shutdowns, as well as emergency
shutdowns. The technology provider has also provided
a plan for final shutdown, which includes disassembly
of all equipment except the GPCR, treatment of all
other process equipment in the GPCR reactor to the 5X
standard, and the removal of all equipment from the
site.
EVALUATION OF TH E TECH NOLOGY PACKAG E
Process Efficacy
Effectiveness of Munitions Disassembly
Rockets. The punching and shearing processes for
the rockets are typical of baseline operations and should
be capable of achieving the desired processing rates. A
unique feature of this technology package is the use of
a gravity feed to drop sheared rocket parts into baskets
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110
ALTERNATIVE TECHNOLOGIES FOR DEMILITARIZATION OF ASSEMBLED CHEMICAL WEAPONS
submerged in the rocket hydrolysis vessel through a
chute and gate. This interface must be capable of (1)
withstanding explosions to protect the rocket hydroly-
sis vessel or disassembly equipment and (2) operating
reliably in the presence of caustic vapors. This opera-
tion should be designed to avoid increasing mainte-
nance requirements and, thus, reducing the munition
throughput rates.
Projectiles/Mortars. The initial disassembly ~ro-
cesses for projectiles are identical to the baseline pro-
cesses and should meet reliability and production ob-
jectives. Modifications to segregate and feed the
various projectile/mortar parts to the downstream pro-
cesses involve multiple, remotely-operated interfaces
with the hydrolysis processes. Here, as in the rocket
disassembly process, initial reliability may be a prob-
lem because of the action of caustic vapors. Another
potential problem to achieving the desired throughput
without increasing maintenance in DPE suits is the seg-
regation of products from the projectile/mortar disas-
sembly process into four streams. Safety and reliability
problems could arise if the parts, similar in size but
different in characteristics, are intermixed.
Effectiveness of Agent Decomposition via Hydrolysis
Decomposition with caustic is a proven process for
bulk agent (see Appendix D). However, because of the
complexity of scaling up mixing processes and the dif-
ficulty of removing agent from the crevices in sheared
rocket parts, the time required to lower the concentra-
tion of agent to the required levels in the various plant-
scale hydrolysis vessels may be longer than anticipated.
A longer residence time would require equipment
modifications to achieve the design throughput. Ad-
dressing this concern will require testing with near pro-
duction-scale equipment. Significant DPE maintenance
may be required for the carts used to convey metal parts
into the rocket hydrolysis vessel bath and for the pro-
jectile baskets that will invert the casings and position
them over wash-out wands in a caustic spray environ-
ment using remotely operated equipment. However, the
committee believes that with a careful design and well
chosen materials of construction, the processing objec-
tives for the hydrolysis of agent on projectile/mortar
parts should be achievable.
Effectiveness of Energetics Decomposition
via Hydrolysis
Significant unknowns remain in the decomposition
and deactivation of energetic materials by base hy-
drolysis (see Appendix E), and the destruction of ener-
getics in the rocket, burster, and nose closure hydroly-
sis vessels may take longer than expected because of
the uncertain reaction rates.
Aluminum rocket parts will also be dissolved in
caustic in the rocket hydrolysis vessel. The committee
is concerned that the exothermic reaction of aluminum
with caustic could produce hot spots and very rapid
reactions. The aluminum reaction also produces hydro-
gen, which could increase the explosion hazard. The
technology provider will have to design and operate
the rocket hydrolysis vessel purge-gas and off-gas han-
dling systems with these possibilities in mind.
Effectiveness of Supercritica/ Water Oxidation
The SCWO process appears to be capable of com-
pleting the destruction of both agent and energetics.
Mustard does contain volatile low molecular weight
chlorinated hydrocarbons that can be difficult to
treat. These are expected to be oxidized by SCWO
but this will have to be demonstrated. A key area of
uncertainty in the technology provider's proposed
application of SCWO is the proprietary transpiring
wall tubular reactor. Although this concept should
be capable of achieving the desired processing rates,
there has been no long-term experience using a tran-
spiring wall in the severe operating environment of
the SCWO reactor. Current experience relates
almost entirely to much larger diameter, non-
transpiring wall reactor vessels and shows that plug-
ging and corrosion are the main problems encoun-
tered. The technology provider proposes using the
transpiring wall to overcome these problems, but
this technology has not been demonstrated in ex-
tended runs, which will be essential to proving the
efficacy of this crucial step in the agent/energetics
destruction process. The technology provider will
also have to verify that the use of the transpiring
wall does not allow waste materials to bypass the
reaction zone via the cooler transpiration-water reg-
ion adjacent to the wall.
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LOCKHEED MARTIN INTEGRATED DEMILITARIZATION SYSTEM
Effectiveness of Decontamination of Meta/
and Other Munitions Parts
Although the GPCR process as proposed has not
been applied to metal parts from hydrolysis reactions,
prior experience in other applications indicates that this
technology should achieve the desired process through-
put and decontamination levels. The nature of the par-
ticulates produced by the hydrogen reduction of or-
ganic materials and salts on the surfaces of metal parts
is one area of uncertainty that should be addressed in
subsequent testing. These particulates may have char-
acteristics (e.g., the formation of sticky soot) that will
increase maintenance requirements.
Effectiveness of Decontamination of Other
Contaminated Materials
The nature of the particulates generated from the
decomposition of fiberglass rocket shipping/firing
tubes, DPE suits, and other organic wastes is still un-
certain. Approximately 10 percent by weight of the
carbon feed is expected to remain as soot, and the tech-
nology provider expects that this solid waste stream
will be disposed of off site. The large amount of soot
generated in the thermal-reduction batch processor
could lead to buildups in gas recirculation paths, which
could restrict throughput and require additional main-
tenance to clear the gas path.
Sampling and Analysis
Sampling and analysis requirements appear to be
reasonably well known for this integrated process. Easy
evaluations of the composition of the hydrolysate can
be made from the hydrolysate feed tanks to the SCWO.
Similar observations can be made for solid wastes that
cannot be released until agent concentrations in adja-
cent gas spaces are below allowable levels. The tech-
nology provider will also have to ensure that agent does
not condense, adsorb, or otherwise accumulate on the
internal surfaces of the GPCR off-gas hold-test-release
tanks, where it would not be detected in the gas analy-
sis but could subsequently revaporize upon depressur-
ization and venting to the boiler fuel system. (The same
problem exists for all gaseous hold-test-release systems
that are subject to significant pressure variations.)
111
Maturity
Disassembly Process. The LMIDS uses much of the
baseline disassembly process that has been proven at
the Johnston Atoll and Tooele, Utah, demilitarization
facilities. Modifying the process to include a wash-out
step is based loosely on ton-container wash-out tests
for the Aberdeen and Newport sites; however, the spe-
cific design modifications have not been tested. One
of Lockheed Martin's partners, Aerojet, has more
than 30 years of experience with hydromining rocket
propellants.
Interfaces between the disassembly process and
downstream processes may limit the throughput be-
cause the reliability of the remotely operated handling
equipment used for the interfaces could be difficult to
maintain. Some of this equipment is new or has never
been used in the harsh environment of caustic hydroly-
sis processes. Materials selection and design of this
equipment will be very important.
Agent Hydrolysis. Neutralization is a proven tech-
nology for the deactivation of chemical agents (see
Appendix D), and agent hydrolysis processes for HD
and VX are being implemented at Aberdeen and New-
port. Hydrolysis for GB has been done on a large scale
at Rocky Mountain Arsenal. Therefore, the hydrolysis
of agent is a mature and well tested technology that
requires simple engineering and control.
Energetics Hydrolysis. Several issues remain to be
addressed about the technology provider's implemen-
tation of hydrolysis for energetics.
The caustic hydrolysis step is intended to dissolve
the aluminum fuze and expose the energetic ma-
terials. The dissolution of aluminum will result in
an exothermic generation of hydrogen gas that
will bubble out of the aqueous alkaline solution.
The production rate of hydrogen and the release
rate of thermal energy will have to be monitored
and controlled to ensure that there is no possi-
bility of ignition. Also, an autocatalytic redox re-
action could occur when the wet aluminum is in
the presence of damp energetic materials. There-
fore, both must be destroyed in the hydrolysis.
2. Many of the hydrolysis vessels for energetics in-
volve mechanical conveyors operating in a hot
20-percent caustic solution, which is a severe
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112
ALTERNATIVE TECHNOLOGIES FOR DEMILITARIZATION OF ASSEMBLED CHEMICAL WEAPONS
environment for this type of machinery. There-
fore, a great deal of maintenance (by personnel in
DPE suits) may be required to keep this equip-
ment in operation. No information has been pro-
vided to the committee on the reliability of this
equipment in a hot caustic environment.
3. The required residence time in the hydrolysis re-
actors is directly related to the size of the sheared
pieces. The size of these pieces will have to be
accurately characterized because they will affect
the design of the hydrolysis reactors for energetics.
SCWO. The SCWO process for the treatment of VX
hydrolysate has been extensively examined in a previ-
ous NRC study (NRC, 1998), and work on the use of
SCWO to treat hydrolysates from agent and energetics
destruction is ongoing. Other SCWO systems have
been under development for more than 20 years; the
Huntsman Corporation of Austin, Texas, for example
operates the only commercial SCWO unit for the treat-
ment of organic-laden wastewater. Nevertheless,
corrosion, erosion, and plugging problems in the
presence of salts. This technology has not been
used with salt-containing supercritical water.
3. Control of the transpiring-wall reactor may be dif-
ficult, and its operation may be very sensitive to
system fluctuations. Fluctuations in pressure can
cause a backflow into the transpiring wall and
plugging.
4. Because the SCWO reactor is a unique and un-
proven piece of equipment in the LMIDS, main-
tenance may be difficult. Furthermore, because
of the difficulty of construction, if the reactor be-
comes nonoperational, there may be a significant
delay before it can be repaired or replaced.
5. The SCWO reactor would be used with a mixture
of energetics and agent hydrol~sates. Because
SCWO is capable of treating a variety of materi-
als (probably simultaneously), this may not be a
problem. However, the system should be exten-
sively tested with mixed hydrolysates.
- 6. The composition of the feed to the SCWO reactor
S(:W(] cannot be considered a mature technology for
destroying agent and energetic hydrolysates.
The proposed LMIDS transpiring-wall reactor pro-
vides a novel solution to the problem of corrosion and
plugging in SCWO reactors. The transpiring-wall
SCWO reactor has been tested at bench scale at Sandia
National Laboratories in collaboration with GenCorp/
Aerojet and Foster Wheeler. A commercial-scale reac-
tor is currently being built for the Army at the Pine
Bluff Arsenal by Foster Wheeler/Aerojet to treat smoke
and dye wastes with a high salt content (similar in some
ways to agent/energetics hydrolysates). This unit is
expected to be operational sometime in 1999 but was
not operational at the time of this writing. The ~ro
O
*' ~.. . .. .. .. .. .
posect ~;wu unit Is essentially ~crent~ca~ to a unit be-
ing constructed for the U.S. Navy for shipboard waste
disposal. No extensive testing of the design has been
done to date. The committee has the following con-
cerns about this technology:
1. The design and manufacture of this unique
SCWO reactor may be quite difficult. Fabrication
of the transpiring wall may present a significant
challenge, both in the choice of materials and in
the construction of the platelets.
2. Long-term testing will be necessary to establish
that the transpiring-wall reactor will not have
. ~ . . .
will change with time, either because of a change
in the mix of weapons or because of an unsched-
uled shutdown of either the agent hydrolysis re-
actor or an energetics hydrolysis reactor. It must
be established that the SCWO reactor will con-
tinue to operate reliably after a sudden change in
the composition of the feed stream.
7. The gaseous effluent from the SCWO reactor will
be continuously filtered, monitored, and released
to the environment. This off-gas will not be passed
through a hold-test-and-release process. Continuous
monitoring must be demonstrated to ensure that
the released off-gas meets safety criteria.
Gas Phase Chemical Reduction. The thermal-reduc-
tion batch processor/GPCR process has been used com-
mercially to treat PCB-contaminated electrical equip-
ment. Two full-scale plants have been operating for
more than two years in Kwinana in Western Australia,
and one plant was operated for a year at a General
Motors of Canada facility in St. Catherine's, Ontario.
The process will be used here with only minor modifi-
cations. Therefore, there is some experience in operat-
ing GPCR reactors of the size to be used in the LMIDS.
The committee has the following concerns about these
units.
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LOCKHEED MARTIN INTEGRATED DEMILITARIZATION SYSTEM
1. The GPCR reactor must be operated in a closed,
contained environment, where fugitive hydrogen
emissions can be a serious hazard. Therefore, the
design and control of this system must take this
danger into account.
2. The monitoring and control system on the GPCR
units must ensure that no oxygen or other oxi-
dants are present before hydrogen is admitted into
the system.
The proposed method of separating soot from the
gaseous effluent from the GPCR reactor may not
be very effective and may result in process reli-
ability problems from the accumulation of soot in
other parts of the gas-flow path.
4. The GPCR of materials to soot, silica, and a us-
able fuel gas must be thoroughly demonstrated.
The waste streams may be more complex than
anticipated.
5. A method must be developed to ensure that agent
(or other hazardous materials) does not condense,
adsorb, or accumulate on the internal surfaces of
the off-gas hold-test-release tanks.
Scale-up. Some aspects of scale-up from demonstra-
tion-size equipment should be relatively easy. The
SCWO reactors will be the same size as an existing
prototype Navy unit. The LMIDS reactors will be de-
signed to operate in parallel, and no problem with scale-
up is planned. Other aspects of scale-up may be more
difficult because not all parts of the process scale in the
same way. For example, many mass-transfer processes
scale with length, whereas surface and surface wash-
out phenomena scale with area; still others, such as the
homogeneous hydrolysis reaction, scale with reactor
volume. The hydrolysis vessels will have to be care-
fully designed to accommodate all three phenomena
simultaneously.
Overall Technology Package. The technologies se-
lected by the technology provider have all been imple-
mented with process streams similar to those in the
ACWA program. However, they have not been oper-
ated as an integrated unit. Furthermore, some of the
methods of implementation are new and all but untried
at this time (e.g., the transpiring-wall SCWO reactor
and the methods for hydrolyzing agent and energetics
remaining on metal parts). Thus, although the basic
technologies are reasonably mature, certain facets of
113
their implementation and their integration or interfac-
ing are still at early stages of development. To prevent
severe operating problems, the integrated system must
be demonstrated prior to full-scale operation. The
full-scale process will have to be designed to be
"forgiving," allowing easy visibility and easy mainte-
nance of remotely-operated and automated equipment.
Robustness
Robustness, or the ability to operate with a wide
range of feed stocks and operating conditions, appears
to be reasonable in all process areas except for the ves-
sels used to remove energetics and agents remaining
on metal parts. If agent or energetic properties are dif-
ferent than anticipated (e.g., more polymerization of
the agent than expected), the cleaning method may re-
quire significant modifications to achieve the required
throughputs.
Monitoring and Contro/
The monitoring and control approaches for the pro-
cesses in this system are widely used and should be
readily implemented. The process materials (with the
exception of agents and energetics), temperatures,
and pressures in this technology package have all
been successfully monitored and controlled in prior
applications.
App/icabi/ity
The technology provider included process design
information for rockets and projectiles/mortars and
stated that land mines could be easily incorporated as
an additional feed stream by adding a disassembly ca-
pability for these munitions. Thus, the proposed sys-
tem has broad applicability.
Process Safety
The technology provider proposes using several
unique pieces of equipment:
· a modified (from baseline) rocket-shear machine
· a rocket hydrolysis vessel for sheared rocket parts,
propellant and energetics
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ALTERNATIVE TECHNOLOGIES FOR DEMILITARIZATION OF ASSEMBLED CHEMICAL WEAPONS
· a nose-closure hydrolysis vessel for projectile nose
closures
· a projectile hydrolysis vessel for projectile bodies
· a burster hydrolysis vessel for projectile bursters
energetics destruction reactors
agent neutralization reactors
a GPCR process that includes a thermal reduction
continuous processor for treatment of projectiles
and a thermal reduction batch processor for other
waste streams
transpiring-wall SCWO reactors for destruction of
agent and energetic hydrolysates
In the LMIDS, the energetics and agent are sepa-
rated early in the process, reducing the possibility of an
energetically driven release of agent. Most of the hy-
drolysis processes operate at low temperatures (90°C
or 194°F) and low pressure (near atmospheric), thus
avoiding significant stored energy and reducing pro-
cess hazards. The burster hydrolysis vessel is slightly
pressurized to achieve temperatures up to 1 35°C but
does not represent a significant stored-energy hazard.
The SCWO reactors operate at 238 aim and 780°C and
do represent major reservoirs of stored energy. The
GPCR processes operate at temperatures up to 850°C
(1,562°F) at low pressure using a hydrogen gas atmo-
sphere for destruction of trace amounts of agents and
other hazardous materials. Commercial facilities em-
ploying this technology are operating (or have oper-
ated) in Canada and Australia. However, all of these
facilities are located outdoors. To maintain control of
potential airborne agent emissions, the GPCR equip-
ment for the LMIDS will be located inside a contain-
ment or confinement building. Therefore, hydrogen
leakage from the GPCR is a safety concern. The team
partner responsible for this technology, Eco-Logic, is
well aware of this and has commissioned a safety study
on this issue (Prugh, 1998~. Recommended safety
measures are being considered or have already been
implemented.
Worker Safety
The LMIDS system is basically "forgiving" in that
agent and energetic destruction are verified after both
of the sequential processes for all ACWs, thus ensur-
ing that all agent and energetic material have been
destroyed. The separation of energetics from agent
and the subsequent destruction of both materials in a
20-percent caustic solution minimizes the risk of ex-
plosions. In addition, both processes are operated in
structures designed to contain explosive overpressure.
Mechanical disassembly processes are derivatives of
the baseline processes and are not considered to repre-
sent new or increased risk levels for rockets, projec-
tiles, or land mines. These processes will be conducted
in vessels or structures designed to withstand explo-
sive overpressure.
The GPCR reactor operates in a hydrogen atmo-
sphere and generates methane and other gaseous hy-
drocarbons that could burn or explode in the presence
of air. Explosion hazards for this process are minimized
by purging with inert gas during start-up and shutdown.
Considerable industrial experience with high-tempera-
ture hydrogen atmospheres has established that these
processes can be operated safely. GPCR off-gas could
contain small amounts of hydrogen sulfide and hydro-
gen chloride, which will be removed in a caustic scrub-
ber. Worker exposure to these gases is unlikely. Simi-
lar gases in much higher concentrations are routinely
handled safely in the petroleum refining and petro-
chemical industry.
The most significant worker safety issue will prob-
ably be maintenance of the hydrolysis vessels in DPE
suits. These vessels have conveyor systems that oper-
ate in hot caustic solutions. Experience with these sys-
tems is limited, and full-scale implementation of this
technology, especially during start-up, may require sig-
nificant maintenance, thereby increasing the risk of
worker exposure to agent.
Hydrogen and other combustible gases will be gen-
erated in the hydrolysis reactions. Therefore, oxygen
must be kept out of the vessel vapor spaces and the
associated vapor piping, and these gases must not be
allowed to collect in air spaces in the contained process
areas. Because these processes operate at very low or
negative gauge pressures, the driving force that causes
gas leaks into ventilated areas is minimal. The hydroly-
sis vessel vapor spaces (which operate under a slight
vacuum) are purged with nitrogen gas to prevent un-
safe oxygen levels from building up from the in-leak-
age of ventilation air. Loss of the nitrogen purge gas
would increase the likelihood of an explosion in the
vessels or off-gas piping.
OCR for page 115
LOCKHEED MARTIN INTEGRATED DEMILITARIZATION SYSTEM
The SCWO reactors and water supply system oper-
ate at high pressure and are a source of stored energy.
Therefore, it is very important that the reactors be de-
signed and maintained in ways that minimize ruptures
and leaks. Failures may not result in release to the envi-
ronment because of secondary containment, but they
could require extensive repair work in DPE suits.
Fuze bodies and booster pellets that are not dissolved
in the caustic solution also represent an explosive haz-
ard in the thermal-reduction batch processor. The tech-
nology provider intends to demonstrate a technology
that will reduce the size of these parts to ensure their
full dissolution. In addition, the thermal-reduction
batch processor will be designed to withstand initiation
of these components.
The primary hazardous materials used in agent and
energetic destruction are sodium hydroxide, liquid and
gaseous oxygen, hydrogen, and methane. Sodium hy-
droxide will be delivered in solid form and dissolved in
water to make a 20-percent caustic solution. All of
these chemicals are handled routinely and safely in
many industries. The technology provider has con-
ducted a preliminary hazard analysis and has identified
reasonable solutions for events that could create unac-
ceptable or undesirable worker safety risks (Lockheed
Martin, 1998).
Public Safety
The likelihood of releases of agent or other regu-
lated substances to the atmosphere or to the facility are
expected to be extremely small. Hold-test-release svs-
tems are applied to all effluent streams except the
containment ventilation air and SCWO off-gas. The
ventilation system uses tested baseline air cleaning
technology. The SCWO off-gas will be cooled con-
tinuously, monitored for agent, and passed through a
carbon filter before release to the atmosphere. This ap-
proach does not meet the hold-test-release criterion for
process effluents that has been requested by some
stakeholders; but it is not expected to reduce public
safety.
The primary cause for a release of material contain-
ing agent or other regulated substances would be a dis-
ruptive explosion. The likelihood of such an event is
expected to be extremely small at the conclusion of the
design process for the full-scale facility. (This design
115
process is understood to include the completion of a
QRA.) A preliminary hazard analysis conducted by the
technology provider revealed no events with unaccept-
able or undesirable public safety risks.
Human Health and the Environment
A full evaluation of the impact of the effluents on
human health and the environment must await the out-
come of health and environmental risk assessments,
which cannot be prepared at the current stage of devel-
opment for this system. However, some general obser-
vations and comments can be made at this time.
Process gases leaving the plant will have been
treated to remove traces of organic materials (includ-
ing agent) and will be monitored or tested to ensure
that they do not contain agent or other regulated sub-
stances at concentrations above levels established by
the EPA for release to the environment.
The solid waste streams are 5X metal parts, salt from
the SCWO reactors, and carbon residue and silica from
the GPCR. All nonmetal solid waste streams are ex-
pected to be suitable for release to a hazardous-waste
landfill. The 5X metal parts are expected to be suitable
for reuse as scrap for metallurgical processes.
Effluent Characterization, Management, and Impact
on Human Health and the Environment
Gas Streams. These streams originate in the SCWO
reactors, the ventilation air exhaust from contained pro-
cess areas, and exhaust gases from the steam boiler (fu-
eled partly by the GPCR reactor) and the hydrogen gen-
erator. Experience indicates that the gas streams will
be free of agent and other regulated substances. Dem-
onstration tests would provide reassurance that the de-
sign works as planned for the treatment of process gas
and that all regulated substances in the effluent gases
are identified and measured.
The gas streams from the SCWO reactors and the
ventilation air exhaust from contained process areas are
monitored, passed through activated-carbon filters, and
released to the environment. (The exhaust gas from the
SCWO reactors has been shown to consist principally
of carbon dioxide and water vapor with trace amounts
of low molecular weight hydrocarbons.) The inlet to
the SCWO reactor will also be monitored, and detection
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116
ALTERNATIVE TECHNOLOGIES FOR DEMILITARIZATION OF ASSEMBLED CHEMICAL WEAPONS
of unacceptable levels of hazardous materials will trig-
ger an emergency response, including isolation and
shutdown. The exhaust gases from the steam boiler and
hydrogen generator will not be monitored. The compo-
sition of these gas streams should be characterized dur-
ing demonstrations of the LMIDS.
Acid gases from the GPCR process will be absorbed
in a caustic scrubber, and the effluent gas will be passed
through a hold-test-release procedure. If shown to have
acceptably low concentrations of regulated substances
and to be essentially agent free, the gas will be used as
fuel in the LMIDS steam boilers. Permits will be re-
quired to use this gas stream as boiler fuel based on full
characterization of the GPCR process off-gas streams
during demonstration.
Metal Parts. These parts will be treated in the GPCR
process and will not be released until they have been
treated to the 5X standard. As long as the treatment
procedure is monitored, the metal parts should need no
further testing and can be released. The cleaned parts
are not expected to pose any threat to human health or
the environment.
Salts. Salts from the SCWO reactors will contain the
sodium salts of fluoride, chloride, sulfate, phosphate,
nitrate, and nitrite and are expected to contain trace
amounts of low molecular weight hydrocarbons. The
committee expects that this stream will be classified as
hazardous, although this has not yet been determined
by testing. The salts will be verified to be agent free
before they are released for off-site stabilization and
placement in a hazardous-waste landfill. Stabilization
of salt wastes is very difficult. The leaching levels of
hazardous constituents in the salt will have to be inves-
tigated to determine if additives will be necessary to
ensure stabilization and whether a formula for a stabi-
lized mixture can be developed. If stabilization and
burial in a hazardous-waste landfill are feasible, they
would provide adequate protection to human health and
the environment. Demonstration tests are necessary to
characterize fully the composition of the salts to
identify all regulated substances and determine their
concentrations.
Dunnage Material. This material is subjected to
silica and will be sent off site for stabilization and dis-
posal in a hazardous-waste landfill. Demonstration
tests will have to characterize fully the composition of
the solids to identify all regulated substances and their
concentrations.
Resource Requirements
The chemicals required for processing are sodium
hydroxide, liquid oxygen, liquid nitrogen, and kero-
sene (or isopropyl alcohol). The level of usage is not
considered to represent an unusual demand on avail-
able industrial sources. The utilities required for opera-
tion and maintenance are electricity, water, and gas.
The amounts required are similar to the amounts for
the Army's baseline facilities except for the larger con-
sumption of methane for the production of steam and
hydrogen. Manpower required for operation and main-
tenance will probably be similar to the manpower for
the Army's baseline facilities, assuming that mainte-
nance concerns expressed earlier are addressed as the
design progresses.
Environmenta/ Compliance and Permitting
Compliance with environmental regulations will re-
quire careful, detailed design of the plant, as well as
careful operation and environmental management.
There are no inherent reasons why the combination of
technologies in the LMIDS technology package should
lead to unusual problems. The absence of liquid emis-
sions is an important advantage of the process.
The same is true for permitting. All process waste
streams except the SCWO off-gas will be evaluated
prior to release to confirm that regulated substances are
absent or at acceptably low concentrations. The SCWO
off-gas will be scrubbed, monitored, and passed
through activated carbon filters.
One aspect of the process that may lead to permit-
ting problems is the use of the cleaned GPCR off-gas
as a boiler fuel. Extensive testing may be required to char-
acterize this stream to ensure that it can be used safely.
STEPS REQUIRED FOR IMPLEMENTATION
n~gn-temperature hydrogen recluct~on In the (~K pro-Overall, the LMIDS appears to be capable of operat
cess. The solid process effluent is carbon residue anding as proposed by the technology provider, but the
OCR for page 117
LOCKHEED MARTIN INTEGRATED DEMILITARIZATION SYSTEM
process must be developed further, especially the inter-
faces between and integration of the nroceL~Ls unites. If
. . ~ ~ ~ ~
the civ~ were to proceed towards full-scale imple-
mentation, the next step should be to design, build, and
operate a pilot-scale system that incorporates all of the
unit operations into a fully functional, integrated pro-
cess. Full-scale implementation will involve interfac-
ing and integrating batch processes (the hydrolysis re-
actors and the thermal reduction batch processor) with
continuous processes (the SCWO reactor, the thermal
reduction continuous processor, and the GPCR reac-
tor). These interfaces must be tested at the demonstra-
tion stage to avoid implementation problems. Also, all
problems with materials of construction and waste
characterization will have to be solved before imple-
mentation. However, no problems have been identified
that would prevent eventual full-scale implementation.
In addition to demonstrating that the overall process
is capable of long-term operation, specific objectives
for three of the pilot-scale unit operations are described
below.
Pi/ot-Sca/e Eva/uation for Hydro/ysis of Energetics
1. Establish that the mechanical equipment used in
the energetics hydrolysis vessels can tolerate the
harsh conditions without excess maintenance.
2. Determine whether the hydrolysis of aluminum
. . . · . . . - .
together with energet~cs presents any problems.
Pi/ot-Sca/e Eva/uation for SCWO
1. Show that the SCWO reactor platelet wall can be
constructed.
2. Demonstrate that the SCWO reactor can be oper-
ated for sufficient periods of time without exces
. . . .
slve clogging or corrosion.
3. Fully characterize the SCWO gaseous effluent
from mixed hydrolysates of agent and energetics.
A-. Establish that the continuous monitoring of the
SCWO gaseous effluent ensures against unac-
ceptable releases of hazardous materials.
Pi/ot-Sca/e Eva/uation for GPCR
117
2. Ascertain whether the large quantity of soot gen-
erated in the thermal-reduction batch process will
create any problems.
FINDINGS
Finding LM-1. The disassembly methods proposed in
the LMIDS are based largely on the baseline disassem-
bly methods. The proposed modifications appear to be
reasonable, but testing will be necessary to verify that
performance, reliability, and production objectives can
be met.
Finding LM-2. Primary agent decomposition and
detoxification is achieved using a strong caustic hy-
drolysis of bulk agent a proven technology. Overall,
the implementation of agent hydrolysis in the LMIDS
is sound.
Finding LM-3. Primary decomposition and deactiva-
tion of energetics is also achieved using a strong caus-
tic hydrolysis. This technology has been tested but is
less mature than agent hydrolysis. The implementation
of this technology in the LMIDS is reasonable but will
require thorough testing at the pilot scale.
Finding LM-4. The method of removing agent from
metal parts caustic solution jet wash-out followed by
the movement of the parts in baskets through a caustic
bath is new and unproven. It is expected that this
method can be made to work, but the effort and time
required to come to acceptable performance goals may
be longer than anticipated and may require alternate
methods. Thus, it will be desirable to have alternate
plans if the desired detoxification efficiencies are not
achieved (e.g., increase the capacity of the GPCR unit
to allow for more than the planned agent cleanup load).
finding LM-5. the hot-caustic environments in the
initial hydrolysis vessels will pose severe challenges
to the reliability and operability of the equipment
. · . .. .
- r - ~ ~ - - --- - - -l -- -r --
~ns~de these vessels, especially the basket transport
mechanisms.
Finding LM-6. The SCWO process appears to be ca-
pable of completing the destruction of both agent and
energetics in the hYdrolYsates. The keY area of uncer-
tainty in the technology prov~cler s proposed application
, , ,
.. ~. .. ..
1. Fully characterize the GPCR gaseous effluent and , a, l l l l l
establish whether it can be used as a boiler fuel. of SCWO is the use of its proprietary transpiring-wall
OCR for page 118
118
ALTERNATIVE TECHNOLOGIES FOR DEMILITARIZATION OF ASSEMBLED CHEMICAL WEAPONS
tubular reactor. The demonstration of this technology
will be essential to proving the efficacy of this crucial
step in the agent/energetics destruction process.
monitored, and passed through activated carbon. This
treatment appears to be appropriate for the anticipated
composition of the SCWO off-gases.
Finding LM-7. The crystallization and evaporation
operations have not been tested for this application.
These conventional technologies, which are expected
to work effectively, must still be tested.
Finding LM-X. The use of GPCR in an enclosed envi-
ronment raises unique safety concerns because of the
presence of hot hydrogen gas. Hydrogen is handled
routinely (and safely) in the chemical industry, and the
technology provider is aware of the hazards. Imple-
mentation of this technology will require a design that
ensures that these hazards are thoroughly understood
and mitigated.
Finding LM-9. The gas stream from SCWO is not sub-
jected to hold-test-release. Instead, the gas is scrubbed,
finding LM-l(). Lot-scale testing will be necessary
to refine the component technologies and demonstrate
that these technologies can be operated as an integrated
system.
Finding LM-ll. The proposed use of the cleaned
GPCR off-gas as a boiler fuel poses unique permitting
challenges. Any demonstration must characterize this
stream to ensure that permitting as a boiler fuel is pos
sible. If this off-gas cannot be used as a boiler fuel,
significant process modifications may be necessary.
Finding LM-12. All of the findings in the NRC report,
Using Supercritical Water to Treat Hydrolysate from
V7( Neutralization (NRC, 1998), apply to the LMIDS
SCWO system (see Appendix F).
Representative terms from entire chapter:
scwo reactor
