Presented to: Kentucky Chemical Demilitarization Citizens’ Advisory Commission and Chemical Destruction Community Advisory Board Presented by: Jeff Brubaker, ACWA Site Manager John Barton, Systems Contractor Chief Scientist

1. BGCAPP Cyanide Treatment
December 11, 2013
Presented to:
Kentucky Chemical Demilitarization
Citizens’ Advisory Commission and
Chemical Destruction Community
Advisory Board
Presented by:
Jeff Brubaker, ACWA Site Manager
John Barton, Systems Contractor
Chief Scientist

2. A Partnership for Safe Chemical Weapons Destruction
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The Technical Challenge
 Neutralizing rocket warhead explosives poses unique
technical challenge at Blue Grass
 Cyanide formation expected during energetics neutralization
process, trapped in caustic liquid energetics hydrolysate
 Cyanide produced during energetics neutralization process
isn’t a public risk, but if not treated, may require additional
protective measures during future plant operations where
cyanide may present a worker hazard
 Specific cyanide hazards may be present during
Supercritical Water Oxidation Process feed preparation
 BGCAPP focused on treating hazard today,
to better protect operations workers for tomorrow

3. A Partnership for Safe Chemical Weapons Destruction
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Treatment Approach
 Year long collaborative effort among BGCAPP scientists,
engineers and corporate subject matter experts
 Mission focused on safely and efficiently treating cyanide
hazard during energetics neutralization processing
 Focus on energetics neutralization process
– Portion of process where cyanide first occurs
– Un-manned, automated process (i.e. no workers)
– Upstream before Supercritical Water Oxidation Process
(where cyanide could pose worker hazard)

4. A Partnership for Safe Chemical Weapons Destruction
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A Safe Solution
 Enhancing auxiliary systems to the Energetics Neutralization
Reactors to increase operating temperature
– Safely and efficiently destroys cyanide
– Does not change the neutralization process
– Does not alter the Supercritical Water Oxidation process
– Does not impact weapons destruction baseline schedule

5. A Partnership for Safe Chemical Weapons Destruction
 Neutralization of energetics
(explosive) and aluminum with hot
caustic under BGCAPP-specific
process conditions occurs in the
energetics batch hydrolyzers
 Hydrolysate will contain many
secondary liquid byproducts that
include ammonia, nitrate, formate,
cyanide and many other
decomposition products.
 Energetics destruction is verified
before hydrolysate is released to
Hydrolysate Storage Area (HSA) and
subsequent secondary Supercritical
Water Oxidation process
Energetics Neutralization
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Energetics Batch Hydrolyzers equipment
will be used during the BGCAPP energetics
neutralization process.
Small piece of energetics in an aluminum pan

6. A Partnership for Safe Chemical Weapons Destruction
Hazard Evaluation
 BGCAPP confirmed cyanide ion formation during the
energetics neutralization process using a series of bench-
scale tests performed in late 2012
 Without treatment, additional protective measures may be
needed during future plant operations where cyanide may
present a worker hazard
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Energetics Hydrolysate

7. A Partnership for Safe Chemical Weapons Destruction
Technical Background:
Energetics Neutralization Process
HSS
Off-gas to MDB
filter banks
Hydrolysate Storage Area
(HSA)
EBH – Energetics Batch Hydrolyzer ENR – Energetics Neutralization Reactor SCWO – Supercritical Water Oxidation OTE – Off-gas treatment for
EBH (acid scrubber) OTM – Off-gas Treatment System APR – Aluminum Precipitation Reactor AFS – Aluminum Filtration System
ENR
Munitions Demilitarization
Building (MDB)
OTE
effluent
Off-gas
to OTE
Off-gas
to OTM
EBH
216°F, 1 atm
240°F, 1.7 atm
AFS
Air
Acid
Off-gas to
carbon
canister
Off-gas to
atmosphere
Filter cake
APR
Waste
Packaging
SCWO
Feed
System
Supercritical Water Oxidation (SCWO) Processing Building
(SPB)
Off-gas to
SCWO
building
140°F, 1 atm
Scrubber condensate
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8. A Partnership for Safe Chemical Weapons Destruction
Technical Verification:
Bench-Scale Characterization Tests
Mettler RC1® Calorimeter Reactor at
Battelle’s HERLA Used to Simulate BGCAPP
EBH and ENR Operations
Aluminum Precipitation System Used to Simulate
BGCAPP APR and AFS Operations
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9. A Partnership for Safe Chemical Weapons Destruction
Verification Results
 Cyanide is produced during energetics neutralization process
(400-600 milligrams per liter (mg/L)
 Without treatment, cyanide will persist at decreasing levels
within energetics hydrolysate streams as they are processed
through to SCWO Process Building
 Because high pH is maintained in the Munitions
Demilitarization Building and HSA, hydrogen cyanide off-
gassing is not a significant hazard in those areas
 Significant levels of hydrogen cyanide will off-gas inside the
aluminum precipitation reactor system (reactor headspace)
during acidification of energetics hydrolysate (> 25 mg/m3)
in the SCWO Processing Building
 Significant levels of hydrogen cyanide will also off-gas in the
aluminum filtration system and from produced filter cake
(> 5 mg/m3)
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10. A Partnership for Safe Chemical Weapons Destruction
Cyanide Health Limits
 National Institute of Occupational Safety & Health assigns
short-term exposure limit, 15-minute time-weighted average,
of 5 mg/m3 for hydrogen cyanide in air
 Centers for Disease Control assign an Immediately Dangerous
to Life or Health limit of 25 mg/m3 for hydrogen cyanide in air
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Aluminum filtercake

11. A Partnership for Safe Chemical Weapons Destruction
 Reviewed Battelle characterization results
 Evaluated strategies using combination of
subject matter expertise and bench-scale
testing
– Increase Energetics Neutralization
Reactors operating temperatures
 Battelle performed small-apparatus
testing to demonstrate proof of concept
– 270, 290, and 309oF
 83, 94, 98% cyanide removal efficiency
Treatment Approach / Proof of Concept
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12. A Partnership for Safe Chemical Weapons Destruction
 Small-scale tests were confirmed at liter-scale with more
representative mixing and pressure control
– 93, 95% cyanide removal efficiencies observed at 290
and 309oF
Liter-Scale Tests
High Pressure Test Vessel
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13. A Partnership for Safe Chemical Weapons Destruction
 BGCAPP selected ENR operating conditions of 300oF
and 45 psig to achieve cyanide removal efficiencies
on the order of 95 percent
 Confirmation tests completed October 2013 using high
pressure liter-scale nickel-lined vessel
– No fouling observed
– No enhanced corrosion
Desired Operating Condition
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14. A Partnership for Safe Chemical Weapons Destruction
 High temperature treatment advantages
– No new chemicals in the batch
– Minimizes change to downstream SCWO recipes
– Minimizes impact to downstream offgas treatment
strategies
– Contact, inhalation, and ingestion hazard significantly
reduced and readily managed
Summary - Status and Path Forward
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15. A Partnership for Safe Chemical Weapons Destruction
 Bench-scale proof-of-concept testing complete
– High temperature treatment validated
 BGCAPP is working to implement higher temperature option
– New heat transfer calculations
– Modification of heat delivery system required to increase
temperature from 240oF to 300oF
 Minimal impact to downstream SCWO chemistry
 No impact to weapons destruction baseline schedule
Summary - Status and Path Forward
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16. A Partnership for Safe Chemical Weapons Destruction
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Questions

17. A Partnership for Safe Chemical Weapons Destruction
Without Treatment With Higher Temperature Treatment
Liquid
(mg/L)
Air/Headspace
(mg/m3)
Liquid
(mg/L)
Air/Headspace
(mg/m3)
Energetics
Batch
Hydrolyzers
600 non-detect 600 non-detect
Energetics
Neutralization
Reactors
350 non-detect 15 non-detect
Aluminum
Precipitation
Reactors
40 > 25 5 < 5
Aluminum
Filtration
System
20 > 5 < 1 non-detect
Anticipated Cyanide Concentrations
treatment occurs during this step
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