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Cyanide mitigationand worker protection
May 7, 2014
Presented to: Kentucky Chemical
Demilitarization Citizens’ Advisory
Commission and Chemical Destruction
Community Advisory Board
Secondary Waste Working Group
Presented by:
Dr. John BartonSystems Contractor Chief Scientist
A Partnership for Safe Chemical Weapons Destruction
2
Agenda
Potential agent and industrial chemical hazards
Health Hazard Assessment methodology and approach
Worker Safety and Occupational Medicine Program
– Personal Reliability Program
– Medical baseline screening
Cyanide challenge for energetics neutralization process
Cyanide treatment during energetics neutralization process
Cyanide exposure limits vs. BGCAPP levels
Hydrolysate Storage Area design, construction, operations
Supercritical Water Oxidation (SCWO) Process Building
A Partnership for Safe Chemical Weapons Destruction
GB
VX
H
aluminum hydroxide
ammonia
carbon monoxide
carbon dioxide
Dicyclohexyl carbodiimide
diisopropylcarbodiimide
diisopropyl methlyphosphonate
diisopropanolamine
diisopropyl urea
EA2192
ethanol
sulfuric acid
3
Potential agent and industrial chemical hazards
tributylamine
tetrytol
tetryl
Composition B
trinitrotoluene
RDX; hexahydro-1,3,5-trinitro-1,3,5 triazine (cyclonite)
M28
HCN
hexane
methylene chloride
compressed air
helium
hydrogen
phosphoric acid
hydrochloric acid
hydrogen fluoride
isopropanol
nitrogen
methyl phosphonate
methyl phosphonic acid
sodium hypochlorite
sodium hydroxide
oxygen
phosphorus pentoxide
dithiane
sulfur
chloroform
Chemical Agents
Hydrogen Cyanide
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4
Health Hazard Assessments
Preliminary Hazard Assessment completed during design phase
Health Hazard Assessments and Job Hazard Analyses identify potential exposure hazards
– Completed to Project System Safety Program Plan standards
– Completed after procedure development initiated
– Completed to appropriate phases of the project (Design, Construction, Systemization, Operations, Closure)
A Construction worker (above) wears personal protective equipment.Systemization workers (below), inspect energized lock-out/tag-out systems.
A Partnership for Safe Chemical Weapons Destruction
Hazard tracking and communication
Health Hazard Inventory updated after Health Hazard Assessment
Documents shared with Medical Director and emergency preparedness
Hazards identified during analyses are tracked in Hazard Tracking Log
BGCAPP has formal Hazard Communication Program and Hazardous Waste and Emergency Response Program
Employees are educated and trained for potential exposure to hazards
5
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6
Worker Safety and Occupational Medicine Program
Personal Reliability Program
Workers’ activities involving the potential exposure to nerve agents receive a medical examination to document
1. Exhibit no physical, mental, or emotional impairment that may result in a higher vulnerability to nerve agent exposure
2. Are physically/mentally able to wear and use the required protective clothing and equipment
Individual baseline nerve-agent testing and ongoing surveillance dependent on type of work categories
Medical Screening Program
Medical and Industrial Hygiene programs are in place for industrial work activities depending on potential exposures
As part of ongoing Health Hazard Assessment, the extent of potential exposures identified determine which programs are required for each worker
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7
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, could require additional protective measures during future plant operations in some work locations(Supercritical Water Oxidation Process feed preparation)
BGCAPP has focused on engineering controls and treatment of hazards, to provide better protection for workers during operations
Small piece of Composition B in an aluminum pan
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
8
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9
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 might have posed worker hazard)
Mettler RC1® Calorimeter Reactor at Battelle’s HERLA Used to Simulate BGCAPPEBH and ENR Operations
A Partnership for Safe Chemical Weapons Destruction
10
A Safe Solution
Enhance auxiliary systems to Energetics Neutralization Reactors (ENRs) to increase operating temperature
– Safely and efficiently destroys cyanide
– Does not change neutralization process
– Does not alter Supercritical Water Oxidation process
– Does not impact weapons destruction baseline schedule
Auxiliary systems enhancements
– Insulating jacket placed around reactors
– Heat exchanger to increase temperatures
– Heat exchanger to cool sampling line
Munitions Demilitarization Building,ENRs (above). A representative heat exchanger (below).
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 > 25 < 1 non-detect
Anticipated Cyanide Concentrations
cyanide treatment occurs during this step
11
Pilot Plant cyanide levels are below worker safety regulatory standards
National Institute of Occupational Safety & Health assigns short-term maximum 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
A Partnership for Safe Chemical Weapons Destruction
Hydrolysate Storage Area tanks
Both energetics hydrolysate tanks may be in service simultaneously
Tanks are designed with both spill and overfill prevention controls
Spill containment = content of a tank + regulatory defined rainfall (25-year, 24-hour maximum rainfall) and freeboard
Spill response procedures define actions for rapid response to contain leaks
12
Hydrolysate Storage Area (above) construction is nearing completion.The Storage Area is designed and built (below) to environmental regulations.
Hydrolysate Storage Area design, construction and operations regulated by Kentucky Department for Environmental Protection, Environmental Protection Agency and in accordance with the Resource Conservation and Recovery Act (RCRA).
A Partnership for Safe Chemical Weapons Destruction
Supercritical Water Oxidation (SCWO)Process Building
Separate HVAC systems service control area, reverse osmosis room, processing area and relief tank room, Aluminum Precipitation/Aluminum Filtration room
HVAC in AP/AF room designed to pull air from worker breathing zone and out facility roof at height greater than 30 feet
Further dilution achieved in HVAC air stream and outside building
SCWO Process Building largely unoccupied by workers except to perform maintenance activities and remove filtercake bins
Based on the automation used in the process, exposure durations expected to be much less than 8 hours/day
13
The SCWO Process Building (above). Workers will access filtercake bins using large rollup doors (below).