Treatment Technologies Treatment Technologies for Perchloratefor Perchlorate
Edward N. CoppolaApplied Research Associates, Inc.
430 West 5th Street, Suite 700Panama City, FL 32401
(850) [email protected]
May 17, 2007Global Demil Symposium
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OverviewOverview
Perchlorate Background
Water WashoutAmmonium Perchlorate (AP) Recovery
Treatment of AP-Contaminated EffluentsBiodegradation of High-Strength Effluents
Ion Exchange of High-Strength Effluents
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Perchlorate Use Perchlorate Use
Oxidizer in Solid Fuel Rockets12 strategic & 40 tactical motors
Oxidizer in Explosives and FireworksOrdnance & Insensitive Munitions
Over 250 items
Gunpowder, Flares, Air BagsFound as a Contaminant in:
Sodium chlorate-based herbicidesFertilizers and nitrates (imported from Chile)
Naturally Occurring in U.S.
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Insensitive MunitionsInsensitive Munitions
Contain Perchlorate Oxidizers to Reduce Shock SensitivityWastewater Generated during Production and Loading OpsPAX-21
Melt Pour ExplosiveComposition B ReplacementRDX, DNAN (2, 4-dinitroanisole), AP (ammonium perchlorate)Mortar explosive
AFX-757Composite explosiveJoint Air-to-Surface Stand-Off Missile (JASSM)
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Pathways to the EnvironmentPathways to the Environment
Manufacture of Propellant & Explosive IngredientsProduction of Propellant & Explosive FormulationsManufacture of Ordnance ItemsOperational Test & Evaluation - TrainingAgeing and Surveillance TestingDestruction or Disposal of Unserviceable ItemsReclamation, Reuse, or ConversionDemilitarization and Disposal
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Perchlorate OccurrencePerchlorate Occurrence
U.S. EPAITRC Technology Overview – Sep 2005GAO-05-462 Report – May 2005
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Perchlorate GuidancePerchlorate GuidanceReference Dose (RfD) Established by EPA
January 26, 2006 U.S. EPA Memorandum to Regional Administrators0.0007 milligram/kilogram-day (mg/kg-day)Drinking Water Equivalent Level: 24.5 parts-per-billion
DoD Guidance Letter Issued January 26, 2006Established 24 ppb as the “ Level of Concern”“DoD will comply with applicable state or federal standards whichever is more stringent”Environmental Quality Status Class I under DoDI 4715.6Military services issued corresponding guidance letters
Current State Health-Based Goals – 1 to 14 ppbCalifornia proposed MCL of 6 ppb
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Perchlorate Perchlorate DemilDemil via Water Washoutvia Water Washout
Water washout is an inherently safe processAmmonium perchlorate exhibits high solubility (>10%)
Water completely desensitizes perchlorate
Water washout is a very mature, proven processFunctional, simple, and robust
Successfully employed by ATK (Promontory, UT) since 1962
Water washout allows reuse of cases and hardwareMetal or filament wound cases
Environmentally Sound ProcessPermits recovery of high purity perchlorate
Aqueous residual streams can be efficiently treated
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ATK THIOKOL PROPULSION
ATK Thiokol Washout Experience
Over 39 million pounds propellant removedPropellant removed from over 4,700 motors and warheadsPropellant removed from 28 different types of motors and warheads
ICBM solid rocket motorsTactical solid rocket motorsSpace booster solid rocket motorsTactical missile warheads
Continually upgrading system for safety, environmental, and efficiency improvementsPresently designing systems for tactical-size production applicationsATK Thiokol evaluation and recommendations based on:
Over 40 years of continuing experienceUsing mature technologies
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ATK THIOKOL PROPULSION
ATK Thiokol Water Washout Operation
Washout Operation
High Pressure Pumps
Head Tank
Dewateringand Filtration
Holding Tank
Ship to APRecovery
Solids
DistillateWater from
AP Recovery
Liquids
Ship to AP Recovery
Water (Low Percent AP)
M-115 Process Flow
Side Stream
Plant Water
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ATK THIOKOL PROPULSION
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Tactical Motor Washout
Typically save the caseHARM, STANDARD Missile, Sidewinder, othersClose-loop waterAP recovery or direct reusePBX warheadsInternal and external customers
Black Brant
Composite
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ATK THIOKOL PROPULSION
AP Reclamation Process
AP Recovery
M721 Evaporator
AP WaterTreatment
AP Recovery
M705 Evaporator
Aluminum Recovery
Inert Propellant Residue
M-705 PropellantSize Reduction and Leach
PropellantTreatment
AP ReclaimTwo Branches
M-115Motor Washout
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ATK THIOKOL PROPULSION
Products
AP wet cake Purity - 99.8% pure APWater content 2-3% moisture
Reclaimed AP productsPerchloric acid productionFireworksCommercial explosivesCommercial rocket motor production
ResidueAluminum recoveryLandfillCurrently exploring fuel alternatives
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Perchlorate Effluent TreatmentPerchlorate Effluent TreatmentDemil & Propellant Production Generate Effluents Biodegradation Processes
Continuous-stirred-tank-reactor (CSTR)Fluidized bed reactor (FBR)Result in Perchlorate Destruction: ClO4
- Cl- + 2O2
Ion Exchange ProcessesNon-regenerable, single-use resinBrine-regenerable, strong base anion resinCaustic regenerable, weak base anion resinResult in Perchlorate Concentration
In resin or regenerating solution
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Biodegradation of PerchlorateBiodegradation of Perchlorate--Contaminated WastewaterContaminated Wastewater
Effective for High ConcentrationsUp to 5000 mg/L or saturated solutions (with dilution)
Effective for High TDS EffluentsFrom 2-3% salt to over 7% for membrane systems
Simultaneous Reduction of Co-ContaminantsNitrate, nitrate esters, nitroaromatics, nitraminesHeavy metals
Treated Water can be Discharged to SewerMature, Robust, Inexpensive TechnologyDemonstrated Track Record
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The ARA Biodegradation ProcessThe ARA Biodegradation Processfor Effluents Containing Perchloratefor Effluents Containing Perchlorate
EffluentFeed Water
EqualizationTank
Nutrient/ElectronDonor
Caustic forpH Control
Anoxic Bioreactors:• Suspended-Growth Process• Two Stages in Series
Continuous-stirred-tank reactorsHRT: 8-24 hrTemperature: 15-40oCpH: 6.5-8.5ClO4
-: 5000 mg/LTDS: 2-3%
Discharge to Sewer
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ARA System at ATK, Promontory, UTARA System at ATK, Promontory, UT1996-97 - Production Prototype
AF Research Lab, Tyndall AFB
Sponsored by ESTCP & JOCG
Dec 1997 - Inoculation and Start-up
First operational ClO4- system
Continuous operation thru present
March 1999 Optimization Project
Reduced nutrient costs >90%
Desugared molasses
2001-2002 – Modification ProjectSimultaneously treats 3 effluentsUp to 8000 lb/month perchlorate
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Performance of System at Performance of System at PromomtoryPromomtoryTreats ~1M Gallons of Wastewater per YearDestruction Rates During 2006
Perchlorate: average 1500 lb/mo – maximum 4000 lb/mo Nitrate: average 1500 lb/mo – maximum 6000 lb/mo
Cost Savings ~$2M per YearEffluent Biodegradation is an Enabling Technology for Perchlorate and Rocket Motor Case Recovery and Reuse
Minuteman remanufacture – 700, 1st and 2nd stage motorsReused cases valued at ~$2M per setCredit for recovered ammonium perchlorate ~$15K/mo.
Space Shuttle RSRM production and case reclamationDelta Strap-on Solid Rocket motor (SSRM) production
Supports Energetic Material Development and ProductionCL20, TTB, PAX, decoy flares, nitration processes
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22ndnd Generation Biodegradation SystemGeneration Biodegradation Systemfor Effluents Containing Perchloratefor Effluents Containing Perchlorate
Hodgdon Powder Company – Pyrodex PlantNear Herington, Kansas
Effluent from Gunpowder ManufacturingPerchlorate >3000 mg/LNitrate >2000 mg/L
~3 gpm Treatment RateInoculated 27 April 03Discharge to POTW
KDHE Permit <100 ppb
Land ApplicationSoil Remediation2006 & 2007
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Performance of the Pyrodex PlantPerformance of the Pyrodex PlantOver 150 Effluent Tanks Filled, Tested, and Discharged
All below discharge limit (100 ppb) and EPA-314 MDL (~20 ppb)Over 3 million gallons of wastewater treated
Kansas Dept. of Health and Environment (KDHE) Reduced Sampling and Analysis Requirement to Every Fourth Tank
Won Kansas Water Environment Association (KWEA) AwardIndustrial Wastewater Pretreatment Category
Remediation Progress16,000 yd3 of soil remediatedPerchlorate reduced >95%
From 45 mg/kg>500 kg of perchlorate destroyedKleinfelder – Topeka, KS
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Wastewater Ion Exchange TreatmentWastewater Ion Exchange Treatment
Effective for Dilute or Concentrated EffluentsDilute (ppb to ppm) – high flow rates (>100 to 1000 gpm)Concentrated (10s to 1000s ppm) – low flow rates
Treatment Capacity is a Function of ConcentrationPerformance affected by other anions
Single-Use ApproachDemonstrated technologyResin and perchlorate destroyed by incinerationExpensive – resin replacement and disposal
$50 to >$150/kg of perchlorate removedLittle or no capital expenditure may be required
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Regenerable Ion Exchange TechnologyRegenerable Ion Exchange Technology
Brine Regenerable Strong Base Anion (SBA) ResinGenerates > 1% perchlorate-contaminated salt brine
Ferric Chloride Regenerable SBA Process (ORNL)Concentrated HCl and ferric chloride solutions
ARA & The Purolite Company Developed a Weak Base Anion (WBA) Resin Process (Patent Pending)
Ion exchange & regeneration pH dependentReduces spent regenerating solution to as little as 0.02%Effluent is safely handled and easily treated
Scavenger process for low concentration applicationsBiodegradation for high concentration applications
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ESTCP Sponsored6-inch Groundwater Extraction WellPerchlorate: 1500–2200 ppbBicarbonate: 150 ppmNitrate: 4 ppmSulfate: 3 ppmChloride: 4 ppmTCE: 3100 ppb
Pilot Demonstration Pilot Demonstration -- Redstone ArsenalRedstone Arsenal
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Pilot System Design & OperationPilot System Design & OperationConventional Lead-Lag Configuration
Integrated Pre- and Post-Treatment
24 hr/day – 7 Day/Week Operation
2-inch Diameter Ion Exchange Columns
Macroporous Polystyrene DivinylbenzeneWBA Resin (Purolite D-4170)
36-inch bed depth
12 to 24 BV/hr Treatment Rate1.5 – 3 gpm/ft3
Regeneration & Residuals Treatment Conducted Off Site
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Benefits of WBA Resin ProcessBenefits of WBA Resin ProcessMore Efficient than Brine Regeneration
Low volume of effluent“Zero discharge” potential
Perchlorate-SelectivePerchlorate removal to less than method detection limitHigh capacity compared to brine-regenerable processes
Effective Wastewater Treatment ProcessFeasibility tests conducted on several wastewatersEffective from ppb to 1000s of ppm perchlorateEffective in presence of high anion concentration
100s to 1000s of ppm NO3-, SO4
-2, and Cl-
Low O&M Cost
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Which Treatment Process do I Need?Which Treatment Process do I Need?
Depends on:Perchlorate concentrationEffluent flow rateCo-contaminants presentDisposition of treated waterDesire to recover perchlorate
A Combination of Processes:May be less expensive that a single unit operationMay reduce the footprint of the treatment systemMay permit perchlorate recovery
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Flow Rate, gpm
10,000
1000
100
10
1.0
0.1
0.01
100,000
1000100101.00.1
mg/L
Disposable Ion Exchange
Perchlorate Treatment AlternativesPerchlorate Treatment Alternatives
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Flow Rate, gpm
10,000
1000
100
10
1.0
0.1
0.01
100,000
1000100101.00.1
mg/L
Regenerable Ion Exchange (zero discharge)
Perchlorate Treatment AlternativesPerchlorate Treatment Alternatives
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Flow Rate, gpm
10,000
1000
100
10
1.0
0.1
0.01
100,000
1000100101.00.1
mg/L
Fluidized bed bioreactor (FBR)
Perchlorate Treatment AlternativesPerchlorate Treatment Alternatives
Continuous-stirred-tank bioreactor (CSTR)
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Flow Rate, gpm
10,000
1000
100
10
1.0
0.1
0.01
100,000
1000100101.00.1
mg/L
Regenerable Ion Exchange with Effluent Biodegradation (CSTR)
Perchlorate Treatment AlternativesPerchlorate Treatment Alternatives
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Flow Rate, gpm
10,000
1000
100
10
1.0
0.1
0.01
100,000
1000100101.00.1
mg/L Perchlorate Treatment AlternativesPerchlorate Treatment Alternatives
Recovery, conversion, reuse
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Flow Rate, gpm
10,000
1000
100
10
1.0
0.1
0.01
100,000
1000100101.00.1
mg/L Perchlorate Treatment AlternativesPerchlorate Treatment Alternatives
Recovery, conversion, reuse with regenerable ion exchange
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SummarySummaryWater Washout is Proven, Safe, Reliable Process
Permits component, AP, and aluminum recoveryPermits perchlorate reuse or conversionCan be performed without perchlorate discharge
Biodegradation of Perchlorate-Containing EffluentsRobust, mature, low cost (~$2/kg of perchlorate)Commercial operation since 1997
Ion Exchange for Perchlorate-Containing EffluentsSingle-use processes in commercial operation
Regenerable WBA Resin TechnologyImproves economics for high-concentration effluents