treatment technologies for perchlorate · 3 perchlorate use oxidizer in solid fuel rockets z12...

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

mailto:[email protected]

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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 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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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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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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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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Wastewater Holding PondsWastewater Holding Ponds

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TwoTwo--Stage BioreactorStage Bioreactor

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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)


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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)


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)


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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

treatment technologies for perchlorate · 3 perchlorate use oxidizer in solid fuel rockets z12...

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