ammonium perchlorate treatment technology development james a. hurley afrl/mlqe tyndall afb, fl...

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  • Ammonium Perchlorate Treatment Technology DevelopmentJames A. HurleyAFRL/MLQETyndall AFB, FL

  • Ammonium Perchlorate - A National Technical AssetIntegral to Strategic Defense Systems - ICBM, SLBM, NRO

  • Peace Keeper 1st Stage (98,000 lb)Requirement

    Increased Demand for Open-Burn/ Open-Detonation (OB/OD) Facilities with Large-Rocket Motor Capacity.START IINunn-LugerNon-Proliferation TreatyMulti-National Force Reduction Treaty

    Decreased Availability of OB/OD Facilities.Clean Air Act Amendment - 1990 (CAAA)Base Realignment and Closure (BRAC)

    Statement of Operational Need (SON 003-90)Joint Logistics CommandersGen McDonald- AFLC/CC

  • High-Pressure Water Washout of Solid Propellant

  • Perchlorate Recovery ProcessConcentratedPerchloratePotassiumPerchlorateReactorKClPerchlorateConcentratorKP FilterPressKP ProductMixedWasteStorageTankH2OIonExchangeNaOHEffluentDischarge Limits:ClO4 < 10 ppmTDS < 3800Dilute PerchlorateHigher ClO4 and TDS Increases Ion Exchange Column Regenerations,More Regenerations Increase Total Dissolved Solids (TDS)APStorageTank

  • Wolinella succinogenes HAP-1

  • Bench-Scale Reactor System

  • Production-Scale AP Reactor System

  • Ammonium Perchlorate Biodegradation ProcessDryNutrientFeederNutrientMixTankInterimEffluentStorageDryYeastWaterCausticAcidNutrientFeedTankAP StorageTanksReactor 1Reactor 2RecycleProgrammableLogicControllerOn-linePerchlorateAnalysisTo Sewage TreatmentReactorsStorageClarifier

  • Effect of Perchlorate Concentration on CapacitySeriesOperationParallelOperation

  • Building at Thiokol Housing the Ammonium Perchlorate Bioreactor System

  • Primary and Secondary Ammonium Perchlorate Reactors

  • Metabolic Pathway for Energy Production in Wolinella succinogenes HAP1

    ClO4-ClO3-ClO2- Cl-H2H22 H22 H2OH2OH2Operchloratechloratechloritechloride

  • AP Treatment Technology vs Process RequirementPerchlorate Concentration [ClO4-]1-20 wt. %Bulk PropellantHigh Concentration10 - 10,000 ppmProduction Waste WaterModerate Concentration10 ppb - 10,000 ppbDrinking Water, Ground WaterLow ConcentrationCatalytic (enzyme) Reactor SystemPerchlorate Recovery and ReuseImplementedUnder DevelopmentImplementedMulti-Stage AP BioreactorMulti-Stage AP Bioreactor with Ion Exchange

  • Low-Concentration AP, High-VolumeWastewater TreatmentTwo Approaches

    New (or Improved) Unit Operations Enabling Utilization of Demonstrated Moderate-Concentration AP Water TreatmentReverse OsmosisLimited CapacityRequires Effluent ReconditioningCapacitive DeionizationSmall Electrochemical Driving Force Limits CapacityRequires Effluent ReconditioningIon ExchangeResin Regeneration Very DifficultEfficacy Uncertain at ppb Concentration LevelSelectivity DifficultMay Require Effluent Reconditioning

  • Low-Concentration AP, High-VolumeWastewater Treatment (cont.)New Process for Treating Low-Concentration AP Water DirectlyConventional Catalytic Reactor SystemNon-SelectiveMass-Transfer LimitedUnknown Kinetics, Unknown EfficacyEnzyme Catalytic Reactor SystemAnion Specific SelectivityHigh CapacityWide Application RangeAffect of Other Contaminants UnknownRequires Multi-Disciplinary EffortSystem Sustainability Uncertain

  • Air Force BenefitThe payoff to the Air Force from this continued effort is reduction of weapon system operational cost as well as ensured continued sustainability.

    Manufacturing and maintenance facilities are under ever increasing constraints regarding the life-cycle management of materials used in weapon systems and their manufacture.

    Technology insertion opportunities are made possible by the continued participation of MLQ in Air Force unique materials selection, development, and management through the weapon system life-cycle.

  • Points-of-ContactJames A. Hurley, Program ManagerAir Force Research LaboratoryMLQE139 Barnes Drive, Suite 2Tyndall AFB, FL 32403-5323(850) 283-6243 (voice)(850) 283-6064 (fax)

    Stan RisingAir Force Research LaboratoryMLQE139 Barnes Drive, Suite 2Tyndall AFB, FL 32403-5323 (850) 283-6203(850) 283-6064 (fax)

    Overview of AFRL/MLQE research and engineering development efforts regarding treatment technology for ammonium perchlorate contaminated water.Requirements, deficiencies, and current events mandating technology development.Lessons learned from fundamental discoveries and engineering practice which posture MLQE for addressing new engineering challenges associated with low-concentration perchlorate contamination.Ammonium perchlorate is the primary oxidizer in all solid propellants used in our strategic national defense systems; including inter-continental and submarine-launched ballistic missiles as well as delivery systems for NRO assets.Ammonium perchlorate is a national technical asset.During the 1980s, a number of strategic arms agreements were put into effect which significantly increased the requirement to demilitarize large rocket motors (144 million pounds of propellant) from excess strategic assets. This placed increased demand on open-burn/open-detonation facilities which has been the only means of large-rocket motor disposal. At the same time, regulations and other events have reduced the capacity and availability of OB/OD facilities.General McDonald and the Joint Logistics Commanders promulgated a Statement of Operational Need (SON 003-90) to develop environmentally acceptable alternative technologies for open-burning and open-detonation. Our approach begins with high-pressure water washout of the solid propellant. The bulk propellant is then macerated, the ammonium perchlorate dissolved in heated water, and separated from the propellant binder.Ammonium perchlorate is then concentrated by crystallization, centrifuged, and collected as AP or reacted with potassium salts to form potassium perchlorate (low-solubility) which is then collected from a filter press operation. To date, over 500,000 pounds of AP has been processed.The high-value ammonium perchlorate and potassium perchlorate are reused in propellant or explosives formulations.As much as 95% of the process water is recycled using ion exchange resin to recover high-concentration perchlorate salts. The effluent contains residual perchlorate and salts from resin regeneration which must be treated prior to discharge.A process for treating this effluent was necessary to ensure a closed loop system and compliance with state discharge permits.In 1989 a consortium of organisms was discovered which demonstrated an ability to degrade perchlorate to chloride. The bacterium responsible for the perchlorate reduction was isolated and identified as Wolinella succinogenes HAP-1. A bench-scale process was developed to answer performance questions necessary for engineering a reactor system. From fourteen months of operation we were able to ascertain the metabolic mechanism for perchlorate reduction, determine operating limitations, improve reaction efficiency, and select an optimum nutrient source.From the results of our bench-scale work we engineered, designed and fabricated a pilot-scale system with 100x the capacity of the bench-scale system.The purpose of the pilot-scale system was to answer the engineering questions necessary for developing a production-scale system for implementation.This is a photograph of the pilot-scale AP Bioreactor System operated at Tyndall AFB. This system provided verification of engineering scaling factors, process performance parameters, process control parameters, system operability, non-steady-state operating characteristics, and preliminary capital and operating cost data.The engineering data obtained from the operation of the pilot-scale system resulted in the design and fabrication of a production-scale (5000 gal/day) reactor system for implementation at a rocket motor manufacturing facility located in Utah (Thiokol Corporation, Brigham City).The production-scale system has been successfully integrated with the Perchlorate Recovery Process and the Industrial Wastewater Treatment Plant which together handle all waste propellant and AP contaminated wastewater for the entire Thiokol facility.The Thiokol Plant produces solid rocket motors for Minuteman, Castor, Titan, and Space Shuttle.

    The Thiokol system was designed for flexibility of operation by using a dual-reactor concept in which the reactors could be configured for parallel operation or series operation.This configuration allows the treatment of high-concentration (to 10,000 ppm) low-flow perchlorate wastewater or low-concentration (>500 ppm) high-flow perchlorate wastewater.This flexibility is important for achieving optimal operation of the perchlorate recovery process1Concurrent with engineering a production-scale reactor system, research was conducted to better understand the process by which HAP1 metabolizes perchlorate.Understanding the metabolic process ensures a robust, predictable, and controllable process for industrial applications.It was discovered that HAP1 produces unique enzymes responsible for the reduction of perchlorate to chlorate, chlorate to chlorite, and finally chlorite to chloride. The first two steps provide energy to the organism for growth and reproduction followed by a detoxification step which eliminates waste products.This knowledge presents opportunities to refine and adapt reactor systems which are more efficient and cost effective as well as applicable to a wider range of engineering challenges. MLQE with industry partners have implemented cost-effective process solutions for treating high-concentration and moderate-concentration ammonium perchlorate contaminated wastewater. The lessons learned and engineering experience gained from the development and implementation of the Perchlorate Recovery Process and the AP Bioreactor System postures MLQ