CATALYTIC OXIDATION TECHNOLOGY TRANSFER PROGRAM

CATALYTIC OXIDATIONTECHNOLOGY TRANSFERPROGRAMDr. Alex BalboaMr. Michael ParhamResearch and Technology DirectorateEdgewood Chemical Biological CenterUS Army, Research Development and Engineering CommandCATOXCBR Filtration TeamTechnology Transfer Program (TTP)

Form ApprovedOMB No. 0704-0188Report Documentation PagePublic reporting burden for the collection of information is estimated to average 1 hour per response, including the time for reviewing instructions, searching existing data sources, gathering andmaintaining the data needed, and completing and reviewing the collection of information. Send comments regarding this burden estimate or any other aspect of this collection of information,including suggestions for reducing this burden, to Washington Headquarters Services, Directorate for Information Operations and Reports, 1215 Jefferson Davis Highway, Suite 1204, ArlingtonVA 22202-4302. Respondents should be aware that notwithstanding any other provision of law, no person shall be subject to a penalty for failing to comply with a collection of information if itdoes not display a currently valid OMB control number.1. REPORT DATE2. REPORT TYPE16 NOV 2004N/A3. DATES COVERED-4. TITLE AND SUBTITLE5a. CONTRACT NUMBERCatalytic Oxidation Technology Transfer Program5b. GRANT NUMBER5c. PROGRAM ELEMENT NUMBER6. AUTHOR(S)5d. PROJECT NUMBER5e. TASK NUMBER5f. WORK UNIT NUMBER7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES)Research and Technology Directorate Edgewood Chemical BiologicalCenter US Army, Research Development and Engineering Command9. SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS(ES)8. PERFORMING ORGANIZATIONREPORT NUMBER10. SPONSOR/MONITOR’S ACRONYM(S)11. SPONSOR/MONITOR’S REPORTNUMBER(S)12. DISTRIBUTION/AVAILABILITY STATEMENTApproved for public release, distribution unlimited13. SUPPLEMENTARY NOTESSee also ADM001849, 2004 Scientific Conference on Chemical and Biological Defense Research. Held inHunt Valley, Maryland on 15-17 November 2004 . , The original document contains color images.14. ABSTRACT15. SUBJECT TERMS16. SECURITY CLASSIFICATION OF:a. REPORTb. ABSTRACTc. THIS PAGEunclassifiedunclassifiedunclassified17. LIMITATION OFABSTRACT18. NUMBEROF PAGESUU4219a. NAME OFRESPONSIBLE PERSONStandard Form 298 (Rev. 8-98)Prescribed by ANSI Std Z39-18

Overall Objective Design, construct and evaluate a catalytic air purificationsystem for collective protection applications– Demonstrate Broader Protection of Catalytic versus Single PassFiltration Technology– Optimize Power, Weight and Size of Catalytic ProcessCATOXCBR Filtration TeamTechnology Transfer Program (TTP)

Approach-Incorporate commercial/newly developed catalysts forchemical, biological and TICs destruction (leverage w/Advanced Adsorbents Program)-Establish design relationships for predicting system size andenergy requirements for potential applicationsCATOX ReactorHeat OXCBR Filtration TeamTechnology Transfer Program (TTP)

Program LeverageDARPA InvestmentTECHNOLOGY READINESS LEVELS- identification and evaluation of acidgas abatement NG(COMPONENT)- evaluation ofcommercial catalystsSYSTEM-SCALE TESTING- evaluation and optimization of catalyst system components- integration of system components- determine size and energy requirements of scalable AP systemCATOXCBR Filtration TeamTechnology Transfer Program (TTP)

DARPA Investment– Objectives Technology maturity level/Technology readiness level Applicability/relevance to DoD CB Defense AcquisitionProgram Potential to mature for evaluation in field environment Availability of other funding to leverage TechnologyTransition investment Availability to government of data bases, methodologydetails, and design conceptsCATOXCBR Filtration TeamTechnology Transfer Program (TTP)

Chemical delivery sensitivities Single pass filters have their capacity defined in terms ofCT (conc x time). This is a misleading indicator for CATOX. CATOX challenges must be as close to the application’sthreat to account for performance sensitivities to:– # of attacks– Dosage per attack– Peak concentration– Frequency of attacks CATOX systems can succeed or fail for a given CT if anyof these variables are changed.CATOXCBR Filtration TeamTechnology Transfer Program (TTP)

BenefitsCurrent filter technology limited capacity for agents that are removed by chemical reaction and/or weaklyadsorbedminimal protection versus several of the toxic industrial chemicals (TICs)prolonged environmental exposure has been shown to reduce the capacity of thesefilters for agents that are removed by chemical reactionCatalytic oxidationAn alternative air purification technology(1)(2)(3)(4)(5)broad and universal protection against the chem-bio threat,reduced logistics due to long operational life,greatly increased capacity for CB agents and TICs compared to current NBCcollective protection technologies andlower energy costs relative to other regenerative filtration technologies.Catalytic oxidation is a destructive technology, converting CB agents and TICs toCO2 (catalysts exist that are capable of decomposing nitrogen-containing compoundswith minimum NOx formation), H2O and haloacids (should halogens be associatedwith the parent compound).CATOXCBR Filtration TeamTechnology Transfer Program (TTP)

Challenges Issues Toxic By-products Catalyst Stability Energy Post treatment State of the Art High activity Stable catalysts NOx, acid retention Improved acid abatement technologies Mitigation of reaction product emissionsMaximize heat recovery to minimize energyutilizationCATOXCBR Filtration TeamTechnology Transfer Program (TTP)

Material Development-Incorporate commercial/newly developed catalysts forchemical, biological and TICs destructionDownselect (light-off curvesand selectivity)CATOXCBR Filtration TeamTechnology Transfer Program (TTP)

Monolithic Bed Catalyst SuppliersManufacturerCatalyst DesignationCell DensityEngelhard CorporationEngelhard Catalyst200 Cells/in2United Emissions CatalystNB001-73-01200 Cells/in2United Emissions CatalystNB001-73-02200 Cells/in2Sud Chemie PrototechLS02-03145400 Cells/in2Sud Chemie PrototechMisc-03144400 Cells/in2Guild AssociatesNo-NOx400 Cells/in2Guild Associates3X400 Cells/in2Johnson MattheyCatalyK6 Sample400 Cells/in2CATOXCBR Filtration TeamTechnology Transfer Program (TTP)

Lab-scale results100%M on ol i thG H S V 9,00 03[C O ] 2,0 00 m g/m(16 50 p pm ))[H 2 O ] 4.1 % vo l u m e80%Conversion, %Catalystoxidation of COby catalyticmaterials underlow and highhumidityconditionsU EC -0 1 C a ta ly s tEng e lha rd C a ta ly s tN o -N O x C a ta ly s tS C P-0 1 C a ta ly s tJ M C a ta lK 6 S a m pleU EC -0 2 C a ta ly s t3 X C a t a ly s tS PS M IS C -0 3 1 4 4N o -N O x plus 3 00oT e m p e ratu re , C100%CATOX3[C O ] 2 ,00 0 m g /m(1 65 0 ppm ))[H 2 O ] 0 .34 % vo l u m e80%Conversion, % good indicatorof catalystactivity (veryclean parent andbyproduct) poor effectivefiltration bycurrent NBCsystemsM o no l i thG H S V 9 ,0 00U EC -0 1 C a ta ly s tEng e lha rd C a ta ly s tS C P-0 3 1 4 5 C a ta ly s tN O -N O x C a ta ly s tJ M C a ta lK 6 S a mpleU EC -0 2 C a ta ly s t3 X Ca t a ly s tS C P M I S C -0 3 1 4 4 C a ta ly s tN o -N O x plus 3 X60%40%20%0%050100150200250300oT e m pe rature , CCBR Filtration TeamTechnology Transfer Program (TTP)

Schematic representationof catalytic reactorGas InletInlet FlangePackingFritCatalystThermocouplesGas OutletCATOXCBR Filtration TeamTechnology Transfer Program (TTP)

Dry NH3 tests100%Conversion, %80%MonolithGHSV 9,000[NH3] 2,000 mg/m3(2,650 ppm)[H2O] 0.34% volume60%40%UEC-01 CatalystNO-NOx CatalystEngelhard CatalystSCP LS02-03145JM CatalK6 SampleUEC-02 Catalyst3X CatalystSCP MISC-03144No-NOx plus 3X20%0%150CATOX200250300Temperature, oCCBR Filtration Team350400Technology Transfer Program (TTP)

100%Humid NH3 testsGHSV 9,000[NH3] 2,000 mg/m3(2,650 ppm)[H2O] 4.1% volumeConversion, %80%60%UEC-01 CatalystNO-NOx CatalyatEngelhard CatalystSCP LS02-03145JM CatalK6 SampleUEC-02 Catalyst3X CatalystSCP MISC-03144No-NOx Plus 3X, Layered40%20%0%150CATOX200250300Temperature, oCCBR Filtration Team350400Technology Transfer Program (TTP)

Selectivity (NOx):NH3 tests (dry)1000UEC-01 CatalystNo-NOx CatalystSCP LS02-03145Engelhard CatalystJM CatalK6 SampleUEC-02 Catalyst3X CatalystSCP MISC-03144No-NOx plus 3X[NOx], ppm100GHSV 9,000[NH 3] 2,000 mg/m3(2,650 ppm)[H 2O] 0.34% volume30 ppm NO 2 Effluent CHPPM MEGGuidelines25 ppm NO Effluent NIOSH Requirement9 ppm NO Effluent CHPPM MEGGuidelines105 ppm NO 2 Effluent NIOSH rature, oCCATOXCBR Filtration TeamTechnology Transfer Program (TTP)

Selectivity (NOx):NH3 tests (humid)1000UEC CatalystNo-NOx CatalystSCP LS02-03145Engelhard CatalystJM CatalK6 SampleUEC-02 Catalyst3X CatalystSCP MISC-03144No-NOx Plus 3X, Layered[NOx], ppm100GHSV 9,0003[NH 3] 2,000 mg/m(2,650 ppm)[H2O] 4.1% volume30 ppm NO2 Effluent CHPPM MEGGuidelines9 ppm NO Effluent CHPPM MEGGuidelines25 ppm NO Effluent NIOSHRequirement105 ppm NO2 Effluent NIOSH Requirement1200220CATOX240260280300320Temperature, oCCBR FiltrationTeam340360380400Technology Transfer Program (TTP)

Selectivity (N2O):NH3 tests (dry)1000UEC-1 CatalystNo-NOx CatalystSCP :S02-03145Engelhard CatalystJM CatalK6 SampleUEC-2 Catalyst3X CatalystSCP MISC-03144No-NOx plus 3X[NOx], ppm800GHSV 9,0003[NH 3] 2,000 mg/m(2,650 ppm)[H2O] 0.34% emperature, oCCATOXCBR Filtration TeamTechnology Transfer Program (TTP)

Selectivity (N2O):NH3 tests (humid)1000UEC CatalystNo-NOx CatalystSCP LS02-03145Engelhard CatalystJM CatalK6 SampleUEC-02 Catalyst3X CatalystSCP MISC-03144NO-NOx plus 3X, Layered[NOx], ppm800600GHSV 9,0003[NH 3] 2,000 mg/m(2,650 ppm)[H2O] 4.1% erature, oCCATOXCBR Filtration TeamTechnology Transfer Program (TTP)

Dry C3F6 tests100%GHSV 9,0003[C3F6] 2,000 mg/m(300 ppm)[H2O] 0.34%Conversion, %80%UEC-01 CatalystEngelhard Catalyst3X CatalystUEC-02 CatalystSCP-01 CatalystSCP-02 CatalystJM CatalK6 Sample3X Plus No-NOx CatalystGuild rature, CCATOXCBR Filtration TeamTechnology Transfer Program (TTP)

Humid C3F6 tests100%GHSV 9,0003Conversion, %80%[C3F6] 2,000 mg/m(300 ppm)[H2O] 4.1%UEC-01 CatalystEngelhard Catalyst3X CatalystUEC-02 CatalystSCP-01 CatalystSCP-02 CatalystJM CatalK6 Sample3X Plus No-NOx CatalystGuild No-NOx60%40%20%Table showing T95?0%100150200250300350400450500oTemperature, CCATOXCBR Filtration TeamTechnology Transfer Program (TTP)

Catalyst PerformanceCatalyst performance summary informationDesign Lim.Chemical1C 3F6Temperature2Guild No-NO x Plus 3XCatalystT 500 CAmmonia[NO x]3 500 ppmAmmonia[N 2O]3 300 ppmC 3F6350 C15 ppm160 ppmGuild 3XC 3F6310 C400 ppm550 ppmEngelhard #164217005C 3F6440 C 1,000 ppm 300 ppmUEC NB001-73-001C 3F6T 500 C 1,000 ppm 300 ppmUEC NB001-73-002C 3F6T 500 C 1,000 ppm 300 ppmSCP LS02-03145C 3F6450 C 1,000 ppm 300 ppmSCP MISC-03144C 3F6450 C 1,000 ppm 300 ppmGuild No-NO xC 3F6 1,000 ppm 300 ppmT 500 C1Chemical requiring greatest temperature to achieve 99% destruction2Temperature required to achieve 99% destruction of design limiting chemical3NO x or N 2O concentration formed during destruction of NH 3 at temperatureJM CatalyK6 SampleCATOXCBR Filtration TeamTechnology Transfer Program (TTP)

NBC Subsystem SummaryHeater/PrecoolerFanContaminatedAir InCatalyst BedPostTreatmentFilterFanAmbientAir OutCleanAir OutTargeted for:FCS ApplicationScalable for building protectionTransportable shelters (JECP)CATOXCBR Filtration TeamTechnology Transfer Program (TTP)

Ammonia (HC):FeedTemperatureECBC 50 SCFMCATOX UNITFeed Conditions10090Temperature (C)80706050403020TC 10 - Water NozzleTC 11 - Chemical NozzleDew Point @4.2 e (min)CATOXCBR Filtration TeamTechnology Transfer Program (TTP)

ATD Experimental Design 6 x 2000 mg/m3 x 10 minutes(CT 120,000 mg-min/m3) 6 x 200 mg/m3 x 100 minutes(CT 120,000 mg-min/m3)CT 240,000 mg-min/m3(under 2.5% water (volume) and 50 cfm)CATOXCBR Filtration TeamTechnology Transfer Program (TTP)