A Wastewater Solution for an Air Pollution Problem

A Wastewater Solution for anAir Pollution ProblemA Cost-Effective Alternative for VOC Control as Requiredby NESHAP [BWON, HON, MON, MACT]Dr. Carl E. Adams, Jr., PE, BCEE Senior Author 1 *Dr. Lial F. Tischler 2Andrew W. Edwards, PE 31ENVIRON International Corporation, Nashville, TN2Tischler/Kocurek, Austin, Texas3ENVIRON International Corporation, Houston, TX

BWON (Benzene Waste Operations NESHAP)• Aqueous Wastewater Considerations− Influent wastewater benzene concentration must be

BWON (Benzene Waste Operations NESHAP)Wastewater Gaseous Emissions Considerations• Title 40: Protection of Environment: 40 CFR § 61.340 presents threebasic Control Devices that are acceptable, pursuant to specific designconstraints:(i) An enclosed combustion device (e.g., vapor incinerator, boiler, orprocess heater)(ii) A vapor recovery system (e.g., a carbon adsorption system or acondenser)(iii)A flare• Title 40: Protection of Environment: 40 CFR § 61.340 also states“other” Control Devices can be used provided that certain conditionsare met.(iv) A control device other than those described in paragraphs (a)(2) (i)through (iii) of this section may be used provided that the followingconditions are met:

BWON (Benzene Waste Operations NESHAP)Wastewater Gaseous Emissions Considerations(A) The device shall recover or control the organic emissions vented toit with an efficiency of 95 weight percent or greater, or shallrecover or control the benzene emissions vented to it with anefficiency of 98 weight percent or greater.(B) The owner or operator shall develop test data and designinformation that documents the control will achieve an emissioncontrol efficiency of either 95 percent or greater for organiccompounds or 98 percent or greater for benzene.(C) The owner or operator shall identify:1) The critical operating parameters that affect the emissioncontrol performance of the device;2) The range of values of these operating parameters that ensurethe emission control efficiency specified in paragraph(a)(2)(iv)(A) of this is maintained during operation of thedevice; and3) How these operating parameter will be monitored to ensurethe proper operation and maintenance of the device.

Overview•••••••••

Prestigious Accolade:National Grand Prize – Research Category 2011VOC BioTreat has garnered thecoveted National Grand Prize in theResearch category of theprestigious American Academy ofEnvironmental Engineers (AAEE)2011 Excellence in EnvironmentalEngineering ® (E3) Competition.The concept was conceived,developed and implemented by Dr.Carl E. Adams, Jr., Global PracticeArea Leader: Industrial WastewaterManagement.

Kirkpatrick Award: SemifinalistKirkpatrick ChemicalEngineering AchievementAward recognizes the mostinnovative chemicalengineering technologyachieved through groupeffort and successfullycommercialized worldwideduring the two years prior toan award year.Chemical EngineeringMagazine has awarded thisbiennial prize continuouslysince 1933.VOC BioTreat was the 2011Semi-Finalist

Louisiana Section of the Air & Waste ManagementAssociation: 2011 Industry Award: Grand Prize

VOC BioTreat Technical Presentations andPublications“A Cost-Effective Alternative for VOC Control as Required by NESHAP [BWON, HON, MON, MACT],” AIChE Workshop,Baton Rouge, LA, November 11, 2011.“Innovative Cost-Effective Control Device for Wastewater VOC Emissions (As Required by NESHAPs [BWON, HON, MON,MACT] and Other Regulations),” ENVIRON, Houston, Texas, November 3, 2011.“Innovative Cost-Effective Control Device for Wastewater VOC Emissions (As Required by NESHAPs [BWON, HON, MON,MACT] and Other Regulations),”WEFTEC 2011, October 17, Los Angeles, California.“Innovative Cost-Effective Control Device for Wastewater VOC Emissions (As Required by NESHAPs [BWON, HON, MON,MACT] and Other Regulations)”, CHEMINNOVATIONS Conference & Expo and the collocated ISA Houston SectionConference & Expo., Houston, TX, George R. Brown Convention Center, Chemical Engineering Magazine, September13 - 15, 2011."A Cost Effective Alternative for VOC Control as Required by NESHAP [BWON, HON, MON, MACT, RACT and OtherRegulations," Air & Waste Management Association's Annual Conference & Exhibition, Orlando, FL on June 21-24,2011.“Biological Control of Benzene-Containing Off Gases”, Petroleum Environmental Research Forum, San Ramon,California, June 15, 2011.“Patented & Innovative Cost-Saving Control Device for Facility-Generated Volatile Organic Compound (VOC) Emissions”,American Academy of Environmental Engineers, Excellence In Environmental Engineering, Conference AgendaNational Press Club, Washington, D.C., May 4, 2011.

VOC BioTreat Technical Presentationsand Publications (cont’d)“Innovative Cost-Effective Control Device for Wastewater VOC Emissions (As Required by NESHAPs [BWON, HON, MON,MACT] and Other Regulations)”, Chemical Engineering Magazine VOC BioTreat Interview, April 15, 2011.Environmental News Record, interview for magazine with Gary Tulacz, April 1, 2011.“A Cost-Effective Alternative for VOC Control as Required by NESHAP [BWON, HON, MON, MACT]”, Annual Mid-WesternAir & Waste Management Association's Annual Conference & Exhibition, Kansas City, December 2010.“Innovative Cost-Effective Control Device for Wastewater VOC Emissions (As Required by NESHAPs [BWON, HON, MON,MACT] and Other Regulations)”, Annual 2010 National Petroleum Refiners Association Environmental Conference,San Antonio, TX, September 20-21, 2010.“A Cost-Effective Alternative for VOC Control as Required by NESHAP [BWON, HON, MON, MACT]”, Annual Conference+American Petroleum Institute’s Environmental Committee, Garyville, LA, June 2010.“A Cost-Effective Alternative for VOC Control as Required by NESHAP [BWON, HON, MON, MACT]”, AIChE Workshop,Chicago, IL, November 10, 2011.“ENVIRON VOC BioTreat, Un sistema innovativo per il controllo delle emissiona di VOC, Italian Environmental EngineersAssociation (Aria y Aqua), Remtech, Ferrara, Itlay, Oct 2011. POSTER SESSION.“Treating Volatile Organics in Activated Sludge Treatment”, Indian Environmental Association, Annual Conference“EnviroVision2011, Advances in Environmental Technologies & Management, Ahmedabad, India, 24 th -26 th Nov,2011.

What is VOC BioTreat TM ?

What is VOC BioTreat?• VOC BioTreat is the process of qualifying an AlternativeControl Device, other than Activated Carbon or ThermalOxidation, for the biodestruction of regulatedbiodegradable VOC emissions.• The Alternative Control Device is cost-effectively anexisting activated sludge process with emission sources inproximity to a WWTP.

Typical Acceptable Control DevicesThermal Oxidizers:Flare or Gaseous IncineratorVapor-Phase Adsorption:Granular Activated CarbonThermalOxidizersGranular ActivatedCarbon Canisters

Alternative Control Device

Alternative Control Device for a Refinery:A Basic OverviewCOMBINED WASTEWATER & AIR VOC BIOTREATMENT USING EXISTING FACILITIESAir VOC Emissions Piped to Existing Bio-BlowersSITE PROCESS/STORMWATERWASTEWATERSAPI SeparatorEQ TankDissolvedNitrogenFlotationUnitAmbientAir InlettoBlowerActivatedSludgeBioreactorP-52SecondaryClarifierFINALEFFLUENTSite Process /Stormwater SumpAPI EntryWellAPIEffluentWellAPI PumpWellDNF WetWellAppropriateValving & LELInstrumentationRecycledBiomass

A Cost-Effective Solution for theBiodestruction of VOC Emissions• Incorporates ENVIRON-developed protocols todemonstrate an Alternative Control Device• Confirms the use of existing biologicalwastewater treatment facilities• Follows exact EPA requirements and protocolsfor approval

A Cost-Effective Solution for theBiodestruction of VOC Emissions• Conclusively demonstrates co-treatment ofgaseous emissions or VOCs and aqueoussoluble organics in existing wastewatertreatment facilities• Using these protocols, most activated sludgebiotreatment systems can be qualified as anAlternative Control Device to treatbiodegradable VOCs• It is transferable to other VOC/HAP andother regulations• Provides excellent configuration flexibilitywith existing facilities

Regulatory Interface & Approval

Regulatory Approval

Regulatory Interface & ApprovalSpecific projectsState of LouisianaState of Wyoming: in process of approvalState of Mississippi: in process of approvalRegular invitation to ENVIRONUSEPA Research Triangle Park: Presented as a Technical Seminars(2)USEPA region 5: Presented as a Technical SeminarUSEPA region 6: Presented as a Technical SeminarUSEPA region 7: Presented as a Technical SeminarUSEPA region 8: Presented as a Technical Seminar

Why VOC BioTreat TM ?

Why VOC BioTreat?• Economics, Economics, Economics!!!Typical systems (carbon or TOs) have much higheroperating costs• O&M costs are typically

VOC BioTreat ApplicationIndustrial Sectors• Refineries: BWON• Organic Chemicals: MACT (e.g., HON, MON, etc)• Pharmaceuticals: Pharma MACT• Coke plants (steel industry): BWON• Soil-Vapor-Extraction remediation systemsRegulatory Drivers• Alternative NESHAP Wastewater Emission Control• WWTP Compliance Assurance Monitoring Optimization(CAM) for biological destruction efficiency (F bio )• Process Vent Control

VOC BioTreat Typical ApplicationsSoil-Vapor-Extraction

VOC BioTreat Projects in 2011Client Location Industrial Classification3M Corporation Cordova, IL Organic ChemicalsAdvocacy Project w/PERF Oakland, CA RefineryAir Products & Chemicals Calvert City, KY Organic ChemcialsCelanese Corporation Meredosia, IL Organic ChemicalsChevron Refining Pascagoula, MS RefineryConocoPhillips-Alliance Belle Chasse, LA RefineryDuPont Corporation Kinston, NC Organic chemicalsExxonMobil Refining Baton Rouge, LA RefineryFrontier Refining Cheyenne, WO RefineryHEXION Louisville, KY Organic ChemicalsMarathon Petroleum Robinson, IL RefineryMarathon Petroleum Texas City, TX RefineryMarathon Petroleum Detroit, MI RefineryMarathon Petroleum Garyville, LA RefineryNOVACHEM Red Deer, Canada Ethylene RefinerySABIC Ottawa, IL Organic ChemicalsShell Chemical Co. Deer Park, TX Organic ChemicalsShell Oil Co. Australia RefineryTEVA Mexico, MO PharmaceuticalsUS Steel Gary, IN Coking FacilityValero Refining Houston, TX RefineryValero Refining Pt. Arthur, TX RefineryValero Refining Corpus Christi, TX Refinery

ConclusionsVOC BioTreat TM – the ProcessHow is it Applicable?

High-Level Assessment:Comprehensive Questionnaire• Existing WWTP amenable to the technology?Diffused aeration systemDeep tanksExisting blowers have adequate air flow treatment capacity(modification may be necessary)• VOC emission sources appropriate for technology?Compounds relatively biodegradableCompounds have sufficient solubility(relatively low Henry s Law constants)VOC air volume compatible with WWTP diffused air treatment capacity• Favorable economics?Reasonable proximity of VOC sources to WWTPCurrent system O&M costsMinimal modifications required to adapt WWTP to technology

VOC BioTreat – The ProcessSTEP 1STEP 2STEP 3STEP 4STEP 5STEP 6High-Level Feasibility EvaluationDevelop preliminary facility-specific model with assumedbiodegradation rate to gauge benzene removal performancerequirements and obtain initial Agency concurrence for approachConduct BOX testing to determine site-specific VOCbiodegradation rate and maximize VOC BioTreat effectivenessConduct Core Column Simulation Full-scale confirmation testingObtain final Agency approval of Alternative Control DevicePrepare detailed engineering plan and implement AlternativeControl Device solutionSteps 1 & 2 must be concluded favorably before proceeding withthe remaining steps.

Case HistoryMarathon Petroleum CompanyGaryville Refinery (MPC)Garyville, LouisianaPetroleum Refinery: BWON Alternative Control Device

Why was MPC-Garyville an Excellent Choice?• Economics, Economics, Economics!− Current MPC system had very high operating cost (energy andcarbon)− Discarding initial capital investment wasn’t a deal breaker− BioTreat alternative costs almost nothing to operate• OK, it wasn’t all economics!− N2 blanket system leakage degrading overall performance ofcurrent system (not an issue for BioTreat alternative)− Reduction in carbon footprint, better sustainability aspects− Substantial reduction in energy requirements− Simplicity of installation and operation of BioTreat alternative(maintenance cost likely much lower)

Current/Proposed Benzene Control DevicesMPC asked ENVIRONto develop protocolsto qualify theexisting activatedsludge system (AIS)as an AlternativeControl Device.

MPC Case History – EconomicEconomic Impacts for VOC Control DevicesMPC – Garyville Refinery WWTPPROCESS TECHNOLOGYCOST-EFFECTIVE IMPACTCapitalcost ($)Annualoperating cost ($)Thermal Oxidizer 600,000 340,000Granular Activated Carbon(6 carbon canisters on each of two APIseparators, 22 change-outs/yr per API)+ Maintenance of N 2 blanketBiological(piping, fans and connection to blowers)240,000 500,000600,000 Minimal

MPC Case History – SustainabilityEconomic Impacts for VOC Control DevicesMPC – Garyville Refinery WWTPProcess TechnologyThermal Oxidizer(calculated)Granular Activated Carbon(in operation)ANNUAL IMPACTEnergy ConsumptionMillion BTUs per yearCO 2 EmissionsTons CO 2 per year45,700 2,690192 10Biological(no additional energy required orCO 2 generated, due to minimalorganics being treated)MinimalMinimal

Proposed Alternative Control DeviceBioReactor ConstructionUNICELLInduced AirFlotation(IGF)Marathon Petroleum CompanyGaryville, Louisiana RefineryClosed-CircuitCooling Tower

Reliable Data on BenzeneCritical Benzene Mass Balance for MPC–Garyville

Inputs to Site-Specific ModelMajor Variables• Benzene Biodegradation Rate− Table 2 represents variousexperimentally-determined bioratesfrom API and ENVIRON databases• Air Flow• Biomass Concentrations• Potential Benzene InjectionLocations into AIS• Benzene Loadings & Mass BalanceOther Significant Variables• Air Distribution in Zones• Depth of BioReactor• Aeration Tank Surface Area• Temperature• Hydraulic Flow Rate & CODLoading

Models for Calculating VOC BioTreat Emissions•−−−•• “ ”•−•−−

BWON Modeling Benzene Biodegradation RatesBENZENE BIODEGRADATION RATES – EXPERIMENTAL VALUESData referred to as APIis from Table 5 of theAPI/NPRA comments toEPA datedDecember 28, 2007.Refinery Test Type Date RunsK1 (L/g VSS-hr) @ 20 o CAverage forMultiple RunsValue Selectedfor ModelEvaluationAPI-A BOX Nov-06 2 48.9 -----API-AMethod304ANov-06 1 120.1 84.5API -B BOX Oct-97 1 79.1 79.1API-C BOX Oct-97 2 78.4 78.4API-D EKR Jul-96 4 17.3 17.3API-D BOX Jul-96 5 122 -----API-E BOX Sept-94 5 122 -----API-E BOX Nov-94 2 31 -----API-E BOX Dec-94 6 199 -----API-E BOX Apr-95 5 199 -----API-E BOX Apr-95 7 172API-E BOX Jun-95 4 206 185.5API-F BOX Jul-95 3 4.4 4.4API-G Mar-00 3 64 64ENVIRON-1 BOX Jul-09 2 23.4 23.4ENVIRON-2 BOX Mar-11 1 19.7 19.7ENVIRON-3 BOX Aug-11 1 10.8 10.8ENVIRON-4 BOX Aug-11 1 6.4 6.4API Water 9 Default Rate (EPA requires that Default Rate be used if industrychooses not to conduct BOX Test to determine site-specific benzenebiodegradation rate.1.4

Benzene Removal with Preliminarily AssumedRates vs. Actual Site-Specific Rate(Corrected to 20°C)

Develop Site-Specific Biodegradation Rate;Select Appropriate EPA-Recommended ApproachSource: EPA 40 CFR part 63, Appendix C, Figure 1

Develop Site-Specific Biodegradation RateBOX Test Apparatus that is typically usedTypical BOX Test ApparatusOption 1Typical BOX Test ApparatusOption 2

Develop Site-Specific Biodegradation RateBOX Test Apparatus Developed by ENVIRON

Develop Site-Specific Biodegradation RateBOX Test Column(without aeration)Air Supply Tank(Supplies BOX TestColumn & GC)Fine-Bubble AirDiffuser (Off)

Develop Site-Specific Biodegradation RateVoyager Photovac OnlinePhoto-ionization GCSample Syringes

Comparative Results of BenzeneStripping with and without BiomassBENZENE IN OFF-GAS EMISSIONS (ppmv)25020015010050WITHOUT BIOMASS~2 mg/L Benzene added to filtered effluentWITH BIOMASS~2 mg/L Benzene added to biomassMLVSS concentration of 800 mg/L00 50 100 150 200 250 300 350 400 450TIME (min)

Development of Preliminary Site-SpecificBenzene Control ModelRerun Calibrated Model with Site-SpecificBiodegradation Rate• The site-specific biodegradation rate, corrected to 20°C, is22.6 L/g VSS-hr @ 20°C at Marathon-Garyville• The Toxchem+ model will adjust the rate to the selectedtemperature for full-scale operating conditions

Benzene Removal with Preliminarily AssumedRates vs. Actual Site-Specific Rate(corrected to 20°C)

Full-Scale Confirmation Flux Chamber:Less Desirable Option

Full-Scale ConfirmationPerformance Validation ofFull-Scale SystemUsing VOC BioTreatColumn Protocols

Full-Scale Confirmation

Off-gas ventSample gas lineto on-line gcGravity overflow line backto full-scale aerobic zoneFull-Scale ConfirmationPerformanceValidation ofFull-Scale SystemUsing VOC BioTreatColumn ProtocolsRecycle biomassPortInfluentWastewaterSample portSupportpipe(empty)Aeration +Benzene inputDrain

Full-Scale Confirmation

Full-Scale Confirmation ResultsBenzene analytical results of full-scale confirmationRun #Benzene ConcentrationppbvOutletBlower InletVentBenzeneBiodestruction(%)Percent ofDesignCondition1 21 < 2.0 > 90.6 100%PerformanceVersus RegulatoryRequirementsInconclusive due toanalytical limitations3A 121 < 2.0 > 98.3 >500% Exceeds3B 153 < 2.0 > 98.7 >700% Exceeds4A 156 < 2.0 > 98.7 >700% Exceeds4B 482 13.3 > 97.2 >2200% Below5A 182 < 2.0 > 98.9 >800% Exceeds5B 226 < 2.0 > 99.1 >1000% ExceedsDesign is 98% at inlet of 14 ppb. Results showed 16 times thatcapacity. Breakthrough at ~400-500 ppbv.

Regulatory ApprovalRepeat ofSlide 15

Case HistoryEconomic Evaluations for SustainabilityConfirmation

Western Refinery, Wyoming, USA: 65,000 bbls/day

Case History – EconomicEconomic Impacts for VOC Control DevicesProcess TechnologyCapital cost($)Cost-Effective ImpactAnnual OperatingCost ($)Granular Activated Carbon (2 large carbonvessels on DAFs, multiple other carboncanisters; over 300,000 lbs/yr activatedcarbon consumption w/ no reactivationoption)VOC BioTreat (validation, engineeringpiping, instrumentation, and connectionto blowers)200,000 780,000460,000 < 10,000

Energy Savings / Sustainability AspectsCase Study No. 2: Replace Activated Carbon Canisters at Wyoming RefinerySustainability AspectsCase StudyScenarioBenzene Control TechnologyEnergy Consumption ActivityTotal Energy Usage(mmBTU/year)Carbon Emissions(tons CO2/year)Activated Carbon CanistersCurrentControlSystemTransport to/from Reactivation Facility 547 63Reactivation Process (315,000 lbs/yr) 1,859 116Totals 2,406 179VOC BioTreatAlternativeBiological Treatment in WWTPAdditional Power for Aeration Blowers 8.1 2.5Total Energy Savings / GHG reductions 2,398 177

Current Benzene Vapor Controls: SE, USA Refinery(Activated Carbon Canisters), 350,000 bbls/dayBOTTOMSMainSumpAPI#7FLOAT3 DNF UnitsCPI #6= 2,000 lb Canister= 1,000 lb Canister= 20,000 lb ContainerAPI #2API#1

SavingsCase Study No. 3: Replace Activated Carbon Canisters at Mississippi RefinerySustainability AspectsCase StudyScenarioBenzene Control TechnologyEnergy Consumption ActivityTotal Energy Usage(mmBTU/year)Carbon Emissions(tons CO2/year)Activated Carbon CanistersCurrentControlSystemTransport to/from Reactivation Facility 422 146Reactivation Process 1,564 98Totals 1,985 244VOC BioTreatAlternativeBiological Treatment in WWTPAdditional Power for Aeration Blowers 10.8 1.0Total Energy Savings / GHG reductions 1,974 243

Redirect Vent Stream from Flare to BiologicalWWTP, MidWest, USA, Refinery, 200,000 bbls/day

Case Study No. 4: Replace Small Dedicated Flare at Illinois RefinerySustainability AspectsCase StudyScenarioBenzene Control TechnologyEnergy Consumption ActivityTotal Energy Usage(mmBTU/year)Carbon Emissions(tons CO2/year)Steam-Assisted FlareCurrentControlSystemNat. Gas Pilot and Refinery Fuel Gas 48,640 2,860Steam Assist and Blower 10,648 632Totals 59,288 3,492VOC BioTreatAlternativeBiological Treatment in WWTPAdditional Power for Aeration Blowers 13.0 4.0Total Energy Savings / GHG reductions 59,275 3,488

Schematic of Wastewater Treatment Plant withCurrent Benzene Vapor Controls (8,000 scfm RTO)RTO

Case Study No. 5: Replace regenerative Thermal Oxidizer at Texas RefinerySustainability AspectsCase StudyScenarioBenzene Control TechnologyEnergy Consumption ActivityTotal Energy Usage(mmBTU/year)Carbon Emissions(tons CO2/year)Regenerative Thermal OxidizerCurrentControlSystemSupplemental Fuel (nat. gas) 12,960 765Electric Power for RTO Blower 260 80Totals 13,219 845VOC BioTreatAlternativeBiological Treatment in WWTPAdditional Power for Aeration Blowers 15.2 4.7Total Energy Savings / GHG reductions 13,204 840

Questions & Answers