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A Wastewater Solution for an Air Pollution Problem A Cost-Effective Alternative for VOC Control as Required by NESHAP [BWON, HON, MON, MACT] Dr. Carl E.

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Presentation on theme: "A Wastewater Solution for an Air Pollution Problem A Cost-Effective Alternative for VOC Control as Required by NESHAP [BWON, HON, MON, MACT] Dr. Carl E."— Presentation transcript:

1 A Wastewater Solution for an Air Pollution Problem A Cost-Effective Alternative for VOC Control as Required by NESHAP [BWON, HON, MON, MACT] Dr. Carl E. Adams, Jr., PE, BCEE Senior Author 1 * Dr. Lial F. Tischler 2 Andrew W. Edwards, PE 3 1 ENVIRON International Corporation, Nashville, TN 2 Tischler/Kocurek, Austin, Texas 3 ENVIRON International Corporation, Houston, TX

2 BWON (Benzene Waste Operations NESHAP)  Aqueous Wastewater Considerations − Influent wastewater benzene concentration must be <10 mg/L to avoid required regulatory inventory accounting procedures − Wastewater treatment bioplant must qualify as an Enhanced Biodegradation Treatment Unit (EBU) − Current approved control is by excellent benzene separation in production processes and use of a NESHAPS Benzene Steam Striper on benzene-laden wastewaters  Wastewater Gaseous Emissions Considerations − Applies to gaseous emissions from wastewater treatment processes − Includes API separators, dissolved air and induced air flotation processes, uncovered tanks and includes sumps and wet wells emissions − Must incorporate an approved Control Device to reduce benzene emissions form these sources by 98% − Current approved controls are thermal oxidizers and vapor-phase activated carbon

3  Title 40: Protection of Environment: 40 CFR § presents three basic Control Devices that are acceptable, pursuant to specific design constraints: (i)An enclosed combustion device (e.g., vapor incinerator, boiler, or process heater) (ii)A vapor recovery system (e.g., a carbon adsorption system or a condenser) (iii)A flare  Title 40: Protection of Environment: 40 CFR § also states “other” Control Devices can be used provided that certain conditions are 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 following conditions are met: BWON (Benzene Waste Operations NESHAP) Wastewater Gaseous Emissions Considerations

4 (A) The device shall recover or control the organic emissions vented to it with an efficiency of 95 weight percent or greater, or shall recover or control the benzene emissions vented to it with an efficiency of 98 weight percent or greater. (B) The owner or operator shall develop test data and design information that documents the control will achieve an emission control efficiency of either 95 percent or greater for organic compounds or 98 percent or greater for benzene. (C) The owner or operator shall identify: 1)The critical operating parameters that affect the emission control performance of the device; 2)The range of values of these operating parameters that ensure the emission control efficiency specified in paragraph (a)(2)(iv)(A) of this is maintained during operation of the device; and 3)How these operating parameter will be monitored to ensure the proper operation and maintenance of the device.

5 Overview  From Nashville, TN:The idea  To Garyville, LA:The testing site and first case study  To Research Triangle, NC (USEPA):The endorsement  To Baton Rouge, LA (LDEQ):The final approval  To Austin, TX:ENVIRON workshop  To weekly conference calls:VOC BioTreat™ Core Group  To creating marketing solutions:Brand, media relations, collateral  To prestigious recognition:AAEE E3 Grand Prize for Research  To today:Learn what you can; communicate to your contacts; bring in Carl, Greg or Andy

6 Prestigious Accolade: National Grand Prize – Research Category 2011 VOC BioTreat has garnered the coveted National Grand Prize in the Research category of the prestigious American Academy of Environmental Engineers (AAEE) 2011 Excellence in Environmental Engineering ® (E3) Competition. The concept was conceived, developed and implemented by Dr. Carl E. Adams, Jr., Global Practice Area Leader: Industrial Wastewater Management.

7 Kirkpatrick Chemical Engineering Achievement Award recognizes the most innovative chemical engineering technology achieved through group effort and successfully commercialized worldwide during the two years prior to an award year. Chemical Engineering Magazine has awarded this biennial prize continuously since VOC BioTreat was the 2011 Semi-Finalist Kirkpatrick Award: Semifinalist

8 Louisiana Section of the Air & Waste Management Association: 2011 Industry Award: Grand Prize

9 VOC BioTreat Technical Presentations and Publications “A Cost-Effective Alternative for VOC Control as Required by NESHAP [BWON, HON, MON, MACT],” AIChE Workshop, Baton Rouge, LA, November 11, “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, “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 Section Conference & Expo., Houston, TX, George R. Brown Convention Center, Chemical Engineering Magazine, September , "A Cost Effective Alternative for VOC Control as Required by NESHAP [BWON, HON, MON, MACT, RACT and Other Regulations," Air & Waste Management Association's Annual Conference & Exhibition, Orlando, FL on June 21-24, “Biological Control of Benzene-Containing Off Gases”, Petroleum Environmental Research Forum, San Ramon, California, June 15, “Patented & Innovative Cost-Saving Control Device for Facility-Generated Volatile Organic Compound (VOC) Emissions”, American Academy of Environmental Engineers, Excellence In Environmental Engineering, Conference Agenda National Press Club, Washington, D.C., May 4, 2011.

10 VOC BioTreat Technical Presentations and 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, Environmental News Record, interview for magazine with Gary Tulacz, April 1, “A Cost-Effective Alternative for VOC Control as Required by NESHAP [BWON, HON, MON, MACT]”, Annual Mid-Western Air & Waste Management Association's Annual Conference & Exhibition, Kansas City, December “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, “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 “A Cost-Effective Alternative for VOC Control as Required by NESHAP [BWON, HON, MON, MACT]”, AIChE Workshop, Chicago, IL, November 10, “ENVIRON VOC BioTreat, Un sistema innovativo per il controllo delle emissiona di VOC, Italian Environmental Engineers Association (Aria y Aqua), Remtech, Ferrara, Itlay, Oct 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.

11 What is VOC BioTreat TM ?

12 What is VOC BioTreat? VOC BioTreat is the process of qualifying an Alternative Control Device, other than Activated Carbon or Thermal Oxidation, for the biodestruction of regulated biodegradable VOC emissions. The Alternative Control Device is cost-effectively an existing activated sludge process with emission sources in proximity to a WWTP.

13 Typical Acceptable Control Devices Thermal Oxidizers Granular Activated Carbon Canisters Vapor-Phase Adsorption: Granular Activated Carbon Thermal Oxidizers: Flare or Gaseous Incinerator

14 Alternative Control Device

15 Alternative Control Device for a Refinery: A Basic Overview

16 A Cost-Effective Solution for the Biodestruction of VOC Emissions Incorporates ENVIRON-developed protocols to demonstrate an Alternative Control Device Confirms the use of existing biological wastewater treatment facilities Follows exact EPA requirements and protocols for approval

17 A Cost-Effective Solution for the Biodestruction of VOC Emissions Conclusively demonstrates co-treatment of gaseous emissions or VOCs and aqueous soluble organics in existing wastewater treatment facilities Using these protocols, most activated sludge biotreatment systems can be qualified as an Alternative Control Device to treat biodegradable VOCs It is transferable to other VOC/HAP and other regulations Provides excellent configuration flexibility with existing facilities

18 Regulatory Interface & Approval

19 Regulatory Approval

20 Regulatory Interface & Approval Specific projects Regular invitation to ENVIRON State of Louisiana USEPA Research Triangle Park: Presented as a Technical Seminars(2) State of Mississippi: in process of approval State of Wyoming: in process of approval USEPA region 5: Presented as a Technical Seminar USEPA region 6: Presented as a Technical Seminar USEPA region 8: Presented as a Technical Seminar USEPA region 7: Presented as a Technical Seminar

21 Why VOC BioTreat TM ?

22 Why VOC BioTreat? Economics, Economics, Economics!!! –Typical systems (carbon or TOs) have much higher operating costs O&M costs are typically <$10K per year –Capital investment quickly recovered (ROI <1 year typically, <2 yrs worst case) –Discarding previously installed system carbon/TO ok OK, it’s not all economics! –N 2 blankets: expensive, maintenance issue, leakage (pressurized) –Sustainable at reduced costs

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

24 Soil-Vapor-Extraction VOC BioTreat Typical Applications

25 VOC BioTreat Projects in 2011 ClientLocationIndustrial Classification 3M CorporationCordova, ILOrganic Chemicals Advocacy Project w/PERFOakland, CARefinery Air Products & ChemicalsCalvert City, KYOrganic Chemcials Celanese CorporationMeredosia, ILOrganic Chemicals Chevron RefiningPascagoula, MSRefinery ConocoPhillips-AllianceBelle Chasse, LARefinery DuPont CorporationKinston, NCOrganic chemicals ExxonMobil RefiningBaton Rouge, LARefinery Frontier RefiningCheyenne, WORefinery HEXIONLouisville, KYOrganic Chemicals Marathon PetroleumRobinson, ILRefinery Marathon PetroleumTexas City, TXRefinery Marathon PetroleumDetroit, MIRefinery Marathon PetroleumGaryville, LARefinery NOVACHEMRed Deer, CanadaEthylene Refinery SABICOttawa, ILOrganic Chemicals Shell Chemical Co.Deer Park, TXOrganic Chemicals Shell Oil Co.AustraliaRefinery TEVAMexico, MOPharmaceuticals US SteelGary, INCoking Facility Valero RefiningHouston, TXRefinery Valero RefiningPt. Arthur, TXRefinery Valero RefiningCorpus Christi, TXRefinery

26 Conclusions VOC BioTreat TM – the Process How is it Applicable?

27 High-Level Assessment: Comprehensive Questionnaire Existing WWTP amenable to the technology? –Diffused aeration system –Deep tanks –Existing blowers have adequate air flow treatment capacity (modification may be necessary) VOC emission sources appropriate for technology? –Compounds relatively biodegradable –Compounds 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 WWTP –Current system O&M costs –Minimal modifications required to adapt WWTP to technology

28 VOC BioTreat – The Process Steps 1 & 2 must be concluded favorably before proceeding with the remaining steps. STEP 1 High-Level Feasibility Evaluation STEP 2 Develop preliminary facility-specific model with assumed biodegradation rate to gauge benzene removal performance requirements and obtain initial Agency concurrence for approach STEP 3 Conduct BOX testing to determine site-specific VOC biodegradation rate and maximize VOC BioTreat effectiveness STEP 4 Conduct Core Column Simulation Full-scale confirmation testing STEP 5 Obtain final Agency approval of Alternative Control Device STEP 6 Prepare detailed engineering plan and implement Alternative Control Device solution

29 Case History Marathon Petroleum Company Garyville Refinery (MPC) Garyville, Louisiana Petroleum Refinery: BWON Alternative Control Device

30 Why was MPC-Garyville an Excellent Choice? Economics, Economics, Economics! − Current MPC system had very high operating cost (energy and carbon) − 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 of current 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)

31 Current/Proposed Benzene Control Devices MPC asked ENVIRON to develop protocols to qualify the existing activated sludge system (AIS) as an Alternative Control Device.

32 MPC Case History – Economic Economic Impacts for VOC Control Devices MPC – Garyville Refinery WWTP PROCESS TECHNOLOGY COST-EFFECTIVE IMPACT Capital cost ($) Annual operating cost ($) Thermal Oxidizer600,000340,000 Granular Activated Carbon (6 carbon canisters on each of two API separators, 22 change-outs/yr per API) + Maintenance of N 2 blanket 240,000500,000 Biological (piping, fans and connection to blowers) 350,000Minimal

33 MPC Case History – Sustainability Process Technology ANNUAL IMPACT Energy Consumption Million BTUs per year CO 2 Emissions Tons CO 2 per year Thermal Oxidizer (calculated) 45,7002,690 Granular Activated Carbon (in operation) Biological (no additional energy required or CO 2 generated, due to minimal organics being treated) Minimal Economic Impacts for VOC Control Devices MPC – Garyville Refinery WWTP

34 Marathon Petroleum Company Garyville, Louisiana Refinery Proposed Alternative Control Device BioReactor Construction UNICELL Induced Air Flotation (IGF) Closed-Circuit Cooling Tower

35 Reliable Data on Benzene Critical Benzene Mass Balance for MPC–Garyville

36 Inputs to Site-Specific Model Major Variables  Benzene Biodegradation Rate − Table 2 represents various experimentally-determined biorates from API and ENVIRON databases  Air Flow  Biomass Concentrations  Potential Benzene Injection Locations into AIS  Benzene Loadings & Mass Balance Other Significant Variables Air Distribution in Zones Depth of BioReactor Aeration Tank Surface Area Temperature Hydraulic Flow Rate & COD Loading

37 Models for Calculating VOC BioTreat™ Emissions  Applicable models −EPA WATER9 −TOXCHEM+ −BASTE  TOXCHEM+ is preferred – can simulate vapor to liquid phase transfer  All are identified in 40 CFR 63 Appendix C as “acceptable” for HAP emissions calculations for biological treatment Units  All three models calculate the following:  VOC emission rates (g/sec, tons/yr) −Fractions of influent VOC mass loading emitted, biodegraded, and discharged-overall and for each process unit individually  Model inputs: −Site-specific physical and operating characteristics −Site-specific compound biorates (each has default rates)

38 BWON Modeling Benzene Biodegradation Rates BENZENE BIODEGRADATION RATES – EXPERIMENTAL VALUES RefineryTest TypeDateRuns K1 (L/g 20 o C Average for Multiple Runs Value Selected for Model Evaluation API-ABOXNov API-A Method 304A Nov API -BBOXOct API-CBOXOct API-DEKRJul API-DBOXJul API-EBOXSept API-EBOXNov API-EBOXDec API-EBOXApr API-EBOXApr API-EBOXJun API-FBOXJul API-GMar ENVIRON-1BOXJul ENVIRON-2BOXMar ENVIRON-3BOXAug ENVIRON-4BOXAug API Water 9 Default Rate (EPA requires that Default Rate be used if industry chooses not to conduct BOX Test to determine site-specific benzene biodegradation rate. 1.4 Data referred to as API is from Table 5 of the API/NPRA comments to EPA dated December 28, 2007.

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

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

41 Typical BOX Test Apparatus Option 1 Typical BOX Test Apparatus Option 2 Develop Site-Specific Biodegradation Rate BOX Test Apparatus that is typically used

42 Develop Site-Specific Biodegradation Rate BOX Test Apparatus Developed by ENVIRON

43 Develop Site-Specific Biodegradation Rate BOX Test Column (without aeration) Air Supply Tank (Supplies BOX Test Column & GC) Fine-Bubble Air Diffuser (Off)

44 Develop Site-Specific Biodegradation Rate Voyager Photovac Online Photo-ionization GC Sample Syringes

45

46 Comparative Results of Benzene Stripping with and without Biomass

47 Development of Preliminary Site-Specific Benzene Control Model The site-specific biodegradation rate, corrected to 20°C, is –22.6 L/g 20°C at Marathon-Garyville The Toxchem+ model will adjust the rate to the selected temperature for full-scale operating conditions Rerun Calibrated Model with Site-Specific Biodegradation Rate

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

49 Full-Scale Confirmation Flux Chamber: Less Desirable Option

50 Full-Scale Confirmation Performance Validation of Full-Scale System Using VOC BioTreat Column Protocols

51 Full-Scale Confirmation

52 Aeration + Benzene input Sample port Influent Wastewater Drain Support pipe (empty) Gravity overflow line back to full-scale aerobic zone Off-gas vent Sample gas line to on-line gc Recycle biomass Port Performance Validation of Full-Scale System Using VOC BioTreat Column Protocols Full-Scale Confirmation

53

54 Full-Scale Confirmation Results Run # Benzene Concentration ppbv Benzene Biodestruction (%) Percent of Design Condition Performance Versus Regulatory Requirements Blower Inlet Outlet Vent 121< 2.0> % Inconclusive due to analytical limitations 3A121< 2.0> 98.3>500%Exceeds 3B153< 2.0> 98.7>700%Exceeds 4A156< 2.0> 98.7>700%Exceeds 4B > 97.2>2200%Below 5A182< 2.0> 98.9>800%Exceeds 5B226< 2.0> 99.1>1000%Exceeds Benzene analytical results of full-scale confirmation Design is 98% at inlet of 14 ppb. Results showed 16 times that capacity. Breakthrough at ~ ppbv.

55 Regulatory Approval Repeat of Slide 15

56 Case History Economic Evaluations for Sustainability Confirmation

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

58 Economic Impacts for VOC Control Devices Process Technology Cost-Effective Impact Capital cost ($) Annual Operating Cost ($) Granular Activated Carbon (2 large carbon vessels on DAFs, multiple other carbon canisters; over 300,000 lbs/yr activated carbon consumption w/ no reactivation option) 200,000780,000 VOC BioTreat (validation, engineering piping, instrumentation, and connection to blowers) 460,000< 10,000 Case History – Economic

59 Energy Savings / Sustainability Aspects

60 Current Benzene Vapor Controls: SE, USA Refinery (Activated Carbon Canisters), 350,000 bbls/day

61 Energy Savings / Sustainability Aspects, SE USA

62 Redirect Vent Stream from Flare to Biological WWTP, MidWest, USA, Refinery, 200,000 bbls/day

63 Energy Savings / Sustainability Aspects MidWest Refinery, USA

64 Schematic of Wastewater Treatment Plant with Current Benzene Vapor Controls (8,000 scfm RTO) RTO

65 Energy Savings / Sustainability Aspects, SW Refinery, 350,000 bbls/day

66 Questions & Answers


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