A Wastewater Solution for an Air Pollution Problem

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 Author1 *Dr. Lial F. Tischler2

Andrew W. Edwards, PE3

1 ENVIRON International Corporation, Nashville, TN2 Tischler/Kocurek, Austin, Texas3 ENVIRON International Corporation, Houston, TX

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

• Title 40: Protection of Environment: 40 CFR § 61.340 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 § 61.340 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

BWON (Benzene Waste Operations NESHAP)

Wastewater Gaseous Emissions Considerations(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.

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

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.

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 1933.

VOC BioTreat was the 2011 Semi-Finalist

Kirkpatrick Award: Semifinalist

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

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, 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 Section Conference & Expo., Houston, TX, George R. Brown Convention Center, Chemical Engineering Magazine, September 13 - 15, 2011.

"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, 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 Agenda National Press Club, Washington, D.C., May 4, 2011.

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, 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-Western Air & 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 Engineers Association (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, 24th-26th Nov, 2011.

What is VOC BioTreatTM?

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.

Typical Acceptable Control Devices

Thermal Oxidizers

Granular Activated Carbon Canisters

Vapor-Phase Adsorption: Granular Activated Carbon

Thermal Oxidizers: Flare or Gaseous Incinerator

Alternative Control Device

Alternative Control Device for a Refinery:A Basic Overview

Site Process /Stormwater Sump

API Separator

API Entry Well

API Pump Well

Dissolved Nitrogen Flotation

Unit

DNF Wet Well

Secondary Clarifier

API Effluent

Well

FINAL EFFLUENTSITE PROCESS/

STORMWATER WASTEWATERS

Ambient Air Inlet

to Blower

Air VOC Emissions Piped to Existing Bio-Blowers

Appropriate Valving & LEL

Instrumentation

COMBINED WASTEWATER & AIR VOC BIOTREATMENT USING EXISTING FACILITIES

Recycled Biomass

EQ TankP-52

Activated Sludge

Bioreactor

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

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

Regulatory Interface & Approval

Regulatory Approval

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 approvalState 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 SeminarUSEPA region 7: Presented as a Technical Seminar

Why VOC BioTreatTM?

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!

– N2 blankets: expensive, maintenance issue, leakage (pressurized)

– Sustainable at reduced costs

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 (Fbio)• Process Vent Control

Industrial Sectors

Regulatory Drivers

Soil-Vapor-Extraction

VOC BioTreat Typical Applications

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 BioTreatTM – the Process

How is it Applicable?

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

VOC BioTreat – The Process

Steps 1 & 2 must be concluded favorably before proceeding with the remaining steps.

STEP 1 High-Level Feasibility Evaluation

STEP 2Develop 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

Case History

Marathon Petroleum CompanyGaryville Refinery (MPC)Garyville, Louisiana

Petroleum Refinery: BWON Alternative Control Device

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)

Current/Proposed Benzene Control Devices

MPC asked ENVIRON to develop protocols to qualify the existing activated sludge system (AIS) as an Alternative Control Device.

MPC Case History – Economic

Economic Impacts for VOC Control DevicesMPC – Garyville Refinery WWTP

PROCESS TECHNOLOGYCOST-EFFECTIVE IMPACT

Capital cost ($)

Annualoperating cost ($)

Thermal Oxidizer 600,000 340,000

Granular Activated Carbon(6 carbon canisters on each of two API separators, 22 change-outs/yr per API)+ Maintenance of N2 blanket

240,000 500,000

Biological(piping, fans and connection to blowers) 350,000 Minimal

MPC Case History – Sustainability

Process TechnologyANNUAL IMPACT

Energy Consumption Million BTUs per year

CO2 Emissions Tons CO2 per year

Thermal Oxidizer(calculated) 45,700 2,690

Granular Activated Carbon(in operation) 192 10

Biological(no additional energy required or CO2 generated, due to minimal organics being treated)

Minimal Minimal

Economic Impacts for VOC Control DevicesMPC – Garyville Refinery WWTP

Marathon Petroleum CompanyGaryville, Louisiana Refinery

Proposed Alternative Control Device BioReactor Construction

UNICELL Induced Air

Flotation (IGF)

Closed-Circuit Cooling Tower

Reliable Data on BenzeneCritical Benzene Mass Balance for MPC–Garyville

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

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)

BWON Modeling Benzene Biodegradation Rates

BENZENE BIODEGRADATION RATES – EXPERIMENTAL VALUES

Refinery Test Type Date RunsK1 (L/g VSS-hr) @ 20 oC

Average for Multiple Runs

Value Selected for Model Evaluation

API-A BOX Nov-06 2 48.9 -----

API-A Method304A Nov-06 1 120.1 84.5

API -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 64

ENVIRON-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 6.4

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

datedDecember 28, 2007.

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

Develop Site-Specific Biodegradation Rate;Select Appropriate EPA-Recommended Approach

Source: EPA 40 CFR part 63, Appendix C, Figure 1

Typical BOX Test ApparatusOption 1

Typical BOX Test ApparatusOption 2

Develop Site-Specific Biodegradation RateBOX Test Apparatus that is typically used

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

Develop Site-Specific Biodegradation Rate

BOX Test Column (without aeration)

Air Supply Tank(Supplies BOX Test

Column & GC)

Fine-Bubble Air Diffuser (Off)

Develop Site-Specific Biodegradation Rate

Voyager Photovac Online Photo-ionization

GC

Sample Syringes

0 50 100 150 200 250 300 350 400 4500

50

100

150

200

250

TIME (min)

BE

NZE

NE

IN O

FF-G

AS

EM

ISS

ION

S (p

pmv)

WITHOUT BIOMASS ~2 mg/L Benzene added to filtered effluent

WITH BIOMASS ~2 mg/L Benzene added to biomassMLVSS concentration of 800 mg/L

Comparative Results of Benzene Stripping with and without Biomass

Development of Preliminary Site-Specific Benzene Control Model

• The site-specific biodegradation rate, corrected to 20°C, is– 22.6 L/g VSS-hr @ 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

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

Full-Scale Confirmation Flux Chamber: Less Desirable Option

Full-Scale Confirmation

Performance Validation of Full-Scale System

Using VOC BioTreatColumn Protocols

Aeration + Benzene input

Sample port

InfluentWastewater

Drain

Support pipe (empty)

Gravity overflow line back to full-scale aerobic zone

Off-gas ventSample gas line to on-line gc

Recycle biomassPort

Performance Validation of

Full-Scale System Using VOC BioTreat Column Protocols


Full-Scale Confirmation Results

Run #

Benzene Concentration ppbv Benzene

Biodestruction (%)

Percent of Design

Condition

Performance Versus Regulatory

Requirements Blower Inlet Outlet Vent

1 21 < 2.0 > 90.6 100%Inconclusive due to

analytical limitations

3A 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% Below 5A 182 < 2.0 > 98.9 >800% Exceeds5B 226 < 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 ~400-500 ppbv.

Regulatory Approval

Repeat of Slide 15

Case History

Economic Evaluations for Sustainability Confirmation

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

Economic Impacts for VOC Control Devices

Process TechnologyCost-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)

200,000 780,000

VOC BioTreat (validation, engineering piping, instrumentation, and connection to blowers)

460,000 < 10,000

Case History – Economic

Energy Savings / Sustainability Aspects

Case Study No. 2: Replace Activated Carbon Canisters at Wyoming Refinery

Case Study Scenario

Benzene Control TechnologyEnergy Consumption Activity

Total Energy Usage (mmBTU/year)

Carbon Emissions (tons CO2/year)

Activated Carbon Canisters

Transport to/from Reactivation Facility 547 63

Reactivation Process (315,000 lbs/yr) 1,859 116

Totals 2,406 179

Biological Treatment in WWTP

Additional Power for Aeration Blowers 8.1 2.5

Total Energy Savings / GHG reductions 2,398 177

Sustainability Aspects

Current Control System

VOC BioTreat Alternative

Main Sump

CPI #6

API #7

API #1

API #2

BOTTOMS

FLOAT

3 DNF Units

= 2,000 lb Canister

= 1,000 lb Canister

= 20,000 lb Container

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

Energy Savings / Sustainability Aspects, SE USA

Case Study No. 3: Replace Activated Carbon Canisters at Mississippi Refinery

Case Study Scenario




Activated Carbon Canisters

Transport to/from Reactivation Facility 422 146

Reactivation Process 1,564 98

Totals 1,985 244







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

Energy Savings / Sustainability AspectsMidWest Refinery, USA

Case Study No. 4: Replace Small Dedicated Flare at Illinois Refinery

Case Study Scenario




Steam-Assisted Flare

Nat. Gas Pilot and Refinery Fuel Gas 48,640 2,860

Steam Assist and Blower 10,648 632

Totals 59,288 3,492



Total Energy Savings / GHG reductions 59,275 3,488




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

RTO

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

Case Study No. 5: Replace regenerative Thermal Oxidizer at Texas Refinery

Case Study Scenario




Regenerative Thermal Oxidizer

Supplemental Fuel (nat. gas) 12,960 765

Electric Power for RTO Blower 260 80

Totals 13,219 845







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A Wastewater Solution for an Air Pollution Problem

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