a wastewater solution for an air pollution...

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, TN

2 Tischler/Kocurek, Austin, Texas

3 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:





(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

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.


MACT] and Other Regulations),”WEFTEC 2011, October 17, Los Angeles, California.


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)


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.


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

WellAPI 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 approval

State of Wyoming: in process of approval

USEPA region 5: 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 2011

Client Location Industrial Classification

3M Corporation Cordova, IL Organic Chemicals

Advocacy Project w/PERF Oakland, CA Refinery

Air Products & Chemicals Calvert City, KY Organic Chemcials

Celanese Corporation Meredosia, IL Organic Chemicals

Chevron Refining Pascagoula, MS Refinery

ConocoPhillips-Alliance Belle Chasse, LA Refinery

DuPont Corporation Kinston, NC Organic chemicals

ExxonMobil Refining Baton Rouge, LA Refinery

Frontier Refining Cheyenne, WO Refinery

HEXION Louisville, KY Organic Chemicals

Marathon Petroleum Robinson, IL Refinery

Marathon Petroleum Texas City, TX Refinery

Marathon Petroleum Detroit, MI Refinery

Marathon Petroleum Garyville, LA Refinery

NOVACHEM Red Deer, Canada Ethylene Refinery

SABIC Ottawa, IL Organic Chemicals

Shell Chemical Co. Deer Park, TX Organic Chemicals

Shell Oil Co. Australia Refinery

TEVA Mexico, MO Pharmaceuticals

US Steel Gary, IN Coking Facility

Valero Refining Houston, TX Refinery

Valero Refining Pt. Arthur, TX Refinery

Valero Refining Corpus Christi, TX Refinery

Conclusions

VOC 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 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

Case History

Marathon Petroleum Company

Garyville 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 Devices

MPC – Garyville Refinery WWTP

PROCESS TECHNOLOGY

COST-EFFECTIVE IMPACT

Capital

cost ($)

Annual

operating cost ($)

Thermal Oxidizer 600,000 340,000


(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) 600,000 Minimal

MPC Case History – Sustainability

Process Technology

ANNUAL IMPACT

Energy Consumption

Million BTUs per year

CO2 Emissions

Tons CO2 per year

Thermal Oxidizer

(calculated) 45,700 2,690


(in operation) 192 10

Biological

(no additional energy required or

CO2 generated, due to minimal

organics being treated)

Minimal Minimal


MPC – Garyville Refinery WWTP

Marathon Petroleum Company

Garyville, Louisiana Refinery

Proposed Alternative Control Device

BioReactor Construction

UNICELL

Induced Air

Flotation

(IGF)

Closed-Circuit

Cooling Tower

Reliable Data on Benzene

Critical 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

−−−

“ ”

−

−−

BWON Modeling Benzene Biodegradation Rates

BENZENE BIODEGRADATION RATES – EXPERIMENTAL VALUES

Refinery Test Type Date Runs

K1 (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 Method

304A Nov-06 1 120.1 84.5

API -B BOX Oct-97 1 79.1 79.1

API-C BOX Oct-97 2 78.4 78.4

API-D EKR Jul-96 4 17.3 17.3

API-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 7 172

API-E BOX Jun-95 4 206 185.5

API-F BOX Jul-95 3 4.4 4.4

API-G Mar-00 3 64 64

ENVIRON-1 BOX Jul-09 2 23.4 23.4

ENVIRON-2 BOX Mar-11 1 19.7 19.7

ENVIRON-3 BOX Aug-11 1 10.8 10.8

ENVIRON-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 dated

December 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 Apparatus

Option 1

Typical BOX Test Apparatus

Option 2

Develop Site-Specific Biodegradation Rate

BOX Test Apparatus that is typically used


BOX Test Apparatus Developed by ENVIRON


BOX Test Column

(without aeration)

Air Supply Tank

(Supplies BOX Test

Column & GC)

Fine-Bubble Air

Diffuser (Off)


Voyager Photovac Online

Photo-ionization GC

Sample Syringes

0

50

100

150

200

250

0 50 100 150 200 250 300 350 400 450

BE

NZ

EN

E IN

OF

F-G

AS

EM

ISS

ION

S (

pp

mv)

TIME (min)

WITHOUT BIOMASS

~2 mg/L Benzene added to filtered effluent

WITH BIOMASS

~2 mg/L Benzene added to biomass

MLVSS 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 BioTreat

Column Protocols

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 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% Exceeds

3B 153 < 2.0 > 98.7 >700% Exceeds

4A 156 < 2.0 > 98.7 >700% Exceeds

4B 482 13.3 > 97.2 >2200% Below

5A 182 < 2.0 > 98.9 >800% Exceeds

5B 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


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)

200,000 780,000

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 Technology

Energy 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

Savings

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

Case Study

Scenario



Total Energy Usage

(mmBTU/year)

Carbon Emissions

(tons CO2/year)

Activated Carbon Canisters

Transport to/from Reactivation Facility 422 146

Reactivation Process 1,564 98

Totals 1,985 244





Current

Control

System

VOC BioTreat

Alternative

Redirect Vent Stream from Flare to Biological

WWTP, MidWest, USA, Refinery, 200,000 bbls/day

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

Case Study

Scenario



Total Energy Usage

(mmBTU/year)

Carbon Emissions

(tons CO2/year)

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


Current

Control

System

VOC BioTreat

Alternative

Schematic of Wastewater Treatment Plant with

Current Benzene Vapor Controls (8,000 scfm RTO)

RTO

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

Case Study

Scenario



Total Energy Usage

(mmBTU/year)

Carbon Emissions

(tons CO2/year)

Regenerative Thermal Oxidizer

Supplemental Fuel (nat. gas) 12,960 765

Electric Power for RTO Blower 260 80

Totals 13,219 845





Current

Control

System

VOC BioTreat

Alternative

Questions & Answers

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