Opening RemarksOpening Remarks

Howard CohenChancellorPurdue University Calumet

Norman PetersonAssistant to the DirectorArgonne National Laboratory

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Multiple Efforts Contributing to Multiple Efforts Contributing to BP Water Technology DecisionsBP Water Technology Decisions

Internal ReviewBP and consultants with global refinery and other industry experience are evaluating and designing source control and water treatment options.

Expert AnalysisExpert consultants are conducting detailed analysis of ideas presented by others to determine if they may be applicable at Whiting.

PWI / Argonne ProjectScientific experts are studying emerging technologies and approaches to minimize discharges into Lake Michigan.

Petroleum Environmental Research Forum (PERF)Industry group is researching and developing environmental technologies for the petroleum industry.

BP Whiting Refinery

Opening RemarksOpening Remarks

Howard CohenChancellorPurdue University Calumet

Norman PetersonAssistant to the DirectorArgonne National Laboratory

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Research PresentersResearch Presenters

M. Cristina Negri, Doctoral (Italy)Soil Scientist/Environmental EngineerArgonne National Laboratory

George Nnanna, Ph.D.Associate Professor, Mechanical Engineering, Purdue University CalumetInterim Director, Purdue University Calumet Water Institute

Eric McLamore, MSc.Ph.D. Candidate, August 2008, Civil Engineering, Purdue University

John Veil, MSc.Manager, Water Policy ProgramArgonne National Laboratory, Washington, D.C.

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Emerging Technologies…and Approaches to Minimize Dischargesinto Lake MichiganProject Update

Community Briefing

Purdue Calumet Water Institute/Argonne

National Laboratory Task Force

June 5, 2008

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OutlineOutline

•Project Team•Study Objectives•Overview•Results:

•Technology search•Comparative Discharges Study

•Next Steps

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Project TeamProject Team

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Objectives of the StudyObjectives of the Study

•Screen emerging technologies that could address wastewater treatment challenges:

•Ammonia•Total suspended solids (TSS)•Metals (e.g. mercury)

•Conduct a comparative analysis of related discharge issues that may help better understand and address environmental concerns.

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OverviewOverview

Collaboration of Purdue Calumet Water Institute and Argonne National Laboratory

Phase I: November 2007-June 20081. Identify emerging technologies (ammonia, TSS)2. Conduct a comparative analysis of overall discharges

into Lake Michigan (southern portion of lake)

Phase II: Through November 20091. Identify emerging technologies (metals, e.g. Mercury)2. Complete comparative analysis of overall discharges

into Lake Michigan (entire lake)3. Test promising technologies

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Technology Screening ApproachTechnology Screening Approach

Established (1)Serve as BaselineNo further study, refer to BP

Emerging (2)Determine future development needs

•Established (1): • technologies widely used

•Emerging (2):• Embryonic: early development

stages• Innovative: more advanced

development stage, but often not tested for/at refineries

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External ReviewExternal Review

Final Report

•Panel convened May 23, 2008, in Hammond•Reviewed list of technologies, provided insight and feedback

•Four external panelists:

• From academia, industry•Technical experts in specific technologies•Technical experts in wastewater technologies field

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FindingsFindings

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• Technologies identified:

Technologies identified by point of application:• Technologies that treat segregated waste upstream

(desalter, sour water stripper)• Technologies applicable downstream at the wastewater

treatment plant

Technologies identified by time to implementability• Technologies applicable in a relatively short term

• Technologies that meet larger-scope, longer term wastewater treatment needs

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FindingsFindings

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• Other opportunities/needs identified:

• Extensive modeling/engineering to determine exact impact of Canadian crudes, treatment needs versus capacity

• Equalization of influent streams to minimize concentration swings and prevent upsets

• Automated controls to provide system-wide monitoring of wastewater quality and treatment processes, allow prompt diversion of anomalous waste and minimize impacts to downstream processes

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TSS OutlineTSS Outline

•Major source of TSS•Existing treatment technologies•Current TSS loading•Canadian crude impact on current TSS loading•Treatment options•Results – Technologies identified•Summary

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Total Suspended SolidsTotal Suspended Solids

TSS in wastewater◦ consists of clays, biological debris, biofloc

(aggregation of bacteria and other suspended solids), etc.

Mean particle size ranging from 0.005 - 100µm (1µm ~ 1/25000th of an inch)

Source of TSS – refinery units◦ Oil storage◦Desalting - is the largest contributor to TSS ◦ Catalytic cracking◦ Sweetening

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Canadian Crude Impacts on WastewaterCanadian Crude Impacts on Wastewater

Desalting Heavy crude could◦ decrease performance of American Petroleum

Institute (API) and Dissolved Air Flotation (DAF) API remove separable oil and suspended solids

by gravity DAF remove dispersed solids, oil and grease

(remaining after primary separation)◦ lead to oily solids carryover into the activated

sludge units that could then lead to higher solids in the effluent

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Canadian Crude Impacts on WastewaterCanadian Crude Impacts on Wastewater

◦ Higher difficulty in solids removal Desalter mudwashing results in upsets

throughout the wastewater treatment plant Range of TSS concentration 150-5,000 ppm (1

ppm = 1g/1,000,000 g) Desalter brine expected to be a major source of

TSS, 40% of the total

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DRAFT 6-3-08

Sludge Treatment

Surge

API Equalization DAF

Activated Sludge

Filters

Oily Biological

TreatedEffluent

Upstream treatment

Surface Water

Potential treatment options for refineriesPotential treatment options for refineries

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Desalter

Fugitive solids

Downstream treatment

Potential treatment options for refineriesPotential treatment options for refineries

Source - Upstream treatment◦ allows for the more effective treatment of smaller

waste streams◦ reduces both total loadings and troubling

upswings in the wastewater influent to the wastewater treatment plant

In-process and downstream treatment◦ fugitive solids and oil require additional treatment

by the API, DAF and downstream filtration processes to maintain performance within regulations

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Technologies identified for TSS Technologies identified for ammonia

Specialized membrane system for Specialized membrane system for Desalter brineDesalter brineMembrane filtrationMembrane filtrationMembrane BioreactorsMembrane BioreactorsFlotation (DAF, electroflotation)Magnetohydrostatic/Magnetohydrodynamic separationSonicationActivated carbon

Upstream ammonia removal/recoveryBiological treatmentMembrane (ED, contactors, Liquicell®)Membrane BioreactorsAmmonia oxidation (chemical , catalytic, biocatalytic, photocatalytic)Electrochemical methodsPhysical methods (sonication)Ion exchange

Technologies foundTechnologies found

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Technologies in bold are viable for further consideration.

Example - TSS leaving the desalter is separated using the ultrafiltration membrane

Heater

Lower electrode

Upper electrode

Wastewater treatment plantDe-Emulsifier

Mixing valve

Wash water

Emulsifier

Source treatment

Crude

Desalter Unit

Source treatmentSource treatment

Example of source treatment– membrane, air flotation, etc.

Downstream treatment Downstream treatment – Membrane Filtration

Microfiltration (MF) or Ultrafiltration (UF) membrane

◦ Refinery Applications Wastewater reuse within the plant (ref: MEMCOR

membrane), No full-scale case studies found Wastewater reuse may require nanofiltration and

reverse osmosis Membrane separation for the treatment of refinery

wastewater to discharge in surface water bodies is not common

Typically considered only when water is at premium, or because of tight regulatory drivers

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Fouling of the membrane surface and/or clogging of the membrane pores

Permeate flux decline by fouling or rejected species (scaling by inorganic deposits of carbonates, etc.)

Pretreatment needs Maintenance issues, frequent backwashing of a

pressure-driven membrane separation Amount of reject waste which would need disposal Membrane filtration uses varying amounts of energy Impact on shock loading

Membrane ChallengesMembrane Challenges

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Summary of TSS treatment Summary of TSS treatment optionsoptions

Treatment options would require a detailed engineering analysis

Source treatment seems more viable than downstream treatment options

Separate treatment of desalter brine to minimize TSS downstream may be considered

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Summary of TSS treatment Summary of TSS treatment optionsoptions

Desalter controls are needed to monitor swings Equalization of influent streams to minimize

concentration swings and prevent upsets Additional treatment capacity via retrofits or new

installations

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Ammonia OutlineAmmonia Outline

•Upstream processes• Stripping and recovery

•Downstream processes• Biological treatment • Biological technologies

•Results•Summary

Upstream Ammonia TreatmentUpstream Ammonia Treatment

•Steam stripping• Current technology in most

refineries•Ammonia recovery

• Potential resource recovery opportunity

• Several processes found to recover ammonia as fertilizer

• Further analysis needed • energy balance• fertilizer quality and market

Feed stream

Steam

Treated liquid

Stripped ammonia

Downstream Ammonia TreatmentDownstream Ammonia Treatment

• Biological treatment systems are capable of removing both ammonia and biodegradable TSS

• Expected ammonia concentrations are within range for microbial uptake (assimilation) during normal operation

• Existing biological system

Biological TreatmentBiological Treatment

•Group of microorganisms responsible for oxidizing ammonia are sensitive to system upsets

• changes in chemical composition, environmental conditions

•This specialty group of microorganisms (nitrifying organisms) requires a relatively long period of time to adapt to changes in influent composition

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Biological TechnologiesBiological Technologies

Partial list of applicable biological technologies

Suspended Growth Biotechnologies

Attached Growth Biotechnologies

Combined Growth Biotechnologies

Activated Sludge Biotrickling Filter Constructed Wetlands

Sequencing Batch Reactors Biological Aerated Filter Aerated Lagoons

Enhanced Oxygen Dissolution Rotating Biological ContactorBiotrickling Filter/Activated Sludge

Membrane BioreactorSubmerged Biological

ContactorMoving Bed Bioreactor

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Biological TechnologiesBiological Technologies

•Short-term developments• Attached or combined growth biosystems

• High resistance to spike loads• Effects of oil and grease on attached growth are

problematic

•Long-term developments• Membrane bioreactor

• High resistance to spike loads (due to membrane filtration)

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Summary of Ammonia Summary of Ammonia Treatment OptionsTreatment Options

•Attached and combined growth systems have been tested at pilot scale

• Unknown effects of oil and grease•A nitrification system designed to address spike loads requires careful loading analysis

• Upstream ammonia control•Stripping

• Current technology at most refineries •Recovery

• Needs further study•All systems need to be further tested for effects of heavy metals (e.g., mercury)

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Comparative Discharges Analysis

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Study Scope and DesignStudy Scope and Design

Target Pollutants

• TSS • ammonia• total nitrogen • total chromium• chromium+6

• mercury• selenium• vanadium

• Develop an inventory of the significant sources of target pollutants entering Lake Michigan • Create database• Estimate loadings (lb/day)

• Point sources (discharges from pipes, ditches, etc.)• Industries• Municipal wastewater treatment plants• Other

• Nonpoint sources• Stormwater runoff from cities, farms, etc.• Air deposition • Sediments

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Scope and Design - continuedScope and Design - continued

• Study is conducted in two phases• Phase I study area extends

southward from the Wisconsin/Illinois border on the west and South Haven, Michigan on the east.

• Phase II study includes all of Lake Michigan

• Includes: • Discharges entering the lake directly• Discharges on tributary streams and

rivers flowing into Lake Michigan in the target study area

Phase I study area

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Point Source Data CollectionPoint Source Data Collection

• Look primarily to National Pollutant Discharge Elimination System (NPDES) program for point source data

• Applications offer a one time sample but often contain analyses on a wide range of pollutants

• Permits contain numerical limits that must be monitored on a regular frequency by the permitted facility

• Discharge monitoring reports (DMRs) must be submitted to the agencies each month

• Also try to corroborate using data from EPA’s Toxics Release Inventory (TRI)

• Data were collected from online sources to the extent possible• Argonne also visited the offices of each of the state NPDES

programs to review the actual files

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Point Source ResultsPoint Source Results

• Illinois, Indiana, and Michigan agencies provided lists of all facilities discharging to Lake Michigan drainage in Phase I region (433 facilities)

• Many of these facilities did not discharge the target pollutants or had very small discharge volumes

• Different filtering methods were used to remove those facilities from the final database

• The final database contained 80 facilities (29 industrial and 51 municipal)

• Facilities were not named but were given IDs (e.g., MUN-04 or IND-11)

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Point Source Loads from DMR Data Point Source Loads from DMR Data SetSet

Pollutant

No. of Facilities

with Available DMR Data

Average Phase I Area Combined Load (lb/day)

Maximum Phase I Area

Combined Load (lb/day)

TSS 79 57,376 683,953

TSS (excluding highest value)

79 43,688 235,348

Ammonia 64 2,245 10,406

Total chromium 17 11.8 51.3

Chromium+6 3 1.8 2.5

Mercury 30 0.024 0.0686

Vanadium 1 No data available 0.117

Selenium 3 2.8 5.2

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Other Point Source DataOther Point Source DataParameter NPDES

DMRsNPDES

ApplicationsNPDES Permits

Toxics Release Inventory

TSS 79 56 55 0

Ammonia 64 41 45 6

Total Chromium

17 11 3 7

Chromium+6 3 0 2 n/a

Mercury 30 15 21 4

Selenium 1 11 2 1

Vanadium 3 0 1 2

• Therefore, DMR data set was used to characterize point sources

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Nonpoint Source DataNonpoint Source Data

• Nonpoint source data were collected from literature studies

• Nonpoint source data are typically generated through targeted one-time or infrequent research programs rather than ongoing regular monitoring programs

• Nonpoint source data are collected from a few sampling points. The results are extrapolated within the studies to make estimates for larger geographic areas

• Modest amounts of nonpoint source data have been collected for TSS, ammonia, total nitrogen, and mercury, but almost no data exist for the other pollutants

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Comparison of Point and Nonpoint Source DataComparison of Point and Nonpoint Source Data

PollutantAverage Point Source Estimate

(lb/day)

Average Nonpoint Source Estimate (lb/day)

TSS 57,376 8,200,000

TSS (excluding high value) 43,688 8,200,000

Ammonia 2,245 619

Total chromium 11.8 No data

Hexavalent chromium 1.8 No data

Mercury 0.024 0.67

Vanadium 26.6 No data

Selenium 2.8 No data

Total nitrogen No data 28,000

• The TSS and mercury loads from nonpoint sources are at least one order of magnitude higher than the point source loads

• The ammonia loads are higher from point sources, but if the nonpoint total nitrogen load is considered, too, the combined nitrogen input (ammonia plus total nitrogen) from nonpoint sources is much higher.

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ConclusionsConclusions

• Data for metals are scarce

• Hopefully more data will become available in Phase II

• Many other sources of pollutants that remain unquantified or poorly quantified (e.g., urban runoff, combined sewer overflows, groundwater exfiltration into surface water bodies, sediment re-release of metals into the overlying water column, excrement from birds and fish) can make substantial contributions of the target pollutants

• The discharges from BP’s Whiting refinery are substantial, but are not the highest or the only point source contributor to the Phase I study area. Other large industries and municipal wastewater treatment facilities discharge comparable or higher loads of the target pollutants

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Next StepsNext Steps

•Complete final reports from Phase I•To be presented to BP by end of June

•Post final Phase I reports to Purdue University Calumet Water Institute Web site

•www.calumet.purdue.edu/pwi•Welcome your feedback•Move to Phase II

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