Measuring Total And Speciated Mercury
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Measuring Total And Speciated Mercury In Process Gas Emissions Solid Sorbent Based Methods: US EPA 324 and FAMS. Hg Monitoring And Monitoring WESTAR Fall Meeting Mercury and Air Quality – Sources, Effects, and Controls San Diego, California September 22, 2005 Bob Brunette

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Hg monitoring and monitoring westar fall meeting

Measuring Total And Speciated Mercury In Process Gas EmissionsSolid Sorbent Based Methods: US EPA 324 and FAMS

Hg Monitoring And Monitoring

WESTAR Fall Meeting

Mercury and Air Quality – Sources, Effects, and Controls

San Diego, California

September 22, 2005

Bob Brunette

Frontier Geosciences Inc

414 Pontius Avenue North

Seattle, Washington 98109

[email protected]

206 957 1461


Frontier flue gas adsorbent mercury speciation topics covered

Frontier Flue Gas Adsorbent Mercury Speciation - Topics Covered -

  • Frontier Geosciences Inc

  • Hg Control Systems – Do They Work?

  • Existing Hg Sampling Methods

  • History Of Solid Sorbent Methods: US EPA 324 and FAMS

  • Measuring Total and Speciated Hg In Process Gas

    • US EPA 324 and FAMS Methods

    • US EPA 1631 & Applications To Coal-Fired Utility

  • Hg Control Systems Evaluated

  • Conclusions


History and background frontier geosciences inc

History and Background- Frontier Geosciences Inc -

  • Bob Brunette

    • Hg Emissions Group Leader

    • Hg Analytical Lab Director

    • 10 Years Research Focus On Hg In Process Gas Emissions

  • Frontier Geosciences Inc

    • Originally an EPRI Contract Research Laboratory

    • Specialized Inorganic Research And Consulting

    • Co-authored US EPA 1631 = Total Hg

    • Co-Authored US EPA 324 and Authored FAMS Methods

    • Authored/Co-Authored US EPA 1600 Series Metals Methods


Frontier geosciences authored co authored methods

Frontier Geosciences Authored/Co-Authored Methods

  • US EPA Method 1630: Determination of Methyl Mercury in Water and Tissues by Distillation, Extraction, Aqueous Phase Ethylation, Purge and Trap, Isothermal GC Separation, Cold Vapor Atomic Fluorescence Spectrometry.

  • US EPA Method 1631: Determination of Mercury in Water by Oxidation, Purge and Trap and Cold Vapor Atomic Fluorescence Spectrometry.

  • US EPA Method 1637: Determination of Trace Elements in Ambient Waters by Off-Line Chelation, Preconcentration and stabilized Temperature Graphite Furnace Atomic Absorption.

  • US EPA Method 1638: Determination of Trace Elements in Ambient Waters by Inductively Coupled Plasma-Mass Spectrometry.

  • US EPA Method 1639: Determination of Trace Elements in Ambient Waters by Stabilized Temperature Graphite Furnace Atomic Absorption.

  • US EPA Method 1640: Determination of Trace Elements in Ambient Waters by On-Line Chelation Preconcentration and Inductively Coupled Plasma-Mass Spectrometry.

  • US EPA Method 1669: Sampling Ambient Water for Trace Metals at EPA Water Quality Criteria Levels.


Why measure hg at the sub ppb range historical perspective hg in waste water effluents

Why Measure Hg At The Sub PPB Range?Historical Perspective – Hg In Waste Water Effluents


How accurate is us utility hg emission inventory based on coal hg measurements

How Accurate Is US Utility Hg Emission InventoryBased On Coal Hg Measurements?

  • 25 Year Record Of Coal Hg Based On ASTM 3684

  • 1999 ICR Prescribed The Use Of ASTM 3684 Method

  • ASTM Method Has Shown High LOD/LOQ Relative To The Range Of Mercury Concentrations Found In Coal.

  • ASTM Method LOQ = ~ 0.06ppm

  • Range Of Coal Hg Concentrations: 0.02 – 0.18ppm


Coal mercury measurements variation between laboratories and methods

Coal Mercury Measurements Variation Between Laboratories and Methods


Benefit of low level sensitive analytical methods

Benefit Of Low-Level Sensitive Analytical Methods

“EPA is now aware of several studies in which the techniques employed in the above guidance (EPA-1631 CVAFS and other 1600 series methods) have been applied and have been of great benefit in determining that either an environment problem does not exist or that the magnitude of the problem is considerably less than initially envisioned. Therefore, the added costs associated with the sample handling and quality control protocols contained in the draft guidance are often trivial when compared to the cost saved by avoiding unnecessary pollution controls that might otherwise have been required.”

  • Source - U.S. EPA Fact Sheet – March 1996


Hg control systems do they work

Hg Control Systems – Do They Work?

  • Evaluate Existing and Proposed Hg Controls

    • Measure Hg Concentrations Throughout Existing APCD

    • Direct Measurements For Each Application To Facility

    • Each System (Existing or Installed) Should Be

      Tested To Understand Optimal/Routine Efficiencies

    • Measure Total Hg and Hg Speciation

      • How Does Mercury Behave In This System?

      • Engineering Controls – Do The Results Make Sense?

    • Manufacture Specifications – Are They Achieved?


Barrier to evaluate hg control systems diagnostic tools needed to evaluate control systems

Barrier To Evaluate Hg Control Systems -Diagnostic Tools Needed To Evaluate Control Systems

  • Existing Impinger Methods: (Ontario Hydro/101A/M29)

    • Difficult To Implement In Field

    • Expensive

    • Poor Field QA/QC

    • Few Data Points Generated For Effort/Cost

      ($10K/Sample for ~ 3-4 Runs)

    • Field and Analytical Methods Are Antiquated (CVAA)

    • High Detection Limit

    • EPRI/DOE Hg Measurement Workshop – retire OH?

    • Not Capable Of Continuous Emission Monitoring

  • Hg Continuous Mercury Monitors (CMM):

    • Alpha/Beta Development Stage

    • Having Difficulty Applied To Coal Fired Flue Gas

    • Expensive (Cost, O&M, Dedicated CEM Staff)

    • Smelter/Roaster Process Gas Too Complex – High Level Hg


Us epa method 324 and fams fully validated methods

US EPA Method 324 and FAMSFully Validated Methods

  • US EPA PBMS Validation Study – 2000

    • Validation Against Gold Standard – ASTM Ontario Hydro Method

  • US Dept Of Energy Validation Study – 2001

    • Validation Against Gold Standard – ASTM Ontario Hydro Method

  • US EPA 301h Validation Study - 2004

    • Validation Against Gold Standard – ASTM Ontario Hydro Method

  • US Dept Of Energy Validation Study – 2004

  • US EPA 301h Validation – 2004 (FAMS Pending)

  • 40 CFR Part 75, Appendix K – March 2005


Us epa method 324 trap view

US EPA Method 324- Trap View -

Quality Control

Hg(0) + Hg(II)

PHg


Us epa 324 short term sampling

US EPA 324 – Short Term Sampling


Us epa 324 spiked trap

US EPA 324 – Spiked Trap


Us epa method 324 principles of operation

US EPA Method 324- Principles Of Operation -

  • High Purity Solid Sorbent

  • Captures All Species Of Gas Phase Mercury

    FSTM = PHg (Semi-Iso) + Hg(0) + Hg(II)

  • Variable Flow Rate (0.10 – 4.0 slpm)

  • Fast (5-15L in 15-30 min) Total Mercury Determination

  • No Temperature Constraints (> dew point to 1000F)

  • Highly Standardized Blank (0.25ng Hg +/- 0.25ng)

  • Trap Hg Capacity - 5% (of the mass of the trap)

    Hg(0) = 7mg/trap Hg(II) = 1mg/trap

    (Or a 1 Hour Test @ 233,000 ug Hg/m^3)


Us epa 324 sampling diagram

US EPA 324 Sampling Diagram


Us epa 324 probe design

US EPA 324 Probe Design


Us epa method 324 total hg sampling options

US EPA Method 324 - Total Hg Sampling Options -

  • Short Term Sampling:

    • 6 mm - EPA 324 Trap

    • 15 minute to 24 hour Sampling

  • Continuous Emission Monitoring:

    • 10 mm – EPA 324 Trap

    • Continuous Integrated Sampling

    • 1 Day to 12 Day Sampling


Flue gas adsorbent mercury speciation fams sample trap view

Flue Gas Adsorbent Mercury Speciation (FAMS) Sample Trap View


Us epa 324 and fams special features

US EPA 324 and FAMS Special Features

  • Fixed Probe – No traversing stack

    • Gas Phase Constituents Do not Behave Like Particles

    • Gas Phase Constituents Are Not Influenced By Gas Velocity

    • Traverse and Iso-Kinetics Designed For Capturing Particulate

    • Greater Than 95% Of Hg In Flue Gas Is Gas Phase

  • Total Hg – Keep Trap Above Dew Point

  • Speciated Hg – Keep Trap @ 95C +/- 5C

  • Maintain 0.25-0.50 Flow Rate


Us epa 324 and fams applications to sources

US EPA 324 and FAMS Applications To Sources

  • Coal-Fired Utilities

  • Coal-Fired Boilers

  • Municipal Solid Waste Incinerators

  • Cement Kilns

  • Steel Mills

  • Smelter/Roasters

  • Landfill Gas

  • Oil/Gas Refineries

  • Mercury Retort


Hg emission controls

Hg Emission Controls

  • Existing Hg Controls: Smelter/MSW Incinerator

  • Key To Hg Emission Control: Chemistry/Measurements

  • Coal-Fired Power Hg Emissions Control

    • Coal: Cleaning/Switching/Blending/Additives/Combustion

    • Co-Benefit APCD Mercury Removal

    • Enhancing Existing APCD Co-Benefit Hg Removal

    • Mercury-Specific Emission Controls

      • Activated Carbon Injection


Existing hg controls zn smelter hg control

Existing Hg Controls: Zn Smelter Hg Control

  • Calomel Process: Hg Removal Tower

    HgCl2 + Hg(0) - > Hg2Cl2

  • Inexpensive to operate

  • 40 foot Calomel Tower Lifetime = 10 yrs

  • 99% efficient at removing Hg


Hg tower polishing system

Hg Tower / Polishing System


Hg removal efficiency hg tower and polishing system

Hg Removal Efficiency – Hg Tower and Polishing System


Existing mercury controls activated carbon injection mw msw hg control

Existing Mercury Controls Activated Carbon Injection – MW/MSW Hg Control

  • * Source – US EPA Web Site (www.epa.gov)


Hg control in coal fired flue gas

Hg Control In Coal-Fired Flue Gas

Hg Emission Controls Governed By:

  • Coal Plant Design

  • Existing Air Pollution Control Device

  • Source Type: Type Of Coal Combusted


Hg control a function of hg chemistry

Hg Control: A Function Of Hg Chemistry

  • Particulate Bound Hg = PHg

    • < 5% Of Total Hg In Coal-Fired Flue Gas

  • Gaseous Oxidized Hg = Hg(II)

    • Water Soluble

    • Easily Removed By Existing FGD/SDA

  • Gaseous Elemental Hg = Hg(0)

    • Not Water Soluble

    • Requires Hg Removal System To Remove


Coal type hg speciation and concentration

Coal Type: Hg Speciation and Concentration

  • East: Bituminous

    ~ 60% Gaseous Hg(II) [Water Soluble]

    ~ 30% Gaseous Hg(0)

    ~ 30% Higher Mercury Than Western Sub Bit/Lignite

  • West: Subbituminous or Lignite

    ~ 20-30% Gaseous Hg(II) [Water Soluble]

    ~ 70-80% Gaseous Hg(0)


Co benefit hg removal

“Co-Benefit” Hg Removal

  • Existing APCD Not Designed For Hg Control

    • Selective Catalytic Reduction (SCR) = NOx Control

      < Shown To Convert Hg(0) to Hg(II) >

    • Flue Gas Desulfurization (FGD) = SOx Control

      < Removes Water Soluble Hg(II) >

    • ESP/Baghouse = Particulate Control

      < Removes Hg Bound To Fly Ash >


Hg removal from existing air pollution control devices apcd ave 35

Hg Removal From Existing Air Pollution Control Devices (APCD) ~ Ave = 35%

DOE NETL - Feeley, et al


Examining co benefit of existing apcd via us epa 324 and fams methods

Examining “Co-Benefit” Of Existing APCD – Via US EPA 324 and FAMS Methods

Flue Gas Sample Location #1

Flue Gas Sample Location #2

Flue Gas Sample Location #3

Flue Gas Sample Location #4

Flue Gas Sample Location #5

Stack

Pulverizer

Boiler

SCR

Air

Pre-heater

ESP

FGD

Coal

SBS

  • Fly Ash

  • B. Ash

  • Limestone

  • Gypsum

  • Supply H20

  • Scrubber H20

  • Scrubber Slurry


Co benefit examination fams and us epa 324 total hg across scr esp fgd

“Co-Benefit” Examination: FAMS And US EPA 324 Total Hg Across SCR/ESP/FGD


Co benefit examination fams method hg speciation across scr esp fgd

Co-Benefit Examination: FAMS Method Hg Speciation Across SCR/ESP/FGD

FGD

SCR/

ESP

U2


Co benefit examination hg removal efficiency assessment

“Co-Benefit” ExaminationHg Removal Efficiency Assessment


Coal and coal combustion modifications

Coal and Coal Combustion Modifications

  • Coal Cleaning ~ 33% Removal Before Combustion (EPRI)

  • Coal Switching (Low Hg Coals) ~ 66% Reductions (EPRI)

  • Coal Blending ~ 80% Reductions (EPRI)

    • Produce Higher Water Soluble Hg(II) – Removal By FGD/SDA

    • Bit. and Subbit. Mix – High Unburned Carbon = ESP/BH/FGD

  • Combustion Operation Parameters ~ 50-80% (EPRI)

    • Burn Coal Less Efficient – Unburned Carbon

      Economic Viability Of These Solutions Difficult To Quantify

      Plant-By-Plant Evaluation


Enhancing existing apcd co benefit hg reductions

Enhancing Existing APCD Co-Benefit Hg Reductions

25% Of Existing Coal-Fired Power Plants Have an FGD/SDA

  • Liquid Polymer Additive

  • Used Affectively For Hg Wastewater Removal

  • Oxidizes Elemental Hg And Retains – 1 step

  • Proof Of Concept: 15-25% Hg(0) Hg Removal

  • Application To Existing Wet Scrubber/FGD/ESP

    • No Additional Capital Equipment

    • Add Polymer To Reservoir/Add Water

  • Additionally Removes Suite Of Metals From Wastewater Down To 95% Reductions (As, Cd, Cr, Cu, Ni, Pb, Zn)


Coal fired hg specific controls activated carbon injection

Coal-Fired - Hg Specific ControlsActivated Carbon Injection

  • The Most Studied And Promising Technology

  • EPRI/DOE Funding and Research 2000-2007

  • Phase I and II (Full Scale Evaluations 2003-2007)

    • Activated Carbons -

    • Chemically Impregnated Carbons

    • Brominated Carbon

    • Regenerable Sorbents (Nobel Metals)

    • Silica Based Chemically Based Sorbents


Challenges of carbon injection in coal fired flue gas

Challenges Of Carbon Injection In Coal-Fired Flue Gas

Activity Carbon Injection (ACI)

  • Large Mass Of Carbon Required To Adsorb Hg

  • Limited Hg Capacity (3%)

  • Low Mercury Capture Efficiency (contact time)

  • Limited Temperature Operation Range (> 75C)

  • Only Operates Well In Dry Gasses

  • Mixed Carbon/Fly Ash Can Not Be Used For Cement

    Generally Not Commercially Viable

    In Application To Most Coal-Fired Power Plants


High capital equipment expense

High Capital Equipment Expense

Additional Capital Equipment - Retrofit

DOE NETL - Feeley, et al


Activated carbon injection lower capital equipment preserves valuable fly ash market

Activated Carbon Injection – Lower Capital Equipment – Preserves Valuable Fly Ash Market

DOE NETL - Feeley, et al


Conclusions

Conclusions

  • US EPA 324 and FAMS – Accurate, Inexpensive, Precision, High Data Generation Method

  • Family Of Activated Carbons:

    • Most Promising Technique To Date (Coal-Fired)

    • Phase II – Long Term Tests To Aid In Longevity of Sorbents

    • Most Promising Sorbent (Halogenated/Silica Based Sorbents)

  • Low Cost/Low Impact Injection System Preserves Fly Ash

  • Baseline Cost: $50K-$70K/lb Hg Removal

  • Goal To Reduce Cost By 25-50% Through 2010


Conclusions cont d

Conclusions (Cont’d)

  • Most Emissions Sources Don’t Know Their Source Hg Concentrations or Emissions With Confidence

  • Recommend Hg Baseline Study Prior Hg Control Decisions

  • “Co-Benefit” Hg Removal From Existing APCD

    • Average Hg Removal Is 30% Across Industry

    • Recent Tests: SCR/ESP/FGD Removes 85%

    • Other Industry Specific Show 99% Hg Removal

  • Hg Specific Controls Are In Phase II Assessment

    • “Long Term Effectiveness Of Controls Uncertain

    • Economy Of Hg Specific Controls Uncertain

    • Phase III Testing DOE/EPRI/EPA 2005-2010


Hg monitoring and monitoring westar fall meeting

Hg Monitoring And Monitoring

WESTAR Fall Meeting

Mercury and Air Quality – Sources, Effects, and Controls

San Diego, California

September 22, 2005

Bob Brunette

Frontier Geosciences Inc

414 Pontius Avenue North

Seattle, Washington 98109

[email protected]

206 957 1461


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