chlorine and bromine in coals and their influence on

Prof. Dr.-Ing. Bernhard W. Vosteen, Vosteen Consulting GmbH, Köln

MBA Tim C. Hartmann, ALSTOM Power Inc., Knoxville, TN M. Sc. Mark S. Berry, PE, Southern Company Services, Birmingham, AL

http://www.vosteen-consulting.de

Berliner Planungs- und Imissionsschutz-Konferenz Am 19. Und 20. November 2012

Hotel Berlin am Lützowplatz

Chlorine and Bromine in Coals and their Influence on Mercury Removal from Flue Gases

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VOSTEEN Consulting

Agenda

•  Introduction: BBA today and 10 years ago

•  EPA’s MATS as issued on December 21, 2011

•  US Coals (Mercury, Chlorine, Bromine, Sulfur)

•  Southern Company – Wet Mercury Capture at Plant Miller

•  Alstom Power – Wet Mercury Capture at Plant WE Plaesant Prairie

•  Dry Mercury Capture

•  US EPRI Balance of Plant Report August 2012

•  Outlook (Cooperation Vosteen/STEAG/AE&E)

•  Conclusions

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Bromine Based Mercury Abatement

German Patent DE 10 233 173 (assigned to CURRENTA GmbH & Co. OHG)

European Patent EC 1 386 655

(assigned to CURRENTA GmbH & Co. OHG)

US Patent 6,878 358 (assigned to Vosteen Consulting GmbH)

Ca Patent 243547

(assigned to Vosteen Consulting GmbH)

In 2004, CURRENTA GmbH & Co oHG granted a worldwide exclusive license

and transferred the North American Patents to Vosteen Consulting GmbH

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VOSTEEN Consulting

ALSTOM Power - Environmental Control Systems,

Knoxville/TN, USA, KNXTM Mercury Control Technology

as Tradename of ALSTOM Power Inc. Exclusive license for USA and Canada

2500 MWe in commercial application since 2010

Electric Power Research Institute,

Palo Alto/CA, USA, Limited R&D License for the States

Southern Company Services, Inc. Birmingham/AL, USA,

License for units owned by Southern Company

Licensees of Vosteen Consulting GmbH in North America

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VOSTEEN Consulting VOSTEEN Consulting Precombustion Bromide Addition to Coal or Boiler Bromide Addition (BBA) – Today a main topic at any large US Conference on Air Pollution Control

Session C2 at EUEC 2012 in Phoenix AZ: “Hg Control Demonstrations & Bromine” sponsored and chaired by Vosteen Consulting GmbH

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VOSTEEN Consulting VOSTEEN Consulting

Today 54 US Power Stations are applying Precombustion Bromide Addition commercially

Electric Power Research Institute (EPRI) at Mega Symposium in Baltimore, August 21 – 23, 2012

Source: Katherine Dombrowski, Katie Arambasick (URS), Ramsay Chang (EPRI), Corey Tyree (Souther Company): “Balance of Plant Effects of Bromide Addition for Mercury Control”, paper # 93,

Power Plant Air Pollutant Control MEGA Symposium, Baltimore MD, August 21-23, 2012

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Source: Vosteen, Kanefke et al.: „Mercury-Related Chemistry in Waste Incineration and Thermal Process Flue Gases“, Air Quality (VI) Conference, Arlington, VA, Sept. 2003

0

20

40

60

80

100

0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000Clges- bzw. alternativ Brges-Gehalt im Kesselrohgas [mg/m? i. N. tr.]

Hg m

et-S

pezi

esan

teil

im K

esse

lrohg

as

nach

Wäs

che

[Hg m

et/H

g ges

in G

ew.%

] Hgmet/Hgges-Speziesanteil nach primärer Hg-Chlorierung in SVA

(Messwert vom 26.11.2001)

Hgmet/Hgges-Speziesanteil nach primärer Hg-Chlorierung

und nachfolgendersekundärer Hg-Bromierung in SVA

(Messwerte vom 26.11.2001)

Bromine > 25 times more effective for Hgmet oxidation than chlorine, in waste incineration as well as in coal combustion

(BAYER patent applications pending world wide)

Hg Oxidation

by Bromine (HWC)

Hg Oxidation

by Chlorine (HWC)

Brtotal or Cltotal in boiler flue gas (mg/Nm3 dry)

Hgm

et/H

gtot

al (

wei

ght-%

)

Air Quality (VI) Conference, Arlington, VA, Sept. 2003

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KNXTM Coal Additive – drums and pumps in a full scale test

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VOSTEEN Consulting

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Agenda

•  Introduction

•  EPA’s MATS as issued on December 21, 2011

•  US Coals (Mercury, Chlorine, Bromine, Sulfur)

•  Southern Company – Wet Mercury Capture at Plant Miller

•  Alstom Power – Wet Mercury Capture at Plant WE Plaesant Prairie

•  Dry Mercury Capture

•  US EPRI Balance of Plant Report August 2012

•  Outlook (Cooperation Vosteen/STEAG/AE&E)

•  Conclusions

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VOSTEEN Consulting

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VOSTEEN Consulting

Agenda

•  Introduction

•  EPA’s MATS as issued on December 21, 2011

•  US Coals (Mercury, Chlorine, Bromine, Sulfur)

•  Southern Company – Wet Mercury Capture at Plant Miller

•  Alstom Power – Wet Mercury Capture at Plant WE Plaesant Prairie

•  Dry Mercury Capture

•  US EPRI Balance of Plant Report August 2012

•  Outlook (Cooperation Vosteen/STEAG/AE&E)

•  Conclusions

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USGS CoalQual data base - data excerpt from Open-File Report 94-177 (1994) 5000 samples - evaluated by Vosteen Consulting

with courtesy of Prof. Dr. Belkin, Febr. 20, 2010

Powder River Basin

Northern, Central and Southern Appalachian

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PRB

Only low mercury coals? (e.g. PRB with 0.1 ppm Hg dry)

What about the other coals - in the long run?

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Source: Allan Kolker and Jeffrey C. Quick, U.S. Geological Survey and Utah Geological Survey: “Geologic Controls on Halogens in Coal”, MEC 9 - Mercury Emissions fromCoal, St. Petersburg (Russia), May 2012

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Source: Allan Kolker and Jeffrey C. Quick, U.S. Geological Survey and Utah Geological Survey: “Geologic Controls on Halogens in Coal”, MEC 9 - Mercury Emissions fromCoal, St. Petersburg (Russia), May 2012

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VOSTEEN Consulting

Source: Allan Kolker and Jeffrey C. Quick, U.S. Geological Survey and Utah Geological Survey: “Geologic Controls on Halogens in Coal”, MEC 9 - Mercury Emissions fromCoal, St. Petersburg (Russia), May 2012

VOSTEEN Consulting

Low Halogen Coals as Subbituminous PRB Coal and Lignite and as imported coals from Columbia, also fired in USA

Cl

Br

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Agenda

•  Introduction

•  EPA’s MATS as issued on December 21, 2011

•  US Coals (Mercury, Chlorine, Bromine, Sulfur)

•  Southern Company – Wet Mercury Capture at Plant Miller

•  Alstom Power – Wet Mercury Capture at Plant WE Plaesant Prairie

•  Dry Mercury Capture

•  US EPRI Balance of Plant Report August 2012

•  Outlook (Cooperation Vosteen/STEAG/AE&E)

•  Conclusions

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Source: M. S. Berry and B. W. Vosteen: „Bromine Injection Technology Demonstrations at Plant Miller for Removing Vapor Phase Mercury “, 12th ICESP in Nuremberg, May 2011

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Source: M. S. Berry and B. W. Vosteen: „Bromine Injection Technology Demonstrations at Plant Miller for Removing Vapor Phase Mercury “, 12th ICESP in Nuremberg, May 2011

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Source: M. S. Berry and B. W. Vosteen: „Bromine Injection Technology Demonstrations at Plant Miller for Removing Vapor Phase Mercury “, 12th ICESP in Nuremberg, May 2011

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Source: M. S. Berry and B. W. Vosteen: „Bromine Injection Technology Demonstrations at Plant Miller for Removing Vapor Phase Mercury “, 12th ICESP in Nuremberg, May 2011

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Source: M. S. Berry and B. W. Vosteen: „Bromine Injection Technology Demonstrations at Plant Miller for Removing Vapor Phase Mercury “, 12th ICESP in Nuremberg, May 2011

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Agenda

•  Introduction

•  EPA’s MATS as issued on December 21, 2011

•  US Coals (Mercury, Chlorine, Bromine, Sulfur)

•  Southern Company – Wet Mercury Capture at Plant Miller

•  Alstom Power – Wet Mercury Capture at Plant WE Plaesant Prairie

•  Dry Mercury Capture

•  US EPRI Balance of Plant Report August 2012

•  Outlook (Cooperation Vosteen/STEAG/AE&E)

•  Conclusions

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VOSTEEN Consulting VOSTEEN Consulting

License granted in 2008 to WE Power Stations Pleasant Prairie (2 x 600 MWe Units with SCR, ESP, WFGD in commercial

opperation since January 1st, 2010)

2 x 600 MWe

Base Load (24 hours/day)

PRB coal

2 x 315 tons/hour 0.11 ppm Hg

KNX (as CaBr2)

25 ppm Br on coal

Hgtotal at stack < 1 µg/dscm (both units)

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July 29h, 2008 September 16th, 2008 date

Power Station WE Pleasant Prairie with SCR, ESP, WFGD 25 ppm Br per Coal only, SCR in service with NH3

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Agenda

•  Introduction

•  EPA’s MATS as issued on December 21, 2011

•  US Coals (Mercury, Chlorine, Bromine, Sulfur)

•  Southern Company – Wet Mercury Capture at Plant Miller

•  Alstom Power – Wet Mercury Capture at Plant WE Plaesant Prairie

•  Dry Mercury Capture

•  US EPRI Balance of Plant Report August 2012

•  Outlook (Cooperation Vosteen/STEAG/AE&E)

•  Conclusions

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Messung

von

Hgges und Hgmet

Messung

von

Hgges und Hgmet

Eindosierung von HgCl2 und NaCl

Spiking with

HgCl2 and NaBr

CEMs for

Hgtotal and Hgmet

CEMs for

Hgtotal

bituminouscoal

bituminouscoal

air

air

FGD

Source: Vosteen, Nolte et al.: „Chlorine- and bromine-enhanced Hg sorption on ESP fyl ash from a coal-fired slag-tap boiler and on cement raw meal“, VDI Seminar 431802, September 29 - 30, 2003 in Duesseldorf (Germany)

Multi-stage APC System – APC Type: dry/wet

BAYER/Currenta GmbH& Co oHG in Uerdingen: PC-fired Boiler (100 MWtherm) Co-Combustion of Industrial Sewage Sludges

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Fire side bromide addition (internal bromination) is improving Hg-adsorption at fly ash UBC by the factor 2,5

170 °C

Hgtotal-concentration in flue gas behind ESP (µg/Nm3 dry)

Source: Vosteen, Nolte et al.: „Chlorine- and bromine-enhanced Hg sorption on ESP flyash from a coal-fired slag-tap boiler and on cement raw meal“, VDI Seminar 431802, September 29 - 30, 2003 in Duesseldorf (Germany)

Sorption isothermes of the ESP-fly ash of high LOI (22,3 % UBC)during test runs in April, 2002

with and without fire side bromide addition to boiler

0

10

20

30

40

50

60

0 20 40 60 80 100 120 140 160 180 200

Hgtotal-concentration in flue gas behind ESP [!g /Nm? dry]

Hg-

conc

entr

atio

n in

ESP

-fly

ash

[mg/

kg]

no bromide addition to boiler

with bromide addition to boiler

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Sharon Sjostrom: „Mercury Control for PRB and PRB/Bituminous Blends“, presented at EUEC, Tucson/Arizona, January 24, 2006

1 lb/MMacf = 16 mg/m3

Meramec

300 MWe, PRB

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VOSTEEN Consulting

Sharon Sjostrom: „Mercury Control for PRB and PRB/Bituminous Blends“, presented at EUEC, Tucson/Arizona, January 24, 2006

1 lb/MMacf = 16 mg/m3 , 290 °F = 143.4 °C

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Richard LaFlesh et al. of Alstom Power Inc. : “Progress Report on Mercury Control Retrofit at the Colstrip Power Station“, Power Plant Air Pollutant Control “MEGA Symposium”, August 30 - September 2, 2010, Baltimore MD (USA) - Paper # 91

Alstom‘s Mer-CureTM & KNX TM

Portable Mer-CureTM Test Trailer

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Synergistic Effect of KNXTM & Mer-CureTM

500 MW PRB with Particulate Scrubber

0

1

2

3

4

5

6

7

8

Baseline Mer-Cure @ 1 lb/MACF Mer-Cure & KNX

Stac

k Hg

Lb/

TBtu

55% incremental performance improvement

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Richard LaFlesh et al. of Alstom Power Inc. : “Progress Report on Mercury Control Retrofit at the Colstrip Power Station“, Power Plant Air Pollutant Control “MEGA Symposium”, August 30 - September 2, 2010, Baltimore MD (USA) - Paper # 91

Colstrip Power Station Units U1 – U4 (2,200 MWe) fired with PRB coal from the Rosebud Mine

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Agenda

•  Introduction

•  EPA’s MATS as issued on December 21, 2011

•  US Coals (Mercury, Chlorine, Bromine, Sulfur)

•  Southern Company – Wet Mercury Capture at Plant Miller

•  Alstom Power – Wet Mercury Capture at Plant WE Plaesant Prairie

•  Dry Mercury Capture

•  US EPRI Balance of Plant Report August 2012

•  Outlook (Cooperation Vosteen/STEAG/AE&E)

•  Conclusions

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VOSTEEN Consulting VOSTEEN Consulting

Source: Katherine Dombrowski, Katie Arambasick (URS), Ramsay Chang (EPRI), Corey Tyree (Souther Company): “Balance of Plant Effects of Bromide Addition for Mercury Control”, paper # 93,

Power Plant Air Pollutant Control MEGA Symposium, Baltimore MD, August 21-23, 2012

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VOSTEEN Consulting

(1) EPRI Study (Status August 2012)

Source: Katherine Dombrowski, Katie Arambasick (URS), Ramsay Chang (EPRI), Corey Tyree (Souther Company): “Balance of Plant Effects of Bromide Addition for Mercury Control”, paper # 93,

Power Plant Air Pollutant Control MEGA Symposium, Baltimore MD, August 21-23, 2012

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(2) EPRI Study (Status August 2012)

Source: Katherine Dombrowski, Katie Arambasick (URS), Ramsay Chang (EPRI), Corey Tyree (Souther Company): “Balance of Plant Effects of Bromide Addition for Mercury Control”, paper # 93,

Power Plant Air Pollutant Control MEGA Symposium, Baltimore MD, August 21-23, 2012

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VOSTEEN Consulting

Agenda

•  Introduction

•  EPA’s MATS as issued on December 21, 2011

•  US Coals (Mercury, Chlorine, Bromine, Sulfur)

•  Southern Company – Wet Mercury Capture at Plant Miller

•  Alstom Power – Wet Mercury Capture at Plant WE Plaesant Prairie

•  Dry Mercury Capture

•  US EPRI Balance of Plant Report August 2012

•  Outlook (Cooperation Vosteen/STEAG/AE&E)

•  Conclusions

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Source: Thomas Lauer und Thomas Riethmann:“Untersuchungen zur Quecksilberabscheidung aus Rauchgasen und Nebenprodukten in Steinkohlekraftwerken”, VDI-Wissensforum Quecksilber-Emissionen, 26.-27. September 2012, Frankfurt

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Source: Michael Kramer und Bernhard W. Vosteen: “Quecksilber im Wäscher – Was dann?”, VDI-Wissensforum Quecksilber- Emissionen, 26.-27. September 2012, Frankfurt

Andritz Energy & Environment (AE&E) – a Licensee and Partner of Vosteen Consulting GmbH in Europe

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VOSTEEN Consulting

Agenda

•  Introduction

•  EPA’s MATS as issued on December 21, 2011

•  US Coals (Mercury, Chlorine, Bromine, Sulfur)

•  Southern Company – Wet Mercury Capture at Plant Miller

•  Alstom Power – Wet Mercury Capture at Plant WE Plaesant Prairie

•  Dry Mercury Capture

•  US EPRI Balance of Plant Report August 2012

•  Outlook (Cooperation Vosteen/STEAG/AE&E)

•  Conclusions

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Conclusions

  The KNXTM technology has been successfully operated for over 2 years.

  The effectiveness of CaBr2 and its rapid response to fuel Hg

variations has been demonstrated in wet and dry APC systems.   The combination of pre-combustion bromide addition and normal

non-brominated activated carbon injection (ACI) reliably controls Hg emissions with variable load and fuel Hg content.

  Many “free riders”

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Preferred approach towards new patents - promising even in case of no inventive height

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Agenda

Questions please ?