chlorine and bromine in coals and their influence on
TRANSCRIPT
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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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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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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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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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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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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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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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
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10
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30
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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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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
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1
2
3
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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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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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(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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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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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 ?