native halogens in coals from usa ... - vosteen consulting
TRANSCRIPT
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Native Halogens in Coals from USA, China, and Elsewhere -
Low Chlorine Coals Need Bromide Addition for Effective Mercury Capture
Bernhard W. Vosteen, Vosteen Consulting GmbH,
Hermann Winkler, Evonik Steag GmbH,
Mark S. Berry, Southern Company Services, Inc.
VDI Technikforum
“Messung und Minderung von Quecksilber-Emissionen”
September 29 - 30, 2010, Park Inn Mannheim
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Agenda
• Precombustion Bromide Addition (Alstom Power in USA, AE&E in Europe)
• Global bromine transfer and distribution in nature
• Native chlorine and bromine in coals
• US coals
• Chinese coals
• South African coals
• United Kingdom coals
• Mercury in coals from USA and China
• Conclusions
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J. M. Pacyna et al.: http://amap.no/Resources/HgEmissions/
Global Anthropogenic Emissions of Mercury to the Atmosphere, 2000:
2269 tons per year
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Precombustion Bromide Addition
as covered by the validUnited States Patent US 6,878,358
Patents granted also in
Australia, Canada, Europe, Germany, Japan,
Korea, South Africa
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Source: Vosteen 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 5000
Clges- bzw. alternativ Brges-Gehalt im Kesselrohgas [mg/m? i. N. tr.]
Hg
met-S
pezie
san
teil i
m K
esselr
oh
gas
na
ch
Wä
sc
he
[H
gm
et/H
gg
es i
n G
ew
.%] Hgmet/Hgges-Speziesanteil
nach primärer Hg-Chlorierung in SVA
(Messwert vom 26.11.2001)
Hgmet/Hgges-Speziesanteil
nach primärer Hg-Chlorierung
und nachfolgender
sekundärer 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)
Hg
me
t/H
gto
tal
(weig
ht-
%)
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ALSTOM Power - Environmental Control Systems,Knoxville/TN, USA,
KNXTM Mercury Control Technologyas 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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EGLV – Zentrale Schlammbehandlung Bottrop
2 Stationäre Wirbelschichtfeuerungen
für die Verbrennung von Klärschlämmen
Annwendung von NaBr seit 2004
Falko Lehrmann, Günter Schwabe
Stadt Karlsruhe – Klärwerk Neureut
2 Stationäre Wirbelschichtfeuerungen
für die Verbrennung von KlärschlämmenAnwendung von NaBr and PRAVO® seit 2007
Martin Maurer, Roland Milz
Lizenznehmer der Vosteen Consulting GmbH in Deutschland
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Lizenznehmer der Vosteen Consulting GmbH in Europa und China
einschließlich ihrer Töchter
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License granted in 2008 to WE Pleasant Prairie Unit 1 and Unit 2
(2 x 600 MWe with SCR, ESP, WFGD) -
In commercial operation since January 1, 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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License granted in 2008 to WE Pleasant Prairie (2 x 600 MWe Units)with SCR, ESP, WFGD - In commercial opperation since January 1, 2010
Test July - September 2008, with 25 ppm Br per PRB-coal,
while SCR was in service with NH3
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TABLE 1. - KNXTM
Reference Base
OWNER FACILITY /
STATION
UNIT
ID
Size
(MW) AQCS
KNXTM
Startup
We Energies Pleasant Prairie 1 605 SCR / ESP / WFGD 1/1/10
We Energies Pleasant Prairie 2 605 SCR / ESP / WFGD 1/1/10
MDU Resources Lewis & Clark 1 57 WFGD 1/1/10
NN NN 2 511 ESP 1/1/10
NN NN 4 330 ESP 1/1/10
NN NN 5 380 ESP 1/1/10
SRP Coronado 1 389 ESP / WFGD TBD
SRP Coronado 2 384 ESP / WFGD TBD
SRP Navajo 1 750 ESP / WFGD TBD
SRP Navajo 2 750 ESP / WFGD TBD
SRP Navajo 3 750 ESP / WFGD TBD
Licensed 5511
Operating 2488
Status 2010, courtesy of Alstom Power ECS
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Source: Michael Rini and Bernhard Vosteen, MEC6 in Ljubljana, Slovenia (April 23, 2009)
CaBr2
Option:
KNX technology
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Source: Michael Rini and Bernhard Vosteen, MEC6 in Ljubljana, Slovenia (April 23, 2009)
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Source: Richard LaFlesh et al., MEGA Symposium in Baltimore, USA (August 31 - September 2,
2010)
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Agenda
• Precombustion Bromide Addition (Alstom Power in USA, AE&E in Europe)
• Global bromine transfer and distribution in nature
• Native chlorine and bromine in coals
• US coals
• Chinese coals
• South African coals
• United Kingdom coals
• Mercury in coals from USA and China
• Conclusions
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Vertical Distribution of Bromine Compounds
CH3Br is photochemically decomposed in the atmosphere (reaction with hydroxyl radicals (OH))
CH3Br is produced by phytoplankton (as algae), zooplankton and bacteria.
CH3Br undergoes biological degradation and hydrolysis (forming Bromide)
Ocean acts as both a source and sink for CH3Br
Source: Shari Yvon-Lewis, NOAA Atlantic Oceanographic and Meteorological Laboratory, USA
http://www.igac.noaa.gov/newsletter/19/yvon-lewis.php
77,000 Mg/year Uptake Emissions 56,000 Mg/year
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Thermohalin oceanic tranport
(driven by density differences caused by temperature and salt content)
Horizontal Distribution of Bromine Compounds
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Source: Z.E. Jolles:
Monograph „Bromine and its compounds“,
London (1966), page 4
Meteorites analysed for bromine show a slightly higher
concentration than rocks (... mainly in form of bromides)
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The Bulgarian power plants are using insignificant proportions of the occasionally Br-rich low-rank coals,
which might be considered as waste coals on behalf of the extreme Br-content
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Agenda
• Precombustion Bromide Addition (Alstom Power in USA, AE&E in Europe)
• Global bromine transfer and distribution in nature
• Native chlorine and bromine in coals
• US coals
• Chinese coals
• South African coals
• United Kingdom coals
• Mercury in coals from USA and China
• 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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Agenda
• Precombustion Bromide Addition (Alstom Power in USA, AE&E in Europe)
• Global bromine transfer and distribution in nature
• Native chlorine and bromine in coals
• US coals
• Chinese coals
• South African coals
• United Kingdom coals
• Mercury in coals from USA and China
• Conclusions
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Source: S. Wang and Y. Wu: Reducing Mercury Emissions from Coal - Combustion in the
Energy Sector, MEC7 International Experts Workshop, Glasgow, June 2010
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Regulations on emission of SO2, NOx and dust given -
different limits for plant categogies I, II, III
Regulations on Hg still not given - but in focus
Meeting in Beijing (October, 2008) - Prof. Vosteen presenting Boiler Bromide Addition
to Yonghong Li, Having Li, Ministry of Environmental Protection, and Prof. Dr. Lei
Duan from Tsinghua University
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Vosteen Consulting GmbH in China - together with
AE&E, Raaba (Austria)
and affiliates as AE&E China
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Total: 120,000 MWe
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Agenda
• Precombustion Bromide Addition (Alstom Power in USA, AE&E in Europe)
• Global bromine transfer and distribution in nature
• Native chlorine and bromine in coals
• US coals
• Chinese coals
• South African coals
• United Kingdom coals
• Mercury in coals from USA and China
• Conclusions
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Agenda
• Precombustion Bromide Addition (Alstom Power in USA, AE&E in Europe)
• Global bromine transfer and distribution in nature
• Native chlorine and bromine in coals
• US coals
• Chinese coals
• South African coals
• United Kingdom coals
• Mercury in coals from USA and China
• Conclusions
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Agenda
• Precombustion Bromide Addition (Alstom Power KNXTM Technology)
• Global bromine transfer
• Native chlorine and bromine in coals
• US coals
• Chinese coals
• South African coals
• United Kingdom coals
• Mercury in coals from USA and China
• Conclusions
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Agenda
• Precombustion Bromide Addition (Alstom Power in USA, AE&E in Europe)
• Global bromine transfer and distribution in nature
• Native chlorine and bromine in coals
• US coals
• Chinese coals
• South African coals
• United Kingdom coals
• Mercury in coals from USA and China
• Conclusions
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Conclusions:
Precombustion Bromide Addition has a strong potential to
greatly improve mercury oxidation and reduce coal-born
mercury emissions, not only in USA, but also in China, South
Africa and elsewhere.
Acknowlegdement
The authors want to thank Prof. Harvey E. Belkin, PhD (USA)
and Prof. Dr. Stanislav V. Vassilev (Bulgaria) for coal data
exchange and helpful discussions.
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Thanks for Your Attention.
Questions?