Native Halogens in Coals from USA ... - Vosteen Consulting

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



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




• US coals

• Chinese coals




• 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




• US coals

• Chinese coals




• 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




• US coals

• Chinese coals




• 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




• US coals

• Chinese coals




• Conclusions

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Agenda




• US coals

• Chinese coals




• Conclusions

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Agenda

• Precombustion Bromide Addition (Alstom Power KNXTM Technology)

• Global bromine transfer


• US coals

• Chinese coals




• Conclusions

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Agenda




• US coals

• Chinese coals




• 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?

Native Halogens in Coals from USA ... - Vosteen Consulting

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