consulting gmbh vosteen€¦ · 2010 aiche spring meeting san antonio, tx, march 21 - 25, 2010...

Boiler Bromide Addition -

A Survey On Bromine Based Mercury Abatement

From Flue Gases at Coal Combustion and Waste Incineration Plants

Prof. h.c. Dr.-Ing. Bernhard W. Vosteen,

Vosteen Consulting GmbH, Cologne (Germany)

VOSTEEN Consulting GmbH Thermal Engineering and Environmental Protection

http://www.vosteen-consulting.de

2010 AICHE Spring Meeting

San Antonio, TX, March 21 - 25, 2010

Session 14: Mercury and Other Trace Elements in Fuel:

Emissions, Control, Measurement

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Agenda

• Introduction

• Industrial Process Development in 2000 - 2002

• Complementary Bench Scale Laboratory Tests in 2002 - 2006

• Fundamental Insights Presented at AQ (IV) in September 2003

• Mercury and Inherent Halogens in US Coals

• Large Scale Applications in Power Generation

• at Coal-fired Units with Wet Flue Gas Cleaning

• Outlook - Bromide Distribution - BOP

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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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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)

Patents granted also in

Australia, Canada, Korea, Japan, USA, Southafrica,

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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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Preferred approach towards new patents -

promising even in case of no inventive height

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Agenda

• Introduction








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BAYER AG - CURRENTA GmbH & Co. OHG, Germany

... speaking about Hazardous Waste Combustion in 2000

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1

8 9

10

11

12

2

3

4 5

7

16

13

1415

176

Fig. 1

1st Successful Industrial Applications, working since 2001

Hazardous Waste Combustion (HWC)

(4 plants with 30,000. .. 80,000 Nm /h dry)

of CURRENTA GmbH & Co OHG in Leverkusen, Dormagen and Uerdingen

Hg-spiking

(continuous)

Hg-spiking

(continuous)

Hg-CEMs

Hg-spiking

(discontinuous)

Quench

Hg-spiking

(continuously)

Hg-spiking

(continuously)

Hg-CEMs

Hg-SCEM

Hg-spiking

(discontinuously)

Quench

Process Developement with CURRENTA GmbH & Co OHG

(Project leader: Prof. Vosteen)

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Dosierbehälter mit

HCl- stabilisierter

HgCl2- Lösung

Schlauchpumpe

zum Dosieren der

HgCl2- Lösung

wassergekühlte

Dosierlanze am

Kopf der NBK

Spiking Mercury

Continuously and Discontinuously

Pump HgCl2 diluted

Injection-

lance

at top of after burning chamber at bottom of after burning chamber

100 … 20,000 g/Nm dry 500,000 … 80 Mio g/Nm dry

„Hg-bombs“ -> „Hg-clouds“

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Hg Oxidation

by Bromine (HWC)

Hg Oxidation

by Chlorine (HWC)

Hgmet/Hgtotal in the boiler flue gas

versus its Cltotal or Brtotal content

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

Hg

me

t/H

gto

tal

(weig

ht-

%)

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How to prevent emission peaks caused by “hidden mercury” ?

with courtesy of Dr.-Ing. Rico Kanefke

Source: Dr.-Ing. Rico Kanefke, CURRENTA GmbH & Co. OHG |

Storage Tank

CaBr2-Solution

CaBr2 Dosing

Lance at ABC

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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

bituminous

coal

bituminous

coal

air

air

FGD

Further Industrial Demonstration in 2008

PC-fired Wet Bottom Boiler (100 MWtherm; 140,000 Nm /h dry)

of CURRENTA GmbH & Co OHG in Uerdingen

ESP, limestone based wet FGD, tail end DeNOx-SCR

NaBr

NaBr

HgCl

Large Scale Tests at Slag Tap Boiler of Bayer AG - Currenta

in Uerdingen (Germany) in 2001 and 2002

Analysis of dry Mercury Capture by Adsorption at ESP Flyash / UBC

Fly ash samples for

fractional laboratory analysis

Source: Vosteen, Nolte et al.: „Chlorine- and bromine-enhanced Hg sorption on ESP fl ash from a coal-fired slag-tap

boiler and on cement raw meal“, VDI Seminar 431802, September 29 - 30, 2003 in Duesseldorf (Germany)

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

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

-co

nc

en

tra

tio

n i

n E

SP

-fly

as

h

[mg

/kg

]

no bromide addition to boiler

with bromide addition to boiler

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)

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Agenda

• Introduction








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Dosing of highly diluted Br2

Thermostated Annular Gap

Reactor

Dosing of Hg(0)

Hovacal Evaporator for HBr

Dosing of Hg2+

CEMs for Hg(0) and Hgtotal

Annular Gap Reactor

Study of Gas Phase Bromination

Diploma Thesis Martin Ziegler (2002)with Prof. Heinz Koeser and Prof. Bernhard Vosteen

at Martin-Luther University Halle-Wittenberg

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Gas Mixing and Gas Analyzer Station

Prof. Heinz Koeser and Prof. Bernhard Vosteen

at Martin-Luther University Halle-Wittenberg (Germany)

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Molar ratio Br2 / Hg(0) (mol/mol)

Elemental mercury bromination by Br2 at 150 °C in humidified air (20 vol.-% H2O, 21 vol.-% O2) without SO2

Elemental mercury bromination by Br2 at 450 °C in humidified air (20 vol.-% H2O, 21 vol.-% O2) without SO2

Merc

ury

oxid

ation r

ate

(%

)

Br2

without SO2

Elemental mercury (100 μg/Nm3 dry) brominated by Br2 at 150 °C and 450 °C

in humidified air (20 vol.-% H2O, 21 vol.-% O2) without SO2 present

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Molar ratio Br2 / Hg(0) (mol/mol)

Merc

ury

oxid

ation r

ate

(%

)

Br2 without SO2

Br2 with SO2

50 ... 100 mg SO2/Nm3 dry

Elemental mercury (100 μg/Nm3 dry) brominated by Br2 at 150 °C and 450 °C

in humidified air (20 vol.-% H2O, 21 vol.-% O2) without SO2 and with SO2 present

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Molar ratio Br2 / Hg(0) respectively 2HBr/Hg(0) (mol/mol)

Merc

ury

oxid

ation r

ate

(%

)

Br2 and HBr

with SO2

50 ... 100 mg SO2/Nm3 dry

Comparison with Tests at HWC (Vosteen, Kanefke in 2000):

NaBr added at 1100 °C, with 2200 mg SO2/Nm3 dry

Elemental mercury (100 μg/Nm3) brominated by Br2 and HBr at 150°C - 650 °C in

humidified air (20 vol.-% H2O, 21 vol.-% O2) without SO2 and with SO2 present

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commercial SCR-DeNOx-catalysts

0 - 0,53 - 2,5 - 4,5 Ma.-% V2O5

ca. 15 g … 31 g

4 x 4 channels

6,5 … 13 cm long

2 x 0,5 g

Einsatz für

Glasringspaltreakto

r

0 - 2000 g Hg/Nm

crashed

Study of Catalysed Mercury Oxidation

Sandra Straube (2004)with Prof. Heinz Koeser and Prof. Bernhard Vosteen

at Martin-Luther University Halle-Wittenberg

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W abenkata lysator (4 x 4 W aben , 12 ,5 cm )

2 ,5 G ew .-% V 2O 5

A V = 10 m /h

160 g H gel

/N m ?

0,5 m g/N m ? H B r + S O 2

0

10

20

30

40

50

60

70

80

90

100

Oxid

ati

on

sg

rad

nach

Kat

%

0 ppm SO 2

70 ppm SO 2

700 ppm SO 2

260 °C 290 °C 320 °C 400 °C

Honeycomb catalyst

4 x 4 canals, 12.5 cm long

2,5 weight-% V2O5, AV = 10 m/h

temperature [°C]

achie

ved

oxid

ation

rate

[% o

f H

gtota

l]

Laboratory tests with humid air, 160 g Hgel/Nm dry and only 0.5 mg HBr/Nm3 added

(no NH3 and no NOx)

In contrast to Hg-chlorination, only small influence of temperature and SO2 on enhanced Hg-bromination at SCR catalyst

presented

at EUEC 2006

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Agenda

• Introduction








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Chlorine less effective in Hg-oxidation

because Cl2/Cltotal << 1

(e.g. < 4 % in HWC and < 1 % in coal combustion)

SO2 is consuming Cl2 during boiler passage

Source: Vosteen et al.: „Mercury-Related Chemistry in Waste Incineration and Thermal Process Flue Gases“ (Poster)

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

Chlorine Enhanced Hg-Oxidation

Main global reactions

4 HCl + O2 2 H2O + 2 Cl2 Chlorine-Deacon-Reaction

SO2 + Cl2 + H2O SO3 + 2 HCl Chlorine-Griffin-Reaction

SO2 + O2 SO3 SO2/SO3-Konversion

Hg + Cl2 HgCl2 direct Hg-Chlorination*)

individual

Stoptemperatures

680 °C

< 380 °C (boiler exit)

900 °C

580 °C …… 480 °C

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Bromine highly effective in Hg-oxidation

because Br2/Brtotal 1

SO2 is not consuming Br2 during boiler passage



Bromine Enhanced Hg-Oxidation

Main global reactions (hypothesis Vosteen)

4 HBr + O2 2 H2O + 2 Br2 Bromine-Deacon-Reaction

SO2 + Br2 + H2O SO3 + 2 HBr Bromine-Griffin-Reaction *)

SO2 + O2 SO3 SO2/SO3-Konversion

Hg+ Br2 HgBr2 direct Hg-Bromination*)

*) The reaction does not procede in the upper boiler temperature range,

but at temperatures < 100 °C , e.g. downstream in WFGD

RG < 0

RG >>> 0

RG << 0

RG << 0

Thermodynamics

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Vosteen‘s Stoptemperature Method- to describe kinetics in relation to equilibrium thermodynamics - is based on experiments

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Halogenation of Mercury by Molecular Halogens (if present)

Evaluation of the Gibbs Free Energy of Reaction ( based on Nist, data Chase)

Non-realistic assumptions lead far away from reality -

though thermodynamic calculations behind may be correct.

Prof. Dr. Bernhard W. Vosteen, November 2009

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Agenda

• Introduction








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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

• Introduction








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800 MW

BOILER

AIR HEATERS

ELECTROSTATIC

PRECIPITATORS

SCRUBBERS

STACK

ID Fans

TXU Energy’s Monticello Steam Electric Station (793 MWe)

Unit 3 tested in 2005 (DOE/EPRI Project on BCA)

50 % PRB coal and 50 % Tx-Lignite

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0

10

20

30

40

50

60

70

80

90

100

0 200 400 600 800 1000 1200 1400 1600 1800 2000

Halogen Addition Rate (ppmw in coal, dry)

Re

du

cti

on

of

Ba

se

lin

e E

lem

en

tal

Hg

(% o

f B

as

eli

ne

Hg

(0))

NaCl - PRB

MgCl2 - PRB

CaCl2 - PRB

HCl - PRB

CaBr2 - PRB

NaCl2 - NDL

MgCl2 - NDL

CaCl2 - NDL

SEA2 - NDL

CaCl2 - TxL/PRB

CaBr2 - TxL/PRB

Reduction of Baseline Elemental Mercury

Overview over all sites tested by EPRI in 2002 … 2005 (chlorine) and repectively 2004 … 2005 (bromine)

S

Monticello 3 Limestone 1

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Alabama Power‘s Plant Miller, 4 x 700 MW

Unit 4 tested 2006 (Phase I) and 2008 (Phase II)

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0

2

4

6

8

10

12

0 50 100 150 200 250 300 350

Bromide Injection Rate (ppm Br in coal, dry basis)

Hg

0 C

on

ce

ntr

ati

on

(g

/dN

m3

at

3%

O2)

SCR Inlet

SCR Outlet

ESP Inlet

ESP Outlet

Miller Average Elemental Mercury Concentrations

Measured During Each Bromide Injection Test (October 2006)

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Plant Miller Unit 4 (710 MWe)

Tests Phase II in 2008 with Pilot-WFGD

PRB coal

Pilot-WFGD

X Hg measuring point

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Day in March 2008

25 ppmw Br in PRB-coal, dry basis

Hg

tota

l at

Pilo

t-W

FG

D I

nle

t a

nd

Ou

tle

t

(mg

/N

m3 d

ry,

at

3 V

ol.%

O2)

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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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Power Station WE Pleasant Prairie with SCR, ESP, WFGD

25 ppm Br per Coal only, SCR in service with NH3

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Further Industrial Demonstration in 2008

PC-fired Wet Bottom Boiler (100 MWtherm; 140,000 Nm /h dry)

of CURRENTA GmbH & Co OHG in Uerdingen

ESP, limestone based wet FGD, tail end DeNOx-SCR

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

bituminous

coal

bituminous

coal

air

air

FGD

CaBr

CaBr

PRAVO

HgCl

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pp

mw

Br

pe

r co

al

Hg

at

sta

ck

(g

/Nm

dry

)

10

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pp

mw

Br

pe

r co

al

Hg

at

sta

ck

(g

/Nm

dry

)

10

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PRAVO®

is a registered trade mark of Vosteen Consulting,standing for the inorganic precipitation agent

containing polysulfide, thiosulfate and bromide

Patents on the combined application of KNX and PRAVO are pending

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In co-operation with Evonik Indstry Services GmbH, Essen:

Combination of two established technologies:

„CaBr2 to Coal” and “PAC to WFGD”,

with subseqquent Selective Mercury Precipitation

Large scale demonstrations in 2009 and 2010

at two Evonik power plants of different design

(w/o and with highdust SCR)

VOSTEEN Consulting GmbH Thermal Engineering and Environmental Protection

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DeNOx

WFGD

ESP

CaBr2

1st Hydro-

cyclone2nd Hydro-

cyclone

Hg-free Gypsum

Stack

PAC

Low-Hg Sludge Fraction

Enhanced Mercury AbatementCaBr2 to Coal and PAC to WFGD

with Selective Mercury Precipitation in WWT

Hg-rich

sludge

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Enhanced Mercury AbatementCaBr2 to Coal and PAC to WFGD

with Selective Mercury Precipitation in WWT

Boiler B

DeNOx

WFGD

ESP

Bituminous

Coal (mixture)

PAC

1st Hydro-

cyclone2nd Hydro-

cyclone

Hg-frtee Gypsum

Hg-rich

sludge

Low-Hg Sludge Fraction

Stack

CaBr2

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3

1 CaBr2 - IPC with 3 pumps

2 Hg measuring station (Lumex)

3 PAC Dosing2

1

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μg/Nm3 dry

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μg/Nm3 dry

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Agenda

• Introduction








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Final meeting after 3 weeks of highly successful testing:

Only 28 ppmw Bromine (as CaBr2) necessary for 95 % mercury oxidation

Former plannings (PAC, tail end bag filter) skipped

in favor of the „German technology“

Dr. Larry S. Monroe

Mark S. Berry

(Southern Company)

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KNXTM Coal Additive –

drums and pumps in a full scale test

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Bromide solution to coal band feeder

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Choose to feed bromide solution to

pulverizers F and G

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Particle trajectories in a Lignite Boiler

(20 m x 20 m x 75 m)

- tangentially fired

- lignite design (pulverizers feed vertical burner row)

- bad internal mixing, i.e. strands of gas

and particles

Three-Dimensional Evaluation (1996)

with courtesy of

Prof. Dr. techn. Reinhard Leithner,

Institute for Thermal and Fuel Technologies ,

Technical University Braunschweig (Germany)

Danger of insufficient bromide pre-distribution

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Thanks for Your Attention.

Questions?

consulting gmbh vosteen€¦ · 2010 aiche spring meeting san antonio, tx, march 21 - 25, 2010...

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