consulting gmbh vosteen...coal to stack, independent of fuel, unit age, capacity and design ......

Bromine Based Abatement of Mercury from

Coal Combustion and Waste Incineration Flue Gases

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

VOSTEEN Consulting GmbH Thermal Engineering and Environmental Protection

http://www.vosteen-consulting.de

Energy Efficiency & Air Pollutant Control

Conference Wroclaw 2009

Wroclav University of Technology (Poland)

SEPTEMBER 21 - 25, 2009

Keynote # 6

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Agenda

• Mercury as a Global Problem

• The Bromine Based Technology

• Licensees and Co-operations

• Large Scale Applications in Coal Combustion

• at Units with Wet Flue Gas Cleaning

• at Units with Dry Flue Gas Cleaning

• Large Scale Applications in Waste Combustion

• Outlook

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Mercury Emissions from Coal and Waste

are experienced as a growing threat

Technical Newsletter from the Center for Air Toxic Metals (CATM), Dezember 2006

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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 (growing + 1.4 % per year)

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acknowledges the need to manage mercury in an efficient,

effective and coherent manner

agrees to further international action consisting the elaboration of

a legally binding instrument on mercury, to reduce risks to human health

and the environment

25th Session of the UNEP Governing Council/

Global Ministerial Environment Forum (GC-25/GMEF) 16-20 February 2009 in Nairobi, Kenya

USA: Clean Air Mercury Rule (CAMR) vacated in 2008

- causing some delay

NO MORE CAP AND TRADE. EPA develops emissions standards under the

Clean Air Act (Section 112) for all HAPs (including mercury) at all power plants

Stringent mercury emission standard expected soon : > 90 % mercury removal coal to stack, independent of fuel, unit age, capacity and design

Europe /NL: Actual stack concentrations << 30 ... 50 μg/Nm3 dry

Recent permits in the Netherlands: < 1 μg/Nm3 dry as yearly mean

(corresponds to „> 90 % mercury removal coal to stack“)

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„Technology commercially available“ Smoldering Filterbags, Hot Spots in 2 of 10 Chambers

Steve Derenne, DOE NETL Conference, Pittsburg, Dec. 2006

Hot-Spot Problems shall be minimized today (2008)

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Agenda








• Outlook

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CURRENTA GmbH & Co. OHG, Germany

... speaking about Hazardous Waste Incineration

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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-CEMs

Hg-spiking(discontinuous)

Quench



Hg-CEMs

Hg-SCEM

Hg-spiking(discontinuous)

Quench

Process Developement with CURRENTA GmbH & Co OHG(Project leader: Prof. Vosteen)

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Mobile Hgtotal and Hgmet CEMs at points 16, 18, 19, 20

Installed Hgtotal- SCEM at point 17 (stack)

Several Mobile CEMs for Simultaneous Measurement of Hgtotal and Hgmet

around and within tail-end SCR-DeNOx in June 2000

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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 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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Erfassung von HgmetErfassung von Hgges

beheizte Entnahmesonde Notebook zum

Auslesen der Daten

Data

notebook

Heated ducts

for flue gas to

CEMs

CEM Hgtotal CEM Hgmet

Two Mobile CEMs for Simultaneous Measurement of Hgtotal and Hgmet

(HM1400 wet of DURAG/Verewa)

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Hg Oxidation

by Bromine (HWC)

Hg Oxidation

by Chlorine (HWC)

Hgmet/Hgtotal in the boiler flue gasversus 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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0

200

400

600

800

1000

1200

1400

1600

1800

2000

08:30 09:30 10:30 11:30 12:30 13:30 14:30 15:30

Time [hh:mm]

98,0

98,2

98,4

98,6

98,8

99,0

99,2

99,4

99,6

99,8

100,0

52

Mass

ratio B

r/H

g

Hg re

moval ra

te [%

]

51

0

Hg removal

rate

mass ratio

Br/Hg

high Hgtotal in the flue gas (9600 g Hg/Nm? dry)

accidental

Br-burner fall out

Mass ratio Br/Hg = 100 … 500 needed (“without high dust SCR”)

Spiking the boiler raw gas with 9600 μg Hg/Nm3 dry)

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Injection of Hg Bombs (4 x 26 g every 5 minutes)under base line conditions, i.e. no bromide added

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Injection of Hg Bombs of Increasing Size(5 ... 340 g every 5 minutes, in total 3.4 kg) under co-combustion of bromine rich waste

Table 1: Injection of Hg bombs [g]

Time Hg g[[amount Time Hg amount [g]

9:24 5 10:32 180

9:32 10 10:37 200

9:38 15 10:43 220

9:49 20 10:48 240

9:54 40 10:53 260

9:59 60 10:58 280

10:04 80 11:03 300

10:09 100 11:08 310

10:15 120 11:13 320

10:20 140 11:20 340

10:26 160

Experimental time [min] Total Hg amount [g]

116 3400

Time Bomb Size (g) Time Bomb Size (g)

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0

5

10

15

20

25

30

35

40

45

50

8:30 9:00 9:30 10:00 10:30 11:00 11:30 12:00 12:30

Zeit [hh:mm]

Hg

met-K

on

zen

tra

tio

n n

ac

h W

äs

ch

e/K

EG

R

[g

/Nm

? t

r.]

0

2000

4000

6000

8000

10000

Br g

es-K

on

zen

tra

tio

n i

m K

es

se

lro

hg

as

[mg

/Nm

? t

r.]

Beginn der

Bomben-Serie

Ende der

Bomben-SerieEinwurf von 3400 g Hg

in der Zeit von

09:24 bis 11:20 Uhr

Hgmet = Hgges

nach Wäsche/KEGR

Brges

im Kesselrohgas

Time [hh:mm]

Hgm

et-

con

cen

tra

tion

aft

er

WE

SP

[g

/dsc

m]

Brto

tal-

con

cen

tra

tion

in b

oile

rra

wgas

[m

g/d

scm

]

Brtotal

In boiler raw gas

Hgmet = Hg total

after WESP

Start EndInjection of Hg bombs

(sum 3.4 kg)

within 9:24 until 11:20

Injection of Hg Bombs of Increasing Size(5 ... 340 g every 5 minutes, in total 3.4 kg) under co-combustion of bromine rich waste

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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

Chlorine Enhanced Hg-Oxidation

Relevant 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

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Bromine Enhanced Hg-Oxidation

Relevant global reactions

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

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

SO2 + Br2 + 2 H2O H2SO4 + 2 HBr Bromine-Bunsen-Reaction

SO2 + O2 SO3 SO2/SO3-Konversion

Hg + Br2 HgBr2 direct Hg-Bromination

Bromine highly effective in Hg-oxidation

because Br2/Brtotal 1

SO2 is not consuming Br2 during boiler passage

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Agenda






• at Units with Dry Flues Gas Cleaning


• Outlook

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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

USA, Kanada, Australia, Southafrica,

Korea and Japan

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Bayer Industry Services GmbH & Co OHG(Leverkusen, GER)

Currenta GmbH & Co. OHGformer BAYER Industry Services

4 Rotary Kiln Incinerators

for Hazardous Wastes

Joachim Beyer, Theodor Bonkhofer,Rico Kanefke

Vosteen Consulting GmbH has exclusive rights

in the patented technology (worldwide)

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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

Michael J. Rini, John Buschmann, Leif Lindau

Electric Power Research Institute,

Palo Alto/CA, USA,

Limited R&D License for the States

George R. Offen, Ramsay Chang

Southern Company Services, Inc.

Birmingham/AL, USA,

License for units owned by Southern Company

Larry S. Monroe, Mark S. Berry et. al.

Licensees of Vosteen Consulting GmbH in North America

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Licensees of Vosteen Consulting GmbH in Europe

Limited R&D License for the Netherlands

Henk te Winkel

AE&E, Raaba (Austria)

and affiliates

Non-exclusive license for Europe

Klaus Bärenthaler, Harald Karl Reissner

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EGLV – Central WWTP in Bottrop2 stationary Fluidized Bed Incineratorsfor the combustion of sewage sludges

Application of NaBr since 2004

Falko Lehrmann, Günter Schwabe

Town Karlsruhe – WWTP Neureut 2 stationary Fluidized Bed Incinerators

for the combustion of sewage sludges Application of NaBr and PRAVO® seit 2007

Martin Maurer, Roland Milz

Licensees of Vosteen Consulting GmbH in Germany

HSE Technik GmbH & Co. KG, Darmstadt

3 MSWC lines (210,000 t /a) 2 months full-scale testingswith NaBr and PRAVO®100 in 2007

PRAVO®100 added constantly since 2008

Urich Mielke

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Worldwide Co-operation since 2006

• Israel Chemical Ltd - Industrial

Products as supplyer of bromine

compounds

(33 % of the world market)

MerquelTM (CaBr2)

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Agenda








• Outlook

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Internal US EPRIReport, March 2006Chapter 3: „Boiler Chemical Additives“

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

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VOSTEEN ConsultingVOSTEEN Consulting

2008: Licenses granted to Power Station NN(2 Units with SCR, ESP, WFGD)

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 NN with SCR, ESP, WFGD25 ppm Br per Coal only, SCR in service with NH3

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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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Miller Measurement Locations(October 2006)

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In total : 16 URS laboratory staff members

3 CEMS, 3 x 8 hours per day

Plant Miller testing (Phase I in 2006)

16 URS personnel per day

3 x 8 hours = 24 hours

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CaBr2 as 52 wt% solution was diluted

with plant water into 2500 gal plastic

holding tanks – 60 feet pumping

distance up to the coal feeder deck

level

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Bromide solution to coal band feeder

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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 ConcentrationsMeasured During Each Bromide Injection Test (October 2006)

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Hg Oxidation at Plant Miller – Modelling Prof. Vosteen:

SCR catalyst lowers the „Stop Temperature of Mercury Bromination“

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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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TOXECONTM:

High Capital costs:

> $420M

High O&M Costs:

$8.4M per year for PAC,

$5.6M per year for bagreplacement

22.4 MW auxiliary power

Estimates for Plant Miller:

4 x 700 MW = 2,800 MW 12M dscm per hour

KNXTM Technology:

Low Capital Costs:

little capital equipment,small footprint within the plant

Low O&M Costs:

$1.6M per year for CaBr2

~ $5,000/lb Hg

(little or no impact on ash)

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Further Industrial Demonstration in 2008PC-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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Agenda








• Outlook

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Further Industrial Demonstration in 2008PC-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

diploma thesis of Michael Nolte, 2002

Analysis of dry Mercury Capture by Adsorption at ESP Fly ash / UBC

Fly ash samples for

fractional laboratory analysis

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Zeitlicher Verlauf der gemessenen Hg-Gehalte nach EGR und

der Abreinigungsintervalle des EGR-Filters (Auszug vom 12.04.2002)

0

20

40

60

80

15:00 15:10 15:20 15:30 15:40 15:50 16:00

Zeit [hh:mm]

Hg

(ges)-

un

d H

g(m

et)

-Geh

alt

nach

EG

R

[g

/Nm

3],

Sp

an

nu

ng

Zo

ne 1

EG

R [

kV

]

0

200

400

600

800

Str

om

Zo

ne 1

EG

R [

mA

]

Hg(ges)-Gehalt nach EGR Hg(ion)-Gehalt nach EGR (Hg(ges) - Hg(met))Hg(met)-Gehalt nach EGR Spannungsmessung EGR (Zone 1)Strommessung EGR (Zone 1)

2002-04-12 15:00

bis

2002-04-12 16:00

ESP amperage

ESP voltage

Hgmet

Hgtotal

Hg2+

running time [hh:mm] on December 4th, 2002

ES

P a

mp

era

ge

zo

ne

1 [

mA

]

Hg

sp

ec

ies

co

nc

en

tra

tio

ns

in

ES

P e

xit

ga

s [

g/N

m d

ry]

ES

P v

olt

ag

e z

on

e 1

[k

V]

Mercury sorption behaviour at normal load (only coal)

Mainly ionic mercury is adsorbed at ESP fly ash,

preferably at the fly ash covering the plate electrodes


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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)

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Particle size distribution of UBC and mercury

in the ESP-flyash

0

100000

200000

300000

400000

500000

600000

700000

800000

900000

1000000

0 50 100 150 200 250 300

mittlere Korngröße ( m)

Re

st-

C-G

eh

alt

de

r F

lug

sta

ub

fra

kti

on

(m

g/k

g)

0

10

20

30

40

50

60

70

80

90

100

Hg

-Ge

ha

lt d

er

Flu

gs

tau

bfr

ak

tio

n (

mg

/kg

)

Flu

gk

ok

s-O

be

rflä

ch

e (

m?

/kg

) .

Siebung einer Probe mit dem zweitgrößten Hg-Gehalt

( Versuchsreihe April 2002)

70 % deutsche Steinkohle

30 % columbianische Steinkohle

Rest-C-Gehalt

der Staubfraktion

Hg-Gehalt

der Staubfraktion

äußere C-Korn-Oberfläche

der Staubfraktion

Fractional UBC

Fractional Hg

Fract. UBC outer area

Mean particle size [ m]

Fra

cti

on

alU

BC

[m

g/k

g]

Fra

cti

on

alH

g [

mg

/kg

]

Fra

cti

on

alU

BC

ou

ter

su

rface

are

a[m

?/k

g]

Sieving of an ESP-flyash probe

with high mercury loading,

April 2002

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Holcomb DFGD, 350 MWe, PRB coals

Sorbent Injection

Sorbent Storageand Feeder

SDA

FF

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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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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

0

10

20

30

40

50

60

70

80

90

100

0 0.5 1 1.5 2 2.5 3

Sorbent Injection Rate (lb/MMacf) or

KNX Injection Rate (ppm Bromine in Coal/100)

Ba

gh

ou

se

Re

mo

va

l (%

of

Inle

t H

g)

MS200 W Harrington MS200 E Harrington C-PAC W Harrington

C-PAC E Harrington Darco Hg LH W Harrington Darco Hg LH E Harrington

KNX W Harrington KNX E Harrington CF Plus W Tolk

CF Plus E Tolk KNX E Tolk Darco Hg/KNX W Tolk

Darco Hg/KNX E Tolk

All data points with Darco Hg and KNX are reprented with the Darco Hg injection rates.

The KNX injection rate for these tests was 41 ppm in the coal unless otherwise noted.

For these points, KNX injection

rate is 25 ppm Bromine in the coal

KNX + Limited ACI is also very effective

in dry systems (APH, FF)

Ref: Dutton et al., 2008

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Synergistic Effect of KNX + Mer-Cure500 MW PRB with Particulate Scrubber

0

1

2

3

4

5

6

7

8

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

Sta

ck

Hg

Lb

/TB

tu

55% incremental performance improvement

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Agenda








• Outlook

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Central SludgeTreatment Plant Bottrop

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Mobile NaBr-solution container and dosing pumps

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VOSTEEN Consulting

Two fluid nozzle lances for bromide injection

into the FBC free board

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VOSTEEN Consulting

Wastewater Treatment Plant Karlsruhe-Neureutwith 2 Fluidized Bed Combustors (FBC) for sewage sludge

„No mercury into the air“

„No mercury into the neighbouring river Rhine“

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VOSTEEN Consulting

SludgeSedimentation

(4 – 5 % dry matter)

PE-Sludge ConditioningMechanical Dewatering

Centripress (25 % dry matter)

Thermal Contact-Drying(43 % dry matter)

Fluidized BedCombustion

(900 °C)

Heat Recovery Boiler(25 bar, 300 °C)

ESP(170 °C)

WFGC2 stages + wet Venturi

(System LAB, 1997)

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VOSTEEN Consulting

FBC Unit 2

stack

CEM

FBC

ESP WFGC

Rotor of Decanter

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VOSTEEN Consulting

NaBr-solution addition to sewage sludge feed (before entering the Fluidized Bed Incinerator)

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VOSTEEN Consulting

Most advanced German High Tech

adding small amounts of the proprietory

Precipitation Agent Vosteen (PRAVOTM) to scrubber

Verbesserte Ausführung der Tropfung

mit Glastrichter zur Sichtkontrolle

an Wäscher 1

counting PRAVOTM droplets

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VOSTEEN Consulting

0

10

20

30

40

50

60

0 5 10 15 20 25 30 35

# of parametric variation in November 2007

Hg

at

the

Sta

ck

0

100

200

300

400

500

600

Hg at stack [ g/Nm?dry]

S2-/Hg scubbers 1 + 2

S2-/Hg scrubber 2

Br/Hg mass ration

Br/Hg

[mg/mg]

Hg at stack

[ g/Nm? dry]

S2-

/Hg scrubber 2

[mg/mg]

S2-

/Hg scrubbers 1 + 2

[mg/mg]

Hg

at

the

sta

ck

[g

/Nm

? d

ry,

11

vo

l%

O2

]

.

Br/

Hg

ma

ss

ra

tio

[mg

/mg

]

.

S2

-/H

g m

as

s r

ati

o

[mg

/mg

]

. 150 g Hg/Nm?dry

in the raw gas

Results from November 2007

NaBr to sludgeVariation of NaBr

NaBr injected in FBC Variation of PRAVO

Hg

tota

l at

sta

ck

(

g/N

m3 d

ry,

11

% O

2)

150 g Hgtotal/Nm3 dry

( g/Nm3 dry)

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VOSTEEN Consulting

How to achieve 95 % mercury removal rate

80

85

90

95

100

0 5 10 15 20 25

S2-

/Hg mass ratio [kg/kg]

Hg

rem

oval

[%]

.

dry

] NaBr added to sludge

NaBr injected via 3 lances

KNX variation

under high PRAVO

PRAVO variation( KNX not strictly constant)

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Variation of Br-/Hg and S2-/Hg mass ratio (1)

PRAVO is permitting lower KNXMode of KNX injection not important

80

85

90

95

100

0 100 200 300 400 500 600

Br/Hg mass ratio [ g/ g]

Hg

re

mo

va

l [%

] .

dry

] NaBr added to sludge

NaBr injected via 3 lances

high PRAVO

S2-

/Hg mass ratio = 20

mainly to Scrubber 1 (pH = 0.5)

low PRAVO

S2-

/Hg mass ratio = 2,5

only to Scrubber 2 (pH = 7)

High Br

high PRAVO

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Day without parameter variations

Br/Hg = 252 mg/mg, S2-/Hg =19.9 mg/mg

Constantly achieved:Hg = 10 g Hg/Nm dry, 11 % O2 at stack

84

VOSTEEN Consulting

Hg = 8 … 25 g Hg/Nm dry, 11 % O2 at stack –

„Only high PRAVO is not enough“

Interrupting bromide-feed to sludge

Br/Hg = 202 mg/mg -> 0 -> 202 mg/mg

S2-/Hg = 19.9 mg/mg = const.

85

VOSTEEN Consulting

Hg = 15 25 g Hg/Nm dry, 11 % O2 at stack

„Only low bromide is not enough“

S2-/Hg = 19.9 mg/mg -> 0 -> 19.9 mg/mg

Br/Hg = 256 mg/mg = const

Interruption of PRAVO®-feed to scubber 1

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VOSTEEN Consulting

Specific additive costs much < 100 US $/gHg

0,00

0,50

1,00

1,50

2,00

2,50

3,00

0 5 10 15 20 25 30

Hg

at

the

Sta

ck

/ g Hg , total for bromide and active sulfur

Logarithmisch ( / g Hg , total for bromide and active sulfur)

Hg at the stack [ g/Nm? dry, 11 vol% O2]

.

sp

ecif

ic c

osts

Br

an

d S

2-

[ /g

Hg

]

.

1 = 1.35

logarithmic

1 = 1.35 US$

KNXTM and PRAVO® – a perfect duo indeed

2.90 /kg Br- (pure)

15.2 /kg S2- (pure)

1 = 1.35 US$

3.00

2.50

2.00

1.50

1.00

0.50

0

Bromide and PRAVO Addition - a perfect duo indeed

Hg at stack (μg/Nm3 dry, 11 vol.% O2)

Total Specific Additive Costs in case of sewage sludge

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HSE MSWC Darmstadt

3 units (220 t waste/year)

88

VOSTEEN Consulting

Testings (2 months)

Spiking Hg,

NaBr, PRAVO®100

3 + 1 SCEM (Mercem)

WFGD-tower with 2 stages (design: von Roll),

89

VOSTEEN Consulting

PRAVO container (diluted 1:10)for continuous addition to

upper WFGD-stage

PRAVO (diluted 1:10)for discontinuous addition to

upper WFGD-stage

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PRAVO®100 was compared with TMT15 and otherscrubber additives to prevent Hg re-emissions

PRAVO was working very well

HSE has got the permit to apply and does applyPRAVO®100 constantly since 2008

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Agenda








• Outlook

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VOSTEEN Consulting

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

93

VOSTEEN Consulting

DeNOx

WFGD

ESP

CaBr2

1st Hydro-cyclone

2nd 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

Tests in Marl at Infracor - Chemistry Services, Power Station 1, Unit 5 (375 MWtherm)

Hg-rich PAC

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VOSTEEN Consulting

3

1 CaBr2 - IPC Behälter mit 3 Dosierpumpen

2 Hg Messplatz (Lumex)

3 A-Kohledosierstation2

1

95

VOSTEEN Consulting

Enhanced Mercury AbatementCaBr2 to Coal and PAC to WFGD with Selective Mercury Precipitation in WWT

Tests in Herne at Evonik Steag GmbH,Power Sation Herne, Unit IV (1176 MWtherm)

Boiler B

DeNOx

WFGD

ESP

Bituminous Coal (mixture)

PAC

1st Hydro-cyclone

2nd Hydro-cyclone

Hg-frtee Gypsum

Hg-rich PAC

Low-Hg Sludge Fraction

Stack

CaBr2

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Thanks for Your Attention.

Questions?

consulting gmbh vosteen...coal to stack, independent of fuel, unit age, capacity and design ......

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