VOSTEEN Consulting GmbH VOSTEEN Consulting Agenda • Introduction - CURRENTA HWC Plant with...

7th International Symposium onAdvanced Gas Cleaning Techology (GCHT-7)

June 23 - 25, 2008Shoal Bay Resort and Spa,Nelson Bay, NSW, Australia

Mercury Retention in the Catalyst Bed of a Tail-End-SCR Downstream of the Wet Flue Gas Cleaning of a Hazardous Waste Incineration Plant

B. W. Vosteen, Vosteen-Consulting GmbHJ. Beyer, T. G. Bonkhofer and R. Kanefke, CURRENTA GmbH & Co. OHG

R. Ullrich, WastePro Engineering Inc.

VOSTEEN Consulting GmbHThermal Engineering and Environmental Protection

2

VOSTEEN Consulting

Agenda

• Introduction - CURRENTA HWC Plant with tail-end-SCR

• Sulphur Granulat Injection

• Continuous Mercury Spiking under High Chlorine Load

• Discontinuous Mercury Spiking under High Chlorine Load

• Hg Sorption Isotherm of Tail-End SCR Catalyst at 305 °C Operating Temperature

• Continuous Mercury Spiking under High Bromine Load

• Discontinuous Mercury Spiking under High Bromine Load

• In-plant Research on Dioxin and Furan De-Novo-Synthesis

• Practical Relevance

• Licensees in USA

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CURRENTA GmbH & Co. OHG, Germany

... speaking about Hazardous Waste Incineration

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Hg-spiking

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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 µg/Nm_ dry 500,000 … 80 Mio µg/Nm_ dry „Hg-bombs“ -> „Hg-clouds“

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

Installed Hgtotal- SCEM at point 17 (stack)

Scrubber

Outlet

Catalyst Beds

OutletHeat Up

Outlet

Cool DownOutlet

Stack

(SCEM)

AmmoniakwasserT= 300 °C

Erdgas und Verbrennungsluft

RG zum gummierten Kamin

T< 100 °C

T= 60 - 70 °C

R G aus VA1

Messstelle nachWT (nach SCR)

Messstellenach WT/ vor Kat

Messstelle nach KEGR

Messstellenach Kat/ vor WT

T= 110 °C

T= 141 °C

T= 270 °C

Messstelleam Kamin (22 m )

RG aus VA2

T= 60 - 70 °C

RG aus VA3 und VA4

T< 100 °C

18

16

19

20

17

AmmoniakwasserT= 300 °C

Erdgas und Verbrennungsluft

RG zum gummierten Kamin

T< 100 °C

T= 60 - 70 °C

R G aus VA1

Messstelle nachWT (nach SCR)

Messstellenach WT/ vor Kat

Messstelle nach KEGR

Messstellenach Kat/ vor WT

T= 110 °C

T= 141 °C

T= 270 °C

Messstelleam Kamin (22 m )

RG aus VA2

T= 60 - 70 °C

RG aus VA3 und VA4

T< 100 °C

18

16

19

20

17

NH3 aq

Scrubber

Outlet

Catalyst Beds

OutletHeat Up

Outlet

Cool DownOutlet

Stack

(SCEM)

Mobile CEMsfor Hgtotal and Hgmet (HM1400 wet of DURAG/Verewa)

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

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Lower SCR heat exchanger, PTFE Upper SCR heat exchanger, steel

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BASF Honeycomb SCR-catalyst(TiO2, WO3 and V2O5 as active components)

Total mass of catalyst: 19,242 kg (2 catalyst beds)

working temperature: 300 °C

gas residence time at 300 °C:

1 sec (half load) ... 0,5 sec (full load)

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Erfassung von HgmetErfassung von Hgges

beheizte Entnahmesonde Notebook zum

Auslesen der DatenData

notebookHeated ducts

for flue gas toCEMs

CEM Hgtotal CEM Hgmet

Two Mobile CEMsfor Hgtotal and Hgmet (HM1400 wet of DURAG/Verewa)at at SCR-DeNOx

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Agenda











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Figure 4a: Screw feeder for sulphur granulate addition into the rotary kiln

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Sulphur Granulate Injection into Rotary Kiln to prevent Cl2 Break Through

(„Sulphur-Dosing Ramp“, Vosteen 1997)

SO2 consumes intermediate Cl2already during boiler passage

(Chlorine-Griffin-Reaction)

SO2 at boiler exit [mg/dscm]

Cl 2

at b

oile

r exi

t [m

g / d

scm

]

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Control Circuit for Sulphur Granulate Injection into Rotary Kiln

to avoid Cl2 break through („Sulphur-Dosing Ramp“, Vosteen 1997)

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SO2 boilerraw gas

Hgmet scrubbedgas

Hgmet diluted gas in front of SCR

SO2 boilerraw gas

Hgmet scrubbedgas


SO2 boilerraw gas

Hgmet scrubbedgas


SO2 boilerraw gas

Hgmet scrubbedgas


SO2 boiler raw gas[µg SO2 / Nm3 dry]Hgmet scrubbed gas

and in front of SCR [µg Hg / Nm3 dry]

running time t [min] on June 8, 2000

SO2 boiler raw gas

[mg SO2/Nm? dry]

Time [min] on June 8th, 2000

Dilution

SO2 boilerraw gas

Hgmet scrubbedgas


SO2 boilerraw gas

Hgmet scrubbedgas


SO2 boilerraw gas

Hgmet scrubbedgas


SO2 boilerraw gas

Hgmet scrubbedgas





SO2 boiler raw gas

[mg SO2/Nm? dry]


SO2 boilerraw gas

Hgmet scrubbedgas


SO2 boilerraw gas

Hgmet scrubbedgas


SO2 boilerraw gas

Hgmet scrubbedgas


SO2 boilerraw gas

Hgmet scrubbedgas





SO2 boiler raw gas

[mg SO2/Nm? dry]


Dilution

Cltotal = ca. 20.000 mg/Nm? dry Cltotal = ca. 20,000 mg/dscm

mg SO2/dscm

µg Hgmet/dscm

Figure 5: Artificially induced oscillations of the SO2 concentration are inducing – without any delay – concurrent oscillations of the Hgmet concentrations

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0

50

100

150

200

780 785 790 795 800 805 810

Zeit [min] ab 00:00 Uhr am 8. 6. 2000

Hg g

es (=

Hg i

on) n

ach

SCR

-Kat

/vor

WT

H

g ges

(= H

g met

) na

ch W

T (a

m S

CR

-Aus

tritt

) [µ

g/m

? i.

N. t

r.]

-500

0

500

1000

1500

Hgges = Hgion nach Kat/vor WT

Hgges = Hgion nach WT am Austritt aus der SCR

SO2 im Kesselrohgas der Anlage A vor Wäsche

Berichtszeitraum2000-06-08 13:00 Uhr -2000-06-08 13:30 Uhr

S

O2 v

or W

äsch

e [m

g/N

m?]

Verweilzeit im WT

Peakverbreiterung und -abflachung im WT

SO2 im Rohgasvor Wäsche

Hgges (= Hgmet)nach Kat/vor WT

Hgges (= Hgmet)nach WT/SCR

SO2 boilerraw gas Hgtotal = Hgion

behind catalystHgtotal = HgionSCR-tower exit

SO2 boiler raw gas

mg SO2/dscmHg behind SCR

µg Hgion/dscm


Figure 6: Artificially induced oscillations of the SO2 concentration in boiler raw gas are inducing countercurrent oscillations of the Hgion concentrations behind SCR

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Agenda











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TetaStopHgChlorination (°C) =

Curve was calculated accordingto the stop temperature modelingmethod of Vosteen

0 5,000 10,000 15,000 20,000 25,000 30,000 35,000

Cltotal concentration in boiler crude gas [mg/dscm]

Hg m

et s

peci

es fr

actio

n [w

t.% o

f Hg t

otal]

Figure 7: Hgmet / Hgtotal species fraction in the crude gas at boiler exit

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Figure 11: Mercury oxidation above baseline by chlorine and by bromine

F ig. 6

0

20

40

60

80

1 00

0 5 00 1 000 1 500 2 000 25 00 3000 3 5 00 4 000 45 00 50 00

Hg m

et/H

g tot

[% b

yw

eigh

t]

B rtot o r C ltot [m g/m ? S .T.P . db]

61

62 63

63´

65

64

Hg oxidationby chlorine (HWC)

Hg oxidationby bromine (HWC)

Hgm

et/H

gtota

l[%

by

wei

ght]

Brtotal or Cltotal [mg/Nm? dry]

low Hgtotal in the flue gas (150 µg Hg/dscm)H

gmet

/Hgto

tal

[wei

ght-

%]

Brtotal or Cltotal [mg/dsm]

100

80

60

40

20

0

100

H

g met-s

peci

es

(w

eigh

t-% o

f Hg t

otal

)

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Why Bromine instead of Chlorine?

„Hg not reacting with HX“

Hg + 2 HX + 0.5 O2 -> HgX2 + H2O

Slow reaction

„Hg reacting with X2 or related radicals“

Hg +X2 -> HgX2

Quick reaction

Much more Br2 than Cl2 formed

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Agenda











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0

200

400

600

800

1000

1200

1400

1600

1800

2000

2200

2400

480 495 510 525 540 555 570 585 600 615 630 645 660

lfd. Versuchszeit [min]

Hg

met

= H

g ge

s v

or S

CR

.

Hg

ion

= H

g ge

s n

ach

SC

R [µ

g/N

m?

tr.]

Hggges = Hgmet nach Wäsche / vor SCR bei Einwurf von vier kleinen Hg-Bomben zu je 26 gHgges = Hgion nach SCRHgmet nach SCR (annähernd Null)

Hgges (= Hgion) nach Tail-End-SCR

Hgges (= Hgmet) nach Wäsche, d.h. vor Tail-End-SCR

Hgmet nach Tail-End-SCR

Hgmet behindtail-end DeNOx-SCR

Hgtotal (= Hgion) behindtail-end DeNOx-SCR

Hgtotal (= Hgmet-peaks) in front of tail-end DeNOx-SCR

running time [min] since 00:00 a.m. on June 15th, 2000

Hg

[µg

/Nm

? dry

]Adsorption ofHgmet No desorption of Hgmet

chemically enhanceddesorption of only Hgion

Hg

conc

entra

tion

[µg/

dscm

]

Figure 8: Hg bomb peaks for verification of the Hgmet retention in the tail-end SCR

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Agenda

• Reference (IT3 Tutorial 2006 on Mercury Capture) and Introduction









• Licensees in Germany and USA

• Appendix

23

VOSTEEN Consulting

Test in plant A (plant B not in operation here)

Hg t

otal a

nd H

g met

be

fore

and

afte

r SC

R

[µg/

dscm

]

Time [minutes since 0:00 ]

Total chlorine load in plant A increased starting at 9:20 PM

(t = 1280 min)

Hgtotal before SCR (measurement point 16 )

Hgmet before SCR Zero point shifted

(measurement point 16 ) Hgtotal after SCR (measurement

point 20 )

Hgmet after SCR

(measurement point

2 0 )

Fig. 9: Second test at plant A on June 15th, 2000 (plant B not in operation) – Hgtotal and Hgmet before and after SCR during the test on June 15, 2000

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SCR

load

ing

[g H

g]

as s

tore

d H

g am

ount

Hgtotal (= Hgion) content in the cleaned off gas after SCR [µg/dscm ]

Can be detected from Hg unloading ("Desorption isotherm " )

Hg sorption isotherm of the SCR with 19,242 kg

catalyst bed mass (according to Vosteen)

Figure 10: Hg desorption isotherm of the tail-end SCR at 305°C (19,242 kg catalyst mass) during test on June 15, 2000, early afternoon

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Adsorption Isotherms of HgCl2 and Hgel at a SCR-DeNOx Catalyst

(Sandra Straube et al., Applied Catalysis B: Environmental , 2008)

Hg el

Hgox (HgCl 2)

0

500

1000

1500

2000

2500

3000

3500

4000

0 0,01 0,02 0,03 0,04 0,05 0,06 0,07Partialdruck Gasphasen-Hg / Pa

Hg-

Bel

adun

g / m

g H

g/kg

Kat

.

0 500 1000 1500 2000 2500 3000

Hg-Gasphasenkonzentration / µg/Nm?

290°C

290°C

Hg-concentration in gas phase [µg/Nm? dry]

Hg-

load

of c

atal

yst

[mg/

kg]

Hg-partial pressure [P]

[mg/dscm]

Hg

load

of c

atal

yst [

mg/

kg]

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Hg-Adsorptionsisobaren bei 160 µg Hg/Nm?eines SCR-Katalysators (2,5 Ma.-% V2O5) in Feuchtluft (15 Vol.-% H2O)

10

100

1000

10000

1 1,1 1,2 1,3 1,4 1,5 1,6 1,7 1,8 1,9 2 2,1 2,2 2,3 2,4

10? K/ T

Hg-

Bel

adun

g /

.m

g/kg

160 µg Hg/Nm? als Hgel in reinerFeuchtluft

160 µg Hg/Nm? als HgCl2 inreiner Feuchtluft

Exponentiell (160 µg Hg/Nm? alsHgel in reiner Feuchtluft)

Exponentiell (160 µg Hg/Nm? alsHgCl2 in reiner Feuchtluft)

160 µg Hg/Nm? in Gasphase,überwiegend als HgCl2

160 µg Hg/Nm? in Gasphase

überwiegend als Hgel

Hgox (HgCl2)

Hgel

Hg-

load

[mg/

kg]

evaluation based onthe different slopes:

Heats of adsorptionin humid air

17 kJ/mol Hgion(as HgCl2)

61 kJ/mol Hgmet

Hg-Adsorption Isobares of Hgel and Hgox (HgCl2) at a SCR-catalyst 160 µg Hg/Nm_ dry, crashed catalyst with 2.5 weight-% V2O5 in humid air, 15 vol.-% H2O

103 K/T

Adsorption Isobares of HgCl2 and Hgel at a SCR-DeNOx Catalyst (S. Straube et al., Applied Catalysis B: Environmental , 2008)

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Agenda











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Fig. 5

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

Mas

sra

tio B

r/Hg

Hg rem

oval rate [%]

51

0

Hg removal rate η

mass ratio

Br/Hg

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

Figure 12: Mass ratio Br/Hg and achieved Hg removal rate in a test run spiking the boiler raw gas with 9,600 g Hgtotal/dscm

accidentalBr-burner fall out

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Agenda

• Reference (IT3 Tutorial 2006 on Mercury Capture) and Introduction









• Licensees in Germany and USA

• Appendix

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VOSTEEN Consulting

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]

Hgm

et-K

onze

ntra

tion

nach

Wäs

che/

KEGR

[µg/

Nm?

tr.]

0

2000

4000

6000

8000

10000

Brge

s-Kon

zent

ratio

n im

Kes

selro

hgas

[mg/

Nm?

tr.]

Beginn derBomben-Serie

Ende derBomben-SerieEinwurf von 3400 g Hg

in der Zeit von09:24 bis 11:20 Uhr

Hgmet = Hgges

nach Wäsche/KEGR

Brges

im Kesselrohgas

Time [hh:mm]

Hgm

et-c

once

ntra

tion

afte

rWES

P [µ

g/ds

cm]

Brtot

al-c

once

ntra

tion

in b

oile

rraw

gas

[mg/

dscm

]

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

Table 1: Injection of Hg bombs [g]

Time Hg g[[amount

[g]

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

Figure 13: Injection of larger and larger Hg-bombs (see Table 1) under sufficient bromine supply [6], [7]

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Agenda











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Town Karlsruhe – Wastewater Treatment Plant2 Stationary Fluidized Bed Combustors

for Sewage Sludgeapplying NaBr and PRAVO® since 2007

Martin Maurer, Roland Milz

EGLV – Central Sludge Treatment Plant Bottrop2 Stationary Fluidized Bed Combustors

for Sewage Sludgeapplying NaBr since 2004

Testing PRAVO® in 2004 and again in April 2008Falko Lehrmann, Günter Schwabe

German Licensees of Vosteen Consulting

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Wastewater Treatment Plant Bottrop andCentral Sludge Treatment Plant Bottrop

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Polychlorinated Dioxins (PCDD/F) as well as

Polybrominated Dioxins (PBDD/F)

analysed w/o and with bromine injection (diluted NaBr)into Fluidized Bed Combustor for Sewage Sludge forMercury Crontrol (Boiler, ESP, 2-stage WFGD):

PCDD/F = 1 … 3 pg TEQ/dscm << 0.1 ng TEQ /dscm

PBDD/F = 0.3 pg TEQ/dscm

(detection limit 0.2 pg/dscm)

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Agenda











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HSE MSWC Darmstadt3 units (220 t waste/year)

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Testings (2 months)Spiking Hg, NaBr, PRAVOTM

3 + 1 SCEM (Mercem)

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

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high Hg-concentrations at stack

<-- Hgtotal at stack(behind tail-end SCR)

Hgtotal entering scrubber -->

Hgtotal exiting scrubber -->

Figure 15: Example of a typical long time mercury elution peak from a tail-End SCR behind the wet scrubbing system of a municipal solid waste incinerator [9]

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PRAVOTM container (diluted1:10) for continuous addition

to upper WFGD-stage

PRAVOTM (diluted 1:10)for discontinuous addition to

upper WFGD-stage

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Agenda











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ALSTOM-Environmental Control Systems,Knoxville/TN, USA,

exclusive licensee for North America KNXTM Coal Additives and Systems

as trademark of ALSTOM Power Inc.Michael J. Rini, John Buschmann,

Leif Lindau

Electric Power Research Institute,Palo Alto/CA, USA,research grant

for demonstration test runse.g. at the sites Monticello, Plant Miller

George Offen, Ramsay Chang

Southern Company Services, Inc. Birmingham/AL, USA,

specific licensee for SC-utilities onlyLarry Monroe, Mark Berry et. al.

US Licensees of Vosteen Consulting

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Bromine enhanced mercuryabatement,invented by Prof. Vosteen in 2000

German Patent DE 10 233 173granted 2005

US Patent 6 878 358granted 2005

Canadian Patent 2 435 474granted 2006

European Patent 1 386 655granted 2008

Australian Patent 2 003 220 713granted 2008

Patent applications pendingin other countries

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KNXTM Coal Additive –drums and pumps in a full scale

test

45

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Agenda

• Appendix

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VOSTEEN Consulting

0

200

400

600

800

1.000

1.200

0 5.000 10.000 15.000 20.000 25.000 30.000Chloridkonzentration im Rauchgas

[mg Cl - / Nm?tr]

Schw

efel

konz

entr

atio

n[m

g S

/ Nm

? tr]

Schwefeldosierschnecken-Input

Schwefel im Rauchgas nach saurer Wäsche voralkalischer Wäsche durch Messungen von W 15

Schwefel aus dem Rest-SO2 vor Quenche

Schwefel im Quenchen-Output

ΔS = 400 mg S / Nm? tr = 12,5 mmol S/Nm? tr

entsprichtΔCl2 = 12,5 mmol Cl 2/Nm?tr = 886 mg Cl 2 / Nm?tr

Cl2-Umsatz noch im Kessel: ΔCl2/ΔCl- =

886 mg Cl2 / 30.000 mg Cl- = 3 %

Anlagenversuch an der VA 2 am 19.10.2000

Schwefelbilanzierung - Chlor

Δ SO3-Schwefel

aus SO2 /SO3 -Konversion : 8%

Sulphur Bilance combusting Chlorinated Wastes

SO2 consumption by Cl2at > 100 °C in boiler flue gas (Chlorine-Griffin-Reaction)

SO3 --> SO42-

in scrubber

SO2/SO3 conversion

Chlorid in flue gas [mg Cl-/dscm]

Sulfu

r per

flue

gas

[mg

S/ds

cm]

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Cl2 in Scrubbed Flue Gas at SCR Inlet

(Henry-behavior, Vosteen 1997)

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Cl2-Gehalt im Reingas vor SCR [mg/m? i. N tr.]

HC

l-Geh

alt i

m R

eing

as

nach

SC

R [m

g/m

? i. N

tr.]

Rück-Konversion von Cl2 zu HCl

in Tail-End-SCR

Cl2-Unterdrückung durch SO2 schon im

Kesselrauchgas

Vermutlich besteht Lastabhängigkeit

Teil-Last / Voll-Last

Cl2 ---> HCl Rück-Konversion

in der SCR

Cl2-Gehalt im Reingas vor SCR [mg/m? i. N. tr.]

HC

l-Geh

alt i

m R

eing

as

nach

SC

R [m

g/m

? i.

N. t

r.]

Cl2 concentration in front of SCR [mg/Nm?dry]

HC

l-con

cent

ratio

nbe

hind

SC

R

[mgC

l-/N

m?d

ry]

Cl2 HCl

Retro-Deacon-Reaction

in tail end SCR

Unit A (50 % load)

Unit B (100 % load)


HC

l-Geh

alt i

m R

eing

as

nach

SC

R [m

g/m

? i. N

tr.]


in Tail-End-SCR


Kesselrauchgas




in der SCR


HC

l-Geh

alt i

m R

eing

as

nach

SC

R [m

g/m

? i.

N. t

r.]


HC

l-con

cent

ratio

nbe

hind

SC

R

[mgC

l-/N

m?d

ry]

Cl2 HCl


in tail end SCR

Unit A (50 % load)

Unit B (100 % load)


HC

l-Geh

alt i

m R

eing

as

nach

SC

R [m

g/m

? i. N

tr.]


in Tail-End-SCR


Kesselrauchgas




in der SCR


HC

l-Geh

alt i

m R

eing

as

nach

SC

R [m

g/m

? i.

N. t

r.]


HC

l-con

cent

ratio

nbe

hind

SC

R

[mgC

l-/N

m?d

ry]

Cl2 HCl


in tail end SCR

Unit A (50 % load)

Unit B (100 % load)

Retro-Chlorine Deacon Reaction

catalysed in tail end SCR

Cl2 suppression in boiler / scrubberby SO2 (Griffin-Reaction)

Cl2 --> HCl

[mg Cl2 /dscm]

HC

l-con

cent

ratio

n at

SC

R o

utle

t

[ m

g C

l- /d s

cm]

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VA2 Versuche zur Ermittlung der Hg-Speicherung in der SCR

nach diskontinuierlicher Hg-Zudosierung

0

100

200

300

400

500

1130 1135 1140 1145 1150 1155 1160

Zeit [min]

Hg(

ges)

am

Kam

in [µ

g/N

m?]

0

1

2

3

4

5

6

7

8

frei

es C

hlor

nac

h S

augz

ug V

A2

[ppm

] und

HC

l am

Kam

in [m

g/N

m?]

Hg(ges) Kamin (bis 500) [µg/Nm? tr] HCl am Kamin 1 [mg/Nm? tr] Cl 2-Drägermessung VA2 (ppm)

Berichtszeitraum2000-05-16 18:50 Uhr -2000-05-16 19:20 Uhr

VA1 außer Betrieb

Cl2 nach VA2

Hg2ges am Kamin

HCl am Kamin

Cl2 vor SCR

Hgges am Kamin

HCl am Kamin

Hgg

es a

m K

amin

[µ

g/m

? i. N

. tr.

]

Cl2

nac

h K

EG

R/v

or S

CR

H

Cl a

m K

amin

[µ

g/m

? i. N

. tr.

]

lfd. Zeit [ min] ab 00:00 Uhr

[mg/

m?

i. N. t

r.]

time [min since 00:00]

Cl2 at SCR inlet

Hgtotal at stack

HCl at stack

C

l 2 at

SC

R in

let

[m

g/ds

cm]

H

g tot

al a

t sta

ck

[µ

g/ds

cm]

Cl2 at SCR inlet

51

VOSTEEN Consulting

0

4.000

8.000

12.000

16.000

20.000

24.000

28.000

7:00 8:00 9:00 10:00 11:00 12:00 13:00 14:00 15:00 16:00 17:00 18:00 19:00

Hal

ogen

idge

halt

im R

ohga

s [m

g/N

m?t

r]

0

1.000

2.000

3.000

4.000

5.000

6.000

7.000

SO2-

Geh

alt i

m R

ohga

s [m

g/N

m?t

r]

Bromidgehalt über Brenner [mg/Nm?tr] SO2gehalt gemessen [mg/Nm?tr]

Schwefelinput als SO2 [mg/Nm?tr]

stufenweise Anhebung der Fracht aus T60 kg/h 350 kg/h 2.800 kg/hZeit [hh:mm]

Skalenzuweisung

VA 1 Versuche zur Ermittlung des Schwefelverzehrsdurch Bromfahrweise

2000-12-19 07:00bis

2000-12-19 19:00

BrtotalSO2 at exit

Brto

tal

in b

oile

rraw

gas

[Nm

? dry

]

SO2

in b

oile

rraw

gas

[mg

/Nm

?dry

]

SO2 at entrance28,000

24,000

20,000

16,000

12,000

8,000

4,000

0

Brtotal[mg/dscm]

SO2[mg/dscm]

Time on December 19th, 2000 [hour]

Figure 14: SO2 at boiler entrance as achieved by injection of sulphur granulate, and SO2 at boiler exit / behind quencher under increasing bromine freight as achieved by co- combustion of highly brominated wastes

52

VOSTEEN Consulting

0

500

1.000

1.500

2.000

2.500

3.000

3.500

0 5.000 10.000 15.000 20.000 25.000

Bromkonzentration im Rauchgas [mg Br - / Nm?tr]

Schw

efel

konz

entr

atio

n[m

g S

/ Nm

? tr]

Schwefeldosierschnecken-Input

Schwefel aus dem Rest-SO2 vor Quenche

Schwefel im Quenchen-Output

Schwefelbilanzierung - Brom

Anlagenversuch an der VA 1 am 19.12.2000

Schwefel als SO3 im Kessel -entstanden aus SO 2 durch KONVERSION:

8%

Schwefel als SO3/SO3* im Kessel -

entstanden durch SO 2 -Verzehr gemäß BUNSEN (Br)

3.080

Schwefelbilanzierung über Bromkonzentration

Chlor-bedingt

375 245

Sulphur Bilance combusting Brominated Wastes

SO2 consumption by Br2

at < 100 °C in scrubber (Bromine-Bunsen-Reaction)

SO42-

formation in scrubber

SO2/SO3 conversion

Bromide in flue gas [mg Cl-/dscm]

Sulfu

r per

flue

gas

[mg

S/ds

cm] 3500

3000

2500

2000

1500

1000

500

0

53

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Martin-Luther-University Halle-WittenbergInstitute for Environmental Engineering

Heinz Köser, Rico and Ewa Kanefke,Sandra Straube, Martin Ziegler et al.

Technical University ClausthalInstitute for Energy Process and Fuel TechnologyBernhard W. Vosteen, Roman Weber,

Michael Nolte et al.

Martin-Luther-Universität

Halle-Wittenberg

TUClausthal

University R&D:

54

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Thanks for Your attention

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