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
3
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CURRENTA GmbH & Co. OHG, Germany
... speaking about Hazardous Waste Incineration
5
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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“
6
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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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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
10
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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
12
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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
Hgmet diluted gas in front of SCR
SO2 boilerraw gas
Hgmet scrubbedgas
Hgmet diluted gas in front of SCR
SO2 boilerraw gas
Hgmet scrubbedgas
Hgmet diluted gas in front of SCR
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
Hgmet diluted gas in front of SCR
SO2 boilerraw gas
Hgmet scrubbedgas
Hgmet diluted gas in front of SCR
SO2 boilerraw gas
Hgmet scrubbedgas
Hgmet diluted gas in front of SCR
SO2 boilerraw gas
Hgmet scrubbedgas
Hgmet diluted gas in front of SCR
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
SO2 boilerraw gas
Hgmet scrubbedgas
Hgmet diluted gas in front of SCR
SO2 boilerraw gas
Hgmet scrubbedgas
Hgmet diluted gas in front of SCR
SO2 boilerraw gas
Hgmet scrubbedgas
Hgmet diluted gas in front of SCR
SO2 boilerraw gas
Hgmet scrubbedgas
Hgmet diluted gas in front of SCR
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
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
Time [min] on June 8th, 200
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
• 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
17
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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
20
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
21
VOSTEEN Consulting
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
22
VOSTEEN Consulting
Agenda
• Reference (IT3 Tutorial 2006 on Mercury Capture) and Introduction
• 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 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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VOSTEEN Consulting
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)
27
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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
28
VOSTEEN Consulting
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
29
VOSTEEN Consulting
Agenda
• Reference (IT3 Tutorial 2006 on Mercury Capture) and Introduction
• 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 Germany and USA
• Appendix
30
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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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
32
VOSTEEN Consulting
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
34
VOSTEEN Consulting
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)
35
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
37
VOSTEEN Consulting
Testings (2 months)Spiking Hg, NaBr, PRAVOTM
3 + 1 SCEM (Mercem)
WFGD-tower with 2 stages (design: von Roll)
38
VOSTEEN Consulting
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]
39
VOSTEEN Consulting
PRAVOTM container (diluted1:10) for continuous addition
to upper WFGD-stage
PRAVOTM (diluted 1:10)for discontinuous addition to
upper WFGD-stage
40
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
41
VOSTEEN Consulting
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
42
VOSTEEN Consulting
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
47
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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VOSTEEN Consulting
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)
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)
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)
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]
50
VOSTEEN Consulting
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
VOSTEEN Consulting
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: