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Bromine Enhanced Dry Mercury Capture · QR SO2 O2 QR Hg(0) (EPM) Vorfilter, beheizt...
Transcript of Bromine Enhanced Dry Mercury Capture · QR SO2 O2 QR Hg(0) (EPM) Vorfilter, beheizt...
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Bernhard W. Vosteen, Vosteen Consulting GmbH
Tim C. Hartmann, ALSTOM Power Inc.
http://www.vosteen-consulting.de
EUEC 2012: The 15th Annual Energy & Environment Conference January 30 - February 1, 2012, in Phoenix, AZ (USA) Track C: Mercury Control Demonstrations and Bromine (paper # C2.3)
Bromine Enhanced Dry Mercury Capture
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Agenda
• Introduction: Low or Near Zero Mercury Emissions?
• What about Single-Stage APC Systems - Wet or Dry?
• Multi-Stage APC Systems
• Dry Stage upstream of wFGD
• Dry Stage downstream of wFGD
• Conclusions
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Mercury Limit lowered by the
Factor 65
Utility MACT -> EPA‘s MATS Rule (December 21, 2011),
Table 3 for EGUs firing high rank coals (excerpt)
Range about: 1.5 µg/dscm @ 5 % O2
Range about : 25 ng/dscm @ 5 % O2
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PRB
Only low mercury coals? (e.g. PRB with 0.1 ppm Hg dry)
What about the other coals - in the long run?
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Source: M. S. Berry and B. W. Vosteen: „Bromine Injection Technology Demonstrations at Plant Miller for Removing Vapor Phase Mercury “, 12th ICESP in Nuremberg, May 2011
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RWE-RheinBraun: Industrial CFB Boiler (270 MWtherm) in Berrenrath Co-combustion of lignite coal and communal sewage-sludge since 1999, ACI in form of HOC Injection (lignite derived PAC)
Source: Wirling et al., RWE-RheinBraun, 2001
Multi-stage APC System – APC Type: dry/dry
What about co-combustion of communal sewage sludges - in the long run?
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Near Zero Hg Emissions can be achieved - but under which “conditions“?
No combustion of coals with elevated mercury content?
No co-combustion of Hg-rich wastes as sewage sludge? Multi-stage APC-Systems mandatory (huge investment)? High sorbent addition rates mandatory (huge O&M costs)?
???
Discussing that, let‘s also look at
European WtE Plants to illustrate the possible diversity.
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Current Trend in Europe: Minimal APC investment
and – as far as possible – minimal O&M costs – in compliance with existing emission limits! Preferred APC Sytems: „Overall Dry“ Characteristics: Stronger legal driver in Europe still missing, but expected to be issued soon.
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Agenda
• Introduction: Low or Near Zero Mercury Emissions?
• What about Single-Stage APC Systems - Wet, Semidry or Dry?
• Multi-Stage APC Systems
• Dry Stage upstream of wFGD
• Dry Stage downstream of wFGD
• Conclusions
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Source: M. S. Berry and B. W. Vosteen: „Bromine Injection Technology Demonstrations at Plant Miller for Removing Vapor Phase Mercury “, 12th ICESP in Nuremberg, May 2011
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Source: M. S. Berry and B. W. Vosteen: „Bromine Injection Technology Demonstrations at Plant Miller for Removing Vapor Phase Mercury “, 12th ICESP in Nuremberg, May 2011
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Source: M. S. Berry and B. W. Vosteen: „Bromine Injection Technology Demonstrations at Plant Miller for Removing Vapor Phase Mercury “, 12th ICESP in Nuremberg, May 2011
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Source: M. S. Berry and B. W. Vosteen: „Bromine Injection Technology Demonstrations at Plant Miller for Removing Vapor Phase Mercury “, 12th ICESP in Nuremberg, May 2011
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MSW Incineration Plant Brno (Czech Republic) in 2010 (Design CNIM /Martin/Siemens)
Source: Vojtěch Doležal: “EU Funding: Financing and Implementa3on”, WtERT Annual Conference“, Brno, October 12 – 14, 2010
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Source: „The BRNO Waste to Energy Plant“, WtERT Annual Conference“, Brno, October 12 – 14, 2010
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PAC
H2O + Ca(OH)2
1989
1995 Cl-
as HCl
Flue Gas + Fly Ash (HCl, SOx, NOx, UBC, CaO...)
90 – 180 °C
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KNXTM Testing with Holcomb DFGD, 350 MWe, PRB coal
Sorbent Injection
Sorbent Storage and 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
2006
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Synergistic Effect of KNXTM + Mer-CureTM
500 MW PRB with Particulate Scrubber
0
1
2
3
4
5
6
7
8
Baseline Mer-Cure @ 1 lb/MACF Mer-Cure & KNX
Stac
k Hg
Lb/
TBtu
55% incremental performance improvement
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Agenda
• Introduction: Low or Near Zero Mercury Emissions?
• What about Single-Stage APC Systems - Wet, Semidry or Dry?
• Multi-Stage APC Systems
• Dry Stage upstream of wFGD
• Dry Stage downstream of wFGD
• Conclusions
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RMVA Köln of AVG mbH – Residual Waste Incineration Plant Cologne, 4 Parallel Units with Multi-Stage APC Systems each - in operation since 1998 (Designed by L&C Steinmueller, Gummersbach, in 1995)
Plant capacity 4 x 200,000 tonnes/year,
4 x 100,000 Nm3/hour (dry, @ 8 % O2) Hg concentration in boiler raw gas: 150- 200 ( ...1000) µg/Nm3/hour
Hg emission concentration (sorbent traps): „non detectable“ (Near Zero)
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Source: AVG Abfallentsorgungs- und Verwertungsgesellschaft mbH, Cologne, 2011
5 APC stages at each of the 4 parallel lines: 1. Ca(OH)2-based Spray Dryer (100 % Evaporation: Closed Loop) 2. Wet HCl-Scrubber ( Quench + 2 Stages at pH = 0 and pH = 0.5) with 100 % Hg Capture at Regenerative Ion Exchange Columns 3. Wet SO2-Scrubber (pH = 6, lime-based -> Gypsum) 4. SCR - DeNOx (including PCDD/F Destruction) 4. HOC-Polishing Filter (4 parallel Moving Beds à 150 tonnes HOC)
Solid APC Byproducts (to be disposed off) - No Liquid Blow Down! 105 °C
180 °C
230 °C
65 °C
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Raw Gas
Clean Gas
Loaden Coke
Fresh Coke
L&C Steinmueller GmbH - Hugo Petersen GmbH (1988) Moving Bed Design as developed by R&D Steinmüller in 1989 (Dr. Vosteen / Dr. Thielen)
1989
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4 x 4 Moving Beds = 16 Beds, each à 150 tonnes HOC (particle size 1.25 – 5 mm) Depth: 0.8 m Height: 15 m
Width: 6 m
CO/O2 control during shut down
Raw Gas
Clean Gas
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AVG Cologne
(concentrations @ 8 % O2)
CEM Data
HCl : 0.1 mg/Nm3 dry SO2: 0.0 mg/Nm3 dry
NO2: 44.5 mg/Nm3 dry Dust: 0.3 mg/Nm3 dry
Single Measurements
Hgtot: << 1 µg/Nm3 dry (n.d.)
PCDD/F: 0.0013 ng TEQ/Nm3 dry
Source: http://www.avgkoeln.de/mva/emissionswerte.php
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Agenda
• Introduction: Low or Near Zero Mercury Emissions?
• What about Single-Stage APC Systems - Wet, Semidry or Dry?
• Multi-Stage APC Systems
• Dry Stage upstream of wFGD
• Dry Stage downstream of wFGD
• Conclusions
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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
bituminouscoal
bituminouscoal
air
air
FGD
Source: Vosteen, Nolte et al.: „Chlorine- and bromine-enhanced Hg sorption on ESP fyl ash from a coal-fired slag-tap boiler and on cement raw meal“, VDI Seminar 431802, September 29 - 30, 2003 in Duesseldorf (Germany)
Multi-stage APC System – APC Type: dry/wet
BAYER/Currenta GmbH& Co oHG in Uerdingen: PC-fired Boiler (100 MWtherm) Co-Combustion of Industrial Sewage Sludges
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Fire side bromide addition (internal bromination) is improving Hg-adsorption at fly ash UBC by the factor 2,5
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)
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-
conc
entr
atio
n in
ESP
-fly
ash
[mg/
kg]
no bromide addition to boiler
with bromide addition to boiler
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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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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)
Bagh
ouse
Rem
oval
(% o
f Inl
et H
g)MS200 W Harrington MS200 E Harrington C-PAC W HarringtonC-PAC E Harrington Darco Hg LH W Harrington Darco Hg LH E HarringtonKNX W Harrington KNX E Harrington CF Plus W TolkCF Plus E Tolk KNX E Tolk Darco Hg/KNX W TolkDarco 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
KNXTM + Limited ACI is also very effective in dry systems (APH, FF)
Ref: Dutton et al., 2008
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Agenda
• Introduction: Low or Near Zero Mercury Emissions?
• What about Single-Stage APC Systems - Wet, Semidry or Dry?
• Multi-Stage APC Systems
• Dry Stage upstream of wFGD
• Dry Stage downstream of wFGD
• Conclusions
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After-burning Chamber
Waste Heat Boiler
Sewage Sludge
Multiple-Hearth Kiln
Chorinated Liquid Waste
Sorbalite (AC + Ca(OH)2 + CaCO3 )
Entrained Flow Adsorber
Quench Rotary Jet Scrubber Scrubber
Stack
BAYER / Currenta Sewage Sludge Combustion Plant VA3 since 1997 Multi-Stage WFGD and Entrained Flow Adsorber as Tail-End Unit
Sorbalite Injection, LUEHR Reactor with Ball-Rotor, LUEHR Flat Bag Filter and Recirculation System
Source: Vosteen, Schulle, Listner: „Flue Gas Cleaning by Dry Sorption behind Sewage Sludge Combustion Plant of BAYER in Leverkusen-Bürrig“, Third Independant Symposium on Air Pollution Control at Combustion Plants and other Thermal Processes of Bergmann Consulting, Dorint Hotel Fontana, Stuttgart, Mach 31 – April 1, 1998
Multi-Stage APC System – APC Type: wet/dry
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LUEHR Entrained Flow Adsorber
Recycling Screw
Ball Rotor
LUEHR Reactor
LUEHR Flat Bag
Fabric Filter
Fly ash discharge
Stack
LUEHR Ball Rotor
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Rauchgas zum Kamin
Hg(0)QR (S-1200)
* Rotationswäscher sauer zweistraßig ausgeführt
Rotationswäschersauer
Strahlwäscheralkalisch
Saugzug
Tropfen-abscheider
Quenche
CKW
Kessel
Nachbrennkammer
Etagenofen
el.
Q Hg(II)
F
TMQ
F
TMQ
Q Hg(II)
KühlerM
M
T F P
TRMR
Hg(0)
Hg(0)
Lühr-Minireaktor
el.
el.
MSO2QR O2
Hg(0)QR (EPM)
Vorfilter, beheizt
Füllkörperkolonne , beheizt
el.
Thermostat mit 5%iger NaOH Lsg
SO2-AbsorptionVersuch 4
After-Burning Chamber
Waste Heat Boiler
Sewage Sludge
Feed
Multiple-Hearth Kiln
Chlorinated Liquid Waste
Feed
Off Gas to Stack
Off Water to WWTP
Heated Filter
Total Scrubber as used in test 4)
NaOH, 5 weight-%
Packed Column
Quench Rotary Scrubber Jet Scrubber Demistor
Fixed Bed in Bypass behind Scrubber (R&D BAYER/Vosteen in August 1995)
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VOSTEEN Consulting
Tests #1 - #5 in July – August 1995
Mea
n H
g R
emm
oval
Rat
es
(%)
Test #1 #2 #3 #4 #5 total scrubbing
10 % HOC
Hg,total
- 40 %-points drop in Hgmet Removal by Norit GL50 in case of missing Selfimpregnation
- 77 %-points drop in Hgmet Removal in case of missing AC ( “Sand only“)
![Page 38: Bromine Enhanced Dry Mercury Capture · QR SO2 O2 QR Hg(0) (EPM) Vorfilter, beheizt Füllkörperkolonne , beheizt el. Thermostat mit 5%iger NaOH Lsg SO2-Absorption Versuch 4 After-Burning](https://reader033.fdocuments.us/reader033/viewer/2022042923/5f716f6f6631711a4562f366/html5/thumbnails/38.jpg)
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VOSTEEN Consulting
Selfimpregnation of Norit GL50 promotes Hgmet-Capture (1)
Bypass-Test # 2 at July 17th, 12:00 until July 18th, 5:30, 1995 Bed content: 340 g Sand + 1 g Norit GL 50, 9 g Ca(OH)2
Test duration (hours)
Hg,total
Out
let:
Hg
spec
ies
(µ
g/ds
cm)
Inle
t: H
g sp
ecie
s
(µg/
dscm
)
Test duration (hours)
Hgmet-Sorption obviously needs Selfimpregnation
While Hgion-Sorption does‘nt need
Selfimpregnation
Hg,total
Test duration (hours)
![Page 39: Bromine Enhanced Dry Mercury Capture · QR SO2 O2 QR Hg(0) (EPM) Vorfilter, beheizt Füllkörperkolonne , beheizt el. Thermostat mit 5%iger NaOH Lsg SO2-Absorption Versuch 4 After-Burning](https://reader033.fdocuments.us/reader033/viewer/2022042923/5f716f6f6631711a4562f366/html5/thumbnails/39.jpg)
39
VOSTEEN Consulting
Selfimpregnation of Norit GL50 promotes Hgmet-Capture (2)
Bypass-Test # 2 at July 17th, 12:00 until July 18th, 5:30, 1995 Bed content: 340 g Sand + 1 g Norit GL 50, 9 g Ca(OH)2
Test duration (hours) Test duration (hours)
Hg,
ion
spci
es re
mm
oval
rate
(%
)
Hg,
met
spe
cies
rem
mov
al ra
te
(%)
Test duration (hours)
Hgmet-Sorption
Obviously: Selfimpregnation
needed
Hgion-Sorption:
Selfimpregnation not needed
![Page 40: Bromine Enhanced Dry Mercury Capture · QR SO2 O2 QR Hg(0) (EPM) Vorfilter, beheizt Füllkörperkolonne , beheizt el. Thermostat mit 5%iger NaOH Lsg SO2-Absorption Versuch 4 After-Burning](https://reader033.fdocuments.us/reader033/viewer/2022042923/5f716f6f6631711a4562f366/html5/thumbnails/40.jpg)
40
VOSTEEN Consulting
Agenda
• Introduction: Low or Near Zero Mercury Emissions?
• What about Single-Stage APC Systems - Wet, Semidry or Dry?
• Multi-Stage APC Systems
• Dry Stage upstream of wFGD
• Dry Stage downstream of wFGD
• Conclusions
![Page 41: Bromine Enhanced Dry Mercury Capture · QR SO2 O2 QR Hg(0) (EPM) Vorfilter, beheizt Füllkörperkolonne , beheizt el. Thermostat mit 5%iger NaOH Lsg SO2-Absorption Versuch 4 After-Burning](https://reader033.fdocuments.us/reader033/viewer/2022042923/5f716f6f6631711a4562f366/html5/thumbnails/41.jpg)
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VOSTEEN Consulting
Conclusions
In general, Near Zero Hg Emissions necessitate multi-stage APC systems
Precombustion Bromide Addition enhances dry and wet mercury capture
Tail-end APC systems behind wFGD need minimal „Selfimpregnation“ or external „Pre-impregnation“ of the AC (e.g. BPAC)
![Page 42: Bromine Enhanced Dry Mercury Capture · QR SO2 O2 QR Hg(0) (EPM) Vorfilter, beheizt Füllkörperkolonne , beheizt el. Thermostat mit 5%iger NaOH Lsg SO2-Absorption Versuch 4 After-Burning](https://reader033.fdocuments.us/reader033/viewer/2022042923/5f716f6f6631711a4562f366/html5/thumbnails/42.jpg)
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VOSTEEN Consulting
Agenda
Questions please ?
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VOSTEEN Consulting
Tail-end Moving Bed and/or Fixed Bed behind Cement Plants
WO 22011/139787 of ALBEMARLE CORPORATION on: Reduction of Mercury Emissions from Cement Plants
2011