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ADVANCES IN BROMINE-BASED MERCURY EMISSION CONTROL AT DIFFERENT FRENCH WASTE INCINERATION PLANTS
BERNHARD VOSTEEN VOSTEEN CONSULTING GMBH, COLOGNE, THIERRY GOSSET AND XAVIER CHAUCHERIE SARP INDUSTRIES-VEOLIA S.A., LIMAY (FRANCE)
VGB WORKSHOP MERCURY CONTROL, MELIA HOTEL BERLIN, JUNE 8 – 9, 2017
VOSTEEN Consulting
VOSTEEN Consulting
Special thanks for cooperation with Vosteen Consulting and SARPI-VEOLIA
to
Dr. Alfred Grissinger, Luc Zonnenberg, Bert Horemans
from
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AGENDA •! SARPI-VEOLIA‘s Hazardous Waste Incineration (HWI) in Europe
•! Developement of the BEMO-Technology with CURRENTA in 2000 - 2009
•! SARPI-Application of the BEMO-Technology at Sedibex since 2016 (3 lines with wet FGD)
•! SARPI-Applications at diverse HWI plants with dry FGD since 2014
•! Experiences with the precipitation agent PRAVO®
•! Influence of Sulfur •! Outlook
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VOSTEEN Consulting
10 SARPI-Hazardous Waste Incineration sites in Europe Testings of the BEMO-Technology already performed at 5 sites (with 10 lines in total)
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Preserving the environment by tackling the most difficult pollutants
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AGENDA •! SARPI-VEOLIA‘s Hazardous Waste Incineration (HWI) in Europe •! Developement of the BEMO-Technology with CURRENTA in 2000 - 2009
•! SARPI-Application of the BEMO-Technology at Sedibex since 2016 (3 lines with wet FGD)
•! SARPI-Applications at diverse HWI plants with dry FGD since 2014
•! Experiences with the precipitation agent PRAVO®
•! Influence of Sulfur
•! Outlook
VOSTEEN Consulting
VOSTEEN Consulting
Hg-CEM
Hg-CEM
Invention of the BEMO-Technology in 2000 by Prof. Vosteen
Bromides (HBr, NaBraq, CaBr2,aq)
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Source: Diploma thesis Andreas Pohontsch (2000)
Injection of 4 small Hg-bombs of 26 g only into the ABC, causing – without bromide-addition – 4 huge Hg(0)-peaks upstream of the tail-end SCR
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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
Source: Diploma thesis Rico Kanefke (2001)
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!! Bromine far more effective than chlorine
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Mass ratio Br/Hg and achieved Hg removal rate in test spiking the boiler raw gas with 9,600 µg Hgtotal/dscm
Source: Diploma thesis Rico Kanefke (2001)
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Final Installation in 2009 (Dr. Rico Kanefke)
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Final Installation in 2009 (Dr. Rico Kanefke)
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Final Installation in 2009 (Dr. Rico Kanefke)
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Numberof injection lances at the ABC varies between 1 and 3
(depending on the mixing situation)
Final Installation in 2009 (Dr. Rico Kanefke)
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Explanation of the control principle: Bromide injection only when needed
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Yearly means in 1999 - 2001
Yearly means in 2005 - 2016
?
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Successful industrial applications of the BEMO-Technology not only within CURRENTA, but at EGLV‘s central WWTP Bottrop
- since 2004, i.e. more than 12 years
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First external testings at the WWTP Bottrop already in December 2003 and June 2004
Little effort during testings in 2004 – Great success
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AGENDA •! SARPI-VEOLIA‘s Hazardous Waste Incineration (HWI) in Europe
•! Developement of the BEMO-Technology with CURRENTA in 2000 - 2009
•! SARPI-Application of the BEMO-Technology at Sedibex since 2016 (3 lines with wet FGD)
•! SARPI-Applications at diverse HWI plants with dry FGD since 2014
•! Experiences with the precipitation agent PRAVO®
•! Influence of Sulfur
•! Outlook
VOSTEEN Consulting
VOSTEEN Consulting
VOSTEEN Consulting
VOSTEEN Consulting
VOSTEEN Consulting
AGENDA •! SARPI-VEOLIA‘s Hazardous Waste Incineration (HWI) in Europe •! Developement of the BEMO-Technology with CURRENTA in 2000 - 2009
•! SARPI-Application of the BEMO-Technology at Sedibex since 2016 (3 lines with wet FGD)
•! SARPI-Applications at diverse HWI plants with dry FGD since 2014
•! Experiences with the precipitation agent PRAVO®
•! Influence of Sulfur
•! Outlook
VOSTEEN Consulting
VOSTEEN Consulting
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3
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Continuous monitoring of the mercury species
Hg(0), Hg2+ and Hgtot under harsh conditions
in the raw gas upstream of the bagfilter
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40
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15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95
Hgt
ot
aba
tem
ent e
ffici
ency
(%)
Hg(2+) (%)
AC GL50 : 130 mg/Nm3 db
AC GL50 : 180 mg/Nm3 db
AC GL50 : 250 mg/Nm3 db
The AC GL50 flowrate is also important !
Filter temperature: 210°C
Mercury oxidation already upstream of dry APC improves sorptive Hg removal at normal (undonated) AC towards 100 %. Lowering the filter temperature slightly is advantageous.
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0
250
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08:30 08:40 08:50 09:00 09:10 09:20 09:30 09:40 09:50 10:00 10:10 10:20 10:30
Time (2014)
Hg
conc
. ups
tream
APC
(!g/
Nm
3 db)
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Hg
conc
. dow
nstre
am A
PC (!
g/N
m3 d
b)
Hg(0)Hg(2+)HgTHgT (Stack)
HgCl2 1% Hg w. (1500 !g/Nm3 db th.)
CaBr2 52% w. 2*7,5 l/h(Br/Hg = 200)
CaBr2 52% w. 2*12,5 l/h(Br/Hg = 320)
AC GL50 : 250 mg/Nm3 db ; Lime : 110 kg/h
Almost 100% Hg oxidation achieved with mass ratio Br/Hg > 300 Bromide need e.g. only: 3 IBC à 1000 liter CaBr2 (52 %) per year
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AGENDA •! SARPI-VEOLIA‘s Hazardous Waste Incineration (HWI) in Europe
•! Developement of the BEMO-Technology with CURRENTA in 2000 - 2009
•! SARPI-Application of the BEMO-Technology at Sedibex since 2016 (3 lines with wet FGD)
•! SARPI-Applications at diverse HWI plants with dry FGD since 2014
•! Experiences with the precipitation agent PRAVO®
•! Influence of Sulfur
•! Outlook
VOSTEEN Consulting
The precipitation agents of PAN Chemie Dr. Fülöp and Vosteen Consulting are
Precipan, PRAVO®100, PRAVO®200 These are inorganic liquid agents containing polysulfides and thiosulfate. The highest content of active sulfur has PRAVO®200. For mercury precipitation at wet FGD, only low injection rates are needed (e.g. < 0.5 liter /hour PRAVO® at 60.000 Nm3/h flue gas). An important initial step in such applications is the formation of highly reactive polysulfanes as H-S-S-S-S-H (PRAVO addition to the acidic milieu as performed at MSWI in Darmstadt, 3 lines since 2008); but PRAVO does also work effectively, when added to a basic/neutral scrubber stage (as performed in sewage sludge combustion at WWTP Karlsruhe –Neureuth, 2 lines since 2007/8). References for successful industrial long-time applications at wet FGD :
Municipal Solid Waste Incineration (Darmstadt) Hazardous Waste Incineration (Leverkusen, Fos-Sur-Mer, Sedibex) Sewage Sludge Combustion (Bottrop, Karlsruhe-Neureuth) Thermal Treatment of Contaminated Soils (Moerdijk) Bituminous Coal Combustion (Block 2 in München Unterföhring)
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Tests in 2007/8
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Regelung der PraVo Dosierung in Abh‰ ngigkeit des Hg-Messwertes nach W‰ scher f̧ r eine Rauchgasmenge von ca. 60.000 m³/h
0,00 g/h
200,00 g/h
400,00 g/h
600,00 g/h
800,00 g/h
1000,00 g/h
1200,00 g/h
1400,00 g/h
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1800,00 g/h
2000,00 g/h
0 µg/m³ 5 µg/m³ 10 µg/m³ 15 µg/m³ 20 µg/m³ 25 µg/m³ 30 µg/m³ 35 µg/m³ 40 µg/m³ 45 µg/m³ 50 µg/m³ 55 µg/m³
Messwert Hg nach W‰ scher
Men
ge a
n Pr
avo
Dosing curve of PRAVO®100 as measured at MSWI line to suppress mercury reemissions
Hgtot in clean gas behind scrubber
PR
AVO
®10
0 flo
w ra
te
Testings in 2008 (Dipl.-Ing. Ulrich Mielke)
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Testing PRAVO®200 at SWM in 2014
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AGENDA •! SARPI-VEOLIA‘s Hazardous Waste Incineration (HWI) in Europe
•! Developement of the BEMO-Technology with CURRENTA in 2000 - 2009
•! SARPI-Application of the BEMO-Technology at Sedibex since 2016 (3 lines with wet FGD)
•! SARPI-Applications at diverse HWI plants with dry FGD since 2014
•! Experiences with the precipitation agent PRAVO®
•! Influence of Sulfur
•! Outlook
VOSTEEN Consulting
SARPI regularly performs 30 d sampling-probes on PCDD/F at all its lines (obligatory in France)
Punctual probes on PBCDD/Fwere performed, as well, confirming the findings of Funcke and Vehlow in the late 1990s.
VOSTEEN Consulting
VOSTEEN Consulting
AGENDA •! SARPI-VEOLIA‘s Hazardous Waste Incineration (HWI) in Europe
•! Developement of the BEMO-Technology with CURRENTA in 2000 - 2009
•! SARPI-Application of the BEMO-Technology at Sedibex since 2016 (3 lines with wet FGD)
•! SARPI-Applications at diverse HWI plants with dry FGD since 2014
•! Experiences with the precipitation agent PRAVO®
•! Influence of Sulfur
•! Outlook
VOSTEEN Consulting
VEOLIA activities global
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SARPI will perform tests of the BEMO-Technology at Veolia’s MSWI sites starting in October 2017
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Prof. Bernhard Vosteen and Ric Ulrich, PE, presenting the VOSTEEN-Technology („BEMO“) at the VEOLIA Hazardous Waste Incineration site in Port Arthur, near Houston, TX (USA) - already in 2006, i.e. more than 10 years ago.