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

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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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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

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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

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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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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

45

50

55

60

65

70

75

80

85

90

95

100

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

500

750

1000

1250

1500

1750

2000

2250

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)

0

10

20

30

40

50

60

70

80

90

100

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

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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

1600,00 g/h

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

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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.

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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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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.