VOSTEEN Consulting

Bromine-Enhanced Mercury Emission Control – an Update

Prof. Dr. Bernhard W. Vosteen, Vosteen Consulting GmbH, KölnXavier Chaucherie, M.Sc., SARPI-Veolia, LimayDr. Gabor Fülöp, PAN Applied Chemistry GmbH, Kerpen

IRRC WEB CONGRESS WASTE-TO-ENERGY

OCTOBER 15 and 16, 2020

VOSTEEN Consulting

Invention of theBromine-Enhanced-Mercury Oxidation-Technology (BEMO)

and its Early Development in Germany

„Going 20 years back!“

Extended Introductionto reconsider

1

VOSTEEN Consulting

2

„Rückstandsverbrennungsanlage RVAD“ at the BAYER Site Dormagen

VOSTEEN Consulting

Hg-CEMHg-CEM

„Halogenides as Mercury Oxidizers“ were tested at the BAYER Site Leverkusen-Bürrig already in 1993 and even more in 1999 – 2002

Bromides

3

VOSTEEN Consulting

4

Spiking the Combustion Gases with HgMeasuring the Hg-concentrations with CEMs (Verewa/DURAG)

VOSTEEN Consulting

Example: Bromine versus Chlorine

5Source: B. W. Vosteen et al., EP 1 386 655 B1

VOSTEEN Consulting

6

VOSTEEN Consulting

Lhoist SorbalitAC/HOK + Ca(OH)2 + CaCO3

ChlorinatedLiquid Waste(Dichlorpropan, 75 % Cl)

CaBr2

7

!"#$%%& '()*+,-.)/

>?/86@ A?/:B3:-!CCC-D "EE!-

>?/86@ A?/:B3:-"EE%-D "E!&

NFGC+GO2C()CF)-G;-.() M/-(- ;-2-KF *-;CD (a -KF'Z11%&$623;*-F2N;);/FLF)-2'F)-FG2.)2SFEFGD+*F)74BGG./

F

VOSTEEN Consulting

Source: B. W. Vosteen et al., DE 101 31 464 B4 9

„Sulfur Dosing Ramp“ – to avoid Corrosion by Sulfation, to reduce Free Halogens and PCDD/F

VOSTEEN Consulting

Pre-combustion bromide addition onto the fired coal respectively in the hot fire-box in 2002 at the Industrial Power Plant N230 of CURRENTA GmbH & Co OHG in Uerdingen

Industrial Tests in Germany by BAYER AGwith Bromides and TMT15 starting already in 2001

10

VOSTEEN Consulting

Invention of the BEMO-Technology in 2000and its Early Development in Germany

BEMO-Technology ExperiencesHazardous Waste Combustion,Municipal Solid Waste Combustion,Sewage sludge Co-combustion with CoalSewage Sludge Mono-combustion

Agenda

11

!"#$%%& '()*+,-.)/

#%I04%d2.*2(WFG;-.)/2U2D.,)7,.)F*2-(2-GF;-2??@]@@@2-())F*YOF;G

!"#$%&#'()*'+ ,-./ .-/01 (2 34567890(.-* 10':0;<-)= &*>'?#*/; 6549@A?""

'%"2N()*.F+G2';W.-;.)F2()2e+,O2U@-K>2?@9T\2J02;L2WG(+<2(a2.-]f

!"

!"#$%%& '()*+,-.)/

&*>'? BC0DE0. F?G################6549@A?""#####################HI54J#&KC1

10':-/L /0-L=M('-/L ,-./ .-/01 *)#30;-M0N B$(/2.0E'G#

!#

!"#$%%& '()*+,-.)/

!$D!

!"#$%%& '()*+,-.)/

!$-D "

VOSTEEN Consulting

15Evaluation of the snapshot-data from the two CEMs

before CaBr2 was injected

VOSTEEN Consulting

Invention of the BEMO-Technology in 2000and its Early Development in Germany

BEMO-Technology ExperiencesHazardous Waste Combustion, Municipal Solid Waste Combustion,Sewage sludge Co-combustion with Coal,Sewage Sludge Mono-combustion

Agenda

16

VOSTEEN Consulting

ENTEGA MSWC Darmstadt3 units (220.000 t waste/y)

17

VOSTEEN Consulting

18

PRAVO®

Tests in 2008 (Dipl.-Ing. Ulrich Mielke)

VOSTEEN Consulting

Invention of the BEMO-Technology in 2000and its Early Development in Germany

BEMO-Technology ExperiencesHazardous Waste Combustion, Municipal Solid Waste Combustion,Sewage sludge Co-combustion with CoalSewage Sludge Mono-combustion

Agenda

19

VOSTEEN Consulting

Pre-combustion calcium bromide addition onto the fired coalin 2008 at the Industrial Power Plant N230 of CURRENTA GmbH & Co OHG in Uerdingen

Industrial Tests in Germany by BAYER AGat PC-fired Wet Bottom Boiler

with CaBr2 and PRAVO®

20

NaCl

CaBr2

CaBr2 PRAVO®

VOSTEEN Consulting

1000 liter IBC-container for the tested CaBr2-solution (52%), membrane dosing pumps with plastic tubings

and injection lances at each coal-feeder 21

VOSTEEN Consulting

Invention of the BEMO-Technology in 2000and its Early Development in Germany

BEMO-Technology ExperiencesHazardous Waste Combustion, Municipal Solid Waste Combustion,Sewage sludge Co-combustion with CoalSewage Sludge Mono-combustion

Agenda

22

VOSTEEN Consulting

Wastewater Treatment Plant Botrop of EGLV with 2 Fluidized Bed Combustors (FBC) for sewage sludge

23applying NaBr and PRAVO®100 since 2004

VOSTEEN Consulting

Wastewater Treatment Plant Karlsruhe-Neureut with 2 Fluidized Bed Combustors (FBC) for sewage sludge

24applying NaBr and PRAVO®100 since 2008

VOSTEEN Consulting

25

VOSTEEN Consulting

News

PRAVO®200 Storage and Dosing System installedat Lignite-fired Power Plant Schkopau (2 x 450 MWe) in 2020.

Commercial application of PRAVO®200 since 2 years

26

VOSTEEN Consulting

Power Plant SCHKOPAU (lignite, 2 x 450 MWe)

27

VOSTEEN Consulting

2 Units (2 x 450 MWe)with2 wet FGD spray towers each

PRAVO®200 dosage at 6 m levelinto the pressure side of two of thecirculation pump circuits at eachspray tower (in total 8 dosingpoints)

28

VOSTEEN Consulting

2 Truck delivery tanks for PRAVO®20029

VOSTEEN Consulting

Dosing tank (1,5 m3) Dosing system30

VOSTEEN Consulting

Redundant Dosing Pumps of PROMINENTfor each wFGD-absorber

31

VOSTEEN Consulting

News

Visit in January 2020 to PGE‘s Belchatów Power Plant (lignite- fired, 13 Units with in total 5,298 MWe), discussion of PGE‘s bromine-based tests at theirBelchatów and Turów Power Plants (as reported byPGE at ICMGP in Krakau, September 9th, 2019)

Tests of the BEMO-Technology at a German Coal-fired Power Plant (SDA, tail-end SCR) successfullyperformed in early 2020, attaining at stack 0.5 µg/Nm3

(dry, at 6 vol.-% O2)

32

VOSTEEN Consulting

The world‘s largest lignite-fired Power Plant Belchatówwith in total 5298 MWe installed capacity

VOSTEEN Consulting

Presentation Jerzy Sawicki et al. at ICMGP, September 9th, 2019 in Krakow33

VOSTEEN Consulting

News

Project TRM MSW Incineration Turino (3 grate combustion lines, dry APCs with tail-end SCR) – testlicense granted, calcium bromide delivered (ICL IP), injection system under construction (WS Engineering)

Project HW Incineration (rotary kiln, ESP, wet FGD) in Italy (SARPI-VEOLIA)

34

VOSTEEN Consulting

Presentation Giovanni Corti et al. at CEWEP, January 2020 in Dusseldorf35

Trattamento dei Rifiuti Metropolitani in Torino operates 3 grate combustion lines with in total

500,000 tonnes/year

VOSTEEN Consulting

Presentation Giovanni Corti et al. at CEWEP, January 2020 in Dusseldorf36

VOSTEEN Consulting

37

Precipitation Agents of PAN Chemie

VOSTEEN Consulting

The inorganic precipitation agents of PAN Applied Chemistry are

PreciPAN®, PRAVO®100, PRAVO®200These are liquid agents containing

Polysulfides and Polythionates

forming - by adequate mixing into acidic milieu - the highly active

Polysulfanes H-S-S- .... -S-S-Hreducing dissolved Hgion to insoluble HgS 38

VOSTEEN Consulting

39

acid added in toPrecipan after 1 min after 2 min

Mixing acid intoPreciPAN®:

Formation of sulfur

Dissolved Hgiondown from 520 mg/l to 391 mg/l

Precipitation agentnot highly effective

AcidColor:

grey, earthy

In case of acidic FGD, the precipitation effectivitystrongly depends on the way of mixing ...

VOSTEEN Consulting

40

In case of acidic FGD, the precipitation effectivitystrongly depends on the way of mixing ...

Precipan added intoacidic solution leads to

„sulfane raw oil“ after 1 min after 2 min

Mixing thePreciPAN® into the

acid:

Formation of milkysolution of

Polysulfanes

Dissolved Hgiondown from 520

mg/l to 0,51 mg/l

Precipitation agenthighly effective

Color:

black

VOSTEEN Consulting

Additional Appendix(not orally presented)

„No relevant PCDD/F and PXDD/F Emissions“

37

VOSTEEN Consulting

see B. W. Vosteen et al., DE 101 31 464 B4

44

Sulfur Addition is mitigatingFree Halogens and PXDD/F Denovo-Synthesis

VOSTEEN Consulting

42

„Sulfur Addition is reducing X2 and likewise PCDD/F“

Tests in March 2000 at an Industrial FBI of BAYER Polymers LLC

VOSTEEN Consulting

43

Tests in March 2000 at an Industrial FBI of BAYER Polymers LLC (USA)

!"#$%%& '()*+,-.)/

C

I.(P.)*2;)< c+G;)*2;-2#-;CD2

#(+GCF\2!(*-FF)Yc+)CDFY!F,(R>22^(*-FG2;-20'N5^2.)2%<.)H+G/K>2?@9U

!"#$%%& '()*+,-.)/

!$D!

!"#$%%& '()*+,-.)/

$%

I.(P.)*2;)< c+G;)*2;-2#-;CD2(a M302^,;)-2U2R.-K <GO26^'

0UTi-7L f8?:45-6/H78/J78@;-L7667P3:X Q'U+-((Zb;-!!-M76YD=-+"1

Z/@-"E!Ce-G(22)f----/J--E;EEF-:X)QA# ODUTi-G(\22)f--/J--E;EE#-:X)QA# ODUTi

+4J7H?8 "E!Ce-G(22)f---/J--E;EE&-:X)QA# ODUTiG(\22)f-/J--E;EE"-:X)QA#-ODUTi

I.(P.)*2;)< c+G;)*2;-2#-;CD2(a M302^,;)-2b2R.-K RF- 6^'

'9836-"E!Ce-G(22)f----/J---E;E#-:X)QA# ODUTiG(\22)f--/J-E;EE$-:X)QA# ODUTi

!"#$%%& '()*+,-.)/

$!

M4G ;-2#-;CD2NF;*+GLF)-* ;-2M302W,;)-2922R.-K <GO26^'2Xb@]@@@22&LUYK2<H[

AM4G E;,+F* )(-2/GF;-FG Mc2E;,+F*J

!"#$%%& '()*+,-.)/

$K;)D 8(+ EFGO L+CK]

l+F*-.()* 7 W,F;*Fm

c(G a+G-KFG .)a(GL;-.()* W,F;*F ;<<GF** -(^G(a]2IG]24FG)K;G<23]2!(*-FF)2X$F,]nbT29=@9T9?b@9[

(G /( -(K--W*\YYRRR]E(*-FF)7C()*+,-.)/]<FYF)YW+H,.C;-.()*Y