bromine enhanced dry mercury capture · qr so2 o2 qr hg(0) (epm) vorfilter, beheizt...

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

2

VOSTEEN Consulting

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

3

VOSTEEN Consulting

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

4

VOSTEEN Consulting

PRB

Only low mercury coals? (e.g. PRB with 0.1 ppm Hg dry)

What about the other coals - in the long run?

5

VOSTEEN Consulting

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

6

VOSTEEN Consulting

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?

7

VOSTEEN Consulting

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.

8

VOSTEEN Consulting

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.

9

VOSTEEN Consulting

Agenda


•  What about Single-Stage APC Systems - Wet, Semidry or Dry?




•  Conclusions

10

VOSTEEN Consulting


11

VOSTEEN Consulting


12

VOSTEEN Consulting


13

VOSTEEN Consulting


14

VOSTEEN Consulting

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

15

VOSTEEN Consulting

Source: „The BRNO Waste to Energy Plant“, WtERT Annual Conference“, Brno, October 12 – 14, 2010

16

VOSTEEN Consulting

PAC

H2O + Ca(OH)2

1989

1995 Cl-

as HCl

Flue Gas + Fly Ash (HCl, SOx, NOx, UBC, CaO...)

90 – 180 °C

17

VOSTEEN Consulting

KNXTM Testing with Holcomb DFGD, 350 MWe, PRB coal

Sorbent Injection

Sorbent Storage and Feeder

SDA

FF

18

VOSTEEN Consulting

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

19

VOSTEEN Consulting

20

VOSTEEN Consulting

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

21

VOSTEEN Consulting

22

VOSTEEN Consulting

Agenda






•  Conclusions

23

VOSTEEN Consulting

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)

24

VOSTEEN Consulting

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

25

VOSTEEN Consulting

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

26

VOSTEEN Consulting

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

27

VOSTEEN Consulting

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

28

VOSTEEN Consulting

Agenda






•  Conclusions

29

VOSTEEN Consulting

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

30

VOSTEEN Consulting

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

31

VOSTEEN Consulting

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

32

VOSTEEN Consulting

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

33

VOSTEEN Consulting

Agenda






•  Conclusions

34

VOSTEEN Consulting

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

35

VOSTEEN Consulting

LUEHR Entrained Flow Adsorber

Recycling Screw

Ball Rotor

LUEHR Reactor

LUEHR Flat Bag

Fabric Filter

Fly ash discharge

Stack

LUEHR Ball Rotor

36

VOSTEEN Consulting

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)

37

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“)

38

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

)


Hgmet-Sorption obviously needs Selfimpregnation

While Hgion-Sorption does‘nt need

Selfimpregnation

Hg,total


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

(%)


Hgmet-Sorption

Obviously: Selfimpregnation

needed

Hgion-Sorption:

Selfimpregnation not needed

40

VOSTEEN Consulting

Agenda






•  Conclusions

41

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)

42

VOSTEEN Consulting

Agenda

Questions please ?

43

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

bromine enhanced dry mercury capture · qr so2 o2 qr hg(0) (epm) vorfilter, beheizt...

Documents