Chlorine and Bromine in Coals and their Influence on Mercury Removal from Flue Gases

Transcription

1 Chlorine and Bromine in Coals and their Influence on Mercury Removal from Flue Gases Prof. Dr.-Ing. Bernhard W. Vosteen, Vosteen Consulting GmbH, Köln MBA Tim C. Hartmann, ALSTOM Power Inc., Knoxville, TN M. Sc. Mark S. Berry, PE, Southern Company Services, Birmingham, AL Berliner Planungs- und Imissionsschutz-Konferenz Am 19. Und 20. November 2012 Hotel Berlin am Lützowplatz

2 Agenda Introduction: BBA today and 10 years ago EPA s MATS as issued on December 21, 2011 US Coals (Mercury, Chlorine, Bromine, Sulfur) Southern Company Wet Mercury Capture at Plant Miller Alstom Power Wet Mercury Capture at Plant WE Plaesant Prairie Dry Mercury Capture US EPRI Balance of Plant Report August 2012 Outlook (Cooperation Vosteen/STEAG/AE&E) Conclusions 2

3 Bromine Based Mercury Abatement German Patent DE (assigned to CURRENTA GmbH & Co. OHG) European Patent EC (assigned to CURRENTA GmbH & Co. OHG) US Patent 6, (assigned to Vosteen Consulting GmbH) Ca Patent (assigned to Vosteen Consulting GmbH) In 2004, CURRENTA GmbH & Co ohg granted a worldwide exclusive license and transferred the North American Patents to Vosteen Consulting GmbH 3

4 Licensees of Vosteen Consulting GmbH in North America ALSTOM Power - Environmental Control Systems, Knoxville/TN, USA, KNX TM Mercury Control Technology as Tradename of ALSTOM Power Inc. Exclusive license for USA and Canada 2500 MWe in commercial application since 2010 Electric Power Research Institute, Palo Alto/CA, USA, Limited R&D License for the States Southern Company Services, Inc. Birmingham/AL, USA, License for units owned by Southern Company 4

5 Precombustion Bromide Addition to Coal or Boiler Bromide Addition (BBA) Today a main topic at any large US Conference on Air Pollution Control VOSTEEN Consulting Session C2 at EUEC 2012 in Phoenix AZ: Hg Control Demonstrations & Bromine sponsored and chaired by Vosteen Consulting GmbH 5

6 Today 54 US Power Stations are applying Precombustion Bromide Addition commercially VOSTEEN Consulting Electric Power Research Institute (EPRI) at Mega Symposium in Baltimore, August 21 23, 2012 Source: Katherine Dombrowski, Katie Arambasick (URS), Ramsay Chang (EPRI), Corey Tyree (Souther Company): Balance of Plant Effects of Bromide Addition for Mercury Control, paper # 93, Power Plant Air Pollutant Control MEGA Symposium, Baltimore MD, August 21-23,

7 Air Quality (VI) Conference, Arlington, VA, Sept Hg Hgmet/Hgtotal -Speziesanteil im (weight-%) Kesselrohgas nach Wäsche [Hg met /Hg ges in Gew.%] Hg met /Hg ges -Speziesanteil nach Hg primärer Oxidation Hg-Chlorierung und nachfolgender sekundärer Hg-Bromierung in SVA (Messwerte vom ) by Bromine (HWC) Hg met /Hg ges -Speziesanteil nach primärer Hg Hg-Chlorierung Oxidationin SVA (Messwert vom ) by Chlorine (HWC) Cl ges - bzw. alternativ Br ges -Gehalt im Kesselrohgas [mg/m?i. N. tr.] Br total or Cl total in boiler flue gas (mg/nm 3 dry) Bromine > 25 times more effective for Hg met oxidation than chlorine, in waste incineration as well as in coal combustion (BAYER patent applications pending world wide) Source: Vosteen, Kanefke et al.: Mercury-Related Chemistry in Waste Incineration and Thermal Process Flue Gases, Air Quality (VI) Conference, Arlington, VA, Sept

8 8

9 KNX TM Coal Additive drums and pumps in a full scale test 9

10 10

11 11

12 12

13 Agenda Introduction EPA s MATS as issued on December 21, 2011 US Coals (Mercury, Chlorine, Bromine, Sulfur) Southern Company Wet Mercury Capture at Plant Miller Alstom Power Wet Mercury Capture at Plant WE Plaesant Prairie Dry Mercury Capture US EPRI Balance of Plant Report August 2012 Outlook (Cooperation Vosteen/STEAG/AE&E) Conclusions 13

14 14

15 Agenda Introduction EPA s MATS as issued on December 21, 2011 US Coals (Mercury, Chlorine, Bromine, Sulfur) Southern Company Wet Mercury Capture at Plant Miller Alstom Power Wet Mercury Capture at Plant WE Plaesant Prairie Dry Mercury Capture US EPRI Balance of Plant Report August 2012 Outlook (Cooperation Vosteen/STEAG/AE&E) Conclusions 15

16 USGS CoalQual data base - data excerpt from Open-File Report (1994) 5000 samples - evaluated by Vosteen Consulting with courtesy of Prof. Dr. Belkin, Febr. 20, 2010 Powder River Basin Northern, Central and Southern Appalachian 16

17 Only low mercury coals? (e.g. PRB with 0.1 ppm Hg dry) What about the other coals - in the long run? PRB 17

18 18

19 19

20 Source: Allan Kolker and Jeffrey C. Quick, U.S. Geological Survey and Utah Geological Survey: Geologic Controls on Halogens in Coal, MEC 9 - Mercury Emissions fromcoal, St. Petersburg (Russia), May

21 21

22 Source: Allan Kolker and Jeffrey C. Quick, U.S. Geological Survey and Utah Geological Survey: Geologic Controls on Halogens in Coal, MEC 9 - Mercury Emissions fromcoal, St. Petersburg (Russia), May

23 Low Halogen Coals as Subbituminous PRB Coal and Lignite and as imported coals from Columbia, also fired in USA Cl Br Source: Allan Kolker and Jeffrey C. Quick, U.S. Geological Survey and Utah Geological Survey: Geologic Controls on Halogens in Coal, MEC 9 - Mercury Emissions fromcoal, St. Petersburg (Russia), May

24 Agenda Introduction EPA s MATS as issued on December 21, 2011 US Coals (Mercury, Chlorine, Bromine, Sulfur) Southern Company Wet Mercury Capture at Plant Miller Alstom Power Wet Mercury Capture at Plant WE Plaesant Prairie Dry Mercury Capture US EPRI Balance of Plant Report August 2012 Outlook (Cooperation Vosteen/STEAG/AE&E) Conclusions 24

25 Source: M. S. Berry and B. W. Vosteen: Bromine Injection Technology Demonstrations at Plant Miller for Removing Vapor Phase Mercury, 12 th ICESP in Nuremberg, May

26 Source: M. S. Berry and B. W. Vosteen: Bromine Injection Technology Demonstrations at Plant Miller for Removing Vapor Phase Mercury, 12 th ICESP in Nuremberg, May

27 Source: M. S. Berry and B. W. Vosteen: Bromine Injection Technology Demonstrations at Plant Miller for Removing Vapor Phase Mercury, 12 th ICESP in Nuremberg, May

28 Source: M. S. Berry and B. W. Vosteen: Bromine Injection Technology Demonstrations at Plant Miller for Removing Vapor Phase Mercury, 12 th ICESP in Nuremberg, May

29 Source: M. S. Berry and B. W. Vosteen: Bromine Injection Technology Demonstrations at Plant Miller for Removing Vapor Phase Mercury, 12 th ICESP in Nuremberg, May

30 Agenda Introduction EPA s MATS as issued on December 21, 2011 US Coals (Mercury, Chlorine, Bromine, Sulfur) Southern Company Wet Mercury Capture at Plant Miller Alstom Power Wet Mercury Capture at Plant WE Plaesant Prairie Dry Mercury Capture US EPRI Balance of Plant Report August 2012 Outlook (Cooperation Vosteen/STEAG/AE&E) Conclusions 30

31 License granted in 2008 to WE Power Stations Pleasant Prairie (2 x 600 MWe Units with SCR, ESP, WFGD in commercial opperation since January 1st, 2010) 2 x 600 MWe Base Load (24 hours/day) PRB coal 2 x 315 tons/hour 0.11 ppm Hg KNX (as CaBr 2 ) 25 ppm Br on coal Hg total at stack < 1 µg/dscm (both units) 31

32 Power Station WE Pleasant Prairie with SCR, ESP, WFGD 25 ppm Br per Coal only, SCR in service with NH 3 32

33 Agenda Introduction EPA s MATS as issued on December 21, 2011 US Coals (Mercury, Chlorine, Bromine, Sulfur) Southern Company Wet Mercury Capture at Plant Miller Alstom Power Wet Mercury Capture at Plant WE Plaesant Prairie Dry Mercury Capture US EPRI Balance of Plant Report August 2012 Outlook (Cooperation Vosteen/STEAG/AE&E) Conclusions 33

34 BAYER/Currenta GmbH& Co ohg in Uerdingen: PC-fired Boiler (100 MW therm ) Co-Combustion of Industrial Sewage Sludges Eindosierung Spiking with von HgCl HgCl 2 und NaCl 2 and NaBr Messung CEMs von for Hg Hg ges total und and Hg Hg met met CEMs for Hg total bituminous coal air FGD bituminous coal air Multi-stage APC System APC Type: dry/wet 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 , September 29-30, 2003 in Duesseldorf (Germany) 34

35 Fire side bromide addition (internal bromination) is improving Hg-adsorption at fly ash UBC by the factor 2,5 Hg-concentration in ESP-fly ash [mg/kg] 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 with bromide addition to boiler no bromide addition to boiler 170 C Hg (µg/nm 3 total -concentration in flue gas behind ESP [!g /Nm?dry] 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 , September 29-30, 2003 in Duesseldorf (Germany) 35

36 Meramec 300 MWe, PRB 1 lb/mmacf = 16 mg/m 3 Sharon Sjostrom: Mercury Control for PRB and PRB/Bituminous Blends, presented at EUEC, Tucson/Arizona, January 24,

37 1 lb/mmacf = 16 mg/m 3, 290 F = C Sharon Sjostrom: Mercury Control for PRB and PRB/Bituminous Blends, presented at EUEC, Tucson/Arizona, January 24,

38 38

39 Alstom s Mer-Cure TM & KNX TM Portable Mer-Cure TM Test Trailer Richard LaFlesh et al. of Alstom Power Inc. : Progress Report on Mercury Control Retrofit at the Colstrip Power Station, Power Plant Air Pollutant Control MEGA Symposium, August 30 - September 2, 2010, Baltimore MD (USA) - Paper # 91 39

40 Synergistic Effect of KNX TM & Mer-Cure TM 500 MW PRB with Particulate Scrubber Stack Hg Lb/TBtu % incremental performance improvement Baseline 1 lb/macf Mer-Cure & KNX 40

41 Colstrip Power Station Units U1 U4 (2,200 MWe) fired with PRB coal from the Rosebud Mine Richard LaFlesh et al. of Alstom Power Inc. : Progress Report on Mercury Control Retrofit at the Colstrip Power Station, Power Plant Air Pollutant Control MEGA Symposium, August 30 - September 2, 2010, Baltimore MD (USA) - Paper # 91 41

42 Agenda Introduction EPA s MATS as issued on December 21, 2011 US Coals (Mercury, Chlorine, Bromine, Sulfur) Southern Company Wet Mercury Capture at Plant Miller Alstom Power Wet Mercury Capture at Plant WE Plaesant Prairie Dry Mercury Capture US EPRI Balance of Plant Report August 2012 Outlook (Cooperation Vosteen/STEAG/AE&E) Conclusions 42

43 Source: Katherine Dombrowski, Katie Arambasick (URS), Ramsay Chang (EPRI), Corey Tyree (Souther Company): Balance of Plant Effects of Bromide Addition for Mercury Control, paper # 93, Power Plant Air Pollutant Control MEGA Symposium, Baltimore MD, August 21-23,

44 (1) EPRI Study (Status August 2012) Source: Katherine Dombrowski, Katie Arambasick (URS), Ramsay Chang (EPRI), Corey Tyree (Souther Company): Balance of Plant Effects of Bromide Addition for Mercury Control, paper # 93, Power Plant Air Pollutant Control MEGA Symposium, Baltimore MD, August 21-23,

45 (2) EPRI Study (Status August 2012) Source: Katherine Dombrowski, Katie Arambasick (URS), Ramsay Chang (EPRI), Corey Tyree (Souther Company): Balance of Plant Effects of Bromide Addition for Mercury Control, paper # 93, Power Plant Air Pollutant Control MEGA Symposium, Baltimore MD, August 21-23,

46 Agenda Introduction EPA s MATS as issued on December 21, 2011 US Coals (Mercury, Chlorine, Bromine, Sulfur) Southern Company Wet Mercury Capture at Plant Miller Alstom Power Wet Mercury Capture at Plant WE Plaesant Prairie Dry Mercury Capture US EPRI Balance of Plant Report August 2012 Outlook (Cooperation Vosteen/STEAG/AE&E) Conclusions 46

47 Source: Thomas Lauer und Thomas Riethmann: Untersuchungen zur Quecksilberabscheidung aus Rauchgasen und Nebenprodukten in Steinkohlekraftwerken, VDI-Wissensforum Quecksilber-Emissionen, September 2012, Frankfurt 47

48 Andritz Energy & Environment (AE&E) a Licensee and Partner of Vosteen Consulting GmbH in Europe Source: Michael Kramer und Bernhard W. Vosteen: Quecksilber im Wäscher Was dann?, VDI-Wissensforum Quecksilber- Emissionen, September 2012, Frankfurt 48

49 Agenda Introduction EPA s MATS as issued on December 21, 2011 US Coals (Mercury, Chlorine, Bromine, Sulfur) Southern Company Wet Mercury Capture at Plant Miller Alstom Power Wet Mercury Capture at Plant WE Plaesant Prairie Dry Mercury Capture US EPRI Balance of Plant Report August 2012 Outlook (Cooperation Vosteen/STEAG/AE&E) Conclusions 49

50 Conclusions The KNX TM technology has been successfully operated for over 2 years. The effectiveness of CaBr 2 and its rapid response to fuel Hg variations has been demonstrated in wet and dry APC systems. The combination of pre-combustion bromide addition and normal non-brominated activated carbon injection (ACI) reliably controls Hg emissions with variable load and fuel Hg content. Many free riders 50

51 Preferred approach towards new patents - promising even in case of no inventive height 51

52 Agenda Questions please? 52