Multimedia Impacts of Halogen Injection for Mercury Control in Coal- Fired Boilers Connie Senior, Ken Baldrey, Will Morris, Sharon Sjostrom Presented at EUEC January 30, 2012 ADA: Innovate, Develop, Commercialize
Motivation for This Presentation Adding halogens increases Hg oxidation, native capture, and removal efficiency of ACI You ll hear a lot about halogens at EUEC sometimes perspective is useful
Why Add Halogens? Adding halogens to fuel or flue gas: Halogen content of US coals varies widely
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Why Add Halogens? Adding halogens to fuel or flue gas: Halogen content of US coals varies widely Br, ug/g Source: USGS COALQUAL database Bromine content typically 1% to 4% of chlorine content 60 50 40 30 20 10 0 Eastern Interior (Illinois Basin) y = 0.0482x R² = 0.1319 0 50 100 150 200 250 300 Cl, ug/g
Why Add Halogens? Adding halogens to fuel or flue gas: 500 ug/g Cl in coal = ~40 ppmv HCl in flue gas 500 ug/g Br in coal = ~17 ppmv HBr in flue gas HX in gas, ppmv, 3% O 2 dry 100 80 60 40 20 0 HCl HBr 0 200 400 600 800 1,000 Halogen in Coal, µg/g dry
Why Add Halogens? Adding halogens to fuel or flue gas: Halogen content of US coals varies widely Oxidation of Hg and capture of Hg on fly ash enhanced with additions of halogens, like Cl and Br %Oxidized Hg at Air Preheater Outlet 100 80 60 40 20 0 Halogen addition at various full-scale PRB boilers 0 500 1000 1500 2000 2500 3000 Halogen in Coal, ppmw dry NaCl MgCl2 CaCl2 HCl CaBr2 Source: Dombrowski et al., 2006
Why Add Halogens? Adding halogens to fuel or flue gas: Halogen content of US coals varies widely Oxidation of Hg and capture of Hg on fly ash enhanced with additions of halogens, like Cl and Br Many plants APCDs can take advantage of native capture Hg Removal across FGD 100% 80% 60% 40% 20% 0% 10 100 1,000 10,000 Coal Chlorine, ppm dry Source: 1999 ICR
100 90 Why Add Halogens? Adding halogens to activated carbon increases the ability to capture elemental Hg in lowhalogen flue gas (subbituminous or lignite) Brominated Carbon % Vapor-phase Hg Removal 80 70 60 50 40 30 20 10 0 Meramec 2, Darco Hg-LH Meramec 2, Darco Hg Stanton 1, Darco Hg-LH Stanton 1, B-PAC Stanton 1, Darco Hg 0 2 4 6 8 10 Sorbent (lb/mmacf) Non- Brominated Carbon
Summary: Why Add Halogens? Adding halogens to fuel or flue gas: Halogen content of US coals varies widely Oxidation of Hg and capture of Hg on fly ash enhanced with additions of halogens, like Cl and Br Many plants APCDs can take advantage of native capture Adding halogens to activated carbon increases the ability to capture elemental Hg in lowhalogen flue gas
How Effective Are Halogens? Halogens increase oxidized mercury: Br more effective than Cl Increased Hg removal across scrubbers Removal of Hg across FGD 100% 80% 60% 40% 20% Dry FGD, FF Wet FGD 0% 0% 20% 40% 60% 80% 100% Fraction Hg 2+ at Inlet Source: DOE/EPRI sampling campaigns
How Effective Are Halogens? Halogens increase oxidized mercury: Br more effective than Cl Increased Hg removal across scrubbers Total Hg Removal (coal-to-stack) 100% 90% 80% 70% 60% 50% 40% 30% 20% 10% 0% Monticello: PRB/lignite, ESP, wet FGD Chlorine addition Bromine injection 1 10 100 1000 10000 Halogen in coal, ug/g
How Effective Are Halogens? Halogens increase oxidized mercury: Br more effective than Cl Increased Hg removal across scrubbers Halogens increase effectiveness of PAC Hg Removal 100 80 60 40 20 0 Plant Hardin: SCR/SDA/FF KNX + 0.14 lb/mmacf PAC KNX 0% 20% 40% 60% Percent recommended KNX rate Source: DOE/EPRI sampling campaigns
Effect of SCRs on Added Halogens Catalysts drive reactions toward equilibrium Results will be catalyst-specific Adding Br to the fuel makes the shift to Hg 2+ take place at higher temperatures (than Cl) 100% %Oxidized Hg 80% 60% 40% Baseline + 3 ug/g Br 20% + 18 ug/g Br + 33 ug/g Br + 328 ug/g Br 0% 600 700 800 900 Temperature, o F Equilibrium modeling of Plant Miller data of Berry et al.
Effect of SCRs on Added Halogens Catalysts drive reactions toward equilibrium Results will be catalyst-specific Adding Br to the fuel makes the shift to Hg 2+ take place at higher temperatures (than Cl) Hg 0, ug/dnm 3 9 8 7 6 5 4 3 2 1 0 SCR Inlet SCR Outlet Equilibrium 0 100 200 300 400 Added Br, ug/g coal equivalent Comparison of Plant Miller data of Berry et al. with calculated equilibrium
Effect of SCRs on Added Halogens Bromine is more efficient (equal mass basis) than chlorine at oxidizing Hg across SCRs Hg 0, ug/dnm 3 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 Equilibrium at 720 o F Subbituminous Coals Bromine Results will be catalyst-specific Subbituminous (low-chlorine) coals only 0.5 0.0 Chlorine 0 100 200 300 400 Halogen, ug/g coal equivalent
Fate and Impacts of Halogens What are the potential impacts of halogen addition on the boiler, APCDs, and emissions? Corrosion Fly ash Stack emissions Scrubber interactions Boiler SCR Air Heater Stack Fuel Burners Particulate Collector SO 2 Scrubber Induced Draft Fan Coal Pulverization Coal Supply
Corrosion in Flue Gas Chlorine corrosion in furnaces can occur for very high levels of chlorine in coal (> 2000 µg/g) Bromine addition at much lower concentrations Indirect evidence that HBr might be more corrosive than HCl at flue gas temperature No direct comparison, but HBr corrosion higher than baseline (no HBr) in simulated flue gas (6-month study) Corrosion loss, mm 0.12 0.1 0.08 0.06 0.04 0.02 0 Baseline 51 ppmv HBr 0 100 200 300 400 Temperature, o F Zhuang et al., 2009
Bromine Addition: Fly Ash Impacts Bromine additive or brominated PAC results in increase in Br in fly ash Example: Br injection at Monticello (C-ESP) Br, µg/g Br in fly ash Br injected 8 7 6 5 4 3 2 1 0 11/1/05 11/15/05 11/29/05 12/13/05 Bromine injection at Monticello (EERC, URS data) 350 300 250 200 150 100 50 0 Br addedm µg/g coal
Bromine Addition: Fly Ash Impacts Fly Ash, µg/g 14 12 10 8 6 4 2 0 Bromine additive or brominated PAC results in increase in Br in fly ash Example: Br injection at Plant Miller (PRB, C-ESP) According to the authors: Br in Fly Ash Br in Leachate 0 20 40 60 Added Br, µg/g coal equivalent 0.4 0.3 0.2 0.1 0.0 Leachate, mg/l Hg concentration in fly ash didn't increase with Br injection 1% of Br captured by fly ash 50% of Br on fly ash leached in SPLP test Dombrowski et al., 2008
Source: 2010 ICR Chlorine Emission from APCDs
Bromine Emission from APCDs PIPP Meramec FF C-ESP Brominated PAC injection Boiler 1 Boiler 2 C-ESP C-ESP Fuel addition Boiler 3 C-ESP 0% 50% 100% Percent of added halogen emitted in stack All boilers are pulverized coal, burning subbituminous coal
Source: 2010 ICR Chlorine Emission from APCDs
Halogens in Wet Scrubbers Adding halogens (Cl or Br) increases oxidized Hg, which increase capture of Hg in scrubber Wet FGD scrubbers remove halogens efficiently Average Cl removals for wet FGDs (2010 ICR): 81% for subbituminous, 97% for bituminous Removal of Br at Plant Miller wet FGD: 94-96% (Dombrowski et al., 2008) Halogens build up in wet scrubber liquor
Halogens in Wet Scrubbers Halogens build up in wet scrubber liquor slowly, depending on scrubber design Br, mg/l, Hg, µg/l 500 400 300 200 100 Br in FGD liquor Hg in FGD liquor Br injected 0 11/1/05 11/15/05 11/29/05 12/13/05 Bromine injection at Monticello (EERC, URS data) 350 300 250 200 150 100 50 0 Br addedm µg/g coal
Halogens and Wet Scrubbers Increased Cl, Br concentration in scrubber liquor can decrease Hg re-emission Recent observations (Air Quality VIII) that Br addition to the fuel increases Se in scrubber liquor Data from bituminous site with C-ESP, wet FGD Se in fly ash, µg/g % Se capture by fly ash Se in FGD liquor, µg/l Baseline 24 70% 300 Br addition 10 20% 4900 (Dombrowski et al., 2011) Less uptake of Se by fly ash means more Se enters FGD
Summary Halogen fuel/flue gas additives OR halogenated PAC Where do halogens go? Some removal in particulate control devices Efficient removal in FGDs Br is new kid on the block information needed: Corrosion Multi-media fate Trace metal interactions Fuel Halogen Injection Boiler Burners Coal Pulverization SCR Air Heater Halogenated Carbon Injection Particulate Collector Fly Ash Coal Supply Stack SO 2 Induced Scrubber Draft Fan Scrubber Blowdown Stack Emission
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