1111thth ECCRIAECCRIA 201620161111thth ECCRIA ECCRIA –– 20162016Comparison of Metal Emissions Comparison of Metal Emissions
from Airfrom Air--Firing of Coal and BiomassFiring of Coal and Biomassfrom Airfrom Air Firing of Coal and Biomass Firing of Coal and Biomass for Carbon Capture Applicationsfor Carbon Capture Applications
Karen N FinneyyEnergy 2050, University of Sheffieldwith Janos Szuhánszki, Khalidah Al-Qayim, Bill Nimmo and yMohamed Pourkashanian
ContentsContentsBECCS and net negative emissions● BECCS and net negative emissions
● UKCCSRC Bio-CAP-UK Programme● PACT facilities and test campaigns● El Cerrejon coal● El Cerrejon coal● Biomass – white wood pellets● Conclusions and future work
BECCSBECCS● BECCS or bio CCS is where biomass● BECCS or bio-CCS is where biomass
energy is combined with carbon capture and storageand storage
● Biomass inherently produces lower net CO2 (biogenic emissions) and thus 2 ( g )combining it with carbon capture can result in zero or net negative emissions
● This project compares two different forms of carbon capture from biomass firing:
b i d b ipost-combustion and oxy-combustion capture
UKCCSRC Bio-CAP-UKUKCCSRC Bio-CAP-UK● The UK Carbon Capture and Storage Research Centre● The UK Carbon Capture and Storage Research Centre
funded five Call 1 research projects on capture ● Bio CAP UK: air/oxy biomass combustion with● Bio-CAP-UK: air/oxy biomass combustion with
CO2 capture technology – a UK study● This aims to accelerate progress towards achieving● This aims to accelerate progress towards achieving
operational excellence for flexible, efficient and environmentally sustainable bio-CCS thermal power y pplants by developing and assessing fundamental knowledge, pilot plant tests and techno economic and lif l dilife cycle studies
UKCCSRC Bio-CAP-UK• fuel, char and ash characteristics and milling requirements• torrefied biomass combustion rate fuel ignition burn outWP1
f UKCCSRC Bio-CAP-UK● The UK Carbon Capture and Storage Research Centre
• torrefied biomass combustion rate, fuel ignition, burn-out and ash quality
• production of biomass database for subsequent WPs
fundamental studies and biomass characterisation
● The UK Carbon Capture and Storage Research Centre funded five Call 1 research projects on capture
● Bio CAP UK: air/oxy biomass combustion with
• air-biomass combustion with post-combustion amine capture
• oxy-biomass combustion with flue gas recycling
WP2pilot-scale plant
campaign at UKCCSRC ● Bio-CAP-UK: air/oxy biomass combustion with CO2 capture technology – a UK study
● This aims to accelerate progress towards achieving
y g y g• solvent degradation studies with biomass-generated CO2
p gPACT
WP3● This aims to accelerate progress towards achieving operational excellence for flexible, efficient and environmentally sustainable bio-CCS thermal power
• process simulations linked to CFD models of rate-controlling components in the power plant
• virtual power plant simulations
WP3power plant simulations
for air-/oxy-biomass combustion y pplants by developing and assessing fundamental knowledge, pilot plant tests and techno economic and lif l di
• developing viable process configurations for different bio-CCS options
WP4bio-CCS value chains inlife cycle studies CCS options
• full life cycle and techno-economic assessmentsbio-CCS value chains in
the UK
Test Campaigns at PACTTest Campaigns at PACT● Coal firing in air with amine based post combustion● Coal-firing in air with amine-based post-combustion
capture – air-fired baseline [current phase: ongoing]● Biomass firing in air with amine based with post● Biomass-firing in air with amine-based with post-
combustion capture [current phase: ongoing]● Oxy coal firing oxy combustion baseline [next phase]● Oxy-coal firing – oxy-combustion baseline [next phase]● Oxy-biomass firing [next phase]
P id i f ti● Provide information on:~ flame imaging, optimal burner settings and combustion efficiency~ ash formation/composition (deposition, slagging, fouling, corrosion)p ( p gg g g )~ heat flux/transfer ~ extensive emissions analysis
Aims and ObjectivesAims and Objectives ● Extensive emissions analysis:● Extensive emissions analysis:
~ standard exhaust gas analysis (CO, CO2, O2, NOx, SOx, UHC)~ suction pyrometry for in-flame measurements
● Inorganic/metal emissions:~ assess variations in metal aerosol emissions, both quantity and
type from coal and biomass firing under different operatingtype, from coal and biomass firing under different operating regimes (air-firing vs. oxy-fuel combustion)
~ investigate element partitioning, particularly of metals between lid d h (b h fl h d l )solid and gaseous phases (bottom ash, flyash and aerosols)
~ consider the impacts of metals aerosols on downstream processes, e.g. solvent-based post-combustion capture and CO2compression/transport/storage
BackgroundBackground● Fuel composition has significant impacts on● Fuel composition has significant impacts on
combustion and downstream processes:~ alkali metals (Na and K) cause slagging/fouling ( ) gg g g
on boiler and heat exchanger components~ transition metals (Fe, Cu, V, etc.) contribute to
oxidative degradation of the capture solventoxidative degradation of the capture solvent~ acidic elements (Cl, S, N) cause corrosion under
deposits through reactions with metal surfaces and form inorganic anion compounds that aidand form inorganic anion compounds that aid solvent degradation
~ particulate matter (particle carryover) can cause solvent degradation as flyash contains highersolvent degradation, as flyash contains higher concentrations of metal contaminants
UKCCSRC PACTUKCCSRC PACT●● PPilot scale AAdvanced CO CCapture●● PPilot-scale AAdvanced CO2 CCapture
TTechnology facilities funded by DECC and EPSRC through the UKCCSRCEPSRC through the UKCCSRC
● Specialist national facilities for research in advanced fossil-fuel energy, bioenergy and gy, gycarbon capture technologies
● Support and catalyse industrial/academic pp yR&D to accelerate the development and commercialisation of novel low carbon
h l i b id b b htechnologies, bridge gap between bench-scale and industrial pilot trials
PACT FacilitiesPACT Facilities ● Technical assessment of up to 100% biomass firing using● Technical assessment of up to 100% biomass firing using
PACT’s 250 kW combustion test facility, coupled with the on-site, solvent-based post-combustion capture planton site, solvent based post combustion capture plant
● Other key facilities and techniques include:~ ICP-OES for metal aerosol emissions in the flue gas~ DMS for particle size assessments in the flue gas ~ FID, chemiluminescence and NDIR for determinations of
combustion gas composition – both in-flame and in the exhaust co bust o gas co pos t o bot a e a d t e e aust~ heat flux probe for total and radiative heat transfer ~ suction pyrometer/thermocouples for in-furnace temperatures~ deposition probedeposition probe ~ ash collection
PACT FacilitiesPACT Facilities ● Spectro CIROSCCD ICP OES can identify the emissions● Spectro CIROSCCD ICP-OES can identify the emissions
spectra (spectral lines) of various volatile/non-volatile major, minor, trace and ultra-trace elementsmajor, minor, trace and ultra trace elements~ Al, Ag, B, Ba, Br, Ca, Cd, Co, Cr, Cu, Fe, Hg, I, K, Li, Mg, Mn, Na,
Ni, P, Pb, S, Sb, Sc, Si, Sn, Th, Ti, V, Zn
● Performs real-time, state-of-the-art, continuous, online diagnostics, for quantitative and simultaneous multi-elemental detection of entrained metal aerosolselemental detection of entrained metal aerosols
● We will look specifically for elements that cause of operational issues are toxic easily vaporised highoperational issues, are toxic, easily vaporised, high concentrations, etc.
Fuel AnalysisFuel AnalysisEl Cerrejon Wood Pellets
Proximate Analysis moisture (ar) 5 07 6 69Proximate Analysis (dry, wt%)
moisture (ar) 5.07 6.69ash 4.63 0.75volatiles 37.35 83.70
fixed carbon 58.01 15.55Ultimate Analysis(wt%)
nitrogen 1.32 0.15carbon 69 44 48 44carbon 69.44 48.44hydrogen 4.55 6.34sulphur 0.07 <0.02chlorine 0.03 <0.01oxygen (by diff) 15.15 37.69
Energy Content GCV 28.70 19.41Energy Content(MJ/kg)
GCV 28.70 19.41NCV 27.68 18.10
Experimental data from the University of Leeds project partner for the UKCCSRC Bio-CAP-UK Project
Fuel AnalysisFuel AnalysisElemental Oxide (%) El Cerrejon Wood PelletsSilicon Dioxide (SiO ) 39 9 13 6Silicon Dioxide (SiO2) 39.9 13.6Aluminium Oxide (Al2O3) 16.6 1.9Iron (III) Oxide (Fe2O3) 10.8 1.3Titanium Dioxide (TiO2) 0.6 0.1Calcium Oxide (CaO) 14.4 27.0Magnesium Oxide (MgO) 1.9 5.5Magnesium Oxide (MgO) 1.9 5.5Sodium Oxide (Na2O) 1.9 1.3Potassium Oxide (K2O) 1.6 10.1Manganese (II,III) Oxide (Mn3O4) 0.1 2.2Phosphorous Pentoxide (P2O5) 0.8 3.1Sulphur Trioxide (SO3) 11.4 2.4p ( 3)
Experimental data from the University of Leeds project partner for the UKCCSRC Bio-CAP-UK Project
Fuel AnalysisFuel AnalysisTrace Metals (mg/kg) El Cerrejon Wood PelletsArsenic (As) 2 4 0 3Arsenic (As) 2.4 0.3Cadmium (Cd) <0.1 0.1Chromium (Cr) 4.7 2.2Copper (Cu) 11.7 2.6Nickel (Ni) 3.6 0.7Mercury (Hg) <0.1 <0.1Mercury (Hg) 0.1 0.1Lead (Pb) 3.8 0.7Vanadium (V) 5.1 <0.6Zinc (Zn) 14.9 10.2
Experimental data from the University of Leeds project partner for the UKCCSRC Bio-CAP-UK Project
El Cerrejon CoalEl Cerrejon Coal● Higher concentrations of Si Al Fe Zn S and Cu in the● Higher concentrations of Si, Al, Fe, Zn, S and Cu in the
initial fuel analysis, as well as other inorganics/metals compared to the biomasscompared to the biomass
● Notable concentrations of Ca, Mg, K and Na● ICP OES analysis of the flue gas in the exhaust duct● ICP-OES analysis of the flue gas in the exhaust duct
revealed the presence of a variety of aerosol species from air-firing of the El Cerrejon coal sample in the PACT g j p250 kW combustion test facility
SPECTRAL LINE CALIBRATION METHOD COAL ICP-OES RESULTS min range max range minimum maximum mean units
Aluminium: Al 167.078 0.000313 2.83 0.409 2.989 (adl) 1.64 mg/m3
Al i i Al 396 152 0 0286 2 83 0 496 3 572 ( dl) 1 774 / 3Aluminium: Al 396.152 0.0286 2.83 0.496 3.572 (adl) 1.774 mg/m3
Arsenic: As 189.042 0.0178 2.83 0 0.039 0.019 mg/m3
Gold: Au 242.795 0.00453 2.83 0 0.016 0.002 mg/m3
Barium: Ba 455.404 0.000553 2.83 0 0.007 0.001 mg/m3
Beryllium: Be 313.042 0.000215 2.83 0 0 (bdl) 0 mg/m3
3Calcium: Ca 315.887 0.00215 70.80 0.254 0.254 0.254 mg/m3
Calcium: Ca 393.366 0.00215 70.80 1.184 8.255 2.677 mg/m3
Calcium: Ca 422.673 0.00215 70.80 0.351 4.019 2.097 mg/m3
Cadmium: Cd 228.802 0.00235 2.83 0 0.001 0 mg/m3
Chromium: Cr 267.716 0.00527 2.83 0 0.008 0.002 mg/m3
3Copper: Cu 324.754 0.00458 2.83 0 0 0 mg/m3
Iron: Fe 259.941 0.00288 2.83 0.625 3.782 (adl) 1.925 mg/m3
Potassium: K 766.491 0.178 28.3 0 0.286 0.104 mg/m3
Lithium: Li 670.780 0.00523 2.83 0 0 (bdl) 0 mg/m3
Magnesium: Mg 279.553 0.000297 70.80 0 0.757 0.387 mg/m3
Magnesium: Mg 285.213 0.000297 70.80 0.284 0.709 0.432 mg/m3
Manganese: Mn 257.611 0.000402 2.83 0 0.053 0.026 mg/m3
Molybdenum: Mo 202.030 0.000201 2.83 0 0 (bdl) 0 mg/m3
Sodium: Na 588.995 0.0338 70.80 0 0.415 0.206 mg/m3
Sodium: Na 589.592 0.0338 70.80 0 0.979 0.457 mg/m3
Nickel: Ni 227.021 0.00529 2.83 0 0 (bdl) 0 mg/m3
Nickel: Ni 231.604 0.00529 2.83 0 0.023 0.003 mg/m3
Phosphorous: P 177.495 0.00313 70.80 0 0.237 0.142 mg/m3
Phosphorous: P 178.287 0.00313 70.80 0.319 0.319 0.319 mg/m3
Phosphorous: P 213.618 0.00313 70.80 0.143 0.322 0.207 mg/m3p gLead: Pb 168.215 0.024 2.83 0.119 0.152 0.136 mg/m3
Lead: Pb 220.353 0.024 2.83 0 0 (bdl) 0 mg/m3
Platinum: Pt 214.423 0.00122 2.83 0 0 0 mg/m3
Sulphur: S 180.731 0.00863 70.80 74.820 (adl) 245.864 (adl) 184.237 (adl) mg/m3
Sulphur: S 182.034 0.0518 70.80 74.445 (adl) 263.704 (adl) 192.686 (adl) mg/m3p ( ) ( ) ( ) gTin: Sn 189.991 0.00539 2.83 0 0.014 0.002 mg/m3
Vanadium: V 292.464 0.00144 2.83 0 0.039 0.02 mg/m3
Zinc: Zn 213.856 0.00079 2.83 0 0.019 0.011 mg/m3
Zirconium: Zr 339.198 0.00323 2.83 0 0 (bdl) 0 mg/m3
100
1000 Al 167.078Al 396.152As 189.042Au 242.795
10
100Ba 455.404Be 313.042Ca 315.887Ca 393.366Ca 422 673
113:12:00 13:40:48 14:09:36 14:38:24 15:07:12 15:36:00
mg/
m3 )
Ca 422.673Cd 228.802Cr 267.716Cu 324.754Fe 259.941
0.1
cent
ratio
n (m K 766.491
Li 670.780Mg 279.553Mg 285.213Mn 257 611
0.01
emen
t Con
c Mn 257.611Mo 202.030Na 588.995Na 589.592Ni 227.021
0.0001
0.001Ele
Ni 231.604P 177.495P 178.287P 213.618Pb 168 215
0.00001
Pb 168.215Pb 220.353Pt 214.423S 180.731S 182.034
0.000001Time
Sn 189.991V 292.464Zn 213.856Zr 339.198
250
300
mg/
m3 )
9
Al 167.078 Al 396.152
150
200
cent
ratio
n (m
7
8
Ca 393.366 Ca 422.673
50
100
emen
t Con
c
S 180.731 S 182.034 6
mg/
m3 )
Fe 259.941
012:36:00 13:12:00 13:48:00 14:24:00 15:00:00 15:36:00 16:12:00
El
Time
5
cent
ratio
n (m
3
4
lem
ent C
onc
● S is present in high concentrations, in excess of 250 mg/m3
● Notable levels of Al Ca and Fe (all
2
3El● Notable levels of Al, Ca and Fe (all averaging ~2 mg/m3)
● Alkali metals present as aerosols:~ K: up to 0 29 mg/m3
1
~ K: up to 0.29 mg/m3
~ Na: up to 0.98 mg/m3
● Toxic/heavy metals only found in limited concentrations (Ni Cd Cr Pb
012:36:00 13:12:00 13:48:00 14:24:00 15:00:00 15:36:00 16:12:00
Time
limited concentrations (Ni, Cd, Cr, Pbaveraging less than 0.01 mg/m3), often below the calibrated detection limit
White Wood PelletsWhite Wood Pellets
ELEMENT DATA FOR COAL COMMENT FOR BIOMASS
Al i i t 3 6 / 3 h l Al l l i biAluminium up to 3.6 mg/m3 much lower Al levels in biomass
Calcium up to 8.3 mg/m3 double the level of Ca in biomass
Iron up to 3 8 mg/m3 much lower Fe levels in biomassIron up to 3.8 mg/m much lower Fe levels in biomass
Potassium up to 0.29 mg/m3 more than 6 x K in biomass
Magnesium up to 0.76 mg/m3 3 x more Mg in biomassMagnesium up to 0.76 mg/m 3 x more Mg in biomass
Sodium up to 0.98 mg/m3 similar Na levels
Phosphorous up to 3.2 mg/m3 higher P in biomass
Sulphur >70 mg/m3 (above detection limit) 1/5 of the amount of S in biomass
White Wood PelletsWhite Wood Pellets● Smaller particle sizes of biomass may result in higher● Smaller particle sizes of biomass may result in higher
particle carryover from combustion ● This coupled with the differences in composition could● This, coupled with the differences in composition could
result in:~ a much greater potential for deposition (slagging and fouling)
throughout the combustion plant, as well as more active sites for corrosion (similar Na and more K)
~ additional impacts on the capture plant due to higher levels of add t o a pacts o t e captu e p a t due to g e e e s otransition metals and particles – faster/more solvent degradation? (more Mg, etc.)
Conclusions and Future WorkConclusions and Future Work● ICP OES analysis is suitable for providing quantitative● ICP-OES analysis is suitable for providing quantitative
data on aerosol emissions from combustion● Coal baseline data is being generated to which biomass● Coal baseline data is being generated, to which biomass
can be compared~ this showed El Cerrejon coal produced notable concentrations of
S, Al, Ca, Mg, Na and Fe emissions in the flue gas
● Biomass is likely to give considerably higher emissions f C fof Ca, K, Mg and P compared to coal, based on the fuel
analysis, but potentially lower emissions of Al, Fe and SDiff t l t t i ill b d d f i● Different clean-up strategies will be needed for various fuels, co-firing and CCS applications
THANK YOU!THANK YOU!THANK YOU!THANK YOU!Comparison of Metal Emissions Comparison of Metal Emissions
from Airfrom Air--Firing of Coal and BiomassFiring of Coal and Biomassfrom Airfrom Air Firing of Coal and Biomass Firing of Coal and Biomass for Carbon Capture Applicationsfor Carbon Capture Applications
Karen N FinneyyThe authors would like to express their thanks to the UKCCSRC for their financialsupport of this research [Bio-CAP-UK: Air/Oxy Biomass Combustion with CO2 CaptureT h l A UK St d (UKCCSRC C1 40)] M th k l t D R h l H llTechnology, A UK Study (UKCCSRC-C1-40)]. Many thanks also go to Dr Rachael Hallfor her technical expertise and advice on the project, for which the authors are verygrateful, as well as Hans Waarlo and Lee Price from Spectro.
Top Related