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.