Chemistry in Biomass Combustion (ChemCom)Åbo Akademi

together with

Helsinki University of TechnologyTampere University of Technology

Umeå University

with support of

Tekes

and industrial partners

Andritz OyFoster Wheeler Energia Oy

International Paper Inc.Kvaerner Power OyOy Metsä-Botnia Ab

Vattenfall Utveckling AB

Presented at the 2nd FFRC Liekki-day, Turku, 24.1.06

Past – Present - Future

- Since 1988 successful national research programs:• Long-term oriented research• Close collaboration between universities• Close cooperation with industrial partners

Excellent experiences and results

- Presently no national research program in combustion

ChemCom

Chemistry in Biomass Combustion (ChemCom)

ProjectSteering Group

Fundamental Research on

Chemistry in Biomass Combustion

Experiment Modelling Information

ProjectCoordination (ÅA)

Åbo Akademi Process Chemistry Centre

Åbo Akademi Process Chemistry Centre

Combustion and Materials ChemistryProf. Mikko Hupa

Materials Chemistry

Combustion Chemistry

Materials Chemistry

Combustion Chemistry• Mikko Hupa

• Christian Mueller• Bengt-Johan Skrifvars• Rainer Backman

• Anders Brink• Edgardo Coda Zabetta• Mikael Forssén• Jukka Konttinen• Patrik Yrjas• Maria Zevenhoven

• Daniel Lindberg• Mischa Theis• Johan Werkelin• Vesna Barisic• Markus Engblom• Mikaela Westén-Karlsson• Tor Laurén

HELSINKI UNIVERSITY OF TECHNOLOGY

Laboratory of Energy Engineering and Environmental Protection

• Carl-Johan Fogelholm

• Mika Järvinen• Ari Kankkunen• Pasi Miikkulainen

Tampere University of Technology

Applied Optics Group

• Rolf Hernberg• Jorma Keskinen

• Toni Laurila• Albert Manninen

Energy Technology and Thermal Process Chemistry

• Rainer Backman• Dan Boström

• Mathias Råberg• Anders Larsson

Energy Technology and Thermal Process Chemistry • Umeå University

ChemCom Mission

To develop improved understanding of

chemical aspects in biofuel combustion –

this way paving the road for development of

future fuel conversion technologies

Research Areas in ChemCom

Waste

Biomass Black Liquor

Gas Phase &Emissions

Characterisation &Conversion Inorganic Material

Furnace Processes Bed Processes

InformationExperiment Modelling

ChemCom – Research Structure

I1 I2

I3 I4

InformationExperiment Modelling

E1 E2M1

E3 E4

M2E5 E6

M3

Waste

Biomass Black Liquor

E7 E8

Research Topics – Solid Fuels

Biomass/Waste

Characterisation &Conversion

Inorganic MatterBehaviour

• Ash Particlesstickiness & depositionaerosols & heavy metals

• Fuel particlesconversion ratesrelease

• Fuel-NNOx formation tendencies

• Ash-forming matterrelease & particle formation

• Trace elementsrelease & particle formation

Researchers – Solid Fuels

Biomass/Waste

ÅABengt-Johan SkrifvarsRainer BackmanPatrik YrjasMischa TheisMicaela Westén-KarlssonTor Laurén

ÅAMikael ForssénJukka KonttinenRainer BackmanJohan WerkelinEdgardo Coda ZabettaMaria Zevenhoven

Characterisation &Conversion

Inorganic MatterBehavior

TUTRolf HernbergJorma KeskinenToni LaurilaAlbert Manninen

Fractionation database

ÅA fuel-, char- and ash databases

Fuel analysis data; proximate and ultimate analyses, selective leaching analyses for ash forming matter & trace elements

Deposit database Data from full-scale deposit measurement campaigns since 1996; process data (fuel, char. temperatures, boiler type, boiler load, etc.) deposit growth, deposit analyses.

Black liquor database Combustion experiments in single droplet reactors; pulping process type, standard liquor analyses, conversion time,swelling, formation of NO, SO2, CO2, and CO, pyrolysis and char yield

Nitrogen database Data from novel combustion experiments in a small-scale FBC; distribution of fuel-N between reactive and non-reactive (N2) volatile components and char-nitrogen.

Mineral Matter and Trace Elements

Characteristics of ash particles and their formation with special focus on trace elements. - selective leaching in combination with ion chromatography- continued evaluation of the stepwise leaching technique - tests on fuels and partly oxidized chars combined with SEM/EDX.

To give a deeper understanding of mineral matter & trace element release/behavior for better predictions and better model input values

Chemical Fractionation

/J. Werkelin, PhD work 2003-2006/

Metals in wood

/J. Werkelin, PhD work 2003-2006/

Co-combustion & Ash Behavior

Characteristic differences for fuel mixturesdeposit formation vs erosion - Lab-scale studies of deposition and erosion tendencies 1) various fuels with strongly differing ash characteristics2) taylor-made model substances

- Full-scale verification measurements of fly ash behavior with in-situ, on-line fly ash measurement equipment

To get validation data of deposition vs erosion submodel developed to be done in M1.

Ash deposition behavior of biofuel blends

0102030405060708090

negative interaction

positive interaction

no interaction

Dep

ositi

on ra

te

[mg/

(g c

m2 )]

0 20 40 60"Dirty Fuel" [mass %]

80 100

/M. Theis, PhD work 2003-2006/

The EFR(University of Toronto)

Gas burner

Sample feeder

Probe

Furnace9 m

Particles

1000 ºC

550 ºC

Deposit Sampling

500 g/40 min

1000 ºC

< 1mm

Deposition Results Peat/Straw Mixtures

020406080

100120140160

0 10 20 30 40 50 60 70 80 90 100Straw fraction (wt-%)

Dep

ositi

on (g

/m2 h)

RestP2O5ClSO3K2ONa2OMgOCaOCr2O3Fe2O3Al2O3SiO2

/M. Theis, PhD work 2003-2006/

Biofuel ash chemistry predictor

Fuelsample

1

Stepwiseleaching,

SEMEquilibrium

Composition+

CFD

Fuelsample

2

Stepwiseleaching,

SEM

Fuelsample

3

Stepwiseleaching,

SEM

Chemical equilibrium calculation45% Plywood + 55% Bark, “reactive flyash”

/Backman, Zevenhoven 2002/

CaCO3 CaO

MgOMg(SiO4)0.5 Ca(SiO4)0.5

KClNaCl

K2 SO4K2CO3

Na2 CO3

Na2 SO4

Na, K)2(CO3 , SO4 , Cl2 )

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

120011001000900800700600500400Temperature °C

amou

nt g

/100

g

liquidsolid

Biofuel ash chemistry predictor

Fly ash particle”hit map”

: Extreme fouling: High fouling: Fouling: Low fouling: No fouling

/C. Mueller: “Wilhelm Jost” prize 2004/

Ash behaviour predictor – CFD- situation today -

Bottom ash,Bed behaviour

Reactive fly

ash

H 2O+NH 4A

c

Stepwiseleaching,

SEM Inert flyash,Cleaning effect

Fuels

In-situ diagnostics of combustion chemistry

To explore the possibilities of developing Laser Photoacoustic Analysis LPA as a research tool for determining the composition of aerosols in combustion:- Analytical modelling of the photoacoustic response of aerosol particles

- Experimental study of the photoacoustic response of aerosol particles containing trace elements

To develop methods able to determinequantitative trace element species selective analysis results

/Rolf Hernberg, Jorma Keskinen/

Manganese (Mn) is one of the “dirty dozen” although important in wood

Manganese (Mn) chemistry in biomass utilisation

(found in the same order of magnitude as Fe and Al)

- To follow up the role of Mn in the trace element emission legislation and to review and report valuable information on environmental effects of Mn.

- To summarize the Mn chemistry at combustion and gasification conditions Summary will focus on the chemical form of Mn in the fuel, Distribution between coarse-, fine ash fractions, and gas phase.

- To determine how Mn reacts with bed materials in FBCs

The experimental methods used in this study are:- Chemical analysis and chemical fractionation- Thermal analysis- Molecular Beam Mass Spectrometry (MBMS)- SEM/EDS analysis

EU directive on incineration of waste containing fuels

Sb + As + Cr + Co +Cu + Mn + Ni + Pb + V 0.5 mg/m3n* (twice a year)

Cd +Tl 0.05 mg/m3n* (twice a year)

Hg 0.05 mg/m3n* (twice a year)

*6 % O2, dry gases

0.5 mg/m3n* in flue gases ≈ 3 – 4 ppm (mg/kg) in dry wood

Metals in 37 wood species

0.0000001 0.000001 0.00001 0.0001 0.001 0.01 0.1 1

Concentration (mass fraction)

CKAl

MgFe

P

NaZn

BCu

PbCr

NiMo

AsCd

HgSe

1 %1 ppm 100 %

Mn

Manganese in wood, Werkelin 2002

0

500

1000

1500

2000

2500

Pine

Asp

en

Spru

ce

Bir

ch

Pine

Asp

en

Spru

ce

Bir

ch

Pine

Asp

en

Spru

ce

Bir

ch

Pine

Asp

en

Spru

ce

Bir

ch

Tree species

mg

Mn/

kg d

ry w

ood

Trunk woodBarktrunk

Bark branches

Twigs

min

max

Average