Chemistry in Biomass Combustion (ChemCom)
Åbo Akademi
together with
Helsinki University of Technology
Tampere University of Technology
Umeå University
with support of
Tekes
and industrial partners
Andritz Oy
Foster Wheeler Energia Oy
International Paper Inc.
Kvaerner Power Oy
Oy 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)
Fundamental Research on
Chemistry in Biomass Combustion
Project
Steering Group
Experiment
Project
Coordination (ÅA)
Modelling
Information
Åbo Akademi Process Chemistry Centre
Åbo Akademi
Process Chemistry Centre
Combustion and Materials Chemistry
• Mikko Hupa
• Christian Mueller
• Bengt-Johan Skrifvars
• Rainer Backman
• Anders Brink
• Edgardo Coda Zabetta
• Mikael Forssén
• Jukka Konttinen
• Patrik Yrjas
• Maria Zevenhoven
Prof. Mikko Hupa
Combustion Chemistry
Materials Chemistry
• 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
Biomass
Black Liquor
Waste
Characterisation &
Conversion
Inorganic Material
Furnace Processes
Experiment
Modelling
Gas Phase &
Emissions
Bed Processes
Information
ChemCom – Research Structure
Biomass
Black Liquor
Waste
Experiment
E1
Modelling
Information
E2
M1
E3
E4
E5
E6
E7
E8
I1
I2
I3
I4
M2
M3
Research Topics – Solid Fuels
Biomass/Waste
• Ash Particles
stickiness & deposition
aerosols & heavy metals
• Fuel particles
conversion rates
release
• Fuel-N
NOx formation tendencies
• Ash-forming matter
release & particle formation
• Trace elements
release & particle formation
Inorganic Matter
Behaviour
Characterisation &
Conversion
Researchers – Solid Fuels
Biomass/Waste
ÅA
Bengt-Johan Skrifvars
Rainer Backman
Patrik Yrjas
Mischa Theis
Micaela Westén-Karlsson
Tor Laurén
Inorganic Matter
Behavior
ÅA
Mikael Forssén
Jukka Konttinen
Rainer Backman
Johan Werkelin
Edgardo Coda Zabetta
Maria Zevenhoven
Characterisation &
Conversion
TUT
Rolf Hernberg
Jorma Keskinen
Toni Laurila
Albert Manninen
ÅA fuel-, char- and ash databases
Fractionation database
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 mixtures
deposit formation vs erosion
- Lab-scale studies of deposition and erosion tendencies
1) various fuels with strongly differing ash characteristics
2) 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.
Deposition rate
[mg/(g cm 2 )]
Ash deposition behavior of biofuel blends
90
80
70
60
50
40
30
20
10
0
negative interaction
n
io
t
c
a
ter
n
i
o
n
positive interaction
0
20
40
60
"Dirty Fuel" [mass %]
80
100
/M. Theis, PhD work 2003-2006/
Deposit Sampling
Sample feeder
500 g/40 min
Gas burner
1000 ºC
The EFR
(University
of Toronto)
Particles
< 1mm
Furnace
1000 ºC
Probe
550 ºC
9m
2
Deposition (g/m h)
Deposition Results
Peat/Straw Mixtures
160
140
120
100
80
60
40
20
0
Rest
P2O5
Cl
SO3
K2O
Na2O
MgO
CaO
Cr2O3
Fe2O3
Al2O3
SiO2
0
10
20
30
40
50
60
70
80
90
100
Straw fraction (wt-%)
/M. Theis, PhD work 2003-2006/
Biofuel ash chemistry predictor
Fuel
sample
1
Stepwise
leaching,
SEM
Fuel
sample
2
Stepwise
leaching,
SEM
Fuel
sample
3
Stepwise
leaching,
SEM
Equilibrium
Composition
+
CFD
Chemical equilibrium calculation
45% Plywood + 55% Bark, “reactive flyash”
1.4
liquid
solid
1.2
amount g/100g
1.0
Na2 SO4
Na2 CO3
K2 SO4 K2 CO3
NaCl
0.8
KCl
Na, K)2
(CO3 , SO4 , Cl2 )
Mg(SiO4 ) 0.5
MgO
0.6
Ca(SiO4 ) 0.5
0.4
CaCO3
0.2
CaO
0.0
400
500
/Backman, Zevenhoven 2002/
600
700
800
900
Temperature °C
1000
1100
1200
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 sh
a
ly
f
ve Ac
i
t
ac NH 4
e
R O+
H2
Fuels
Stepwise
leaching,
SEM
Inert flyash,
Cleaning effect
Bot
Bed tom a
beh sh,
a vi
our
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 determine
quantitative trace element species selective
analysis results
/Rolf Hernberg, Jorma Keskinen/
Manganese (Mn) chemistry in biomass utilisation
Manganese (Mn) is one of the “dirty dozen” although important in wood
(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
1%
1 ppm
P
Mn
Ni
As
Hg
0.0000001
0.000001
100 %
B
Cu
Pb
Cr
Zn
K
Al
Mg
Fe
C
Na
Mo
Cd
Se
0.00001
0.0001
0.001
0.01
Concentration (mass fraction)
0.1
1
Manganese in wood, Werkelin 2002
2500
Bark
trunk
2000
Twigs
max
1500
Average
1000
min
500
Tree species
Birch
Spruce
Aspen
Pine
Birch
Spruce
Aspen
Pine
Birch
Spruce
Aspen
Pine
Birch
Spruce
Aspen
0
Pine
mg Mn/kg dry wood
Trunk wood
Bark
branches