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ETH No 13531
Fuel
Staging
of
Technology Zurich
Degree
of
presented
bv
Roger Salzmann
Eggfwil (BE)
Switzerland
Accepted
on
the recommendation of
Z ui it h 2000
11
Ordering
address:
Roger Salzmanu
rossina @swissonline. ch
Ill
Dedicated to my parents,
in
love.
IV
! Blank leaf
Acknowledgements
was
Thermodynamics
is the result of
founded
was
by
in
Emerg
The work
part of the
was
Energy
and
First of
Specials
during
appreciated
I
am
Laboratory
during all my
developing of new
helping advises arc strongly
time at the
ideas
all,
my work
by
I would like to express thanks to Tiba-Mllcr AG in Balsthal for the generous support
and
the time. In
particular,
let
me
we
developed finally
am
and electronics.
completion of
knowledge
experimental work.
Their
my
and
experience
providing
productive
and very
pleasant
lot to the
Zurich,
in
success
April
patient and
indispensable
environment.
Finally,
were
doing
colleagues
of this work.
2000
Roger
Salzmann
vi
CjLVu
Vf*
l^f
vu
Abstract
Emissions of
nitrogen
primary
various
is known to be
nitrogen in
has already
Staged
suitable
meaning
techniques
combustion
oil,
or
have been
pulverized
future,
coal.
as
the
can
be
The
for
are
Afterwards, they
during
by
either oxidized to NO
are
mainly caused
pyrolysis
biomass.
to the
amounts of
compared
nitrogen
NOx, because
to fossil fuels.
(O, H, OH)
path by the
creation of
the fuel-
from the
0.8 and
combustion
primary
completed
in the burnout
is reached for
zone
temperature of 1100
or
In air
rich
NH3.
the
important challenge.
an
non-pulverized
nitrogen in
fuels,
scale power
large
heating
the lower
staging,
of renewable energy
importance
applied
for
investigated mainly
But
measures
and fuel
primary
staging
air
to minimize the
measure
about
done, whereas
sources
combustion,
they
the fuel.
been
primary
to reduce the
developed
Staged
during
plants
have been
measures
photochemical
zone
stoichiometric ratio
to
of the
by injection
excess
(SR)
emission
of 0.7 to
the combustion is
zone
air.
staging, also called reburning, operates the first stage of the combustion process
slightly fuel-lean, whereby the NOx production is high. Then, additional fuel is added
Fuel
which creates
hydrocarbons
zone
consecutive reduction
used
are
initialize
can
an
as
zone
hydrocarbon
radicals
reaching
When
the reduction
rccyclc-
mochanism.
The aim of the present
pulverized
an
All the
experiments presented
measured
new
optimum combustion
on a
The
The measured
are
fuel
staging
NOx reduction of nona
about 75 kW thermal
and
on
is to demonstrate whether
conditions for
staging.
investigation
well
as
unstaged
combustion for
zone.
generating
as
reburn fuel.
high (8085c/c),
Also the
staging conditions
nitrogen
wood is
highly
reactive and
vin
leads to additional
ductions achieved
reducing species. The experiments show that low NOx emissions are
at relatively low temperatures, meaning at 900 to 1000C. The NOx re
for UF-chipboard as main fuel is higher than with air staging, about
78% compared
already
seems
achievable
to
than air
staging
which
can
be
an
for the
important advantage
zone
seems
use
of
application
to be
zone
nitrogen
of about 1.5 is
A furnace model
zone
of fuel
staging.
already sufficient fol
the
optimum temperature
significant. Concerning the potential of the reburn fuel
UF-chipboard as reburn fuel, a certain amount of primary
ou
staging
one
measures
even
the examined
reactor
higher NOx
provided for
as
mean
emission
can
result
facility.
(PSR)
and
plug
flow reactor
(PER)
investigate the
influence of the main parameters. Moreover, a reaction mechanism including the nitrogen
chemistry was implemented. The mechanism chosen for the reburning was the GR1mechanism. Being aware of the limitations of such a global model with all its simplification
designs
and
was
assumptions,
it still allows
staged
combustion and to
on
the
are
in
chemistry.
a
From this
good agreement.
IX
Zusammenfassung
Stickoxidemissionen
wichtigen Beitrag
Smog
von
und
Verbrennungsprozessen
aus
zur
saurer
nahmen
Luftverschmutzung
zu
die Stickoxide
zu
vom
Bildung
da Stickoxide einen
Regen.
Um die Stickoxidemissionen
worden.
unerwnscht,
sind
gebildet
gestufte Verbrennungsfhrung
Verfgung: die Luft stufung und die
eine
werden.
am
Mass
Wenn
effektivsten durch
Mglichkeiten
stehen dabei
zur
Brennstoffs tufung.
Luftstufimg hat ihr Potenzial zur Reduzierung der Stickoxidemissionen bei ver
Verbrennungssystemen schon unter Beweis gestellt. Dies gilt auch fr die
Verbrennung von schnitzel- oder pelletiormigcn Biomassebrennstoffen.
Die
schiedenen
Brennstoffstufung ist noch wenigei verbleitet. Testergebnisse von Kohle-, 01und Gas-gefeuerten Labor- und Pilotanlagen sind jedoch sehr vielversprechend. ber die
Eignung dei Brennst offstufung fur schnitzel- oder pelletfrmige Biomassebrennstoffe ist
allerdings noch nichts bekannt. Da abei gerade die erneuerbaren Energietrger wie die
Die
Biomasse in Zukunft
an
Bedeutung gewinnen,
mssen
Brennstofleigcnschaften
gezeigt werden,
muss
eingesetzt
werden knnen.
von
umgewandelt.
Dies
zu
Biomasse werden
Pyrolyseprozess
reagieren
am
Anfang
der
Verbrennung
in
ver
Frderung des letztgenannten Reaktionsweges durch die Schaffung geeigneter Reaktionsbedingungen ist das Hauptziel der Primrmassnahmen zur Stickoxidreduktion.
Die
Bei der
Luftstufung
wird die
Bildung
von
NO dadurch
zu
Zwischenprodukten,
Luftzahl
von
Bildung
von
NO
verhindert,
begrenzte Angebot
gehemmt,
Zugabe
von
einer
an
primre
oxidierenden
stickstoffhaltiger Vcibindungen
indem die
von
vollstndigen
entsprechenden Menge Sekundarluft er
Der
reicht.
Bei der
Brennstoffsfufung, englisch
gebildet
Hauptbrennstoff
entsprechend
viel NO
wird. Dann wird in einer zweiten Stufe der Stufonbreimstoff eingebracht, wodurch
unterstoichiometiisehe,
Zone
geschaffen
wird.
wendung
von
kohlenwasserstoffhaltigen
Kohlenwasscrstoffradikalc gemss
vorliegenden
Brennstoffstufuug
fr
Brennstoffen
erfolgt
dem sogenannten
Arbeit ist
zu
Recycle-Mechanismus.
zeigen, ob ein neu entwickeltes Konzept
der
ist fr
konventionelle
Verbrennung
zum
Vergleich
Die
Reduktionszone erzeugt.
schon bei relative tiefen
nung
Spanplatte
von
eigentlich
Stickstoffgehalt
aus
bestens
sein, da
er
Flchtigenanteil (80-85%).
zustzliche NO reduzierende
Experimente zeigen,
Temperaturen auftritt,
Sie
Auch der
in der
Minderung
Luftstufung,
gegenber 72%.
Fr Waldhackschnitzcl
lagen
Brennstoffstufimg
Die
der Reduktionszone
erwiesen,
von
derung
zu
erreichen.
was
fr die
praktische Anwendung
die
optimale Temperatur
signifikant.
Stickstoffverbindungen abgebaut
Feuerung wurde
Rohrstrmungsreaktoren aufgebaut,
wichtigsten Betriebsparameter dient. Das Model beinhaltet
Rhrkessel- und
der
wichtiger
in
Vorteil sein
um
Stufenbrennstofftyps auf
forderlich ist.
ausreichend,
ein
welches
zur
werden.
aus
einer
Analyse
einen
Folge
von
des Einflusses
vollstndigen
Reak
gewhlt. Obwohl des Model aufgrund der zahlreichen Vereinfachungen und Annah
men nur beschrnkte Aussagen zulsst, erlaubt es doch Abschtzungen ber die Auswirkun
So stimmen die er
gen von Parameternderungen betreffend der Chemie zu machen.
isnius
warteten
berein.
Ergebnisse
Beobachtungen
Contents
Abstract
vii
Zusammenfassung
ix
List of Tables
xv
List of
xx
Introduction
1.1
General
Background
1.2
Figures
Wood
9
9
2.1.1
Characteristics
2.1.2
Chemical
Composition
10
2.2
Combustion Process
16
2.3
Emissions
25
2.4
NOx Formation
26
2.5
Fuel
34
2.6
Nitrogen
2.6.1
Air
2.6.2
Fuel
36
Staging
39
Staging
40
Literature Review
45
3.1
3.2
Air
3.3
Fuel
45
Staging
Research
45
Staging
48
Facility
4.1
Design
4.2
Operation
4.3
Energy
4.4
Measurement
53
53
Modes
54
Flows
57
Equipment
4.4.1
Basic
14.2
Hot Gas
58
Equipment
58
Analysis
59
xi
xii
CONTENTS
4.4.3
5
Results
63
Experiments
63
About the
5.1.1
Wood Fuels
63
5.1.2
Parameters
65
5.1.3
Temperature Measurements
68
5.2
Conventional Combustion
69
5.3
Air
73
5.4.1
Influence of the
76
5.4.2
77
5.4.3
80
5.4.4
Practical
80
76
Experience
Modeling
6.2
Modeling
Approach
6.2.2
6.3
83
About
6.2.1
83
88
Plug
Perfectly Stirred
88
Reactor PSR
89
Furnace Model
90
6.3.1
Design
90
6.3.2
Input Generation
92
6.3.3
93
General
7.2
Reaction Mechanism
7.3
Reburn Zone
7.4
62
5.1
6.1
Analysis
Experimental
5.4
Flue Gas
99
99
102
106
7.3.1
7.3.2
Burnout Zone
Temperature
106
109
Ill
7.4.1
Influence of Burnout,
7.4.2
Influence of CO
on
Modeling
NOx emission
Conclusions
Ill
116
121
8.1
Summary
121
8.2
Outlook
123
Nomenclature
Experimental
B.I
B.2
B.3
Gas
125
Details
129
Analysis
B.l.l
Continuous
B.1.2
FT-IR
129
Analyzers
Spectroscopy
Additional Equations
Error Analysis
129
130
138
139
CONTENTS
xiii
B.3.1
B.3.2
Measurement of Emissions
140
B.3.3
141
Bibliography
139
148
CONTENTS
XIV
Seite Leer /
Blank leaf
List of Tables
currently
l.i
Solid fuels
1.2
2.1
Molar ratios in
2.2
2.3
2.5
important nitrogen
Properties
Air pollution control measures for solid fuel combustion
Secondary measures for NOx reducton
2.6
Primary
2.7
Advanced
4.1
Measurement
5.1
2.4
raw
firing
25
26
Reburning
43
variants
59
equipment
analysis of
the
investigated
investigated
64
wood fuels
64
fuels
5.2
Fusibility
5.3
5.5
6.1
Classification of
5.4
19
pyrolysis
oxides
of the most
measures
systems in Switzerland
65
from measured values
...
66
77
84
practical flames
6.2
93
6.3
94
7.1
Notation in
7.2
Input
99
figures
116
129
B.i
Gas
B.2
FT-IR
specifications
132
B.3
FT-IR
analysis
132
analyzers
xv
XVI
LIST OF TABLES
/
/
Apf
List of
1.1
Figures
primary
1.2
1.3
1.4
1.5
Change
energy
supply
region
generation
in Switzerland
1997
1.6
Batch
2.1
Cross section of
2.2
Thermal
2.3
The differential
2.4
Structure of cellulose
12
2.5
Building
13
2.6
Structure of softwood
2.7
2.8
2.9
2.10
Rate-controlling regimes
2.11
Calculated
run
of fuel
staged
wood combustion
trunk
gravimetric analysis of
some
of the thermal
curves
wood fuels
11
degradation
of wood
12
lignin
14
heating
on
of
value
17
18
heterogeneous
on
L5
degradation by pyrolysis
equilibrium composition
2.13
reactions
20
24
wood combustion
24
27
on
NOx emission
29
2.15
30
2.16
Reaction mechanism
by
31
by
which
31
NLI3 is converted
on
the conversion to
on
NOx emission
to NO and
N-species
Specific nitrogen
2.21
Fuel-N reaction
2.22
Principle
of air
2.23
Principle
of fuel
2.21
34
paths
35
staging
40
staging
41
zone
fuel rate
Application of
32
33
2.20
2.25
N2
the
reburning technology
xvu
to
utility boiler
44
LIST OF FIGURES
xviii
3.1
3.2
3.3
46
com
(air staging)
zone on
staging
Influence of
nitrogen
content
on
the
NOx.NI4j,
and
48
IICN emission
of reburn
stoichiometry
NOx emission
3.4
Impact
3.5
Effect of the
3.6
3.7
primary NO
on
concentration
on
49
nitrogen from
...
the reburn
zone vs
primary
52
Research
4.2
Mixing element
Operation modes
4.4
Energy
4.5
Energy
facility
50
51
NO concentration
4.1
4.3
zone
55
56
56
57
staging
58
staging
59
4.6
Inputs
4.7
Hot gas
4.8
Suction pyrometer
61
4.9
Flue gas
sampling
62
5.1
Wood
5.2
UF-chipboard
5.3
5.4
Time
5.5
68
5.6
5.7
70
5.8
70
5.9
71
60
sampling
64
chips
64
of
history
an
experiment
with fuel
at air
5.11
staged
67
staging
UF-chipboard combustion
during reburning
zone on
73
staging
74
5.13
NOx emission
versus
on
Shapes
NOx emission
mean
zone
76
78
at
750C
79
on
NOx emission
79
80
an
understoker furnace
zone on
5.17
69
combustion
Comparison of
66
zone
on
6.1
6.2
81
...
combustion models
.
81
83
87
LIST OF FIGURES
xix
6.3
Effort
on
6.1
Effort
on
6.5
Influence
6.6
6.7
6.8
Influence of
6.9
O/N
ratio
on
curves
87
88
91
92
92
during pyrolysis
gasification at 800C
simulations, UF/UF
simulations, UF/W
zone
6.11
Calculated
zone
7-1
7.2
7.3
using
7.4
using
input
UF/UF
7.13
Calculated
7.7
7.8
7.9
7.10
7.11
N-specics
zone
for
101
104
N-species
97
104
7.12
7.6
96
fOl
zone
UF/UF
using
UF/W
Gas concentrations in PFR using the Leeds-mechanism for UF/W
Influence of tempcratme on reduction rate R for RFR =0.25, UF/UF
Influence of temperature on reduction rate R for RFR=0.30. UF/UF
Influence of temperature on reduction rate R for RFR=0.35. UF/UF
Influence of temperature on reduction rate R for RFR-0.20, UF/W
Influence of temperature on reduction rate R for RFR-=0.30, UF/W
Burnout in PER at, 1300C for RFR=0.30. UF/UF
7.5
zone
94
95
105
105
....
107
....
108
....
108
....
109
....
110
112
PFR, RFR=0.30
UF/UF
113
7.14 Calculated
PFR with
RFR=0.30, UF/UF
113
RFR=0.30,
UF/W
114
RFR=0.30;
114
on
UF/W
on
RFR=0.30;
UF/W
115
RFR0.30,
UF/W
115
on
CO, NO,
NO2. and
118
(PER),
800C
L19
(PFR),
1300C
119
B.l
Layout
B.2
Procedure of
IJ.3
IR spectrum of NO
135
B.4
IR spectrum of N02
135
B.5
IR spectrum of N2O
135
B.6
TR spectrum of CO
136
B.7
IR spectrum of NH3
136
of
FT-IR apparatus
sample
131
134
LIST OF FIGURES
xx
B.8
IR spectrum of HCN
136
B.9
Calibration
137
B. 10
Examples of Gaussian
curves
139
141
Chapter
Introduction
General
1.1
Background
Energy Outlook 1998 of the International Energy Agency projects world energy
by 65% and CO2 emissions by 70% between 1995 and 2020, without, the
required policy changes. The world total primary energy supply by fuels expected in 2020
is illustrated in Figure 1.1. Two-thirds of the increase in energy demand and energy-related
The World
demand to grow
CO2 emissions
1990
period
occm
supply
Fossil fuels
expected
to meet
is
sources
increasingly
be put in
new
Figure
primary
1.2.
projected
to
change marginally.
to meet
in power
preferred
to
The market
slightly
rapidly growing
fuel for
pipelines exist, or
applications, especially
Where
generation.
many
power stations.
2020. New
generating plants
developing
it will still
policies
will be built.
general,
required
period
use
developed
some
fast
but, without
cent of world
electricity
sources are
to
help
gas emissions.
projections of biomass
accounts for
countries. In
although
growing
if renewable energy
1995 to 2020.
at
The
a
3500 GW of
projected
new
electricity
energy
can
be
as
countiies.
high
as
consumption of biomass
lower
rate
developing countries.
supply in developing
biomass supplies about a
use
in
developing
is
biomass energy
sources
will be
Over the
countries, and
countries than in
In
important
place,
to the total
share of gas will increase while the share of oil will decline
can
developing
By
levels, the basis for the Kyoto Protocol 1997. The fuel shares
energy
2020.
the
over
2020 worldwide
countries.
than
population and
con
conventional energy.
There
arc
many
CHAPTER, 1.
Total
INTRODUCTION
13700 Mtoe
Figure
1.1:
primary
energy
meet the
Kyoto
measures
wind, etc.
commitments
gases.
and
geothermal, solar,
on
the emissions of
large
need to be
reducing
Major
new
place urgently by
put
particular biomass, will have
in
an
important role
to
policies
objectives.
play
in climate
stabilization.
The
use
sustainable
supply
use
can
be described
The
in emission of
growth
anthropogenic CO2. Biomass energy is renewable, but can also be transported and stored,
allowing heat and power generation on demand. Biofuels may be solid, liquid, or gaseous,
depending on the conversion process. Beside combustion, other thermochemical biomass
conversions for energy purposes are possible.
Pyrolysis
as
thermal
oils
(tars),
but, also
Temperatures of 400-600C
are
weight
pyrolysis.
Liquefaction
can
temperatures
oxygen
be defined
(250-350C)
as
or
and
high
pressures
liquid phase
with
at low
a
high
1.2.
World 1996
Figure
OECD 1996
primary
supplv: World
energy
only
(IEA, 1998)
*mcludcs
etc.
and/or
to
ways for
promising
mostly due
to economical reasons.
more
favorable
prices
the
augmented
unmerchantable
production
However,
some
countries the
European
use
offering
wood,
processes
for low
forest
as
the theoretical
well
quality
residues,
as
supply
wood.
waste
Therefore,
wood from
an
manufacturing
and industrial
higher
potential
Figure
possible sustainable consumption are displayed.
The
has
for lower
waste of this
1.2
generation
shows
consumption
is. The
history
supply.
covering of
the
gas.
Todav, being
aware
new
of many
trialized economies
sources
of energy
were
sources
more
for indus
sixties of the
20th
CHAPTER 1.
C02 Emissions
INTRODUCTION
1996
Middle East
53 4%
3 9%
22700Mt of
Figure
century. In the
overview
being
are
on
C02
used
again
in
increasing quantities. An
supply today gives
Table 1.1.
Three classes of solid fuels may be
distinguished:
fossil
fuels,
help
combustion environment
or
technology.
Numerous
technologies
have been
developed
on
application
combustors
are
are
technology
populai
beds
the
of the
bed
for wastes.
into fine
for
large
units
(200
to 800
MW0).
pulverized
fuel
particles
are
(FBC), cheulating
supported by
an
upward moving
Fluidized bed
fluidized beds
(CFB),
com
potentially
technology includes
and
pressurized
flu
(PFB).
idized beds
Generally,
are more
bubbling
probably
conventional
placed
firings,
pulverized
including
are
in the
at, the
may be
higher efficiency
Fluidized bed
used
which
due to their
bed.
of
used
Commonly
rotary kiln
Alternatively, solids
Suspension
or
production
all combustion
technologies
boilers and
are
installed.
are
reasons,
an
1.2.
sustainable
use
6
54
2
1 4
0
theoretical
available
consumption
potential
1996
1.4: Wood
Figure
alternative for
biomass
only
consumption for
sizes
plant
higher
energy
generation
in Switzerland
(Rutschmann, 1998)
burning
availability of
transportation of biomass
over
long
distances is
nor
economical
nor
ecological.
In
5 MW unit size
Table
1.2,
installed.
are
most energy is
combustion systems
are
They
produced by
possible
were
life
and
significant
e.g.
see
significant
fixed bed
to about
As listed in
systems.
centralized
production
cycle,
that
use
mostly
on
as
To increase the
based
the
arc
analyzing
(Jungmcicr
et
ah.
important,
it is
cycle
inventories of biomass
1998).
to know the
are
Consequently,
cycle
over
plants
the entire
inventories show
fundamental research is
is under control,
photochemical
practicable solutions
at
for the
specific
research
has been
on
compounds
designers
on
.smog, is still
challenge.
has been
spe
elaborating
as
(Nussbaumer, 1989),
primary
measure
and
more
passed studies
are:
CHAPTER 1.
currently
INTRODUCTION
Biomass fuels
Wood from
forestry
manufacturing
Wood
residues
Demolition wood
Energy crops
Agricultural wastes
Food and crop processing
wastes
Peat
Fossil fuels
Coal
Coal
processing
wast es
Petroleum-based solids
Wastes
Mixed
municipal
solid wastes
Table
1.2:
firing
systems in Switzerland
(Kessler. 1998)
^___^
Domestic
heating systems
601.060
9l>54l)3
MWh
56,426
897,082
MWh
3.156
1,454,511
MWh
56
391,871
MWh
Automatic furnaces
Renewable waste furnaces
Energy production
Number
Category
originate
from the
nitrogen
In
general,
nitrogen
to
content.
With air
can
staging,
be lowered bv
more
staging and
ah
NOx reduction. Both air staging and fuel staging take advantage of the chemical reactions
going
on
in
zone
1.2.
renewable waste
funaces
automatic furnaces
domestic
heating
systems
heating
room
systems
-60%
-40%
-20%
0%
change
Figure
At fuel
staging
has
some
80%
100%
120%
of installed power
staged
an
an
(reburn fuel)
ash
per
is created
by
to
the
melting temperature
zone
zone
an
60%
1.5:
1997; data
Air
40%
20%
more.
Air
staging
not
neces
also needs
advanced furnace control because the process parameters have to be well controlled to
achieve
good NOx
reduction rates
over
fuel
on
staging
as
(Good
et
questions
staging and air staging seem to have an equivalent NOx reduction potential
(Pershing and Eighty, 1996).
First experiments on fuel staged wood combustion using wood as reburn fuel indicated
fuels,
fuel
were
done
on
conventional undcrstokcr
added batch-wise
a
arose.
on a
second grate
the
conditions
main
stage
dining
by these experiments,
developed.
energy for
lower level
The
non-pulverized
experiments
reburn fuel
of the
pyrolysis phase of
was
1.6 shows
the reburn
fuel,
starting
again.
Stimulated
been
on a
and
beginning
decreases, remains
furnace,
(Salzmann
where
a new
fuel
changing
the size
is also used
as
or
shape
reburn fuel.
same
furnaces has
expense and
fuel
as
for the
CHAPTER 1.
100
INTRODUCTION
-B demolition wood
90
-TAwood
chips
8070
601"^
50 J
DC
40-
30-
20
10
10
20
15
time
Figure
R
1.6: Batch
^^pa
ddie work
run
of fuel
(Salzmann
presented
Experiments
staged
to continuous fuel
[min]
and Nussbaumer,
in this report,
35
30
25
was
versus
time,
1995)
following
aims:
Practical
operation shall be tested and experience gained for future development of the
concept.
Along
with the
experiments simulations
with
simplified furnace
model
approach
shall
Chapter
Fundamentals of Wood
Combustion
2.1
2.1.1
Wood
Wood
Characteristics
can
be defined
as
up the
greater part of the stems and branches of trees and shiubs beneath the bark.
Woody plants
vascular, possessing conducting tissues consisting of wood (xylem), baik (phloem)
and a growing layer (cambium) that annually forms new wood and new bark which are
are
Wood is both
anisotropic and
hygroscopic.
The wood and baik
95% of the
are
of the woody
mass
plants.
during their life: cell division, cell enlargement,
as
cell wall
comprise as much
phases of development
thickening, lignification,
and cell
death.
thickening,
sapwood
Figure
cambium
and
liunk
phases, considerable
lignification phases
may
CHAPTER 2.
10
take
place.
recently formed wood, performs the role of support, conduction,
food-storing
some
Then
time
elapses, the
amount of which is
The
pigments.
area
vessels that
softwoods
classified into
are
are
responsible
trees),
opposed
Chemical
2.1.2
hemicelluloses
lignin
knowledge
acids.
extractives,
Goldstein,
(evergreen
(deciduous trees).
the soluble
compounds
that
are:
phenolic
most softwoods
some
cellulose
Composition
by
most hardwoods
shedding by
The
perform
and support.
dark-
to
and hardwoods.
longitudinal
light-colored
physiologically
as
with
the
only.
Trees
color from
species-dependent,
are
more
are
often
mav
be overshadowed
by suberins and
species-
or
quantity
genus-specific (Lewin
are
and
1991).
clearly during
thermal
gravimetric
analysis (TGA). The result of a TGA run may be presented as a mass versus temperature
time curve. Examples of resulting TGA curves for some wood types are displayed in
or
Figure
2.2.
visible in
Cellulose,
chain
mass versus
even
temperature
polymer of glucose
units
nization of individual cellulose chains into bundles with crystalline order held
degree
crystalline regions,
of
to
fibrous state.
the
crystaffinity depends on
origin
pulp, mercerized cellulose,
are
or
polymer
of
glucose, cellulose
only
amorphous regions
including
more
and
as
The
cellulose,
regenerated cellulose. Despite
is insoluble in water.
hydroxyl
highly
well.
and decreases
However, reagents
strong acids and bases, concentrated salt solutions, and valions metal
together
of the
complexes
hygroscopic, and it readily absorbs and desoibs water in the amorphous regions
where the hydroxyls are not involved in interchain bonding. The availability and the ac
cessibility of these hydroxyl groups is an important factoi in all cellulose icactions, i.e.
is very
also
during combustion.
11
WOOD
2.1.
0.1-
P50
175
200
250
225
325
300
275
375
350
400
450
425
Temperature [ C]
Figure
2.2: Thermal
gravimetric analysis
(20-25%). They
celluloses
hexoscs. and
sugars in
are
of
are
some
carbohydrate polymers
are mannose.
loses
are
also
susceptibility
molecular
more
to
known
hemi-
as
constituent sugars
principal
insoluble in water,
they
readily hydrolyzed by
hydrolysis
In
galactose,
certain exceptions
(Gr0nli, 1996)
usually branched
decreasing abundance
and
wood fuels
can
Alt
are
xylose,
mannose,
the hemicelluloses
hough
amorphous
glucose,
are
with
Hemicellu
In
solubility
and
weights.
During
between the
newly
development phase,
called
lignification,
(20-30%).
It
serves
as
barrier to the
the formation of
place. Lignin
cement
is the third
between wood
Lignin
major
fibers,
enzymatic degradation
as
of the cell
stiffening
wall. Lignins are three-dimensional network polymers of phenylpropane units with many
different linkages between the monomers leading to a complicated structure. Figure 2.6
shows a typical building block of softwood lignin. The random structure arises from an
enzymatically initiated fiee radical polymerization of lignin precursors. Thus, lignin has
Softwood and hardwood liguins differ in methoxyl
an aromatic and phenolic character.
content and in the
Depending
Bark fiers
lignin.
arc
on
degree
the
of
as
erosslinking.
species, bark
chemically similar
may
comprise 10-15%
of the total
mass
of the tree.
but in lower concentrations. Because of the presence of extractives and two other
12
CHAPTER 2.
herruccllulose cellulose
Figure
hgnm
curves
lignin
of the thermal
cellulose
degradation
hcmicellulose
of wood
CHjOH
OH
CH2OH
as
low
as
REDUCING END
components unique
20-25%.
OH
NON-REDUCING END
Figure
(GrOnli, 1996)
to bark
Suberins
(Tillman
(suberins
are
and
et al.
1981)
(DP= degree
of
They
polymensation)
content may be
consist of
long-chain
monobasic acid esters. The suberin content may vary from 2-8% in the barks of
pine, fir,
and oak, whereas it is much more abundant in birch and coik oak
(30-40%). Phenolic
acids
their
Extractives
(0-10%)
extraneous wood
oils, terpenes, fatty acids and their esters, waxes, polihvdric alcohols, mono- and
polysaccharides, alklaoids. and aromatic compounds (acids, aldehydes, alcohols, stilbeues,
flavonoids, tannins, and quinones).
Wood
belongs
of wood
are
C. H, and O
nitrogen, phosphorus,
(Schobert. 1990).
In addition, calcium,
as
magnesium,
well
as
manganese,
traces of many
2.1.
WOOD
13
CHO
CHO
HO
CHO
OH
OH
OH
HO
HO
-OH
OH
OH
-OH
CHpH
CHpH
CHpH
HO
OH
HO
HO-
HO
HO-
expressed
weight
dry weight basis (index df: drv fuel).
as a
wood,
is used
storage.
only.
fraction either
(2.2)
governed by species, type
drying typically
are
covered with
or
55%,
of
wood residues
12%. The porosity of wood, along with its hygroscopic nature, leads
point
weight
<i!
water content of 40 to
of
(2.1)
mii2o
m
use
Mdf
lumber
total
operations after
on a
n,o
miiiO +
wjj
(Tillman, 1991)
very
and
Talose
Galactose
In this report
CHpH
CHpH
CHpH
Mannose
or on a
OH
OH
OH
basis
HO-
OH
HO
2.5:
CHO
CHO
CHO
Figure
Glucose
Xylose
Arabinose
to afiber saturation
strong influence
on
woody
heating
(LUV)
representation of the energy which can be captured from the combustion of any fuel.
The lower heating value for woody biofuels is in the order of 18 to 20MJ/kg. The range
is
are
anvwav.
The lower
value
of the fuel
is caused
calculated
lower
of carbon and
by varying percentages
as
heating
value shows
Figure
hydrogen.
The
heating
value
can
on
be
the
2.7.
LUV
(1
w)LHVdf
2 air
(2.3)
CHAPTER 2.
14
C\ EOH
G
C-h
KT
k^0Me
CHpOH
HC
nc-
r>
MO
'
p. ion
CH2H
j,_c__
H-C
Ok
i
YM.^'M
H(C
OH
c We
c-h
-TA,.
<p)
ChEOH
AR-C-H
Jk^
PM&
CI EON
J
-
OMo
OMe
^ 05)N-0-C-H
9t,2H
OMe
O-
C -O
-0
C
,
ji-y
o
II
CH.OH
HO
n-cH
lv-%
'
OMo
OH
Figure
2 6: Stiuctural
stmctuie
(Idllman, 1991)
2.1.
WOOD
15
Figure
on
heating
value
CHAPTER 2.
16
Combustion Process
2.2
Combustion is
mass
heat and
very
transfer with chemical reaction and fluid flow. Substantial differences exists between
gases. The
liquids and
fundamentals,
different when
the
to solid
fuels,
applied
chemistry, arc significantly
principles
resulting largely from the inclusion of the complex reactions and processes during the
thermal degradation of the solid into the overall combustion process.
The combustion of solid fuel particles is a process which consists of several phases.
Depending on the combustion conditions, they may be difficult to distinguish. Usually,
of combustion
particles
can
be described
and
Step
2: Devolatilization
Step
3:
Ignition
Step
4:
Gas-phase
Step
5:
Heterogeneous
affected
Heating
where
can
occur
required
(about,
place
particle
up and for
depend
on
be
(char) components.
to
is
strongly
pyrolysis temperature
evaporation.
of the
core
since
of the
particle
until the
center of the
core
(Tillman
heterogeneous
et
reactions
reaction temperatures.
al, 1981).
are
responsible
for different
fuel parameters
separated by their
can
and solid
practical
and
products
procedure
particle. Additionally,
conductivity of the particle, thus increasing the rate of
ddiis
energy for
C).
200 450
for
particle.
particles
heating
ceiling on the temperature
vaporized, normally from the surface to the
particle size)
2.9
combustion
pyrolysis
consumes
of moisture is to
water is
Figure
(pyrolysis)
combustion
wood
pyrolysis,
by the
drying-
1:
temperature
large
as
wood
are:
Step
Prior to
The tars
can
be treated
as
intermediate
products
of
pyrolysis
combustion purposes.
over
the kinetic
cellulose
are
degradation.
The
processes which
2.2.
COMBUSTION PROCESS
17
CH'OH
CH OH
Ring
Opening
*H,0
at low
(caibon
species)
temperatures
different oilcous
out of
and
oxides,
piimary prod
Tertiary
processes:
ondary products
Carbon monoxide and
Xew
or
bv
products
are
created at
repolymeiisation
to
high temperatures
heavy
aromatic
bv
cracking
sec
compounds
18
CHAPTER 2
solid
phase
condensed
gas
phase
phase
Products of
complete combustion
-1
Burnout
02
o,
tars
1
CD
O
CD
15%
85%
Ignition
Pyrolysis
100%
CD
c
CD
Drying
Air
Fuel
water
dry
Figme
2 9
wood
charcoal
ash
COMBUSTION PROCESS
2.2.
The data of
too.
a
wood
rates.
change
of tobacco show
different experi
and oxygen
The nitrogen in
fuel.
(oats). Hydrogen
original
dglaciation
hydrocarbon
maximum
mental
(Burton, 1976)
19
raw
(oats)
biomass
pyrolysis (Rdiger
ah, 1995)
Raw
Char
fuel
Temp.
600 C
800 C
1.62
2.35
1200C
1000 C
"
C/II
C/O
C/N
0.66
4.22
1.13
50.7
6.24
50.1
5.56
2.91
7.55
10.1
62.4
57.5
74.5
particles
is
governed by the diffusion of oxidizer (Oo. OH, O. CO2, etc.) to the carbon surface and
by surface reaction kinetic. Char is highly porous and presents a surface area that is
much larger than the external surface.
Figure 2.10 shows the three typical modes of
In the first regime the observed reaction rate is controlled strictly
surface reactions.
by surface reactions, allowing the reactions to take place uniformly throughout the char
volume. In the second
rate,
In the third
regime both
regime
limited combustion is
As either
temperatures.
Diffusion-
reasonable
particle
assumption for
size
or
combustion of
temperature decreases,
large particles
of small
is
char to
many
area
an
other
practical
particle
depending
uses.
have been
on
as
problem,
another.
function
the devolatilization
To solve this
high
generally
However, The effective global rate expressions vary widely from one char to
prediction of the combustion rate requires knowledge of the reaction rate as a
The
of surface
at
history,
there is
lack
on
one
data for
Still
some
uncertainties in
Important
mal
The ultimate
containing
particle
complete
trace metals
content, ash fu
technology
must, take
pollu
guaranteed.
analysis of the fuel delivers the
necessary
followdng
CHAPTER 2.
20
transition
ln(Ut
region:
pore diffusion
ncreasingly important
chemical kinetics
controlled
region
1/T
Figure
2.10:
Rate-controlling regimes
of
heterogeneous
reactions
(Bartok
and
Sarofim,
1991)
metrically, t,he
over
all combustion
C{s)
If the solid fuel contains both
02
hydrogen
is
given by
(2.4)
OCT + heat
as
follows:
CaHbOc
+ *
(a
aCOo +
) 02
fiTO
+ heat
(2.5)
amount of oxygen
three combustion
modes
SR
stoichiometric combustion
1:
possible:
are
SR > 1
ratio
heated up.
The combustion
using
the
equation for
wH20
CaHbOc
aCO-2
(w
|)
following assumptions:
+ SR
H20
-r
{Ch
A(SR
^N2)
-
1)02
as
>
+ SR
(f A)
N2
+ heat
(2.6)
21
COMBUSTION PROCESS
2.2.
combustion to
complete
no
composition of combustion
NOx formation
soot and
neglected
T^Y^
Consicleiing
[O2]
this
can
is then
A(SR
[O2]
Evaluating
(2.7)
1)
(2-8)
-t^^tF^
+ l
A(SR~~l) +
A^SR
OT=2i^!L
21
,2.9)
v
100[O2]
Thus,
the
more common
-j)
is about I.
is
equation
sn=2T^7]
In
case
of
incomplete
becomes much
of
Equation
more
2 6.
so
combustion
or
complicated.
like
Equation
species
species distiibution
Tilh
global
(i.
case
is
gasification)
e.
equilibrium
at
shortly
on
described
the combustion
the
equation
product side
has to calculated
the
following part.
equation could
look
2.11.
CVI6(%
Idie
<lI0>
reaction
wH20
r2CO
SR
^C02
equation above
gAT2)
(02
iH20
includes the
r-,CUi
following
rb02
set of
77C{s)
i&N2
independent
(2.11)
read ions:
C02^H2
>
CO + H20
(2.12)
30))trfl,
>
100 4 2iTO
(2.13)
C02
-^
2C0
(2.14)
+ 2CO
->
2C02
(2.15)
Ch)
O2
CHAPTER 2.
22
An
namic
function G is
the
an
independent,
same
an
unknown
overview
thermody
system of
given
mass
by
G(T.p)
All other
calculate
thermodynamic quantities
H(T.p)
can
(2.16)
TS(T.p)
are
expressed
in these
is
,v
clG(T.p. n)
introducing
the chemical
potential
of the Ar
Thus,
a common
equilibrium
of
]T p,ch,
(2.17)
(?r\
(2T8)
n(7\p)
(>)
(2,19)
meaning
dGpp
optimization problem
+ RT hi
The
Vdp
ti,(niri.'I\p)
The criterion for
-SdT +
(2.20)
to be solved is
N
minG(n)
of
V\?,//,
(2.21)
M elements.
one
equation
for each
element.
Y
bk--J2k,n,
k=L2
(2.22)
COMBUSTION PROCESS
2.2.
the
Introducing
{ni,
unknowns
by the
problem
....-jy. tti,
Lagrangian multipliers
function 6,
write:
(2-23)
The N
For
we can
YliTk\hk E c'k->'"'
provides
phases)
number of
]C n'i-''
km}.
equations (<T>
M
now
....
species
Lagrange
0(n>7r)=
The minimization
23
set of
(M
N) equations
must be
determined
ultimately
(M
in the
N)
be substituted
can
(M
set of
by iteration,
4>)
linear
where the
phase
the
are
unknown variables.
If the temperature is also unknown, the energy balance of the system at
under standard pressure conditions po has to be evaluated
prod.
additionally.
teact
^
(*?s
11
^o)
(AHfh
(i7n
n>
equilibrium
temperature of reactants
"
nn)
(AHf)r0
to the adiabatic
(2-24)
temperature. T\
entering
(=298.15 K).
In
a
principle,
the
problem
describe
of cdiemical
to be done,
equilibrium have
has
eciuilibrium
by
as
been solved.
to be solved
numerically.
subroutine in MATLAB.
on
Figure
2.If and
the calculated
Dissociating
reactions at,
In
practice,
equations that,
now
high temperatures
according
to
Equation
neglected.
are
combustion process is
heating and drying. The water content increases the energy required
to heat the wood particle to pyrolysis temperature. Thus, the specific calorific value of
the particle is reduced (see Equation 2.1.2). Consequently, the water content reduces the
flame temperature in the combustion chamber
the surface temperature and the
of volat iles from
DeGroot,
pyrolysis
core
shown in
as
temperature of the
is decreased and
more
fuel is
pyrolyzed
to char
decreasing
phase and
char reactions.
concentration of the
increasing
an
excess
important OF
by smothering
reactive sites. In
by
a sum
highly complex
item of research.
and
mary, the role of water in the combustion process of moist, solid fuels is
and still
(Shafizadeh
1976).
high
potential
are
controlled
carefully
impacts.
water content
to draw maximal
CHAPTER 2.
24
1 2
-C02
H20
CO
1 0
X-ce?)
0 8
06
04
02
SSi^xX-X-X-X-XX-XX-X-X!-(5^<-"X'X
00
00
02
04
06
08
10
12
SR H
Figure
2.11:
at f bar
Calculated
(wood= CHi2eOo66,
0.0
0.5
E0
(JANAF, 1985))
E5
2.0
2.5
SR[-
Figure
2.12:
(JANAF. 1985))
1 bar
on
(wood=
CTI
l 2c
o 66.
EMISSIONS
2.3.
25
Emissions
2.3
In addition to useful
heat,
can
be
various
quantities of
airborne emis
separated
sions.
products
unavoidable
complete
combustion.
using
carbon and
typical
are
hydrogen containing
fuels.
Particulates
creation of
fuel
particulates.
particles
only
particles entering
to short
or
as
flyash.
pyrolyzed only
are
inert residue
particles
byproduct
are a
analogous
now
to the
are
which is
oxidized, leaving
prior, but the fuel
optimal,
serving
be
promoted be the
entering
particle
cooler
regions
particles,
site wdiere condensation is favored. Also inerts may volatilize and recondense
on
tubes,
or
elsewhere in the
combustion system.
Characteristic
Emission
unavoidable
N(\-
CO2. IhO
particulates (flyash)
avoidable
N20, NII3
acid gases (HCL.
heavy
Avoidable emissions
component. Focusing
HCl.
are
etc.)
or
possible airborne
on
arc
or
One
family
by changing
of air
generated during
wood
furans, acid
(SO2,
gases
usually
metals
heavy metals
be avoided
SO2, etc.)
or
ameliorating
pollutants has
HC,
and
organics
may
the oxides of
nitrogen.
Nitro
(NO)
nitrogen
(NO2)
important nitrogen
pollutants. They are frequently lumped together under the designation NOx. Of the two,
NO2 is the more toxic and irritating compound. NO2 can alter lung function and increase
susceptibility to respiratory infections. Natural sources of NOx are volcanoes, bacterial
gen oxide
and
dioxide
are
the two
most
oxide air
CHAPTER 2.
26
(usually
and
about
afterwards.
atmosphere
as
(Flagan
in literature
and Seinfeld.
Melting point
-163.6
-11.2
-90.8
Boiling point
-151.8
21.2
-88.6
-93
temperature
crit. pressure
bar
Solubility
m3/m3
1.96
64,8
0.07
72.6
1.26
1.31
pungent
none
are never
homogeneous.
combustion chamber
Even in situations
good conditions for complete combustion it, is normal to find both, NOx
conditions, and CO or hydrocarbons formed at, fuel rich conditions, in
is due to the fact that the gas in
spots
with
typical
non-premixcd flames
by
36.5
none
mixing
are
processes.
fluctuations
time scales of
and
Usually,
sensors.
leading
mixing
mixing times,
to
the flue
history (Malm-
responding
some
be detected fast
can
with,
formed
the
158
101.3
Odor
number gas
Figure
2.05
colorless
phenomena
gren ct
44.02
1.34
brown
of
large
46.01
colorless
gas. This
a
30.01
Color
The conditions in
average,
N20
Density
crit.
on
N02
kg/kmol
kg/NnE
mass
be found
most
NO
Molar
can
Properties of the
Table 2.3:
impacts
i.
e.
NOx formation
are
slow
compared
to
2.4
NOx Formation
(NO)
Nitric oxide
and
nitrogen
dioxide
(NO2)
are
produce
minor
sources,
though
effectively
source
compound being
NO2 in the atmosphere.
to
emitted
was
pro
the
largest anthro
agricultural operations
NOx compound emitted by most
arc
arc
generally reported as
be oxidized quite
can
2.4.
27
NOx FORMATION
Turbulent
Chemical Reactions
Mixing
NO formation
industrial furnaces
CO oxidation
combustion chamber
of gas turbines
formation of radicals
Figure
There
arc
three
commonly known
thermal NO
prompt NO
NO from fuel-N
key parameter
wrays of NO formation:
of the temperature
on
high-temperature
X'2
+ O
N +
N
known
as
Figure
02
OH
occurs
primarily through
NO + N
(2.25)
NO + O
(2.26)
NO + H
(2.27)
important
com
rate-limiting
relatively high
Because of the
radicals, which
high
production.
play
also
an
role in the fuel oxidation mechanism. Since the overall rate of the thermal NO
formation is slow
compared
can
be
decoupled
assumed,
that the
Hence,
CHAPTER. 2.
28
For
O2, N2,
are
calculated assuming
equilibrium
O and OH.
time and
Most,
is the temperature.
important
availability of oxidizer
Decisive
are
arc
Above 1300C
1400C the
or
Prompt NO
first
was
tional NO
the
"prompt'' NO
explained by
the Zeldovich-inechanism
Prompt
in methane
zone,
where
only.
compared
hydrocarbon
to thermal
NO.
air.
N2
CH2
N2 + CH
N2
C2
-4
N? + C
HCN + Nil
(2.28)
HCN + N
(2.29)
2CN
(2.30)
cTV + AT
(2.31)
HON + II
(2.32)
CN + H2O
>
IICN + OH
(2.33)
path
to
following
one
possible
NO. This reaction scheme is also valuable for the reaction of the HCN
CN + lh
(2.34)
CN~\-C02
NCO + CO
(2.35)
NCO + O
>
CO+NO
(2.36)
on
Figure
2.14
for the combustion of biomass. Beside the thermal NO and the prompt NO formation the
NO
resulting
Generally,
nitrogen which
nitrogen containing fuel has a high NOx emission potential. Hence, the
NOc from nitrogen in the fuel is of considerable greater consequence in the
any
formation of
mainly
released
as
Figure
2.15.
During
the
pyrolysis phase
possible
reaction
paths
or
the fuel
nitrogen is
N2 depending
for fuel
nitrogen
are
on
the
shown
NOx FORMATION
2.4.
29
Typical
[mg/Nrr,3]
Biomass Combustion
800
Thermal
,
7oo
02
Fuel-NOx
NOx
for
05s
11 Vol-%
UF-Chip Boards
600
500
400
FueI-NOx
Herbaceous Biofuels
300
200
Fuel-NOx
Wood
100
Prompt-NOx
800
Figure
2.14:
1400
1200
Influence of temperature
on
tC]
1800
(Nussbaumcr, 1997)
HCN is the
ing
starting point
key
(Williams
et
following
starting
generated.
place
>
NCO + II
(2.37)
HCN + 0
Nlf-r CO
(2.38)
CN \ OH
(2.39)
by
O
>
NO+ CO
(2.40)
NU-{OH
->
NO + lhO
(2.41)
CN + O
>
N + CO
(2.42)
the reaction
HCN + O
NCO
production,
al, 1997):
IICN + O
followed
NH2 + RH
NH-y + NO
>
>
>
are
formed,
to.
Nil2 -^CO
(2.43)
NIU
+ R
(2.44)
N2
U20
(2,15)
CHAPTER. 2.
30
Figure
Simplified
2.15:
the gas
reaction
path diagram
phase
using
mixture of oxygen, argon, and carbon dioxide instead of air for combustion. Such
experiments
and from
are
(Nussbaumer, 1989)
species
specific
are
reactions
reported
outlined in
Once
to which
as
by
main
paths
clearly
coal combustion
demonstrated the
and Bowman,
1989)
as
isolated fuel
nitrogen
are
2.17.
simulating
the
Subsequent
flames.
>
NO+H
N f NO
AT2
Figure
by which
oxidized to NO and
governed by
OH
studying
(Equations 2.37
2.39) even
hydrogen atoms lead
NH3/O2
pulverized
(Miller
and Figure
from
source
For
for
dominated
1977)
Figure 2.16
they studied H2/02/Ar
were
and Wendt.
(2.46)
(Miller
in
to
(2.47)
NO is converted to molecular
nitrogen.
In
general, NH3
is
2.1.
NOx FORMATION
31
HCN^s
NGO
Figure
(Miller
and
Bowman, 1989)
converted to NH2
+ OH
>
N112
(2.48)
H20
For lean conditions, reactions with oxygen atoms and for rich conditions reactions with
hydrogen
with H
or
reactions
1.
by
one
oxidation
NO/N2
(NH
and
NH2)
can
Further reactions
undergo subsequent
leading
2. reaction with NO
The
significant
to NO
formation
leading
distribution
to the formation of
primarily depends
on
N2
ture.
NH,
OH, +H, +0
+NO
Figure
Bowman.
Even
by
which
Nip is converted
to NO and
N2 (Miller and
1989)
though
is converted to
the fuel
of N0X, not
the fuel
all of the
nitrogen
nitrogen
content
on
the
CHAPTER 2.
32
conversion to NO in
biomass
also
unstaged
nitrogen
content of the
fuel,
nitrogen
combustion conditions.
measures
content,
At,
(<0.2%)
produce
high
contents, i.e.
laboratory
have the
high nitrogen
bed
of data about
high
lower NOx emissions than fuels with low volatile matter at the
same
usually
nitrogen
content.
80
Nussbaumer 1989, lab. FB
70
60
-I
50
40
o
w
30
>
c
?n
10
Fuel-N
Figure
The
nitrogen
from industrial
the conversion to
production and
or
wood
structure.
composites
Hence,
strongly depends
urea
in
bond
on
nitrogen
the
nitrogen, peat
regarded plant
elements
Figure
specified precisely
1.2 to 1.6% for hard coal and 0.4 to 1.2% for bituminous coal.
contents of
oxidising atmosphere
N-species
on
[%]
More
typical
values
The
nitrogen content
typical specific nitrogen
fuels,
were
found to be
important, for
NOx FORMATION
2.4.
33
N0X
as
N02
at 11 %
02
1000
Conventional
NOx
Combustion
[mg/Nm3 ]
Low-NOx with
Air
Staging and
Reduction Chamber
SNCR
100
'///////////////s
Miscanthus
10
0.01
"*"
Native Wood
Grass
-a
-
Straw 4|
SCR
UF
0.1
Chip
Boards
10
[wt.-%]
Fuel-N
Figure
the
on
reduction of NO
by CO,
char
partial
being
the
more
pressure.
>
CC)2
N2
(2.49)
2.YO + 2C
>
2CO-riY2
(2.50)
Beside the direct interaction of NO with the carbon. NO may also be transformed to
NH3 if hydrogen as H2, H, or OH is present.
ATT
XO
Simulations with
with
of NO
+ Off
>
NH2
H20
(2.51)
XH2
~^
H2O
N2
(2.52)
mathematical model of
kinetic model for NO formation and reduction have confirmed that the reduction
by CO catalyzed by
are
verv
important, especially
high (Jensen
and
at, low
Johnsson, 1996).
34
CHAPTER 2.
2500
2000
150
"
"5
1000-
E
500
miscanthus
Figure
All
organic
fuel
triple binding
simple binding
sludge
more or
nitrogen compounds
less
chemically
bound
nitrogen.
Most
frequent
are
converted
during
the
pyrolysis product
pyrolysis
process to HCN
structures of
higher
amounts of
N-containing
general,
oxygen and
produces NII3.
may
phenolic OH
It
the fuel
hard coal
N-H
In
sewage
N=N
particle,
UF-
chipboard
are:
heterocyclic
case
Specific nitrogen
nitrogen bindings
and NH3.
2.20:
chips
Nitrogen
Fuel
2.5
wood
straw
is
means
also
NH3 intensifies.
2.5.
FUEL NITROGEN
Expciiments
in
35
pulverized pyiolysis
leactoi showed
(Rdiger
1995).
C/N of the residual char from
pyrolysis increases with increasing pvrolysis temperattue, charcoal shows the opposite
trend (see Table 2.1). This diffeient behavior indicates the strong
binding of nitiogen in
and wood
et
al..
coal
Nitrogen
resulting
compared
in the
NH3 yields,
to wood.
were
found
coal
coveiing
an
higher
the
portion of
wood
pyrolysis
Figure
2.2P
gasification
oxidation
Simplified
fuel-N eaction
.._
NU
paths
formation
reduction
CHAPTER 2.
36
2.6
given by
Fuel is
Co-firing:
emissions then
(i.e.
partially
are
the
following
measures:
pen'
are
or
replaced by
an
com
other fuel
coal).
by
the lower
by
co-fiiing.
same
chlorine content,
or
substituted
Fuel contents
purification:
fuel of the
gas instead of
reduced
interaction effects of
Fuel
by
nitrogen, sulfur,
i.e. lower
general by
input.
position,
are
Higher efficiency of the system: Increasing the system efficiency lowers the emission
unit of energy
pollutants
some
be reduced in
can
an
input
eliminated
by biomass.
of undesired element
by special
treatment and
or
The
by positive
preparation of
the fuel.
Process
or
change
of the
End
of
adsorption,
or
auxiliary systems
filtration, absorption,
cleaning systems:
pipe gas
by
chemical reactions.
they make the process more complicated because they often introduce additional agents
produce other products which increases the logistical effort. In any case, secondary
or
measures
remove
it
by
an
other
sense
one.
first to
Thus, end of
pipe
one
process
ddie most
important primary
measures
for
are
special focus
is put
NOx reduction
are
on
measures,
briefly presented.
the most
by piimary
important secondary
measures.
measures
for
37
2.6.
pollution control
measures
Pollutant
Control Measures
NO,
staged
combustion
(air staging
or
fuel
staging)
ammonia
CO,
HC
optimized
-
stoichiometric ratio
combustion temperature
residence times
mixing
HCl, S02
limestone
Dioxins, furans
Particulates
combustion
staged
furnace
design
fabric filters
(baghouses)
electrostatic
prcipitt ors
wet scrubbers
during
secondary
measures
2NO
Since NO itscdf is
list of
N2
the
resulting products
nitrogen.
to be
are
(2.53)
promoted by
given
reducing agent. A
in Table 2.5.
NOx by ammonia
selective
4NO + 4ATJ3 + 02
(2.54)
4 AS + (UFO
Actually, the NH3 molecule does not react directly wdth NO. but reacts with the radicals
OH, O or II and forms an intermediate that may react with NO afterwards, ddie same is
true if
urea
is the
reducing agent.
NH-, + NO
The
optimal temperature
(2.55)
N2 + H20
efficiency
is
quite
narrow,
about
Above
CHAPTER 2.
38
the ammonia burns and forms NO itself. Below 800 C, the reaction slows clown
1000C,
and the
efficiency
the reactions
decreases
fast,
going. Depending
too.
on
At low temperatures,
the
catalyst
to 400C
is necessary to
keep
needed for
high
are
reduction rates.
Secondary
Table 2.5:
Reducing
measures
Products
agent
Reactions in gas
phase
non-selective
carbon monoxide
NT, C02
hydrocarbons
hydrogen
N2, I120
selective
-
No, H20
ammonia
-urea
Reactions in
-
Primary
measures
pends strongly
main
on
liquid phase
No, sulfates
sulfur dioxide
are:
temperature
oxygen
supply
residence times
fuel
nitrogen
content
on
the
with respect to
origin
single
fuel
As
or
in combination. A list of
primary
measures
already mentioned,
nitrogen
the
major
source
formation in
increasing
fuel-N content.
The
higher
the
The
bonding
on
2.6.
The combustion
measures
Table 2.6:
Primary
measures
lower air
water,
Staged
air
first,
combustion
staging
fuel
staging
amount of fuel
long enough
before
completing
provides
primary combustion
zone,
(Total
Fixed
Air
proceed. Staged
some
course.
The
sum
zone
products
are
formed in
mixing conditions,
primary
on
in detectable
quantities
IICN,
are
N02
+ 2
(2.56)
N20
Staging
required for
fuel rich
zone
created where less NO is formed from HCN and NH3 than at fuel lean conditions.
as
the
of all
HCN + Nlh f NO +
Air
NO
of
Nitrogen).
TEN
2.6.1
can
because it allowed
and intermediate
species that
stable
NO,
the
N2-forming
NOx,
as
reactions
Beside NO other
the furnace
nitrogen leaving
applied
rejected
by
heating temperature
minimizing the
02 only
or
surface burner
(=* primary
cooled surfaces
the
the
the heat, to be
by
excess air
reduction
Temperature
-
was
affected
combustion
strongly
or
For
fuel-N is
high
stoichiometric
39
molecular
zone
nitrogen
key
air is
zone,
i.
e.
the
decreasing
is
The
concentration
factor to NO reduction.
the
up
as
CHAPTER 2.
40
staging
optimization of the
An
zone
(SRt).
It
can
(SR)
zone.
staging
air
primary
can
(primary
air flows
input
and
(Equation 2.57).
zone
If the
input
also be used.
V
a
SR,
'pint)
pi
(2.57)
rise
im
'
SR,
pi
SR
im
(2.58)
AS m in
air
flue gas
Figure
Fuel
2.6.2
staging
process is shown in
at
complete
fuel lieh
completes the
formation
zone
Figuie
combustion,
zone
is about the
namely.
2.23.
The
staging
air
means
global
zone
place,
ddie
injection
NOx
eduction
emissions
zone
leducing NO
(stage 2)
aims
leads to
no
thermal NO
Depending
on
the reburn
formulated
may be
staging
the creation of
staging,
2(m
staged combustion,
for air
during
fuel,
the
as
2NO T 200
N2
2C02
(2.59)
2ATM 2H2
N2
2H2O
(260)
n/4)NO+ CmHn
same as
Unlike air
nitrogen
of
Principle
Staging
2.22:
mam
under discussion
(m4n/l)A"i
nitrogen, Equation
n/2H20
mC02
(2.61)
(Milien
and Bowman,
1989).
2.6.
41
reburning
with
In fuel rich
removal process
was
H + NO 4- M
HNO + M
(2.62)
UNO + H
NH 4 OH
(2.63)
NH 4 II
N + H2
(2.64)
N + NO
O + N2
(2.65)
air
V3
Vi
->
fuel 1
stage
SR.,>
stage
stage 3
2
1
-+-
SR>1
SRr<1
flue gas
fuel 2
2.23:
Figure
systems
reburn
reburn
mixing of
zone
zone
analogy
temperature
zone
stoichiometric ratio
to air
staging,
means now
zone
zone,
zone
is
(SR
1)
<
which is
is called
actually the
mathematical
value,
properties.
Substituting
reburn
instead of reduction
zone
fuel flcnvs, the oxygen content of the combustion gas from the
reburn
for fuel
staging.
calculated with the input
same
are:
In
reburning
zone
oiii1JAS
l<3lm?n
(2.66)
ratio in the
becomes
5T?r-
rJliSRiASimn,
rn{AS[mm
m2AS2r
(2.6'i
CHAPTER 2.
42
ddie fuel
input
be calculated from
can
an
balance, resulting
oxygen
in
Vi
rhi(SR[
m2
Dit
more
is defined
l)ASirni,i
,.,
used for
Ji-D2mnt
reburning
is the reburn
fuel
rale
(RFR)
which
as
i?FR---->?g\
(2 69)
mxLH\\-\-m2LHV2
can
arc
known.
link between the reburn fuel rate and the stoichiometric ratio in the reburn
fuel
mass
flows.
Assuming
the
mass
RFR
=
SR,
zone
is basically
the
mass
flow of the
(2J0)
Figure
properties:
(2.71)
( Lm}\ ( \S2
\-TirR) \IH\2J \A^im:
RFR
^TL^
stage
the
zone aie
LH\\
However,
v=1Tfr lhv2
is
'
as
7112
first fuel
rcA
(2-68)
qp7~T5
'
2.24.
key parameter.
zone
significantly.
ot
effect of the
pounds.
N-agent s
may
even
be enhanced
by the
Reburning
use
m
comparison
with basic
com
ichurning
are:
Lower heat
input of reburning fuel' onlv slightly fuel rich conditions in the reburning
zone are
necessary
N-agent injection
at
Lower
ddie
(SRftd) 99)
one or
and/or
two
locations,
principles
2.7, accoicling
of the different
to
(Zamansky
including
in the
churning
zone,
along
with
Advanced
et al.
1997).
provides
Reburning
bet ten
NOx reduction.
pioccsses
aie
summarized in liable
2.6.
43
1.5
0.2
LHVi/LHV^I.O
LHV1/LHV2
0.3
1.8
0.5
RFR FT
Figure
(SRj)
in the reburn
(RFR)
Reburning (AR)
AR Technology
Description
AR-Lean
injection
of the
variants
N-agent along
AR-Rich
Multiple Injection
AR
into
reburning zone
injection of N-agents both into
the reburning zone and with
the burnout
an
zone
and the
CHAPTER 2.
Ovorfife Air
Burnout Zone
Reburn Fuel
Rebufn Zone
Primary Zone
Primary Fuel
Combustion
Ar
2.25:
to
coal-fired
utility boiler
Chapter
Literature Review
3.1
chapter
This
staging
reported
are
Of course, there
this
chapter
Air
Air
staging
conditions.
more
two
optimum
by
air
from
(Takagi
species with
the
nitrogen
the most
as
was
et
al.,
premixed hydrocaibon
flame
1979).
zone
(propane) doped
nitrogen
reached that
was
was
increasing nitrogen
content.
with
is about 0.72 to
saturated
independent of
the added
as
The second
staging.
to increase at
more
reported
the reduction
decreasing
nitrogen
With
NH3
et
fuel
interest
as
(Smoof
0.75
special
significant
The
Of
modeling.
techniques.
means
stage
or
Staging
stoichiometric
fuel-N
dominant.
intents to present
both combustion
3.2
are
are
air
on
knowledge concerning
in literature.
Lowering
decreasing
the temperature in
originating
15
injecting
It,
was
revealed
46
CHAPTER 3.
LITERATURE REVIEW
that the N0X emission increase at lower stoichiometric ratios than the
optimum, mainly
due to the conversion of HCN and NH3 into NOxin the fuel lean stage.
The
that
scarcely
compound
any HCN
zone
higher
non-hydrocarbon
hydrocarbons
with
was
compared
the characteristic
nitrogen
NH3. ddie conversion of NH3 into NOx in the second combustion stage
was
remarkably
was
H2)
4-
explain
accompanying HCN
formation
hypothesis.
Systematic investigations on the influence of coal type and operating combustion condi
tions for pulverized coal combustion are reported from (Kremer and Schulz, 1991). The
experiments were executed on laboratory facility with a feed rate of 2 kg coal per hour.
The NOx reduction measured for air
most,
liquid fossil
fuels
were
(petroleum
earlier from
reported
different
Legend:
Coal N
800
V Shale N
>1
"O
Coal N
Shale N
600
0.44*
0,46
0.99*
2.08?
0'
53
400
0.
200
-v*
'**..
X
0.60
stoichiometric
Figure
0.80
ratio
in
et
al.
0.90
primary
tion conditions
An
0.70
zone
1980)
important aspect for air staging is the distribution between volatile nitrogen and coke
47
AIR STAGING
3.2.
nitiogen
in the reduction
to volatile species is
an mcicase
tempeiatuie
nitrogen
zone
nitrogen
than
high
different
low,
i.e.
sensitivity
to the
increasing temperature
coals, whereas for brown
reducing species,
optimum
in the reduction
increasing temperature
Air
an
optimal
0.15%)
and for
was
slightly
from
reported
primary
zone
nitrogen
has
zone.
staged
content
ddie
stoichiometric ratio
great influence
(Keller, 1994).
i.e.
Nip
as
to
were
Responsible species
optimum NOx i eduction was
(SNCR)
identified
found
hydrocarbons (CHi)
as
as
as
3.2
Figure
amino deriva
1100 to 1200C.
is about 250C
higher,
ddie difference
was
They promote
chips (N-
on
Compared
He also found
primary
nitrogen intermediate species at
lower temperatures.
1000
A
wood
UF-chipboard
900
800
chips
-I
700
to
CO
E
z
600
9
500
400
300
200
100
0
*i
A4Aaa
AA
-,
Figure
0.2
0.4
(Kellci,
199
1)
(T\
0.6
111
117tfC
the
1.2
eduction
residence
zone on
time m 1
1.4
eduction
zone
0 3- 6
s)
48
LITERATURE REVIEW
CHAPTER 3.
Staging
Fuel
3.3
Optimum N()x
reduction
performance
is
be
combustor
using
Advanced
Fundamental research
were
done
on
on
fuel staging
350 kW test
facility
was
reported
et
(Kolb, 1990).
from
The
zone
experiments
The optimum
was
found to be
Of
special
interest
on
the
are
the
investigations
nitrogen
content of
ddie
as
was
some
simulated
using
by
natu
optimum
beneficial.
600
600
NO,
NH/VolV.
NO
NO
NH,
NH,
HCN
HCN
Ippwl
IPP>I
\
\
\
*
300
'
/
300
*'/
\"
4
1.00
400
>
200
'
/
/
.\
/
/
**
A*
200
p
/
/
/
V*
B-.J' V"/\
100
100
J3"
"
"rtJr
\\
0.80
Figure 3.3:
Influence of
0 85
nitrogen
0.90
x2
0 80
0.95
content
0.85
0*
0.90
on
zone
the
0.95
NOx, NH3,
Further
/one
0 8s.
and
stoichiometric
doped
with NH3.
A>=SR,)
was
achieved
by adding H2 (up
to
3.3.
FUEL STAGING
25%)
49
doped
with 3% NH3
(Kolb
and
the
highly
conditions could
non-optimal mixing
possible explanation for the incieased NOx reduction is the augmented pool
of radicals which is generated by the H2 addition. Howevei, at, optimum mixing conditions
reactive H2 to the reburn fuel the NOxreduction for
be lowered. A
Expeiintents
were
stoichiometry
reburn
zone
of coal
viability
reburn fuel
as
natural gas
using
in the reburn
zone
as
Figtue
main fuel
by the addition of
stoichiometry
to simulate
compared
improvement.
facility designed
scale
pilot
on a
additional
110
more
supposed
reburn fuel
(coal)
provide
it does not
that
optimal
decreasing
the
eduction.
450
Reburn Coal
Bituminous
Open Symbol
Sub-Bltumtnous
400
Lignite
ClosM
Symbol
Ha* Opn
-, 350
o
30
q"
250
u-
200
150
100
III!
Illll
08
0.7
Reburn Zone
Figure
3.4:
(Moyeda
et
Impact of reburn
ah, 1995) (initial
Compaiisou
zone
content
coals
are
aie more
and
15
11
Stoichiometry
on
residence time
lebmn
/one
400
ms)
effective
as
(Morgan
et
1997)
10
stoichiometry
100 ppm NO
high-rank
L.
09
The
same
char that is
conclusions
can
are
more
higher
volatile
reactive which
have
significant
ct
inlluence
ah,
on
reburning performance.
Concerning
the
primary NOx
level
reburning performance
significantly as the initial NOx level decreases below about 400ppm. due to the
increasing significance of fuel nitrogen added to the reburn zone with the reburn coal.
Increasing the lesidence time in the rebuilt zone improved the NOx reduction for all coals.
the coal
decreases
About the
reported
NO
from
reburning
same
(Yang
with coal
1997).
was
lebmning
with
pulveiized
bituminous coals
less than
produce
leading eventually
even
are
200ppm
to
net
LITERATURE REVIEW
CHAPTER 3.
50
production of NO. At higher primary NO concentrations (> 600 ppm) the NO reduction
efficiency remained constant with increasing primary NO as shown in Figure 3.5. The
optimum residence time in the reburn zone for the investigated facility was around 450 ms.
In
products
may
can
(Cha
i.e.
perfect mixing,
hypothesis.
'
60
nitrogen
et
plug
comparisons
mixing
between dif
and furnaces.
to the
coupled
is
zone
zone.
experimental systems
rapid mixing
but
optimum residence
the
general,
'
"
A
A
"c
20
T5
-20
>
200
400
Primary
zone
efficiency
(Alzueta
et ah.
1997).
In this
or
case,
zone
1995).
ah,
coal
as
primary
and different
Figure
fuels
no
minimum
stoichiometric ratio.
of that
zone,
are
it is
19)
on
used
nitrogen
dependent
are
as
on
reburn fuel
the inlet NO
low concentration of
reported by (Kicherer
on a
(natural
et
(coals, biofuels)
as
gas,
reburn fuels.
highest
zone
of 0.8 to 0.9.
points
on
the
using
was
resulting NOx
a
negligible effect
impoitant
pulverized
(ppm)
made
were
1200
on
1000
exit NO concentration
__1__J
800
primary NO concentration
ah, 1997) (SRi l 01 1 03.
(Yang
et
et
600
Figure
bituminous coals
tion
one
hand at
For the
decreasing
mixing prob-
FUEL STAGING
3.3.
lern, and
on
51
heterogeneous
by homogeneous
leactions.
reduction
potential
differences in the
the reburn
zone
as
gaseous
or
by
the volatiles
delay
Then,
at
longer
residence times in
Figure
chemistry of reburning
(Kilpincn et ah, 1992). ddie
The
was
rapid
natural gas
(methane)
investigated by
on
chemistry
ideal, isothermal plug flow
investigated by applying
complex
reaction scheme to
1994)
was
the reburn
conditions.
With respect to
stage
arc
reburning.
NO and 02.
the most
piimaiv NO emissions
the emission of
total fixed
increases
the
high piimaiy
NO level.
it should be noted that the absolute level of the TFN from t he reburn
higher
at
zone
However,
will remain
Other calculations where the stoichiometric ratio and the NO concentration of the first
stage
a
was
kept
optimum reburn
zone
stoichiometry,
i.e. where
minimum of the TEN results, is about 0.9 to 0.95. A decrease in temperature shifts the
is
ratios.
Howevei,
reburning
shown to be
governed by
hydrocarbon radicals conveitmg part of NO to HCN. The IICN
fuit her via isocyano species to amines which finally react with NO to N2.
was
NO -^ HCN
^N
UNCO
>
NH, -^ N2
(3.1)
CHAPTER 3.
52
position
reactions,
NO
reburn
paths for
(HCN, NO, NII3)
i>
^-T
N2
(3.2)
NO-Z+N ^T
N2
(3.3)
HNO
NH
reaction
zone
found to be effective.
were
NO
Important
LITERATURE REVIEW
to N>
HCN
in the burnout
NCO
>
(3.4)
N2
A,0
Nlli01^1 Nlh^y
"-??
from the
shown to be
(3.5)
N2
(3.6)
N2
0 6>
0 '3
L"
600
400
?00
800
1000
1200
Figure
zone
m
3.7:
NO concentration
cburn
0 5
zone
The burnout
complete
possible
zone
fly
ash.
vs
primary
time
NOx formation.
burnout
design
(see
is
et
SNCR
technique).
as
However, the
N>0 and CO
optimal reduction
emissions.
of NO must be balanced
zone
for NO
by
nitrogen
(Kristensen
is
et
s)
suppress thermal
(Kilpinen
with
staged
air
supply
moie
efficient.
Chapter
Facility
Research
4.1
Design
research
new
facility
designed
was
to
investigate
both air
in
is derived
for fuel
staging
concept proposed
experiments to fuel staged wood combustion at the laboratory (Salzmann
and Nussbaumer, 1995). The reburn fuel then was put batch-wise downstream of the
a
new
combustion
of the
zone
of the
The
design
facility are
two
unit is modular. It is
new
composed
an
air
design
input,
on
zones
stage of
the
one
provides
an
adapted
is equal.
injection
At the
part
entrance a
mixing
static
highei
on
protected by
mixing
the lebuin
passing
keeps the leburn
on
at
the heat
injection of
at
zone
low temperatures.
(0.4
sampling
s).
4.2
The
Accoiding
the top is the burnout segment which leads the gases further to
exchanger
no
zone.
zone
Figure
The reburn
openings
be influenced bv the
can
straight plug
gas flux.
interesting
bricks.
by
is
approximate
firing
The minimize the heat loss of the combustion gas the cooled surface
enhanced
to
components
the whole
to the
stacked and
reduction
are
design of
or
line, ddie
equipped
secondary air. The second clement contains the burnout
primary and
dead
preventing
supply for
Figure
with
creating
is
designed
to
53
is
as
RESEARCH FACILITY
CHAPTER 4.
54
operation. A part of the flyash is collected in a box at the last redirection of the gas
entering the heat exchanger.
Besides the fuel and the ash handling, the operation of the research facility is com
pletely automated, controlled by a PLC. The first fuel stage is equipped with an oxygen
of
before
control. This
means
continuously with
The fuel
11.
For fuel
set value.
zone
(position 6)
feeding
staging.
then is
is measured
regulated
the oxygen content and thus the stoichiometiic ratio of the first
a narrow
rich
reaches
zone
Howevci, the
values.
high
possible
stage
is
save
Operation
facility
shown in
Figure
A Conventional
B Air
according
guarantees
as
fuel
small
as
legulated
second
The research
probe,
complete
burnout
4.2
handling.
closed
zone.
is achieved at
are
amount of
the
conditions.
Modes
can
be
operated
(unstaged)
combustion
combustion
staged
C Fuel
staged
combustion
For air
staged
arc
accomplished by
only
one
Conventional combustion
bed.
This
means
means
given
to the fuel
supplied
gas.
Air
that
Fuel
staging
bustion takes
uses
place
metric conditions
establishing
11 1.3).
(SR
=
given
zone.
is
as
operated
(SR
com
1),
4.2.
Figure
4.1: Research
1. understoker
2),
55
OPERATION MODES
8.
(stage 1),
ventilator,
9.
facility
2.asli
mixing element,
5.
primary
7. understoker
zone, 6. burnout, zone,
flyash box,
13. boiler
(stage
CHAPTER 4
RESEARCH FACILITY
N*.
Figuie
t-
1 2
Mixing
JO
A
>
.^-^*
element
<""
|/y/y/>
L_J
pr^^
^^<-
zZ
z.
r'~3
-N
Eigm e
13
B. An
icsean
h facility
Conventional
combustion,
57
ENERGY FLOWS
4.3.
Flows
Energy
4.3
Typical energy
fuel staging are
shown in
4.1 and
Figure
on
the research
Figure
facility with
ddie values
4.5.
displayed
input
staging
air
are
and
calculated
is set, to 100%.
staging,
For air
on
experiments
zone recovers
about
understoker box 3%. The heat loss to the environment is about 2%. The energy content
of the flue gas at the boiler exit is calculated
resulting efficiency
of the
facility
as
Summarizing,
the
staging.
11 %
2%
t
59%
25%
100%
h
3%0
r"V
4.4:
Figure
For fuel
staging, the
stage plays
an
Energy
larger.
other role
The
now.
cooling
The
as
staging
higher
since the
area
of the heated
meaning
of this
little influence
cooling
to
as
possible
high combustion gas temperatures are beneficial for the gasification of the reburn
fuel. Although cooling system is siniplv designed, it recovers about 24% of the total input
energy. Due to the high temperatures in the combustion chamber of the first fuel stage.
because
(1000
to
by the
1200C).
reburn
compared
to
the
zone
to air
higher
the heat transfer is mainly clue to radiation, ddie part of heat recovered
heat loss of the facility to the environment and the heat, loss
efficiency
of the boiler.
by
CHAPTER 4.
58
RESEARCH FACILITY
12%
5.5 %
37%
21.5%
h
25
%i
24%
^ 75 %
Figure
4.4
Measurement
Energy
staging
Equipment
Equipment
Basic
4.4.1
1 5:
on
various
object
during
measurement
its
i.e.
systems
composition
were
the process.
Beside the outputs of the combustion process, the flue gas, the ash. and the
one
quantitatively,
An overview
marized in
velocity,
but it
on
enoimous
effoit
The measurement
analysis
better
understanding
equipment available
or
at any
techniques
of combustion
The fuel
arc manv
the main
Figure 4.6.
species concentration
requires
more
heat, the
other process
possibilities.
and
an
Additionally, there
too.
the process.
happening dining
applied.
and temperature
is
were
given
equipment for the gas analysis is the topic of the following sections.
by the EMPA1, section Motor Fuels/Combustibles. The amount
is done
air was
determined
by
velocity
tubes fixed
on
MEASUREMENT
4.4.
EQUIPMENT
Research
Facility
gas
combustion
process
ash
heat
4.6:
Figure
Parameter
air flows
gas
tempera!
gas
composition
ures
Measuring Method
velocity
temperature
thermocouples type
enthalpy
weight difference
fuel
weight
composition
Hot Gas
analysis
methods is
little time
absorption
fractions
proximate
or
and ultimate
analysis
Analysis
difficult task.
delay.
analysis
gas
drying balance
K. S
of water
fuel moisture
4.4.2
The
Quantity
species concentrations
heat output
equipment
The
The
sampling
sampling
or
reduction chamber
train should be
as
by
short
sampling
possible to have
extractive
as
non-catalytic to avoid
analysis, the sampled hot gas has to
be filtered and cooled down from about 1000C to temperatures suitable for the
During
the
taken from
a
cooling
a
process,
liquid phase
may be water
some
this
gas
components have
demand,
the hot
is
to be
analyzed before
only. If the
c.
arc
temperature is
thought
analyzers.
If the gas is
to be
condensation takes
above 200C
occur.
heated
kept
by
passed. The instruments of the cold analysis
the gas
analysis
i.
incomplete combustion,
may
analyzed. Thus,
place. According
sampling
measure
to
system until
dried gas.
Being aware of the entire problematic, the hot gas sampling for continuous analysis was
designed as shown in Figure 4.7. The gas analysis is clone bv commercial analyzers and by
More details about the analyzers
an FT-IR (Fourier Transform Infrared) spectrometer.
and the FT-IR spectroscopy
are
given
in the
appendix.
RESEARCH FACILITY
CHAPTER 4
60
300 C
250 C
240C
\
800
1200C
x
'
\T--^
ceramic
probe
-r~1
-l
CO vse
\ <ls
rr1
<<
|0-
filter
ne
Analysis
-On
Hof
pump
filte r
CLD
>
(NO N02)
0
o
FID
(CH,)
CN
\\
FTIR
chamber
NDIR
(CO
Param
i_
CO
_zzr:
HCD
OAO
<
5 C
CH4 NO)
ii!1
(02)
(H2)
ind
Cold
lometa, displayed
Figuie
<
omposition
within paits of
Hot gas
(type
second
can
oi
is
Analysis
special
BOSCH LSM
the combined
puipose
11)
absorption
sampling
this
r-" E
Cooling
r_j
condensation
I lginc 4 7
ov erflow
with
no
suction py-
only
can
With this
sampling
piobe
delay
is
installed
time
4 4
MEASUREMENT
ceramic
61
EQUIPMENT
tube
Figiiie
4 8
piobe
foi 02 detection
CHAPTER 4.
62
Flue Gas
4.4.3
NO2
was
Analysis
is determined
original
by
facility,
ddie content
sampling
continuously.
sampling channels. One channel contains the
NO2 is converted
gas. i.e. NO +
RESEARCH FACILITY
to
passes first
is shown in
Figure
heated converter
by cooling.
dTe scheme
4 9.
Analysis
Param
(02)
NDIR
200
300C
(CO, C02)
140C
140"C
CLD
(NO, N02)
|TTsToTy-
fine filter
heated
samiing
Cooler
line
chimney
Figure
sampling
Chapter
Experimental
About the
5.1
Experiments
Wood Fuels
5.1.1
Results
strong influence
wood
UF- chipboard
on
experiments:
chips
high nitrogen
the
glue
for the
experiments
relatively
was
on
content
small
pressed
the
to
characteristics
can
pieces
are
guessed
with
chipboaid.
from
cm
Figure
length by
chips
diameter of about 8
grate by
cm.
But the
briquettes
(sciew feeders).
were
The
cut into
chipboard
were
crushed
fusibility of
concerning
be
ol about 5
briquettes
to the
way
dTe
compared
ash is also
an
puts limits fixed bed combustion. Native wood usually has the highest melting range, the
one
of
can
be much
UF-chipboard
is lower
(see
lower, depending
on
Table
then
5.2).
composition
oi
whether they
compositions with
low
amounts of various
melting points
63
inoiganic
aie
melting point
substances which
can
form
new
EXPERIMENTAL RESULTS
CHAPTER 5.
64
Figure
5.1: Wood
chips
Figure
water
ash
wf
volatiles
wf
char
wf
HIIV
wf
LHV
wf
wf
II
wf
wf
wf
wf
NO2
of the
UF-chipboard
investigated
wood fuels
Method
Wood Chips
UF-ClIIPBOARD
17.9
4.7
DIN 51718
1.0
1.3
DIN 51719
83.0
79.9
DIN 51720
16.0
18.8
DIN 51720
19.64
19.85
DTN 51900
16.13
18.91
18.47
18.53
DIN 51900
Md/kg
14.71
17.54
g/100g
g/lt)0g
g/100g
g/100g
g/100g
49.6
49.2
ASTM D 5291
6.0
ASTM D 5291
5.31
by addition
41.1
44.9
0.18
3.58
DIN 51722-1
0.03
0.12
DIN 51724-1
maximum
from N ; it 11% Oa
wf
g/100g
g/lOOg
g/100g
g/100g
Md/kg
Md/kg
Md/kg
analysis
5.2:
mg/Nmd
720
12300
watt;r hoc
Table 5.2:
Fusibility
investigated
fuels
Ash op
Ash
Wood Chips
UF-Chipboar
128CFC
1230C
Hemispherical temperature
13UTC
1260O
Fluid temperature
1360C
1290C
Melting
range
of
ash
of
DIN 51730
65
5.1.
Parameters
5.1.2
following dble 5.3 gives an oveiview on all the experiments on the research facility
reported in this chapter. The table indicates that the total stoichiometric ratio was the
only variable parameter for the experiments wdth conventional combustion.
ddie
For air
staging,
SR for
was
zone
SIT
was
the
only variable
regulated separately. Figure 5.3 shows the resulting correlations between SRi and
air staging, ddie temperature in the reduction zone was not controlled and therefore
important
kept
as
are
zone.
experiments
staging
zone was
vaiied
only
experiments
for the
comparable.
more
experiments
with
was
dTe
UF-chipboard
Table 5.3:
Rebvrri
VARIABLE
FIXED
fuel
(Mode A)
Pth
SR
35 kW
UF-chipboard
SR
35 kW
staging (Mode B)
chips
UF-chipboard
Pth
SR, (SR)
2s
35 kW
SR, (SR)
2s
35 kW
Wood
chips
Air
Wood
Fuel
staging (Mode C)
SRi
UF-chipboard
UF-chi.pboard
T,
RFR,
UF-chipboard
Wood
T,,
RFR
T,
RFR
1.2-1.3
T:,
RFR
1.2-1.25
Wood
Wood
Index I
According
chips
chips
Wood
F/F-chi pboard
to the
chips
chips
reduction
or
cbuin
1.2
1.2-1.3
2s
s
35 kW
35 kW
zone
UF-chipboard
UF-chipboard
wood
wood
is main fuel.
is main fuel,
chips
are
main fuel.
chips
are
main
45 50 kW
2s
are
used in the
following
figures:
UF/UF
UF/W
W/UF
W/W
Pthi
40-50 kW
1.3
text and
66
CHAPTER 5.
dble 5.4:
Dependencies of
the most
Parameter
Function
SRt
O2
SR
EXPERIMENTAL RESULTS
of
conccntiation
pnmary
zone
SR,
air
air
moisture contents,
Figure
5.4 picsents
an
example of
heating
fuels,
values
emissions,
fuel
level to
also be
higher
seen
heat up
which
overlap
the
as
stage
general
well
as
phase of
given
the most
calculating
in time
in the
Appendix B 3.
important parameters
possible
An
is
are
errors
overview on
given
in Table 5.4.
E50
E25
UF-chipboard
wood
chips
1.00-
icc
0.75
0.50
0.25
0.00
*--
0.0
Figure
can
trends.
the tolerance is
during
temperature
one
is
important
0.5
E0
SR[-]
1 5
2.0
2.5
air
staging
5 1
67
00 00
00 15
00 30
00 45
0100
0115
0130
0145
02 15
02 00
30
SR
25
SR
CC
SR 1
20
15
1 0
05
Lf
00 00
Elgin
5 1
00 15
Time
00 30
histoiy of
00 45
an
0100
0115
ih
0130
0145
1i
02 15
02 00
time
in
horns
CHAPTER 5.
68
Measurements
Temperature
5.1.3
EXPERIMENTAL RESULTS
were
generally
measrued with
thermocouples. There
fore, the values measured in the hot gases have to be interpreted cautiously, because the
effective gas temperature diffeis fioin the
exchange
bv ladiation.
ieduction
zone was
one
measured
by thcimocouplcs
effects.
5.5 shows the difference between the tempeiafure measured with the suction
Figure
pyrometer:
turned
once
The
on.
80 to 100C
comparative
higher
as
simple thermocouple,
ples,
and
kept
once
with suction
iempeiature is about
simple thermocouples.
aie
in mind.
25
1200
start ot suction
1180
-temperature
"Vv,-%VvV"
oxygen
20
1160
1140
1120
15
1000
00 00
00 43
0126
02 10
time
Figuie
10
02 53
03 36
04-19
05 02
[min]
zone
69
CONVENTIONAL COMBUSTION
5.2.
Conventional Combustion
5.2
facility
can
be
operated separately
as an
understoker furnace
primary
zone
already higher
is
than
I, the
Figure
chipboard
5.6 and
Figure 5.7 show the NOx and CO emissions of wood chip and UF-
combustion. The
figures
on
the NOx and CO characteristics. The NOx formation decreases with lower stoichiometric
ratio, while the CO emissions
suddenly
vJUU
450
1000
NOx
-
4-CO
900
CS
O 400
800
700
600
500
-5
350-
300
%A&&
O>250
ImmmJ
400
^200
O
z
O)
JL
150
300
o
o
0*100
200
50
0
100
0
3.5
2.5
1.5
SR[-]
Figure
more
furnaces exists
an
mixing problems
typical characteristic
optimum stoichiometric
zone
facility.
950-1020C)
In technical
complete
inhomogenitics. ddiis discrepancy
each furnace, ddicrefore, in tecdmical
and
of
combustion (Tt
typical
chip
If the
surplus
complete oxidation of the
gas. As
consequence,
again.
sically
on
the furnace
design,
idealized CO characteristics of
typical
furnaces.
on
the fuel.
Figure
5.8 shows
complete
70
CHAPTER 5.
1200
O1000-
1000
NOx
CO
&
800
900
800
-
600
CM
40
200
600
500
"7
400
"1
300
CO
700
S5
jfF
E
O)
EXPERIMENTAL RESULTS
++
-200
-
Z
-
-^WWPPPW1-!
100
"Tw
1.5
2.5
3.5
SR[-]
Figure
5.7:
970C)
can
be found in
(Nussbaumer, 1989).
10000
ideal furnace
good
design
automatic furnace with
good
design
05
1 5
SR
Figure
2 5
3.5
930
71
CONVENTIONAL COMBUSTION
5.2.
The
optimum stoichiometric
UF-chipboard (~ 1.5)
than
means
chips (i=s 2.0) at almost, equal
design also the fuel plays an important role. This influence is also true for the NOx for
mation, of course. The effect of decreasing NOx emission with decreasing stoichiometric
ratio is much more significant with UF-chipboard.
temperatures. This
for wood
the emissions at
Regarding
by
chip
gas, the
combustion
are
300mg/Nin3
about 280 to
about
UF-chipboard produces
or more are also possible.
oOOmg/NnE
NOx
at
at,
11% 02-
The
optimum conditions,
mg/Nm3
An
important
the
Figures
hint to the
probably
easiest
If the furnace is
primary
operated
measure
at
optimal stoichiometric
But,
furnace, the
fuel
same
produces
on
OJ
800
Y">
UF-chipboard
Dwood chips
^-*s
other furnaces.
900
given
ratio for
700
^*
ri
600
B> 500
E
400
CJ
O
z
300
(/)
co
X
200
100
0
1.0
1.2
1.4
1.6
1.8
2.0
SR[-]
Figure
5.9:
chipboaid
UF-
TC=11L0C)
TC=960C,
shown in
Figure
5.9.
zone
again,
chip
during reburning
UF-chipboard
and
decreasing
stoichiometric
ratio.
are
less
progressive compared
to the
experiments with
conven
CHAPTER 5.
72
up to
3g/NnE
at
EXPERIMENTAL RESULTS
emissions for
residence time.
to the
example
wTere
almost
different combustion
Basic research
further work
The
on
on
testing
(Salzmanu
in
reported
Staging
Air
5.3
is
73
5.3.
improving
this
and Nussbaumer,
1995)
on
the
one
and for
hand,
staging
primary
was
measure
and
comparison
facility
with fuel
serve
staging
on
as
vali
the other
hand.
the
Again,
(SR,)
has
prcwided
distinct influence
(temperature,
mean
on
zone
(Figure 5.10),
also
accomplished
important
residence time,
are
mixing).
500
oUF-chipboard
450
."v
CM
wood
chips
400
i?
*-5
0^
350
Oo
^^B**
o?>
11
CO
E 300
?#ROo
250
E
i__j
<N
200
150
CO
X
100
50
0.6
0.4
0.8
1.2
1.0
SRr [-]
Figure 5.10: Influence of stoichiometric ratio in the reduction zone on
staged combustion (IT T,= LOO-1080'C, W I\=r 1110-1180C, CO <
at air
Although
value of SR!
measurements at
ratio
seems
to be
as
found
slightly
are
mg/Xm3)
missing,
the
optimum
by (Keller. 1994).
UB'-chipboard.
For wood
by
air
staging. Figure
staging
zone
created
NOx reduction potential of air staging clearly visible. The NOx emissions for air staging
correspond
to the values in
stoichiometric ratio
zone
(SR,)
(SR).
Figure
corresponding
total
and the total stoichiometiic ratio is almost constant, the trends of the
points
74
are
CHAPTER 5.
EXPERIMENTAL RESULTS
rather similar.
500
A air
450
staging
wood
conventional
chips
400 4,
350
300
250
iE
CM
o
(/)
CO
x
200
150
100
50
0
1.0
1.5
2.0
2.5
3.0
3.5
4.0
SR[-]
1200
C1000
air
conventional
staging
UF-chipboard
<*>
800
-j
CO
E
o>
600
IE
o
Z
400
C8
x
200
1.0
1.5
2.0
2.5
3.0
3.5
4.0
SR H
Figure
staging
5.11:
5.3.
can
be reduced below
staging
75
100mg/Nm3, meaning
is
ieduction of
lowered to about
more
chip
combus
than 65%.
175mg/Nm3
dTe
which is
Fuel
5.4
5.4.1
Staging
Influence of the
Chemical reactions
tems, there
usually
are
Temperature
exists
staging efficiency
EXPERIMENTAL RESULTS
CHAPTER 5.
76
apply
increases with
more,
staging.
more
test
in literature the
reported
facility
sys
product
increasing temperature
experiments on the
As
to the desired
was
to
usually
investigate
practical
fuel arise.
the
are
use
using
the
same
fuel both
as
primary fuel
and
as
logistics
especially necessary for fuels with high nitrogen content,
experiments wdth UF-chipboard were expected wdth highest, interest. Of course, there
other fuel combinations with are possible in practical applications. However, all these
reburn fuel.
Thus,
the
same
can
be used and
no
combinations
were
investigated
\
\
O 200
here.
*W/W, RFR
0.3
^WAV, RFR
0.4
MUF/W,
D
150
RFR
0.2
UF/W, RFR
0.3
A---UF/UF, RFR
0.25
--UF/UF, RFR
0.3
A-
JE
i
!
<5
X
i
'
50
600
700
800
900
1100
1000
1200
Tr [C]
Figure
(information
about the
A summary of the
presents Figure
experiments gives
dble
zone
on
5.5)
zone
are
displayed
(RFR).
evaluated measurements
with
few
clearly demonstrate
measurements
500mg/Nm3
at least below
were
settings
measured,
were
at
UF-chipboard
of
lOOmg/NnEat
than
can
with air
chip
t20mg/Nm3
cases.
significantly
combustion is
comparable
to the
optimum temperature
one
are
potential
fuel staging
staging.
The
to be above
begins
to be effective.
increasing temperature
chips at wood chip
seen
A decrease of
combustion
with wood
(W/W)
seems
to
1/Fuel
W/W
W/W
UF/W
UF/W
UF/UF
UF/UF
W/UF
W/UF
el
*mg/Nm3
ai
RFR
SRi
0.3
1.25- 1.3
staging experiments
Ti
CO*
0.88
1000-1035C
200-250
SR,
0.4
1.25
0.75
1030-1050C
220-250
0.2
L.2-1.25
0.95
1010
1040C
250-280
1.25
0.86
1030-1060C
220-250
0.92
1010 1080C
200-250
0.3
0.25
1.2
1.25
0.3
1.25
0.85
1025-1045C
180-220
0.25
1.25
0.94
1060C
400-500
0.3
1.25
0.88
1055C
350-450
11% O2
by using
means
wood
zone
indicate
chips
reburn fuel
as
as
Although
0.2 at
UF-chipboard
alternative.
arc
presented
the most
In any
case,
can
are
re
be reduced
the temprt
lire
in the
important parameters.
points
5.4.2
are
cannot be
reburn
The emission
measured.
seems
range
already
with
data, although
a
staging.
the reduction
towards
NOx reduction. At
a
be decreased
trends
visible, ddie
to decrease.
already begin
are
pass
are
some
reburning.
77
5.4.
(RFR)
is the most
given stoichiometric
zone
(SR,)
parameter for
important
zone
zone,
ddie
which is
a,
func
characterizing
higher
RFR
the
means
experiments with UF/W. ddie Figure also shows the influence of the temperature
in the
CHAPTER 5.
78
reburn
zone
creases
and
With
the
EXPERIMENTAL RESULTS
experiments
seems
to be around
0.8.
500
OUF/W,750C
450
XUF/W,900C
400
350
300
250
E
CNJ
o
z
0
200
o o
150
ro
X
100
X"*
50
0
0.6
0.4
1.2
1.0
0.8
SRr
Figure
UF/UF.
0.25
more
at
750C. With
suitable for NO
higher RFR,
consuming
zone
regarded
become
on
in the reburn
0.3
for
UF/W (in
reburning
compared
with
to RFR
zone
reactions.
NOx emission by
more
than 50%. If the reburn fuel rate is increased from 0.25 to 0.3 at
be abated further.
period
can
reducing
contrary which
means
aie
still far
carefully, otherwdse
way
the
pioblem
to the
higher nitrogen
higher
from
54
79
250
200
RFR
0 25
RFR
j -26%
TU
O)
M||g
E
"
111
100
llliiii
^^^^^^g
z
0
CO
_*
llllll
50
H
Tr
Eiguic
Influence of RFR
5 14
03
150
on
NOx
750C
at
emission
750C foi
UF/UF (mfoimation
about
5)
720C
850C
X
200
-52%
150
-68%
^3)
\
IN
100
o
z
0
CO
X
50
RFR
Figuie
5 15
0.25
RFR
5)
on
0.25
\0\
RFR
emission
foi
0.3
W/UE (mfoimation
EXPERIMENTAL RESULTS
CHAPTER 5.
80
5.4.3
with the
approximated
If the air is
geometric position
injected through
the nozzles at
that
the
of about 10%
5/9 r
calculated
position 2,
the
(air
nozzles at
resulting
mean
5/9 r.
genera] trend of
was
Figure 5.16,
In
not measured, ft
position 3).
zone were
zone,
compared
ddie
figure
shows
are
plotted
weak increase of
significant, meaning
practical applications.
curves
500
0-
450-
5/9t
-Xx
400
350
300
.
250
E
\mmmt
200
O
z
150
100
50
0
600
800
700
1000
900
Tr [C]
Figure
on
5.16:
Influence of the
Table
5.4.4
The
mean
UF/UF
at RFR=0.3
(information
about, the
zone
experiments gives
5.5)
Practical
experiments
Experience
on
stage of the
presented fuel
regarding
facility, an
are
few
practical experience.
an
test
understoker
as
shown in
Figure
5.17.
81
5.4.
well known, of
However,
course.
This
resistance, the
phenomena
is
"bypassing"
staging
completely for the gasification of the
following reduction chamber is designed like a plug flow
in
this
of fuel
case
pyiolvsis
accomplished by
an
adequate design of
homogeneous
5.17:
Measurements with
Figure
Shapes of
suction
the reburn
Wood
chips
are
in the reburn
used
as
has to be
an
bed
V"
understoker furnace
zone
zone.
zone
of the
zone.
inhomogeneous
bed
probe
complete mixing
or even
J\Figure
local
point
at the
reburn fuel.
1000
00 00
01 26
02 53
04 19
time
Figuie
5.18:
reburn
zone
Two
phases
be
07-12
[min]
can
05 46
on
1 theie
is
no
zone.
CHAPTER 5.
82
EXPERIMENTAL RESULTS
The
while,
oxygen is consumed
Although
mixing
during
the
gasification
of the
oxygen
can
element is installed above the fuel bed of the reburn stage which mixes
entering
homogeneous again,
the reduction
zone, some
UF-chipboard
as
oxygen is wasted.
wav
zone
that the
most
reburning. meaning
during
the heat up
period
of the
is
more
movement has
again.
of the furnace
temperature ol
at least
not
into
700C.
higher NOx
account.
emissions
nitrogen species
that they are converted to NOx during buinout. Theiefore,
reburn fuel should only begin after that the conditions in the
temp erat m es,
some
with
gasification
the
feeding
reburn
of
chipboard
zone are
so
as
suitable for
Chapter
Modeling
About
6.1
Since
predicting
remains
aims
passing
all aspects of
simulation still
(Figure 6.1) by
on
future
Figure
A
are
Modeling
6.1:
Physical
general, comprehensive
can
typically
be
applied
include the
1991):
t urbulent fluid mechanics
particle dispersion/motion
solid devolatilization
heterogeneous
given
here,
model that
is
report.
to the
description of complex
with different
char reactions
83
key components
following (Bartok
and
Sarofim,
CHAPTER 6.
81
radiation
pollutant formation
ash/slag
formation
practical combustion
Simplifications
the
processes
on
MODELING
and
assumptions
require
be considered
can
processes. However,
complete description
as
can
are
an
The classi
missing
obtaining
an
inadequate
or
adequate
information
process
descrip
practical
flames
Classification
KX AMPLES
Mathematical
zero-dimensional
complexity
one-diniensioiial
multi-dimensional
transient
steady
Solid
particle
size
state
large
intermediate
small
Flow type
well stirred
plug
flow
recirculating
Process type
fixed bed
moving
bed
fluidized bed
suspension firing
Flame type
well-st ired
premixed
diffusion
ddie mathematical
damental
equations
description of
of
reacting
for
an
mass
combustion system in
flow, wdiich
general
the conservation
arc
species.
is
given by
equations
the fun
of mass,
are:
balance:
dP
dt
OP")
Ox,
(6.1)
momentum balance:
dpa,
pu tu
di
or-,
dp
drn
dr,
Oi,
__
(6.2)
6.1.
85
ABOUT MODELING
energy balance:
..,
j ^T
dpu,fl
.,
_.,
at
..,
OY,
species balance:
OpYn
_
dpVjYn
equations
can
0Yn\
_(^_j+Wn
be found in
(6.4)
or
in other
When
dealing
wdth
stagnation enthalpy
flows, the
compressible
is often used.
H^h+1-^
(6.5)
Ey"/?"
(6-6)
where
/?
N-l
the
a
gas
is
only
function of temperature
hn=
(6.7)
cpn(T)dT
/o'o
For
On,
T"
equation of
'T^
du,\
^J
set of
completes the
state
2
t
Oui
(6'8)
5"^*'
eciuation.
pRT
(6.9)
Ey-Tr
(6-10)
where
v
/.
i-
The chemical
source
the coiisideied
tenu T in
can
exchange
AVA
Ou
k -1
energy
consumption of
species.
E K'a
Cas molecules
equation
react
that
can
H[Xn]"
A
khk
UlXn]<^ \
n--=l, ...,N
(6.11)
A_l
come
bieakmg.
close
enough
theory, the
rate
MODELING
CHAPTER 6.
86
expressed
of reaction is
in
required
pre-exponential
If the
A(T)
factor
energy.
A(T)exV>(~yic,
the
(6.12)
approximately
is constant, which is
for small
k(\Cj
true
Aexv(^^j
equations 6.1
become
(6.13)
6.4
can
equations
describing the turbulence are needed, ddie main difficulties consists of
and length scales and the nonlinearity of the chemical source term.
Several model
flows
approaches
different levels of
by
overview
on
have been
more
and
of the
approaches
approximation
can
be found for
developed
simplification
Nussbaumer, 1997).
even
reacting
physical reality.
An
(Ecrreira
and
example
in
given
approaches. The models
are
presenting
only introduced by name.
corresponding literature.
computational fluid dynamics
(CED)
The most
flows
facilities with
practical
popular model approaches used for the analysis of practical chemical reacting
are:
RANS
Function Method
PSR/PFR Perfectly
Models,
Stirred Reactor
ID
or
developed
differences
figures
points
are
illustrated in
some
are
compared
The
under different
of view.
compares the
means
also demonstrated in
that the
Figure
6.3.
highly
are provided.
right
2D
Model/Plug
Hence, the
weighting
of the
high Reynolds
complexity
importance of
the
6.2.
ABOUT MODELING
87
DNS
RANS
1D laminar
LES
Transport
Persumed PDF
Flamelet
PFR/PSR
numerical effort
Figure
premixed
occur,
ddie
and how
questions
modeling
aie
mixed then.
is the
(Ferreira
degree
of
Nussbaumei, 1997)
and
mixing
are
unmixed
or
partially
they
important aspect
mixing regime
improving furnace designs wdth respect to flame stabilization or pollutant formation.
Figure 6.4 compares the effort on chemistry versus the mixing of the different models. The
comparison shows again the different preferences of the models.
are
The
can
be
an
for
However, before
lation should
choosing
model,
one
has to be
aware
of the
answer.
chemistry
PFR/PSR
1D Flamelet
DNS
LES
RANS
->-
Figure
6.3: Effort
on
chemishy
veisus
tuibulence
(Fcireira
and
Re
Nussbaumer, 1997)
MODELING
CHAPTER 6.
88
chemistry
1D Flamelet
reduced
PFR/PSR
RANS
LES
DNS
->-
Figure
6.4: Effort
on
chemistry
mixing (Ferreira
versus
and
mixing
Nussbaumer, 1997)
Approach
6.2
staging by
concessions
simple
on
placed
to fuel
experiments
the
on
necessary to
are
computational effort.
operation conditions
on
the
oxides
nitrogen
and their precursors. dTe measured parameter ranges shall be checked and validated
by
the simulation.
common
reactor
(PFR),
Plug
plug
cdiemical
only the
are
(PSR).
arc
of
special
real
plug
facility
interest.
flow reactor is
one
mixing
approximation of
systems is the
reacting
continuous system,
6.2.1
ddie
describing
by
flow reactor
is
way of
through
the reactoi is
occur,
or
reactor.
orderly
behind.
no
is
It is characterized
wdth
no
Actually,
mixing
the
same
or
as
by
element of fluid
lateral
the
plug flow,
overtaking
or
diffusion
APPROACH
6.2.
The characteristic
89
equations describing a plug flow reactor can by easily derived from the
equations (Eq. 6.1- Eq. 6.4), considering the specific flow conditions.
fundamental balance
For
steady
state
flow, equation
6.4 becomes
(dpuYn)
dx
Neglecting
molecular
diffusion,
'
dY\
dx \
+lo
pD,,-^
d,v
elY
(6.15)
ax
is
proportional
species history
to the
at
fixed
point
mass
flow,
time,
x(t)
resulting
,\
obtain
we
piirIL=ujn
which describes the
(6.14)
udt
pur^-
and
p^r~r~
dx
Jo
at
(6.16)
dx
in
p^i
Assuming
(6.17)
c.f + ^
LP
6.17 and
Equation
Equation
6.18
arc
simultaneously.
The
(,.18)
'
71-1
equation becomes
integration
reactor
T.
Perfectly
6.2.2
The
perfectly stirred
throughout.
by chemical
infinitely
This
means
by
convection,
ddie
mixing
fast. Thus the exit, stream from the reactor has the
mass
flow
through
products
rates
same
are
is controlled
assumed to be
composition
as
the fluid
V, equation
6.4
becomes
pV^
ddie
holding
time
or
the
mean
-m(r!!-Yl,)+nV
mass
pV
flow rate
stimulus
by
(6,20)
Lrrn
leading
(6T9)
to
1
(111)
//
--0-)
U, t)
(6.21)
MODELING
CHAPTER 6.
90
dh
2~ln=i y"/?"
and cp
pressure)
constant
leads to
^E(o;:-rX)-^
~~n'
r^-n-n
(it
With h
(assuming
Analogous
Yin
,i
YiNP
JU,
dT
dh
Cp
dt
obt am
we
n<
'
df
(^2)
pV
711
flYr,
(6-23)
^""
E^
dt
n
--[
6.21. 6.22. and 6.23 leads to the form of the transient energy
Combining equations
equation
'
Equation 6.24
is
'
mean
*-
residence time
pV
n-I
t.
Furnace Model
6.3
Design
6.3.1
plug
(PFR)
flow reactor
patterns. Although
be
'""->'
nonlinear ordinary-different
The
T^
dt
case
fluid, by recycling
perfectly
fully
never
approximated by
and the
real reactors
can
of fluid,
by
with
ois
be considerable.
stirred reactor
(PSR)
negligible
dTe deviations
bypass of fluid,
or
by
In other
error.
can
be caused
creation of
cases
deviations
by channeling of
stagnant regions
in the
reactor.
degree
the
of
models for
backniixing
predictions
have been
example
or
considei
intermixing.
With
varying
Intensities of
flow at
backmixing
or
turbulence
plug
dispersion number of the eactor measures the extent of axial dispersion.
It is the product of the intensity of the dispersion coefficient and the geometric factor of
the reactor. The reciprocal product is also called Bodenstem number.
one
)(i)--iL
Figure
9
output signal of
accoidmg
pulse
stimulation of
(6.26)
The
a
figure
Tf-
where
to
dispeision
plug
Foi
How
>
oo.
91
FURNACE MODEL
6.3.
1.0
0.5
0.0
2.0
E5
Figure
6.5: Influence of
chain
parallel.
or
as
There
flow;
plug
are
or
dispersion
flow
The
resulting
6.6.
Figure
With
increasing number N,
the reactors
flow reactor.
also models that describe the deviation of real stirred tanks from ideal mixed
on
the
complexity of
problem,
the
can
other
or
the models
can
be found in
heterogeneous devices.
vary from
one-
presented study
bases
on
nor
modeling
combustion. dTe
(gaseous only)
nor
is
input of
placed
on
the model
arc
to multi
(Lcvenspicl, 1972).
However, since neither the complete velocity distribution within the furnace
staged
plug flow
Depending
plug
on a
combined in different
the resi
known,
the
manner.
are
the combustion
products
input
separated and modeled as plug flow or mixed flow or both. In Figure 6.7 the design of
the considered models is presented. Not all of the possible combinations were evaluated,
is
The chemistry
cause
provided
considers
congruent
sense.
to other literature.
only homogeneous
phase dominates
in wood combustion.
This
phase, be
assumption
is
92
CHAPTER 6.
MODELING
Cfll.O
Figure
curves
1
PFR
PFR
burnout
zone
PSR
S
X
)
A,
jy >_
PFR
PFR
fuel 2
r?E
reburn
zone
PSR
conversion
model
| VvV
combustion_
\7.
gas
\yt^f
to;
|.^VjiiVy\^y\
Figure
6.3.2
An
Input Generation
important,
inputs for the
zone
modeling.
adequate
fixed
FURNACE MODEL
6'.3.
93
species, the
step, assuming complete fuel
At
first,
presented
calculated
effectively
composition,
for
SRt
should be
reduced,
are
done for
specific
amount
UF-chipboard
Hence, the
ratio, using
are
the correlations
NOx emissions.
high primary
at,
stoichiometric
given
neglected. Since
separate
the main components of the combustion gas of the fuel-lean first fuel stage
calculated
of the
a,
conversion.
input
as
the research
on
main fuel
only because
measurements well.
as
reburn fuel.
6.3.3
NH3 is based
experimental
on
data
and
found
et
implemented
ddius,
the
seems
fuels,
it is also base
model.
pyrolysis
input
data for a MATLAB program which calculates the conversion of the reburn fuel under the
assumption of chemical equilibrium at, a given process temperature for a given reburn fuel
rate
(RFR)
are
given.
Table 6.2: Fuel
water
wf
II
wf
wf
wf
LHV
Aomin
at
SRi
The
pyrolysis
50
5.5
44.3
0.2
14.3
3.54
1.2:
Nm3/kg
Vc,d
wf
g/100g
g/100g
g/100g
g/100g
g/L00g
Md/kg
Nm3/kg
UF-Chipboard
20
4.65
water free
gas
temperature of 800C.
noting
products
as
pyrolysis
Figure
Figure
6.8.
6.9 shows.
An amount of char
depending
on
CHAPTER. 6.
94
the water content of the fuel and the process temperature remains. But in
completely, also
burns out
place
after the
in the reburn
MODELING
real furnace
stage.
pyrolysis. According
to
this, the
amount
of oxygen needed for the char burnout is computed and subtracted from the amount of
O2 available in the gas coming from the first fuel stage. Then, the pyrolysis gas and the
combustion gas
are
proportionally
mixed
to the
given
1.0
0.8
0.6
A^
0.4
0.2
HCN/NH,
fasa^.
J
$-"
'A--|
20
80
60
40
Figure
at
O/N
ah, 1993)
6.8: Influence of
800C
(Alio
et
ratio
on
during pyrolysis
All simulations
and
Figure
6.10 and
Table
6.3:
Figure
Assumed
6.11.
conversion
of fuel-N
into
HCN
and
NH3,
data
(Hmlinen, 1995)
O/N
'
Wood Chips
UF-Chipboard
223
Predicted conversion to
HCN
NH3
[-]
-
0.03
0.007
-05
-005
derived
from
6.3.
FURNACE MODEL
95
0.0
0.0
0.2
SR
Figure
0.6
0.4
[-]
equilibrium composition
(w=0.05 (top)
0.8
and
of wood
w=T.20)
gasification
at 800C for
CHAPTER 6.
96
MODELING
5.0E-04
4.0E-04
'g
3.0E-04
*-
0)
NO
NH3
HCN
2.0E-04
w
CO
1.0E-04
O.OE+00 4-^
0
0.1
RFR
0.3
0.2
0.4
[-]
zone
simulations, UF/UF
6.3.
97
FURNACE MODEL
0.2
0.18
0.16
c
o
0.14
0.12
c
m
0.1
-,
0.08
o
w
<c
0.06
0.04
en
0.02
0
5.0E-06
~NH3
--
2.0E-06
HCN
en
1.0E-06 4
O.OE+00 t-=
0
0.1
RFR
Figure
6.11: Calculated
0.3
0.2
0.4
[-]
zone
simulations, UF/W
98
CHAPTER 6
Seite
Leer
Blank ieaf
i
MODELING
Chapter
General
7.1
in this
presented
UF-chipboard/UF-ehipboard
are
under
interesting
probably
that produces high NOx emission
of view since
practical points
because of its
high nitrogen
are
simple plug
flow
(PFR)
zone
is
mean
imposed
same
There
once a
residence times.
cases on
zone
mixing conditions,
once
combination of
The total
are
fuel
mean
mixed flow
(PSR)
and
seconds, hence
r
dTe
and
UF-chipboard
is
content.
and the reburn fuel rate RFR. To simulate the influence of the
a
limited to fuel
UF-chipboard/wood chips.
and
the most
chapter
tpsr + tpfr
(7.1)
2s
flow
or
TPSR
PFR
ddie simulations
are
[s]
figures
TFFR
[s]
PSR
0.1s
0.1
1.9
PSR
Is
carried out
CHEMKIN is
soft
of two
99
an
Interpreter
and
100
CHAPTER 7.
dTe CHEMKIN
Interpreter
ementary, user-specified
highly
is
symbolic description of
library
thermodynamic properties,
and chemical
are
used for
following
comparison
of the limits
runs
can
also be linked
evaluated with
on
the
and may
7.1 and
even
the
nitrogen species
following example is presented.
Figure
as
XSENKPLOT,
an
in
are
the calculated:
figures
scries,
where the
displayed
for
once
mean
to demonstrate the
a,
inhomogenities
that
and
once
is used. Two
mean
curves
for 2 s, values.
However,
neglects
residence time
present, in
0.1s,
expected
NO,
and has to be
specie
dangerous and
interpretations, especially
considered.
are
surprising
the
driver
zone.
The
together by
are
on
rates.
for each
equa
on
done.
were
are
el
Figure
dTey
simulations
production
describing
an
tions of state,
Being
one
point
all local
phenomena and
furnace. Variable
more
can
postulated
happens during
the simulation.
Consequently,
as:
TFN
where
simulations.
According
to the
assumptions
to the reburn
made in
zone
at the
beginning
of the
to
7.1.
GENERAL
600
101
500
E
a
400
NO(1)
CL
NO
C
"g
300
4-
c
eu
(2)
HCN
(1)
HCN
(2)
NO exp.
HCN exp.
200
100
0 T
0
Figure
(PSR==0.1s,
900C, (1)
means r
Is, (2)
means t
zone
s)
50
40 i
E
Q.
C
O
30
N20(1)
N20(2)
CO
N20 exp.
20
o
o
10
0.1
0.2
RFR
Figure
T
0.3
0.4
[-]
900C, (1)
means r
ls, (2)
means
2s)
zone
(PSR
ls,
102
CHAPTER 7.
Reaction Mechanism
7.2
investigating
natural gas
or
(methane)
the gas
phase
combustion
elementary
in
1.
arc
reactions.
of the
modeling
reactions. There
An overview
on
on
comparison
Bowman, 1989).
are:
GRI-Mechanism
v.
2. Leeds-Mechanism
2.11:
49
1.3:
56
v.
Energy2
bustion and
on
and
one
oped by
more
at, the
The heeds-mechanism is
University
it.
The
comparison of the mechanisms is made for isothermal plug flow conditions (PFR,
t=2s) at 900C using the inlet, conditions at, RFR =0.3 for the two fuel combinations
UF-chipboard/UF-chipboard (UF/UF) and UF-chipboard/wood chips (UF/W).
Comparing
intermediate
mechanism
dicates
reaction
profiles of
products
predicts almost
no
are
the
present
net destruction
(Figure
7.3 and
Figure 7.4).
dif
the
The Leeds-
increasing NO abatement towards the end of the running time. The main
path for the NO reduction is a little different, and the reaction rates for the
an
GRE mechanism
are
much
higher.
NO + H + M
HNO + M
(7.3)
NO + NH
>
N2O
+ H
(7.4)
NO + O + M
N02
+ M
(7.5)
H02
NO2
+ OII
(7.6)
NO + N
-+
N2
+ 0
(7.7)
NO + NH
>
N2
+ OH
(7.8)
NO +
Following
path is
by
NO + H + M
HNO + M
NO + H02
>
NO2
+ OH
(7.10)
NO + NIh
N2
H2O
(7.1 L)
NO + O + M
NO2
+ M
(7.12)
>
NNII + OH
NO
NH2
<http://euler.berkeley.edu/gri\_mech/>
<http://chem.leeds.ac.uk/Combustion/Combustion.html>
(7.9)
(7.13)
REACTION MECHANISM
7.2.
103
more
are more
equalized
NHscosiuning and producing reactions calculated by the Leedsthan fO times higher than for the GRI-mechanism, but the net rate
at any time.
intermediate products.
rates of some
reverse
reactions
Similar observations
and
the
Figure 7.6).
plug flow under
In
strate.
compared
given boundary
are
higher formingconsuming
total rate.
same
concerning NO
good agreement
from
arc
the
comes
in the
hydrocarbon
predicts negligible
UF/W (Figure
NO reduction
7.5
along
conditions.
decomposition
as
is in the range of
milliseconds,
nitrogen chemistry
longer.
However, different concentration profiles for minor species which arc present in the
range of 108 or lower are unimportant for practical uses anyway. Nevertheless, the com
parison makes clear that each reaction mechanism produces a different result, for the same
takes much
are
comparison
this work.
cation.
arc
on
the
work,
et
No research is
planned
already
for
adapting
or
as
et
tool and
ameliorating
provided
appli
given mechanism. There
simulations, namely
et
for the
comparison.
for fuel
and
The
reburning
Williams,
104
CHAPTER 7
1 0E04
1 OOE 02
Js
1 OOE 06
time
Figuie
7 3- Gas concentiations
[s]
UF/UF
at 900C
1 OE 04
1 OOE 02
1 00E 07
time
Figuie
7 4
Gas concentiations
[s]
UF/UF
at 900C
7 2.
REACTION MECHANISM
105
1 OE 04
1 OOE 02
1 00t 07
time
Figure
[s]
UF/W
at 900C
1 0E04
1 OOE 02
i:
1 00E 06
1 OOfc 07
1 00E 10
i-
time
Figure
[s]
UF/W
at 900C
106
CHAPTER 7.
Reburn Zone
7.3
7.3.1
First,
the reburn
zone
of the fuel
staging
is
Temperature
param
variable
plug
arc
splitting
of the
mean
(PFR).
flow reactor
(PSR)
and the
Figures 7.7, 7.8, and 7.9 show the reduction rate for different RFR, with inlet conditions
according to the reburning with UF/UF. Considering the curves for plug flow (PFR) only,
their trends indicate a more or less wide optimal temperature range starting at, about
850C and ending at 950C or 1L00C, depending on RFR. With increasing RFR, the
temperature range with high reduction becomes wider. The maximum reduction rate
attained is between 78% and 85%. The highest reduction is calculated for RFR=0.30.
When mixed flow is
simultaneously
premixing
1.0
s.
The
influence
on
the
Compared
ranges from
Figure
results,
to
to the
to
considerable
too.
plug flow,
According
shifted towards
are
the reduction rate when the residence time of the PSR is varied from 0.1
figure
on
premixed
flow
up to
s.
GRI-mechanism,
the
decomposition
of HCN and
reac
tions
HCN + O
~+
NCO + H
(7.14)
IICN + OH
CN + II2O
(7.15)
HCN + O
-^
CN + CO
(7.16)
HCN + OH
HNCO + H
(7.17)
+ OH
>
NII2
H20
(7.18)
NHZ
+ H
NH2
H2
(7.19)
NH)
+ O
>
NH2
+ OH
Nl-h
This reaction
path
is valid
over
(7.20)
higher
increasing temperature
rates than
more
and
more
NO
or
a,
are
drastically.
decomposed, HCN
The
higher
O to NO.
forming
and
However,
reducing
with
in
decrease of
cause
is
increasing temperature
reactions fall.
7.3.
107
REBURN ZONE
Regarding
nitrogen species forming and consuming reactions, the characteristic reaction time at
the
distinct, influence
on
100%
PFR
90%
PSR
80%
70%
1.0s
60%
tt
50% Hi
\ \
\
\
\
40%
\
N
\.
30%
s,
^
~
.-
fs
20%
10%
0%
600
1000
800
1200
1400
Tr [C]
Figure 7.7:
UF/UF
Influence of temperature
on
(SRr?0.92),
108
CHAPTER 7.
100%
90%
PFR
-
--
80%
--
70%
0.1s
0.25s
PSR
0.5s
PSR
0.75s
--
60%
PSR
-PSR
PSR= 1.0s
r-i
i
CC
50%
"~
40%
30%
20%
10%0%
600
Figure
7.8:
1400
Influence of temperature
on
(SRr~0.85),
UF/UF
100%
-r
PFR
90%
PSR
1.0s
80%
70%
60%
50%
*"
40%
30%
20%
10%
V
0%
600
800
1000
1200
1400
Tr rc]
Figure
UF/UF
7.9:
Influence of temprt
lire
on
(SRr;0.79),
REBURN ZONE
7.3.
7.3.2
An
109
important question
type
on
staging is. How does the nitiogen content the influence the final NOx emissisons,
example. Comparing the simulation results of inlet conditions according to the fuel
combinations UF-chipboard/wood chips and UF-chipboard/UF-chipboard may give some
fuel
for
answers.
Figure
with
UF/W
of the
curves
than with
the
is
slightly
UF/UF.
flow
Assuming plug
only
with
the
shape
the shift
range is about
be observed wdien
can
UF/UF,
higher
Depending on
towards higher
temperatures
RFR=0.2,
Even with
on
Compaied
different.
temperature
lange is different.
premixed
Again,
flow is allowed.
850 to 1000C. With RFR=0.3 the reduction rate between 850C and 1300C remains at
about the
same
a mean
achieved
higher temperatures.
nitrogen of
Wood
shifts
higher.
are even
the fuel
are
are
100%
chips
zone.
UF/UF
with
and
UF/W
low
nitrogen
Therefore,
content
produce
non-
much lower because less HCN and NII3 remains unreacted and less
formed.
PFR
90%
PSR
80%
1,0s
70%
60%
"
50%
r-,
l
\
\
*~
40%
30%
20%
10%
0%
600
1000
800
1200
1400
Tr [C]
Figure
UF/W
7.10:
Influence of tcmperatiue
on
(SRj~0.98),
CHAPTER 7.
110
100%
-PFR
90%
PSR
80%
1.0s
70%
60%
I
50%
1
r
40%
30%
-i
20%
10%
0%
600
1000
800
1200
1400
Tr [C]
Figure
UF/W
7.11:
Influence of tempeiature
on
(SRr0.86),
BURNOUT ZONE
7.4.
111
Burnout Zone
7.4
Influence of Burnout
7.4.1
zone
presented
Modeling
in this work
are
(PSR
flow
modeling
the burnout
Figure
series),
are
with
a mean
plug
as a
zone
models,
residence time of 2
(isothermal
PFR at
PFR
and
once
higher reduction
for the PFR
rates
only
However, the
the
compared
Towards
curves.
1300C).
PSR
once
The two
plus
curves
higher
show that
transformed to
especially
negligible.
reactions
figures
are
zone
Figure
to
in
must,
nitrogen
N-spccies depending on
UF/UF. NO is lowest be
Figure
tween
The
s.
premixed
or as a
species.
(PFR)
flow
7.12 and 7.15 show the TFN reduction in the flue gas
the burnout
reburn
modeling
that the
means
zone
and PFR in
This
plug
compared with
facility.
700C and 1000C and rises above this range, whereas the other species all fall with
increasing temperature. At low temperatures, the amounts of N2O, HCN, and NH3 are
higher than NOx. Figure 7.14 shows the corresponding concentrations after burnout in a
PFR at 1300C.
The
leading only
small
compared
to NO. The
may
modify
conclusion
be made for
can
UF/W
change
modeling. A
tempera
NO2 is
UE/W.
hang together with
burnout zone for example
different temperature
regime
in the
at RFR=0.3
(Figure 7.11)
is used
as
1300C,
burnout
temperature
variation for
zone.
(Figure 7.15).
same
at, low
negligible
The observed
the burnout
same
are
is also reduced to
zone
HCN
on
PSR
are
simulated.
Figure
(r
,s) plus
plug
assuming
on
In addition to
PER in series
PER,
as
and
Figure
reburn model.
more
reburn model PFR. If the burnout temperature could be raised to 1100C and more, the
TFN present at
premixed flow.
Even
on
significantly.
change
much
(Figure 7.17).
An other burnout model first mixes the burnout air and the combustion gas from the
reburn
length.
zone
in
PSR wdth
a mean
s.
followed
by
as
plug
flow of f .5
reburn temperature
112
CHAPTER 7
once
Again,
PSR
resulting
models,
once
plus PFR.
Especially
for
reburn temper
ature below 900 C the trend of the reaction rate deviates from the other burnout models
presented before.
The
comparison of
the measured data with the calculated NOx reduction indicates that
facility
staging
have demonstrated.
is
This is
the trends
even
generally
show
satisfying
concordance. The
lower reduction rates at, low temperatures confirms the role of the temperature not only
in the reburn zone, but also in the burnout zone. Additionally, the simulations points at,
100%
mixing
-r-
PFR
90%
80%
70%
PSR=EOS
D
60%
50%
40%
30%
Exp.
*"
20%
10%
0%
6C)0
700
800
900
1000
1100
1200
1300
1400
T,[C]
Figure 7.12: Burnout
(SRr0.85), UF/UF
7.4.
113
BURNOUT ZONE
1.0E-03
1.0E-04
D1300C
1100C
D900C
P800C
H700C
1.0E-09
NH3
NO
N02
HCN
N20
zone
for
PFR, RFR=0.30
(SR,0.85), UF/UF
1 .OE-03
1 0E-04
1.0E-05
D1300C
c
o
4-
1100C
D900C
1.0E-06
D800C
c
<u
o
g
H700C
1.0E-07
1.0E-08
1.0E-09
NH3
Figuie
7.14:
Calculated
N-species
NO
N02
N20
(SR^O.85), UF/UF
HCN
114
CHAPTER 7.
100%
PFR
90%
PSR
80%
1.0s
Exp.
70%
60%
50%
40%
30%
20%
-r
10%
0%
600
700
800
900
1000
1100
1200
1300
1400
Tr [C]
Figure
7.15:
(SRr0.86), UF/W
100%
-,
PFR, 800C
90%
PFR, 1100C
80%
PFR, 1300C
70%
Exp.
60%
50%
40%
30%
20%
10%
0%
600
800
1000
1200
1400
Tr [C]
Figure
(SIT-0.86):
UF/W
on i
7.4.
BURNOUT ZONE
100%
90%
800C; PSR
80%
1.0s
110OC; PSR
1.0s
1300C; PSR
1.0s
70%
Exp.
60%
rI
I
50%
40%
30%
20%
10%
0%
600
800
1000
1200
1400
Tr [C]
Figure
(SRr0.86);
reburn model:
on
PSR=E0s, UF/W
100%
PFR
90%
PSR
80%
70%
60%
tt
1.0s
Exp.
-J
50%
""
40%
30%
20%
10%
0%
600
800
1000
1200
1400
Tr [C]
Figure
(SR^O.86), UF/W
as
116
CHAPTER. 7.
Influence of CO
7.4.2
During
NOx emission
on
assumption
that there is
as
can
an
one
burnout is answered
by
the
question
following
The
input
was
done
using
gas is assumed to be
mixture of
and N2
adjusted by
arc
500mg/Nm3
is
chosen, whereas the CO concentration is varied. A summary of the input data shows Table
7.2. The temperature range of the isothermal plug flow is set from 800 to f300C. The res
idence time is 2
Table 7.2:
Input
Omg/Nm3
Specie
[%]
[%]
[%]
[%]
[ppm]
[pPm]
C02
H20
02
N2
CO
NO
1000mg/Nm3
CO*
CO*
on
NOx
10000mg/Nm3
11.65
11.51
10.54
9.14
9.13
9.09
7.16
7.21
7.65
72.01
71.97
CO*
71.63
1050
10500
320
320
320
*at 11% O2
no
arc
shown in
Figure
7.19.
Under the
given
reaction
thermore, NO
con
Fur
HO2,
O2
II2O
HO2
H2O
(7.21)
N2
H02
N2
(7.22)
HO2 + NO
>
NO2
+ OTI
II +
However, the CO
02
NO2 formation
at low
(7.23)
temperature. It
Looking
direct
occurs.
CO +OH
and with
must be
no
H +
CO2
(7.24)
CO2
+ M
(7.25)
7.4.
117
BURNOUT ZONE
an
optimum
corresponds
Below,
the natural CO
not, all CO is
whereas
CO2 equilibrium.
ddie amount of initial (JO also affects N2O formation at, low
ent
oxidized,
temperature, due
to differ
preferences of the radicals H, O, and OH. The formation of other nitrogen containing
species
as
HCN
or
NH3 is
out, of range.
significant
influence
on
as
Figure
7.20
Although the question whether CO may reduce NO in the burnout, stage cannot be
answered ultimately, the simulation presented disproves this supposition under the given
assumptions. Consequently, there must be other explanations for the low NOx emissions
at high CO emissions.
Since high CO levels indicate incomplete combustion, many other combustible products
beside CO may be present in the flue gas. too. Hence,
levels at
incomplete
responsible
according to
agents (see Chapter 2.6). However,
under
locally
fuel rich
118
CHAPTER 7.
600
800
1000
1200
1400
1 0E-03
NO, 0 mgCO
NO
(1000
10000
and
mgCO)
N02, 0 mgCO
-N02
(1000 and
mgCO)
10000
1 0E-08
J-
600
800
1000
1200
1400
1.0E-05
1 0E-06
CO, OmgCO
-CO
1 0E-07
N20, 0
mgCO
(0
V>*
c
o
c
(1000 and
mgCO)
10000
-N20, 1000
1.0E-08
mgCO
-N20, 10000
mgCO
1.0E-09
1.0E-10
TTC]
Figuie
on
7.4.
BURNOUT ZONE
119
time
Figure
1 OE-04
1
[s]
0E-01
1 0E-3
1 0E-01
CO
1 0E+00
10E07
time
Figure
fs]
120
CHAPTER 7.
fcank If
Chapter
Conclusions
Summary
8.1
produces NOx
mainly
in the fuel.
from
nitrogen
temperatures in practical
the
heating
values. The
nitrogen
content, of the
nitrogen
creates
decreases wdth
nitrogen
be reduced
can
increasing nitrogen
content.
combustion which
zone
nitrogen species
complex reaction mechanism. Air staging and fuel staging make both
principle.
important parameters
Experiments
are
on
research
facility
However, air
practical
may have
as
own
or
high
staging
has
limitations
use
zone arc
of
the
nitrogen conversion.
staging
NOx reduction
UF-chipboard (fucl-
an
ash content, and low ash fusion temperature, i.e. below 1000C.
The
be
more
most
potential
N
3.5%).
because
negligible
this
originate
at
are
fuel rich
N2 by
to
content,
emissions which
an
presented
operable
fuel
and
staging system
practicable
which
uses a
fixed bed
as
reburn
up to
stage promises
staging
even
to
higher
For
an
equivalent, NOx
in the reduction
zone
zone
lower temperature
staging (
L100 to
1200C).
zone
during
the
has to be
to
Good
hydrocarbons
experiments
1000C)
mixing
of
significant advantage
for the
application
121
to
guarantee
in the gas.
which may be
(900
Observations
of at least 1
complete
staging
of this
staging
than air
is less
staging
technique. Provided that
zone
122
CHAPTER 8.
operated constantly
at
CONCLUSIONS
significant
input.
A model to
investigate
oped based
on
the mechanisms of
nitrogen
convexsion
reactor
(PFR)
(PSR). Because the physical model was kept simple, a detailed reaction mechanism
(GRl-Mechanism) could be used for modeling the chemistry in the reburn and burnout
reactor
zone.
An
fuel
on
important
process of fuel
using
are
oxidising agent,
as
an
staging
gasification
of the reburn
still under
development.
was
calculated
However,
in
are
the calculated NOx reductions and the effects of the process parameters. The calculated
and the measuied
identical.
optimum temperature
nitrogen (TFN)
NOx reduction
by
improved furnace
was
calculated,
are
about,
The measured
which maximum
control.
Regarding
the reburn
longer residence
zone,
influence
an
on
the
mixing
conditions
shift towaids
of the
to decrease
again.
though
optimum
range
lange is
can
chipboard
zone.
than
nitrogen
without
incieasing
Regarding
usually
are
burnout decreases
significantly
zone
optimum reburn
10()0C, but
zone
more
should be
high,
favorably
presented model
process parameters.
allows
some
is
Although
variations,
the
inputs
qualitative study
can
tem
premixed flow
Al
be noted. At
also. Other
zone
the reduction
at
can
least
lead
reality
relatively fast
and
easily be
OUTLOOK
8.2.
123
simulated.
Summarizing
that fuel
the work
is
staging
the
presented,
suitable
experiments
measure
and
promising technique
Outlook
8.2
ddie present
on
investigation
the combustion of
non-pulverized
wood fuels.
reduction of the
staging
staging
zone
high
be
can
staging.
high nitrogen
content.
staging
with
accomplished by
high enough
for
Fuel
efficient
should be
non-pulverized
an
successfully applied
be
can
biomass
are some
exchangers. As
complete
on
reasonable
the fuel
the temperature in
preheating of
using
demands
heat
reburning
properties
has shown to be
fusion temperature of the reburn fuel should be lower than the temperature in the reburn
zone, otherwise
slagging
cause
may
problems
to the
reburn process.
Consequently,
reburn
high voidage
reburning
feeding system
also
are
plays
an
because
deep penetration
improves the mixing of the
a
important role
imaginable,
i.
c.
in this concept.
spreading system
an
staging demands
zone
may
should
higher
124
CHAPTEE 8
CONCLUSIONS
Seite Leer /
Blank leaf
Appendix
Nomenclature
Symbol
Dfinition
Units
molar coefficient
species
AS
air
element vector
concentrt ion
matrix
Nm3/kg
supply
Cp
D
specific
diameter
Si,
Kronecker delta
heat
capacity
diffusion coefficient
mass
activation energy
mass
H
h
mol/rrE
kJ/kgK, k.T/molK
m2/s
m
fraction
kd
-
HHV
specific enthalpy
higher heating value
rate constant
characteristic
length
LHV
lower
value
concentration
heat
nunibei of elements
molecular
mass
dynamic viscosity
Pi
chemical
number of species
molar
sum
kJ/kg, kJ/mol
kJ/kg, kJ/mol
kd/kg, kj/inol
Md/kg
1/c"
heating
conductivity
weight
flow
quantity
of all N
species
Md/kg
(any)
W/m K
kg/mol
kg/s
Pas
kd/mol
mol
mol
APPENDIX A.
NOMENCLATURE
11
stoichiometric coefficient of
chemical
pressure
bar
heat flux
reduction rate
specific
reaction rate
mass
RFR
entropy
source
products
kg/m3 s
term
kd/kg K
kJ/mol K
mol/s
gas constant
density
kg/m3
Sq
SR
stoichiometric ratio
standard deviation
source term
d/kg K, J/inol
W/m3
temperature
time
mean
Tj,
e
stress
residence time
bar
dimensionless time
_.
velocity
volume
water content
mole fraction
stoichiometric coefficient
mass
m/s
m5, Nm3/kg
or
coordinate
fraction
Subscxipts
a
molar coefficient
backward
molar coefficient
molar coefficient
dry
df
dry
forward
or
combustion state
fuel base
index number
index number
prim
primary
reburn
solid
sec
secondary
initial value
first stage
second stage
or
reduction
zone
(main fuel)
(reburn fuel)
127
Superscripts
(25nC. 100kPa)
standard state
order of reaction
APPENDIX A.
128
*VlN
NOMENCLATURE
,*5i\
**# <W
'if1 i
l $yf
s\s*
W*
Appendix
Details
Experimental
B.l
Gas
are
Analyzers
Continuous
B.l.l
The gas
Analysis
analyzers which
were
2%) coriesponding
to the
are
the
experiments
deviation from
were
expected
duiing
sampled
(error
gas.
Company
Specie
Range
Method
Thermor 6N
Maihak
H2
0-25%
HCD
Uras 10E
CHt
0-5%
NDIR6
CO
0-10%
NDIR
NO
0-1000 ppm
NDTR
o2
0-25%
Par am d
CO
0-2%
NDIR
C02
0 15%
NDIR
IIC
0-10
NO. N02
CITE
CED
Leybold
Brnos 100
FID 3006
Bernt h Atomic
CLD 700 EL ht
Eco
Physics
to0-l0E5;ppm
FIDrf
CLD 502
Tecan
NO. N02
Binos 1.2
Leybold
CO
0-300 ppm
NDIR
co2
0-15%
NDIR
o2
0-30%
Param.
AS AG instruments
Ox-T-19
"Heat-conductivity
''Non-dispeisive
detection
mfraied detection
Paramagnetism
detection
once
dete< tion
129
EXPERIMENTAL DETAILS
APPENDIXE.
130
B.l.2
FT-IR
Spectroscopy
on
based
on
by polyatomic
physical properties
and bond
absorption changes
absoipfion therefore depends on the
strengths,
ddiis
means
as
as
02
angles
"signature".
or
'.
enr
Wavenumber
10l
\em~~l]
(B.l)
Wavelength [pm\
For the
is most
procedures (fast-fourier-transformation).
ical
illustrated in
Figure
The
mathemat
interferogram by
typical layout
of
FT-TR apparatus is
B.l.
general, the great detail in the infrared spectia of the gases allows every molecule
to be readily distinguished from all the others. The fundamental infrared region wheie
the rotation and vibrations of the molecules give lise to infrared absorption is across
3700 cm"1 to 500cm"1. It has become fashionable to call this region mid-infrared (MIR),
In
to
distinguish
In the
it from the
study of
of molecules in the
near
gases, the
path
infiared
intensity
(NIR)
-dl
the
are
Along
on
interchangeable.
through a thin layer
of intensity is proportional to the intensity (I)
transition probability (a). Thus,
and
absorption depends
of infrared
of the radiation. At
pathlength (L)
of
,
an
absorbing
medium
(dx),
the reduction
(c),
(B.2)
lacdx
-log--
and the
to:
(B.3)
acL
h
dTe
equation
frequency
The
are
or
band of
frequencies
single
absorption coefficient.
same
to
equation is not valid when a number of hequencies with various absorption coefficients
In these cases, the relationship between absorbance and the
seen simultaneously.
concentration-pathlength product
must be determined
empirically,
i.e.
calibration
curve
must be constructed.
acquisition
pressme is
of calibration spectra.
there
Spcetial
lowered, the absoiption lines get tallei
logarithmic absorption
spectia created at
one
atmospheie
other
aie
reasons
Thus,
nairowei.
a
set of
sample
quantitative calibration
apply
at
sample taken
at,
BT.
GAS ANALYSIS
131
1
beamsplitter
moving
mirror
IR detector
laser
sampling
one-half
an
of
FT-IR apparatus
atmosphere.
changes
sample tcmperatiue
is lower
or
This
recorded
spectral
line is
narrower
sample
causes
single absorption
any
changes
change the
shape
in the
is
of the spectrometer, the line will appear wider and shorter than it
of
is to
higher.
spectrum. When
at
on
actually
When
at
fully
resolved spectrum
can
be de-resolved to match
used.
is determined
specie
by
the
pathlenght
and the
signal-to-noise
ratio in the
resolution, the types of optical filters used, the stability of the optical components, and the
quality of the detector itself. The noise level is made lower by choosing a low noise detector
and
bringing
saturation.
to
that detectoi
In addition,
more
maximum
interferometer
scans
avoiding detector
level, but extend the
measuring time. For maximum spectral detail and maximum line heights the spectrometer
fully resolve the spectral lines, i. e. a resolving power of 0.125 cm"1 would be needed.
should
But, going
to
higher
resolution also
signifies increasing
faster
EXPERIMENTAL DETAILS
APPENDIX B.
132
usually
dTe
are a
height
of the lines.
principle
of the
procedure
to the
for
Figure
determining
B 2
This
sample evaluation
is
analogous
in
to the
before minor
species
are
(Stapfand
1997), (Kleemann, 1997).
related
problems
are
Leukel.
For the
12
species
are
Galaxy 7020
Device
Matt
Company
ATI Enicam
Detector
MCT
IR-range
400-4000cnr1
Gas
heatablc
sampling
Pathlength
4.0
Window material
BaF2
son
specifications
(20 passes),
cooled
gas cell
6.4
max.
(32 passes)
Peak/Range
Specie
Calibrated Range
1875.5 cm"1
0-500 ppm
N02
1599enrJ
0-100 ppm
NO
N20
2192.97-2193 94 enr1
0-100 ppm
NH}
1084.07-1085.52 cm"1
0-100 ppm
HCN
3328.15-3329.36 enr1
0-100 ppm
CO
2102-2113 enr1
0-2500 ppm
co2
0-20%
H20
1960-1962enr1
0-35%
The characteristic spectra of NO. N02, Nf20, CO. NII3. and HCN
Figure
peak
or
range of each
other
species
are
shown at
is obvious.
typical
is
concentrations. A
selected the
way
that
displayed
in
representative peak
or
no
are
overlap with
water
oveilap
B.l.
GAS ANALYSIS
calibration curves, i.
e.
the
133
specie has
to be calibrated in
N2 where
water vapor of
used
are
on
known
the measured
the calibration
procedure
APPENDIX B
EXPERIMENTAL DETAILS
Start
scan
background
scan
sample gas
spectrum calculation
original sample file
determinate
H20
content
choose comparison
subtract
from
sample
file without
H20 spectrum
original sample
file
H20
determinate
NO,
HCN
determinate
C02
content
choose comparison
subtract
H20
and
C02
determinate CO
End
me
B 2
Pioccdme of
sample
B 1
GAS ANALYSIS
135
0 30
NO
0 25
as
-p
0151
xi
010
I.
I'
<
>
0 05
0 00
"l
I,'
1900
1950
I'd'
|
1800
1850
Wavenumbers
Figuie
B 3
IR spedium of NO
(500ppm)
N2
195C, 970mbai
at
0 25
NO,
0 20
4>
c
CO
0 15
6
Q
010
X!
<
0 05
1600
1620
Wavenumbers
Figuie
B 4
IR speck
um
of
N2
in
195C, 970mbai
at
N,0
<D
03
02
TT
XI
<
01
2240
2220
2200
2180
2160
Wavenumbers
Figuie
B 5
IR spedium of N20
(lOOppm)
\> at
195C,
970mbai
APPENDIX B.
EXPERIMENTAL DETAILS
0 30
CO
0 25
(B
0 20
ro
XI
015
010
X)
< 0 05
0 00
0 05
2150
2100
Wavenumbers
Figure
B 6: IR spectrum of CO
(200 ppm)
in N2 at
195C,
970mbar
NH,
03
02
X)
<
'
1200
1150
1100
'
1050
950
1000
Wavenumbers
Figure
(100 ppm)
N2
at
195C,
970mbar
HCN
0 12
0 10
08^
ra
X!
o
X)
<
>f
006-.
0 02
li
,
0 04
li,'
(Uiid^y/iff'Jiv^11
il
'V 'li'1 '''i" i
IV T 'Ei I
ooo 'H
3350
'
3300
'
!T" m
3250
Wavenumbers
Figme
B 8
IR spedium of HCN
(100 ppm)
NE at
195C,
970mbai
B.l.
GAS ANALYSIS
137
p
i
1.6
/*
'/X
1.4
//
/ / ,'
'/
/,
1.2
Serie b
Serie
(0% H20)
Serie
(4 9 %)
Serie
(17.6 %)
Serie
(26.2 %)
.2
o
0,8
LSM 0%
(D
0.6
LSM 17.6%
0.4
1 M A O /
LSM 26.2 %
0.2
oo
J-.
-L<-
10
15
20
25
C02 (%)
Figure
2429
B.9:
enr1)
Calibration
curves
(C02:
2394-
APPENDIX B.
138
B.2
Additional
Assumptions
Equations
complete combustion
no
composition
soot and
supply for
composition
to
given
is
Air
EXPERIMENTAL DETAILS
as mass
II,
NOx formation
of combustion air: 21% 02 and 79% N2
kg
neglected
AS^
(dry)
Vc,d
+T^[u+T^32){i^w)
of I
kg
^(1
(B'4)
solid fuel:
w) fc
(SR
0.21) ASimn
(B.5)
CO2
content in
dry flue
_i_(l_ti,)//,
(B.6)
___u;
gas:
C02nal
Normalization of
22 41
22 41
yu,
^(i-w)p-
'norm
,/%
hi the
N02mat
01
11
,-.
_
dry flue
(B.7)
Vc,d
1-^
specific O2
reference value:
(B.8)
<m
U2m
gas at ll%
(l-w)l^
O2 (SR=2T):
(B.9)
B.3.
ERROR ANALYSIS
B.3
Analysis
Error
B.3.1
139
equations of the
analysis
error
(Barford, 1985)
are
and
(Lichten, 1988).
Generally, the
error.
If the
systematic
error
systematic
of
error
error
can
is
systematic
by eliminating
the measurement
known,
can
error
of
sources
be corrected
and
a,
random
systematic
or
error.
adjusted.
The
remaining variations of the measurements, also called random errors, which arise from
ambiguities or uncertainties in the process of measurement can be treated by the means
of the statistics.
The measurements
are
usually
quantities X
about and
value and
mcan
peaked
diminishes with
at the value
assumed to form
measured variable
is
standard deviation.
Gaussian
as
illustrated in
or
normal distribution,
Figure
two
symmetrical
peak
a.
EO
Gaussian distributions
0.8
"S"
12
0.5
0.6-
x"
X
ST
0.4
X
cr
0.2
0.0
10
12
14
16
probability
P(x;X,a)dx
AU such distributions
can
be reduced,
y
(x
2a2
2(T
by changing
A")/ct.
dy
by
(x^Xy
7YTr-exP
y2ir)
Distributions
dx
(B.10)
to the variable
dx/a.
(B.ll)
140
EXPERIMENTAL DETAILS
APPENDIX B.
to the standard
form,
,T
-^- )dy
V 2/
=--r exp
(2tt)3
the
Thus,
probability of
Hy)dy
all measurements of
,r
be
can
(B.12)
the standard Gaussian
expressed by
distribution.
/>00
"OO
P(r\X.a)dr
'
./ X,
OO
an
infinite set of
errors r
(BAS)
A' distributed
according
to the
/Oo
(.r
J oo
-oo
is, of
given by
/OO
which
d>(y)dy
course,
the
reason
a2
(B. 14)
distribution.
The
probability
that
/
J CT
The
P(e,a)di
(B.15)
0.683.
is
integral
A'-ft
P(x;X,a)dv
probability of obtaining
is the
(B.16)
P(c,a)de
,/0
,/Y-f
less than
an error
e.
ddiis
probability
may also be
expressed
as
C
T
Jxc
P(x:X.a)dx
(B.l7)
d'(y)
where
*(y)
The Gaussian
and its
probability
integral
form
both shown in
Figure
B.l 1.
are
conditions, the
or
as
given by
mean
bars of the
an
estimate of the
true
sampling
interpretation
value of
figures
two
The
ddicrefore. to get
error
are
and chemical process measiued fluctuate within the observed time range.
physical
values
(B.18)
Measurement of Emissions
B.3.2
process
ly$(y')dy'
Jo
quantity
of the
at certain
statistically.
different forms:
as
measured
experimental
means
values
that about 95% of the measured values lie within the range.
However, The standard deviation indicated describes the fluctuations of the measured
process, ddie
precision of
EU.
ERROR ANALYSIS
141
1.0
Integral Gaussian/
probability
Standard Gaussian
0.8
0.6
>?
0.4
distribution
0.2
0.0
-2
B.3.3
rate,
are
c.
error
independent
of the parameters is
sets of measured
analyzed
quantities
z.
precision
on
next.
values of
ax
or
For
can
be combined
linear combination, i.
e.
(B.19)
by
a2a2 + b2a2
More
general, for
(B.20)
(B.21)
Equation
three
following
and RFR.
Thus,
assuming
only
a precision of the
oxygen analyzer of 2%, the
(see Eciuation 2.10) is about 2%, too.
error
142
APPENDIX B.
EXPERIMENTAL DETAILS
zone
ters is
given
the known
in the
or
supposed
Equation
in Text
rh\
rh2
ddie
based
measurement
Parameter
A
are
on
derived from
Measurements
Error
8%
B.4
Equ.
Equ.
2.66
air flow.
2.68
air flow.
02
in gas, fuel
properties
02 in gas, fuel properties
function
precision.
Equ.
errors
10%
18%
measurement of the
of about, f 0%.
Thus, combining the errors according to the Equation B.21 the maximum
expected for the stoichiometric ratio in the reburn zone SRr is about, 23%.
error
An other important parameter is the reburn fuel rate RFR. ddie definition is given
be
Equation 2.69.
for the
error
zone.
depends
on
the
same
quantities
resulting
error
arc
as
the
also valuable
about 30%.
The direct measurement of the fuel
inputs
the measurement of
auxiliary quantities
dTe maximum
of
errors
error
wdth limited
could be reduced.
now
precision
would be
more
on
favorable.
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Personal Data
Salzmanu
Name
Roger
Date of birth
22nd of
Marital status
married
Nationality
Swiss
Citizen of
Eggiwil,
April
1968
BE
Education
1976
1981
1981
1983
1983- 1987
September
1987
College
in Olten
Graduation
Type C (sciences)
Study
1988
1994
Study
Engineering
February 1994
Graduation
as
Diplom Ingenieur
in Mechanical
Engineering
Research
1994-
1999
Zurich,
Thermodynamics
Laboratory
Working field: Emission control
by primary
measures.
in
Institute of
Energy Technology,
Emerging Technologies.