Fuel Staging For NOx Reduction in Automatic Wood Furnaces

Diss.
ETH No 13531
Fuel
Staging
for NOx Reduction in Automatic Wood

Furnaces
A dissertation submitted to the
Swiss Federal Institute

for the
of
Technology Zurich
Degree
of
Doctor of Technical Sciences
presented
bv
Roger Salzmann
Dipl. Masch.-Ing. ETH Zuiich

born 22nd Apiil L968
citizen of
Eggfwil (BE)
Switzerland
Accepted
on
the recommendation of
Pi of. Di. D. Poulikakos. examiner

Pi of. Dr. F. Widmcr, co-examinei
Z ui it h 2000
11
Ordering
address:
Roger Salzmanu
rossina @swissonline. ch
Ill
Dedicated to my parents,
in
love.
IV
! Blank leaf
Acknowledgements
The present dissertation
was
carried out at the Laboratory of
Thermodynamics
ing Technologies of the Institute of Energy Technology

It
an intense cooperation between science and industry.
is the result of
EU-Project JOR3-CT-96-0059 and
founded
was
by
in
Emerg
The work
at, the ETH Zurich.
part of the
was
the Swiss Federal Office of
Energy
and
the the Swiss Federal Office for Education and Sciences.
First of
Specials
during
appreciated
I
am
Laboratory
and for his academic
during all my
developing of new
helping advises arc strongly
thanks to Dr. habil. Thomas Nussbaumer for his constant support
time at the
ideas
giving me the opportunity

guidance and friendly support.
1 would like to thank Prof. Dr. Dimos Poulikakos for
all,
to do this thesis at the
Laboratory. His suggestions
and demands stimulated the
this research. All the fruitful discussions and the

and well remembered.
expressed his interest in
also indebted to Prof. Dr. Fritz Widmer who
my work
by
the careful examination of the dissertation.
I would like to express thanks to Tiba-Mllcr AG in Balsthal for the generous support
and
encouraging cooperation during all
for the many enthusiastic and
the time. In
particular,
let
me
enlightening discussions. Several ideas
thank Oskar Leiser
we
developed finally
ended in innovative solutions.

I
am
also thankful to Max Hard and Martin Meuli for
and electronics.
completion of
knowledge
experimental work.
Their
my
and
experience
Furthermore, I wish to thank Christian Bruch.

for
providing
productive
and very
pleasant
I thank my wife Doris for her
lot to the
Zurich,
in
success
April
Philipp Morf, and

are
patient and
great job in mechanics
indispensable
environment.
persons who contributed in any form to the work
Finally,
were
doing
for the successful
all the other
colleagues
All the students and other
also well remembered.
continuous support which contributed
of this work.
2000
Roger
Salzmann
vi
CjLVu
Vf*
l^f
vu
Abstract
Emissions of
oxides from combustion processes should be avoided since
nitrogen
contribute to the formation of acid rain and
primary
various
is known to be
nitrogen in
has already
Staged
suitable
meaning
techniques
combustion
oil,
will grow in the
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.
process to HCN and
the reaction with radicals
(O, H, OH)
path by the
creation of
the fuel-
staged combustion systems the reduction of fucl-N to N2 is favored in

primary combustion zone. A minimum of the Total Fixed Nitrogen (TFN)
from the
0.8 and
combustion
primary
completed
in the burnout
is reached for
zone
temperature of 1100
or
optimized combustion conditions.
In air
rich
NH3.
N2. The goal of the staged combustion techniques is the promotion
reacts with NO to form
of the second reaction
the
important challenge.
an
non-pulverized
NOx formation usually produces negligible
the fuel is converted
nitrogen in
fuels,
scale power
large
it remains to show which
values leads to lower combustion temperatures
heating
the lower
staging,
of renewable energy
importance
applied
The NOx emissions from biomass combust ion systems

in the fuel. Thermal
for
investigated mainly
But
clean combustion of solid biomass is
for low-NOx combustion
measures
and fuel
staging for non-pulverized biomass combustion

fuel staging no studies are published yet.
Since the fuel characteristics of biomass differ from fossil
primary
staging
air
NOx emissions caused by the
to minimize the
measure
about
done, whereas
fired with gas,
sources
combustion,
they
Following this aim,

formation of nitrogen oxides
smog.
Research about air
the fuel.
been
primary
to reduce the
developed
Staged
the combustion process.
during
plants
have been
measures
photochemical
zone
stoichiometric ratio
1200C. After the reduction
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
with fuel-rich combustion conditions.
zone
reburn fuel, the
hydrocarbon
radicals
reaching
When
the reduction
additional NO reduction mechanism which is also called
rccyclc-
mochanism.
The aim of the present
concept for furnaces based
pulverized
an
All the
fixed bed systems is suitable for the
efficient NOx reduction.
experiments presented
measured
new
optimum combustion
potential is compared with air
on a
pilot-scale research facility of
The
the stoichiometric ratio in the reburn

as
The measured
are
fuel
staging
NOx reduction of nona
facility is fired with wood chips (low nitrogen content)

input.
UF-chipboard (high nitrogen content). The main parameters are the temperature and
about 75 kW thermal
and
on
is to demonstrate whether
wood fuels. Eocus of the research is the elaboration of the
conditions for
staging.
investigation
well
as
unstaged
combustion for
zone.
generating
Because the volatile content of wood is

therefore well suited
as
The furnace also allows air
reburn fuel.
reference values for comparison.
high (8085c/c),
Also the
staging conditions
nitrogen
wood is
highly
reactive and
content may be beneficial since it
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
72%. For wood chips both
already
seems
achievable
to
to be less sensitive to variations of
than air
staging
which
can
be
an
and stoichiometric ratio is not

can
for the
important advantage
zone
seems
The influence of the reburn fuel type
low NOx emissions.
say that for the
use
of
application
to be
chips have shown that outside optimum conditions

reduction
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
NOx emission is provided. The experiments using UF-chipboard

due to the additional
staging
the stoichiometric ratio in the reduction
A stoichiometric ratio below 0.9 in the reduction
one
attained about 66%. Fuel
measures
even
the examined
assuming perfectly stirred
reactor
reburn fuel for wood
higher NOx
species added to the process. A
provided for
as
mean
emission
can
result
residence time in the
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
constructed to simulate the fuel
assumptions,
it still allows
staged
combustion and to
important conclusions concerning the influence of the
parameters varied in the experiments
on
measurements and the simulation results
the
are
in
chemistry.
a
From this
good agreement.
point of view, the
IX
Zusammenfassung
Stickoxidemissionen
wichtigen Beitrag
Smog
von
und
Verbrennungsprozessen
aus
zur
saurer
nahmen
Luftverschmutzung
zu
die Stickoxide
Verbrennungsprozess durch geeignete
beeinflussen, dass die Stickoxide gar nicht erst
zu
vom
Bildung
vermindern, sind verschiedene Massnahmen entwickelt
Primrmassnahmen versuchen den

so
da Stickoxide einen
Regen.
Um die Stickoxidemissionen
worden.
unerwnscht,
sind
leisten. Bekannte Phnomene sind die
gebildet
Stickstoff im Brennst off abstammen, kann dies
gestufte Verbrennungsfhrung
Verfgung: die Luft stufung und die
eine
erreicht werden. Zwei
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
stoffreduktion bei den
geeignete Massnahmen zur Schad

Umwandhmgsprozesscn erforscht und geprft werden. Insbesondere
an
Bedeutung gewinnen,
mssen
Brennstofleigcnschaften
wegen den unterschiedlichen
nten Primrmassnahmen auch bei Biomassebrennstoffen
dass die bekan
gezeigt werden,
muss
eingesetzt
werden knnen.
hauptschlich vom im Brenn

Verbrennung
stoff enthaltenen Stickstoff gebildet. Thermische Stickoxide fallen meist nicht ins Gewicht,
da die Veibreimungstemperaturen aufgrund des geringeren Energieinhaltes der Biomasse
wesentlich tiefer sind verglichen mit fossilen Brennstoffen.
Die Stickoxide bei der
von
Der Brennstoffstickstoff ward beim
HCN und NH3
umgewandelt.
schiedene Teilschritte weiter
Dies
zu
Biomasse werden
Pyrolyseprozess
reagieren
am
Anfang
der
Verbrennung
mit O-, H- oder OH-Radikalen ber
in
ver
NO, knnen aber auch als N2 den Brennraum verlassen.
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
Zone unterstchiometrisch betrieben wird. Durch das
Radikalen wird einerseits die

NO
zu
Zwischenprodukten,
Ein Minimum aller
Luftzahl
von
Bildung
von
NO
verhindert,
begrenzte Angebot
gehemmt,
0.7 bis 0.8 und Temperaturen
Ausbrand der Gase wird durch die
Zugabe
von
einer
an
primre
oxidierenden
andererseits wird der Abbau
wekhe den Stickstoff schliesslich als N?
stickstoffhaltiger Vcibindungen
indem die
von
brig lassen, gefrdert.
in der Reduktionszone tritt bei einer
1100 bis 1200 C auf.
vollstndigen
entsprechenden Menge Sekundarluft er
Der
reicht.
Bei der
Brennstoffsfufung, englisch
auch reburn mq genannt, wird der
in einer ersten Stufe leicht berstchiometriseh umgesetzt, wobei
gebildet
Hauptbrennstoff
entsprechend
viel NO
wird. Dann wird in einer zweiten Stufe der Stufonbreimstoff eingebracht, wodurch
eine brennstoffreiche, d.h.
unterstoichiometiisehe,
Zone
geschaffen
wird.
Bei der Ver-
wendung
von
kohlenwasserstoffhaltigen
Kohlenwasscrstoffradikalc gemss
vorliegenden
Das Ziel der
Brennstoffstufuug
fr
Brennstoffen
dann ein NO-Abbau durch
erfolgt
dem sogenannten
Arbeit ist
zu
Recycle-Mechanismus.
zeigen, ob ein neu entwickeltes Konzept
der
ist fr
Schnitzelfeuerungen basierend auf Festbettsystemen geeignet

Der Schwerpunkt der Untersuchungen ist die Erarbeitung
die Reduktion der Stickoxide.
optimalen Verbrennungsbedingungen fr hchstmgliche NOx Minderung. Ebenso

werden Vergleiche zur Luftstufung angestellt,. Alle Experimente wurden an einer Pilotan
lage von ca. 75 kW thermischer Leistung durchgefhrt. Als Versuchsbrennstoffe wurden
Waldhackschnitzel und zu Briketts gepressten Abfllen von Spanplatten Typ UF einge
setzt, stellvertretend fr Brennstoffe mit, einem tiefen und einem hohen Stickstoffgehalt.
Die am meisten interessierenden Versuchsparameter sind die Temperatur und die Luftzahl
Die Versuchsanlage ist so gebaut, dass auch Luftstufung und
in der Reduktionszone.
der
konventionelle
Verbrennung
zum
Vergleich
Holzbrennstoffe zeichnen sich

sind sehr reaktiv und daher
Die
Reduktionszone erzeugt.
schon bei relative tiefen
nung
Spanplatte
von
werden als mit
gemessen werden knnen.
durch einen hohen
eigentlich
kann ein Vorteil
Stickstoffgehalt
aus
bestens
sein, da
er
Flchtigenanteil (80-85%).
geeignet als StufenbrennstolT.

Spezies
zustzliche NO reduzierende
Experimente zeigen,
Temperaturen auftritt,
Sie
Auch der
dass eine deutliche NOx
in der
Minderung
d.h. bei 900 bis 1000C. Fr die Verbren
konnte mit Brennst offstufung eine hhere NOx Reduktion erreicht

nmlich 78%)
Luftstufung,
gegenber 72%.
Fr Waldhackschnitzcl
lagen
die maximalen Reduktionen bei etwa 66% fr beide Massnahmen.
Brennstoffstufimg
Die
hat sich als
der Reduktionszone
erwiesen,
kann. Eine Luftzahl
von
derung
zu
erreichen.
was
weniger empfindlich gegenber Schwankungen
fr die
praktische Anwendung
0.9 ist scheinbar bereits
Der Einfluss des
Stufenbrennstoffes lsst sich sagen, dass eine

nmlich
Die Versuche mit,
gezeigt, dass ausserhalb
eine deutliche NOx Min
die
optimale Temperatur
Bezglich der Wirkung des

minimale
primre NOx Emission er
gewisse
signifikant.
Stickstoffverbindungen abgebaut
Feuerung wurde
ein Model bestehend
Rohrstrmungsreaktoren aufgebaut,
wichtigsten Betriebsparameter dient. Das Model beinhaltet
Rhrkessel- und
der
wichtiger
in
Vorteil sein
Spanplatte als Stufenbrennstoff fr Holzschnitzel haben

der optimalen Bedingungen sogar hhere NOx Emissionen
auftreten knnen weil nicht mehr alle

Fr die Simulation der
um
Stufenbrennstofftyps auf
und Luftzahl in der Reduktionszone ist nicht,
forderlich ist.
ausreichend,
ein
welches
tionsmechanismus inklusive Stickstoffchemie.
zur
werden.
aus
einer
Analyse
einen
Folge
von
des Einflusses
vollstndigen
Reak
Als Mechanismus wurde der GRI-Mechau-
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
basierend auf der Simulation gut mit den gemessenen
Beobachtungen
Contents
Abstract
vii
Zusammenfassung
ix
List of Tables
xv
List of
xx
Introduction
1.1
General
Background
1.2
Aim and Motivation
Fundamentals of Wood Combustion

2.1
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
Measures for Emission Control
Nitrogen
2.6.1
Air
2.6.2
Fuel
36
Staging
39
Staging
40
Literature Review
45
3.1
About the Literature Review
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
Staging for NOx Reduction

Fuel Staging for NOx Reduction
73
5.4.1
Influence of the
76
5.4.2
Influence of the Reburn Fuel Rate
77
5.4.3
Influence of the Residence Time
80
5.4.4
Practical
80
76
Temperature in the Reduction Zone
Experience
Modeling
6.2
Modeling
Approach
6.2.2
6.3
83
About
6.2.1
83
88
Flow Reactor PFR
Plug
Perfectly Stirred
88
Reactor PSR
89
Furnace Model
90
6.3.1
Design
90
6.3.2
Input Generation
92
6.3.3
Reburn Fuel Conversion
93
Results and Discussion

7.1
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
Influence of Reburn Fuel Rate and
7.3.2
Influence of Reburn Fuel
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
Interpretation of the Measurements
B.3.2
Measurement of Emissions
140
B.3.3
Combinations of Measured Values
141
Bibliography
139
148
CONTENTS
XIV
Seite Leer /
Blank leaf
List of Tables
used for combustion
currently
l.i
Solid fuels
1.2
Statistic of installed wood
2.1
Molar ratios in
2.2
Possible airborne emissions form wood combustion
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
Proximate and ultimate
2.4
raw
firing
biomass and residual char after
25
26
in fixed bed systems 37

38
39
for NOx reduction
Reburning
43
variants
59
equipment
analysis of
of bed ash from the
the
investigated
investigated
64
wood fuels
64
fuels
5.2
Fusibility
5.3
5.5
Experiments and parameters

Dependencies of the most important parameters
Data to the fuel staging experiments
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
Fuel propert ies for simulation
93
6.3
Assumed conversion of fuel-N into HCN and NH3
94
7.1
Notation in
7.2
Input
99
figures
data for the simulation of the CO influence
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
Outlook for world total
primary
1.2
Fuel shares of total
1.3
World CO2 emissions bv
1.4
Wood consumption for energy
1.5
Change
energy
supply
primary energy supplv
region
generation
in Switzerland
of installed heat output pei category in Switzerland from 1990 to
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
Influence of water content
2.8
Possible mechanism for cellulose
2.9
Schematic of wood combustion
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
blocks for cellulose and the heniicelhiloscs
lignin
14
heating
on
of
value
17
18
heterogeneous
on
L5
degradation by pyrolysis
equilibrium composition
2.12 Influence of water content
2.13
reactions
20
for adiabatic wood conversion with air
24
the calculated adiabatic flame temperature of
wood combustion
24
Characteristic time scales in turbulent combustion
27
2.14 Influence of temperature
on
NOx emission
29
2.15
NOx formation and destruction
30
2.16
Reaction mechanism
by
which HCN is converted to NO and N2
31
2.17 Reaction mechanism
by
which
31
NLI3 is converted
2.18 Influence of fuel-N content
on
the conversion to
2.19 Influence of fuel-N content
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
Relation between the stoichiometric latio in the reburn
contents of solid fuels
34
paths
35
staging
40
staging
41
zone
fuel rate
Application of
32
33
2.20
2.25
N2
and the reburn

43
the
reburning technology
xvu
to
utility boiler
44
LIST OF FIGURES
xviii
3.1
N0X emissions of coal-derived and shale-derived liquids under staged

bustion conditions
3.2
3.3
46
Influence of the stoichiometric ratio in the reduction

sion for air
com
(air staging)
zone on
the NOx emis

47
staging
Influence of
nitrogen
of the reburn fuel
content
on
the
NOx.NI4j,
and
48
IICN emission
of reburn
stoichiometry
NOx emission
3.4
Impact
3.5
Effect of the
3.6
NOx emissions of flames using different reburn fuels
3.7
primary NO
on
concentration
Calculated emission of total fixed

zone
on
49
the overall NOx reduction
nitrogen from
...
the reburn
zone vs
primary
52
at, the ETH Zurich
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
flows for air
57
staging
flows for fuel
58
staging
and outputs of the combustion process
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
Relation between SR and SRr for the
5.4
Time
5.5
Hot, gas measurement with suction pyrometer

NOx and CO emission of conventional wood chip combustion
68
5.6
5.7
NOx and CO emission of conventional
70
5.8
Ideal and real CO emission characteristic of wood furnaces
70
5.9
NOx emission of the first stage
71
60
sampling
64
chips
64
of
history
an
experiment
experiments with air staging
with fuel
at air
5.11
staged
67
staging
UF-chipboard combustion
during reburning
5.10 Influence of stoichiometric ratio in the reduction
zone on
73
the NOx emissions from conventional combustion and air
staging
74
5.12 Influence of temperature in reburn
5.13
NOx emission
versus
5.14 Influence of RFR
on
5.16 Influence of the

zone on
Shapes
NOx emission
mean
zone
76
78
at
750C
79
on
NOx emission
79
residence time and the temperature in the reburn
the NOx emission

of the fixed bed in
80
an
understoker furnace
5.18 Influence of the fuel bed movement

reburn
NOx emission for different, RFR
zone on
stoichiometric ratio in the reduction
5.15 Influence of temperature and RFR
5.17
69
the NOx emissions
combustion
Comparison of
66
zone
on
the stoichiometric conditions in the
6.1
Physical fundamentals for
6.2
Numerical effort of combustion models
81
...
combustion models
.
81
83
87
LIST OF FIGURES
xix
6.3
Effort
on
6.1
Effort
on
6.5
Influence
6.6
Residence time distribution
6.7
Scheme of furnace model for simulation
6.8
Influence of
6.9
Calculated chemical eciuilibrium composition of wood
chemistry versus turbulence

chemistry versus mixing
of dispersion on a plug flow
O/N
ratio
on
curves
87
88
91
for PSR in series
92
92
fuel-N conversion to HCN and NIT
during pyrolysis
gasification at 800C
simulations, UF/UF
simulations, UF/W
6.10 Calculated input data for the reburn
zone
6.11
Calculated
zone
7-1
Calculated and measured concentrations of NO and HCN in the reburn
7.2
Calculated and measured concentration of N2O in the reburn
7.3
Gas concentrations in PFR
using
7.4
using
input
data for the reburn
the GRl-mechanism for
UF/UF
7.13
Calculated
7.7
7.8
7.9
7.10
7.11
concentrations after reburn
N-specics
concentrations for PFR after
zone
for
101
104
the GRI-mechanism for
N-species
97
104
the Leeds-mechanism for
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
burnout, reburn model
RFR=0.30, UF/UF
113
7.15 Burnout in PER at 1300C for different reburn models with
RFR=0.30,
UF/W
114
7.16 Influence of burnout temperature in PFR

reburn model: PFR with
reburn model: PSR=-i.0s.

as
reduction rate R for
RFR=0.30;
114
7.17 Influence of burnout temperature in PER

7.18 Burnout modeled
on
UF/W
on
reduction rate R for
RFR=0.30;
UF/W
115
PSR+PFR for different reburn models with
RFR0.30,
UF/W
115
7.19 Influence of temperature
on
CO, NO,
NO2. and
N2O emission after burnout
for different CO addition
7.20 Gas concentrations in burnout, stage

7.21 Gas concentrations in burnout, stage
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
evaluation from FT-IR spectroscopy
131
134
LIST OF FIGURES
xx
B.8
IR spectrum of HCN
136
B.9
Calibration
137
B. 10
Examples of Gaussian
curves
of CO2 for different H2O concentrations

distributions
B.ll Standard Gaussian distribution
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
1995 to 2020 could
period
in China and other
occm
supply
Fossil fuels
in 1996 worldwide and in the OECD countries shows

are
expected
to meet
The balance among energy
remain stable. Oil will be used
is
sources
increasingly
air transport. Coal will remain

for
be put in
new
Figure
primary
1.2.
projected
to
change marginally.
to meet
in power
preferred
to
The market
slightly
and that of coal will
rapidly growing
demand for road and
fuel for
pipelines exist, or
applications, especially
Where
generation.
many
power stations.
Electricity generation from

post-Kyoto policy changes,
generation by
2020. New
reduce fossil fuel
generating plants
developing
it will still
policies
will be built.
Idie Outlook includes also
general,
required
period
use
developed
some
fast
but, without
cent of world
electricity
sources are
to
help
Unit costs of renewable
gas emissions.
About half of the total is
projections of biomass
accounts for
countries. In
countries of Africa and Asia.
although
growing
if renewable energy
1995 to 2020.
at
The
a
3500 GW of
projected
new
electricity
for China and other
energy
can
be
as
countiies.
high
as
consumption of biomass
lower
rate
developing countries.
supply in developing
biomass supplies about a
use
in
greater share of energy
developing
third of total energy needs, but the share

tinue to increase
is
third for OECD countries.
biomass energy
sources
represent less than 1 per
will be
Over the
countries, and
countries than in
other renewable energy
consumption and greenhouse
energy must be reduced.
In
important
natural gas will be the
place,
to the total
95% of additional global energy demand from 1995
share of gas will increase while the share of oil will decline
can
developing
energy-related CO2 emissions could rise by 75% above the
By
levels, the basis for the Kyoto Protocol 1997. The fuel shares
energy
2020.
the
over
2020 worldwide
countries.
than
80% to 90% in the poorest

in these countries will
population and
con
much lower rate than
conventional energy.
There
arc
many
possible combinations of energy saving

I
and fuel substitution that would
CHAPTER, 1.
Total
INTRODUCTION
Primary Energy Supply 2020
13700 Mtoe
Figure
Outlook for world
1.1:
primary
energy
supply (IEA, 1998)
încludes marine bunkers
**includcs combustible rencwables and waste

***includes
meet the
Kyoto
measures
wind, etc.
commitments
But all involve
gases.
and
geothermal, solar,
on
Renewable energy, and in
the emissions of
CO2 and other greenhouse
deviations from past energy trends.
large
need to be
reducing
Major
new
Governments to meet the
place urgently by
put
particular biomass, will have
in
an
important role
to
policies
objectives.
play
in climate
stabilization.
The
use
of biomass for energy
sustainable
supply
has many associated environmental benefits.
use
of biomass energy enables countries to slow the
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
degradation in absence of an externally supplied

pyrolysis products are mainly a high reactive char (or simply
oxidising agent. The

charcoal).and pyrolysis
gaseous components.
as
thermal
oils
(tars),
but, also
certain amount of low molecular
Temperatures of 400-600C
are
used for biomass
weight
pyrolysis.
Gasification is the thermal
degradation in presence of an externally supplied oxidising

agent. While pyrolysis usually is optimized with respect to a maximum charcoal and
tar yield, gasification aims at, a maximum gas yield. Temperatures of 800-1200C
are usually applied for biomass gasification. The gas produced contains mainly CO,
CO2, Lp, II2O, CH] and other hydrocarbons in varying amounts, depending on the
oxidising agent, (air,
Liquefaction
can
temperatures
oxygen
be defined
(250-350C)
as
or
steam), the fuel and the gasificr design.
thermochemical conversion in the
and
high
pressures
liquid phase
(100-200 bar), usually
with
at low
a
high
AIM AND MOTIVATION
1.2.
World 1996
Figure
OECD 1996
1.2: Fuel shares of total
primary
supplv: World
energy
and OECD countries
only
(IEA, 1998)
*mcludcs
geothermal, solar, wind,
etc.
hydrogen partial pressure and catalysts

improve the selectivity of the process.
The
to enhance the rate of reaction
and/or
to
of biofuels in closed carbon
cycle as a substitute for fossil fuels is one of the most

stabilizing the CO2 concentration in the atmosphere (Schwaiger and
Schlamadinger, 1998). Especially the utilization of woody biomass should be considered
as a potential source of renewable energy or as a feed stock for conversion to other fuels or
durable products. This potential is still quite unused especially in the developed countries,
use
ways for
promising
mostly due
to economical reasons.
In the last years, in

become
more
has cut the
favorable
prices
the
augmented
unmerchantable
production
However,
some
countries the
European
use
of wood for energy
again. The demand of higher quality wood for industrial purposes

qualities. Storms, diseases, and varmints have additionally
offering
wood,
processes
for low
forest
as
the theoretical
well
quality
residues,
as
supply
wood.
waste
Therefore,
wood from
an
alternative utilization for
manufacturing
and industrial
for demolition wood is the thermochemical conversion.

is still much
higher
than the actual
potential
Figure
possible sustainable consumption are displayed.
The
has
for lower
waste of this
1.2
generation
shows
1.4 where the actual wood
consumption
is. The
consumption and the
Aim and Motivation

history
of industrialization is also the
history
wide range of combustible fuels. Initially, biomass

thermal energy
supply.
As the demand for fuel increased,
developed, first coal, then oil and
covering of
from discovery and development of a

fuels, particularly wood, provided the
the
gas.
Todav, being
aware
new
of many
increasing energy demand by fossil fuels causes,

acceptance again also in the economically leading countries.
Liquid
and gaseous fuels
trialized economies
sources
of energy
biomass fuels obtain
emerged as the dominant thermal energy

during the fast growing prosperity of the fifties and
were
problems that the
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
by region (TEA, 1998)
1 3: World COi emission
recent years, solid fuels
being
are
the solid fuels burned in substantial
on
C02
used
again
in
increasing quantities. An
supply today gives
quantities for energy
Table 1.1.
Three classes of solid fuels may be
distinguished:
fossil
fuels,
biomass fuels and wastes.
All of these solid fuels have dis
The transition between biomass and fossil fuels is peat.

tinct
physical, chemical, thermodynamic, and transpoit properties. These characteristics
help
to define the behavior of any
given solid fuel within
combustion environment
or
technology.
Numerous
technologies
have been
developed
to burn solid fuels for the
useful energy and the reduction in volume of material to be discarded.
combustion systems include grate

reactor
on
bed, also called fixed
oldest for industrial
application
18th century and still
combustors
are
are
technology
populai
beds
the
of the
bed
for wastes.
into fine
for
large
units
(200
to 800
MW0).
represents the third class of systems available for solid
pulverized
fuel
particles
are
The fuel oxidizes in
(FBC), cheulating
supported by
an
upward moving
bed of inert material
Fluidized bed
fluidized beds
(CFB),
com
potentially
technology includes
and
pressurized
flu
(PFB).
idized beds
Generally,
are more
sand and inerts contained in the fuel itself,
bubbling
probably
particles and burned in suspension.

superseded fixed bed systems for electrical power production
stream of air and combustion gas.
conventional
placed
technologies. They appeared

beginning
popular technologies. Other types of fixed
firings,
pulverized
bustion. In fluidized beds, the
including
are
in the
at, the
may be
higher efficiency
Fluidized bed
used
Grate and bed fired systems
which
fired systems have
due to their
bed.
of
used
Commonly
bed fired systems where the fuel is
among the most
rotary kiln
Alternatively, solids
Suspension
or
production
all combustion
technologies
industrial wood combustion systems.
boilers and
suspension fired systems
for solids mentioned above

Because of economical
are
installed.
are
reasons,
also suitable for
mainly fixed bed
Fluidized bed systems may be
an
AIM AND MOTIVATION
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)
then 10 MW thermal. The maximal size of units
burning
availability of
is limited to about 50 MW thermal due to the limited local
transportation of biomass
biomass since the
over
long
distances is
nor
economical
nor
ecological.
In
Switzerland, wood combustion systems from 2kW (room heating systems)
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.
automatic wood furnaces. Furthermore, automatic
centralized
heating plants (CHP).
of biomass for energy
production
environmental effects. Thus, life
done with the purpose of
cycle,
that
use
mostly
on
categories with the highest growing rate in Switzerland since

They are mainlv used for heat or steam production for various
as
To increase the
based
the
Fig in e 1.5 shows.

purposes in industry or for
1990
arc
analyzing
(Jungmcicr
et
ah.
important,
it is
cycle
inventories of biomass
the different environmental burdens
1998).
The results of the live
contributions to the emission of NOx mid CO
conversion in conventional combustion systems.
to know the
are
Consequently,
cycle
over
plants
the entire
inventories show
due to the thermal fuel
fundamental research is
necessary to reduce these emissions.
While the emission of CO and other unburned

naces
is under control,
contribute to the formation of acid rain and
photochemical
ddic formation and reduction of emissions

cial scope of interest
practicable solutions
at
the ETH Zuiich.
for the
limitations. Basic research
specific
research
has been
on
compounds
the reduction of the nitiie oxides,
designers
on
.smog, is still
during wood combustion
challenge.
has been
The research pursues the aim of
spe
elaborating
of wood furnaces to meet future restrictive emission
emissions of wood furnaces
NOx reduction by air staging
published (Keller, 1994).
from automatic wood fur
which have been shown to
as
(Nussbaumer, 1989),
primary
measure
The main conclusions of the
and
more
for wood combustion
passed studies
are:
CHAPTER 1.
Table 1.1: Solid fuels
currently
INTRODUCTION
used for combustion
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
Medical and infectious wastes
Solid hazardous wastes
Table
1.2:
Statistic of installed wood
firing
1997; data from
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
The NOx emission from wood combustion
mal NO formation is of minor
originate
from the
nitrogen
in the fuel. Ther
importance because of the relatively low combustion
temperatures of about 1200 to 1600C.
In
general,
the conversion of fuel
nitrogen
to
NOx decreases with increasing nitrogen
content.
With air
can
staging,
the NOx emissions from wood
be lowered bv
more
than 60%, those from
chip combustion (low fuel-N content)

UF-chipboard combustion (high fuel-N
content) by about 75%.

This report presents studies about fuel
staging and
ah
staging in wood combustion for
NOx reduction. Both air staging and fuel staging take advantage of the chemical reactions
going
on
in
fuel rich combustion
zone
undei certain bouudarv conditions which reduce
AIM AND MOTIVATION
1.2.
renewable waste
funaces
automatic furnaces
domestic
heating
systems
heating
room
systems
-60%
-40%
-20%
0%
change
Figure
At fuel
the formation of NOx.

addition of
staging
has
some
80%
100%
120%
of installed power
staged
extra amount of fuel
an
an
combustion, this reduction
(reburn fuel)
ash
sary temperatures in the reduction
category in Switzerland from 1990
per
is created
by
to
the
to the combustion process.
melting temperature
zone
zone
practical applications. Air staging is
limitations for certain
suitable method for fuels with
an
60%
Change of installed heat output

adapted from (Kessler. 1998)
1.5:
1997; data
Air
40%
20%
below 1000C due to the
of about 110CPC and
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
of these restrictions the interest
over
the entire load range
fuel
on
increased and fundamental
staging
as
(Good
ah, 1999). Because
et
alternative method for NOx reduction
As known from combustion processes of other
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
great, potential for NOx reduction and motivated further research.
were
done
on
conventional undcrstokcr
added batch-wise
a
arose.
on a
second grate
result of these experiments. At the
the
conditions
main
stage
dining
by these experiments,
developed.
energy for
lower level
The
non-pulverized
experiments
reburn fuel
Nussbaumer, 1995). Figure
of the
pyrolysis phase of
was
1.6 shows
the reburn
fuel,
As the fuel conversion goes on, the reduction

the char burnout and finally meets the
starting
again.
Stimulated
been
on a
and
beginning
N()x reduction reaches about 90%.
decreases, remains
furnace,
(Salzmann
where
a new
fuel
The reburn fuel added is not
changing
the size
is also used
as
or
shape
staging concept for fixed bed

pulven/ed. i.e. no additional
of the reburn is necessary. The
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]
wood combustion: NOx reduction rate R
and Nussbaumer,
in this report,
35
30
25
was
versus
time,
1995)
started with the
following
aims:
staging with wood fuels on a new research facility shall

potential of this primary measure at different con
demonstrate the NOx reduction

ditions.
Practical
operation shall be tested and experience gained for future development of the
concept.
Along
with the
experiments simulations
with
be used for examination of the process.
simplified furnace
model
approach
shall
Chapter
Fundamentals of Wood
Combustion
2.1
2.1.1
Wood
Wood
Characteristics
can
be defined
as
hard fibrous substance,
basically xylem. that, makes
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
inserted between the oldei wood and baik
(see Figure 2.1).
Wood is both
anisotropic and
hygroscopic.
The wood and baik
95% of the
are
made up of individual cells. Cell walls may
of the woody
The wood cells pass several
mass
plants.
during their life: cell division, cell enlargement,
as
cell wall
comprise as much
phases of development
thickening, lignification,
and cell
death.
Although the development of wood cells

overlap, especially among the enlaigcmcivt,
is classified into distinct

wall
thickening,
sapwood
Figure
cambium
2.1: Cross section of
and
liunk
phases, considerable
lignification phases
may
FUNDAMENTALS OF WOOD COMBUSTION
CHAPTER 2.
10
take
place.
recently formed wood, performs the role of support, conduction,
The sap wood, the most
and food storage. After

cells die.
food-storing
some
Then
time
elapses, the
amount of which is
The
pigments.
area
vessels that
softwoods
classified into
are
are
responsible
trees),
to the annual leaf
opposed
Chemical
2.1.2
hemicelluloses
lignin
knowledge
acids.
extractives,
Goldstein,
(evergreen
(deciduous trees).
Wood components that
the soluble
compounds
that
and type of chemical
of the chemical constituents is useful.
are:
However, in bark these structural components
phenolic
most softwoods
product of the arrangement
some
major chemical components of wood
cellulose
the support role.
Composition
constituents that make up the wall,
by
most hardwoods
shedding by
Because cell wall structure of wood is the
The
perform
tracheids that have the dual roles of conduction
Another classification is the retention of leaves
and support.
dark-
to
dead cells forms
The wood of hardwoods contains
and hardwoods.
longitudinal
light-colored
physiologically
for water conduction and fibers that
Softwoods contain cells called
as
with
the
only.
the heartwood which functions in the support role
Trees
color from
they often change their
colored due to the secretion of
species-dependent,
are
more
are
often
mav
be overshadowed
by suberins and
variable in structure and
species-
or
quantity
genus-specific (Lewin
are
and
1991).
Idie different structural components show up
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
The characteristic behavior of the different substances becomes

rate of
Cellulose,
chain
mass versus
even
(differential or DTG) curve as Figure 2.3.

(40-50%) and skeletal polysaccharide, is a long(see Figure 2.4). The cellulose structure favors the orga
temperature
the chief wall component
polymer of glucose
units
nization of individual cellulose chains into bundles with crystalline order held
by hydrogen bonds, leading

ordered
degree
crystalline regions,
of
to
fibrous state.
Cellulose consists not
but contains disordered
the
crystaffinity depends on
origin
pulp, mercerized cellulose,
the fact that it, is
are
or
polymer
of
glucose, cellulose
only
amorphous regions
and the history of the
in the order cotton, wood
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
able to dissolve cellulose. Due to the
together
of the
complexes
groups in the cellulose chains cellulose
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
Associated with the cellulose in the cell wall
(20-25%). They
celluloses
hexoscs. and
sugars in
are
of
are
some
hardwoods hemicelluloses. the
carbohydrate polymers
(see Figure 2.5).
are mannose.
loses
are
also
susceptibility
molecular
more
to
known
hemi-
as
glucose, both pentoses and

softwoods, the principal constituent,
constituent sugars
principal
insoluble in water,
they
readily hydrolyzed by
hydrolysis
In
xylose, glucose, galactose, and arabinose.
with minor amounts of arabinose.
galactose,
certain exceptions
(Gr0nli, 1996)
consist mainly of sugars other than
usually branched
decreasing abundance
and
wood fuels
can
Alt
are
xylose,
mannose,
the hemicelluloses
hough
than cellulose result from their
amorphous
glucose,
are
with
Hemicellu
be dissolved in strong alkali.
acid than cellulose, ddieir greater
In
solubility
and
structures and low
weights.
During
the last cell
between the
newly
development phase,
called
lignification,
formed cells and their cell walls takes
wood cell wall component
(20-30%).
agent within fibers, and
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
to wood fibers and contain
mass
of the tree.
cellulose, hemicelluloses. and
but in lower concentrations. Because of the presence of extractives and two other
12
CHAPTER 2.
herruccllulose cellulose
2.3: The differential
Figure
hgnm
curves
lignin
of the thermal
cellulose
degradation
hcmicellulose
of wood
CHjOH
OH
CH2OH
as
low
as
REDUCING END
2.4: Structure of cellulose
components unique
20-25%.
OH
NON-REDUCING END
Figure
(GrOnli, 1996)
to bark
Suberins
(Tillman
(suberins
are
and
et al.
1981)
(DP= degree
of
phenolic acids), the cellulose
found in the bark cork cells.
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
high-molecular-weight phenols that are often confused with lignins because of

insolubility in sulfuric acid, but they differ from lignin in their lower molecular weight,
alkali solubility resulting from their high carboxyl content, and lower
methoxyl content.
are
their
Extractives
(0-10%)
extraneous wood
components that may be separated from the

by their solubility in water or organic solvents. Classification of
made difficult by their great varietv. Major categories of extractives include
are
insoluble cell wall material

extractives is
volatile
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
to the cat egory of
C. H, and O
nitrogen, phosphorus,
hydrocarbon fuels. Hence, 1 he principal chemical elements
(Schobert. 1990).
In addition, calcium,
potassium, silicon, sodium, and sulfur
other elements have been detected.
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-
for cellulose and the hemicelluloses
Hie water content of the wood is
expressed
weight
dry weight basis (index df: drv fuel).
as a
wood,
is used
storage.
which result from

to
only.
fraction either
(2.2)
governed by species, type
drying typically
are
which defines the moisture level when the pores
covered with
to the wood fiber
layer of water, ddiis layer

by hydrogen bonding.
The water content has

bio fuels
or
55%,
of
wood residues
have water contents of about 8
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
The water content of wood is
lumber
total
Green wood may have
operations after
on a
n,o
miiiO +
wjj
(Tillman, 1991)
important parameter for the thermal
very
wood. The water content may be
and
Talose
Galactose
Typical building blocks
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
interior surfaces of the wood fibers
is "bound water*' because of its attachment
strong influence
on
the calorific value of wood since
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
modest in heat content
anvwav.
The lower
value
of the fuel
is caused
calculated
lower
of carbon and
by varying percentages
as
heating
function of the water content.
value shows
Figure
hydrogen.
The
heating
value
The influence of the water content
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
repiesentation of softwood lignin
stmctuie
(Idllman, 1991)
2.1.
WOOD
15
Figure
2.7: Influence of water content
on
heating
value
CHAPTER 2.
16
Combustion Process
2.2
Combustion is
mass
heat and
complex phenomenon involving simultaneously coupled
very
transfer with chemical reaction and fluid flow. Substantial differences exists between
the combustion of solids and the combustion of
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
the combustion of solid fuel
particles
can
be described
illustrates the solid combustion process for

fuel combustion
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
The second influence
of the
particle
until the
center of the
core
(Tillman
heterogeneous
et
reactions
reaction temperatures.
al, 1981).
are
responsible
for different
Devolatilization and chemical
(fuel type, composition, moisture content,

(pressure, heating rate, temperature). The pyrolysis
aggregate state into gaseous (volatiles), liquid (tars)
fuel parameters
separated by their
can
and solid
practical
and
and process parameters
products
procedure
particle. Additionally,
conductivity of the particle, thus increasing the rate of
transmission of heat from the surface to the
behavior of the fuel
ddiis
ddie first influence of fuel moisture content is to
energy for
During pyrolysis homogeneous

product composition at different
C).
200 450
to heat up the wood
the moisture increases the thermal
for
particle.
have to be heated from ambient conditions to that
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
The main steps of solid
(pyrolysis)
wood moisture content,
increase the energy

the moisture
five step process.
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.
modeling of solid fuel degradation is presented by (Blasi,

a challenge to formulate the pyrolysis process in all
1993).
details for wToocl. For some of its structural components, there1 exist, established approches
for describing the thermal degradation mechanisms. Figure 2.8 shows a mechanism for
A review
over
the kinetic
However, it still remains
cellulose
are
degradation.
pyrolysis as process may be divided further into three consecutive

very important for the resulting product distribution:
The
processes which
2.2.
COMBUSTION PROCESS
17
CH'OH
CH OH
Ring
Opening
CO tCH, +C,HS +CH.0

CO,
Figure 2.8: Possible

DcGroot, 1976)
mechanism for cellulose
*H,0
degradation by pyrolysis (Shafizadeh
Primary processes: Products are formed in the fuel

aliphatcs, oxygen containing carbon hydrogens,
at low
(caibon
species)
temperatures
different oilcous
Secondary processes: Products are formed in the gaseous phase

ucts by cracking reactions or by reactions of the gaseous species
out of
and
oxides,
piimary prod
with the solid surface
while temperature increases
Tertiary
processes:
ondary products
Carbon monoxide and
Xew
or
bv
products
are
created at
repolymeiisation
to
high temperatures
heavy
aromatic
bv
cracking
sec
compounds
hydrogen arc generated in a higher share with increasing pyrolysis

temperature: hydrogen is significantlv generated at temperatures higher than 800C as
reported by (Rdiger et al., 1995). CO2 production is not strongly influenced by the re
action temperature. The production of hydrocarbons reaches a maximum around 800C,
18
CHAPTER 2
solid
phase
condensed
gas
phase
phase
Products of
C02! H20, 02, N2, NOx
complete combustion
-1
Burnout
02
o,
tars
CO, H2, CH4, CmHn,

02, C02, H20, NO,
N20, HCN, NH3,
.
1
CD
O
CD
15%
85%
Ignition
Pyrolysis
100%
CD
c
CD
Drying
Air
Fuel
water
dry
Figme
2 9
wood
charcoal
Schematic of wood combustion
ash
COMBUSTION PROCESS
2.2.
The data of
too.
a
obtained from the thermal
setup and different heating
during the pyrolysis of
wood
rates.
change
of tobacco show
different experi
of the molar ratios
containing species are formed

the char is usually lower than in the
and oxygen
The nitrogen in
fuel.
Table 2.1: Molar ratios in

et
Table 2.1 shows the
(oats). Hydrogen
earlier than the fuel-N is released.
original
dglaciation
formation between 475 C and 550 C due to
hydrocarbon
maximum
mental
(Burton, 1976)
19
raw
(oats)
biomass
pyrolysis (Rdiger
and residual char after
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
The combustion of the residual char and other entrained carbonaceous
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.
the pore diffusion and surface reactions influence the
Diffusion-
the external diffusion controls the oxidation rate.
reasonable
particle
assumption for
size
increasingly important. Combustion

within the second regime.
or
combustion of
temperature decreases,
large particles
particles (pulverized combustion)
of small
is
char to
many
and oxidizer concentration. But
area
an
other
practical
particle
depending
uses.
have been
on
as
problem,
another.
function
the pore structure varies also from
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
reaction kinetic become
history,
there is
lack
on
one
data for
numbei of models of combustion of porous
developed (Smith, 1982). (Simons, 1982).
Still
some
uncertainties in
char oxidation rates remain.
Important
solid fuel characteristics for combustion processes
mal
conductivity, heat capacity, elemental composition or

analysis and associated thermogravimetiic characteristics,
sion temperature, calorific value, and
these characteristics into account if
tants wants to be
The ultimate
containing
particle
complete
specific gravity, ther

ultimate analysis, proximate
are
trace metals
size. The combustion
content, ash fu
technology
must, take
conversion with minimal emission of
pollu
guaranteed.
analysis of the fuel delivers the
elements which is the base for the
necessary
followdng
information about the fuel
combustion calculations. Stoichio-
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
equation of solid carbon
all combustion
C{s)
If the solid fuel contains both
02
hydrogen
is
given by
(2.4)
OCT + heat
and oxygen, the equation is modified frther
as
follows:
CaHbOc
+ *
(a
aCOo +
) 02
fiTO
+ heat
(2.5)
The ratio between the amount of oxygen
amount of oxygen
is also called stoichiometric
three combustion
modes
SR
stoichiometric combustion
1:
supplied and the stoichiometric

(SR). According to this definition,
possible:
are
SR > 1
ratio
fuel lean combustion
SR < 1: fuel rich combustion
roughly a mixture of about, 21% oxygen and 78% nitrogen and

1% argon is used as oxidising agent rather than pure 02. From the chemical point of
view, stoichiometric combustion (SR=T) is needed for complete fuel oxidation. In tech
nical applications the stoichiometric ratio is somewhat higher than 1 to ensure complete
combustion mainly due to limitations of fluid mixing. Increasing the stoichiometric ra
tio leads also to a reduction of the combustion efficiency since additional mass has to be
Usually
ambient air which
heated up.
The combustion
using
the
equation for
wH20
CaHbOc
aCO-2
(w
moist, wood may be written
|)
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
CO2 and H2O
complete
no
composition of combustion
moistme of combustion air is
ideal behavior of the gases
NOx formation
soot and
air: 21% Oo and 79% No
neglected
and the definition
T^Y^
Consicleiing
the combustion gas without H2O.
ratio and the oxygen content in the gas

the combustion gas
[O2]
this
relation between the the stoichiometric
be denved. The volumetric oxygen content in
can
is then
A(SR
[O2]
Evaluating
(2.7)
1)
(2-8)
-t^^tF^
+ l
A(SR~~l) +
A^SR
equation further results in
OT=2i^!L
21
,2.9)
v
100[O2]
Usually, Equation 2.9 is simplified by the assumption that the factor (1
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.
that the molar
fuel rich adiabatic combustion
like
Equation
then listed appeal
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>
fuel lieh combustion the overall combustion

Moie
numerically. The solution method for that

For
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
only condensed phase considered while no attempt is made to include

tars as gasification products. Other hydrocarbons than CIp arc not, stable products under
adiabatic gasification conditions.
Solid carbon is the
beginning of the sixties several computational methods were developed to

complex chemical equilibria (White and Johnson, 1958), (Boynton, 1960). An
on some methods gives (Smith and Missen, 1982).
At the
An
namic
elegant method to solve the mass

equilibrium is the minimization of
function G is
the
an
independent,
same
an
unknown
overview
thermody
the Gibbs free energy of the system. The Gibbs
appropriate fundamental relation describing
system of
given
mass
by
variables temperature and pressure.
G(T.p)
All other
and energy balance for
calculate
thermodynamic quantities
H(T.p)
can
(2.16)
TS(T.p)
be obtained from G and
variables, ddie total differential of G for
are
expressed
in these
system considering variable composition
is
,v
clG(T.p. n)
introducing
the chemical
potential
of the Ar
Thus,
a common
equilibrium
of
]T p,ch,
(2.17)
species of the system.
(?r\
(2T8)
n(7\p)
(>)
(2,19)
meaning
dGpp
optimization problem
+ RT hi
cdiemical system at constant temperature and pressure
is that the free energy is at minimum,
The
Vdp
formulation of the chemical potential is
ti,(niri.'I\p)
The criterion for
-SdT +
(2.20)
to be solved is
N
minG(n)
To solve the constrained
of
V\?,//,
(2.21)
optimization problem of the equilibiium formulation, the method
Lagrangian multipliers (tti)
M elements.
is used to satisfy the element-abundance constraints for the
The conservation of the chemical elements leads to
one
equation
for each
element.
Y
bk--J2k,n,
k=L2
(2.22)
COMBUSTION PROCESS
2.2.
where a, is the element vector of

in the system.
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}.
total number of moles.
equations (<T>
M
now
....
i and b is the fixed number of mole of element k
species
Lagrange
0(n>7r)=
The minimization
23
set of
(M
N) equations
unknown mole numbers
multi-phase systems finally
must be
determined
ultimately
(M
in the
N)
be substituted
can
(M
set of
by iteration,
and T values of the total number of moles in each
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
ô)
(AHfh
(i7n
n>
T2 is the temperature of the products and corresponds

is the
equilibrium
temperature of reactants
"
nn)
(AHf)r0
to the adiabatic
(2-24)
temperature. T\
the system and Tq is the reference temperature
entering
(=298.15 K).
In
a
principle,
the
problem
great deal remains
describe
of cdiemical
to be done,
equilibrium have
has
eciuilibrium
by
as
been solved.
to be solved
numerically.
subroutine in MATLAB.
influence of the stoichiometric ratio
on
equilibrium has been implemented
Figure
2.If and
the calculated
Figure 2.12 illustrate the

equilibrium composition and the
adiabatic reaction temperature of the considered C-H-0 system

2.11.
Dissociating
reactions at,
ddie water content has
In
practice,
equations that,
because the solution of the nonlinear
A code for the numerical solution of the chemical

the author
now
high temperatures
according
to
Equation
neglected.
are
multi-faced role in wood combustion. The first step of the wood
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
Figure 2.12, and lowers both

particle. Hence, the production
pyrolyzed
to char
ddie water content may contribute to

radicals for gas
decreasing
phase and
char reactions.
concentration of the
increasing
the temperature of char reactions and
an
excess
important OF
by smothering
reactive sites. In
by
a sum
highly complex
item of research.
For clean and

and
and
It, may reduce the rate of char oxidation
mary, the role of water in the combustion process of moist, solid fuels is
and still
(Shafizadeh
1976).
high
efficient wood combustion it is
air levels, i.e. stoichiometric ratio,
benefit of the energy
potential
are
important that both
controlled
and minimal environmental
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
equilibrium composition for adiabatic
(wood= CHi2eOo66,
0.0
thermochemical data from
0.5
E0
wood conversion with air
(JANAF, 1985))
E5
2.0
2.5
SR[-
Figure
2.12:
Influence of water content
of wood combustion with air at
(JANAF. 1985))
1 bar
on
the calculated adiabatic flame temperature
(wood=
CTI
l 2c
o 66.
thermochemical data from
EMISSIONS
2.3.
25
Emissions
2.3
In addition to useful
heat,
sions. The emissions
can
wood combustion leads to
be
various
quantities of
airborne emis
into two classes: avoidable and unavoidable emis
separated
sions.
Unavoidable emissions results from
products
unavoidable
complete
of all combustion processes
combustion.
using
C02 and II2O
carbon and
typical
are
hydrogen containing
fuels.
Particulates
creation of
fuel
particulates.
particles
The fine fuel
only
particles entering
to short
or
as
siniplv entrainment of finely divided

products of combustion within the furnace.
The first mechanism is the
flyash.
pyrolyzed only
are
of solid fuel combustion. Three mechanisms dominate the
and inert matter in the gaseous
inert residue
particles
byproduct
are a
the combustion gas stream may
The second mechanism is
analogous
now
to the
the combustion conditions
are
of the furnace. This condensation may be

as a
which is
oxidized, leaving
prior, but the fuel
because the residence time within the combustion chamber is

not
optimal,
ddre third mechanism for
formation from solid fuel combustion is the condensation of volatiles
serving
be
promoted be the
entering
particle
cooler
presence of inert solid
regions
particles,
site wdiere condensation is favored. Also inerts may volatilize and recondense
responsible for slag buildup
on
furnace walls, boiler
tubes,
or
elsewhere in the
combustion system.
Table 2.2: Possible airborne emissions from wood combustion
Characteristic
Emission
unavoidable
N(\-
CO2. IhO
particulates (flyash)
COfHC, organics (PAH)

dioxins and furans
avoidable
N20, NII3
acid gases (HCL.
heavy
Table 2.2 lists all

combustion.
Avoidable emissions
component. Focusing
HCl.
are
etc.)
or
possible airborne
on
arc
or
One
family
by changing
of air
emissions that could be
generated during
wood
mainly clue to incomplete combustion of any fuel
furans, acid
(SO2,
gases
out of discussion because the precursors of these emissions
almost inexistent in native wood.
usually
metals
native wood, emissions like dioxins and
heavy metals
be avoided
SO2, etc.)
or
Other emissions like CO,
ameliorating
pollutants has
HC,
and
organics
may
the combustion process.
not been discussed vet:
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
activity, forest fires,

processes
(usually
and
about
afterwards.
atmosphere
lightning. NO which is the dominant product from combustion

90%) is oxidized further to NO2 in the chimney yet or in the
NOx is a key element in smog chemistry and contributes to the
acid rain formation.
important naturally generated oxide of nitrogen. It is well

glass house gas. ddierefore, N2O emissions from combustion
Nitric oxide is the most

known that NoO acts
as
processes has to be avoided. More information about environmental
(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
at, fuel lean
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
ah, 1998). The resulting

2.13 shows
typical
non-premixcd flames
by
36.5
none
mixing
are
processes.
fluctuations
time scales of
and
Usually,
sensors.
leading
mixing
the fuel conversion reactions for
mixing times,
to
the flue
history (Malm-
responding
basic combustion reactions and the
some
much faster than the

The reactions
be detected fast
can
with,
formed
real combustion chamber consists
varying stoichiometry, temperature
time scales in technical combustion processes.
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
important nitrogen oxides
most
NO
Molar
can
1988), (Kolar, 1990), (Glassman, 1996).
Properties of the
Table 2.3:
impacts
i.
e.
the combustion is limited
NOx formation
are
slow
compared
to
the other combustion reactions.
2.4
NOx Formation
(NO)
Nitric oxide
and
nitrogen
dioxide
(NO2)
are
typical by-products of combustion
Mobile combustion vehicles and combustion power plants

cesses.
pogenic sources of NOx. In addition, industrial processes and
quantities. Although NO is the dominant
produce
minor
sources,
NO2 fractions varies with

the
though
effectively
source
compound being
NO2 in the atmosphere.
to
emitted
was
pro
the
largest anthro
agricultural operations
NOx compound emitted by most
type. Thus, emissions
arc
arc
N02. Once emitted. NO
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
2.13: Characteristic time scales in turbulent combustion
commonly known
thermal NO
prompt NO
NO from fuel-N
key parameter
wrays of NO formation:
for NOx formation is the temperature.
of the temperature
on
Thermal NO arises from the
high-temperature
bustion air. The oxidation of N2 by the O2
X'2
+ O
N +
N
known
as
Figure
2.14 shows the influence
the three different NOx formation mechanisms.
02
OH
reaction between N2 and 02 of the
occurs
primarily through
NO + N
(2.25)
NO + O
(2.26)
NO + H
(2.27)
The first, reaction has
activation energy, due to the need to break the strong NT bond.

The reactions 2.25
important
the two reactions
the enhanced Zeldovich mechanism.
activation energy, the first reaction is the
com
rate-limiting
relatively high
Because of the
step for thermal NO
2.27 involve the 0 and the OH
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
to the fuel oxidation reactions, it is often
thermal NO formation reactions
can
be
decoupled
assumed,
that the
from the fuel oxidation process.
Hence,
CHAPTER. 2.
28
the NO formation rates

concentrations of
For
O2, N2,
are
calculated assuming
equilibrium
O and OH.
practical applications, temperature, residence
time and
the determinant parameters for thermal NOx formation.

of these parameters.
values of temperature and
Most,
is the temperature.
important
availability of oxidizer
Decisive
are
arc
the local values
Above 1300C
1400C the
or
NOx production becomes significant and increases exponentially with temperature.
Prompt NO
first
was
tional NO
the
"prompt'' NO
explained by
the Zeldovich-inechanism
because its formation is much faster
NO is formed in the fuel rich flame
Prompt
in methane
reported by Fenimore. He measured NO concentrations
flames that could not be
nitrogen of the combustion
zone,
where
only.
He called the addi
compared
hydrocarbon
to thermal
NO.
radicals react, with
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)
Additional reactions may lead to HCN.

CN + II2
HON + II
(2.32)
CN + H2O
>
IICN + OH
(2.33)
HCN may be oxidized frther to NO. The

reaction
path
to
following
reaction scheme indicates
one
possible
NO. This reaction scheme is also valuable for the reaction of the HCN
formed from fuel-N to NO which is discussed next.

HCN + H
CN + lh
(2.34)
CN~\-C02
NCO + CO
(2.35)
NCO + O
>
CO+NO
(2.36)
Prompt, NO formation is less temperature sensitive than thermal NO formation. Most

important parameter is the local amount on oxidizer. Premixcd flames generally show
higher prompt NO production rates than diffusion flames. Prompt, NO formation occurs
hydrocarbon flames. Thus, prompt NO was also observed in pulverized coal flames.
However, in technical applications the contribution of prompt NO formation to the overall
in all
NOx emissions is of minor importance.

The influence of temperature
on
the NOx formation processes is shown in
Figure
2.14
for the combustion of biomass. Beside the thermal NO and the prompt NO formation the
NO
resulting
Generally,
from the fuel
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
combustion of fossil fuels and biomass.
mainly
released
as
Figure
2.15.
During
the
pyrolysis phase
HCN and Nip wdiich may react further to NO
combustion conditions. A summary of

in
is discussed next is also marked.
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
Thermal NOxanc! Prompt-NOx
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
NOx emission for biomass combustion systems
(Nussbaumcr, 1997)
HCN is the
ing
starting point
of NOx formation from fuel
that, HCN formation is also the
key
mechanism is similar to the prompt, NO formation

Under fuel lean conditions the
(Williams
et
following
starting
after that HCN is
generated.
place
reaction scheme is assumed to take
>
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)
Under fuel rich conditions,

the
the reaction
HCN + O
NCO
production,
al, 1997):
IICN + O
followed
nitrogen. Therefore, remember
element for prompt NO
hydrogenated nitrogenous species

production of species such as NTT and N2 according
HCN-*-OH
NH2 + RH
NH-y + NO
>
>
>
are
formed,
which may result
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
of the NOx formation and destruction in
phase
nitrogen to the NOx emissions is most clearly shown by experi

possibility of forming NO from N2 is eliminated. This can be clone by
The contribution of fuel

ments in which the
using
mixture of oxygen, argon, and carbon dioxide instead of air for combustion. Such
experiments
and from
are
reported from (Pershing
(Nussbaumer, 1989)
importance of fuel nitrogen

ddie
species
specific
are
reactions
reported
outlined in
Once
to which
as
by
main
paths
clearly
coal combustion
demonstrated the
for NOx emissions.
and Bowman,
1989)
as
isolated fuel
nitrogen
in details. The reaction schemes
are
2.17.
flames at low pressure at different stoichiometric ratios
simulating
the
ddie sensitivity analysis of the reaction

experiments indicated that the HCN consumption is
Subsequent
flames.
>
NO+H
N f NO
AT2
the conversion of NTp to NO.
Figure
by which
oxidized to NO and
governed by
OH
studying
(Equations 2.37
2.39) even
hydrogen atoms lead
reactions of NCO and Nil with
N-atoms. The distribution of NO and N2 in the flame is
NH3/O2
pulverized
of HCN and Nip considered
(Miller
and Figure
from
source
the reaction of HCN with oxygen atoms
the fuel rich flames.
For
for
added HCN in different amounts,
mechanism used for
dominated
1977)
for wood combustion. The results
Figure 2.16
they studied H2/02/Ar
were
and Wendt.
the N-atom reactions.
(2.46)
(Miller
2.17 shows schematically the
in
to
(2.47)
Bowman, 1989) considered

principal reactions by which NH3 is
and
NO is converted to molecular
nitrogen.
In
general, NH3
is
2.1.
NOx FORMATION
31
HCN^s
NGO
Figure
2.16: Reaction mechanism by which HCN is converted to NO and N2
(Miller
and
Bowman, 1989)
converted to NH2
by hydrogen abstraction, mostly by

Nils
+ OH
>
N112
(2.48)
H20
For lean conditions, reactions with oxygen atoms and for rich conditions reactions with
hydrogen
with H
or
reactions
1.
atoms also make
contributions to NH2 formation.
OH lead to NH. Each amine free radical
by
one
oxidation
NO/N2
(NH
and
NH2)
can
Further reactions
undergo subsequent
of the two mechanism:
leading
2. reaction with NO
The
significant
to NO
formation
leading
distribution
to the formation of
primarily depends
on
N2
the stoichiometric ratio and the tempera
ture.
NH,
OH, +H, +0
+NO
Figure
2.17: Reaction mechanism
Bowman.
Even
by
which
Nip is converted
to NO and
N2 (Miller and
1989)
though
is converted to
the fuel
nitrogen is the major source

NOx. Figure 2,18 shows the influence of
of N0X, not
the fuel
all of the
nitrogen
nitrogen
content
on
the
CHAPTER 2.
32
conversion to NO in
general, and Figure
firing systems including

Figure 2.18 demonstrates that
biomass
also
est conversion rates at
unstaged
2% and more, the the conversion
nitrogen
content of the
fuel,
2.19 shows the measured NOx emissions of various
primary and secondary
fuels wdth low
nitrogen
combustion conditions.
measures
content,
At,
for NOx control.
(<0.2%)
Beside the influence of the
particle size. The
conversion rates measured in
scale fluidized bed combustor
conversion rates also shows that fuels with
produce
high
contents, i.e.
the data indicate also the influence of the combustion system
(Winter et ah, 1996) are higher

systems (Nussbaumer, 1989), (Marutzky, 1991). Closer consideration
laboratory
have the
high nitrogen
rate becomes about constant.
and with it the influence of the related
bed
of data about
volatile matter like biofuels
high
lower NOx emissions than fuels with low volatile matter at the
than for fixed
same
usually
nitrogen
content.
80
Nussbaumer 1989, lab. FB
70
--Marutzki 1991, small FB
60
-I
-O-Winter 1996, lab. FBC
50
40
o
w
30
>
c
?n
10
Fuel-N
Figure
The
2.18: Influence of fuel-N
nitrogen
from industrial
the conversion to
production and
or
wood
structure.
composites
Hence,
strongly depends
For comparison, the

are
urea
in
bond
on
nitrogen
the
nitrogen, peat
contains about 0.7 to
contents of biofuels have to be
regarded plant
elements
Figure
specified precisely
(bark, stem, leaves, etc.).
coal varies between 0.4 and 3.5%.
of crude oil varies between 0.1 and 1.0%.

some
0.3%. Wood residues
higher nitrogen contents

chipboard has a fuel-N content of
1.2 to 1.6% for hard coal and 0.4 to 1.2% for bituminous coal.
contents of
oxidising atmosphere
may have much
Herbaceous fuels contain 0.3 to 1.8%
3.4% nitrogen. Generally, the nitrogen

since it also
N-species
content of native wood is usually between 0.1 and
due to their treatment

2.5 to 4.0%.
on
[%]
2.20 shows the
More
typical
values
The
nitrogen content
typical specific nitrogen
fuels,
In fluidized bed combustion both char and bed material
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
Urban Waste Wood
"*"
Native Wood
Grass
-a
-
Straw 4|
SCR
UF
0.1
Chip
Boards
10
[wt.-%]
Fuel-N
Figure
the
2.19: Influence of fuel-N
on
NOx emission of furnaces (Nussbaumer, 1997)
heterogeneous catalytic and non-catalytic
reduction of NO
by CO,
effective. The reaction rate increases with temperature and CO
char
partial
being
the
more
pressure.
The char introduces two factors. The char
particles consume 02, thereby providing a

locally reducing atmosphere that, can promote the conversion of NO to N2. Second, there
is evidence of NO being reduced on carbon surfaces by the following reactions:
2NO + C
>
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
pressurized fluidized bed combust or combined
kinetic model for NO formation and reduction have confirmed that the reduction
by CO catalyzed by
char and bed material is
temperatures where CO concentrations in the bed
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
triple binding C=N
simple binding N-C
simple binding
The parent fuel
sludge
more or
nitrogen compounds
contents of solid fuels
less
chemically
bound
nitrogen.
Most
frequent
are
converted
during
the
pyrolysis product
pyrolysis
process to HCN
when the fuel is bound in
structures of
pyrrolic type and pyridinic type which dominate in coals. In

nitrogen is largely contained in the more reactive form of amine
higher
part of the HCN formed from
amounts of
N-containing
NH3 appear during pyrolysis. Additionally,

volatiles reacts with OH radicals inside the
where the oxygen concentration is low. and
general,
oxygen and
produces NII3.
nitrogen would be expected
different times. However, the existence of temperature

that the release of those elements
may
phenolic OH
It
the fuel
hard coal
N-H
functional groups. Hence,
In
sewage
N=N
of wood, the fuel
particle,
UF-
chipboard
are:
HCN appears to be the principal
heterocyclic
case
Specific nitrogen
derived matter contains
nitrogen bindings
and NH3.
2.20:
chips
Nitrogen
Fuel
2.5
wood
straw
groups of the fuel.
is
gradients inside the particle
means
also
overlap. The OH radicals are formed from

suggested that the ratio of OH/HCN inside of
particle increases with the fuel-O/fuel-N
NH3 intensifies.
to be liberated from the fuel at
ratio and the conversion of fuel-N to
2.5.
FUEL NITROGEN
Expciiments
in
35
pulverized pyiolysis
leactoi showed
different behavioi of hard coal
(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..
While the molai ratio
coal
the coal matrix
Nitrogen
resulting
compared
in the
nitrogen release horn
from 500C to 1000C.
NH3 yields,
to wood.
in coal is believed to exist in heteroatomie
were
found
coal
coveiing
an
ling systems of a wide range of sizes

extremely wide range of temperature,
Nitiogen distributions during coal pyiolysis, especially HCN and

to change with coal lank, with the low-volatile coals giving lower
HCN and NH3 yields than the
high-volatile coals (Li and Nelson, 1996).

nitrogen between volatiles and residual char during devolatiliza
tion of coal under conditions pertinent to piessurizecl fluidized bed combustion was investi
gated by (Laughlin et ah, 1994). ddie results showed that, at devolatilization temperatures
The distribution of coal
higher
than 850C the coal
nitiogen was distributed pieferentially in the volatiles. The in

particle size, lesidence time, pressure, and oxygen concentration
nitiogen remaining m the char was small within the studied ranges.
fluence of coal type, coal

on
the
portion of
wood
pyrolysis
Figure
2.2P
gasification
oxidation
Simplified
fuel-N eaction
.._
NU
paths
formation
reduction
CHAPTER 2.
36
Measures for Emission Control
2.6
Combustion is the thermal conversion of fuel to heat and gaseous

are
given by
the choice of the react ants and
The emission of such air
Fuel is
Co-firing:
emissions then
(i.e.
partially
are
the
following
measures:
pen'
are
type but with other
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
with lower emissions
general by
input.
Fit el substitution: Fuel is substituted
position,
due to the combustion conditions.
are
Higher efficiency of the system: Increasing the system efficiency lowers the emission
unit of energy
pollutants
some
be reduced in
can
products. Some products
other fuel, i.e. coal
an
input
eliminated
by biomass.
of undesired element
by special
treatment and
or
The
by positive
preparation of
the fuel.
modification: Design optimization,
Process
other process parameters,
or
change
of the
whole process lead to lower emissions.
End
of
reduce the emissions in the flue gas
adsorption,
or
auxiliary systems
filtration, absorption,
After the combustion process,
cleaning systems:
pipe gas
by
additional processes like
chemical reactions.
description above are also known as primary measures and

secondary measures. Secondary measures have been developed for almost all important air
pollutants and successfully applied for many systems. Thev often are the only alternative
to meet the future emission regulations. But secondary measures are usually expensive and
ddie last two items of the
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
lowers the overall system efficiencv.
However, it, does not make much

and then to
remove
it
by
an
other
sense
one.
first to
produce high emission by
Thus, end of
pipe
one
process
solutions should be avoided
completely and substituted by primai y measures or at least reduced to a minimum expense

by combination of primary and secondary measures.
Indeed, before the formation of air pollutants may be suppressed by primary measures,
the mechanisms of pollutant formation have to be well understood. After the elaboration
of the fundamental knowledge, concepts for the emission control have to be formulated
and transferred into practical solutions.
The most fundamental perception concerning emission control is that many air pol
lutants are due to incomplete combustion. Additionally, many pollutants originate from
fuel elements,
ddie most
important primary
measures
for
preventing these emission
are
listed in Table 2.4.

In this report,
But before
special focus
is put
discussing the primary
NOx reduction
are
on
the1 NOx emission control
measures,
briefly presented.
the most
by piimary
important secondary
measures.
measures
for
37
MEASURES FOR EMISSION CONTROL
2.6.
Table 2.4: Air
pollution control
measures
Pollutant
Control Measures
NO,
staged
combustion
for solid fuel combustion in fixed bed systems
(air staging
or
fuel
staging)
flue gas recirculation
ammonia
CO,
HC
optimized
-
injection (SCR. SNCR)

furnace design and operational parameters:
combustion temperature
residence times
mixing
injection into furnace

wet scrubbers (Calcium or Sodium based)
wet/dry scrubbers
dry injection systems
HCl, S02
limestone
Dioxins, furans
complete burnout before entering the economizer

minimization of the particulate transport, into the economizer
fuel pretrcatment
Particulates
combustion
staged
furnace
design
fabric filters
(baghouses)
electrostatic
prcipitt ors
wet scrubbers
The aim of the

formed
during
secondary
measures
2NO
Since NO itscdf is
list of
for NOx reduction is the conversion of the NO
the combustion process into molecular

>
N2
quite stable, this reaction has
possible agents and
the
resulting products
nitrogen.
to be
are
(2.53)
promoted by
given
reducing agent. A
in Table 2.5.
or urea can be promoted by temperature

it
or
can be activated by a catalyst, (SCR:
reduction)
non-catalytic
(SNCR:
for both methods describes Equation
reaction
The
selective catalytic reduction).
global
2.54. The molar ratio NII3/NO is equal to one. Some oxygen in the gas is provided.
The selective redaction of
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
850C to 950C namely.
(2.55)
N2 + H20
window for maximal reduction
efficiency
is
quite
narrow,
A residence time of about 0 5s should be sufficient.
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 material, 250
catalyst
to 400C
is necessary to
keep
needed for
high
are
reduction rates.
Secondary
Table 2.5:
Reducing
measures
for NOx reduction
Products
agent
Reactions in gas
phase
non-selective
carbon monoxide
NT, C02
hydrocarbons
N2. C02, H20
hydrogen
N2, I120
selective
-
No, H20
ammonia
N2, C02, H20
-urea
Reactions in
-
Primary
measures
pends strongly
main
on
liquid phase
No, sulfates
sulfur dioxide
may be very efficient for
NOx control, because NOx formation de
the combustion process and the
parameters for NOx formation
gxwerning combustion conditions. The
are:
temperature
oxygen
supply
residence times
fuel
nitrogen
content
by the application of primary measures, their

efficiency, power output, flame stability, drive-
However the combustion process is modified
application has to be done

ability, corrosion, slagging,
Depending
on
the
with respect to
and burnout of ash and gases.
origin
fuel-N bound NO, several methods for
single
fuel
As
or
meaning thermal NO. prompt, NO, or

NOx control are developed, ddiey may be applied
of the NOx emission,
in combination. A list of
primary
measures
for NOx reduction with focus of solid
systems gives Table 2.6.
already mentioned,
nitrogen
the
major
contained in the fuel.
source
for the NOx emission of wood combustion is the
Summarizing all important aspects of NOx

following points may be emphasized:
formation in
conventional combustion systems, the
ddie conversion rate to NO decreases with
increasing
fuel-N content.
The
higher
the
fuel-N content, the lower the conversion rate.
The
bonding
characteristics of the N-atom within the molecules have little influence
the conversion to NO.
on
2.6.
ddie minimum N0X emission reachable with
The combustion
measures
Table 2.6:
technique can promote

for NOx control).
Primary
measures
Combustion with low
Combustion with Oo enriched ail
lower air
water,
Staged
air
first,
steam, gas injection
combustion
staging
fuel
be maintained fuel rich
staging
amount of fuel
long enough
before
completing
provides
primary combustion
zone,
NH3, NO2, N2O, and NO of

called TFN
(Total
Fixed
Air
proceed. Staged
some
course.
The
sum
zone
products
are
formed in
species depend strongly
mixing conditions,
primary
on
in detectable
quantities
IICN,
are
N02
+ 2
(2.56)
N20
Staging
staging is a two stage combustion. In

complete combustion is supplied with the
the first stage onlv part of the air

fuel
(see Figure 2.22). Thus,
required for
fuel rich
zone
created where less NO is formed from HCN and NH3 than at fuel lean conditions.
limitation of the oxygen
availability in the fuel rich
of the O and OH radicals, is the
After the reduction

or
as
the
and the residence time. The
nitrogen containing species is also
of all
HCN + Nlh f NO +
Air
NO
of
Nitrogen).
TEN
2.6.1
can
the gases has to
because it allowed
and intermediate
ddie concentrations of the
may leave the
species that
stable
NO,
required time for N2 formation.
the
nitrogen containing species
stoichiometric ratio, the temperature, the

more
N2-forming
NOx,
as
reactions
the combustion process, but it, is much better
suited to fuel NOx control since it
Beside NO other
the furnace
nitrogen leaving
for that the
to the control of thermal
applied
rejected
by
heating temperature
flue gas recirculation
minimizing the
02 only
or
surface burner
(=* primary
cooled surfaces
the
the
lower thermal load
the heat, to be
by
excess air
reduction
Temperature
-
was
affected
for the i\Ox reduction of solid fuel combustion systems
combustion
strongly
hinder the NOx formation
or
For
fuel-N is
high
conditions, less by the temperatures.
stoichiometric
39
molecular
zone
nitrogen
key
air is
zone,
i.
e.
the
decreasing
is
The
concentration
factor to NO reduction.
injected and all
the
after the burnout stage.
nitrogen species usually end
up
as
CHAPTER 2.
40
piimary stage is a distinct indicator for the

NO^ emission after the burnout stage, provided that the temperatures in the burnout zone
the lower the
are below the initiation of thermal NO. ddie smaller the TFN content is,
N0X emission, ddierefore, NOx control by two stage combustion is equivalent with the
For air
staging
the TFN content after the
optimization of the
An
zone
TEN content in the
important parameter for
(SRt).
It
can
(SR)
known, Equation 2.58
zone.
is the stoichiometiic ratio in the reduction
staging
air
be calculated with the
the total stoichiometric latio

fuel flow is
primary
can
(primary
air flows
input
alt ci the burnout
and
secondary air) 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
fuel rich combustion
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
reactions in the fuel lieh
zone
place,
ddie
injection
NOx
eduction
emissions
zone
leducing NO
(stage 2)
aims
leads to
no
thermal NO
of the combustion process
Depending
on
the reburn
formulated
may be
staging
of buinoui air finely
(stage 3). Again, assuming
the burnout stage, minimum

i
the creation of
the fust stage of fuel
staging,
Afterwaids, the input of the reburn fuel
combustion of the reburn fuel
2(m
staged combustion,
for air
principle of the resulting three stage combustion
where NOx reduction should take
during
fuel,
the
as
2NO T 200
N2
2C02
(2.59)
2ATM 2H2
N2
2H2O
(260)
n/4)NO+ CmHn
If the reburn fuel contains also

reduction. Ilowcvei, two
are
same as
Unlike air
minimal TFN emission after the
nitrogen
of
Principle
Staging
The idea behind fuel

a
2.22:
mam
under discussion
(m4n/l)A"i
nitrogen, Equation
n/2H20
mC02
(2.61)
2 55 may also contribute to the NO
icaction mechanisms for the conveision of NO to moleculai
(Milien
and Bowman,
1989).
In hvdrocaibon flames and in
2.6.
41
reburning
hydrocarbon fuels, the primary NO-removal piocess is NO HCN> N2.

II2/O2/Ar flame where small amounts of NO were added, the principal NO-
with
In fuel rich
removal process
the NO> HNO> No sequence:
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
Principle of fuel staging (Reburning)
ddie most critical parameters of the
systems
primary NOx level
reburn
residence time in reburn
reburn
mixing of
zone
zone
analogy
temperature
zone
the reburn fuel with the bulk furnace gases
to air
SRj. The index
staging,
the stoichiomeliic ratio in the fuel rich
means now
zone
zone,
zone
is
(SR
1)
<
which is
is called
actually the
mathematical
value,
properties.
input of the first stage is

7111
Substituting
reburn
instead of reduction
zone
fuel flcnvs, the oxygen content of the combustion gas from the
first fuel stage, and the fuel

The fuel
reburn
The stoichiometric ratio in the rebum
for fuel
staging.
calculated with the input
same
process for all kinds of technical combustion
are:
In
reburning
zone
the combustion air flow
oiii1JAS
l<3lm?n
by Equation 2.66. the stoichiometric
(2.66)
ratio in the
becomes
5T?r-
rJliSRiASimn,
rn{AS[mm
m2AS2r
(2.6'i
CHAPTER 2.
42
ddie fuel
of the reburn fuel stage
input
be calculated from
can
an
balance, resulting
oxygen
in
Vi
rhi(SR[
m2
Dit
more
practical parameter often
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
ddie reburn fuel rate
can
easily be determined if the fuel inputs
arc
known.
link between the reburn fuel rate and the stoichiometric ratio in the reburn
fuel
mass
flows.
Assuming
reburn stage then results
the
flow of the first stage to be t, the
mass
RFR
=
stoichiometric ratio in the reburn
SR,
zone
is basically
the
mass
flow of the
(2J0)
Figure
properties:
(2.71)
( Lm}\ ( \S2
\-TirR) \IH\2J \Aîm:
RFR
stage (SR l) is known, the
function of the fuel
^TL^
The result of this relation is visualized in
stage
the
zone aie
LH\\
ratio of the first fuel
However,
v=1Tfr lhv2
However, Provided that the stoichiometric
is
'
as
7112
first fuel
rcA
(2-68)
qp7~T5
'
The stoichiometric ratio of the
2.24.
It influences the amount of icburn fuel necessary for
key parameter.
creation fuel rich conditions in the reburn
zone
significantly.
In the field of power
generation, reburning is going to be a commercial technology

providing about 60% NOx ieduction m the flue gas from coal-fired utility
boilers. Figure 2.25 illustrates the application of reburning to an utility boiler.
However, research is going on and Advanced Rebuning technologies (AR) has been
developed, an integration of basic reburning with natuial gas and N-agent injection. The
capable
ot
effect of the
pounds.
N-agent s
may
even
be enhanced
The main featuies of Advanced
by the
Reburning
use
m
of promoters, i.e. sodium
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
the burnout air,
Lower
ddie
(SRftd) 99)
one or
and/or
two
locations,
temperature in the rebuimng
principles
2.7, accoicling
of the different
to
(Zamansky
including
in the
churning
zone,
along
with
downstream of the burnout air injection.

zone
Advanced
et al.
1997).
provides
Reburning
bet ten
NOx reduction.
pioccsses
aie
summarized in liable
2.6.
43
1.5
0.2
LHVi/LHVÎ.O
LHV1/LHV2
0.3
1.8
0.5
RFR FT
Figure
2.24: Relation between the stoichiometric ratio
reburn fuel rate
(SRj)
in the reburn
(RFR)
Table 2.7: Advanced
Reburning (AR)
AR Technology
Description
AR-Lean
injection
of the
variants
N-agent along
with the burnout air
AR-Rich
injection of the N-agent

the
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:
Application of the reburning technology
to
coal-fired
utility boiler
Chapter
Literature Review
About the Literature Review
3.1
chapter
This
summarizes the actual base of
for NOx control
staging
reported
The focus is put
present fundamental and applied research, experimental

reports where solid fuels
are
Of course, there
this
chapter
Air
Air
staging
conditions.
more
two
ah, 1998). However,
terminates the combustion
optimum
by
air
from
(Takagi
species with
the
stoichiometric ratio in the reduction zone,
nitrogen
content have been identified
the most
as
was
et
al.,
premixed hydrocaibon
flame
used to simulate the fuel
1979).
zone
(propane) doped
nitrogen
reached that
was
was
increasing nitrogen
content.
with
is about 0.72 to
At lower stoichiometric ratios
saturated
independent of
the added
For HCN and NH3 the concentrations increased with
stoichiometric ratio and with

zone
as
The second
staging.
NO concentration in the reduction

content.
to increase at
contribute to the NO reduction.
more
the oxidation of residual combustible
stoichiometric ratio for
reported
the reduction
decreasing
indicates that at low stoichiometric conditions the
operating conditions such
different amounts of Nip which
nitrogen
With
point where the Nil3 and HCN concentrations begin
important parameters for
NH3
et
ratio, the NO formation decreases. Further diminishing of the stoichiomet
temperature levels, fuel types and fuel
fuel
interest
stage combustion where the fuel is converted under fuel rich
amounts. This phenomena

products Nfp and HCN do no
as
(Smoof
The fuel rich combustion suppresses the NOx formation.
burnout, air. The
0.75
special
information about the different effects and aspects in
significant
The
Of
modeling.
techniques.
means
ric ratio leads to
stage
or
Staging
stoichiometric
fuel-N
staging and fuel

references which
dominant.
other reviews about NOx control
intents to present
both combustion
3.2
are
are
air
on
knowledge concerning
in literature.
Lowering
decreasing
the temperature in
resulted in the decrease of NO emission but in increase of HCN and
emission, ddie HCN and Nip
originating
and decreased in the burnout stage, i.e. after
15
from the fuel rich combustion stage burned
injecting
the burnout air.
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
comparison with non-hydrocarbon flames (CO
scarcely
compound
any HCN
zone
with added NH3 showed
and that the residual
lower than that, of HCN. The
higher
conversion rate of HON into NO
difference of fuel-NO formation between
non-hydrocarbon
hydrocarbons
with
was
compared
the characteristic
with NH3 at fuel lean conditions in the burnout stage may

and
nitrogen
NH3. ddie conversion of NH3 into NOx in the second combustion stage
was
remarkably
formed in the reduction
was
H2)
4-
explain
accompanying HCN
formation
flames without HCN formation. Kinetic calculations confirmed this
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,
80% for brown coal compared
0.7 to 0.75. Similar results
liquid fossil
fuels
were
(petroleum
staging ranged from 68%
for bituminous coal to al
to mist aged combustion at a stoichiometric ratio of
(England ef ah, 1980) for

liquids) as Figure 3.1 shows.
earlier from
reported
oils and alternative
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
(air staging) (England
et
al.
0.90
primary
3.1: NOx emissions of coal-derived and shale-derived
tion conditions
An
0.70
zone
liquids under staged combus
1980)
important aspect for air staging is the distribution between volatile nitrogen and coke
47
AIR STAGING
3.2.
nitrogen. Foi low

lot of
reactive coals the conversion of
nitiogen
in the reduction
the conversion of fuel
to volatile species is
an mcicase
Low leactive coals also shows
the second combustion stage.
tempeiatuie
nitrogen
remains in the coke and contiibirtes to
zone
nitrogen
than
high
different
low,
i.e.
of the NOx emission in
sensitivity
to the
reactive coals. With
to NO increases for low leactive
increasing temperature
coals, whereas for brown
increasing temperature clue to the higher formation

temperature range investigated was fOOO0 -1300C. However,
coal the NO emission decreases with

rates of
reducing species,
optimum
foi all coals the
in the reduction
Air
an
stoichiometric ratio in the
optimal
0.15%)
and for
However, the fuel

demonstrates.
was
slightly
from
reported
primary
zone
chipboard (N-content 1.96%).
nitrogen
has
shifted towards lower values with
zone.
combustion with wood fuels is
staged
content
ddie
great influence
(Keller, 1994).
i.e.
Nip
as
to
foi the NO reduction
were
Responsible species
optimum NOx i eduction was
the selective non-catalytic reduction
reducing agent the temperature level
attributed to the presence of

zone.
(SNCR)
identified
found
hydrocarbons (CHi)
as
as
as
3.2
Figure
amino deriva
1100 to 1200C.
of NOx in the flue gas with
is about 250C
higher,
ddie difference
was
at fuel rich conditions in the
the formation of HCN and other
They promote
chips (N-
independent of the fuel nitrogen.
the NOx emission levels
on
tives. The temperature range for
Compared
He also found
of about 0.7 for wood
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
3.2: Influence of the stoichiomeliic i.itio
for different wood fuels
(Kellci,
199
1)
(T\
0.6
111
117tfC
the
1.2
eduction
residence
zone on
time m 1
1.4
the NOx emission
eduction
zone
0 3- 6
s)
48
LITERATURE REVIEW
CHAPTER 3.
Staging
Fuel
3.3
Optimum N()x
reduction
performance
typically achieved when the reburn zone is oper

ratio, which is slightly fuel rich. NOx reduction
is
ated at about 90% of the stoichiometric
adjusted by varying the reburn fuel rate, typically over the

total boiler heat input. Up to 95% NOx reduction was achieved for
can
range of 10-25% of the
be
combustor
using
Advanced
Fundamental research
were
done
on
on
Reburning technologies (Zamansky
fuel staging
350 kW test
facility
was
reported
et
high sulfur coal-fired

ah, 1997),
a
(Kolb, 1990).
from
The
driven with various gaseous fuels.
for maximum NOx reduction
zone
experiments
The optimum
was
found to be
between 0.84 and 0.92 for all test conditions.
Of
special
interest
the reburn fuel
on
the
are
the
investigations
about, the influence of the
nitrogen
content of
NOx emission because many reburn fuels considered contain
nitrogen (oil, coal, biomass).

nitrogen
adding NH3 to natural gas. Figure 3.3 shows the NOx
content of the reburn fuel
ddie
ral gas with and without NH3
as
was
some
simulated
emissions after burnout
using
reburn fuel. The addition of 3% NH3 shifts the
by
natu
optimum
higher values and simultaneously improves the NOx reduction ef

At
fuel
rich
ficiency.
(SRr< 0.85) and at conditions close to stoichiometry (SRr>
very
0.96) the positive effect of the fuel nitrogen may turn into a negative, meaning that higher
NOx emission result. The concentration of NH5 after the reburn zone is significantly
higher at fuel rich conditions when NH3 is added. Concerning the reburn fuel properties
Kolb concluded that the a high hydrocarbon content and a high nitrogen content are both
stoichiometric ratio to
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
of the reburn fuel
0*
0.90
on
HCN emission after burnout

ratio in reburn
zone
the
0.95
NOx, NH3,
(left) and after reburn zone (right) versus

(Kolb, 1990) (mam fuel natural gas, lebmn fuel natural gas
T, 1300-1330e, residence time in reburn
Further
/one
0 8s.
and
stoichiometric
doped
with NH3.
A>=SR,)
optimization of the NOx reduction potential
was
achieved
by adding H2 (up
to
3.3.
FUEL STAGING
25%)
to the natural gas
49
doped
with 3% NH3
(Kolb
Sybon, 1992). By adding
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
the IE addition effectuated
Expeiintents
have confirmed the

tested and
were
stoichiometry
reburn
zone
of coal
viability
reburn fuel
as
natural gas
using
in the reburn
zone
as
3.4 shows the data obtained for the
Figtue
The icsiilts indicate that the
main fuel
is close to 0 9. The authois
by the addition of
stoichiometry
representative boiler conditions

(Moyeda ct ah, 1995). Several coals
to simulate
with natural gas.
compared
different reburn fuels
improvement.
facility designed
scale
pilot
on a
additional
110
more
supposed
reburn fuel
(coal)
NOx emission since the additional fuel onlv contributes nitrogen

additional NOx
provide
it does not
that
optimal
decreasing
the
increases the final
to the reburn zone, but
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
NOx emission for different reburn fuels
residence time
lebmn
/one
400
ms)
of NOx emission for low-rank and

less effective.
effective
as
(Morgan
et
high-rank coals to that of natural gas as

geneially pei form equivalent to natural gas, while
Further results suggest that coals with
reburn fuel and generate
is beneficial for the char burnout.
1997)
10
stoichiometry
100 ppm NO
reburn fuel indicates that low-rank coals
high-rank
L.
09
The
same
char that is
conclusions
ah, 1998). ddius. fuel properties
can
are
more
higher
volatile
reactive which
reported from (Liu
have
significant
ct
inlluence
ah,
on
reburning performance.
Concerning
the
primary NOx
level
they found that
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
observations foi the

et al,
with coal
1997).
was
lebmning
with
pulveiized
For low-NOx burners that
found to be not suitable,
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
conditions in the reburn

ferent
Rapid mixing enhances the reaction processes;

a disadvantage since poorer mixing of the reburn
form fuel rich pockets in the reburn zone, which
products
may
therefore improve NO reduction and prevent oxidation of
can
(Cha
to NO. The results from
i.e.
perfect mixing,
in the reburn fuel
hypothesis.
'
60
nitrogen
al., 1998) comparing finite-rate mixing and instantaneous
et
flow confirm this
plug
comparisons
mixing
between dif
and furnaces.
may also prove to be
fuel and the combustion
to the
coupled
is
zone
Therefore, it is difficult to make
zone.
experimental systems
rapid mixing
but
time in the reburn
optimum residence
the
general,
'
"
A
A
"c
20
T5
-20
>
200
400
Primary
zone
efficiency
(Alzueta
primary stage has
et ah.
1997).
In this
concentration to the reburn
or
case,
zone
nitrogenous species at the outlet

of NO in the primary zone.
1995).
ah,
coal
as
primary
and different
Figure
3.6 shows the
different reburn fuels.

lowest NOx emissions
solid fuels
fuels
no
minimum
stoichiometric ratio.
of that
zone,
are
it is
19)
on
the NOx reduc
used
nitrogen
dependent
are
as
on
reburn fuel
the inlet NO
low concentration of
to minimize the formation
reported by (Kicherer
on a
(natural
et
ah, 1991) and (Rdiger
facility using pulverized

pyrolysis gas), liquids (light, fuel oil)
(coals, biofuels)
as
gas,
reburn fuels.
emissions for bituminous coal combustion
highest
zone
of 0.8 to 0.9.
detectable, but the NOx emissions decreased with
This different behavior
points
on
the
using
volatile content reached the
was
0.5MW coal combustion
resulting NOx
a
negligible effect
impoitant
The reburn fuels with the

at
the overall NOx reduction for two
the final NOx emission is
fuel and gaseous fuels
pulverized
(ppm)
and therefore, in order to obtain
made
were
1200
SR,= 0 94, EFB
other fuels without
Experiments with different reburn fuels

ddie tests
on
1000
exit NO concentration
when natural gas
__1__J
800
primary NO concentration
ah, 1997) (SRi l 01 1 03.
(Yang
et
The NOx concentration of the
et
600
3.5: Effect of the
Figure
bituminous coals
tion
one
hand at
For the
decreasing
mixing prob-
FUEL STAGING
3.3.
lern, and
on
51
the other hand visualizes the effect of the
heterogeneous
reactions of the char.
of the lebum fuel,
by homogeneous
leactions.
reduction
potential
differences in the
the reburn
zone
as
gaseous
devolatilization and the
or
by
the volatiles
It is theicfore necessary to piomote
release and uniform distribution of the volatiles.

same
delay
The main NOx ieduction is caused
Then,
liquid fuels. Other experiments showed that the
resulting NOx emissions almost disappeared
at
longer
residence times in
which compensate the time for devolatilization.
NOx emissions of flames using different reburn fuels (Kicherer et ah.

(initial (bituminous coal onh) 585 ppm NOx SRi= 1 1, residence time in lebum zone 0 6-1 2 s)
3.6:
Figure
chemistry of reburning
(Kilpincn et ah, 1992). ddie
The
was
rapid
solid reburn fuels may have the
natural gas
(methane)
in coal fired boiler
investigated by
on
chemistry
ideal, isothermal plug flow
effect of different process parameters
investigated by applying
complex
reaction scheme to
1994)
was
the reburn
conditions.
With respect to
stage
arc
reburning.
NO and 02.
the most
Important components in the
The influence of the
piimaiv NO emissions
gas of the first fuel

on
the emission of
total fixed
increases
the
nitrogen is illustrated m Figure 3.7. The relative TFN reduction efficiency

eleaily with increasing piimaiy NO concentration. Consequently, reburning has
greatest potential for combustion systems with
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
higher primary NO.
Other calculations where the stoichiometric ratio and the NO concentration of the first
stage
a
was
kept
constant showed that the
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
optimum stoichiometry toward highei stoichiometiic

reduction
For
is
ratios.
Howevei,
the maximum TFN
relatively independent of the temperatme
reburning
with pure methane, the NO reduction
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
the reactions of NO with

reacts
NO -^ HCN
^N
UNCO
>
NH, -^ N2
(3.1)
CHAPTER 3.
52
Also the reactions of NO with CO and H
position
reactions,
NO
reburn
paths for
(HCN, NO, NII3)
i>
^-T
N2
(3.2)
NO-Z+N ^T
N2
(3.3)
HNO
NH
the conversion of the
reaction
zone
radicals, both products of the methane decom
found to be effective.
were
NO
Important
LITERATURE REVIEW
to N>
HCN
in the burnout
NCO
>
(3.4)
N2
remaining fixed nitrogen

zone were
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
PRIMARY NO CONCt NI RA HON 'ppm
Figure
zone
m
3.7:
Calculated emission of total fixed
NO concentration
cburn
0 5
zone
The burnout
complete
stage after the reburn
possible
from the reburn
zone
fly
has two tasks.
ash.
vs
primary
time
Fiist, it is responsible for the
Secondly, it burnout conditions should
NOx formation.
burnout
design
(see
is
the combination with
et
SNCR
technique).
othei parameters such
as
However, the
N>0 and CO
optimal reduction
emissions.
of NO must be balanced
At low temperatures, the burnout
becomes less efficient and the

be
zone
05, SRi=0 9, Tr=1700K, lesidence
staged an supply as proposed by

ah, 1996). Low tempeiature burnout undei slightly fuel lean conditions
favorable, because NH3 and HCN can act under these conditions as reducing agents
for NO
by
nitrogen
ah, 1992) (SRj
burnout of the flue gas and
(Kristensen
is
et
s)
suppress thermal
(Kilpinen
decomposition of N2O becomes slow, i. e. N2O emissions may

piobable. Thciefoie, burnout at 1 datively high tempeiatuics, meaning 1000-1200C,
with
staged
air
supply
may turn out to be
moie
efficient.
Chapter
Facility
Research
4.1
Design
research
new
facility
designed
was
to
The idea for the
investigate
staging and fuel staging
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
fixed bed furnace.
new
from the first,
combustion
of the
into the furnace
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
of the second grate is
provides
an
The heat transfer
adapted
is equal.
injection
also has several
At the
part
entrance a
mixing
static
highei
the othet hand.
on
protected by
mixing
the lebuin
passing
keeps the leburn
on
at
the heat
injection of
different locations for
at
zone
low temperatures.
(0.4
sampling
the burnout air.

to 2
s).
4.2
The
Accoiding
ddie reburn section
and othei measurements.
the top is the burnout segment which leads the gases further to
exchanger
no
zone.
zone
Figure
The reburn
composition of the insulation layeis.
levels, different lesidence times leign
openings
It forms the reburn
element which is shown in
of the gases before
be influenced bv the
can
The furnace has

an
straight plug
The theoietical power
gas flux.
section of the facility.
interesting
the boiler unit. The lower part of the boilei unit

upper
bricks.
by
watci cooled shell which
The foith clement
is
approximate
The second understoker is
reburn section has tluee levels of nozzles for the

to the
firing
boiler unit, which
The minimize the heat loss of the combustion gas the cooled surface
enhanced
element has also
to
components
the whole
conventional small understoker furnace
to the
Idle third element is the most

zone.
stacked and
hand and the second fuel stage
most of the understoker box is sheltered
reduction
are
design of
and other flow anomalies.
of both understokei systems
water cooled shell.
or
line, ddie
equipped
secondary air. The second clement contains the burnout
primary and
chamber of the first stage

The
of four elements which
dead
preventing
supply for
4.1. The main
Figure
top. The chosen alignment tries
ddie first element is the first
with
second fixed bed.
understoker grates build up in
is connected lateral at the
flow of the gases,
creating
research facility is shown in
is
designed
where the flue gas
automatic ash removal
ash box. ddie ash of the second stage has
to
53
is
as
combustion chamber. The
cooled down to 200 to 250C.
ddie ash of the first stage is collected in

be icmoved manually after 8 to 12 hours
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
that the oxygen content in the burnout
probe type BOSCH LSM
way that the oxygen content follows
The fuel
11.
For fuel
set value.
zone
(position 6)
feeding
staging.
then is
is measured
regulated
stage is controlled within
the oxygen content and thus the stoichiometiic ratio of the first
a narrow
range. Otherwise, the amount of reburn fuel which is necessary to create
rich
reaches
zone
Howevci, the
values.
high
possible
ddie reburn fuel of the second

in the reburn
stage
is
pressure in the furnace and
save
Operation
facility
shown in
Figure
A Conventional
B Air
according
guarantees
as
fuel
small
as
the desired stoichiometric ratio

the way that
legulated
second
The research
churn fuel should be
probe,
complete
burnout
The oxygen content in the flue
stoichiometiic ratio between 1.5 and 2 0.
gas is also measured continuously with
4.2
handling.
closed
The amount of burnout air is
zone.
is achieved at
are
amount of
to ieduce the effort for the robinn fuel
the
It, is fundamental that
A flue gas ventilator controls the
conditions.
Modes
can
be
operated
4.3. The modes
(unstaged)
in three different modes. The schemes of these modes

are:
combustion
combustion
staged
C Fuel
staged
combustion
For air
staged
combustion and conventional combustion
Both combustion modes
arc
accomplished by
only
using the upper
one
fuel bed is necessary.
part of the research facility
with the second understoker furnaces.
Conventional combustion
bed.
This
means
means
that the whole combustion air is
given
to the fuel
beginning (SR > 1). Some

complete burnout of the combustion
that the combustion is fuel lean from the
additional air may be
supplied
above the grate for
gas.
staging means that part of the total air supply

the primary combustion zone is fuel rich (SR <. 1).
Air
that
burnout of the gases after the ieduction
Fuel
staging
bustion takes
uses
place
in the first fuel stage, which is
metric conditions
establishing
11 1.3).
(SR
=
given
to the fuel bed the way
The rest of the air is used for the
zone.
the second understoker furnace
mode with the aim of
is
as
the rebuin stage. The main
operated
fuel lean conditions
(SR
com
in the conventional combustion

>
1),
but close to the stoichio
4.2.
Figure
4.1: Research
1. understoker
2),
55
OPERATION MODES
8.
(stage 1),
ventilator,
9.
facility
2.asli
at the ETH Zurich
boX, 3.,4. ventilator,
mixing element,
5.
primary
7. understoker
zone, 6. burnout, zone,
10. reduction zone, 11. burnout zone, 12.
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
Possible opeiation modes of the
Eigm e
13
B. An
staging; C Fuel staging
icsean
h facility
Conventional
combustion,
57
ENERGY FLOWS
4.3.
Flows
Energy
4.3
flows for the
Typical energy
fuel staging are
shown in
average values based
4.1 and
Figure
on
the research
Figure
facility with
ddie values
4.5.
measurements. The energy of the fuel
displayed
input
staging
air
are
and
calculated
is set, to 100%.
recuperated by the boiler, ddie cooling

25% of the input, the cooling system of the
almost 60% of the heat is
staging,
For air
on
experiments
system of the reduction
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
11% of the input.
is about 87% for air
Summarizing,
the
staging.
11 %
2%
t
59%
25%
100%
h
3%0
r"V
4.4:
Figure
For fuel
staging, the
surface is also much
stage plays
an
Energy
flows for air
heat loss to the environment is
larger.
other role
The
now.
cooling
The
of the understoker box, but with
as
staging
higher
since the
area
of the heated
system of the understoker box of the second fuel
meaning
of this
little influence
cooling
to
is to reduce the thermal load
the hot gas temperature
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
cooling system (22(/() and the boiler (37%) is consequently lower

staging. Hence, the lower efficiency of 82.5% for fuel staging is manly clue
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
because of the lower
efficiency
of the boiler.
by
the flue gas
CHAPTER 4.
58
RESEARCH FACILITY
12%
5.5 %
37%
21.5%
h
25
%i
24%
^ 75 %
Figure
4.4
Measurement
For the measurements

The main
flows for fuel
Energy
staging
Equipment
Equipment
Basic
4.4.1
1 5:
on
the research facility
various
of interest is the combustion gas,
object
at different times and locations
during
measurement
its
i.e.
systems
composition
were
the process.
Beside the outputs of the combustion process, the flue gas, the ash. and the
inputs have to be known

parameters that
of what is
one
quantitatively,
would like to have
affordable puts the limits to the
An overview
marized in
velocity,
but it
on
information about for
But the measurement
enoimous
effoit
The measurement
analysis
better
understanding
equipment available
or
point inside the combustion process is possible,

(LDA. LIF, CARS, etc.). However, for the work pre
at any
techniques
parameters and the measuring pi maples used
of combustion
inputs, outputs, and parameters of the process are sum

Indeed, the measmement of the fluid parameters temperature,
sented only "conventional" measurement
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
available. A list of the measured

Table 4.1.
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
the measuimg of the gas
the suction side of the ventilators.
Swiss Federal Laboratories for Materials
testing and Research
velocity
tubes fixed
on
MEASUREMENT
4.4.
EQUIPMENT
Research
Facility
gas
combustion
process
ash
heat
Inputs and outputs of
4.6:
Figure
the combustion process
Table 4.1: Measurement,
Parameter
air flows
gas
tempera!
gas
composition
ures
Measuring Method
velocity
hot wiie anemometer
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
of the hot gas in the combustion
K. S
flow meters and Pt 100
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
train material has to be inert and
surface reactions. However, before any
be filtered and cooled down from about 1000C to temperatures suitable for the
During
the
taken from
a
cooling
a
process,
particulate formation and condensation
fuel lean zone, the
fuel rich zone, components of
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
gas is extracted from
to be
condensation takes
above 200C
occur.
tars, may condensate first, ddie
heated
kept
by
passed. The instruments of the cold analysis
the gas
analysis
i.
incomplete combustion,
condensates then may also dissolve components that
may
analyzed. Thus,
place. According
sampling
measure
to
system until
the cooled and
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
(N,0 NH3 HCN)
chamber
NDIR
(CO
Param
i_
CO
_zzr:
HCD
OAO
<
5 C
CH4 NO)
ii!1
(02)
(H2)
ind
Cold
An other hot gas
lometa, displayed
Figuie
of the ical hot gas temperatme at

of the local gas
111
<
omposition
the gas flow system
within paits of
Hot gas
analysis method used

1 b
(type
second
can
oi
is
Analysis
special
BOSCH LSM
the combined
puipose
11)
absorption
sampling
defined location but also
this
r-" E
Cooling
Ihe suction pyiometei not

a
r_j
condensation
I lginc 4 7
ov erflow
with
no
suction py-
only
allows the measurement
can
be used for the detection
piobe foi O2 detection
With this
be momtoicd with almost
sampling
piobe
delay
is
installed
also short fluctuations
time
4 4
MEASUREMENT
ceramic
61
EQUIPMENT
tube
Figiiie
4 8
Suction pyiometei with
piobe
foi 02 detection
CHAPTER 4.
62
Flue Gas
4.4.3
ddie due gas

of CO,
NO2
was
Analysis
sampled right after the
CO2, O2, NO,
is determined
original
the difference of two
by
facility,
ddie content
sampling
continuously.
sampling channels. One channel contains the
NO2. The gas oi the othei channel
NO2 is converted
of the flue gas
boiler exit of the rcseaich
and NO2 in the dry Hue gas is measured and lecorded
gas. i.e. NO +
wdiere all the
RESEARCH FACILITY
to
passes first
NO before the water is removed
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
4.9: Flue gas
sampling
Chapter
Experimental
About the
5.1
Experiments
Wood Fuels
5.1.1
ddie fuel has

were
Results
strong influence
chosen for the
wood
UF- chipboard
on
the NOx emission. Theiefore, two types of wood fuels
experiments:
chips
important fuel types used namely natural wood from forest

harvesting and industrial wood residues. The two fuels differ especially from the nitrogen
content and from the water content. LTF-chipboard (EF= Urea Formaldehyd) has a very
The fuels represent the most
high nitrogen
the
glue
for the
experiments
relatively
was
on
content
small
pressed
the
to
characteristics
can
to native wood because most of the
pieces
are
guessed
with
chipboaid.
from
cm
Figure
length by
The size and the
shape of the fuels used
5.1 and 5.2. The wood

an
chips
ordinal y wood hacker.
diameter of about 8
the transport system
grate by
nitrogen origins from
cm.
But the
briquettes
(sciew feeders).
were
The
cut into
chipboard
were
crushed
The individual fuel
listed in Table 5.1.
fusibility of
concerning
be
ol about 5
briquettes
to the
way
dTe
compared
that holds the matrix of the
ash is also
biomass fuels. Ash
important fuel characteristic and of particular interest
an
sintering and slagging
disturb the combustion process and
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).
However, for other biomass the
composition
oi
whether they
components. Herbaceous fuels for example have melting points

they contain relatively high
compositions with
low
amounts of various
melting points
63
inoiganic
aie
melting point
mixed with other
at 800 to 900C because
substances which
can
form
new
EXPERIMENTAL RESULTS
CHAPTER 5.
64
Figure
5.1: Wood
chips
Figure
dble 5.1: Proximate and ultimate
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
of bed ash from the
investigated
fuels
Ash op
Ash
Wood Chips
UF-Chipboar
128CFC
1230C
Hemispherical temperature
13UTC
1260O
Fluid temperature
1360C
1290C
Melting
range
of
ash
Initial deformation temprture
of
DIN 51730
65
ABOUT THE EXPERIMENTS
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,
the stoichiometric ratio in the reduction
parameter. With SRr the total stoichiometric ratio

not be
SR for
was
zone
SIT
was
the
only variable
influenced too, since both could
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
could not bo influenced.

ddie most
variable parameters for fuel
important
the temperature in the reburn
kept
constant for all the
as
are
the reburn fuel rate and
The stoichiometric ratio of the first fuel stage
zone.
experiments
residence time in the reburn
staging
which makes the
zone was
vaiied
only
experiments
for the
comparable.
more
experiments
with
was
dTe
UF-chipboard
main fuel and reburn fuel.
Table 5.3:
Experiments and parameters
Experiment/ Par ameters

Fuel
Rebvrri
VARIABLE
FIXED
fuel
Conventional combust ion
(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
fnst fuel stage,
to the
chips
chips
reduction
or
cbuin
1.2
1.2-1.3
2s
s
35 kW
35 kW
zone
initials, the following abbreviations
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
UF-chipboard is reburn fuel

wood chips are reburn fuel
UF-chipboard is reburn fuel

fuel, wood chips aie reburn fuel
text and
66
CHAPTER 5.
dble 5.4:
Dependencies of
the most
important parameters from measured values
Parameter
Function
SRt
O2
SR
of
conccntiation
pnmary
zone
O2 concentration in flue gas

flows, SRl. SR, composition of fuels
SR,
air
and moisture contents

RFR
air
flows, SRl. SR, composition of
moisture contents,
Figure
5.4 picsents
an
example of
heating
fuels,
values
the time history measured for the most
parameters temperatures, stoichiometric ratios,
emissions,
fuel
the icburn stage from
staging, ddie figure shows
level to
also be
higher
seen
heat up
while the first fuel
which
overlap
The stoichiometric ratios

on
the
as
stage
general
well
as
phase of
given
the most
calculating
in time
the reburn fuel rate
in the
Appendix B 3.
important parameters
possible
An
is
are
calculated parameters based
errors
due to the measuiement and
overview on
the measured values used for
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.
measured parameters. An analysis of the
the tolerance is
during
temperature
one
already stationary. Fluctuations
is
important
and reburn fuel rate
0.5
5.3: Relation between SR and
E0
SR[-]
1 5
2.0
SRt for the experiments wdth
2.5
air
staging
5 1
67
ABOUT THE EXPERIMENTS
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
expcimient with fuel staging UE/W,
1i
02 15
02 00
time
in
horns
CHAPTER 5.
68
Measurements
Temperature
5.1.3
ddie temperatures in the test facility
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
due to the heat
For the deteimination ol this influence, the temperature in the
also measured wdth
suction pyrometer wdiich eliminates the radiation
effects.
5.5 shows the difference between the tempeiafure measured with the suction
Figure
pyrometer:
turned
once
The
on.
80 to 100C
without suction, i.e.
comparative
higher
as
simple thermocouple,
measurements showed that the real gas
than the temperature measured with
Since all the gas temperatures indicated in this eport
ples,
and
the diffeience to the real value has to be
kept
once
with suction
iempeiature is about
simple thermocouples.
aie
measmed with thermocou
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]
5.5: Hot gas measuiement with suction pyrometer in the rebuin
zone
69
CONVENTIONAL COMBUSTION
5.2.
Conventional Combustion
5.2
The upper part of the research
facility
can
be
operated separately
as an
understoker furnace
(see Figure1 4.3). Conventional, unstaged combustion

primary air is equal or higher than the stoichiometric amount,
in conventional combustion mode

means
that the amount of
ddicrefore, the stoichiometric ratio in the
primary
zone
already higher
is
than
I, the
combustion is fuel lean.
Figure
chipboard
5.6 and
Figure 5.7 show the NOx and CO emissions of wood chip and UF-
combustion. The
figures
show the neat influence of the stoichiometric ratio
on
the NOx and CO characteristics. The NOx formation decreases with lower stoichiometric
ratio, while the CO emissions
inciease at low- stoichiometric ratios.
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
5.6: NOx and CO emission of conventional wood
ddie CO emissions indicate

scale reactors much
more
furnaces exists
an
characteristic of the research
mixing problems
typical characteristic
optimum stoichiometric
zone
facility.
950-1020C)
In technical
and thereby hinders the
the CO emissions increases
complete
inhomogenitics. ddiis discrepancy
each furnace, ddicrefore, in tecdmical
and
of
ratio wdiere the CO emission is lowest.
stoichiometric ratio is increased further, the

the burnout
combustion (Tt
oxidizer than the stoichiometric amount is needed for
burnout of the gas because of
from the ideal behavior is
typical
chip
If the
of air lowers the flame temperature in
surplus
complete oxidation of the
gas. As
consequence,
again.
Summarizing, the emission of unburned compounds, represented by CO, depends ba
sically
on
the furnace
design,
the operation conditions and
idealized CO characteristics of
typical
furnaces.
on
the fuel.
Figure
More research and data about
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)
++
-200
-
Z
-
-^WWPPPW1-!
100
"Tw
1.5
2.5
3.5
SR[-]
Figure
5.7:
NOx and CO emission of conventional UF-chipboard combustion (T(
970C)
burnout of wood furnaces
can
be found in
(Nussbaumer, 1989).
10000
ideal furnace
manual furnace with
good
design
automatic furnace with
good
design
05
1 5
SR
Figure
2 5
3.5
5.8: Ideal and real CO emission charac teilst ic of wood furnaces
930
71
CONVENTIONAL COMBUSTION
5.2.
The
ratio measured is lower for
optimum stoichiometric
UF-chipboard (~ 1.5)
than
that beside the furnace
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
for conventional wood

combustion of
but f 000
by
chip
gas, the
complete burnout of the
combustion
are
300mg/Nin3
about 280 to
about
UF-chipboard produces
or more are also possible.
NOx emission achieved
oOOmg/NnE
NOx
at
at,
11% 02-
The
optimum conditions,
mg/Nm3
An
important
the
Figures
hint to the
5.6 and 5.7.
probably
easiest
If the furnace is
primary
operated
measure
at
for NOx reduction is
optimal stoichiometric
minimal CO emissions the NOx emission may be lowered, too.
But,
between the NOx emission and the stoichiometric ratio is also
furnace, the
fuel
same
produces
different NOx emissions
on
OJ
800
Y">
UF-chipboard
Dwood chips
^-*s
since the correlation

characteristic of the
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
NOx emission of the first stage during reburning (wood chips
UF-
TC=11L0C)
The NOx emissions measured in the burnout

are
TC=960C,
shown in
Figure
show similar trends
5.9.
zone
of the first fuel stage
ddie emission characteristics for wood
again,
ddie NOx emissions decrease with
chip
during reburning
UF-chipboard
and
decreasing
stoichiometric
ratio.
However, the trends

tional combustion.
are
less
progressive compared
to the
The NOx emissions of the first hid stage
stoichiometiic ratios for both
experiments with
conven
are at higher levels at low

UF-chipboard and wood chips. Additionally, the content on
CHAPTER 5.
72
unburned components in the gas is much

arc
up to
3g/NnE
at
higher, ddie measured CO
11% 02. Since the operating conditions for both fuels
identical, the difference in the NOx emissions may be due
design wdth smaller
emissions for
residence time.
to the
example
wTere
almost
different combustion
Basic research
further work
The
on
on
wood combustion with air

and
testing
(Salzmanu
in
reported
for NOx Reduction
Staging
Air
5.3
is
73
AIR STAGING FOR N0X REDUCTION
5.3.
improving
this
and Nussbaumer,
1995)
experiments with air staging carried
dation of the known
on
the
one
and for
hand,
presented by (Keller, 1994).

under practical conditions
(Salzmanu and Nussbaumer, 1998).
staging
primary
was
measure
and
out at the research
comparison
facility
with fuel
serve
staging
on
as
vali
the other
hand.
the
Again,
(SR,)
has
prcwided
experiments demonstrate that the stoichiometric ratio in the reduction
distinct influence
that the other
(temperature,
mean
on
zone
the NOx emission of the combustion process
(Figure 5.10),
also
accomplished
important
residence time,
conditions for NOx reduction
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
very low stoichiometiic ratios
may be assumed between 0.7 and 0.8
chips the optimum stoichiometric-
ratio
seems
to be
as
found
slightly
are
the NOx emissions

250
mg/Xm3)
missing,
the
optimum
by (Keller. 1994).
UB'-chipboard.
For wood
lower than for
But the minimum is not that distinct.
Nevertheless, the experiments confirm the
by
air
staging. Figure
5.11 opposes air
staging
important role of the fuel rich
zone
created
and conventional combustion and makes the
NOx reduction potential of air staging clearly visible. The NOx emissions for air staging
correspond
to the values in
zone
(SR,)
(SR).
Figure
5.10, but this time correlated to the
corresponding
total
Since the ratio between the stoichiometric ratio in the reduction
and the total stoichiometiic ratio is almost constant, the trends of the
points
74
are
CHAPTER 5.
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:
Comparison of the N()x
emissions from conventional combustion and air
AIR STAGING FOR N0X REDUCTION
5.3.
ddie experiments show that wdth air

tion
can
be reduced below
staging
75
the NOx emissions of wood
100mg/Nm3, meaning
NOx emission of UF-chipboard combustion

reduction of more than 72%.
is
ieduction of
lowered to about
more
chip
combus
than 65%.
175mg/Nm3
dTe
which is
Fuel
5.4
5.4.1
for NOx Reduction
Staging
Influence of the
Chemical reactions
tems, there
usually
are
Temperature
exists
staging efficiency
about, lOOO^C and
in the Reduction Zone
strongly affected by the temperature. For complex reaction

small
temperature range only that leads
distribution. These fundamentals

fuel
CHAPTER 5.
76
apply
increases with
more,
also for fuel
staging.
more
test
in literature the
reported
facility
sys
product
in the reduction zone,
experiments on the
ddie aim of the
the lower temperature range wdiich may be
As
to the desired
was
to
usually
investigate
relevant for the combustion of wood and
wood residues and fuels wdth low ash fusion temperatures.

For
practical
fuel arise.
the
are
use
the main hiteiest is
using
the
same
fuel both
as
primary fuel
and
as
additional costs for the reburn
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
Since NOx control is
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
5.12: Influence of temperature in reburn
(information
about the
A summary of the
presents Figure
experiments gives
dble
zone
on
NOx emission for different, RFR
5.5)
experimental results for fuel staging with different fuel combinations
5.12. The measured NOx emissions
perature in the reburn
zone
are
for different reburn fuel rates
displayed
(RFR).
in function of the tem
ddie CO emissions of the
evaluated measurements
with
few
clearly demonstrate
measurements
500mg/Nm3
at least below
were
250mg/Nm:!. Although only
settings
measured,
were
11% O2, but usually below
at
that, the NOx emission
UF-chipboard
of
lOOmg/NnEat
than
level for wood
can
with air
chip
t20mg/Nm3
cases.
significantly
combustion is
comparable
to the
But above 700C
optimum temperature
one
are
potential
fuel staging
staging.
The
about, 25% lower than
to be above
begins
to be effective.
chips at wood chip
seen
A decrease of
with the measured
combustion
with wood
800O for all
(W/W)
seems
to
minimum at about 800C.
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
ddie data show that with all fuel combinations

duced. That
by using
means
wood
zone
indicate
that the NOx emission from
chips
reburn fuel
as
as
and the reburn fuel rate
Although
most of the data
0.2 at
UF-chipboard
alternative.
arc
presented
the most
In any
the NOx emissions

combustion
case,
can
are
re
be reduced
the temprt
lire
in the
important parameters.
decreasing NOx emissions, some points also

potential. For the reburning with UF/W for example,
points
limit of the NOx reduction
minimum for RFR
5.4.2
are
cannot be
Table 5.5: Data to the fuel
reburn
The emission
measured.
measured with air
seems
range
the NOx reduction
already
with
data, although
a
Minimum NOx emissions
staging.
the reduction
towards
temperature above 850C is identifiable.
Influence of the Reburn Fuel Rate
Beside the temperature, the stoichiometiic ratio in the reburn

tion of the reburn fuel rate
NOx reduction. At
a
be decreased
trends
reached, wdiereas for wood chip combustion less
temperature between 800 and 900C
The lower end for the
visible, ddie
to decrease.
already begin
are
NOx emissions reached for the combustion of UF-chipboard
pass
are
some
reburning.
Around 750 C the NOx emissions

for
77
FUEL STAGING FOR N0X REDUCTION
5.4.
(RFR)
is the most
given stoichiometric
zone
(SR,)
parameter for
ratio of the first fuel stage,
lower stoichiometric ratio in the reburn
ratio in the reburn
important
zone
zone,
and the measured
ddie
which is
a,
func
characterizing
higher
RFR
the
means
elation between the stoichiometric
NOx emission illustrates Figure 5.13 for the
experiments with UF/W. ddie Figure also shows the influence of the temperature
in the
CHAPTER 5.
78
reburn
zone
creases
and
increasing temperature the NOx emission de

the dependency from the stoichiometric ratio becomes less distinct. However,
on
the NOx emission.
With
optimum value of the stoichiometric
the
ratio for these
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 5.13: NOx emission versus stoichiometric ratio

formation about the experiments gives Table 5.5)
Figure
UF/UF.
0.25
5.14 shows the influence of RFR
more
at
750C. With
suitable for NO
higher RFR,
consuming
zone
the NOx emission for
The NOx emission is about 25% lower with RFR
regarded
become
on
in the reburn
0.3
for
UF/W (in
reburning
compared
with
to RFR
the process conditions in the reburn
zone
reactions.
0.25 at twTo different temperatures

Figure 5.15 compares the NOx emissions for RFR
(720 and 850C) for reburning wdth W/UF. The increase of the temperature reduces the
=
NOx emission by
more
than 50%. If the reburn fuel rate is increased from 0.25 to 0.3 at
850C. the NOx emission

The
be abated further.
experiment shows that
fuel is also suitable for
period
can
reducing
of the reburn stage
reburn fuel wdth
contrary which
means
aie
still far
carefully, otherwdse
way
the
content than the main
is that during the heat,up

chips have to be taken into
pioblem
emissions than wdth wood
account because then the conditions
to the
higher nitrogen
the NOx emission, ddie
higher
conditions have to be controlled
from
being ideal. Therefore, the

reduction potential turns ciuickly
that the NOx emission may increase.
54
79
F UEL STA GING FOR N0X RED UC4 ION
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
the expei intents gives Table 5
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
Influence of tempeiatuie and RFR
about the evpeiiments gives Table 5
5)
on
0.25
\0\
RFR
emission
foi
0.3
W/UE (mfoimation
CHAPTER 5.
80
Influence of the Residence Time
5.4.3
ddie residence time of the gas in the reduction
with the
approximated
gas flow, the known
If the air is
residence time is about
geometric position
injected through
the nozzles at
that
the
of about 10%
5/9 r
the NOx emission at,
calculated
position 2,
the
(air
nozzles at
resulting
mean
5/9 r.
related to the temperature in the reduction
genera] trend of
was
of the burnout, air nozzles
the NOx emissions for the two different residence times
Figure 5.16,
In
not measured, ft
The maximum residence time is
and the reduction chamber volume.
position 3).
zone were
zone,
compared
ddie
figure
shows
are
plotted
weak increase of
to the maximum residence time. The
significant, meaning
practical applications.
is identical. However, the difference is not
curves
lower residence time than the maximum could be sufficient for
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
the NOx emission for
Table
5.4.4
The
mean
UF/UF
residence time and the temperature in reburn
at RFR=0.3
(information
about, the
zone
experiments gives
5.5)
Practical
experiments
Experience
on
staging concept with
the laboratory furnace have demonstrated that the

two fixed bed is
factors that have to be mentioned

For the reburn
stage of the
presented fuel
operable and practical. Flowevcr, there

the
regarding
facility, an
are
few
practical experience.
feeding system is used. Due to

this fuel feeding, an asymmetric fuel bed may be created, especially if the fuel is coarse,
blade shaped with bad flow capabilities, ddie result of an inhomogeneous, asymmetric fuel
bed is also
an
test
understoker
asymmetric flow field of the penetrating gas
as
shown in
Figure
5.17.
81
FUEL STAGING FOR N0X REDUCTION
5.4.
well known, of
However,
course.
This
gas follows the easiest way.
resistance, the
Because of the lower
phenomena
is
of the gas is not,
"bypassing"
staging
completely for the gasification of the
following reduction chamber is designed like a plug flow
in
this
of fuel
case
desirable because the combustion gas is not used
reburn fuel. Furthermore, if the
reactions that lead to
reactor, the remaining oxygen in the combustion gas hinders the

NOx reduction. The reduction potential is reduced. Thercfoic,
pyiolvsis
gas and the combustion gas in
accomplished by
an
adequate design of
homogeneous
5.17:
Measurements with
the fuel bed.
Figure
end of the reburn
Shapes of
suction
the reburn
Wood
the fixed bed in
chips
are
in the reburn
used
as
has to be
an
bed
V"
understoker furnace
zone
could visualize the influence of
5.18 shows the measured oxygen concentration at
zone.
zone
of the
zone.
inhomogeneous
bed
probe
complete mixing
better before the lebum
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]
Influence of the fuel bed movement
can
05 46
distinguished. Dining phase
on
the stoichiometric conditions in the
1 theie
is
no
oxygen in the reburn
zone.
CHAPTER 5.
82
All oxygen in the combustion gas of the first stage is consumed.

reburn fuel is effective due to an homogeneous fuel bed. After a
be
The
while,
measured, phase 2 begins. The fuel bed has become asymmetric.
oxygen is consumed
Although
mixing
the gas before
during
the
gasification
of the
oxygen
can
Therefoie, not all

zone.
element is installed above the fuel bed of the reburn stage which mixes
entering
homogeneous again,
the reduction
zone, some
the oxygen in the reburn
created easy passages for the gas

An other observation is that
UF-chipboard
as
oxygen is wasted.
wav
zone
that the
shape of the fuel bed
disappears until the bed
most
reburning. meaning
during
the heat up
period
reburn fuel have to be taken

do
of the
is
more
movement has
again.
of the furnace
temperature ol
at least
not
into
700C.
higher NOx
account.
emissions
Because of the low
take part at reduction reaction
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
process, but passes unreacted the reburn
Then, after the fuel bed is manipulated the
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
real combustion process
on
future
to the model used for the simulations in this
Figure
A
challenge because of its complexity, several approaches

followed. Therefore, a little overview on the possible approaches
are
Modeling
6.1:
Physical
general, comprehensive
can
typically
be
applied
include the
1991):
t urbulent fluid mechanics
gaseous turbulent combustion
particle dispersion/motion
solid devolatilization
heterogeneous
given
here,
fundamentals for combustion models
model that
is
report.
to the
description of complex
solid fuel combustion systems combines several model components, ddie

used for solid fuel reaction models
with different
char reactions
83
key components
following (Bartok
and
Sarofim,
CHAPTER 6.
81
radiation
pollutant formation
ash/slag
formation
ddie characteristic features of

fication.
practical combustion
Simplifications
the
processes
Some of the different ways for classification
fication of the combustion process
on
MODELING
and
assumptions
physical and cdiemical
tion does not
require
be considered
can
processes. However,
complete description
as
have to be made due to
can
be used for t heir classi
listed in dble 6.1.
are
an
The classi
important step for modeling.
missing
obtaining
an
inadequate
or
adequate
information
process
descrip
of all aspects of the combustion process.
Table 6.1: Classification of
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
momentum, energy, and chemical
for
an
mass
infinitesimal fluid element
combustion system in
flow, wdiich
general
the conservation
arc
For the ; coordinate of
species.
is
given by
equations
the fun
of mass,
system, the equations
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
_
ddie derivation of these
dpVjYn
equations
can
0Yn\
_(^_j+Wn
be found in
(6.4)
(Kee, 1978), (Wendt, 1996)
or
in other
literature about fluid mechanics.
When
dealing
wdth
stagnation enthalpy
flows, the
compressible
is often used.
H^h+1-^
(6.5)
Ey"/?"
(6-6)
where
/?
N-l
the
a
enthalpy is of the gas mixture. Assuming perfect
gas
behaviour, the enthalpy
is
only
function of temperature
hn=
(6.7)
cpn(T)dT
/o'o
For
Newton fluid the stress tensor would be
On,
T"
ddie ideal gas
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
6.4 balances the formation and
consumption of
species.
E K'a
Cas molecules
equation
react
that
can
H[Xn]"
A
khk
UlXn]<^ \
n--=l, ...,N
(6.11)
A_l
only wdien they

lead to bond
come
bieakmg.
close
enough
to one another for direct
From elementary kinetic
theory, the
rate
MODELING
CHAPTER 6.
86
expressed
of reaction is
in
required
fraction of molecules that exceed the
pre-exponential
If the
frequency of collision and
form that accounts for both the
A(T)
factor
energy.
A(T)exV>(~yic,
the
(6.12)
approximately
is constant, which is
temperature ranges, equation 6.12 changes with
for small
to the well known Arrhenius
k(\Cj
true
form where k is the rate constant.
ddie set of nonlinear differential
Aexv(^^j
equations 6.1
become
turbulent flows, the
(6.13)
ouly be solved numerically. For

complicated and additional models for
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
that deal with the solution of
and
of the
approaches
approximation
can
be found for
A summary of this literature is
mathematical details to the model
wdde range of time
developed
simplification
the different model
Nussbaumer, 1997).
even
reacting
physical reality.
An
(Ecrreira
and
example
in
next, but without
given
approaches. The models
are
presenting
only introduced by name.
corresponding literature.
computational fluid dynamics
More information about the models has to be taken from the
Publications about simulations of
(CED)
The most
flows
facilities with
practical
may be found also.
popular model approaches used for the analysis of practical chemical reacting
are:
DNS Direct Numerical Simulation

LES
Large Eddy Simulation

Probability Density
PDF
RANS
Function Method
Reynolds Averaged Navier-Stokes equations
Laminar Flamelet Elamelef
PSR/PFR Perfectly
Models,
Stirred Reactor
ID
or
developed
differences
figures
points
are
illustrated in
some
Flow Reactor Model
wdth different aims for different tasks.
wdiere the models
are
compared
The
under different
of view.
computational effoit of the models. Assuming a given

chemistry has to be simplified with increasing effort
calculation, particulailv in turbulent flows, ddiis oppositional behavior is
First, Figure 6.2

computer power it
for the flow field
compares the
means
also demonstrated in
that the
Figure
6.3.
Models that handles
turbulent flows, but concessions to the
highly
are provided.
right
2D
Model/Plug
The models mentioned have been
wdth Persumed PDF
Hence, the
choice of the model.
weighting
of the
high Reynolds
numbers may solve
of the chemical reaction scheme
complexity
importance of
the
chemistry determines the
6.2.
ABOUT MODELING
87
DNS
PDF
RANS
1D laminar
LES
Transport
Persumed PDF
Flamelet
PFR/PSR
numerical effort
Figure
6.2: Numerical effort of combustion models
An other aspect in reaction flow

reactions may
premixed
occur,
ddie
and how
questions
modeling
aie
mixed then.
is the
(Ferreira
degree
of
Nussbaumei, 1997)
and
mixing
wdiether the icactants
are
of the fluids before
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
question that the simu
answer.
chemistry
PFR/PSR
1D Flamelet
PDF
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
PDF
PDF
RANS
LES
DNS
->-
Figure
6.4: Effort
on
chemistry
mixing (Ferreira
versus
and
mixing
Nussbaumer, 1997)
Approach
6.2
dTe aim of the
staging by
concessions
simple
on
is the simulation of the
modeling approach presented

model. Focus is
placed
the model for the flow field
solvable with moderate
to fuel
experiments
chemistry during reburning. Therefore,

keep the model simple and
the
on
necessary to
are
computational effort.
The scope of interest is the influence of the
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
three types of ideal reactors: batch reactor,
are
(PSR).
last two reactors
Since the considered research
arc
of
special
real
plug
facility
interest.
Flow Reactor PFR
flow reactor is
one
of the ideal flow reactors. It is also known
piston flow, ideal tubular, and unmixed flow

the flow of fluid
mixing
approximation of
systems is the
reacting
and mixed flow reactor
continuous system,
6.2.1
ddie
describing
ideal reactor types. There
by
flow reactor
is
way of
through
the reactoi is
with any other element ahead
flow reactor may
occur,
ddicrefore, the residence
or
reactor.
orderly
behind.
but there must be

time in the reactor
no
is
It is characterized
wdth
no
Actually,
mixing
the
same
or
as
by
element of fluid
lateral
the
plug flow,
the fact, that
overtaking
or
mixing of fluid in a plug

along the flow path,
diffusion
for all elements of the fluid.
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
in the PFR. At constant
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
pî
Assuming
(6.17)
const ant pressure and constant volume the energy
c.f + ^
LP
6.17 and
Equation
Equation
6.18
arc
the two balance
simultaneously.
The
(,.18)
'
71-1
which has to be solved
equation becomes
integration
equations of the plug flow
reactor
time / is also called residence time
T.
Perfectly
6.2.2
The
perfectly stirred
throughout.
by chemical
infinitely
This
Stirred Reactor PSR

reactor is
means
reactor in wdiich the content is well mixed and uniform
that, the rate of conversion from react ants to
reaction rates and not
by
convection,
ddie
mixing
fast. Thus the exit, stream from the reactor has the
within the reactor. For constant
mass
flow
through
products
rates
same
are
is controlled
assumed to be
composition
reactor with volume
as
the fluid
V, equation
6.4
becomes
pV^
ddie
holding
time
or
the
mean
-m(r!!-Yl,)+nV
residence time of the exit age distribution of
response is related to the reactor volume V and the
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
Ê(o;:-rX)-^
~~n'
r^-n-n
(it
With h
(assuming
the energy balance of the eactoi
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
that has to be solved,
'
Equation 6.24
is
'
mean
*-
residence time
pV
n-I
ial-equation initial value problem. The only
t.
Furnace Model
6.3
Design
6.3.1
plug
(PFR)
flow reactor
patterns. Although
be
'""->'
nonlinear ordinary-different
free parameter is the
The
T^
dt
case
fluid, by recycling
perfectly
fully
never
the idealized react
approximated by
from the ideal
and the
real reactors
can
of fluid,
by
with
ois
be considerable.
stirred reactor
(PSR)
consider idealized flow
follow these flow patterns many of them may
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.
Many types of model

Dispersion
degree
the
of
models for
backniixing
predictions
have been
example
or
developed t o charact ei ize nonideal flow within reactors.

a plug flow, on top of which is superimposed some
considei
intermixing.
With
varying
of this model will range from
Intensities of
flow at
backmixing
or
turbulence
extreme to mixed flow at
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
the other. The
)(i)--iL
Figure
9
6.5 shows the
output signal of
Is the normalized time
accoidmg
pulse
stimulation of
dispcised plug flow,
(6.26)
The
a
figure
shows the influence of the extent of
mixed flow. For
Tf-
where
to
dispeision
0, the flow approximates
plug
Foi
How
>
oo.
the flow becomes
91
FURNACE MODEL
6.3.
1.0
0.5
0.0
2.0
E5
Figure
6.5: Influence of
Other process models build

reactors connected in series
chain
parallel.
or
mixed reactors in series is shown in

behave
as
There
flow;
plug
are
or
dispersion
flow
network of ideal mixed reactors and
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
parameter models. More details about that
can
other
or
the models
can
be found in
heterogeneous devices.
vary from
one-
dence time distributions
presented study
bases
ddie focus of the
on
nor
any other information about the real flow field is
ideal flow patterns which
modeling
combustion. dTe
(gaseous only)
nor
is
input of
placed
on
the model
and the reburn fuel.
arc
to multi
(Lcvenspicl, 1972).
However, since neither the complete velocity distribution within the furnace
staged
plug flow
residence time distributions of N
and still others attempt to account fluidized beds
Depending
plug
on a
combined in different
the resi
known,
the
manner.
the reburn and burnout section of the fuel
are
the combustion
products
of the first stage
The combustion process after the reburn fuel
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
because not all of them make
The chemistry
cause
provided
considers
the reactions in the gas
congruent
sense.
to other literature.
only homogeneous
phase dominates
reactions in the gas
in wood combustion.
This
phase, be
assumption
is
92
CHAPTER 6.
MODELING
Cfll.O
Figure
6.6: Residence time distribution
curves
for PSR in series
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
6.7: Scheme of furnace model for simulation
Input Generation
important,
inputs for the
and critical process of the simulation is the calculation of the

reburn
zone
modeling.
adequate
Since all of the reburn fuel is converted in
fixed
FURNACE MODEL
6'.3.
93
bed into gaseous
conversion of the solid reburn fuel is evaluated in
species, the
step, assuming complete fuel
At
first,
presented
(O2, N2, CO2, H2O)

in section 2.2. CO is
contains NOx that
calculated
effectively
composition,
for
SRt
should be
reduced,
are
done for
specific
amount
UF-chipboard
Hence, the
1.2, which represents the
ratio, using
are
the correlations
the combustion gas of the first stage also

of NOx is added to the
ddie amount is derived from the measurements
NOx emissions.
high primary
at,
stoichiometric
given
neglected. Since
facility, ddie presented simulations

NOx
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
value is assumed to be 385 ppm
measurements well.
Afterwards, the calculated gas of the fuel-lean

donor of oxidising agents for the gasification of the
first stage is used in the next step
as
reburn fuel.
Reburn Fuel Conversion
6.3.3
nitrogen during pyrolysis into HCN and

of single particle pyrolysis at 800 C. (Hmlincn,
The model for the conversion of the fuel bound
NH3 is based
experimental
on
data
a correlation between the HCN/NII3 ratio and the

ah, 1993)
(Aho
1995)
hiel-O/fuel-N ratio as shown in Figure 6.8 which is right, for various nitrogen containing
and
found
et
substances. Since this correlation

for the
implemented
ddius,
the
seems
to be suitable for many solid
fuels,
it is also base
model.
pyrolysis
of the reburn fuel will be calculated next. In Table 6.2 the
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
properties for simulation

Wood Chips
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
composition of the reburn fuel is evaluated, assuming a conversion

Then, the specific amount of HCN and NH3 corresponding to the
temperature of 800C.
conversion ratio noted in dble 6.3 Is added, wdiich is derived from

It is worth
noting
converted into gaseous
here that under
products
as
pyrolysis
Figure
Figure
6.8.
conditions not, all of the reburn fuel is
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
however, the charcoal
completely, also
burns out
Of course, char burnout takes
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
reburn fuel rate.
1.0
0.8
0.6
A^
0.4
0.2
HCN/NH,
fasa^.
J
$-"
'A--|
20
80
60
40
O/N ratio in the fuel
Figure
at
O/N
ah, 1993)
6.8: Influence of
800C
(Alio
et
ratio
on
fuel-N conversion to HCN and NH3
during pyrolysis
presented are done for the fuel combinations UF-chipboard/UF-chipboard

UF-chipboard/wood chips. A summary of the corresponding input data are given in
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
6.9: Calculated chemical
0.6
0.4
[-]
equilibrium composition
different water contents of the fuel
(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
Figure 6.10: Calculated input
0.3
0.2
0.4
[-]
data for the reburn
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
[-]
input data for the reburn
zone
simulations, UF/W
98
CHAPTER 6
Seite
Leer
Blank ieaf
i
MODELING
Chapter
Results and Discussion
General
7.1
The simulation results
in this
presented
UF-chipboard/UF-ehipboard
are
under
interesting
probably
that produces high NOx emission
These two combinations
of view since
practical points
because of its
high nitrogen
Beside the fuels the other variable parameters
are
simple plug
flow
(PFR)
PFR for different
zone
is fixed for all
is
mean
imposed
same
There
once a
residence times.
cases on
the temperature in the reburn
zone
mixing conditions,
once
combination of
The total
are
fuel
mean
mixed flow
(PSR)
and
residence time for the reburn
seconds, hence
r
dTe
and
UF-chipboard
is
content.
and the reburn fuel rate RFR. To simulate the influence of the
a
staging with the fuels
limited to fuel
UF-chipboard/wood chips.
and
the most
chapter
tpsr + tpfr
(7.1)
2s
modeling of the burnout zone of the furnace.

premixed plug flow (PSR and PFR in series) are possible
in the following figures are explained in Table 7.1.
convention is also valid for the
again, simple plug
flow
or
scenarios. The notations used
Table 7.1: Notation in
TPSR
PFR
ddie simulations
are
[s]
figures
TFFR
[s]
PSR
0.1s
0.1
1.9
PSR
Is
carried out
using the CHEMKIN-II package.
CHEMKIN is
soft
package whose purpose is to facilitate the formation, solution, and interpretation of

problems involving elementary gas-phase kinetics (Kee et ah, 1980). It provides a flexi
ble and powerful tool for incorporating complex chemical kinetic into simulations of fluid
ware
dynamics. The package consists

Gas-Phase Subroutine Library.
of two
major software components:
99
an
Interpreter
and
100
CHAPTER 7.
dTe CHEMKIN
Interpreter
ementary, user-specified
highly
is
program that reads
symbolic description of
chemical reaction mechanism. The
library
thermodynamic properties,
Two established subroutines which
and chemical
are
used for
SENKIN subroutine and the PSR subroutine.

program.
That, is how the
following
ddie output data of the simulation
teractive, graphics post-processor

dimensional correlations in
aware
comparison
of the limits
runs
can
the mentioned the
the furnace models
also be linked
evaluated with
on
the
and may
7.1 and
even
lead to wrong conclusions and
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
difference between the measurement taken at
since the chosen model
present, in
0.1s,
influence of the total
at the end of the reburn zone and the calculated values.
expected
NO,
For the calculated curves, the model of
total residence time of 1
show that, there is
and has to be
For the illustration of
7.2 show the calculated and measured concentrations of
residence of the PSR
specie
dangerous and
interpretations, especially
considered.
are
PSR and PFR in
surprising
the
driver
assumption of ideal flow patterns,
zone.
The
together by
are
highly coupled systems.
HCN and N20 at the exit, of the reburn
on
rates.
that, enables visualization and identification of multi
model which is based
if minor components such
for each
equa
on
done.
were
are
el
between the measured gas concentrations and the calculated is
not, very reasonable
Figure
dTey
simulations
production
describing
an
consists of about 100
modular FORTfllAN subroutines that may be called to return information
tions of state,
Being
RESULTS AND DISCUSSION
one
point
this difference is not
all local
phenomena and
furnace. Variable
turbulence, slippage, segragation,

easily produce significant local differences. This is especially
true for the reburn zone chemistry as further simulations will show. Additionally, the input
parameters of the model itself are values wdth an uncertainty which also influences the
model outputs. Hence, there are many explanations possible for the observed discrepancy.
However, since the prediction of absolute emission values is not the aim of the following
simulations, a reference value is introduced, allowing a dimensionless presentation of the
results. Regarding the nitrogen species, they are treated in a summary as TEN to get a
are
and other flow anomalies
more
can
concentrated information about what
the reduction rate R is
postulated
happens during
the simulation.
Consequently,
as:
TFN
where
TFNq is the input, of nitrogen species
simulations.
According
to the
assumptions
the NOx emissions of the first fuel stage.
to the reburn
made in
zone
at the
beginning
of the
Chapter 6.3, TF'N, corresponds
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
7.1: Calculated and measured concentrations of NO and HCN in the reburn
(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
[-]
7.2: Calculated and measured concentration of NEO in the reburn
900C, (1)
means r
ls, (2)
means
2s)
zone
(PSR
ls,
102
CHAPTER 7.
Reaction Mechanism
7.2
dTe main advance of the chosen model is the

anisms for
investigating
natural gas
or
(methane)
less species and
the gas
phase
combustion
elementary
mechanisms and the
in
1.
arc
several reaction mechanism for
including nitrogen chemistry available, including
reactions.
of the
modeling
possibility of handling detailed reaction mech
reactions. There
An overview
on
on
comparison
Bowman, 1989).
the results is demonstrated in this section
are:
GRI-Mechanism
v.
2. Leeds-Mechanism
2.11:
49
species, 279 reactions
1.3:
56
species, 354 reactions
v.
The GRI-meehanism is the mechauism of the Gas Research

many contributors.
Energy2
bustion and
on
and
simulation step is calculated with two different mechanisms. The mechanisms
one
oped by
more
the evaluation of combustion
nitrogen chemistry gives (Miller
The influence of the reaction mechanism

where
at, the
The heeds-mechanism is
University
Institute1 and has been devel
product, of the Centre for Com
of Leeds where several contributors have worked
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
the exit concentrations of the calculated
ferences for the concentration
intermediate
mechanism
dicates
reaction
profiles of
HNO and CH3
products
predicts almost
no
are
the
plug flow for UF/UF, significant

nitrogen species NO, NO2, NH3, and
present
net destruction
(Figure
7.3 and
Figure 7.4).
dif
the
The Leeds-
of NO, whereas the GRI-mechanism in
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.
For the GRI-mechanism the reaction
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
the Leeds-mechanism, the NO is consumed
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
The reaction rates for

mechanism
is
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.
The Leeds-mechanism also shows lower oxygen
consumption and differences
methane oxidation mechanism which results in different concentrations of
intermediate products.
rates of some
reverse
The difference in oxygen conversion
reactions
reactions results in about the
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
to the GRI-mechanism. The oxygen
arc
valid for the simulation of
Here also the Leeds-mechanism
the
comes
in the
hydrocarbon
predicts negligible
UF/W (Figure
NO reduction
7.5
along
conditions.
the characteristic reaction times
The time scale for the fuel gas
decomposition
whereas the reactions of the
as
the simulations demon
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
inputs, also if differences for small numbers

ddiere
are
still other reaction mechanisms that
comparison
this work.
cation.
arc
applied for modeling. However, the
and evaluation of suitable mechanisms for fuel

There is many literature
on
the
including the nitrogen chemistry (Glarborg

Nilsson, 1997).
In this
may also be due to numerical effects.
work,
et
ah, 1994), (Steel
the reaction mechanism is treated
No research is
planned
fore, the GRI-mechanism

GRI-mechanism
staging is not the scope of

comparison of chemical reaction mechanisms
already
for
adapting
or
as
et
tool and
ameliorating
ah, 1995), (Mauss and
provided
appli
given mechanism. There
is used for all other simulations beside this
has been used for various
applications (Zamansky et ah, 1998b), (Zamansky

1998), (Berget ah, 1998).
simulations, namely
et
for the
comparison.
for fuel
al, 1998a), (Dupont
and
The
reburning
Williams,
104
CHAPTER 7
1 0E04
1 OOE 02
Js
1 OOE 06
time
Figuie
7 3- Gas concentiations
[s]
PFR using the GRI-mechanism for
UF/UF
at 900C
1 OE 04
1 OOE 02
1 00E 07
time
Figuie
7 4
Gas concentiations
[s]
PFR using the Leeds-mechanism foi
UF/UF
at 900C
7 2.
REACTION MECHANISM
105
1 OE 04
1 OOE 02
1 00t 07
time
7.5: Gas concentrations
Figure
[s]
PER using the GRI-mechanism for
UF/W
at 900C
1 0E04
1 OOE 02
i:
1 00E 06
1 OOfc 07
1 00E 10
i-
time
Figure
[s]
7.6: Gas concentiations in PFR using the Leeds-mechanism for
UF/W
at 900C
106
CHAPTER 7.
Reburn Zone
7.3
Influence of Reburn Fuel Rate and
7.3.1
First,
the reburn
zone
of the fuel
staging
is
Temperature
simulated, using different models. The
param
analogous to the experiments on the research facility. The main results

of the simulations are diagrams showing the influence of the temperature in the reburn
zone on the reduction of the TFN, represented by the reduction rate R. Other variable
parameters are the reburn fuel rate (RFR) and the mixing mode which is modeled by a
eters varied
variable
plug
arc
splitting
of the
mean
(PFR).
flow reactor
residence times between the mixed reactor
(PSR)
and the
The reaction mechanism used is the GRI-mechanism.
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
higher temperatures, but
7.8 shows the distinct influence of
demonstrates that the choice of the model parameters has
results,
to
the maximum reductioti rates obtained for
77% for RFR=0.25
to the
to
considerable
too.
plug flow,
PSR is assumed 1.0
According
shifted towards
are
the reduction rate when the residence time of the PSR is varied from 0.1
figure
on
allowed, the trends
the reduction rates increases.
premixed
flow
97% for RFR =0.35 when the residence time of the
up to
s.
GRI-mechanism,
the
decomposition
of HCN and
NII3 follows the
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)
the entire temperature range
temperatures, almost all NO is reduced, but the model
investigated. Towards low

predicts an increasing formation
of N20 and N02.

Wdth
higher
rates than
more
and
more
HCN and NII3
NFI3. The Ôformation is reduced
the reduction rate for RFR=0.25 is clue to

the recombination of HNO wdth H. OH.
at low RFR the reaction rates of
NO
or
a,
are
drastically.
decomposed, HCN
The
higher
diminished NO reduction. The main
O to NO.
forming
and
However,
reducing
with
in
decrease of
cause
is
reactions fall.
7.3.
107
REBURN ZONE
Regarding
nitrogen species forming and consuming reactions, the characteristic reaction time at
The temperature has also
the
distinct, influence
on
the reaction velocities.
800C is about fO times slower than at 1300C.
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
on
reduction rate R for RFR=0.25
(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
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.
Influence of Reburn Fuel
7.3.2
An
109
important question
to be answered is wdiat the influence of the reburn fuel
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
for different RFR.
curves
than with
the
7.10 and 7.11 show the influence of the
is
slightly
UF/UF.
flow
Assuming plug
only
with
the
shape
the shift
RFR=0.2, the optimum temperature
range is about
be observed wdien
can
UF/UF,
higher
Depending on
towards higher
model, the optimum tcmperatiue
temperatures
the reduction rate R
At low temperatures, the reduction rate is still
RFR=0.2,
Even with
on
to the results obtained with
Compaied
different.
temperature
the reduction rate is about 85%.
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
level. Piemixed flow with
same
a mean
the temperature ranges about 200C towards
achieved
residence time for the PSR of 1
higher temperatures.
nitrogen of
the reburn fuel.
Wood
lower levels of HCN and NH3 in the reburn

ideal conditions
NO2 and N2O
shifts
higher.
are even
The differences between the fuel combinations
the fuel
The leduction rates
are
are
100%
chips
zone.
UF/UF
with
and
UF/W
low
nitrogen
Therefore,
content
produce
the amount of TFN at
non-
much lower because less HCN and NII3 remains unreacted and less
formed.
PFR
90%
PSR
80%
show the effect of
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
dTe NOx emissions

of the test
zone
presented
Modeling
in this work
measured in the flue gas, after the burnout
are
gas of the fuel rich reburn
(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
assuming plug flow
higher
show that
transformed to
especially
temperatures the influence of the burnout is
negligible.
occurring during burnout,
reactions
figures
are
zone
7.8 and 7.11. This observation is true
Figure
to
in
represent the two different
PFR in series. Both
also influence the
must,
nitrogen
N-spccies depending on
UF/UF. NO is lowest be
7.13 shows the calculated concentrations of the
Figure
temperature assuming plug flow for the fuel combination
tween
input data for
The
s.
premixed
or as a
the output data of the reburn simulations.
the low reduction rates at, lower temperatures in the reduction
species.
(PFR)
flow
7.12 and 7.15 show the TFN reduction in the flue gas
the burnout
reburn
modeling
that the
means
has to react wdth the burnout air to the flue gas.
zone
and PFR in
This
of the burnout stage.
As described in section 6.3, burnout is modeled
plug
compared with
Therefore, the measured emissions have to be
facility.
simulation results that include the
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.
comparison clearly demonstrates that NH3 and
The
leading only
to weak increase of the
tures in the reduction
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
the reduction rates for low temperatures in the reburn
at RFR=0.3
the PFR at 1300C
(Figure 7.11)
is used
as
1300C,
1100 and 800C
burnout
temperature
variation for
zone.
model, the output data for reburning

input for other burnout models beside
(Figure 7.15).
The burnout temperature of the isothermal
same
at, low
amount. The emission of
negligible
To demonstrate the influence of the burnout

with
destroyed during burnout
of the reduction rate at low temperatures may
The observed
the burnout
same
are
NOx emission. N2O which is formed
is also reduced to
zone
HCN
on
PSR
are
simulated.
Figure
the reburn model
(r
,s) plus
plug
assuming
on
In addition to
7.16 shows the influence of the varied
PER in series
The effect of the burnout, temperature
flow is also varied.
PER,
as
and
Figure
7.17 shows the
reburn model.
the reduction rate is
more
distinct, for the
reburn model PFR. If the burnout temperature could be raised to 1100C and more, the
TFN present at
reburn temperature below 900C could be reduced
The burnout temperature has less influence

with
premixed flow.
Even
on
significantly.
the reduction rate for the reburn model
low burnout temperature does not
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
residence time of 0.5
s.
followed
The temperature for both isothermal reactors is chosen
by
as
plug
flow of f .5
reburn temperature
112
CHAPTER 7
plus 100C. Figure

PFR and
once
Again,
7.18 shows the
PSR
resulting
reduction rates for both reburn
models,
once
plus PFR.
the two reburn models show different behavior.
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
the theoretical potential of fuel

search
facility
staging
have demonstrated.
chipboard/wood chips. However,
is
This is
the trends
higher than the experiments on the re

especially true for the fuel combination UF-
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,
the importance of the
100%
mixing
and flow conditions within the furnace.
-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
in PFR at 1300C for different reburn models with RFR=0.30
7.4.
113
BURNOUT ZONE
1.0E-03
1.0E-04
D1300C
1100C
D900C
P800C
H700C
1.0E-09
NH3
NO
Figure 7.13: Calculated N-species
N02
HCN
N20
concentrations after leburn
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
PFR with RFR=0.30
N-species
NO
N02
N20
concentration for PFR
(SRÔ.85), UF/UF
HCN
after burnout, reburn model
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:
Burnout in PER at 1300C for different reburn models with RFR=0.30
(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
7.16: Influence of burnout tempeiature in PFR
(SIT-0.86):
reburn model: PFR with
UF/W
on i
eduction rate R for RFR=0.30
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
7.17: Influence of burnout temperature in PFR
(SRr0.86);
reburn model:
on
reduction rate R for RFR=0.
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
7.18: Burnout modeled
(SRÔ.86), UF/W
as
PSR+PFR for different reburn models with RFR=0.
116
CHAPTER. 7.
Influence of CO
7.4.2
During
NOx emission
on
continuous measurements in the flue gas of furnaces
the NOx emission decreases when the CO emission rises.

the
assumption
that there is
of whether CO may act
as
often observe that
can
This observation could lead to
interaction between CO and NOx emission. dTe
an
one
reducing agent, during
burnout is answered
by
the
question
following
simulation of the burnout stage.

ddie simulation
The
input
was
done
using
gas is assumed to be
simple plug flow model (PFR) for the burnout stage.

CO2, H2O, O2, and N2 according to a stoi
mixture of
chiometric ratio of f .6. Defined amounts of CO and NO

of
CO2, H2O, O2,
and N2
adjusted by
arc
added and the concentrations
iteration. For the NO concentration
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
for all simulations. The reaction mechanism used is the GRI-mechanism.
Table 7.2:
Input
data for the simulation of the CO influence
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
ddie results of the simulations

ditions
no
arc
shown in
Figure
7.19.
Under the
given
reaction
direct interaction between CO and NO in the gas phase can be found.

is only oxidized to NO2 at low temperatures. The oxidising agent Is
thermore, NO
con
Fur
HO2,
which is formed via

H +
O2
II2O
HO2
H2O
(7.21)
N2
H02
N2
(7.22)
HO2 + NO
>
NO2
+ OTI
II +
However, the CO
02
content influences the
NO2 formation
at low
(7.23)
temperature. It
due to the different amounts of intermediate species when CO is introduced since

interaction with CO
Looking
direct
occurs.
at the main reactions of CO. we find
CO +OH
and with
must be
no
H +
CO2
(7.24)
increasing temperature additionally

CO + O^M
CO2
+ M
(7.25)
7.4.
117
BURNOUT ZONE
The CO oxidation has
an
above the amount of CO
optimum
at, about, 950 C.
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
The temperature has
out, of range.
significant
influence
on
the reaction time scales
as
Figure
7.20
and 7.21 show.
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
for the low NOx emission
hydrocarbons and/or nitrogen intermediates

the reactions of secondary measures with reducing
combustion may also be
which reduce the NO
according to
agents (see Chapter 2.6). However,
under
be ween CO and NO cannot be excluded.
locally
fuel rich
conditions, direct, interation
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
7 19: Influence of temperature
for different CO addition
on
CO, NO. NO2. and N2O cmissison after burnout
7.4.
BURNOUT ZONE
119
time
Figure
7.20: Gas concentrations in burnout

stage
1 OE-04
1
[s]
0E-01
1 0E-3
(PER); 800C, 1000mg
1 0E-01
CO
1 0E+00
10E07
time
Figure
fs]
7.21: Gas concentrations in burnout

stage
(PER), 1300C, 10000mg CO
120
CHAPTER 7.
fcank If
Chapter
Conclusions
Summary
8.1
produces NOx
The combustion of wood and wood residues
mainly
in the fuel.
from
nitrogen
temperatures in practical
the
heating
values. The
nitrogen
content, of the
nitrogen
creates
important, ddie higher the
decreases wdth
nitrogen
be reduced
can
increasing nitrogen
content.
combustion which
significantly by using staged
consumed and converted
zone
nitrogen species
complex reaction mechanism. Air staging and fuel staging make both
principle.
important parameters
Experiments
are
that, influence the fuel
on
research
facility
However, air
practical
may have
as
own
or
research has demonstrated.
advanced furnace control and flue gas recirculation air
high
staging
has
and 72% for
chips (fuel-N 0.18%)

staging with non-pulverized biomass
limitations
use
zone arc
of
the
nitrogen conversion.
have shown that air
of about 65% for wood
staging
NOx reduction
UF-chipboard (fucl-
other renewable fuels
Beside the need of
an
is not suitable for fuels with
ash content, and low ash fusion temperature, i.e. below 1000C.
The
be
more
fuel, the higher is the NOx emission of conventional furnaces. But
most
potential
N
3.5%).
because
negligible
The temperature and the stoichiometric ratio in the reduction
this
originate
moderate levels due to the low
at
are
of the fuel is much
where NO and other
fuel rich
N2 by
to
fixed bed furnaces
content,
the conversion rate of the fuel

The NOx emission
emissions which
Thermal induced NOx formation is
an
presented
operable
fuel
and
staging system
practicable
which
uses a
fixed bed
as
reburn
concept for wood furnaces. With fuel
NOx reduction is achieved than with air staging,
up to
stage promises
staging
even
to
higher
78% for UF-chipboard combustion
and about 66% for native wood.
For
an
equivalent, NOx
in the reduction
zone
reduction with fuel
the combustion gas and the

in the reburn
zone
lower temperature
staging (
L100 to
1200C).
zone
during
the
has to be
to
Good
hydrocarbons
experiments
high enough (above 900C)
1000C)
mixing
of
significant advantage
lead to the conclusion that fuel
for the
application
121
to
guarantee
in the gas.
sensitive to fluctuations of the stoichiometric ratio in the reduction
which may be
(900
pyrolysis products of the reburn fuel and a mean residence time

s are provided for an efficient NOx reduction. Furthermore,
burnout of the CO and
Observations
of at least 1
the temperature in the burnout
complete
staging
is necessary than with air
of this
staging
than air
is less
staging
technique. Provided that
zone
122
CHAPTER 8.
the first fuel stage is
operated constantly
of the reburn fuel for
at
CONCLUSIONS
stoichiometric ratio of about f .2, the input
NOx reduction has to be 25% to 35% of the total energy
significant
input.
A model to
investigate
oped based
on
the mechanisms of
two idealized flow
nitrogen
convexsion
patterns: plug flow
reactor
during reburning was devel

and perfectly stirred
(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
the combustion gas
using
More detailed models
are
with solid fuels is the
oxidising agent,
as
empirical correlation for
an
staging
gasification
of the reburn
ddie model for this process is based
the formation of HCN and NH3 from the reburn fuel.
still under
components from fuel gasification
development.
was
calculated
The concentration of the other main
assuming paitial equilibrium.
the aim of the simulations
However,
is to demonstiatc whether the proposed model is

prediction of the influence of the impoitant process parameters temper
ature, stoichiometric ratio, mixing conditions, and lesidence time on reburn efficiency.
suitable tool for
The results of the simulations and the measurements
in
are
good agreement regarding
the calculated NOx reductions and the effects of the process parameters. The calculated
and the measuied
identical.
optimum temperature
nitrogen (TFN)
is at 95%. ddiis indicates that there is

an
NOx reduction
dTe calculations and the measurements show similar trends.
reduction of the total fixed
by
ranges for maximum
improved furnace
was
lower than the
calculated,
are
about,
The measured
which maximum
higher reduction potential which may be attained

design particularly in view of mixing and an adequate furnace
a
control.
Regarding
the reburn
of the reactants has
longer residence
zone,
the simulations have shown that the
influence
an
on
the
mixing
conditions
position of the optimum temperature range. A
time in the PSR results in
shift towaids
higher temperatures. In any

predict a 1 eduction rate of 70% above 850C already. The other end
optimum temperature range is at about 1200C. ddiere, the reduction on NO begins
a
case, the simulations
of the
to decrease
again.
The type of reburn fuel influences the
though
optimum
range
lange is
can
chipboard
zone.
than
high temperatures, the lower NO reduction is

for wood chips. Consequently, the NO reduction after
nitrogen
without
species like HCN,
incieasing
Regarding
NII3. and NEO
the NO\ emission
usually
are
burnout decreases
significantly
zone
optimum reburn
is about 900C, and for
about 1100C. However, the temperature in the burnout
10()0C, but
calculated for UF-
reduced in the burnout
the calculated reduction after the burnout stage, the
perature assuming plug flow in the reburn
zone
more
should be
high,
favorably
presented model
process parameters.
allows
some
is
suitable tool for the
Although
variations,
the
inputs
qualitative study
may deviate from
the inffuence of each modification
can
tem
premixed flow
1100 to 1300C, because low burnout temperatures

to N2O emission wdiich should also be avoided.
ddie
Al
potential of wrood chips and UF-chipboard as reburn fuel inside the

equivalent, the higher concentrations of TFN for chipboard outside this
be noted. At
also. Other
zone
species concentiation in the reburn
the reduction
at
can
least
lead
of the effect of the main
reality
and the model itself
relatively fast
and
easily be
OUTLOOK
8.2.
123
simulated.
Summarizing
that fuel
the work
is
staging
the
presented,
suitable
experiments
measure
and
and the model simulations have shown
for NOx reduction of
promising technique
automatic wood furnaces.
Outlook
8.2
ddie present
on
investigation
the combustion of
has demonstrated that fuel
non-pulverized
wood fuels.
reduction of the
staging
The temperature range for
staging
is also favorable for fuels with
ture because it allows to
The temperature control

the burnout
use
zone
high
be
can
staging.
high nitrogen
content.
staging
with
ash contents and low ash fusion tempera
accomplished by
high enough
for
of the transferred heat could also be the
Fuel
efficient
keep the combustion temperature of the first stage below 1000C.
should be
non-pulverized
feasible. However, there
an
reactions is lower than for air
nitrogen species by homogeneous

Therefore, fuel staging may be a favorable method for fuels with
Fuel
successfully applied
be
can
biomass
are some
exchangers. As
complete
on
reasonable
the burnout air.
fixed bed for
the fuel
the temperature in
burnout of the gas,
preheating of
using
demands
heat
reburning
properties
has shown to be
of the reburn fuel. The
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
fuels with low ash fusion temperature should be avoided.

A
high voidage
of the fuel bed is beneficial to the
reburning
of the combustion gas increases the fuel conversion rates and

gas. However, the reburn fuel
feeding system
Other systems than the understoker grate

approve the
also
are
plays
an
because
deep penetration
improves the mixing of the
a
important role
imaginable,
i.
c.
in this concept.
spreading system
NOx emission potential. Additionally, the design of the reburn
promote the mixing and prevent

In any case, fuel
an
staging demands
furnace. On the other
zone
may
should
inhomogeneous flow field.
higher
investment in the hardware and software of
costs for additional
reducing agents and catalysts are saved.

A sophisticated management of the furnace switching between air staging and fuel stagingmay even result in advantages of the part-load behavior compared to other NOx reduction
techniques.
hand,
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
-
specific Gibbs free energy

total specific enthalpy
HHV
specific enthalpy
higher heating value
number of chemical reactions
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
potential of the ith specie
quantity
of all N
species
Md/kg
(any)
W/m K
kg/mol
kg/s
Pas
kd/mol
mol
mol
APPENDIX A.
stoichiometric coefficient of reactants
NOMENCLATURE
11
stoichiometric coefficient of
chemical
pressure
bar
heat flux
reduction rate
specific
universal gas constant
reaction rate
mass
RFR
reburn fuel rate
entropy
source
products
kg/m3 s
term
kd/kg K
kJ/mol K
mol/s
gas constant
density
kg/m3
Sq
radiative heat loss
SR
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
used for the continuous measurement
were
listed in Table B.l. All the instruments
linearity of maximum 2%. ddie analyzers

less than
2%) coriesponding
to the
are
the
experiments
deviation from
calibiatcd with analyzed gas mixtures
were
expected
duiing
certified and guarantee
concentration lange of the
sampled
(error
gas.
dTble BT: Gas analvzers

Device
Company
Specie
Range
Method
Thermor 6N
Maihak
H2
0-25%
HCD
Uras 10E
Hartmann & Braun
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
0-0.5 toO-fOEl ppm
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
0-0.5 to 0-10 Ed ppm
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
"Flame ionisation detection

eChemilumines(
once
dete< tion
129
EXPERIMENTAL DETAILS
APPENDIXE.
130
B.l.2
FT-IR
Spectroscopy
FT-IR spectroscopy is based
on
based
on
by polyatomic
the molecular rotation and vibration. The pattern of
physical properties
and bond
absorption of infrared radiation
the effect of the
absorption changes
absoipfion therefore depends on the
molecules and hetero-nuclear diatomic molecules. The
of the molecule such
strengths,
ddiis
means
as
the number and type of atoms, the bond
that each infraied spectium of
from all others and may be considered the molcculai

homo-nuclear diatomic molecules such
as
02
angles
gas component differs
Monoatomic gases and
"signature".
N2 do not have infrared bands due to
or
their symmetry. Characteristic parameter in spectroscopy is the wavenumber indicated in
'.
enr
Wavenumber
10l
\em~~l]
(B.l)
Wavelength [pm\
For the
acquisition of the spectral information the principle of the Michelson-interfcromcter
is most
commonly used. The spectrum
is calculated from the
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
optical path length
infiared
intensity
(NIR)
and far infrared.
-dl
the
the total number
are
When radiation passes
Along
on
fixed total pressme, trace gas concentration
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)
and the incident
of
,
an
absorbing
medium
(dx),
the reduction
the conccntiation of absorber
(c),
(B.2)
lacdx
intensity (E), the eciuation integrates
-log--
and the
to:
(B.3)
acL
h
dTe
equation
frequency
The
are
or
above is the absoibanee law. ddie

to
band of
frequencies
eciuation actually only applies
with that all have the
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.
Beside this non-linearity of the absorbance.
acquisition
pressme is
of calibration spectra.
there
Spcetial
lowered, the absoiption lines get tallei
logarithmic absorption
spectia created at
one
law then become greatei.
atmospheie
other
aie
reasons
that force the
line widths vary with piessure. If the

and
Thus,
nairowei.
a
set of
total piessuie will not
sample
Deviations from the
quantitative calibration
apply
at
sample taken
at,
BT.
GAS ANALYSIS
131
1
beamsplitter
moving
mirror
IR detector
laser
gas cell for
sampling
Figure B.l: Layout
one-half
an
of
FT-IR apparatus
The effect of temperature
atmosphere.
changes
distribution of intensities among the lotational lines.

and size of
spectral features. Calibration spectra
invalid when the
sample tcmperatiue
is lower
or
This
recorded
spectral
line is
narrower
sample
causes
single absorption
the fine stiucture in

even
any
changes
change the
shape
in the
normal temperature may be
is
unresolved fine structure in the
in wavenumbers than the resolution bandwidth
of the spectrometer, the line will appear wider and shorter than it
of
is to
higher.
Inaccuracies of absorpt ion coefficient arise when there
spectrum. When
at
on
actually
is. The width
line at normal temperature and piessure is about 0.2 cm"1.
When
spectrum is fully resolved, the absorption law is always obeyed,
high absorbance values.

smaller degree of resolution
at
ddie detection limit of
fully
resolved spectrum
can
be de-resolved to match
used.
is determined
specie
by
the
pathlenght
and the
signal-to-noise
ratio in the
spectrum. Deteetabilitv is increased in diicct response to the reduction of the

noise. The noise level is a function of the source intensity, the number of
scans, the spectral
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
number of photons, while
interferometer
scans
lower the noise
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
the noise in the spectrum at
faster
APPENDIX B.
132
rate than it increases the
usually
dTe
are a
height
of the lines.
compromise with respect
principle
of the
procedure
frared spectrum is shown in
to the
for
Figure
However, the optimal sampling parameters

desired detection limit.
the
determining
B 2
This
procedure proposed by (Moschallski, 1990).
specie concentration from the
sample evaluation
is
analogous
in
to the
Because of the water vapor which dominates
regions of the IR-spcctrum. the determination of other species is impossible due

to overlapping. Hence, the water vapor concentration has to be determined first and a
corresponding wrater reference spectrum has to be subtracted from the sample spectrum
several
before minor
species
are
evaluated. Other references to FT-IR spectroscopy in gases and
(Stapfand
1997), (Kleemann, 1997).
related
problems
are
1992), (Brill. 1992), (Hcland, 1996), (Jaakkola,
Leukel.
presented experiments, the samples weie scanned with O.ScnrTesolution, using

The specifications of the Fd'-IR arc listed in Table B.2. Details
scans for averaging.
For the
12
about the evaluation of the
species
listed in Table B.3.
are
Table B.2: FT-IR
Galaxy 7020
Device
Matt
Company
ATI Enicam
Detector
MCT
IR-range
400-4000cnr1
Gas
heatablc
sampling
Pathlength
4.0
Window material
BaF2
son
specifications
(HgCdTe), liquid nitrogen

long path
(20 passes),
cooled
gas cell
6.4
max.
(32 passes)
Table B.3: FT-IR analysis
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
2394 2429 cm"1
0-20%
H20
1960-1962enr1
0-35%
The characteristic spectra of NO. N02, Nf20, CO. NII3. and HCN
Figure
peak
or
B.3-B.8. ddie gases
range of each
other
species
are
shown at
specie for evaluation
is obvious.
typical
is
concentrations. A
selected the
way
that
displayed
in
representative peak
or
no
are
overlap with
water
However, the 11011-lmearitv of the relation between the ab
sorbance and the concentration clue to the
oveilap
with water has to be considered in the
B.l.
GAS ANALYSIS
calibration curves, i.
e.
the
133
specie has
to be calibrated in
N2 where
water vapor of
concentration is added. The influence of the water vapor concentration

extinction of
used
are
C02 is shown in Figure B.9, More details about

reported by (Kaufmann. 1997) and (Papina, 1997).
on
known
the measured
the calibration
procedure
APPENDIX B
Start
scan
background
scan
sample gas
spectrum calculation
original sample file
determinate
H20
content
choose comparison
spectrum for H20
scale file for subtraction
subtract
from
sample
file without
H20 spectrum
original sample
file
H20
determinate
NO,
N02, N20, NH3
HCN
determinate
C02
content
choose comparison
spectrum for C02
scale file for subtraction
subtract
H20
and
C02
spectrum from original file

sample file without
HoO and CO,
determinate CO
End
me
B 2
Pioccdme of
sample
evaluation horn F EIR spedioscopy
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
N02 (50 ppm)
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.
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)
B.7: IR spectrum of NH3
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
of C02 at different HoO concentrations
(C02:
2394-
APPENDIX B.
138
B.2
Additional
Assumptions
Equations
for the calculation of fuel parameters:
water free fuel
complete combustion
no
composition
moisture of combustion air is
ideal behavior of the gases
soot and
supply for
composition
to
given
is
Air
as mass
fractions of the elements C.
II,
C02 and H20
NOx formation
of combustion air: 21% 02 and 79% N2
kg
neglected
solid fuel at SR=1:
AS^
Combustion gas volume
(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)
Water vapor in flue gas:
CO2
content in
dry flue
_i_(l_ti,)//,
(B.6)
___u;
gas:
C02nal
Normalization of
22 41
22 41
yu,
^(i-w)p-
measured gas concentration to
'norm
Maximum NO2 formed from
,/%
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
Interpretation of the Measurements
The references for the fundamental
equations of the
analysis
error
(Barford, 1985)
are
and
(Lichten, 1988).
Generally, the
error.
If the
systematic
error
systematic
of
error
error
measured value consists of

be be avoided
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
ddie Gaussian distribution of
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,
entirely determined by the

The distribution is
Figure
two
symmetrical
BTO. The width of the
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
Figure BTO: Examples of Gaussian

ddie
probability
of the distribution is then defined
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
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
'
The standard deviation of

Gaussian law is
./ X,
OO
an
infinite set of
errors r
(BAS)
A' distributed
according
to the
/Oo
(.r
X)} P(x: X. a)dv
J oo
-oo
is, of
given by
/OO
which
d>(y)dy
course,
the
why the symbol
reason
e'} P(e, a)de
a2
(B. 14)
is used for the standard deviation of the
distribution.
The
probability
that
measurement lies somewhere between the limits X
/
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
All the measurements described in this work
precision ol* the measurement

apparatus also implies limits
measurements,
both shown in
Figure
B.l 1.
are
actually functions of the time, because the
conditions, the
or
as
given by
mean
bars of the
the accuracy of the
an
estimate of the
true
sampling
interpretation
value of
measurements have to be evaluated
figures
and tables appear in
two
The
and the detection
to which has to be considered for the
ddicrefore. to get
Emission values in the
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
of the measured values
experimental
range X + 2a. which
means
values
representing reading points of interest. The

displayed in the figures of Chapter 7 represent the
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
the apparatus has to be considered also.
EU.
ERROR ANALYSIS
141
1.0
Integral Gaussian/
probability
Standard Gaussian
0.8
0.6
>?
0.4
distribution
0.2
0.0
-2
Fieure B.ll: Standard Gaussian Distribution
B.3.3
Combinations of Measured Values
All the experimental parameters used, i.
rate,
are
c.
the stoichiometric ratios
calculated functions of measured quantities.
the overall standard

For two
error
independent
with any of the y, to
of the parameters is
sets of measured
give equally significant

z
analyzed
quantities
the reburn fuel
z.
precision
on
next.
and y. any of the x%
values of
ax
or
The influence of the
For
can
be combined
linear combination, i.
e.
(B.19)
by
the standard deviation is then
a2a2 + b2a2
More
general, for
f(x. y). supposing
(B.20)
that the function is continuous and diffcrentlable.
the standard deviation is
(B.21)
Equation
three
B.2f forms the base for the
following
experimental parameters SR. SR,
estimation of the standard deviation of the
and RFR.
For the calcult ion of the stoichiometric ratio, the

concentration.
Thus,
assuming
of the stoichiometric ratio
only
measured value is the oxygen
a precision of the
oxygen analyzer of 2%, the
(see Eciuation 2.10) is about 2%, too.
error
142
APPENDIX B.
ddie stoichiometric ratio in the reduction
zone
of several parameters which
measured quantities. A list of the parame
ters is
given
the known
in the
or
supposed
Equation
in Text
rh\
rh2
ddie
based
measurement
Parameter
A
are
on
following table, together
SRr (sec Equation 2.67) is
with the calculated
derived from
Measurements
Error
8%
B.4
fuel propert ies
Equ.
Equ.
2.66
air flow.
2.68
air flow.
02
in gas, fuel
properties
02 in gas, fuel properties
precision of the fuel properties is about 5% for each. dTe

an error
function
precision.
Equ.
air flow may have
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.
The reburn fuel rate
for the
error
zone.
estimation of RFR. The
depends
on
the
same
quantities
Hence, all the suppositions
resulting
error
arc
as
the
also valuable
of the reburn fuel rate is then
about 30%.
The direct measurement of the fuel
inputs
the measurement of
auxiliary quantities
dTe maximum
of
errors
error
instead of t he indirect determination based
wdth limited
SRr and RFR which is
could be reduced.
now
precision
would be
more
on
favorable.
the result of the combination of several
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Curriculum Vitae
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
Primary school in Niedergsgen
1983
District school in Schnenwerd
1983- 1987
September
1987
College
in Olten
Graduation
Type C (sciences)
Study
1988
1994
Study
in Mechanical and Process
Engineering
at the ETH in Zurich
February 1994
Graduation
as
Diplom Ingenieur
in Mechanical
Engineering
Research
1994-
1999
Research assistant at the Eddd

of
Zurich,
Thermodynamics
Laboratory
Working field: Emission control
by primary
measures.
in
Institute of
Energy Technology,
Emerging Technologies.
of biomass combustion systems

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Diss.

for NOx Reduction in Automatic Wood

A dissertation submitted to the

Swiss Federal Institute

Doctor of Technical Sciences

Dipl. Masch.-Ing. ETH Zuiich

Pi of. Di. D. Poulikakos. examiner

The present dissertation

carried out at the Laboratory of

ing Technologies of the Institute of Energy Technology

EU-Project JOR3-CT-96-0059 and

at, the ETH Zurich.

the Swiss Federal Office of

the the Swiss Federal Office for Education and Sciences.

and for his academic

thanks to Dr. habil. Thomas Nussbaumer for his constant support

giving me the opportunity

1 would like to thank Prof. Dr. Dimos Poulikakos for

to do this thesis at the

Laboratory. His suggestions

and demands stimulated the

this research. All the fruitful discussions and the

expressed his interest in

also indebted to Prof. Dr. Fritz Widmer who

the careful examination of the dissertation.

encouraging cooperation during all

for the many enthusiastic and

enlightening discussions. Several ideas

thank Oskar Leiser

ended in innovative solutions.

also thankful to Max Hard and Martin Meuli for

Furthermore, I wish to thank Christian Bruch.

I thank my wife Doris for her

Philipp Morf, and

great job in mechanics

persons who contributed in any form to the work

for the successful

all the other

All the students and other

also well remembered.

continuous support which contributed

oxides from combustion processes should be avoided since

contribute to the formation of acid rain and

will grow in the

process to HCN and

the reaction with radicals

staged combustion systems the reduction of fucl-N to N2 is favored in

optimized combustion conditions.

N2. The goal of the staged combustion techniques is the promotion

reacts with NO to form

of the second reaction

NOx formation usually produces negligible

the fuel is converted

it remains to show which

values leads to lower combustion temperatures

The NOx emissions from biomass combust ion systems

clean combustion of solid biomass is

for low-NOx combustion

staging for non-pulverized biomass combustion

Since the fuel characteristics of biomass differ from fossil

NOx emissions caused by the

fired with gas,

Following this aim,