Johannes W.

Judex
Diss. No. 18865

Diss. No 18865

Paul Scherrer Institut

Research Department General Energy
5232 Villigen PSI, Switzerland
Selbstverlag/self-publishing
ISBN: 978-3-909386-33-8

Grass for Power Generation

Grass for Power Generation

Extending the Fuel Flexibility for IGCC Power Plants

Johannes W. Judex

DISS. ETH N

o 18865

 Grass for Power Generation 

Extending the Fuel Flexibility
for IGCC Power Plants

A dissertation submitted to

ETH ZURICH
for the degree of

Doctor of Sciences
presented by

Johannes W. Judex
Dipl.-Ing. TU-Berlin

Born on
July 6

th 1977

Citizen of Germany

accepted on the recommendation of

Prof. Dr. Alexander Wokaun

Prof. Dr. Massimo Morbidelli
Dr. Serge M. A. Biollaz
2010

Paul Scherrer Institut

Research Department General Energy
CH-5232 Villigen PSI
Selbstverlag/ self-publishing
ISBN: 978-3-909386-33-8

Contents

Abstract

Kurzfassung

ix

Nomenclature

xiii

Introduction

xv

Structure of this thesis

xviii

Scope

xix

1 IGCC power systems with grass

1.1 IGCC power plants . . . . . . . . . . . . . . . . . . .
1.2 Options to integrate grass into existing power plants
1.3 Manufacturers implementation of syngas . . . . . . .
1.4 Gas turbine restrictions . . . . . . . . . . . . . . . . .
1.5 Relevance of the restricted elements and condensibles
1.6 Power scales and biomass supply . . . . . . . . . . . .

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2 Grass for power generation 

a view on the fuel
2.1 Why do we need to know ? . . . . . . . . .
2.2 Thoughts about climate change and CO2 .
2.3 Denition and classication of energy grass
2.4 Availability: literature digest . . . . . . . .
2.5 Availability: GIS analysis for Switzerland .
2.6 Critical observations - energy vs. food . . .

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Contents

2.7 Common properties and their impact on thermal processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.7.1 Material . . . . . . . . . . . . . . . . . . . . . . . .
2.7.2 Mass loss and stability . . . . . . . . . . . . . . .
2.7.3 Physical analysis . . . . . . . . . . . . . . . . . . .
2.7.4 Chemical analysis . . . . . . . . . . . . . . . . . .
2.8 Manipulation of the properties . . . . . . . . . . . . . . .
2.8.1 Drying . . . . . . . . . . . . . . . . . . . . . . . .
2.8.2 Late harvest . . . . . . . . . . . . . . . . . . . . .
2.8.3 Leaching . . . . . . . . . . . . . . . . . . . . . . .
2.8.4 Torrefaction . . . . . . . . . . . . . . . . . . . . .
2.8.5 Acid treatment . . . . . . . . . . . . . . . . . . . .
2.9 Intermediate conclusions . . . . . . . . . . . . . . . . . .
2.10 Recommended literature . . . . . . . . . . . . . . . . . .
3 Sampling raw gas from gasication processes
3.1 Basic expressions and denitions . . . . . . . .
3.1.1 Tar, denitions and usage . . . . . . . .
3.1.2 Permanent gases . . . . . . . . . . . . .
3.1.3 Particles and aerosols . . . . . . . . . .
3.2 Standard methods, advantages and drawbacks
3.3 Sampling approach in this work . . . . . . . .
3.4 Evaluation of the particle slip-stream . . . . .
3.5 Signal change due to the sampling system . . .
3.6 Challenges with the sampling system . . . . .

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4 Fluidised bed experiments

4.1 Brief review of gasication processes . . . . . . . .
4.2 Basic expressions and denitions . . . . . . . . . .
4.2.1 Air to fuel ratio . . . . . . . . . . . . . . .
4.2.2 Carbon conversion . . . . . . . . . . . . . .
4.2.3 Cold gas eciency  hot gas eciency . .
4.3 What literature tells about grass gasication . . .
4.4 Brief introduction of uidised beds . . . . . . . . .
4.4.1 Fluidisation . . . . . . . . . . . . . . . . . .
4.4.2 Bed materials . . . . . . . . . . . . . . . .
4.5 Experimental setup of the bench-scale gasier . .
4.5.1 Construction of the bubbling uidised bed
4.5.2 Sampling . . . . . . . . . . . . . . . . . . .
4.5.3 Controlling system . . . . . . . . . . . . . .

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Contents

4.5.4 Safety concept . . . . . . . . . . . . . . . . . .

4.5.5 Instrumentation and measurement methods .
4.5.6 Heat losses of the reactor . . . . . . . . . . . .
4.5.7 General experience . . . . . . . . . . . . . . .
Experimental procedures . . . . . . . . . . . . . . . .
Experimental matrix . . . . . . . . . . . . . . . . . . .
Fuel characterisation . . . . . . . . . . . . . . . . . . .
4.8.1 Fuel preparation . . . . . . . . . . . . . . . . .
4.8.2 Ash melting . . . . . . . . . . . . . . . . . . .
Results and discussion . . . . . . . . . . . . . . . . . .
4.9.1 Fluidisation . . . . . . . . . . . . . . . . . . . .
4.9.2 General stability of the process . . . . . . . .
4.9.3 Axial prole measurements . . . . . . . . . . .
4.9.4 Monitoring the permanent gas data . . . . . .
4.9.5 The carbon balance . . . . . . . . . . . . . . .
4.9.6 The heating value . . . . . . . . . . . . . . . .
4.9.7 Tar content and composition . . . . . . . . . .
4.9.8 Water content . . . . . . . . . . . . . . . . . .
4.9.9 Comparing the gas compositions to literature
4.9.10 Monitoring of the contaminants . . . . . . . .
4.9.11 Verication of the hot gas lter . . . . . . . .
4.9.12 Note about sulphur and ammonia . . . . . . .

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144

5 A novel single pellet gasier MiV

5.1 Motivation for this approach . . . . . . . . . . . . . .
5.2 Realisation of the MiV . . . . . . . . . . . . . . . . . .
5.3 Controlling and safety aspects . . . . . . . . . . . . .
5.4 Measurement techniques . . . . . . . . . . . . . . . .
5.4.1 Mass spectrometer . . . . . . . . . . . . . . . .
5.4.2 Surface Ionisation Detector . . . . . . . . . . .
5.5 Experimental setup and procedures . . . . . . . . . .
5.6 Results and discussion of the basic behaviour . . . . .
5.7 Results and discussion of the pretreated grass . . . .
5.7.1 The dried pellet . . . . . . . . . . . . . . . . .
5.7.2 The leached pellet . . . . . . . . . . . . . . . .
5.7.3 The doped pellet . . . . . . . . . . . . . . . . .
5.7.4 Summary of the tests with the pretreated fuel
5.7.5 The inuence of hot gas ltration . . . . . . .

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4.6
4.7
4.8
4.9

iii

Contents

6 Conclusions
6.1 Fuel review . . . . . . . .
6.2 Sampling system . . . . .
6.3 Fluidised bed gasication
6.4 Single pellet gasier MiV

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7 Outlook
173
7.1 Fluidised bed gasication . . . . . . . . . . . . . . . . . . 173
7.2 The single pellet gasier MiV . . . . . . . . . . . . . . . . 175
Epilogue

177

Bibliography

179

Additional analysis
I
.1 Preliminary test with wood . . . . . . . . . . . . . . . . . II
.2 TGA for grass . . . . . . . . . . . . . . . . . . . . . . . . III
.3 GC/MS tar analysis . . . . . . . . . . . . . . . . . . . . . III

Photographs from the set ups

Methane slip stream in a biogas plant

Subject index

iv

VII
IX
XIV

Abstract
The situation of the current electrical power production is characterised
by a trend to use more and more alternative energies and the fact
that the European power plant eet is ageing. Since the electrical
consumption is expected to increase further, old power plants which are
to be switched o need to be replaced. There are two main candidates
of large power plant types being discussed:
G natural gas combined cycle plants
G nuclear power plants

Nuclear power plants are not suited to implement alternative energies,

whereas combined cycle power plants can be equipped with a biomass
gasier. In this way an IGCC power plant is designed, which can fully
or partially run on biomass. There is also a need to employ additional
biomass feed stock types like annual plants. In this work grass is studied
as additional energy resource for IGCC applications. Being able to use
grass as supplementary feed stock would increase the fuel exibility of
IGCC power plants.
G A review of the chemical and physical properties of grass as solid

fuel was carried out. Grass contains a very large number of different inorganic elements mostly in minor amounts. It revealed
that in addition to the elements causing corrosion in gas turbines
at least Sr and Ba are found in grass. Both show similar corrosiveness to the known alkalis K and Na. Earth alkali elements
(Mg, Ca) also being known for depositions and corrosion enhancement, are present in critical amounts in the fuel. It is unsure
whether the positive eects (binding sulphur or vanadium) or the
negative eects (deposition, surface damage) will prevail. The
generally low energy density can be avoided by on-eld densica-

Abstract

tion or immediate pyrolysis. The water content can be expected

to be lower than for all other biomasses owing to good drying
properties and the possibility of on-eld drying.
G For the integration into IGCC power plants the grass must be

thermally gasied. A lab-scale uidised bed gasication reactor

was designed and put into operation. Air blown gasication experiments were conducted with grass and thereby the stability of
the process and emission of contaminants, relevant for gas turbine
applications, was analysed (i. e. K, Na, Mg, Ca, Pb, V).

G Gasication experiments were carried out between 700 and 750 C

for fuel to air ratios between 0.17 and 0.35. Dierent bed materials (dolomite, SiO2 , Al2 O3 ) were tested: dolomite was excluded
after rst trials, because it appeared unsuitable for uidised bed
applications due to its mechanical weakness. Silica sand was used
for 700 C only since the ash melting behaviour of grass together
with silica indicated agglomeration above 700 C. The experiments at this temperature were conducted without bed agglomeration or deuidisation. Alumina bed material was used for 700
and 750 C, since the ash melting behaviour of grass together with
alumina proved to be less critical at higher temperatures. A 10 h
run was conducted to see if unstable situations in the gasication process can occur. All experiments succeeded without any
deuidisation or agglomeration. Axial temperature prole measurements proved an isothermal behaviour. The axial devolution
of the supercial gas velocity is evident but still moderate. Despite the low temperature of 700 to 750 C, the tar concentration is
lower than for uidised bed wood gasication given in literature.

G The contaminants in the gas phase where analysed by means of a

dedicated sampling train and an ICP-OES device. It was shown

that by applying a hot gas lter at 400 C all the contaminant
concentrations aside from potassium and sodium were low enough
to satisfy the gas turbine limits. Sodium was found in concentrations higher than the allowed limit for mono-fuel applications.
The concentrations are low enough if a coring approach with
natural gas is targeted. Potassium could not be quantied at the
given concentration level due to the insensitive response of the
ICP-OES to potassium. Secondary measures other than hot gas
clean up to reduce contaminants were not employed.

vi

Abstract

G A novel single pellet gasier was designed and commissioned in

order to investigate the transient gasication of a single pellet.

The reactor showed similar characteristic as the uidised bed
with respect to gas devolution, fuel size and heating rate of the
fuel. The experiments proved to be fully reproducible. By means
of a surface ionisation detector, the alkali emission for dierent
grass pellets was monitored qualitatively. The results revealed
that around 90 % of the alkalis are emitted during the combustion phase of the char. The remaining 10 % are released due to
the volatilisation during the pyrolysis and gasicaition. Leaching
and doping with potassium and sodium of the grass inuenced
the emission during the combustion phase much stronger than
during the volatilisation. The implementation of a hot gas lter
at 400 C resulted in a heavily reduced alkali emission. The results indicated, that the passing alkali fraction is released during
the pyrolysis, wheras the larger fraction emitted from the char
combustion could be separated.

Grass is by any means suitable to be gasied in a uidised bed gasier.

Hot gas ltration at 400 C is sucient if the coring concept is followed. However, secondary measures are required to further reduce the
sodium concentration if the mono-fuel concept is chosen.

vii

Kurzfassung
Die momentane Situation der Elektrizittsproduktion ist gekennzeichnet durch die Tendenz steigender Anteile an erneuerbaren Energien sowie eine stetige Veralterung des europischen Kraftwerksparks. Kraftwerke, die altersbedingt vom Netz genommen werden, mssen durch
neue und ezientere Kraftwerke ersetzt werden. Da ein weiterer Anstieg des Elektrizittskonsums erwartet wird, mssen zudem zustzliche
Kraftwerke geschaen werden. Zur Zeit sind zwei Kraftwerkstypen vorzugsweise in der Diskussion.
G Erdgas gefeuerte Gas- und Dampfkraftwerke (GuDs) und
G Atomkraftwerke der neusten Generation

In Atomkraftwerke knnen keine erneuerbaren Energien im Sinne eines

Ersatzes implementiert werden. Im Gegensatz dazu knnen in GuDs
Biomassevergaser integriert werden, die beliebige Teile des ansonsten
verwendeten Erdgases duch sogenanntes Syngas ersetzen knnen. Die
Vergaser werden heute in der Regel mit Kohle betrieben, lassen aber
die Mglichkeit oen auch Biomasse einzusetzen.
Aufgrund der zum Teil mangelnden Verfgbarkeit herkmmlicher Biomasse (Holz, Restholz) besteht die Notwendigkeit zustzliche Ressourcen wie z. B. jhrige Panzen auf ihre Eignung zu prfen.
In dieser Arbeit wird die Eignung von naturbelassenem Gras fr den
Einsatz in GuDs mit integrierter Vergasung berprft. Die Mglichkeit Gras als Brennsto zu nutzen wrde die Brennstoexibilitt fr
zuknftige Anlagen erhhen. Folgende Bereiche und Themen wurden
deshalb in der vorliegenden Dissertation bearbeitet:
G Eine bersicht ber die physikalischen und chemischen Eigen-

schaften von Gras als fester Brennsto wurde herausgearbeitet

ix

Kurzfassung

und vergleichend mit anderen festen Bioenergietrgern dargestellt.

Gras enthlt eine vergleichbar grosse Anzahl an anorganischen
Elementen, die meisten davon jedoch in geringen Mengen. Zustzlich zu den bekannten Elementen wie K, Na, Mg, Ca oder V,
die zu Beschdigungen an der Gasturbine fhren, sind in der Vergangenheit im Gras Barium und Strontium nachgewiesen worden,
die eine hnliche oder strkere Korrosivitt zeigen als die oben erwhnten Alkalimetalle. Insgesamt sind besonders die Alkali- und
Erdalkalimetalle im Gras in kritischen Mengen vorhanden. Aus
der bersicht geht nicht hervor, ob z. B. bei Elementen wie Ca das
Binden von Schwefel als positiver Eekt oder eine hhere Emission und letzlich Ablagerung und Oberchenzerstrung berwiegen werden. Die im Vergleich zu verholzter Biomasse niedrigere
Energiedichte von Gras kann teilweise durch das Trocknen auf
dem Feld und schnellstmgliche Verdichtung zu Ballen oder Pellets oder durch Pyrolyse kompensiert werden. Durch eine Feldtrocknung kann ein geringerer Wassergehalt erwarten werden, als
bei herkmmlichen biogenen Brennstoen.
G Fr die erfolgreiche Integration in ein GuD mit integrierter Ver-

gasung muss das Gras ezient und problemlos vergast werden

knnen. Um dies zu demonstrieren wurde eine luftbetriebene Wirbelschichtvergasungsanlage im Labormassstab (5kW) aufgebaut
und betrieben. Verschiedene Experimente wurden durchgefhrt,
um die Prozessstabilitt zu demonstrieren, sowie die fr die Gasturbine relevante Strstoemission (K, Na, Mg, Ca, Pb, V) nachzuweisen.

G Vergasungsexperimente wurden fr Luft-Brennstoverhltnisse zwischen 0.17 und 0.35 und Temperaturen zwischen 700 und 750 C

durchgefhrt. Verschiedene Bettmaterialien (Dolomit, SiO2 , Al2 O3 )

wurden getestet: Dolomit wurde nach den ersten Versuchen ausgeschlossen, da die mechanische Beanspruchung in der Wirbelschicht das Material aufrieb und der verbleibende Staub ausgetragen wurde. Siliziumoxid wurde fr Experimente bis 700 C
verwendet, da aufgrund des hohen Kaliumgehaltes von Gras fr
hhere Temperaturen die Gefahr der Bettagglomeration gegeben
ist. Bei dieser Temperatur konnten jedoch alle Experimente ohne
Deuidisierung oder Bettagglomerationen durchgefhrt werden.
Aluminiumoxid wurde fr Temperaturen bis 750 C verwendet,
da fr diese Temperatur noch keine Gefahr der Ascheschmelze ge-

Kurzfassung

geben ist. Ein 10 h Langzeitversuch wurde durchgefhrt, um fr

eine lngere Zeitspanne die Prozessstabilitt zu demonstrieren.
Alle Experimente wurden ohne Probleme wie Deuidisierung oder
Ascheagglomerationen durchgefhrt. Durch axiale Prolmessungen wurde eine gute thermische Durchmischung nachgewiesen.
Trotz der niedrigen Prozesstemperatur ist der Teergehalt niedriger als fr die in der Literatur angegebene Wirbelschichtvergasung fr Holz.
G Die Strstoe in der Gasphase wurden mit Hilfe eines eigens dafr

optimierten Probenahmesystems und eines ICP-OES online und

oine analysiert. Durch die Anwendung eines Warmgaslters bei
400 C, waren alle Strstokonzentrationen mit Ausnahme von
Kalium und Natrium niedrig genug, um die Gasturbinenrichtlinien einzuhalten. Die Konzentration von Natrium war geringfgig
zu hoch, um die Grenzwerte fr ein rein grasbetriebenes GuD
(Graskraftwerk) einzuhalten. Kalium konnte aufgrund der geringen Sensitivitt des Messgertes nicht nachgewiesen werden. Die
Nachweisgrenze war zudem zu hoch, um eine ausreichend niedrige
Konzentration fr ein Graskraftwerk zu messen. Alle Konzentrationen sind jedoch ausreichend niedrig, um ein GuD zu betreiben,
in dem 10 % des Heizwertes durch die Vergasung von Gras, der
Rest durch Erdgas zur Verfgung gestellt wird. Sekundrmassnahmen um die Strstokonzentration zu beeinussen, wurden
mit Ausnahme des Warmgaslters nicht eingesetzt. Solche Massnahmen mssen jedoch eingesetzt werden, um die Grenzwerte fr
ein Graskraftwerk zu erreichen.

G Ein neuartiger EinpelletReaktor wurde konstruiert, um die tran-

siente Vergasung eines einzelnen Pellets zu beobachten. Der Vergaser zeigte eine hnliche Charakteristik wie die Wirbelschicht
hinsichtlich der Brennstogrsse, Heizrate und Gasentwicklung
whrend der Pyrolyse. Durch die Verwendung eines Oberchenionisierungssensor (engl. SID) konnte die Alkali (K + Na) Emission qualitativ whrend der Vergasung und Verbrennung eines
einzelnen Pellets dokumentiert werden. Die Ergebnisse ergaben,
dass die Hauptemission der Alkalien (90 %) whrend der Restkoksverbrennung stattndet. Die verbleibenden 10 % werden whrend der Trocknung, Pyrolyse und Vergasung freigesetzt. Das
Auswaschen der Alkalien aus dem Gras sowie das Zusetzen von
Alkalien zu dem Gras fhrte in beiden Fllen hauptschlich zur

xi

Kurzfassung

Beeinussung der 90 % aus dem Reskoks freigesetzen Alkalien.

Der Einsatz eines Warmgaslters bei 400 C fhrte erwartungsgemss zu einer stark reduzierten Alkaliemission. Die durch den
Filter passierenden Alkalien stammten aus dem kleinen Anteil,
der whrend der Pyrolyse freigesetzt wird.
Die vorliegenden Untersuchungen haben eindeutig gezeigt, dass sich
Gras zur Vergasung in einer Wirbelschicht bei moderaten Temperaturen bis 750 C sehr gut eignet. Eine Warmgasltration des Rohgases
bei 400 C ist ausreichend, wenn das Gas im obigen Sinne in einer CoVerbrennung mit Erdgas verwendet werden soll. Zustzliche Sekundrmassnahmen sind jedoch erforderlich, wenn das Gas in einem Graskraftwerk verwendet werden soll.

xii

Nomenclature
Symbol

Unit
Explanation
Latin symbols

cp

kJ/(kg K )
m/s2
MJ/kg, MJ/m3
MJ/kmol
MJ/kg, MJ/m3

g
HHV
HR0

LHV
i
M

M
V i
Q i

um f

w
xi
yi

ATP
CCA
CPC
DL
DS
ECN
eDaB
FC
FID
FP
GC
GE
HTSG
ICP-OES
IGCC
MP
MS
pH

kg/s
g/mol

m3 /s
W
K
m/s
kg/kg
%, ml/m3
g/l

Abreviations

Specic heat
Standard gravity
Higher heating value
Standard enthalpy of formation (25 C,1 bar)
Lower heating value
Mass ow of the component i
Molar mass
Volume ow of the component i
Energy ow of the component i
Kelvin temperature
Minimum uidisation velocity
Water content
Gas phase concentration
Contaminant concentration in the solvent
Adenosine triphosphate
Chromium copper arsenate
Condensation particle counter
Detection limit
Dry substance
Energieonderzoek Centrum Nederland
elemental Data Base
Fixed carbon
Flame Ionization Detector
Flow point
Gas chromatograph
General Electric Power
High Temperature Steam Generator
Inductively coupled plasma optical emission
spectrometry
Integrated gasication combined cycle
Melting point
Mass spectrometer
Potentia Hydrogenii (measure of the acidity
or basicity)

xiii

Nomenclature
PM1
PSI

Particulate matter smaller than 1 m

Paul Scherrer Institute (research institute in
Switzerland)
Residue Derived Fuel
Rheinisch-Westflisches Elektrizittswerk
Spectral database for organic compounds
Surface ionisation detector
Sinter point
Thermal Conductivity Detector
Thermo gravimetric analysis
Volatile mater
Valtion Teknillinen Tutkimuskeskus (Technical Research Centre of Finland
X-ray Photoelectron Spectroscopy

RDF
RWE
SDBS
SID
SP
TCD
TGA
VM
VTT
XPS

C
em f
e
C
H

Ar
Nu
Re
Gr
Pr
AR
at
da
el
FP
MP
SP
th
vol
w

xiv

Greek symbols



Pa s
C

m2 /s
kg/m3
kg/kg
kg/kg

Eccentricity factor
carbon conversion
Void fraction at minimum uidisation
Emission factor for raditation calculations
cold gas eciency
hot gas eciency
dynamic viscosity
Celsius temperature
air to fuel ratio, equivalence ratio
Kinematic viskosity
density of the component i
Stefan-Boltzmann constant
Ratio of exhaust gas ow to fuel gas ow
Mass ratio of component i

Dimensionless numbers






Archimedes number
Nusselt number
Reynolds number
Grashof number
Prandtl number

Subscripts and unit extensions

as received
By atomis, mainly as %at
dry ash
electrical
Flow point
melting point
Sinter point
thermal
By volume, mainly as %vol
By weight, mainly as %w

Introduction
Renewable energy is not a topic for green activists anymore for quite
some time. Companies like Nuon start to introduce biomass into their
large size power plants [1]. In many countries the power plant eet
is ageing and compensation is needed. This is an excellent chance
to introduce biomass into the power plant installations. There are
mainly two reasons: rstly this strategy would lessen the dependency
on fossil fuels, which are nite and emit much CO2 ; and secondly the
compensation for CO2 emissions will be reduced.
In the age of considerable increase of alternative energy in power production, the shortage of wood as energy resource in Europe is becoming
more evident. The Pulp and Paper Industry in Germany [2] depicts that
the extensive use of wood for energy production increases its market value, which in return locally raises the production costs of paper. On the
other hand paper price is traded on international markets. Production
of paper in this situation will become less protable. A phenomenon
arising from the shared exploitation of resources. The material will go
the the technology that generates the largest revenue.
The consequence is the increased search for additional biomass feed
stocks. Annual plants are a family of feed stocks gaining more and
more interest. Among those, agricultural residues as well as energy
crops play a major role. A neglected part of this family is native grass.
It becomes available due to a steady increase in preserving the cultural
landscape.
In some regions grass may be available as energy resource and could
be used as such if adequate characterized. At this moment grass is
considered to be one of the more dicult and least economical biomass
fuels due to its low bulk density and high amount of inorganic com-

xv

Introduction

ponents. The idea of gasifying grass for energy production has been
followed before [35] but not consequently.
The usage of grass can be positively linked to environmental issues [6].
Erosion is a problem, which can be addressed by planting energy crops
and grass [7; 8]. Reduced nitrate leaching was observed by Christian
and Riche [9] when miscanthus was established. Those plants reach a
very fast cover of exposed soil. It was also reported that growing perennial grasses in suitable places can remove CO2 from the atmosphere
into constant soil carbon [1012] (via root material) and subsequent
increase in soil carbon [13]. This again improves soil quality by preventing leaching of essential nutrients. Plants can also be used to retrieve
contaminations from industrial soils. The elements they bind, can be
extracted later on in thermal processes [14].
Mostly native grass is considered to be used in fermentation processes
(e. g. [15]). The product consists of roughly 60 % CH4 and 40 % CO2 ,
which must be separated in order to get a feeding allowance into the
existing natural gas grid. The technologies are not yet as sophisticated
as they should be. The slip stream of methane in the exhaust line is far
too high [16]  between 2 and 10 %  that could lead to second thoughts
about the ecological impact of the concept. Fritsche et al. [17] reported
that the energy potential of grass can be used more eciently when
being combusted. Also, the oor space required for a fermentation unit
of an equal energy output, is beyond those for equivalent thermal units.
This is mainly based on the much longer residence time of the fuel and
thus a larger plant for the same output. Around 50 MWth of methane
is planed to be produced in Gstrow (D) on a site with 20 ha space
oor 1 . The Skyve gasication plant uses approx.. 1 ha for an output
of 14 MWth . Raising the output to 50 MWth would increase the space
oor by a factor of 3.5 max. The carbon conversion is also much lower
compared to thermal units. But still the technology is competitive
being much simpler and easier to implement.
Another option is the combustion [18]. It produces only heat for steam
applications including steam turbines. Steam turbines show a lower
eciency than gas turbines. This option is not considered here on
purpose because the process should produce a maximum of electrical
energy. At this time the state of the art technology is an IGCC plant
(section 1.1). Fuel cell technologies for gasication applications are still
1 http://nawaro.ag

xvi

Introduction

not fully developed and therefore not available on the market. Also,
the given eciencies normally do not include the production of the fuel
gas and can not be compared as they come.
At this time woody biomass is characterised and reviewed very nicely
in various publications [1926]. Some publications deal with special
types of plants to study their use as biomass feedstock [2729; 10].
These are mostly of local interest. Only a few already try to tackle the
biomass feedstock of natural grassland species [3; 4; 20; 30]. In 1993
uidised bed gasication experiments were carried out for ryegrass [3].
In 1995 some experiments were conducted to proof the feasibility of
the gasication of alfalfa residues in a uidized bed gasier [4]. In 1997
modelling of a B-IGCC power plant was taken up to investigate the
economic feasibility of various solid fuels among, which verge grass was
a candidate [31]. The author calculated net eciency of the combined
cycle being 39 % by using an Aspen Plus model. The chosen gas
turbine was a GE LM 2500 with a gasier input of almost 70 MWth .
Being ten years old, these results would likely improve due to better
system eciencies. Grass was assumed to be partially availabe as waste
product.
Being a neglected fuel so far, there is still need to a much more detailed
analysis of the grass as fuel and the gasication process with grass.
This thesis especially aims to the characterisation of grass as fuel for the
application in integrated gasication combined cycles. This includes the
characterisation of the fuel, the stability of the gasication process and
the contaminant monitoring in the product gas. A dedicated sampling
system was used especially capable of collecting not only tars and water
but also aerosol particles to a high degree. See the next graph for a
visualised structure of the thesis.

xvii

Visualised structure of this thesis

Visualised structure of this thesis

Chapter 1
IGCC power plants and gas
turbine requirements
Chapter 2
Characterisation of grass as fuel
for power generation. Elemental
analysis and technical implications
4.0026

1.00794

He

TB =-269

TB = -253

x = 5.95
6.941

Li

TB = 1342
22.98977

TB = boiling temperature, C
x = major elements, %

gaseous @ 20C

9.01218

Be

solid @ 20C

TB = 2471

39.0983

TB = 759

x = 1.88

x = minor elements, g/kg

24.305

85.4678

87.62

TB =1382

137.327

Cs Ba

TB = 671

44.95591

Ca Sc

TB =1484

x = 6.57

Rb Sr

TB = 688
132.9054

x = minor elements, mg/kg

TB =1090
x = 2.04

40.078

TB =1897

x = 29.15

TB =2836

47.88

Ti

50.9415

51.9961

Cr

TB = 2671

x = 60.53 x = 7.06

TB = 3287

TB = 3407

x = 6.24

91.224

92.9064

95.94

Zr

TB = 4744
180.9479

Hf

TB = 4603

54.93805

Ta

TB = 5458

TB = 4639

x = 4.54
183.84

TB = 5555

55.847

Mn Fe

TB = 2061

x = 86.7
98.9063

Nb Mo Tc

TB = 4409
178.49

12.011

14.0067

15.9994

18.9984

TB = 4000 TB = NA

liquid @ 20C

Na Mg

TB = 883
x = 509

10.811

TB = 2265

186.207

58.9332

101.07

102.9055

63.546

65.39

28.0855

32.066

Al

Si

TB = 3695

192.22

106.42

112.411

114.818

TB = 5012 TB = 4428

196.9665

74.92159

TB = 357

x = 0.011

TB = NA

x = 0.79
121.757

Sn Sb

TB = 2072 TB = 2602

204.383

Au Hg Tl

TB = 3825 TB = 2856

118.71

TB = 767

200.59

x = 0.09

Ne

39.948

Cl

Ar

79.904

72.61

TB = 2204 TB = 2833

107.8682

35.4527

69.723

Cu Zn Ga Ge As

TB = 2963 TB = 2562

TB =-34
TB =-186
x = 6.616

TB = 907

Pt

TB =-246

TB = 2519 TB = 3265 TB = 281

TB = 445
x =184.6 x = 9.421 x = 2.173 x = 2.08

x = 37.16

195.08

30.97376

20.1797

TB =-188

26.9815

TB = 2913 TB = 2562
x = 6.63

x = 2.74

TB = -183

x = 43.21 x = 18.9

Ru Rh Pd Ag Cd In

TB =4150
190.23

Re Os Ir

TB = 5596

58.34

Co Ni

TB = 2861 TB = 2927

x = 308.8 x = 0.72

TB = -196

x = 12.07 x = 48.48 x = 1.77

207.2

Pb

TB = 1473 TB = 1749
x = 2.57

TB = 1587

x = 0.95

78.96

Se

TB = 685

83.8

Br Kr

TB = 59

TB =-153

x =1
127.6

Te

TB = 988

126.9045

131.29

TB = 184

208.9804

Bi

TB = 1564

Chapter 5
Single pellet gasification with
a novel reactor. First tests
and online alkali monitoring

Chapter 4
Fluidised bed gasification
experiments of grass. Stability,
and contaminant analysis

xviii

Chapter 3
Sampling system to support
online analysis of permenaent
gases and contaminants

Xe

TB =-108

Scope
The scope of this thesis by summarising the introduction is split into
three distinct parts:
G the properties of grass and the corresponding impacts on gasi-

cation and subsequent combustion

G the stability of grass gasication for various conditions

G the monitoring of the concentrations of the contaminants in the

product gas

The rst part is covered by a literature review about grass, its physical
and chemical properties with regard to gasication and gas turbine
application. By this review grass is also compared to other types of
solid fuel such as wood, agricultural residues, energy crops ans coal.
The second part requires the construction of a uidised bed gasication
reactor seeming best suitable. With this reactor experiments are carried
out to prove or disprove that stable operation of grass gasication is
possible.
The third part requires the further development and characterisation of
an appropriate sampling system to be able to monitor the contaminants
in the raw gas continuously.

xix

Chapter

IGCC power systems with grass

1.1 IGCC power plants

An IGCC (Integrated Gasication Combined Cycle) power plant consists
of three major units. The classic gas turbine cycle, the steam turbine
cycle, which draws its energy out of the exhaust gas of the gas turbine
and the gasication island that provides the combustible gas to the gas
turbine (gure 1.1) [32]. The natural gas red combined power plant
 as a base case  shows eciencies up to 60 % (see gure 1.4). The
major draw back in the past was the comparably high specic cost for
the installation. Today this technology oers new opportunities due to
the increase of the overall eciency. Additionally, there is a tendency
of the suppliers to incorporate gasication technologies in order to be
able to oer an entire power plant, which decreases the costs.
Figure 1.2 shows a brief history of IGCC installations (detailed numbers
in [3338]). The rst demonstration unit was built in Lnen, Germany
in 1972. The installation used the Lurgi gasier and a Siemens V93
gas turbine  the plant size was 163 MWel . The next installation followed in 1984 in Cool Water, USA. The gas turbine was delivered by
GE1 . The gasier was an entrained ow type Texcao. Famous coal
IGCC installations are Buggenum (253 MWel ) in Netherlands, Puertollano (300 MWel ) in Spain or Wabash River (262 MWel ) in the US. The
1 General Electric Power

1 IGCC power systems with grass

Figure 1.1: Simplied process ow of an IGCC power plant with optional CCS

rst biomass IGCC (B-IGCC) plant was set up in Vrnamo, Sweden in

1993 by Sydkraft. The gas turbine was a typhoon type from Alstom.
The thermal power of the pressurised circulating uidised bed gasier
was 18 MWth . Many plants followed most with coal gasiers  some as
big as 700 MWel . From the graph it can be derived, that the importance of IGCC power plants is still growing. Current IGCC proposals
usually include the promise to be carbon capture ready . This aims
to decrease the CO2 emission, which will safe expenses for CO2 penalties. This on one hand makes the installation more attractive, but
on the other hand reduces the overall eciency due to the additional
unit. Plans for the future have been proposed and partially started.
Examples are: Siemens [39] plans large plants with its newly bought
gasication technology now called SFG (former Future Energy GSP)
in China. Nuon2 started to built its Magnum plant in Eemshaven,
Netherlands [40; 1]. It is planned to be nished by 2011 and is supposed to run partially on biomass. The biomass portion will be increased
from year to year with the goal of replacing natural gas. RWE3 began
planning an IGCC-CCS plant (with carbon capture and sequestration)
in 2008 [38]. It is planned to be commissioned in 2015.

1.2 Options to integrate grass into existing power plants

The general options to integrate biomass into an IGCC installation are
listed below:
2 Dutch energy electricity company now owned partially by Vattenfall
3 Rheinisch-Westflisches Elektrizittswerk AG

1.2 Options to integrate grass into existing power plants

Figure 1.2: History of IGCC power plant installations. Not all power plants

depicted here are still running

G mono-fuel type: building a new B-IGCC like Vrnamo. This

usually limits the size of the power plant, due to the limited fuel
supply.

G coring type: building a new natural gas combined cycle and

include a gasier, which replaces certain amounts of the natural

gas energy.

G retrotted type: retrot an existing combined cycle plant with a

biomass gasier.

G blending type: blend a coal or waste gasier of an existing IGCC

plant with biomass supplies.

The mono-fuel plant clearly is the option with the most limited size
due to the comparably low availability of grass.
Building a new plant and integrating the gasier from the start would
certainly yield on optimised infrastructure and a larger plant size.
Retroting an exiting plant with a gasier is a matter of space, because
for energetic reasons the gasier installation should be located close the
bottoming cycle.
Blending an existing coal red IGCC plant with grass depends on the
type of gasier. It is, e. g., by all means possible to feed grass into an
entrained ow reactor, where the low melting point of the ash is even
welcome. It is however dicult to feed grass into an existing uidised

1 IGCC power systems with grass

bed gasier running at temperatures up to 900 C, and hereby risking

bed agglomeration.
As history and science showed, a mono-fuel plant needs adopted turbine
burners due to the dierence in combustion properties between syngas
and natural gas [41]. But this type also yields the lowest emission
impacts. In contrast, a blend of natural gas with up to 20 % hydrogen
and CO can be burned in a standard burner without modication [42].
For short termed introduction of grass  with a comparably limited
availability  into future installations the option to blend the syngas
with natural gas will likely to be more successful. Otherwise the plants
will be too small to replace a substantial part of the aging power plant
eets (see section 1.6).
From the point of the gasier the contaminant emission only is relevant.
From the point of the gas turbines there are only two types of plants
which dier in their gas composition. For the above reasons only the
mono-fuel and coring type will be considered further in this thesis
enclosing the other two types automatically.

1.3 Manufacturers implementation of syngas into gas turbine cycles

Adopted low LHV gas burners have been available for quite some time
now and were successfully installed e. g. in Vrnamo. Now the major
gas turbine manufacturers like GE [34], Siemens [43] or Alstom [44]
put much eort in developing syngas burners capable of burning not
only syngas but also various blends of syngas and natural gas. As it
is reported by Brdar and Jones [34] GE already has a burner, that is
capable of changing blends under full load. The diculties are mainly
the content of H2 in the gas. Hydrogen does stabilize the ame up to
a certain amount, which is related to its high laminar ame speed (fast
ame propagation). When using premixed combustion, there is a limit
for the H2 concentration, when the ame ashes back into the burner
nozzle at this point the burner has to be modied [42]. The reacted gas
should enter the turbine quickly to avoid early cooling; the combustion
chamber must be shorter for short ames. At the other end the ame
becomes long (slow ame propagation) if less hydrogen is in the gas and
the reactions are not fully completed when the gas enters the turbine

1.4 Gas turbine restrictions

blades. The burner must be modied accordingly to ame properties

being expected from the entire range of dierent blends.
The hydrogen content in air blown gasication usually does not exceed
15 %. For the combustion set this is a moderate concentration even
more if mixed with natural gas. The proposed mixture of 10 % LHV
(44 %vol) would lead to a mixture like the one listed in table 1.1 column
3. As it will be obvious the hydrogen content is very moderate. The
table lists only the major components. The blend though was calculated
including the minor components C2 H2 , C2 H6 , C3 H6 from the gasier
and C3 H6 , C3 H8 from the natural gas grid. The blend now can not be
considered as low LHV fuel anymore. As it was reported in Judex et al.
[45] this mixture can be processed in normal gas turbine combustors
without any modications. It is therefore suitable to retrot existing
natural gas combined cycles.

% LHV syngas blend

5.00 10.00 15.00 20.00 25.00

CH4
CO
H2
C2 H4
CO2
N2

70.64
3.04
3.30
0.23
5.53
16.41

55.32
4.68
5.08
0.35
8.51
25.29

45.72
5.70
6.20
0.42
10.39
30.84

39.14
6.41
6.96
0.48
11.67
34.65

34.36
6.92
7.52
0.51
12.60
37.42

LHV, MJ/m3

26.90

21.79

18.59

16.40

14.80

Table 1.1: Example of syngas/ natural gas blends based on the gasication

experiments (dry) and commercial natural gas

1.4 Gas turbine restrictions

It is very dicult to get coherent data on gas turbine requirements,
since it always depends strongly on the type of turbine, age, manufacturer and experience of the operator. This is probably the reason
why the published data is so heterogeneous e. g. in [46; 47; 31; 4852].
From table 1.2 it can be concluded that in the rst step of research,
elements like given in reference [52] (Na, K, Pb, V, Ca, Mg) should be
monitored more closely. An then secondary measures can be applied.
For further analysis the data given by [52] only is taken into account.
It is the most restrictive data found in literature. It may be that a
dierent manufacturer allows higher concentrations of contaminants.

1 IGCC power systems with grass

The numbers are given as concentrations in the fuel ow. The value
depends on the eective ow at the turbine inlet (combustion chamber
outlet see gure 1.3). Thus, the table gives dierent values for dierent
ratios of turbine inlet ows to fuel ows as dened by equation (1.1).
Conguration 7
assumed 7
7

K + Na
Pb
V
Ca
Mg

mg/kgf uel
mg/kgf uel
mg/kgf uel
mg/kgf uel
mg/kgf uel

GE**

50

coring
2
18*

GE**

12

mono-fuel
3.8
4.5*

0.3
1
0.5
2
2

0.108
0.36
0.18
0.72
0.72

0.072
0.24
0.12
0.48
0.48

0.027
0.04
0.02
0.08
0.08

Table 1.2: Gas turbine specications and inlet limits (*interpolated [52], **as

published)

so

et

nl
ir i

p
om

res

r
e
t
sto ine
bin
us
bu turb
tur
m
ha
Ex
Co HP
LP

General Electric LM2500 gas turbine

Figure 1.3: GE LM2500 aero derivative gas turbine [53] (HP: high pressure,

LP: low pressure)

exhaust gas ow, kg/h

fuel gas ow, kg/h

(1.1)

To get appropriate numbers for for the cases of coring and monofuel, must be assumed. The interpolated columns were calculated for
the 10 % LHV mixture ( = 18) and mono-fuel ( = 4.5). The air to
fuel ratio in the gas turbine was proposed to be = 2 ( = 18). This is
a good value for syngas mixtures. Increasing the combustion air would
lead to higher tolerances of the elements. For a mono-fuel plant with

1.5 Relevance of the restricted elements and condensibles

a low LHV gas, the limits are more restrictive, since will be much
smaller. The combustion air was proposed to yield = 3.8 according
to the B-IGCC plant in Vrnamo.
From the fuel review in the rst part of this work it was derived, that
additional elements with similar corrosiveness can be part of grass (gure 2.18). It is strongly suggested that these elements are monitored
as well though no restrictions are given at the moment. As a rst approximation the alkali type elements (Li, Ba, Sr) can be set below the
restrictions for potassium and sodium as well. Since the limits are set
as a sum this now means the sum of all ve elements should not exceed
the given limit.
Sulphur is an element, which is not limited by GE. This is justied by
the argument that sulphur levels up to 1 % does not cause any problems
in the gas turbine as long as alkalis are restricted [52]. Sulphur may be
a problem for downstream units like the heat recovery steam generator.
Still Roberge [54] reports alloy degradation by simple H2 S penetration
into the alloy.
The manufacturers want to make sure that their turbines run with the
lowest possible risk. Hence the limits are set rather low. Potassium
is much more restricted than sodium [52] though sodium seems to be
more corrosive then potassium [55] and volatilises in equal amounts.
Vanadium, calcium and magnesium are elements mainly known from
oil driven turbines. Sodium and potassium instead can also be present
in the combustion air or process steam (Cheng cycle). This can become
a problem especially if the plant is located close to the sea. In natural
gas usually only sodium can be found.
Particulate matter can cause deposits and erosion. There is a dependency of the combustion temperature and the particle size when particle
based deposits can occur [56]. The empirical study taking into account
experience from running gas turbine units revealed that the higher the
combustion temperature, the lower the limits for the particle size must
be in order to avoid depositions.

1.5 Relevance of the restricted elements and condensibles

Sodium and potassium Together with sulphur alkalis can lead to
severe sulphidation attacks through the deposition of the alkali melts
on the turbine. The reported compound is usually Na2 SO4 and K2 SO4 .
7

1 IGCC power systems with grass

The melt destroys the protective oxide layer of the alloys and the alkalis
react with the unprotected metal (see [57; 54] for more information).

Magnesium and calcium Magnesium and calcium are mainly res-

ponsible for depositions in lining and valves, which may also hinder
awless operation of the installation. Calcium is also known to be
able to damage the protective oxide layers in steel [54]. This makes
subsequent active corrosion more easy to take place. Magnesium melts
have been reported to destroy zirconium. It is also known to be existent
in alkali melts that are responsible for corrosion.

Lead and vanadium Vanadium pentoxide (V2 O5 ) with a low mel-

ting point can be formed after the combustion of V2 O3 , which is a

possible component in the gasication product. In the turbine, the
molten vanadium is considered to cause severe damage. Lead is also a
corrosive element if it gets into contact with the metal surface [54].

Particles Particles can lead to fouling and erosion of hot gas parts

as well as plugging and erosion of nozzles and valves. Normally this

problem is solved by dedusting the gas. Since dedusting is a standard
installation and hot gas ltration is a proven technology [56], hot gas
particulate removal will be included as part of the sampling system.
The temperature will be set to be 400 C which corresponds to a study
of Siemens [58]. The study was about retrotting a NGCC into an
IGCC. Here the syngas was proposed to be cooled down to 370 C
before entering downstream units. The exhaust heat can be used in
the bottoming cycle.

Tars Tars can lead to depositions in the lines or in the nozzle before
the burner if gas is cooled below their dew points. This is usually not
critical if the gas can be kept above 400 C.

Corrosion can be considered a three component mechanism. Firstly

the corrosive elements need to precipitate on a surface as a melt, then
the protective oxide layer must be cracked and last the oxidation of
the metal compounds can take place with subsequent removal of material [57; 54].

1.6 Power scales and biomass supply

1.6 Power scales and biomass supply

To get a better impression of the meaning of coring in terms of power

plant size and availability, the following gure 1.4 was created. The
replacement of 10 % of the gas turbine input heat with syngas would
result in a gure as depicted in the graph. The diagram shows the
eciency of combined cycles over the ISO base load4 output as given
by [59]. The brown dots mark combined cycle plants as oered by
a supplier. The two tting curves mark the trend for aero derivative
turbines (upper left line) and heavy duty turbines (lower right line). On
the right hand side the biomass amount is given to replace the named
10 % LHV of NG in each of the given plants (green squares).

Figure 1.4: The meaning of blending 10 % LHV of syngas into a natural gas

combined cycle

As it was calculated from a GIS analysis (section 2.5), a reasonable

amount of grass is 32 kt/a. This amount is depicted on the right hand
axis. The resulting size of a possible combined cycle plant could be
around 90 MWel . The gas turbine can either be an aero derivative or
a heavy duty turbine with latter having a lower eciency. From gure 1.5 it can be derived, that the specic costs for both installations
are comparable. Still aero derivative turbines oer the advantage of a
4 data corrected for xed output conditions, T, p, moisture

1 IGCC power systems with grass

high load and ow exibility. Especially the ow exibility is an important feature when blends of natural gas and syngas are used. Changing
the blend involves signicant dierences in turbine inlet ows, which
the turbine and burner must be able to cope with.

Figure 1.5: Specic costs of combined cycle installations 2008 [59]

10

Chapter

Grass for power generation 

a view on the fuel

In the rst part of chapter 2 general ndings, thoughts and the availability of grass will be discussed. Whereas in the second part the physical
and chemical properties of grass are given based on extensive literature
research. The investigated elemental composition and properties are
collected in a database and evaluated subsequently.

2.1 Why do we need to know ?

The general characterisation of the fuel is a necessary task since the
possible uctuations of characteristic properties will always exceed the
possible variations in such experiments.
The elemental composition of solid fuels strongly inuences the process
of gasication and combustion. While some elements like hydrogen or
carbon add to the process in a positive way, most of the others have
negative eects or both. They can inuence the process by decreasing
or increasing the ash melting point, harming downstream components
by fouling, deposition or/and corrosion and nally by polluting the
environment when being emitted. The successful introduction of grass
as an energy carrier, depends strongly on the knowledge of the fuel and
the capability of the available technologies.

11

2 Grass for power generation 

a view on the fuel

The gas turbine technology is highly developed nowadays. This includes special materials that allow higher entrance temperatures but
also are much more sensitive to contaminants. This especially aects
contaminants coming from the gasication unit. Trying to feed gas turbines with biomass syngas implies a extensive knowledge of both the gas
and the fuel. Otherwise gas turbine manufactures would never agree to
conduct real tests, which is a necessary step before implementation of
the technology.
Eventually the argument of the importance of grass as an energy carrier
is a fundamental task. There are countries, which possess enough grass
for a substantial contribution but others that do not. Yet, to prepare
the path to such a technology this characterisation is necessary.

2.2 Thoughts about climate change and CO2

The common opinion about renewable energy is that the fuel itself
has to be regenerative. But the crucial point is rather how fast the
produced CO2 can be xed into biomass again. Oil and coal too are
likewise renewable  if certain environmental conditions are set, only
the time until the carbon cycle is closed, is much longer compared to
biomass, see gure 2.1. The characteristic feature, which is relevant
is the residence time of the carbon dioxide in the atmosphere. This
part of the carbon cycle is the most important when discussing climate
change.
Oil
Natural gas
Coal
Peat
Wood

Usage of fuel
Formation of fuel
Primary growth

Grass
0

10

10
10
10
Carbon holdup time, years

10

10

10

Figure 2.1: Simplied stations of carbon during a life cycle

The faster this part of the cycle is accomplished the lesser problems
will occur. The conclusion is that the basis can not be "if" the carbon
will be bound again but rather how much time it needs. Hence the

12

2.3 Denition and classication of energy grass

expression renewable is rather dened by time than by properties. To

be totally consequent if a stable CO2 concentration in the atmosphere
needs to be maintained only as much CO2 may be emitted as it can be
xed again immediately.
The situation we face is an enrichment of CO2 in the atmosphere
(380 ml/m3 rising) caused by the intensive use of fossil fuels. The belief, that switching to renewable energies would solve that problem is
wrong. By using alternative energy resources we are just able to hold
a status-quo in terms of current CO2 level in the air. To resolve that
problem completely, carbon from the atmosphere (CO2 ) has to be stored away permanently. Ideas like carbon removal from the exhaust of
power plants by using algae or other technologies, which transfer the
gaseous CO2 into solid carbon mostly conceal one important point:
Having the carbon xed, the obvious thing is to use it again by selling a carbonaceous product. This would nance the expenses of the
plant but the carbon is released again eventually. Storing away the
solid carbon would end up in a plant that would cost a lot of money
but produces hardly anything worth selling. Something in between
as proposed by Reed 1 could be: using the volatiles and storing the
carbon rich char in soils. This would also lead to carbon enrichment
respectively improvement of the soil quality.
In terms of CO2 emissions even biomass can not be considered as alternative as long as fossil fuels were used to harvest and process the
material [60]. But going to alternative energy supply is not a matter of
instant switching but rather of stepwise and reasonable replacement as
well as increase in ecient energy use. There is one fundamental rule
that any process applied to the resource will consume a part of it and
thereby energy will be lost.
Obviously the biomass with the shortest cycle is annual and perennial
grasses as well as algae, where the retention time of carbon in air reaches
one or less than a year.

2.3 Denition and classication of energy grass

To proceed with the denition of energy grass it must be known that
there is already an expression for dedicated energy plants. Energy crops
is an expression mostly used in terms of specially grown C4 plants
1 http://www.biomassec.com/

13

2 Grass for power generation 

a view on the fuel

optimized in yield of biomass like Miscanthus, Panicum (switchgrass),

Phalaris (canary grass), Sorghum, Arundo Donax and Pennisetum purpureum (bana grass) [61]. Those plants have low or middle fertilizer
and water requirements and high biomass yields. Energy grass should
not include dedicated energy crops or agricultural residues, which are
already pooled in a technical expression. Figure 2.2 displays the classication of the three terms for young biomass products for energy use
as it will be used in this context.
DEDICATED
ENERGY CROPS

AGRICULTURAL
RESIDUES

Grown for the reason

of energy production.

Residues and waste

from agricultural and
food industry.

- Miscanthus
- Switchgrass
- Reed Canary
- Sorghum
- Hemp
...

- Straw
- Husk
- Shells
- Corncob
- Sheath
- Shuck
...

ENERGY-GRASS
Herbaceous products
from open grassland
- recreation areas
- low value pasture
- sport areas
- streetside greenings
- crop rotatation
...

Figure 2.2: Denition and separation of the term energy grass

Energy grass can be understood as herbaceous plants that grow in

natural grassland cultures, but is not fertilized and is not harvested for
a variate of reasons. Still it bears chemical energy, which could be used
for power or fuel production.
The big dierence between energy crops and energy grass is the fact,
that the rst ones are cultivated in mostly monoculture, which must be
taken care of, while the other one is only maintained showing a blend
of some 30 and more species. Dedicated cultivation of grass is pointless
since energy crops would be much more suitable for this task. More
about energy crops can be read elsewhere [61; 10]. It is of course obvious
that some species (e. g. Alfalfa/ Lucerne) can be sorted as energy-crop
and energy grass at the same time at dierent places, depending on
whether it is cultivated or not.
Grassland contains three major groups of plants: grasses (approx. 2/3),
legumes and herbs (approx. 1/3). The majority of the grass leads to the
general expression grassland regardless of the other two types. Some
titles use herbaceous biomass; this refers mainly to the herbs. Since

14

2.4 Availability: literature digest

grass gives the major contribution, other expressions should be avoided

to make sure everybody talks of the same subject [62]. In the Phylis
database from ECN2 [63] the term verge grass was used to express an
undened blend of grassland genotypes.

On this note the simple term grass  will be used in the

further context.

2.4 Availability: literature digest

The occurrence and availability of grass is still uncertain at the moment
and can only be estimated. A study from BFE3 [64] reports around
1'000 kha grassland area in Switzerland, from which a biomass yield
of around 5'000 kt DS/a is derived4 . This is most likely too optimistic
because normal extensive grassland cultures produce between 1 and
3 t DS/ha [6; 17]. This would rather yield an annual biomass of around
2'000 kt DS/a. Florine et al. [30] reported a biomass yield of up to
8 t DS/ha in the US. This is hardly achievable without fertilizing the soil
or otherwise using a soil having a huge storage of nutrients at this time.
A comparable scenario for Germany calculates with 3 t DS/ha having
a potential area of roughly 315'000 ha in 2010 [17]. Another scenario
from Germany Raab et al. [65] reports 20 % excess grassland provoked
by the cutback of the cattle number and the transition from extensive
grassland to cultivated cattle feed [17]. The development shows that
more and more areas are freed of feed production because the stock
of cattles decreases continuously. The remaining cattles produce more
milk and therefore need more concentrated feed. The protection of
species on the other hand forces a maintainance strategy for these areas
(Oenhaltungschen).
In Switzerland a rst estimation gives a total area of low usage grassland
of around 26 kha [66; 67] and another ten kha of other areas of biomass
maintenance.
Not all of the reported biomass can be eciently used, since there are
losses from storing, transporting and preprocessing. Mass loss due to
rain can be up to 20 % (see section 2.7.2).
2 Energy research Centre of the Netherlands
3 Bundesamt fr Energie
4 DS: dry substance

15

2 Grass for power generation 

a view on the fuel

The cost of supply can be estimated between 80-90 e/t DS (2006),

Rsch and Raab [68]. Slightly higher numbers were reported by Eltrop et al. [69]. In Switzerland the current hay price (2009) is around
270 CHF/t DS5 . Rentizelas et al. [70] reports that storage and handling accounts for around 50 % of the total costs of logistic. Worley
and Cundi [71] calculated a total delivery cost of hay type sorghum
of around 57$ (1996). Cundi et al. [72] computed delivery costs for
switchgrass without harvest handling of around 19$ (1997). Harvest
and storage costs account between 20 and 30$ (1996) [73]. Storage
consumes space even more when the material  as it is the case here
 is delivered only once maybe twice a year. This is the reason why
the density (see section 2.7.1.2) is the most important parameters for
pre-treatment. Simulations of logisitical and storage concepts always
depend on a few very sensitive assumptions like moisture of the fuel,
drying expenses or constant availability of the material. The results
must always be discussed critically.
The plant growth follows an expected curve of slow progressive increase
at the beginning, when the leaves are few and small followed by a high
production period when the leaves have optimal number and coverage
and a slowing down period, when leaves and plants start to grow into
each others zone of light, soil and moisture (see gure 2.3) [74; 75].
The mortality rate equals the production rate until another parameter
limits the growth.

Figure 2.3: Development of crude bre (celluloses, lignin) during spring re-

produced from [74]

5 www.agrigate.ch

16

2.5 Availability: GIS analysis for Switzerland

The main increase in biomass is normally found in late spring (gure 2.3). Followed by the summer recession when the temperature
gets hot, the soil dry and the humidity is low. This leads to hindered
water and nutrient uptake.
The number of possible cuttings do depend on the type of vegetation
and soil. For extensive grassland usually two cuttings per year can be
done. A distinct higher or lower usage will lead eventually to a lower output. Dierent species have dierent regenerations abilities after
being injured by mowing or animals. This results in dierent regenerations times, which in return determines the interval of the possible
swath [76]. The production rate  if the system is maintained properly
 is normally increased by doing regularly cuttings [77].
There is a distinct limitation of utilization regarding the swath. After
the mowing the reservoir of NPK6 must be built up again and the plants
must unfold their leaves to be able to produce biomass. If the grassland
is cut too often the harvest will become poor [76]. Late harvest and
lower cut frequency can improve the biomass yield [78]. It must be
noted, that the species and richness change after each cutting.
Figure 2.4 illustrates a possible concept of how the grass can be taken
economically to a power plant. The green dots represent the harvested
areas, the orange dots mark the primary processing plants where the
grass is condensed to a high degree. The big red dot is a central power plant where the processed grass will be transformed into electrical
energy.

2.5 Availability: GIS analysis for Switzerland

A GIS7 study for Switzerland has been conducted [80], though it was
not a main issue of this thesis. It was conducted on behalf of the
BFE and together with and managed by J.-L. Hersener (Ingenieurbro
Hersener). It revealed the grass yield for selected areas. The locations
were chosen along the infrastructure, where the construction of a GT
combined cycle plant seemed reasonable. In the north of Switzerland
(Gsgen) an area of about 27 km radius produces a grass yield of about
32 kt/a of grass (gure 2.5). This would correspond to a gasier size of
about 20 MW input. The mean transport length would correspond do
6 Sodium-Phosphorus-Potassium
7 Geographical Informations System

17

2 Grass for power generation 

a view on the fuel

Figure 2.4: Provision concept for Switzerland as suggested by Ganko et al.

[79] for Poland

approx. 30 km. Other authors calculated with only 20 km [69] so 30 km

can be considered rather an upper limit.

Figure 2.5: GIS analysis for grass in Switzerland [80]. Each circle yields

about 32 kt DS/a of grass.

For the analysis the georeferenced statistics (Arealstytistik) for Switzerland was used and evaluated with various lters like tilt, sunshine,
precipitation, altitude, exposition and soil suitability. Due to this lters
grassland, which is qualied for cattle food was excluded. Grassland

18

2.6 Critical observations - energy vs. food

with an exceeding tilt, altitude and so on compared to a boundary value

were excluded too. Detailed information can be taken from [80].
For the type of grass mentioned above the logistical concept of transportation from the eld to some place is already established. At the
moment the harvest is either transported to farmland where it is ploughed in the soil for enrichment or it is used if suitable for feeding or
nally it is disposed. The eort left is the redirection of the material
to a central processing point. This is a minor change in the logistical
structure and the stimulus for the owner to do it.
From this analysis it becomes obvious, that for Switzerland the availability is a very critical parameter. As is was stated before the plant size,
which can be expected for the coring concept is about 90 MWel . Replacing a substantial part of the current power plant eet would rather
aim to sizes larger than 500 MWel . Especially for Switzerland, where the
areas that are available for such plants are rather scarce. Still grass can
be used in a mixture together with agricultural residues. This would
yield a bigger amount of available fuel, much more likely to satisfy the
named size.

2.6 Critical observations - energy vs. food

We must always be aware of the fact, that there is no resource or
arable land that is not under stress of being exploited by competing
faculties [81]  Forrest land is lost to agricultural land, which intensively used is eventually lost being unproductive. Giving priority to one
interested party is most of the time not a matter of reason but rather of
money. Political guidelines are responsible for not letting economy become unreasonable and unsustainable. There is exactly such a situation
for natural grassland. There are several options how to use it, among
which are: the bio bre industry, biogas producers, soil improvement
and not least feed extender. The latter is loosing more and more importance because of the increase in high potential cattle needing high
value feed.
Within the last two year the discussions about energy vs. food surfaced
rapidly. Grain, soya and corn prices increased based on the usage of
those food stocks for biofuels. This eect was enhanced by people
who started trading with those values [82]. Bio-fuel dedicated energy
plants bear more environmental threats than their title suggests [8385].

19

2 Grass for power generation 

a view on the fuel

The change in land-use conceals light to heavy long term consequences,

which are not easily visible. This includes carbon release from forest
clearing or breaking of soil surfaces, which subsequently must count as
additional CO2 release and soil degradation.
Grass should not be competing with food in terms of used acres. There
are quite a number of areas, where grass has to be maintained but growing high quality feed or other usage is not possible or not allowed.
Good feed for cattle are not equally good as fuel. It contains much
raw protein and thus nitrogen and minerals being not wanted in the
gasication process. Extensive grassland cultures (not fertilized) normally show a high amount of species (high diversity) but also fail high
biomass yields. The quality for feed is very poor. In contrast fertilized grassland shows high biomass yield, good nutrition values but low
number of species [62].
In addition, plants rich in nitrogen show unfavourable drying mechanisms [77]. Further does extensive grassland cultures cope with low
nutrient contents. This will reduce the amount of alkali elements in the
fuel. All this leads to the conclusion that extensive grassland products
are more suitable for gasication than the intensive ones.
There is one thing to be noted: using grass for energy production has
complex eects leading to unexpected situations. One is that agriculture may start to produce grass which completely misses the point of
the idea, but may be more protable than to feed it to the cattle in
times when energy costs are climbing high enough; another one if grass
is left on the ground rotting, the fermentation process produces CO2
and also methane, which is even worse in terms of climate impact [86].

2.7 Common properties and their impact on thermal processing

Natural grass diers signicantly from wood and coal with respect to
certain elements. There are three major points, which cause problems
in almost all steps of processing.
G material structure (pre-processing)
G elemental composition (process management)
G hazardous products (post-processing)

20

2.7 Common properties and their impact on thermal processing

Thus structural, physical and chemical properties must be identied

and characterised, which will be done in the following sections.

Remarks on the graphs The graphs in this section show compa-

risons of various fuels. The data was collected from published data
and inserted into a database now referred as eDaB8 . The square mark
shows the algebraic average values; additionally the median is plotted
as a diamond mark. The data itself is printed as dots in order to see
the distribution clusters. The numbers in brackets show the number
of data available for each element in the specied group. All numbers
refer to dry biomass unless specied otherwise.
Dry biomass is assumed to be not completely dry, but dry with respect
to an appropriate method of drying. Not many authors give the applied
procedures or uncertainties together with the published data. For this
reason no error bars or condence regions can be told. The data shall
give an impression of the level and range to be expected.
Demolition wood is not included in the data, since it contains additional compounds from impregnation or colouring. Such feedstocks need
special care when thermally processed.

2.7.1 Material
Material properties are macro-physical properties like bre structure,
storage density and other bulk properties. These properties are relevant
for harvest engines, pre-processing units and storage facilities but less
relevant for the gasication process [87].
2.7.1.1 Lignin and cellulose
Annual or perennial plants have low lignin contents due to the lack of
the secondary wall of the cells. Lignication takes primarily place in
the secondary wall of the cells, which hardens and stiens the material
when plants grow old. The primary walls of the cells instead show lower
lignin contents and are thus much more fragile against environmental
inuences. As Ghetti et al. [88] stated, the dierence of the bonding
of the two materials lead to dierent devolatilisation behaviour. As
mentioned before fuel containing less lignin is expected to produce less
8 elemental Data Base

21

2 Grass for power generation 

a view on the fuel

char [89]. This is enhanced by catalytic char reactions if an increased

alkali content is given [90; 91]. This was tested mostly by doping char
with certain alkali components such as K2 CO3 . In contrary, it was reported by DeGroot and Richards [92]; von Scala [93] that with increased
alkali content the char production rate is increased The higher cellulose
content and light structure of grass will result in a fast and high volatilization [94], which in return enables a lower process temperature and
subsequent sensible heat loss through the exiting gas ow. Though von
Scala [93] stated that the heating rate does not have an inuence on
the char formation, Williams and Besler [89] observed otherwise. The
heating rate as well as the end temperature had a signicant eect on
the fraction left after the process.
Biomass containing more lignin will likely produce more liquid during
fast pyrolysis [95], since the majority of heavier molecular weight derived compounds present in pyrolysis oil originate from the lignin monomers present in the biomass. Since grass contains less lignin than wood
it must be specically tested if the path via pyrolysis oil is reasonable.

2.7.1.2 Density
The density of the fuel or bulk density inuences on one hand the
economy of the logistics and on the other hand the handling of the
feed into the power plant. Thready material like straw and grass are
harvested loose and normally transported as bales or other compressed
forms. Decreasing the void fraction both enhances the handling and
the logistics economy.
If the material is compressed to clusters the density increases to 150 kg/m3
at least [69] (table 2.1). On site pelletizing was successfully tried in the
90es [61] but terminated because of the lack of protability in those
days [96]. The pellets produced this way showed a density of 8001200 kg/m3 . Rabier [97] reported similar values. A centralised pellet
manufacturer communicated to need around 4 % of the fuel energy 
straw in this case  to produce a high quality pellets (including milling
and drying)9 . Other types of equally high density fuels are pyrolysis
oil or slurry (mixed oil and coke), or torreed pellets [98].
9 http://www.buhlergroup.com

22

2.7 Common properties and their impact on thermal processing

State

Density, kg/m3

On site
Fresh (grass)
Standard Fill (chaed grass)
Dried and chopped grass pellets
Bale (grass)
Compact roll
Bale (straw)
Dust (crops)
Pellets (bulk straw)
Pellets (single, straw)
Pellets (agricultural)
Pellets (grass)
Oil (rape)
Pyrolysis oil (general)

1.4

(kg/m2 )

50
85-100
170-380
120-150
350
800-1200
150
540-660
1100
950-1250
1300
920
1200-1300

Reference
calculated
[7]
[21]
measurement
[7]
[61]
[96]
[99]
[23]
[97]
[97]
measurement
[99]
[100]

Table 2.1: Typical densities of dierent states of grass and comparable fuels

in

kg/m3

2.7.2 Mass loss and stability

To ensure continuous operation of the power plant, storage of the fuel is
unavoidable. But there are several steps, at which mass loss of the solid
material can occur, thus as little steps as possible should be ensured.
1 harvest losses due to pick up eciency
2 respiration and crumble losses due to on eld drying
3 leaching losses due to rain on cut material
4 storage losses due to hygroscopic behaviour of the material (fungi,
bacteria)
5 abrasion losses due to mechanical exposure during transport
Most problems can be addressed by enhancing the processes of drying,
preprocessing and compacting.
Harvest loss can not be avoided since pick up eciencies can not be
100 %. It is directly linked to the time given for the harvest. Respiration losses can be reduced by drying the material as quick as possible
below 38 % moisture. Then respiration activity of plants is very low.
But bacterial degradation still goes on until the grass is at least as dry
as 15 % moisture. But if the grass is too dry before being transported
crumble losses will increase [77]. Tedding is still the most simple way

23

2 Grass for power generation 

a view on the fuel

to dry grass. To increase the drying rate the grass must be bruised
as much as possible to free the water from within the plant. The unbruised plant will close its stomata shortly after being cut and thus the
intracellular water ill not be driven out easily. When stored in natural
form the material can take up moisture again due to its hygroscopic
behavior [101]. In a highly humid atmosphere funghi and bacteria will
then start to decompose the material.
Leaching as mentioned above has two eects the rst one is reduction
in material, which is negative and second a large part of nutrients and
minerals are lost which is only negative if the material is used as feed
for cattle. Instead it is a highly appreciable result if used as feed for
energy production for two reasons: lower nutrient removal from the soil
and lower contaminants in the gas stream. Watson (taken from [102])
reported some numbers for rain losses listed in table 2.2.
Treatment
No rain - mechanical losses
Rain
1-2 showers (1-20 mm)
5-6 showers (12-63 mm)

Loss DS ( %)
14.7
23.7
18.9
27.1

Table 2.2: Losses of dry substance (DS) during haymaking [102]

During transport of the solid material, whether as pellets or packed,

abrasion losses will occur. In general it can be noted that less losses
will occur, when the material is more compacted [61]. It will also use
less storage space, which is economically interesting. The abrasion of
pellets was studied by Obernberger and Thek [23]. The results show a
signicant loss of mass if the pellet quality is low  it can be as high
as 20 % with an average value is 4 %.
If the fuel is processed to pyrolysis oil or even slurry, losses are signicantly reduced. But then long term stability of the uid must be
considered [103]. Producing slurry has some other advantages: the
density is comparably high (table 2.1), which in return decreases the
necessary storage and transport volume; biological degradation (mass
loss) can only take place slowly; liquid fuel is much easier to transport
than solid or rather brous fuel. But the demand on the material of
the storage facility is much higher since pyrolysis oil is very aggressive
(pH 2.8 [100]) and toxic.

24

2.7 Common properties and their impact on thermal processing

The bio-degradation rate of pyrolysis oil is around 50 % within 28 days,

which means that it is degraded if spilt twice as fast as fossil oil [104].
This is an important environmental aspect, since accidents where oil is
lost through damage is almost unavoidable as history shows.

2.7.3 Physical analysis

The physical properties are properties that dene the material in terms
of weight, state of aggregation, energy content, melting point, volatility
in other words thermal and material attributes.
2.7.3.1 Energy content
Energy in biomass is derived from solar energy. Photosynthesis transforms the energy in solar radiation into solid biomass or phytomass.
The maximum eciency that can be theoretically obtained is around
5 % [105] (exergy analysis). Experimental studies [106] showed around
4 %. The Energy content of biomass is expressed either as HHV (Higher
heating Value) or LHV (Lower Heating Value). The dierence is the
state of aggregation of water (H2 O) after combustion. If the energy of
the steam can be recuperated as usable heat the HHV is obtained. If
the steam must be discharged only the LHV can be obtained.
There are several empirical formulas to calculate the energy content
of biomass. The most familiar one is probably the formula of Boie
(equation (2.1)) where C, H, O are the mass fractions of the elements
in the biomass.
LHV, MJ/kg = 34.8 C + 93.9 H 10.8 O

(2.1)

Other formulas return the HHV of Biomass like the one published by
Channiwala and Parikh [107] (N: Nitrogen content, Ash: ash content
from proximate analysis):
HHV, MJ/kg = 34.91 C + 117.83 H 10.34 O

1.51 N + 10.05 S 2.11 Ash

(2.2)

Typical LHV values of dry biomass are around 17 MJ/kg, where the
dierence between LHV and HHV depends on the available hydrogen.

25

2 Grass for power generation 

a view on the fuel

The hydrogen forms water vapour, which stores the enthalpy of evaporation. Oasmaa et al. [100] gives the correlation equation (2.3) to
calculate the LHV from the HHV
(2.3)

LHV, J/g = HHV, J/g 218.13 H (w %)

Grass normally shows slightly lower LHV values than wood because of
its higher ash content. Oil or lignin containing plants show higher heating values since the heating value for cellulose is much lower (17 MJ/kg)
than for oil (36 MJ/kg, C40 H44 O6 ) and lignin (29 MJ/kg, C6 H10 O5 ) [20].

35

LHV, MJ/kg

30
25
20

od

Wo

[48

]
]
[60
[42
d.
ps
esi
o
r
r
.
yc
ric
erg
Ag
En

10
5

18

al [

Co

15
8]

s [8

data
average
median

as
Gr

Fuel type

Figure 2.6: LHV of various fuels from eDaB

Carbon is the main energy carrier followed by hydrogen as indicated in

table 2.3. This is one reason why a good carbon conversion is such an
important factor.
Element

mass fraction
kg/kg

H2
C

0.0298
0.4848

molar fraction
mol/kg

Energy of combustion
MJ/kg ([108])

27.56
40.36

-6.67
-15.88

Table 2.3: Energy content of elements

When gasied the energy content is reduced according to the cold gas
eciency of the process. This is normally below 80 %. The produced
raw gas is called low LHV gas (Schwachgas) referring to its low energy

26

2.7 Common properties and their impact on thermal processing

content (usually between 3 and 6 MJ/m3 ). To run a gas turbine around

its ISO rating, higher ow rates must be realised. This can lead to
serious changes in ow patterns. Generally aero derivative gas turbines
seem to be much more suitable for this application since they can cope
better with changes of the gas ow than heavy duty turbines [109].
Low LHV gas (from 2.5 MJ/m3 ) can be burned in gas turbines [110]
(ALSTOM burner). There are gas turbines especially adapted for the
use of low LHV gas (GE LM2500 [31]). In Vrnamo a gas turbine was
used from European Gas Turbines LTD that aparently is a subcompany
of ALSTOM power now. The gas turbine was provided with dierent
syngases from wood, bark or straw. New turbines are made of high
tech material and elaborate coatings in order to increase the inlet temperature. The fuel requirements are getting even more strict for this
type of turbines.
2.7.3.2 van Krevelen diagram
The following diagram shows the process of coalication of biomass. It
was set up by Prof. van Krevelen [111] to reconstruct the mechanisms
of coalication by the sub-processes dehydrogenation, dehydration etc.

40

molar ratio H/C

2.5

Wood [63]
Agric. resid. [80]
Energy crops [51]
0.7
Grass [94]
30
Coal [37]
Lignin
Cellulose
LHV isergo, MJ/kg [Boie]
6 H, mol%
0.iso

1.5
1
0.5
0
0

35

0.2

0.4

0.6

15

20

25

0.5

0.5

10
0.4

0.4

0.3

0.3

0.2

0.2
0.1

0.1

0.6

0.8

molar ratio O/C

1.2

1.4

Figure 2.7: van Krevelen Diagramm

It was also extensively used to evaluate the quality of fossil fuel resources. High quality fuel is always on the lower left side of the diagram
showing a high carbon content like anthracite. So called low LHV fuels

27

2 Grass for power generation 

a view on the fuel

(see [56]) show a much lower carbon content, is rather found way up
and on the right hand side in the diagram with a high oxygen content.
The coloured thick isolines mark the lines of constant LHV calculated
from the formula of Boie equation (2.1). Though this equation is overruled in the meantime and replaced by better ones (see section 2.7.3.1),
it only needs the C, H, O amount to get an good suggestion of the
LHV.
The dashed blue lines are the isolines for constant hydrogen content.
The 0.5 line marks CH2 O being a simple carbohydrate. Around 95 %
of the plants (dry matter) consists of carbohydrates [112] as depicted
by the graph.
In the diagram one can track the process of drying, which is the removal
of H2 O. For any oxygen removed two hydrogen atoms are removed as
well. The direction the fuel will be shifted is accordingly to the lower
left corner, if CO2 is released the fuel shifts to the upper left corner, if
CO is released the fuel shifts straight to the top and so on.
2.7.3.3 Water content
The water content further reduces the LHV and thus the eciency,
since more water vapour leaves the system carrying away energy. The
reduction is given with the following formula:
LHV, MJ/kg = LHVw f (1 w) h LV w

(2.4)

Where the index wf means water free , w is the water content dened
as
w=

MH2 O
MH2 O + MB

(2.5)

and h LV is the heat of vaporization.

Typical water contents for wood are 10-50 % (up to 50 % if newly
cut) [20], for grass before drying or torrefaction it would rather be
around 50-70 % [112]. In contrast, the eort to dry the material is
much less for grass than for wood based on the open structure of grass.
40 % water content would reduce the LHV to 55 %. It becomes just zero
when the heat of evaporation equals the HHV at around 90 % water
content.

28

2.7 Common properties and their impact on thermal processing

The other term to express the water fraction in the fuel is moisture. Its
referred to the dry substance (DS) instead of the wet substance (WS)
equation (2.6). This denition leads to the result, that the moisture
can very well exceed 100 % whereas the water content can not.
w=

MH2 O

(2.6)

MB

The water content strongly inuences the ability of the material to be

stored. More than 15 % moisture will lead to bio-degradation of the
material and development of fungi and bacteria. This would end in a
signicant loss of biomass or even auto ignition. Hence it is unavoidable
to dry the energy grass before storing [7].
70
60
Water, %w

50

27

d[

o
Wo

.
sid
. re
ric

data
average
median

]
[30

Ag

5]

s [2

40
30

erg
En

p
cro

20

s
ras

[32

17

al [
Co

10
0

Fuel type

Figure 2.8: Water content as received for dierent fuels from eDaB

Figure 2.8 depicts some values for the water content as received. Grassland material shows one of the lowest moistures of all. This is simply
due to the drying on eld. Most likely it was dried on eld before being
transported. The DIN 51 718 explains the procedure of drying. It
takes place in a drying oven at 106 2 C at atmospheric pressure until
the weight does not change any more.
2.7.3.4 Volatile matter and xed carbon
Volatile matter is the weight fraction of the material that evaporates
during the process based on the applied temperature. The ISO norm
ISO DIN 51720 [113] says the sample has to be coked at 900 C for 7

29

2 Grass for power generation 

a view on the fuel

minutes. The sample must be cooled down in an exsiccator to prevent

it from drawing moisture and is then weighed.
The volatility strongly inuences the reaction kinetics in the gas phase
and thus the composition of the product gas. A range of values for the
volatile fraction is given in gure 2.9

100

data
average
median

VM, %w

80
60

0]

s [4

as
Gr

40
20

od

Wo

id.

]
[46 gri
A

es
c. r

]
[61

]
[43
ps

ro
yc

erg

En

al
Co

]
[36

Fuel type

Figure 2.9: Volatile matter for various fuels from eDaB

The interpretation of this data is very dicult since it can not be assumed, that all data have been acquired under consistent temperature
and pressure. Some authors report 950 C, most do not even specify
the parameters or norm of their tests. The residue is called coke and
consists of xed carbon (FC) (gure 2.10) and ash [113] (gure 2.12).
The FC content in grass can be expected to be lower than in other types
of biomass. The high alkali contents will lead to an improved char
decomposition. Corresponding to the high volatility the FC content
must be lower than for coal.
The amount of FC, is quite relevant to the residence time of the particles in the reactor since the char reactions are the limiting step in the
gasication process [114]. The carbon conversion is obviously much dependent on the completeness of the char reactions. Higher temperature
and addition of steam will lead to more ecient and faster char reactions. Grass based on its low lignin content is suspected to produce
a low char yield and therefore lower gasication temperatures and a
higher throughput may be feasible.

30

2.7 Common properties and their impact on thermal processing

80

data
average
median

FC, %w

60

]
25

3]

. [4
sid
. re

40

40
d[

ric
Ag

Wo

al [

Co
4]

[3
ps

ro
yc

erg
En

8]

s [2

as
Gr

20

Fuel type

Figure 2.10: Fixed carbon for various fuels from eDaB

2.7.3.5 Volatilization diagram

The volatilization diagram (gure 2.11) shows the part of the fuel that
gasies according to section 2.7.3.4 versus the carbon plus ash content.
These two are the main contributors to the remaining coke. The volatile
matter is a very important parameter providing information about the
reactivity of the fuel.

100

Volatility, %

80
60
40
20
0
20

Wood [45]
Agric. resid. [61]
Energy crops [43]
Grass [40]
Coal [33]
30

40

50
60
70
Carbon + ash, %m

80

90

100

Figure 2.11: Volatility of various fuels from eDaB

31

2 Grass for power generation 

a view on the fuel

2.7.3.6 Ash content and melting behaviour

The average ash content is higher in grass compared to other biomass
based on its high content of inorganic compounds (mainly Si and K).
The elements are normally bound in mineralized complexes. The major
part is given by SiO2 and K2 O. Depending on the process management
and additives the elements will be partially bound to the ash. The other
part will leave the reactor with the gas as either particle or gas.
40

30

data
average
median

8]

. [7

id
res
ic.

Ash, %w

Ag

ass

Gr
s [4

rop
yc
erg

59
d[

Wo

34
al [

Co

9]

20

10

[95

En

Fuel type

Figure 2.12: Ash contents in various fuels from eDaB

Graph 2.12 shows, that the amount of ash in grass is not necessarily
higher than in some coals but still higher than in wood. Figure 2.13
gives the ash components distribution for grass. The high amount of
silicon and potassium is signicant dierent from other fuels.
The amount of ash also inuences the eciency of the cycle. Larger
amounts of ash will lead to a higher eort for ash removal and higher
particle or dust entrainment and thus better and more expensive dust
removal units. It also request a higher throughput of biomass to reach
the given energy output. This is especially important for plants where
downstream components are dependent on a constant input stream.
Ash fractioning is one way to achieve a separation of the elements,
which may be recycled as fertilizer from those that should be retained
like heavy metals [115].
Ash can be used in two ways: either to be recycled as fertilizer then the
best way is hot gas ltration above 800 C, which also results in emission
of heavy metals and alkalis into the gas turbine or engine [116]. Another

32

2.7 Common properties and their impact on thermal processing

60

Grass, %m da

50
40

SiO 2

]
[17

O3
Fe 2

]
17

O[
Ca

O
Na 2

10
0

[17

O3
Al 2
[7]
TiO 2

]
[17

gO

]
[17

17

O[

K2

30
20

data
average
median

[2]
O4
n
3
M

[17

[9]
CO 2
]

[10
]
Cl
[17 15]
[
P 2O 5 SO 3
[1] ]
SrO O [1
Ba

Ash components

Figure 2.13: Ash components for energy grass from eDaB

option is to use the ash as sorbent for gas cleaning, then the heavy
metals are bound to the ash and can not be used without additional
conditioning.
The melting point of ash is quite important for the process because
this is when slagging and sintering starts. When the slag cools down
it becomes a very hard glass like material that is very hard to remove.
In entrained ow gasication slagging is wanted, for it shields the units
wall from the immense heat the process needs (e. g. GSP gasier [117]).
It must be noted that for ash there is no homogeneous melting point. It
already starts at a certain temperature when most grains are still solid.
For coal there is a denition to determine the ash melting numbers:
DIN 51730 [118]. For biomass a new standard will be dened, which
should be released soon by the CEN10 . An cuboid of ash is positioned
in a heater and optically recorded. Then the temperature is increased
continuously. The characteristic temperatures are dened by the shape
of the particle.
A rough estimation of the melting point (MP), begin of sintering (SB)
and ow point (FP) was given by Hartmann et al. [20] in equations ((2.7))
to ((2.9) elements in %w). The calculated temperature can deviate
by as much as 100 C from the real one. This is based on the hetero-

10 European Committee for Standardisation

33

2 Grass for power generation 

a view on the fuel

geneous form of the ash particles and also on the fact that process ash
melts over a range of temperatures not at a xed one.
MP , C

SB , C
FP , C

1172 53.9 K + 252.7 Ca 788.4 Mg

1159 58.7 K + 237.9 Ca 743.8 Mg

1369 43.4 K + 192.7 Ca 698 Mg

(2.7)
(2.8)
(2.9)

The equations indicate, that the components K, Ca and Mg turned out

to be the main inuencers of the melting point. Since these components
are more abundant in grass than in wood, the melting and sintering
point is lower but not as low as expected. Using this equation for grass
the melting point of grass is still as high as 1077 C. Agglomeration
experiments of lucerne (alfalfa) gasication showed a lower temperature
of 840 C [119].
1400
]

. [8

ric

Sinter, C

1200
d

1000

800

600

id
res

o
Wo

[4]

data
average
median

Ag

ass

[6]

Gr

]
s [4

rop
yc
erg

En

Fuel type

Figure 2.14: Sintering point of various ashes from eDaB

It seems a remarkable point that equation (2.7) state a lower ash melting point for higher Mg content, whereas the melting temperature of
MgO is quite high (table 2.4). The ash composition is normally determined after soft combustion of the fuel. This means the elements are
fully oxidised. In gasication processes these elements are most likely
not fully oxidised but rather form other minerals like potassium silicate.
hman et al. [119] reported some behaviour of agglomeration in a uidized bed reactor. One of the materials used was lucerne showing similar elemental composition as a natural grass blend. The molten ash

34

2.7 Common properties and their impact on thermal processing

1800

Deformation, C

1600

od

Wo

[6]

]
. [9

sid

1400

. re
ric

Ag

y
erg

800

[4]

4
al [
Co

En

1200
1000

s
rop

0]

data
average
median

as
Gr

600

s [1

Fuel type

Figure 2.15: Deformation point of various ashes from eDaB

1800

Hemisphere, C

1600

2]

d[

o
Wo

]
. [8

sid

. re
ric

rop
yc
erg

En

1200

800

Co

s [4

1400

1000

3]

al [

Ag

ass
Gr

[8]

data
average
median
Fuel type

Figure 2.16: Hemisphere point of various ashes from eDaB

particles seem to consist of several layers showing varying compositions. The main components responsible for the melting were alkali
silicates, like K2 SiO3 , MgCa3 Si2 O8 , K2 Si2 O5 and potassium chloride.
This result shows clearly, that equations (2.7) to (2.9) assume a sucient abundance of silicon and calcium. The equations are a result of a
multi component analysis, where those elements did not seem to have
a major inuence because their amount was not limiting.
Moilanen [121, recited] reported that pressure has a negative inuence
on the ash melting behaviour. Pressurized gasication seems to carry
a greater risk of ash agglomeration for a given temperature.

35

2 Grass for power generation 

a view on the fuel

1800

Flow, C

1600

od

Wo

[4]

[8
d.
esi
r
.
ic

Ag

1400

s [4

rop

c
gy
ner

1200
1000

9]

al [

Co

data
average
median

800

s [9

as
Gr

Fuel type

Figure 2.17: Flow point of various ashes from eDaB

Component
K2 O
P2 O5
BaO
SiO2
CaO
MgO
V 2 O3

Melting point, C
740
562
1973
1722
2613
2825
1957

Table 2.4: Melting points of ash components [120]

Coal gasication and combustion has a long tradition and much experience can be taken from literature. There are some important key
numbers [87; 25], which can be used as indicators whether the ash tends
to sinter, form slags, or the alkalis tend to vaporise. One of the numbers
is the vitrication number. If the number is between 0.5 and 1, there
is a higher risk of the formation of low melting point compounds. The
elements are inserted as molar amounts. For grass it gives:
2(0.48 + 0.022)
2(K + Na)
=
= 1.0
3Si
30.335

(2.10)

This value shows, that grass is at the upper boundary of the critical
range. Another key value is the alkalinity number. It places the amount
of alkaline elements in relation to the acidic mineral formers [25]. If this
value is larger than 0.8 there is a higher risk of sintering, due to the

36

2.7 Common properties and their impact on thermal processing

excess of alkalis, which can form silicates if sand is used in the process.
For grass it gives:
2Ca + 3Fe + Na + 2Mg + K
= 1.1
2Si + Al + 3P + 2Ti

(2.11)

There are more of these numbers (see Strmberg [25]) but all of them
must be treated with care, since the reactions are very complex and
much dependent on process parameters. The numbers only give clues
about problems that may turn up during the process.

2.7.4 Chemical analysis

Chemical properties can simply be seen as the elemental composition.
Figure 2.18 shows the elements of the the periodic system reported in
grass. The colours of the boxes give an overview, in which class the element is found with respect to its amount in the fuel. gives the amount
in %, g/kg or mg/kg, respectively. B is the boiling temperature of the
element.
The chemical elements aect processes in many dierent ways, energy
production, ash composition, ash melting behaviour, deposition, fouling, corrosion and plant emissions. They can act catalytically, mechanically or chemically and obviously in a combination.
Among those, only a few elements are essential for the growth of the
plants (table 2.5). These elements will mostly be found in rough amounts,
though some plants manage to push the main part of these nutrients
into the roots by the time they fade. Potassium seems to be existing
mainly (>90 %) in water soluble forms (KNO3 , KCl) [24]. This is in
agreement with the results for water leaching of the fuel. Here the authors report a highly reduced concentration of potassium after leaching
(see section 2.8.3).

37

38

24.305

22.98977

qB =1484

qB =1382

137.327

x = 20.5

qB =1897

x = 29.15

qB =2836

qB = 3287

qB = 3407

50.9415

qB = 4603

Hf

178.49

Zr

qB = 4409

91.224

qB = 2671

qB = 5458

Ta

180.9479

qB = 5555

183.84

x = 4.54

qB = 4639

95.94

x = 6.24

Cr

51.9961

qB = 2927

qB = 5596

65.39

190.23

qB =4150
192.22

qB = 3695

qB = 907

107.8682

x = 37.16
112.411

qB = 2913 qB = 2562

x = 2.74 x = 6.63
106.42

qB = 5012

qB = 4428

qB = 2519 qB = 3265

Si

28.0855

qB = 445

78.96
74.92159

qB = 767

200.59

x = 0.09

qB = 357

x = 0.011

32.066

qB = 281

30.97376

69.723

72.61

x = 2.57

qB = 1473 qB = 1749

Pb

207.2

qB = 2072 qB = 2602
204.383

qB = NA

x = 0.79

Bi

qB = 1564

208.9804

x = 0.95

qB = 1587

121.757

Sn Sb

118.71

qB = 2204 qB = 2833

114.818

qB =-188

18.9984

Te

qB = 988

127.6

x =1

qB = 685

Se

qB =-34

He

qB =-269

83.8

Ar

qB =-186

39.948

Ne

qB =-246

20.1797

qB = 184

126.9045

qB = 59

Xe

qB =-108

131.29

qB =-153

Br Kr

79.904

x = 6.616

Cl

35.4527

x = 43.21 x = 18.9

qB = -183

15.9994

x =184.6 x = 9.421 x = 2.173 x = 2.08

Al

26.9815

Au Hg Tl

qB = 3825 qB = 2856

Pt

196.9665

qB = 2963 qB = 2562

195.08

qB = -196

Cu Zn Ga Ge As

63.546

14.0067

x = 12.07 x = 48.48 x = 1.77

12.011

qB = 4000 qB = NA

10.811

Ru Rh Pd Ag Cd In

x = 0.72
102.9055

qB = 2861

101.07

x = 309

58.34

Co Ni

58.9332

Re Os Ir

186.207

qB = 2265

98.9063

x = 86.7

qB = 2061

Mn Fe

55.847

x = minor elements, mg/kg

x = minor elements, g/kg

54.93805

Nb Mo Tc

qB = 4744

92.9064

x = 60.53 x = 7.06

Ti

47.88

LHV = 17.52 MJ/kg

Ash = 7.78 %w

liquid @ 20C

solid @ 20C

gaseous @ 20C

qB = boiling temperature, C
x = major elements, %

4.0026

Figure 2.18: Periodic table of elements in grass (molar mass Mills et al. [122]; boiling points Lide [120])

qB = 671

Cs Ba

132.9054

qB = 688

Rb Sr

x = 6.57

87.62

x = 1.88

85.4678

qB = 759

44.95591

Ca Sc

40.078

39.0983

qB =1090

x = 2.04

x = 509

qB = 883

Na Mg

qB = 2471

Be

9.01218

qB = 1342

Li

6.941

x = 5.95

qB = -253

1.00794

2 Grass for power generation 

a view on the fuel

O 2 , H2 O
CO2
H2 O
NO3 , (NH4+ )
K+
Ca 2+
Mg 2+
H2 PO4 , (HPO42  )
SO42 
uptake in form of
Cl 
Fe 2+ , (Fe 3+ )
Mn 2+
H3 BO3
Zn 2+
Cu 2+ , (Cu + )
MoO42 
Ni 2+

Oxygen
Carbon
Hydrogen
Nitrogen
Potassium
Calcium
Magnesium
Phosphorus
Sulphur
Micro elements

Chlorine
Iron
Manganese
Borum
Zinc
Copper
Molybdene
Nickel

0.01
0.01
0.005
0.002
0.002
0.0006
0.00001
yet unknown

45
45
6
1.5
1.0
0.5
0.2
0.2
0.1
% of dry mass

% of dry mass

Cl 
Fe 2+ , Fe 3+
Mn 2+ , Mn 3+ , Mn 4+

KNO3 , KCl
Ca(NO3 )2 , CaCl2 , Ca3 (PO4 )2
Mg(NO3 )2 , MgCl2 , Mg3 (PO4 )2
PO43 
SO42 
possible compund in plant

possible compound in plant

Table 2.5: Essential nutrients of higher plants [112; 77; 24]

uptake in form of

Macro elements

2.7 Common properties and their impact on thermal processing

39

2 Grass for power generation 

a view on the fuel

All other elements can full useful tasks in plant cells and structure like
Si but are not considered as essential since the plant can live without
it. It must be noted, that the composition not only depends on the
type and species of a plant but also on the age of the plant, the type of
the soil and season of the year. The data provided does not distinguish
between those eects but rather gives average data. The measurement
methods for ultimate elemental analysis are complex and can be found
elsewhere DIN/ ISO norms or [123].

Clean sampling One of the main sources of errors in the data is the
sampling of the material. Scientically spoken the data is wrong when
other materials like soil and sand are introduced into the sample when
collecting the fuel. But the data might still represent the real situation
much more precisely. This argument pictures the point of what the
data should be used for. If in the real situation the collection of the fuel
leads to the entrainment of other materials this is based on economical
budget and the process must cope with it. It is then a bad sample but
probably the more realistic value for commercial applications.
2.7.4.1 About the next chapters
In the next chapters more detailed information about the most relevant
elements in grass is given. This includes general statements about the
uptake and sources of the element as well as their part in gasication
and gas turbine combustion.
Hot corrosion of gas turbine blades is a large area, which can not be
covered here. Continuative literature is recommended for further review [124128; 54; 55; 49; 87].
2.7.4.2 C Carbon
Carbon is the central element of carbohydrates, proteins, lipids, nucleic
acids or any other organic structures of biomass [129]. Nonetheless
carbon is hardly more than a trace element on earth compared to others.
Its share is only around 0.04 %w of the earths crust. Still carbon is the
main energy carrier in biomass.
The stable state is CO2 , whereas CO is one of the main combustible products in the product gas after gasication. Though carbon monoxide

40

2.7 Common properties and their impact on thermal processing

is not counted as real greenhouse gas because of its short lifetime (13 months), it does indeed provoke the formation of other greenhouse
gases. The net reaction is
(2.12)

*
CO + 2 O2 )

CO2 + O3

The interesting point is that ozone in the troposphere is counted as a

greenhouse gas while being in the stratosphere it forms a shield and
prevents the UV-B radiation from being transmitted to earth [130].
This means for one emitted CO two greenhouse gases are produced.
The carbon content of grass is similar compared to wood and coal see
gure 2.19.
100
80

C, %w

od

60

d.

si
. re
ric

Wo

[63

Ag

]
[80

1]

s [5

rop
yc
erg

En

al
Co

40
20
0

[37

4]

data
average
median

s [9

as
Gr

Fuel type

Figure 2.19: Carbon content of various fuels from eDaB

To be consequent it must be told that besides from being the most

important element carbon can cause metal dusting or carborisation,
which are two types of corrosion. This eect depends entirely on the
way the process is run. It happens when materials are exposed to CO,
hydrogen or hydrocarbons. This process already starts at 430 C [131].
Carbon can agglomerate as coke or tar or leave the system as such,
which decreases the eciency. This loss is expressed in the carbon
conversion value. Tar is generally a disturbing component that must
be removed to prevent downstream components from damage. The
type of gasier and gasication temperature has a major inuence on
the tar formation and destruction.

41

2 Grass for power generation 

a view on the fuel

2.7.4.3 H Hydrogen
Though the mass fraction of hydrogen is much smaller compared to
carbon the molar fraction is about twice as much. The major part of
the dry plant consists of starch, which can be written as C6 H10 O5 .
This tells that the plant consists of approximately 50 %mol hydrogen
and around 25 % each carbon and oxygen. All other elements are minor
parts. This becomes very illustrative in gure 2.7.

15

data
average
median

0]

. [8

d
esi

H, %w

.r
ric

Ag

10

y
erg
En

1]

s [5

p
cro

ass

Gr

[93

37

al [

Co

od

Wo

[63

Fuel type

Figure 2.20: Hydrogen content of various fuels from eDaB

Hydrogen plays a major role in gas turbine combustion. It strongly

inuences the ame propagation in the combustion chamber. If to
much hydrogen is in the mixture there can be a ash back or even
an auto ignition within the mixing zone in front of the burner. But
by adding only a minor part of hydrogen the ame stability can be
enhanced [42].
2.7.4.4 O Oxygen
The oxygen content of biomass is very high compared to other fuels
(gure 2.21). It reduces the amount of oxygen input needed for the
process. But on the other hand is the reason why the energy density of
biomass is comparably low. The oxygen has to be transported all the
way along with the carbon and hydrogen.
Oxygen is a part in the celluloses structure, which itself is a major part
of the cell structures.

42

2.7 Common properties and their impact on thermal processing

60

data
average
median

50

O, %w

40
30

63

d[

o
Wo

sid

. re

20
A

c
gri

0]
. [8

y
erg

]
[51
ps
o
r
c

En

37

al [

3]
s [9

Co

as
Gr

10
0

Fuel type

Figure 2.21: Oxygen content of various fuels from eDaB

Pyrolysis or torrefaction are the options to increase the energy density (see section 2.8.4) by removing oxygen in a medium temperature
process.
2.7.4.5 N Nitrogen
As a component of proteins, nucleic acid, co-enzymes and chlorophyll,
nitrogen is essential for all plants and needed in rough amounts. Plants
normally incorporate nitrogen from soil and water, which is inorganically bound as nitrate (RNO3 ). Legumes can x air nitrogen by
means of bacteria. In the absence of nitrate plants are able to pick up
nitrogen in the form of ammonia. This is important, since much of the
applied fertilizer is distributed in this form.
Most of the nitrogen is found in pyrrolrings that form other compounds [132]. They are an important part of chlorophyll. Pyrrol and
pyridine are also types of tar known from gasication experiments even
after a scrubbing unit. Exchanging the nitrogen with sulphur pyrrol
becomes thiophene.
Woody biomass normally contains half of the amount of nitrogen than
coal, this is why it is sometimes used to decrease the NOX emission of
coal power plants by co-ring. Grass can contain as much nitrogen as
coal and even more gure 2.22. The one extremely high value comes
from a single analysis of Poa Pratensis. If removed, the natural range
is 0.3 to 4.0 %w, which is about the same range as coal.

43

2 Grass for power generation 

a view on the fuel

14
12

N, %w

10

data
average
median
id.

s
. re
ric
Ag

8
6

]
[77

ass

1
s [5

4
2

od

Wo

[60

y
erg
En

[97

Gr
cro

al
Co

[37

Fuel type

Figure 2.22: Nitrogen content of various fuels from eDaB

If fuel bound nitrogen is considered as the main factor of NOX production, using grass gives no advantage in NOX emissions (combustion).
The major components formed during the process are NH3 and HCN,
aside of which nitrogen containing tars can also be found. In uidised
bed gasication between 50 and 100 % of fuel bound nitrogen conversion into ammonia can be expected [133].
If ammonia is formed in the product gas or exhaust gas nitridation
can occur. This is a type of corrosion based on the absorption of ammonia in alloys. It causes embrittlement of the material [131]. All
nitrogen compounds formed in gasication except N2 are poisonous to
environment and must be scrubbed and catalysed back before discharged. Especially N2 O is a very eective greenhouse gas and was emitted
distinctly during the last decades. A very extensive work about nitrogen and its fate in gasication was done by de Jong [134] and can be
recommended for further studies.
During combustion the ammonia from fuel bound nitrogen reacts to
NO. Experiments using an ALSTOM gas turbine burner showed a
conversion of around 30 % [110], whereas simulations returned up to
60 %.
2.7.4.6 S, Sulphur
Sulphur is available for plants mainly in the form of sulphate SO42  .
They are soluble in water and can be assimilated by plants. SO2 can
44

2.7 Common properties and their impact on thermal processing

also be assimilated by some plants via the leaves. Other available compounds must undertake various reaction steps from H2 S, SO2 , S, FeS
to become eventually sulphates [132].
Sulphur is essential for plants since it it is part of many amino acids
(e.g. cysteine and methionine) [135]. Grass contains more sulphur than
woody biomass but less than coal (gure 2.23).

S, %w

data
average
median
1]

. [7
sid
. re

3
2
1
0

ass

Gr

ric
Ag

Wo

28

al [
Co

7]

[4
ps

55

[
od

[96

ro
yc

erg
En

Fuel type

Figure 2.23: Sulphur content of various fuels from eDaB

Sulphur is a very reactive element at higher temperatures, which are

given in gasication and combustion processes. It is one of the elements
that can cause fouling and successively severe corrosion on downstream
components [127; 125]. It is oxidised during combustion to SO2 being
the main component in the atmosphere to cause acidication. Though
H2 S is known as corrosive element, it has been reported that alkali
levels are usually limiting the corrosion of hot gas path materials [52].
H2 S is combusted quickly to SOX in the combustion chamber and is for
this reason not counted as a threat to the turbine blades. Since grass
contains large amounts of alkalis and sulphur, the corrosion problem
is suspected to become more severe. But grass also contains a large
amount of calcium. Ca is able to bind sulphur to the ash. In coal
gasication calcium is added for this reason. Nevertheless special care
must be taken to prevent alkalis and sulphur species from travelling
freely through the lining. Still much more care must be taken to avoid
sulphur poisoning of catalysts if such are used in the process [136]. On
the other hand there are catalysts that need a certain amount of sulphur

45

2 Grass for power generation 

a view on the fuel

to work properly if there is not enough sulphur in the gas it must be

added [137].
2.7.4.7 Al Aluminium
Aluminium is not known so far to be involved in any plant processes,
though it was observed that it slightly enhances growth. Some plants
still take up some aluminium if available in the soil [132; 112]. In higher
amounts aluminium becomes very toxic aecting the growth of plants
and forests. It also decreases the uptake of nutrients [138].
6
5
.

d
esi

c. r

4
Al, g/kg

data
average
median

]
[13

ri
Ag

3
2
1

oo

]
s [7

rop

10
d[

c
gy
ner

ass

]
[30

Gr

Fuel type

Figure 2.24: Aluminium content of various fuels from eDaB

Regarding gasication and gas turbine processes aluminium is reported

to bind alkalis as alkali alumino silicates, which are minerals with a high
melting point.
2.7.4.8 As Arsenic
Arsenic is mainly emitted by the copper producing industries, but also
during lead and zinc production and in agriculture [139]. It can be taken
up by plants very easily, so that arsenic enters the food cycle quite fast.
Hence the content in plants is proportional to the content in the soil. In
gure 2.25 various concentrations of arsenic in fuels are shown. Wood
can display much higher contents. The reason is most likely CCA11
11 Chrome-Copper-Arsenate

46

2.7 Common properties and their impact on thermal processing

treatment of the material since these materials show higher contents of

arsenic [140; 141].

2
20

As, mg/kg

15

1]

data
average
median

al [

Co

10
]

9]

Wo

[
od

id.

ri
Ag

es
c. r

[12

e
En

s [8

rop

c
rgy

1]
s [1

as
Gr

Fuel type

Figure 2.25: Arsenic content of various fuels from eDaB

Arsenic is considered to be totally mobilized at temperatures above

1500 C [142] (equilibrium calculation). The retention of arsenic in the
ash was measured to be around 50 % [143] whereas ash from coal shows
clearly better absorbence than ash from wood or straw. Arsenic can
be retained from leaving the system almost completely by recycling the
y ash as sorbent [144]. But as mentioned before the ash may not
be used as fertilizer anymore after this step. The leaching of arsenic
from wood is reported to take a long time [145]. Only after three days
one can expect to have reduced the As level in the wood siginifcantly.
The retention of arsenic on activated carbon was shown to be rather
poor [146].
2.7.4.9 B Boron
Boron is taken up as boric acid H3 BO3 . Experiments, in which the
absence of boron showed decrease of the cell dividing activity prove the
need for this element. Boron also inuences the usage of calcium [132]
But the specic task of boron is not known so far. Figure 2.26 shows a
few contents for boron published for fuels.
Boron is sometimes used in high temperature alloys for gas turbine
blades and structural enhancements for plastics [147]. It is so far not
mentioned as critical to process units. Leaching of coal y ash for 24h

47

2 Grass for power generation 

a view on the fuel

35
30

B, mg/kg

25

data
average
median

1]

al [
Co

20
15
10

6]
d[

[1
ps

o
Wo

ro
yc

erg
En

ass

[3]

Gr

5
0

Fuel type

Figure 2.26: Boron content of various fuels from eDaB

with pure water leads to a reduction of around 40 % of the boron in the

ash [148].

2.7.4.10 Ba Barium
Barium does not occur in pure form. Mostly it is found as barite
BaSO4 . Most of the barium available in plants and animals was set
free by human activities [139]. Naturally occurring barium is not very
mobile and is not taken up by plants easily. It is not needed by plants
for any known reason.
There are not many datasets available of barium in biomass. Some of
those are printed in gure 2.27.
Though barium is more corrosive than phosphorus very similar to potassium [126], it is not mentioned by the gas turbine manufacturers.
Presumably, the reason is that so far no barium concentrations worth
mentioning has found its way into a gas turbine or it was not measured.
It still bears the danger of corrosion like all the other alkalis when they
volatilise as chloride. Regarding grass, barium is only a tenth of sodium
and a 100th of potassium in mass. Since this is well within the natural
uctuation of potassium contents in the fuel it is usually neglected.
But in the gas phase those elements may be as well as important as
potassium when mobilized to a higher degree.

48

2.7 Common properties and their impact on thermal processing

700

data
average
median

600
Ba, mg/kg

500
y
erg

400

s
rop

[4]

En

300

1]

200

2]
d[

Wo

100

al [

[3
d.
esi
c. r

ri

Ag

ass

Co

[2]

Gr

Fuel type

Figure 2.27: Barium content of various fuels from eDaB

2.7.4.11 Ca Calcium
Calcium is needed for the cell structure, cell division and thus like
magnesium is essential for the growth and yield of grass [149]. It has
a mechanically stabilising nature but also is a part of chlorophyll and
enzymes and is needed for the metabolism [112]. It is not dangerous
unless inhaled as dust. The main component of natural calcium is
calcium carbonate CaCO3 , which is the main part of limestone. This
is abundant in most places. If not (acid soils) it must be introduced
articially as fertilizer.

Ca, g/kg

15

data
average
median

7]

20

od

Wo

]
[14

[2
id.

es

c. r

ri
Ag

1]

s [1

rop
yc

erg

En

0]

s [7

10

as
Gr

1]

al [

Co

Fuel type

Figure 2.28: Calcium content in various fuels from eDaB

49

2 Grass for power generation 

a view on the fuel

In gasication reactions calcium can form silicates, sulphates and phosphates [119]. Like K, Ca may catalyse char reactions and in contrast is
not reduced in this function by silica as it was found for potassium [150].
It was also found that Ca does change its catalytic behaviour dependent
on the state of the mineral.
Like potassium, sodium and vanadium, calcium causes deposition as
gypsum [46; 49]. But unlike the rst four calcium does not appear to
be corrosive to gas turbine blades unless it is volatilised as chloride.
Then Ca may be able to crack the protective oxide layer. There is
a limit for gas turbines (table 1.2). It contributes to the ash melting
behaviour by increasing the ash melting point [20].
2.7.4.12 Cd Cadmium
Cadmium is known to be carcinogen. Especially endangered are smokers who directly volatilize the cadmium in the plant (tobacco) and
inhale it [151; 139].
Up to 26 g/kg can be found in commercial fertilizer [152; 139]. It comes
as a component of phosphate rocks e. g. in Morocco, which is used to
produce the fertilizer12 . Another source is surely the emission from
anthropogenic processes [153]. Despite the fact that it does not seem
to be needed by plants it can still be taken up by them in considerable
amounts. It inhibits photosynthesis in most plants [154]. For this
reason some studies propose to use certain plants to remove cadmium
from soil and waters [155]. Soils must be considered as contaminated
if too high amounts of cadmium are found.
About 75 % of industrial cadmium is used in Ni-Cd batteries. The battery companies emit large amounts of Cd [156]. Most of the remaining
25 % is used for pigments, coatings or plating, and as stabilizers for
plastics. A very large amount of cadmium is naturally released into
the environment. About half of this cadmium is released into rivers
through weathering of rocks and some cadmium is released into air
through forest res and volcanoes. The rest of the cadmium emission
is based on human activities, such as manufacturing [139].
In the process stream, the main part of cadmium is found in the ne
particles likewise y ash or cyclone ash [153]. This fractionation is also
12 Communications of International Food Policy Research Institute

(http://www.ifpri.org)

50

2.7 Common properties and their impact on thermal processing

data
average
median

Cd, mg/kg

4
3

14

d[

o
Wo

s
rop

2
2]
. [1

c.
gri

id
res

[8]

c
rgy

En

3]

as
Gr

s [1

1]

al [

Co

Fuel type

Figure 2.29: Cadmium content in various fuels from eDaB

depending on the size of the feed (dust, chips). Equilibrium calculations

show that from roughly 400 C, gaseous Cd is the main species [157;
144]. A maximum of 10 % can be retained using y ash as sorbent.
Cadmium is rather an environmental threat than disturbing to gas
turbines but it volatilises very early (<300 C) in thermal processes [14].
So it has to be expected in the hot gas path.
2.7.4.13 Cl Chlorine
It is supposed that all chlorine exists in the biomass as inorganic components as diluted ions K+ , Cl  . It is needed for osmotic processes
and cell division activity. Absence of Cl in nature is rare and plants
can take up more Cl  than actually needed. This behaviour is pushed
by chlorine fertilizer, from which potassium is distributed as KCl. The
Use of K2 SO4 in fact increases the sulphur level in the soil but analysis
of the grown straw did not show a signicant inuence on the fuel [19].
Figure 2.30 depicts various chlorine contents in fuels.
It was found that chlorine tends to volatilize other elements like Si, K,
Na and others. It is supposed that it can even stabilize the gas phase
alkali compounds [158].
Since it is so reactive chlorine is one of the most unwanted elements
in biomass gasication. It does not only volatilize other elements causing deposition and fouling but also causes high temperature corrosion
itself. This can take place either as a direct corrosion or as induced

51

2 Grass for power generation 

a view on the fuel

data
average
median

50

Cl, g/kg

40
]

id.

30

es
c. r

[40

ri

Ag

20
10

od

Wo

[3

0]

7]

s [3

rop
yc

erg

En

ass

[58

Gr

7]

al [

Co

Fuel type

Figure 2.30: Chloride content of various fuels from eDaB

corrosion. Alkali sulphates were used to stress the surface, which was
much more successful when the surface was prepared with chlorine before [159; 160]. Chlorine starts to vaporize at very low temperatures 
below 200 C [158]. It forms HCl and HCN during gasication. HCl is
one of the main components to cause acidication in the atmosphere.
In combustion systems dioxin is formed within a temperature window
between 300 and 600 C [161]. But the formation needs excess oxygen,
which is not the case in gasication process. For this reason in the
energy grass gasication the formation of dioxins are of minor concern.
Around 80-90 % of those Cl components were found to be water leachable after 1h treatment. This means natural or deliberate leaching
will reduce the clorine content e. g. if the harvest is delayed over the
winter period but at least over a raining period [162; 20; 163]. This is
 as mentioned before  accompanied by a biomass loss; mechanically
and by decomposition. Since grass shows a very ne structure and large
surface the leaching will take much less time than for energy crops.

2.7.4.14 Co Cobalt
Cobalt is not one of the essential elements. It is taken up by plants in
small amounts if available. Though accumulation can occur. Cobalt
is not generally poisonous unless eaten or inhaled in large amounts.
Figure 2.31 shows some measurements of the cobalt contents in fuels.

52

2.7 Common properties and their impact on thermal processing

12

data
average
median

Co, mg/kg

10

8
]

id.

0]

4
2

o
Wo

1
d[

s
. re
ric

[16

s [7

rop

c
gy
ner

1]

al [

Co

Ag

2]

as
Gr

s [1

Fuel type

Figure 2.31: Cobalt content of various fuels from eDaB

Cobalt is mostly mined in combination with zinc. It is used especially

for corrosion resistant alloys and not mentioned as corrosive itself. At
temperatures below 1200 C cobalt and its compounds are mostly crystals and thus in particulate form, which can be ltered. Above this
temperature Co is also found in the gaseous phase (equilibrium approach [164]).

2.7.4.15 Cr Chromium
As far as it is known Chromium is not needed for plant organisms. It
can occur in dierent oxidation states such as Cr(II) or Cr(III). Where
Cr(III) is considered as not toxic, Cr(VI) is very poisonous and water
soluble [139].
At standard reducing conditions Cr2 O3 (cr)13 is the stable form of chromium up to 1800 K (equilibrium approach [164]). It is corrosive as CrF2
and chromium potassium sulphate [126]. Due to its high boiling point
retention in a particle lter even at higher temperatures  600 C could
be managed. Experiments with CCA treated wood showed that under
slow pyrolysis conditions around 98 % of the cromium is left in the
residue [141].
13 crystalline

53

2 Grass for power generation 

a view on the fuel

60

Cr, mg/kg

50

data
average
median

0]
. [2

sid

. re
ric

40

0]
s [1

Ag

30

rop
yc

erg

En

20

3]

s [1

d
oo

10

[13

as
Gr

1]

al [

Co

Fuel type

Figure 2.32: Chromium content of various fuels from eDaB

2.7.4.16 Cu Copper
Copper is used in the redox system of the plants. In absence of copper
 being quite rare in nature  the leaves become dark green, deformed
and show necrotic spots [112].
Copper is used in a very wide range of applications, which is connected
to an increased occurrence of copper in the soil [139]. Copper is not
poisonous unless absorbed in large amounts or inhaled as aerosol.
3

10

.
ric

10

ps

10

data
average
median

]
[26

Ag

Cu, mg/kg

d.
esi

17

d[

o
Wo

ro
yc

erg

En

]
[10
]
[53
ass
r
G
1]

al [
Co

10

Fuel type

Figure 2.33: Copper content of various fuels from eDaB

Copper is commonly used as a material with good thermal conductivity. It is also used in alloys for gas turbine components. Together with

54

2.7 Common properties and their impact on thermal processing

nickel it is also known as catalyst for carbon formation and methanation [165]. Copper is volatilized by chlorine forming CuCl. This can
potentially cause corrosion on the downstream components if deposited or condensed at any metallic wall. Though copper is not included
directly in the analysis of gas turbine restrictions it is critical if it is
mobilised as particle like all other metals.
2.7.4.17 F Fluorine
For plants uorine is not needed and if available in large amounts it
destroys the leaves and bork [132]. At normal conditions it is gaseous.
Since uorine is extremely reactive it can not be found in its pure form
but always in mineral compounds like calcium uorite (CaF2 ). The
uptake of uorine in the plants is entirely dependent on the type of
plant and type of the uorine compound. A normal concentration in
the soil is around 300 mg/kg. Contaminated soil shows values around
3000 mg/kg [139].
250

F, mg/kg

200

1]
al [

data
average
median

Co

150
100

id.

50

Wo

1]
d[

s
. re
ric
g
A

[2]
ass

[2]

Gr

Fuel type

Figure 2.34: Fluorine content of various fuels from eDaB

As mentioned earlier uorine normally occurs as minerals needing high

temperatures  mostly above 1000 C to decompose. Under pyrolytic
conditions (coal gasication) around 50 % of the uorine is vaporized
at 900 C. By adding more calcium to the fuel less gaseous uorine
will be formed [166]. In grass similar contents of uorine can be found
as in wood (gure 2.34), but more calcium is available (gure 2.28).
It was reported recently that uorine tends to form solid CaF2 under
55

2 Grass for power generation 

a view on the fuel

gasication conditions which theoretically is stable up to temperatures

of 1600 C [167].
2.7.4.18 Fe Iron
Iron is also one of the essential elements. It is needed for the photosynthesis, respiration, redox processes and xation of nitrogen. Lack of
iron in the soil is one of the most frequently observed problems for plant
growth. The result is displayed by pale and yellow leaves14 [112]. Ferrous compounds are rather common in nature since iron is considered
as the most abundant element on earth. Iron was reported to rapidly
4

data
average
median

Fe, g/kg

3
id.

s
. re
ric
Ag

s [8

rop

11

[
od

]
[20

yc
erg
En

Wo

6]

as
Gr

s [3

1]
al [

Co

Fuel type

Figure 2.35: Iron content of various fuels from eDaB

form Fe2 O3 during gasication and enhances char gasication [168].

In gas turbine technology iron is mostly used in combination with nickel as high temperature alloys. The element itself is not considered
as hazardous to units. According to thermodynamic equilibrium studies iron is not expected to be volatilized at all at normal gasication
conditions [169]  it is rather bound to ash. Still it is told that it can
form iron carbonyls when the raw gas is cooled down. Iron carbonyl is
formed in the presence of CO and is toxic [87]. Hydrogen sulphide H2 S
and also ammonia can catalyse this reaction. Especially grass contains
large amounts of sulphur and fuel bound nitrogen that will form H2 S
and NH3 during gasication.
14 Absence of chlorophyll called chlorosis

56

2.7 Common properties and their impact on thermal processing

2.7.4.19 Hg Mercury
In nature mercury occurs rather in ore in combination with sulphur
e. g. HgS than purely. It also occurs organically bound or rarely as
salt (Hg2 Cl2 ). Normally mercury enters the environment by being washed out of rocks. But human activity has increased the amount being
emitted mainly from fossil fuel and waste combustion, mining and agricultural processes [139]. But it can also enter through extraction by
inappropriate deposition of waste in the environment. Once entered, it
goes any available path through sh, vegetables, water and accumulates
by being reintroduced through sewage an waste water. If emitted from
industrial processes it is a severe environmental and physical threat.
0.15

Hg, mg/kg

data
average
median

1]

al [

Co

0.10
]

6]

d[

0.05

o
Wo

ric
Ag

[6
ps

1
. [1
sid
. re

ro
yc

erg

En

ass

[9]

Gr

Fuel type

Figure 2.36: Mercury content of various fuels from eDaB

Figure 2.36 shows the contents of mercury in various types of fuels.

The highest amounts were measured in energy crops (a switch grass
sample). This might be caused by extensive fertilizing or other types of
contamination, but is still not outside the expected range. As mentioned before the location of the harvested biomass is mainly responsible
for the Hg content of the biomass. Thus the dierences might be based
on the location and not on the fuels itself.
Mercury is not considered to be corrosive to most materials. It is liquid
under standard conditions and forms salt with chlorine HgCl. It is also
very volatile (boiling point at 357 C) and thus it can be expected that
only a small part will be retained in the ash fraction [143]. Most of it
will be found in the ne dust lter or else in the ue gas [170]. HgCl
itself is corrosive and poisonous.

57

2 Grass for power generation 

a view on the fuel

For gas turbines mercury is not mentioned to be hazardous according

to GE [52]. Mercury can be removed by sulphided activated carbon at
around 90 % eciency [171]. Mercury is absorbed or transformed to
HgS, which is a stable product and can be used for recycling or safe
disposal.
2.7.4.20 K Potassium, Na Sodium
Since potassium and sodium behave much alike, these two elements will
be discussed together. Mainly potassium but in some extend sodium
as well plays an essential part in plant metabolism [149]. It takes part
in osmotic processes. Also it is required for the transport of signals in
the nerve tracts in humans and for controlling of the gas exchange of
plants [135] and is essential for the photosynthesis process. It is also
needed for the synthesis of proteins [132] but also for enzyme activation,
osmoregulation, pH regulation and even the ripening process. Only
the osmotic function can be replaced by sodium or even calcium and
magnesium [138].
At the beginning the lack of potassium leads to increased sugar production [149] and eventually it ends in the termination of the growth
while the leaves start to show necrotic spots [112]. When provided in
huge amounts, some plants can built in far more K than needed, which
is called K-culmination. Sodium seems to act as nutrient only in some
special plants (C4 species, halophyte), but normally is not considered
to be essential. Potassium has antagonistic eects on the uptake of Na,
Mg and Ca [77]. Usually potassium is considered to exist in sucient
amounts in the soil, since it is very soluble it is easily washed out [62].
Young plants show a very high uptake of potassium while the matured
plants tend to decrease the uptake, which leads to a dilution of the
potassium in the total substance. El-Nashaar et al. [172] reported a
decrease in potassium, chlorine and phosphorus content in matured
plants. The potassium content in annual plants decreases signicantly
(around 40 %) during spring and summer [173]. This process is far less
distinct in willow and poplar [20]. This is the reason why young plants
 when they are rich in nutrients  make very good feed for cattle. For
gasication older species with lower nutrients would be preferable.
The alkalis are suspected to get more volatilized with increasing chlorine
content at high temperatures [174] and therefore get much more mobile.

58

2.7 Common properties and their impact on thermal processing

50

K, g/kg

40
ric
Ag

30

4]

s [1

ass

rop
yc
erg

20
10

data
average
median

0
. [3
sid
. re

[51

Gr

En

4]

16

d[

o
Wo

al [

Co

Fuel type

Figure 2.37: Potassium content in various fuels from eDaB

data
average
median

10
5]

Na, g/kg

. [2

sid

. re
ric

Ag

s [9

rop
yc

4
2
0

13
d[

g
ner

6]
s [4

as
Gr

4]
al [

Co

o
Wo

Fuel type

Figure 2.38: Sodium content in various fuels from eDaB

Thus the volatilization of potassium and respectively sodium is not

only dependent on the potassium content itself but even more on the
presence of Cl. Airborne alkalis condensate at around 800 C [175] into
particles forming aerosols and cause damage like corrosion, deposition
and fouling on downstream components [49]. Aerosol particles are very
hard to remove and are able to pass through most lters and even
scrubbers. At usual gasication conditions alkali components like KCl
can exist as particles but also in gaseous forms [176]. There is a good
chance to retain most of the potassium in the cyclone ash or lter
dust [177]. Sodium sulphates have been shown to posses a signicantly
greater potential of corrosion than potassium [55; 178].

59

2 Grass for power generation 

a view on the fuel

As it can be seen from the plots there is much less sodium in grass
than potassium. This often leads to the decision to neglect sodium
because it is within the uctuation range of potassium. But the mere
elemental data does not predict the concentration in the gas phase, in
contrast the transfer of sodium into the gas can be as well higher than
for potassium Turn et al. [179] (for bagasse and banagrass) and Pintsch
and Gudenau [180] for coal.
The main part of the nutrients will stay in coarse particles like bottom
ash and cyclone ash [153]. Once bound to ash the alkalis can lower the
ash melting point signicantly [20]. This depends on the formation of
alkali silicates (low melting point) or otherwise alkali alumina silicates
(high melting point) [181; 182; 180; 183].
Na and K are also known to have catalytic eects on the combustion[184;
163], pyrolysis [163] and gasication [150]. It catalyses char gasication during the presence of CO2 and H2 O [90]. This is the case under
reducing conditions and especially pyrolysis. If high silica fuel is used,
the catalytic eects are reduced when potassium forms silicates [150].
Once reached the gas turbine combustion chamber alkalis are known
to cause severe damage to gas turbine blades at temperatures higher
than 600 C [46]. To operate the gas turbine at lower temperatures
would reduce the eciency signicantly. This is based on the fact that
the eciency of the cycle is proportional to the temperature dierence
between in- and outlet but also to the temperature level.
Salts of alkali metals usually are water soluble and can be leached applying passive (rainwater) or active (rinsing) leaching. This will reduce
the gas cleaning task [173; 20]. Thus the time of harvest is a parameter
with a high inuence on the soluble elements.
The two Figures 2.39 and 2.40 depict the correlation of the content
in biomass of potassium and chloride. The current data conrms the
correlation, which Sander [19] published for straw in 1997. The graph
also shows the line for KCl salt. The content in plants shows always
more potassium, than chloride. This is most likely because potassium
is mostly transferred as KCl but can only be taken up by the plants
as K+ and Cl  (table 2.5). Chlorine is not easy to measure, so the
line gives a clue about the maximum content of chloride in the plant
depending on the potassium content. The mean value is less than half
of this amount. No direct correlation of potassium fertilization and
potassium content was found [19].

60

2.7 Common properties and their impact on thermal processing

15
Wood [14]
Agric. resid. [19]
Energy crops [12]
Grass [18]
Coal [3]

Cl, g/kg

10

0
0

10

20

K, g/kg

30

40

50

Figure 2.39: Correlation of K to Cl of various fuels from eDaB

Figure 2.40 illustrate the correlation of potassium content of the plant

to the ash content. This information must be translated carefully since
the amount of potassium going into the ash is dependent on the ashing
process itself. The data is evaluated regardless of the process. Still the
data suggests, that a minimum value for the ash can be assumed if the
potassium content is known.
50

Wood [13]
Agric. resid. [28]
Energy crops [12]
Grass [44]
Coal [4]

K, g/kg

40
30
20
10

10
Ash, %w

15

20

Figure 2.40: Correlation of potassium to ash content for various fuels

2.7.4.21 Mg Magnesium
Magnesium is also one of the most important elements in plant metabolism. It is part of the chlorophyll, takes part in photosynthesis and

61

2 Grass for power generation 

a view on the fuel

also in the gas exchange processes. Too little Mg will result in chlorosis [149] and decreases biomass yield. The data in gure 2.41 shows
some values for magnesium in solid fuels. The upper points among the
agricultural residues are from the same author, but from dierent residues from India. Since the author also reported residues with lower
values systematic errors in the measurements can be excluded.
12
10

d.

8
Mg, g/kg

data
average
median

esi
c. r

[29

ri

Ag

4
2

Wo

[14
od

4
s [1

y
erg
En

cro

8]

as
Gr

s [6

1]
al [

Co

Fuel type

Figure 2.41: Magnesium content of various fuels from eDaB

Magnesium is known to damage downstream components by deposition

and corrosion if present as chloride. Only 40 mg/kg are allowed in the
gas turbine inlet in GE turbines [52]. But it is also used to prevent
vanadium corrosion by binding the vanadium [185]. Since vanadium
is also present in grass its not quite clear how helpful or damaging
magnesium is eectively. It is surely one of the elements that must be
observed more closely.
2.7.4.22 Mn Manganese
Manganese is an essential micro element for plants [112; 135]. It takes
part in photolysis (photo-hydrolysis) and metabolism, and is part of
chloroplasts and ATP15 . Lack of Mn does not occur naturally, since it
is an abundant element on the earth.
Technically manganese is used in catalysts for combustion processes [186].
It is so far not mentioned to be hazardous to gas turbines or any other
unit.
15 adenosine triphosphate

62

2.7 Common properties and their impact on thermal processing

data
average
median

700
]

Mn, mg/kg

600

od

Wo

500

[15

3]

s [4

400

as
Gr

4]

300

. [2
sid
. re

ric
Ag

200
100

ps

ro
yc

[10

1]

al [

Co

g
ner

Fuel type

Figure 2.42: Manganese content of various fuels from eDaB

2.7.4.23 Mo Molybdenum
Molybdenum is one of the trace nutrition elements shown in table 2.5.
It is essential for some enzymes. In the absence or lack of Mo, chlorosis
occurs. If delivered in high amounts it is toxic. Figure 2.43 shows the
elemental contents of some fuels. Grassland can easily accumulate Mo
if available and therefore shows a wide range of this element.
Molybdenum is solved much better in alkaline soils and thus the availability to plants is dependent on the pH value of the soil [139].

14
12

Mo, mg/kg

10

data
average
median
]

ass

6
4
2
0

[31

Gr
3]

od
Wo

. [1

[10

Ag

ric

sid
. re

[8
ps

ro
yc

al
Co

[1]

erg
En

Fuel type

Figure 2.43: Molybdenum content of various fuels from eDaB

63

2 Grass for power generation 

a view on the fuel

Molybdenum is used as a compound to manufacture alloys since it

increases the durability of steel. Molybdenum is also a catalyst in
the rening of petroleum. It is used in alloys e.g. Hastelloy (NiMo)
to increase the corrosion resistance in reducing atmospheres [187]. The
melting point is very high at around 2600 C and the boiling point above
4800 C [139]. So far it is not mentioned as hazardous to materials.
2.7.4.24 Ni Nickel
Nickel is essential for plants and higher organisms in small amounts.
Some plants can accumulate nickel much more than needed. Nickel
takes part in the metabolism of carbo-hydrates. It is used to make
high temperature and low corrosion alloys.
It is mostly released by power and waste incineration plants in form of
ne particles. They can stay in the atmosphere for a very long time
and eventually get washed out by rain. They are nally immobilized
by being adsorbed by soil or sediment.

300

Ni, mg/kg

250

data
average
median

id.

es
c. r

200

[26

ri
Ag

150
100
50
0

ps

Wo

13
d[

ro
yc

erg

En

[7]
2]
s [1

as
Gr

1]
al [

Co

Fuel type

Figure 2.44: Nickel content of various fuels from eDaB

Metallic nickel can be released by sulphur components in cooling gasication product gas like hydrogen sulphide (H2 S). It then forms nickel
carbonyl. Airborne nickel is afterwards most likely bound to y ash [87].
Nickel is not one of the elements GE or others mentioned to be hazardous to gas turbines and is generally allowed as long as it stays below
the particle limits. Though it might lead to metallic nickel deposition.
General care should be taken in any case. Nickel is widely used as

64

2.7 Common properties and their impact on thermal processing

catalyst for methanation, cracking and shift reactions by lowering the

activation energy of the reactions. At lower temperatures it catalyses
the reverse Boudouard reaction. It can thereby destroy the surface of
the lining and provoke metal dusting. Sulphur interferes and poisons
the catalyst by depositing and removing the nickel from the support
by forming nickel carbonyl as mentioned. If any sulphur is present it
inhibits metal dusting by employing the nickel for its own reactions [87].
The retention in the ash from gasication experiments is around 80 %
[188]. It is equally distributed between bottom ash and cyclone dust.
Cooling the product gas below 400 C should increase the retention rate
to 100 %.
2.7.4.25 P Phosphorus
Like nitrogen and potassium, phosphorus is absolutely essential for the
formation of sugars, proteins and nucleic acids (DNA, RNA) [135].
In most soils phosphorus restricts the biomass growth if not added
articially [112]. But if not manufactured in high quality, it would lead
to entrainment of heavy metals. The extensive use of phosphorus in
fertilizing, results in eutrophication of lakes and rivers. This would also
lead to an increased concentration in the surroundings and subsequently
in the plants.
Most of the available forms can not be taken up by plants [132]. Since
most natural phosphates are hardly soluble in water, only through
complex decomposition mechanisms phosphorous becomes accessible
to plants [132]. For this reason phosphates are articially made and
used as fertilizer.
Frandsen et al. [164] found that under normal gasication conditions
(670-1250 C) P2 O5 is the main stable phosphorus compound (equilibrium approach). It is suspected to form particles in the PM1 category16 [189]. Though the main part will be bound into the ash as an
oxide.
Phosphorus is not listed in the gas turbine manufactures black list
of contaminants. Still it is considered to be able to produce depositions and consequently corrosion [126] but it is far less hazardous than
sulphur or alkali components. Phosphorus is used as a component for
corrosion inhibiting lms. Phosphorus is also mentioned to be poiso16 particulate matter smaller than 1 m

65

2 Grass for power generation 

a view on the fuel

10

P, g/kg

data
average
median
ric

Ag

ass

[70

Gr
]

s
rop
yc

[12

erg

4
2

9]

. [2

sid
. re

13
d[

En

Wo

Fuel type

Figure 2.45: Phosphorous content of various fuels from eDaB

nous to Ni catalysts [190], which are used as bed material for catalytic
gasication.
2.7.4.26 Pb Lead
Lead is poisonous to plants and humans. It inhibits the synthesis of
chlorophyll and replaces calcium in bones and teeth and is deposited
in the brain, where it causes development dysfunctions. It is lethal if
consumed regularly even in small amounts [149].
It is released into the environment from lead processing industry and
accumulated in the soils by atmospheric deposition and released waste
water [191]. It was also mixed to the petrol to secure a larger runtime
for car engines and was subsequently emitted into the environment. It
is used extensively in batteries. Though it is not very common on earth
the content in the soil is comparably high because of human interaction.
Figure 2.46 depicts some values for Pb in various fuels. There are two
very high values for grass being around 14 mg/kg from two dierent authors. The other samples make an average of 1.35 mg/kg. The samples
were taken from locations close to roads, which suggests the deposition
from lead emission from cars.
Contents of about 20 mg/kg of lead is allowed in the gas turbine inlet [52]. Otherwise it will lead to substantial depositions and eventually
corrosion on the blades [46]. Lead starts to volatilize at around 1100 C
boiling temperature 1755 C where it forms PbCl2 and PbO [164]
66

2.7 Common properties and their impact on thermal processing

40

Pb, mg/kg

30

data
average
median

[9]

ps

ro
yc

erg
En

20

10

6
. [1
sid
. re

]
ic
14
d [ Agr

1]

s [2

as
Gr

1]
al [

Co

o
Wo

Fuel type

Figure 2.46: Lead content of various fuels from eDaB

(coal, equilibrium approach). Above 1300 C it shifts to gaseous Pb.

Lead but also zinc-sulphides solidies below 800 C; it deposits at the
linings and can block the entire process [87].
The retention of lead in biomass gasication is as low as 10 % [188] for
hot gas. Cooled down, the lead is expected to condensate and to be
removed by downstream lters.

2.7.4.27 Sb Antimony
The availability of antimony in soils is increased by anthropogenic emissions mainly around ores. Nevertheless it is very mobile and once emitted it can travel the water paths a great distance. There is no functional
coherence known so far between plants and antimony.
Antimony is one of the elements scarcely measured (see gure 2.47)
when applying ultimate analysis to the fuels. Still it is very volatile
and considered to be completely evaporated above 700 C [188; 192].
This also leads to the conclusion, that cooling the raw gas will lead to
condensation of antimony at the y ash. It can be removed by ltering [192]. Predictions show that at higher temperatures the fraction
in the gas phase is strongly pressure dependent [142]. Higher pressure
leads to a signicant reduction of antimony in the gas phase.

67

2 Grass for power generation 

a view on the fuel

14
12

Sb, mg/kg

10

od

Wo

data
average
median

[2]

8
6
]

s [1

4
2
0

rop
yc
erg

En

ass

Gr

[2]

1]
al [

Co

Fuel type

Figure 2.47: Antimony content of various fuels from eDaB

2.7.4.28 Se Selenium
Selenium can occur in various forms. Though it is not really known to
be essential to plants it is for animals and humans. However the range
from toxic amounts to decits is very small [149]. It is brought into the
environment among others mainly by phosphate fertilizer and waste
disposal sites. Since it is immobile in its pure form it can accumulate
at the site where it occurs. But it can travel via water ways to other
areas where plants can take it up and thus it can intrude the food chain
easily [139]. The immobility is dependent on the oxygen content of the
soil. If it increases selenium will start to spread. Selenium is also very
rarely measured for fuel analysis (gure 2.48). It was reported that recycled y ash used as sorbent removes up to 80 % of the selenium [144].

2.7.4.29 Si Silicon
Silicon is mainly found in shoots of grasses [132]. In leaves and sheaths
an average amount is found and the least amount was measured in
stems of the plant [193]. Naturally annual grass shows little eort to
produce many stems. The silicon content is therefore expectedly high.
It is up to now not considered to be essential for grass species [112]
but rather taken up because it is simply available. Nonetheless it can
have positive eects in structure, against dehydration and strengthens
resistance against pathogens. To humans silicon and its components

68

2.7 Common properties and their impact on thermal processing

4
s
rop

3
Se, mg/kg

[1]

1]

al [

yc
erg

Co

En

2
ass

od

Wo

[4]

Gr

[1]

data
average
median

Fuel type

Figure 2.48: Selenium content of various fuels from eDaB

are not considered to be toxic. Though as it is the normal case, taken

up as respirable particles it will cause damage.

data
average
median

200
id.

Si, g/kg

150

s
. re
ric

]
[20

Ag

100
s
rop

50
od

Wo

[8]

ne

c
rgy

[6]

ass

[20

Gr

Fuel type

Figure 2.49: Silicon content of various fuels from eDaB

The bandwidth shown by the agricultural residues are quite wide. This
is caused by two very high values from the same author. These two
values are most likely to be understood as contaminated samples. The
high values are mostly a result from a soil plant mixture [193]. Without
these two numbers the average value is 24 g/kg.
Technically silicon is one of the main ash forming elements. It is found
in any ash fraction downstream of the reactor. It hardly gets volatilized
because of its high boiling temperature, though in some forms it can

69

2 Grass for power generation 

a view on the fuel

become sticky [176], especially when low melting potassium silicates

are formed during gasication.
Silica is often used as bed material in combustion and gasication because it is a cheap material. But when high alkali biomass is gasied,
the probability to form low melting alkali silicates is very high.

2.7.4.30 Ti Titanium
For plants as well as for other organisms titanium does not play any
specic role. It is not needed but is not toxic either. It is taken up
as available. The titanium content in the fuel is not measured as a
standard value (gure 2.50).

0.20
.
sid
. re

Ti, g/kg

0.15

[3]

ric
Ag

ass

[3]

data
average
median

Gr

0.10

0.05
od

Wo

[2]

s
rop

c
rgy

En

[2]
1]

al [
Co

Fuel type

Figure 2.50: Titanium content of various fuels from eDaB

Titanium is found in the ash as TiO2 but is generally a minor part of

the ash. Under normal conditions titanium can not be volatilized and
is a stable crystal up to 2000 C. But it is reduced to crystalline TiO2
above around 350 C when uorine is present [164] (coal gasication,
equilibrium approach).
Titanium is technically used because of its nature to be very inert
against temperature and chemicals. And at the same time being very
light. Downstream components are not at risk because of titanium
unless it comes as very ne particles and passes the lter barriers.

70

2.7 Common properties and their impact on thermal processing

2.7.4.31 V Vanadium
Vanadium is not an essential nutrient for the plants, though it is said to
have positive eects on the formation of chlorophyll [135]. Fossil fuels
can contain high amounts of vanadium being emitted consequently by
combustion. Figure 2.51 shows some measurements of vanadium done
for dierent fuels.
35
30

V, mg/kg

25

data
average
median
1]

al [

Co

20
15
d.

si
. re
ric

10
5
0

o
Wo

4]
d[

Ag

[3]

erg
En

[5
ps

ro
yc

ass

[7]

Gr

Fuel type

Figure 2.51: Vanadium content of various fuels from eDaB

Vanadium is used as part of alloys showing high resistance against

corrosion and deformation. On the other side being an element of
the fuel, vanadium is able to increase the corrosion rate together with
sulphur species [194]. Vanadium pentoxide (V2 O5 ), which is present in
combustion systems can decrease the sulpidation inhibition of the alloys
and subsequently salts like Na2 SO4 can act more aggressively (see [57]
for detailed information). It needs high amounts of vanadium to take
place. Grass contains comparable amounts of vanadium to other biofuels. There is one extremely high data point from an intensive grass
sample in Germany and no hint available if this value is possible or a
measurement mistake.
Combustion measurements show that vanadium is retained in the ash
at levels between 60 and 90 % [143]. In reducing environments (gasication, pyrolysis) vanadium forms V2 O3 , which is solid up to high
temperatures (table 2.4). Care must be taken during start up and shut
down of the gasier when oxidising atmospheres is present [87]. Then
V2 O5 can be formed, which has a melting point of 681 C [120].
71

2 Grass for power generation 

a view on the fuel

2.7.4.32 Zn Zinc
Zinc is a micro element needed by all plants and other organisms [132].
It is only found in ore together with copper and lead [135]. Most of
the zinc emitted is assumed to come from steelworks and electroplating
industry. Accumulation from atmospheric deposition and waste water
is therefore unavoidable [191]. This of course leads to accumulation in
plants, which is the entrance to the food chain. Figure 2.52 shows the
elemental zinc found in fuels. There is one extremely high value for
salix from Sweden. It increases the average value for the wood group
distinctly. Also for agricultural residues there is a data point for rice
husk from India being very high. Without these data points the average
data is rather 54 mg/kg for wood and 26 mg/kg for agricultural residues.

10

6]
. [2

Zn, mg/kg

od
Wo
2

10

[16

sid

. re
ric
Ag

ps

erg

ro
yc

En
1

[9]

2]

s [2

as
Gr

data
average
median

10

Fuel type

Figure 2.52: Zinc content of various fuels from eDaB

In combination with other materials zinc is used to produce sorbents

for gas cleaning units mainly for desulphurisation [195; 196].
As Miller [143] states, zinc is not equally retained in the ash for dierent
fuels. Coal combustion seems to bind zinc much better (80 -100 %)
than biomass combustion (around 20 % at 900 C). This is roughly
conrmed by gasication tests carried out by Konttinen [188] whereas
the equilibrium calculations stated no zinc in the ash. Cooling down the
gas just before the lter increased the retention rate to nearly 100 %.
Zinc appears to volatilize in measurable amounts above 850 C using
equilibrium calculations [164]. A newer publication [144] reports much
earlier volitilization of ZnCl2 above 400 C.
72

2.8 Manipulation of the properties

2.8 Manipulation of the properties

Of course there are many ways to manipulate the properties of the
fuel. But only those, which can be applied after the harvest shall be
mentioned here.

2.8.1 Drying
Drying describes the reduction of water content in any material. Natural drying always takes an uncertain amount of time whereas forced
drying needs large amounts of energy input. Applying the drying process to grass, natural drying is favourable, based on the low mass per
area. Spreading the grass after cutting, on place, where it was cut,
allows a maximum exposure of the surface for the mass transfer. Matured grass contains much less sugars than younger plants with many
leafs, which leads to less degradation and heat development by respiration. The water content must be lower than 22 % to limit degradation
and lower than 15 % to stop it. In this regard matured grass is also
less sensitiv to degradation and therefore a higher water content may
be alowed [102; 77]. Bruising the plants during cutting will quicken the
drying process.
There are many ways to force drying but all include some kind of energy.
The two most important parameters to enable a good mass transfer is
to have a dry gas ow and a large surface. It does not necessarily
need heat to dry grass properly but at least a fan to produce forced
convection and possibly an air drier. Still, it must be noted that any
energy applied to the grass is a reduction of the eective energy benet
unless it is a waste stream.
As it was mentioned before when the grass is dried too much it becomes
brittle and mechanical treatment will result in loss of biomass.

2.8.2 Late harvest

With growing age the uptake of potassium decreases while the total
mass still increases. This leads to a decreasing potassium content of
the total plant [173]. A rather late harvest must be considered as
benecial. Some plants actively push nutrients back into the roots,
which are usually not harvested.

73

2 Grass for power generation 

a view on the fuel

2.8.3 Leaching
There are two types of leaching:
G natural leaching [162; 20; 19]
G forced leaching [197; 145; 198200]

Where the rst one is simply based on the rain falling on the already
cropped biomass, the second one is active rinsing of the material after
the harvest. A special type of natural leaching is to leave it on the eld
until spring. This of course also leads to a massive biomass loss [201]
and is not honestly applicable to grass because the main parts, which
decay are leaves and seed heads. The economic value also decreases if
the amount of grass per area decreases.
Active leaching can be performed with simple water or other solutions.
The process applies to water soluble elements like chlorine, potassium,
sodium and magnesium, which show a high response to leaching [199].
It has been shown that leaching can reduce the content of soluble elements to less than 10 % of the natural value.

2.8.4 Torrefaction
Torrefaction or carbonisation is also referred to as mild pyrolysis. The
process applies controlled heat to the material, where volatile matter
is released. The product shows around 70 to 90 % of the original mass
and is brittle and easy to grind. This brings much advantage to the
conveyance of the fuel. Especially regarding the coring of biomass
into a coal burner torreed biomass shows advantages [202; 203]. Also
the energy density of the product is increased compared to the original
matter by 10-20 % at a eciency of 95 % [202]. The torreed materrial
is much more brittle und thus can be grinded very well. Therefore it
is suitable for entrained ow gasication [204] But it is an additional
process, which is located upstream of the real gasier and is also an
additional eort with respect to energy and costs. Torrefaction is not a
best option for any plant, but rather dependent on the type of gasier
used and the overall costs and eciency.
There is a company in Australia 17 , which operates on place torrefaction
of hay and agricultural residues. The company is based on the idea that
the transportation of char is much less costly compared to hay.
17 www.BIGChar.com.au

74

2.9 Intermediate conclusions

2.8.5 Acid treatment

Acid treatment was mainly studied in relation with the CCA impregnated wood. The acid used was humic acid, which is a bio-organic
solvent with a variety of small structures. The leaching of CCA showed
signicant eects after one day [145]. This is most likely not protably
for industrial applications. With respect to energy grass acid treatment
will unlikely be necessary.

2.9 Intermediate conclusions

Many elements poisonous and hazardous to gasication systems, are
essential for the growth of (energy) grass. Hence, reducing the elements in the soil will only result in less biomass yields. Matured plants
show lower contents of critical elements like potassium, sodium and
phosphorus.
Whether an element is desirable in the reaction is not only a matter
of the element itself but rather what sort of compounds are formed
and, which path the element nally takes to leave the system. Some
elements would be considered hazardous but leave through the cyclone
bound to the ash and are not getting in touch with the gas turbine or
environment in the rst place. Others would be considered as essential
for the process but form aggressive components when getting in touch
with other elements under certain conditions. And then there are some
elements like Ca and Mg, which are used to bind certain other elements
to ash and are thus useful but at the same time problematic if reaching
the hot gas path.
For this reason it is obviously important to consider the gasication
process as a part of the decision whether a certain element needs to be
observed or can be considered rather harmless or even helpful.
From the elemental composition of grass it becomes clear that just
the elements critical in gas turbine applications (K, Na, Ca, Mg, S)
are found in rough amounts. Elements like vanadium and lead, which
complete the list given in table 1.2 are also present in varying amounts.
Especially for lead, the location of the grass plays a major role.
Additional elements can be located in grass fuel, which show similar
or worse corrosion or deposition behaviour than the one given above.
These elements are Ba, Sr, Li and P.

75

2 Grass for power generation 

a view on the fuel

Where the technical specications are only relevant for the raw gas
cleaning, the exhaust gas processing has to handle the environmental
aspect. This means the two restrictions can be handled separately.
Fixed bed gasication is not a good choice in this case because in order
to reach a high conversion, the temperature must be as high as possible.
Since the temperature in a xed bed can not be controlled properly the
gasier must be operated at a sucient low temperature to make sure
no temperature peaks can cause slagging. This experience was made
in an attempt to gasify grass in a xed bed in 1998 [205]
Fluidised bed gasication is a proven technology and widely available.
In two projects the gasication of grass in uidised beds, proved to be
feasible. Fluidised beds need solid input but processing the grass in
a solid state, results in considerable losses depending on the distance,
type of compression and water content. Concerning the ash melting,
the uidised bed is a good choice too since the temperature distribution is very uniform due to the good mixing behaviour. The process
temperature can be set closer to the probable ash melting point.
Processing the fuel locally into a liquid pyrolysis oil or slurry would
clearly show the smallest material losses and the best logistical features
at the same time. During pyrolysis the inorganic compounds are not
removed. There is no advantage from this point of view. An entrained
gasication would be the best choice in this case. But the material and
technological eorts here are much higher not including the preprocessing plants. The high temperature (1200-1600 C) would also lead to a
much higher mobilisation of inorganic compounds into the gas phase.
This increases the gas cleaning eort to a uncertain degree.
Catalytic gasication is not an option as long as there are high amounts
of elements, which can and will damage the catalyst. Pressurized gasication seems to be unfavourable based on the negative eects on the ash
melting behaviour. Hydrothermal gasication could be an option but it
would need a good preprocessing to make the grass pumpable. Further
on, hydrothermal gasication is not a state of the art technology at the
moment.
From this review only two ways seem feasible for the gasication of
grass. This is based on sole material and process properties.
G compression of the grass and gasication via uidized beds

76

2.10 Recommended literature

G pyrolysis or torrefaction and gasication via entrained ow gasi-

cation

2.10 Recommended literature

Some special literature is recommended for extended studies.
G Bassam [61] Energy plant species
G Eltrop et al. [69] Leitfaden Bioenergie: Planung, Betrieb und
Wirtschaftlichkeit von Bioenergieanlagen
G Hartmann et al. [20] Naturbelassene biogene Festbrennstoe umweltrelevante Eigenschaften und Einussmglichkeiten
G Higman and van der Burgt [87] Gasication
G Miles et al. [206] Alkali deposit found in biomass power plants
G von Puttkamer [24] Charakterisierung biogener Festbrennstoe
G von Sengbusch [132] Botanik online  The Internet Hypertextbook
G Strmberg [25] Fuel Handbook
G Zevenhoven and Kilpinen [185] Control of Pollutants in Flue Gases
and Fuel Gases
G Hart and Cutler [124] Deposition and Corrosion in Gas Turbines

77

Chapter

Sampling raw gas from gasication

processes

In chapter 3 the sampling system is presented. It was used for all tests.
The sampling system is characterised by slip-stream measurements and
step response analysis. Experience made with the sampling system can
be found in section 3.6.

3.1 Basic expressions and denitions

3.1.1 Tar, denitions and usage
Tars are generally summarized as all aromatic and poly-aromatic hydrocarbons present in the gas, Moersch et al. [207]. The author states:
hydrocarbons ... that condense at ambient temperature are considered
tar. According to this denition benzene, in the concentrations in which
it is typically present in the producer gas, does not belong to the tar.

van Paasen et al. [208] reports a similar denition for tar. Tar is a:
generic (unspecic) term for entity of all organic compounds present

in the producer gas excluding gaseous hydrocarbons (C1 through C6).

Benzene is not included in tar.

One way of determining tar is the gravimetric measurement. The tar

is scrubbed from the raw gas by a solvent. The solvent later undergoes

79

3 Sampling raw gas from gasication processes

a distillation under reduced pressure, in a way that all volatile components like water, solvent and benzene will evaporate. The rest can be
determined by weighing. The residue consists only of heavy tars, the
light tars will evaporate during the distillation. The complementary
way to measure the light tars is a analysis GC/MS device [209]. Online
tar measurements have been proposed by Moersch et al. [207] using
FID1 sensors or with mass spectrometer as suggested by Carpenter
et al. [210]; Neubauer [211]. Tar will not be a major issue in this work
but for the general characterisation of the process, tar measurements
were conducted.

3.1.2 Permanent gases

The expression permanent gases will be applied to all gases, that do
not condensate under moderate pressure (<5 bar) and -10 C. These
conditions govern the sampling system as described in section 3. The
inuence of absorption-desorption processes between the gas and the
solvent is not considered. Permanent gases discussed in this thesis are:
CO, H2 , CO2 , N2 , CH4 , C2 HY , C3 H6 , He, H2 S, COS, NH3 and O2 .

3.1.3 Particles and aerosols

According to Hinds [212], particles are solid or liquid materials showing
sizes smaller than 1 mm. Fines are a subgroup of particles within the
designated range of 10 to 1000 nm. An aerosol is dened as a suspension
of solid or liquid particles in a gas. The Suspension is not considered
an aerosol if the particles can not stay in suspension (oating) for at
least several seconds. The aerosol produced by condensed components
in combustion or gasication products is called fume.

3.2 Standard methods, advantages and drawbacks

Gas from gasication units is more dicult to handle than gas from
other gas streams like combustion ue gas or atmospheric gas. This
is based on the composition of the raw gas, which includes permanent
gases but also particles of various sizes and condensible matter.
Generally two dierent types of measurements must be distinguished:
1 Flame Ionization Detector

80

3.2 Standard methods, advantages and drawbacks

1 Direct measurements: the sensor measures non-destructive within

the main gas stream or a by pass. Direct measurements are very
dicult to apply because the optical access to the components
is very limited in fume. Optical systems like LIF2 , FTIR3 or
NDIR4 could in principal be used without a sampling system but
normally fail because the access to the raw gas stream is dicult.
The elements to be analysed, must be visible to the optics, which
is not the case if the elements are hidden within tars or particles.
Many optical systems are described in [213; 214].
2 Indirect measurements: a sampling system is applied to prepare
the sample stream for the sensor. Preprocessing of the gas by
a sampling train mostly results in at least three distinguished
samples: the permanent gas stream, a liquid sample containing
the condensible matter and a solid sample containing the dust.
The analysis of the three dierent samples demands a higher effort. Another option is to dilute the gas until the condensables
fall beyond their dew point. This leads to a lower concentration
of all compounds. The solid particle stream must be collected in
a lter.
Preprocessing is the commonly applied method to get access to the gas
data. The sampling train must be capable of delivering the components
in such a way that they are detectable by the measurement device.
Permanent gases like CO, H2 , CO2 , N2 or CX HY can be extracted
quite easily by scrubbing and dedusting. The much more complicated
exercise is the proper sampling of the contaminants like the mentioned
elements in table 1.2. Those can be present as fume, which is dicult
to sample.
The nes passing the particle lter need to be collected directly at the
outlet. It is well known that large particles are subject to sedimentation
phenomena, whereas small particles are subject to diusion phenomena.
But all types of aerosol particles can hardly be recovered once attached
to the wall of the lining. The adhesion forces are higher than the forces
applied through the gas velocity [212].
At this time, systems with good particle sequestration eciencies are
lters and impactors [212]. The current standard to measure elements
2 Laser Induced Fluorescence
3 Fourier Transform Infra Red
4 Non Dispersive Infra Red

81

3 Sampling raw gas from gasication processes

in particles like Pb, Ba, Sr or V is given in standards such as VDI [215].

The proposed sampling equipment is puried silica wool with a bre
not larger than 0.4 m diameter in a lter cartridge. This approach
does not allow a continuous monitoring of contaminants.
A few sampling systems were reviewed by Stahlberg et al. [216]. The
state of the art procedure at the moment is described in the tar protocol [208]. The main scrubbing part consists of three to six bottles,
the rst of which is operated at 20 C and the last ones between -15
and -20 C. The gas is cooled down to at least -15 C to ensure ecient
condensation of water and tars. Fast cooling of the raw gas would result
in formation of aerosols, which can escape the impinger bottles.
The major draw backs of the protocol is the limited capacity of the stationary solvent, which accumulates tars, water and to a certain degree
particles. Due to the low temperature there is a maximum allowable
water concentration which will lead to the formation of ice.
Another possible method is the Petersen column  [208]. This scrubber
is a semi continuous device, in which two scrubber stages (isopropanol)
are installed. It can be operated in ow through mode. Additionally,
an aerosol lter (G3 glass frit) is positioned between the two stages.
This lter can not be exchanged during the operation.
For all sampling systems the extraction of the condensables works reliably (table 3.1) but the collection of nes involves particle lters, which
can not be operated continuously. Thus, using the available systems,
the synchronous analysis of permanent gases and contaminants can not
be achieved. For this reason a dierent approach was chosen in this
work.
Sampling type

Continuous

Condensables

Ultra nes

Remark

Tar protocol
Peterson column

7
3

3
33

7
7

complex
simple

Quartz wool lter

heated

Porous fritt lter

heated

react with
alkalis
react with
alkalis

Table 3.1: Properties of the common sampling systems

82

3.3 Sampling approach in this work

3.3 Sampling approach in this work

A dedicated sampling system that can handle the requirements was invented at PSI56 and further optimised and characterised in this work.
A ow chart is presented in gure 3.1. The system is a continuous and
pressurized scrubber. The raw gas is sampled and instantly quenched
by a fresh solvent at room temperature to avoid the formation of aerosols. The two phase ow is compressed and cooled down to -10 C
to ensure a high condensation rate for water and tars. A 10 m long
tubing at this temperature ensures an excellent mass transfer due to
a higher area of the gas liquid interface. It also results in a longer residence time of the solvent and gas compared to impinger bottles (see
section 3.5). After this tubing the gas is separated from the solvent
and both streams are guided out of the cooling box. The system delivers two streams, which can be analysed separately: a dry gas stream
containing the permanent gases, and a solvent stream containing the
water, tars and particles. The gas stream is analysed by a micro GC
but can as well be analysed by an FTIR , MS, etc. The solvent stream
can be analysed e. g. by means of an ICP-OES or GC/MS dependent
on the information that needs to be found.

Figure 3.1: Flow chart of the dedicated sampling system

5 Paul Scherrer Institut
6 based on the idea and eorts of Jrg Schneebeli

83

3 Sampling raw gas from gasication processes

The solvent used in the described system is Arcosolv PM 7 . It shows

good solvent properties for tars and at the same time mixes well with
water. The solvent stream was set around 1.5 ml/min. The mean gas
ow was around 1 l/min. The sample gas ow depends on the compression and the gas composition. It was therefore constantly monitored.
The contaminants in one litre of dry sampling gas will be found in
1.5 ml of solvent.

3.4 Evaluation of the particle slip-stream

In order to proof the performance of the sampling system experiments
were conducted to verify dierent scrubbers for particle slip-streams.
Three general types of scrubbers were evaluated.
G four laboratory impinger bottles in series connection
G a continuous atmospheric scrubber
G a continuous pressurised atmospheric scrubber

The aerosol was produced by vapourising KCl in a TG8 at 900 C using

a condensation interface as described in Ludwig et al. [217]. The particle size distribution peaked around 200 nm as described in Kowalski
[218]. The sensor used was a surface ionisation detector (SID) being
described in literature several times [219; 214; 220] (see section 5.4.2).
This sensor is qualied to analyse airborn alkali components (K, Na,
Cs). The strategy was a measurement of the alkali particles before entering the scrubber and directly after the scrubber. The inlet signal
was set to 100 %. The ratio of outlet to inlet signal is described as
slip-stream (bar 1-3 gure 3.2). These particles will be lost if this type
of sampling is applied. Additionally, a slip-stream measurement during
the gasication of a single grass pellet (see section 5) was conducted
using an improved version of the rst SID (bar 4 gure 3.2).
Impinger bottles were never thought to operate as particle retention
system. But as an example the retention of the particles in the series of 4 impinger bottles is expressed in bar 1 showing 60 % slip. A
continuously operated scrubber at atmospheric conditions still shows a
slip-stream of 20 %, wheras the pressurised scrubber already reduced
the particle slip to 1 %. Bar 4 in the graph shows the slip for the alkalis
7 Propylene Glycol (Mono) Methyl Ether
8 Thermo gravimeter

84

Scrubber system

3.5 Signal change due to the sampling system

1
2
3

< 0.1%

4
0

10

20

30
40
Particle slip, %

50

60

Figure 3.2: Slip-stream of particles through dierent sampling systems.

(1) four impinger bottles at 0 C,

(2) atmospheric scrubber at -25 C,
(3) pressurised scrubber at 20 C,
(4) PSI pressurised scrubber at -10 C

emitted during the gasication and subsequent combustion of a real

grass pellet. With the improved design of the SID the slip-stream was
just detectable (see gure 5.5) and smaller than 0.1 %.
The reason why the scrubber shows an excellent particle sequestration
is the fact that the sampling stream is compressed after it was quenched. This leads to a saturation of the gas phase with the solvent, which
condenses at the particles during the compression and subsequent cooling. This behaviour is very similar to a condensation particle counter
(CPC). Here particles are guided through an n-Butanol saturated atmosphere and subsequent cooling leads to condensation and an increase
in particle size.
From gure 3.2 it can be derived that only the PSI invented pressurised
scrubber led to a satisfying result. For all sampling jobs in this thesis
this sampling system is chosen.

3.5 Signal change due to the sampling system

By its nature, the chosen sampling system leads to an increased delay
between the actual process and the measurement data. Additionally
the signal may be blurred due to backmixing of components. In order
to evaluate this behaviour step response measurements were carried out
for both the GC and the ICP-OES.

85

3 Sampling raw gas from gasication processes

concentration, normalised

Figure 3.3 illustrates the step response for the gas measurements. The
step was produced by the addition of H2 S to the gas stream. Sulphur
was selected because both used measurement devices (micro GC, ICPOES) can detect sulphur adequately. From the graph it can be read
out, that for the gas measurements the delay to detect 90 % change
in concentration is below 5 min. This value is valid for both: step up
and step down. Since the experiments are set to last for 5 h and are
conducted in steady state mode this response is sucient.
Air
H2S

1.0
0.9

Start H 2S
Stop H2S

0.5
0.1
0
00:00

00:10

00:20
elapsed time, hh:mm

00:30

00:40

Figure 3.3: Step response of the sampling system including lines to the micro

GC

Figure 3.4 illustrates two step responses for the ICP-OES installation.
The rst step was done by adding constant amount of Ca to the solvent
the second step was the addition of H2 S to the gas phase. Two things
can be observed here. The delay for the ICP measurements is longer
and depends on the direction of the step. A 90 % increase in concentration can be detected much faster (10 min), than a decrease (34 min).
This includes the dead time of 9 min. This behaviour can not be explained solely by the method of the sampling system. The step down
should proceed exactly like the step up. The fact that the step up was
performed from a clean system to a Ca doped system indicates, that
this eect is maybe due to adsorption- desorption precesses in the lining
or in the vaporiser of the ICP-OES.
The second step response corresponding to the sulphur addition to the
gas stream, shows a response of 9 min to reach 90 % for the step up;
but 11 min for the step down. From this result, it can be concluded,
that the gas travels much faster through the lining than the solvent.
The measurement dynamic for changes in the gas phase concentration
is much better. For a steady state 5h run the dynamic is fast enough
to detect signicant uctuations with both described systems.

86

concentration, normalised

3.6 Challenges with the sampling system

S
Ca
Start Ca
Stop Ca
Start H 2S

1.0
0.9
0.5

Stop H2S

0.1
0
00:00

01:00
02:00
elapsed time, hh:mm

03:00

Figure 3.4: Step response of the sampling system including lines to the ICP-

OES

There is an further characteristic of the sampling system: being able

to measure substantial amounts of sulphur in the ICP-OES analyser
means, that there are signicant amounts of sulphur being absorbed in
the solvent (gure 3.4). The micro GC measurements during the gasication experiments revealed that after about 20 min, H2 S and COS
broke through; about 10-40 ml/m3 could be measured. This means
sulphur is not separated properly but distributed in both solvent and
gas phase. Sulphur also adsorbs at metallic surfaces and thus without
a specially equipped reactor and lining (e. g. sulnert coated) the
diagnostic of sulphur components is always imprecise. For further measurements sulphur will be excluded from the analysis.

3.6 Challenges with the sampling system

The sampling system had to be optimised during the rst tests to
achieve stable operation. The changes were mainly related to the compressor and phase separation part. The major trouble  only during the
gasication of grass  was the formation of ammonium hydrogen carbonate (NH4 CO3 H), which fell out as a powder. Figure 3.5 shows two
infra red (IR) spectra: one ammonia hydrogen carbonate for lab us and
one for the sample. The spectra are in agreement with the SDBS9 [221].
The marked peaks correspond to the double bond stretching of CO
(around 1630 cm1 ) within the carbonate and nitrogen bond stretching
NH (around 3120 cm1 ) within the ammonia structure. The two distinct signals at 830 and 700 cm1 correspond to the bending vibration
of NOC and OCO. The dierence of the transmittance amplitude can
be due to unevenly pressed samples or inhomogeneous sample.
9 Spectral database for organic compounds

87

3 Sampling raw gas from gasication processes

Transmittance, AU

25
C=O

20

NH

15
10
5

830

NH4CO3H

700

Sample

0
4500

4000

3500

3000

2500
2000
Wavenumber

1500

1000

500

Figure 3.5: IR spectra of the sample and ammonia hydrogen carbonate

Ammonium hydrogen carbonate is formed under low temperature pressure when ammonia, CO2 and water is present [222] (equation (3.1)).

*
NH4 CO3 H )

NH3 + CO2 + H2 O

(3.1)

The mere existence is not a problem in general but the large amount of
carbonate leads to clogging of the capillary tubing. Especially the tubing to the ICP-OES device was aected. Because this did not happen
during the gasication of wood it indicates there large amount of ammonia in the grass gas. The measurement of ammonia was not a topic
in general, but there were some measurements yielding concentrations
over 2000 ml/m3 dry. This corresponds to roughly 15 % of the grass
bound nitrogen. The ammonia concentration in uidised bed gasication of wood is usually <900 ml/m3 [223]. Turn et al. [169] reported as
much as 1710 ml/m3 for the gasication of banagrass 10 . But values as
high as 3 % were reported by Zhou et al. [224] for Leucaena. Figure 3.5
also shows a part that is clogged by the carbonate. The sampling system could always be reactivated by reducing the pressure and increasing
the temperature. The maintenance could always be done within less
than an hour.
ICP-OES devices are normally used with aqueous solutions. Running
the ICP on a solvent loaded with tar turned out to be very challenging
and not yet state of the art. The calculated detection limits are not
trustworthy anymore.
For the important elements the detection limits were determined manually by comparing spectra, baseline and background noise. Table 3.2
10 Pennisetum purpureum

88

3.6 Challenges with the sampling system

lists the elements with a major dierence. These dierences lead to

substantial misinterpretation for measurements close to the detection
limits. Sodium and calcium can be detected in much lower concentrations than expected, whereas potassium is much less sensitive for the
used solvent.

Na
K
Ca

DL Software

DL by hand

69
21
38

5.6
92.9
0.3

Table 3.2: Dierence of detection limits as determined by software or by hand

89

Chapter

Fluidised bed experiments

In the rst part of chapter 4, a short introduction is given to gasication

in general and specically grass gasication.
From section 4.4 page 99, the construction and setup of the bubbling
uidised bed will be presented, including the theoretical background of
uidisation. Methods and measurement techniques as well as heat loss
calculations of the reactor will be given from section 4.5.5 page 111.
Section 4.6 page 118 treats the general procedures used for the experiments and the characterisation of the fuel used.
In section 4.9 page 123 all the results concerning the uidised bed experiments are presented and discussed. This includes the permanent
gas data, process stability, contaminant readings and the axial prole
experiment.
The monitoring of the contaminants were conducted as a cooperation
with the working group of Christian Ludwig (Chemical Processes and
Materials at PSI). The development of the method to run the ICPOES on solvent instead of aqueous solutions was decisively realised by
the group members and further tested and optimised in the presented
experiments.

91

4 Fluidised bed experiments

4.1 Brief review of gasication processes

Gasication is as old as re itself. Burning a solid fuel is always a combination of gasication and combustion. Industrial gasication technologies started at the beginning of the 19th century, at which time the
gas was used mainly for illumination and cooking [87]. At the beginning of the 20th century a considerable knowledge about gasication
was established and rst books written [225228]. The gasiers were
xed bed reactors of various types. One is illustrated in gure 4.1.
Since then gasication became very sophisticated based on its potential to transform solid fuels into all kinds of gaseous fuels or chemicals.
There is much interesting literature on the history of gasication and
its technology progress.
Very early publications about gasication or partial combustion as it
was called too are Gas Producers and Producer gas power plants 
by Wood [225] or Modern power gas producer  practice and application  by Horace [228] and a few more [226; 227]. Amazingly, they
already managed to built plants with sizes as large as 30 MW , processing coal at rates of 10 t/h at the turn of the 19th century. The reason
to pass from combustion onto gasication was: The chief reason why

the preliminary gasication of coal is advantageous is that the direct

combustion of raw coal can only be eected by the employment of a
very considerable excess of air. Horace [228]. Another reason was the
idea to use the gas in gas-engine cylinders , exible process heat or

lighting. The solid and gas analysis were already surprising sophisticated, still not as convenient as today. Some years later the liquefaction
of coal became an interesting application due to an increased need of
liquid fuels for various applications like aero planes, ships and cars, or
stationary power engines (Fischer [229]).

Later publications added better understanding of the kinetics of the

reactions, pre-treatments, post-treatments and a variety of additional
applications and products ([230; 223; 231; 127; 87]). It is recommended
to review the cited literature if deeper insight is needed by the reader.
Gasication takes place in several steps, which can overlap depending
on a variety of parameters like fuel size or moisture. The rst step is
the drying of the fuel followed by pyrolysis and gasication by which
the volatile matter is driven out of the fuel due to the high temperature.
The remaining char is gasied by H2 O (equation 4.3) or if oxygen is
92

4.1 Brief review of gasication processes

Figure 4.1: Historical Siemens gas producer 1906 Wyer [226]

present combusted (equation 4.1 and 4.4). The char gasication process
takes much longer and is the limiting step. This step is additionally
dependent on the type of the char. Char produced by grass gasication
shows a very open structure and thus good access to the reacting gases.
For wood or coal the char is much more compact and the residence time
can be expected to be longer.
Equations (4.1) to (4.7) are the major gasication and combustion reactions as given in [232; 223; 87]. Equation (4.6) is the methanation reaction. It is of minor inuence since the equilibrium favours H2 and CO
at gasication conditions. The rst three reactions ((4.1)(4.3)) correspond to the solid-gas reactions, whereas the later four ((4.4)(4.7)) are
homogeneous gas phase reactions. Following equilibrium calculations
(stoichiometric input), H2 and CO are promoted at higher temperatures the other species at lower temperatures. The carbon conversion
is better at higher temperatures.

*
C + 21 O2 )

CO

*
C + CO2 )

2 CO

*
C + H2 O
)

CO + H2

(4.1)
= +173 MJ/kmol )
(4.2)
( HR0 = +131 MJ/kmol ) (4.3)

( HR0 = 111 MJ/kmol )

( HR0

93

4 Fluidised bed experiments

*
CO + 12 O2
)

CO2

*
CO + H2 O
) H2 + CO2

*
CH4 + H2 O )

3 H2 + CO

*
H2 + 12 O )

H2 O

( HR0 = 283 MJ/kmol ) (4.4)

(4.5)
= +206 MJ/kmol ) (4.6)
= 242 MJ/kmol ) (4.7)

( HR0 = 41 MJ/kmol )
( HR0
( HR0

If the gasication is autothermal, the heat for the endothermic reactions

(H > 0) is taken from partial combustion equation (4.1) or total
combustion (4.4) and (4.7). For allothermal gasication the required
heat must be introduced from outside.
The basic gasication types are depicted in table 4.1. From the left xed
bed i. e. downdraft, xed bed updraft, uidised bed and entrained ow.
The uidised bed can be designed as bubbling uidised bed without
recirculation of bed and nes or as depicted as circulating uidised
bed.
Furthermore, there are a variety of modied gasiers like the Battelle/FERCO process [233], Blauer Turm [234] or annular reactors [183;
27]. The goal is usually to better control the various types and completeness of the reactions in the reactor; mainly the gasication and char
conversion. The main motivation is the heat control between those two
processes. While the char gasication is endothermic (equation (4.3)),
the entire process should be autothermic. The named processes aim
to either separate the processes and transfer the heat from the char
through combustion back or bring them closer together so the exothermic reactions can feed the endothermic char gasication without
producing local cold spots.
The main advantages of the basic types are noted in the table 4.1
below the pictures. Concerning the gasication of grass the ash melting
being critical property, excludes the xed bed gasication due to both
experience (see below) and theory. During xed bed gasication local
hot spots can not be avoided based on the nature of the process. The
tendency of the xed bed to form channels and can lead to temperatures
as hot as 1000 C. This would certainly lead to bed agglomeration and
eventual termination of the process. Leaving aside special designs, this
leaves the two remaining options. Entrained ow gasication is fed
by a slurry or powder. This makes fuel preparation a crucial point.
For uidised bed gasication the fuel can be heterogeneous instead.
The high temperatures of the entrained ow reactor would inevitably
lead to a high volatilisation of inorganic components, which later on

94

4.1 Brief review of gasication processes

need to be removed by possibly additional gas cleaning units. The

SFG gasier e. g. uses water quenching to cool the gas and scrub it
partially. The contaminant load in the water would further lead to an
increased waste water treatment. From this point of view, the uidised
bed technology with a dry hot gas particulate removal seems more
suitable. The complexity of a uidised bed is smaller, which is an
important point when it comes to the economic value of the fuel. Lower
costs for the plant maybe essential for a realisation of a demonstration
unit (see also [235]).

95

96

Downdraft
6001000
< 10
0.1-6
medium
low

Updraft
6001000
< 10
10-150
medium
low

Fluidised bed
700 900
< 200
1.30
high
medium

Table 4.1: Comparison of basic gasier types (pictures taken from [216])

Type
Temperature, C
Size, MW
Tar load [223], g/m3
Fuel exibility
Complexity

Entrained ow
1200 1600
< 1000
< 0.1
low
high

4 Fluidised bed experiments

4.2 Basic expressions and denitions

4.2 Basic expressions and denitions

4.2.1 Air to fuel ratio Lambda
Lambda () is the Greek symbol usually chosen for the air to fuel ratio.
It is dened as 1 when the molar amount of air, which is added to the
fuel exactly matches the amount needed to get a complete combustion
of the elements C, H and S to CO2 , H2 O and SO2 (Baehr [236]). The
reaction scheme is given in formula (4.8), by which the meaning of
lambda becomes quite clear.
Cm Hn Op Sq + (m +

n p
n
+ q)O2 => mCO2 + H2 O + qSO2 (4.8)
4 2
2

By this denition is
=

Oxygen added
Oxygen necessary to reach complete combustion

(4.9)

If the fuel contains oxygen like bio-fuels do, it is subtracted in the

denominator as can be seen from equation (4.8). This denition refers
to dry fuel since water takes no part in the combustion other than
reducing the temperature.

4.2.2 Carbon conversion C

The carbon conversion tells about the ability of the process and the
applied settings to convert the solid carbon into gaseous carbon. This
equally applies to combustion and gasication, since solid carbon is not
meant to be a product of both processes. It is thus
C =

Carbon converted
Carbon provided in the fuel

(4.10)

A high carbon conversion is always desirable, but it does not give any
information about the energetic eciency.

4.2.3 Cold gas eciency C and hot gas eciency H

The cold gas eciency C and hot gas eciency H describe the energetic eciency of the conversion process. The dierence between these
two eciencies is the sensible heat and heat of condensation of the hot
gas, which can be useful if the gas has not to be cooled down, or the

97

4 Fluidised bed experiments

heat included the heat of condensation can be used in another part of

the plant. This is the case for IGCC power plants, where the heat can
be used in the bottoming cycle. The eciencies are dened according
to Basu [127]
C

V gas LHVgas
f uel HHVf uel
M

V gas HHVgas + Q sensible

f uel HHVf uel
M

(4.11)
heat

(4.12)

4.3 What literature tells about grass gasication

In table 4.2 projects are listed, which seriously tried to gasify grass or
grass-like biomass. The rst experiments were conducted in 1993 in a
100 kW HTW1 gasier. It is a uidised bed invented by Fritz Winkler in
1921 [127]. In the tests rye grass was successfully gasied at moderate
temperatures (620-640 C) in order not to risk ash melting. In 1995
Alfalfa was tested for its gasication suitability in the IGT Renugas
process (bubbling uidised bed). Tests were successfully conducted
up to 800 C with additions of dolomite to inuence the ash melting
behaviour. A trial which employed the xed bed was not successful
due to problems with the fuel. The higher density of the ner particles
of grass compared to wood in the bed resulted in a higher pressure
drop and bad gasication behaviour [237]. It was stated that the fuel
fell apart in a way such that a good air fuel contact could not be
ensured anymore. The experimental reactor [27] produced very low
heating values and thus is considered not competitive. The uidised bed
experiments reported by hman et al. [119] were conducted in order
to analyse the deposition layers on the bed material not to analyse the
gas composition. The supercritical gasication is not available in large
scales at the moment.
In all projects permanent gas data was collected but apart from [169]
no analysis for inorganic compounds other than sulphur compounds
was accomplished. Turn et al. [169] reported measurements for alkalis
using a batch lter setup for 3 h experiments. The bed material used
was likely of olivine type and alkali adsorbing as it can be seen from
the experiments. Banagrass belongs to the fuel type of energy crops
1 High Temperature Winkler

98

4.4 Brief introduction of uidised beds

and shows lower alkali contents than native grass. Due to the analysis
above, the uidised bed technology seems the best suitable approach.
Ref.

Gasier

Fuel

Size, MW

Success

[3]
[4]
[5; 237]
[169]
[119]
[238]
[27]

Fluidised bed
Fluidised bed
Fixed bed
Fluidised bed
Fluidised bed
Supercritical
Fluidised bed

Rye grass
Alfalfa
Native grass
Banagrass
Alfalfa
Clover grass
Blue grass

640
*800

**800
600
900
650

0.1
1.7
0.2

0.05
Lab scale
0.02

Yes
Yes
No
Yes
Yes
So far
No

Table 4.2: Review of projects with the topic grass gasication (*with additives

to avoid ash melting, **with reactive bed material)

4.4 Brief introduction of uidised beds

The uidised bed as a reactor was introduced in section 4.1 for gasication applications. Fluidised beds can be used for almost any gas-solid
interactions. Besides gasication, this may be combustion boilers, catalytic reformers, absorption- desorption processes or the production of
chemicals.
The main advantages of a uidised bed as described above are the
uniform bed temperature due to the good mixing possibilities and the
option to use the bed material in order to inuence the reactor behaviour. Here adsorbing, reactive or even catalytic bed materials have
been employed.

4.4.1 Fluidisation
A uidised bed is established when the velocity through the reactor is
just high enough to lift the material which is in the reactor. The oating of the material marks the transition from a xed bed to a uidised
bed. This point is called minimum uidisation with the characteristic
minimum uidisation velocity um f . Increasing the velocity leads to an
expansion of the material until the grains are entrained. Before this
point the bed is called bubbling. If the material is deliberately entrained and recirculated into the bed it is called circulating uidised bed.
Then the velocity in the reactor is higher than the terminal velocity ut .

99

4 Fluidised bed experiments

From a certain point the ow rather resembles a pneumatic transport

of particles, then the process is called transport reactor. A bubbling
uidised bed consists of two phases a bubble phase which is considered
particle free and a dense bed, where a mixture of gas and particles is
found. From this view it becomes clear that heterogeneous reactions
like char gasication will take place only in the dense phase, whereas
homogeneous reactions can take place in both phases. Further reading
of uidised beds may be found in Yang [239], more specialised literature
on uidised bed gasication can be found in Basu [127]; Higman and
van der Burgt [87].

4.4.2 Bed materials

The bed material can be of various types. The reacting particles may
form the bed themselves or additional bed material can be used which
may be catalytically active or inert. There are several important properties of the bed material which should be considered:
G reactivity (inuence on the reaction mechanisms)
G density and size of the particles (responsible for the uidisation

characteristic)

G specic heat (responsible for the temperature texture in the bed)

G Moh's hardness (responsible for abrasion of the reactor or the bed

itself)

As long as there is not a need for a reactive bed material the inert
material should be preferred. Reactive bed material has to be replaced, which increases the maintenance eort. Furthermore, reactive bed
material changes its properties after taking part in the reaction, e. g. if
CaCO3 forms CaSO4 Moh's hardness will be reduced to only 2. This
would lead to an increased grinding activity of the bed and the dust
would be carried away with the gas. Whereas MgCO3 can form MgSiO3
which has an increased Moh's hardness of 7.
Table 4.3 lists basic information about three dierent bed materials
which are commonly used in gasication applications. The solid density
of the materials can dier due to the changing porosity. Porous alumina can have density of only 1300 kg/m3 . This type is mostly used for
catalyst applications. It has to be noted, that real inert bed material is
almost impossible for a gasication environment. It has been reported

100

4.5 Experimental setup of the bench-scale gasier

Mineral

Silica

Dolomite

Alumina

Chemical composition
Inuence (reactivity)

SiO2
alkali silicates

Al2 O3
alkali-aluminosilicates

Solid density, kg/m3

Specic heat, kJ/(kg K )
Moh's hardness
Heat expansion, %
Geldart classication

2650
0.962
6.5
1.3
B
200

CaMg[CO3 ]2
ash
melting
point, sulphur
retention
2860
1.01
3.5
1.7
B
200

d p (50) m

3970
1.1
9
1.2
B
270

Table 4.3: Bedmaterials and properties (specic heat and heat expansion

from [240], Moh's hardness and density from [120])

that silica bed material combines with alkalis which leads to a sticky
surface, whereas alumina can form alkali-alumina-silicates [180; 119].
However, the latter reaction is not expected to have any grave inuence
on both gasication and uidisation.

4.5 Experimental setup of the bench-scale gasier

4.5.1 Construction of the bubbling uidised bed
The bubbling uidised bed test rig is depicted below (image 4.2). It is
a semi continuous system since it possesses a fuel feeder and a storage
large enough to run a test of several hours but is not equipped with
an ash removal system. This means the ash stays in the bed for the
entire time of the experiment or is entrained if the particles become
small enough.
The fuel enters the system from the silo , which contains most of
the grass. It is released from the silo into a dosing container by a
rotary feeder . About 90 ml/min of nitrogen is given into both the silo
and dosing feeder to prevent the product gas from owing upstream
into the fuel container and thus causing a back-burning. From the feed
container the fuel is transported into the reactor close above the
frit by a feed auger . The auger runs within a water cooled double
jacked (gure 4.7) to prevent early heating of the fuel, which would
result in slow pyrolysis. Within the uidised bed the fuel reacts with

101

4 Fluidised bed experiments

Figure 4.2: General design of the bubbling uidised bed test rig.

air to mainly H2 , CO, CO2 , CH4 and steam. The ash stays in the bed,
whereas the product gas leaves the system through the freeboard .
Several sampling lines are available directly after the gas exit e. g. .
The product gas ows through a cyclone and then into a are . To
secure no reactive product gas is emitted the are is equipped with a

102

4.5 Experimental setup of the bench-scale gasier

pilot burner running on methane. The hardware will be described in

the order of downstream components as far as possible.
Feature

Value

Reactor height
Freeboard height
Solid feed
Gasication agent
Temperature
Pressure
Reactor diameter
Bed material
Size
Fuel
Bed material size range
Reactor material

1m
0.5 m
0.3-3 kg/h
air
600-900 C
atmospheric
52 mm
SiO2 / CaMg(CO3 )2 / Al2 O3
2-10 kW
chaed wood/ chaed grass
100-300 m
high temperature alloy (Inconel )

Table 4.4: General properties of the bubbling uidised bed

4.5.1.1 Silo
The silo is a 25 l container with a conical exit onto a rotary feeder. Here
the biomass is placed before running a test. The bulk density of chaed
grass is 377 g/l ; thus the container may keep around 9.4 kg of fuel. For
shredded wood the capacity is slightly higher because the bulk density
is 400 g/l .
Based on the conical shape of the exit, bridging will inevitably occur
unless special care is taken. Extra devices normally result in extra
sealings which should be avoided as long as possible. The solution is
a simple approach best explained by means of the picture given below.
It is a system, which is not dependent on extra machines or controlling
devices but self-sustaining and reliable.
It is made of a hollow steel sphere, into which a steel tube is soldered.
Several steel wires are soldered into the tube to form a gure similar
to a dead tree. The sphere is placed directly onto the rotary feeder.
Since the radius of the sphere is much bigger than the hight of the
blades of the feeder, the force applied by the passing blade will lift
the sphere. The weight of the structure will pull it back down again.
If the system runs properly, there will be always material within the
cabins and the sphere will oat on top not stressing the blade or vice

103

4 Fluidised bed experiments

Figure 4.3: Device to avoid bridging of the fuel in the exit of the silo.

versa. If the cabins stay empty in the case of bridging the movement
of the structure will rupture all bridges. The system proved to be very
reliable.
4.5.1.2 Feed auger
To generate a continuous gas stream a controlled fuel stream has to
be ensured. This is done by a feed auger, which takes the fuel from
a small container and feeds it by a screw into the reactor. The mass
ow is proportional to the fuel column above the screw if a constant
rotation of the auger is applied. This means the level in the container
must be controlled. This is managed by a level sensor which controls
the switch of the rotary feeder. Fuel from the silo is then released into
the container of the feed auger. The auger is controlled by a special
system bought with the feeder. The speed can be adjusted from zero
to 2000 rounds per minute referred to the engine. There is a gear box,
which transforms the speed to 100 rounds per minute at the screw.
The controller gives out an alarm signal if the auger is blocked and the
current of the motor rises above the given limit.
Two augers were manufactured from a 18 mm standard hammer drill
and a wood snake-drill. The shafts were changed to match the dosing
feeder (gure 4.4).
Feeding augers are always one of the major failing points in thermal
process engineering. The dimension and geometry of the screws must be

104

4.5 Experimental setup of the bench-scale gasier

Figure 4.4: Feeding augers of dierent sizes.

optimized for each task they have to do. Transporting fuel showing nes
and bigger clusters at the same time is one of the most dicult tasks.
First of all the screw must not block itself by forming plugs, which is the
case, when the downstream part of the screw transports faster, than
the upstream part. Second the auger must not push the fuel to the
inner wall of the outside tubing, which is the case if the transporting
shoulder of the auger is tilted too little. Then the fuel is ground between
the auger and the wall of the tube and compacted and the screw will
be blocked by the densied nes. Instead the shoulder must show a
geometry such that the fuel is moved back into the auger. And third
the auger must be much more smooth then the wall, otherwise it will
not transport the fuel properly. The drills were manually adopted to all
of these criteria. Additionally at the tip of the screw the shoulder was
sharpened to avoid the clogging of the exit. This blade was added to
cut the coke away from the wall which is formed during the transition
from the cooled feeding tube into the hot reactor. This also means, the
auger must reach slightly into the reactor to achieve this goal. To avoid
the heating of the auger  this would result in an uncontrolled pyrolysis
of the fuel in the transport tubing  The shaft was drilled open. This
results in less heat transfer through the material gure 4.5.

Figure 4.5: Tip of the auger showing a drill hole for less heat transport into

the fuel pipe.

The feed augers were calibrated in place using the original setup of silo
and rotary feeder. The calibration curves are plotted below. For the
tests the stone auger was used since its feeding characteristic was more

105

4 Fluidised bed experiments

suitable. It has to be noted, that the auger transport rather by volume

than by mass. Usually it is more important to feed a constant heat rate
(LHV per time). To achieve this the feed rate needs to be corrected for
the water content of the fuel. For each experiment the fuel was weighed
before the test and after the test. So the overall amount of fuel could
be properly determined.

Figure 4.6: Calibration of the feeding screws.

The auger and fuel within is cooled by a double jacket . For construction
reasons the cooling uid must enter and leave the jacket at the same end
(, in gure 4.7). Therefore a double helix was chosen to separate
the inbound and outbound stream and distribute the cooling eect
circumferentially along the tubing.
The dosing feeder is not mounted xed to an external frame but connected to the bottom of the reactor by a metal wire. This is necessary
because the thermal expansion of the reactor between 20 and 800 C
leads to a lowering of the feeding entrance of about 18 mm. As illustrated in gure 4.8, the wire runs from the reactor to the bottom of the
test rig over a pulley up to the top of the test rig over a second pulley and down to the dosing feeder. This way, the dosing feeder moves
exactly the same distance as the bottom of the reactor does. This is
very important since the auger would clamp otherwise. A thermocouple
ensures that any increase in temperature is detected in case there is a
back-burning.

106

4.5 Experimental setup of the bench-scale gasier

Figure 4.7: Double jacket for the cooling of the feeding screw.

4.5.1.3 Reactor
The reactor  which is also depicted in gure 4.2  is made of Inconell
600, which is a high temperature alloy. It contains around 72 % nickel
and minor amounts of chromium and iron. The inner diameter of the
reactor is 52 mm. The maximum diameter at the outlet of the cone
is 220 mm. The gasication agent enters through the bottom of the
reactor after it is preheated. It then passes through a frit made of
sintered Hastallloy having a mean pores size of 40 m.
4.5.1.4 Cyclone
A cyclone was used to remove particulate matter of the gas before the
gas is burned in the are. According to Perry [242], the calculated cut
o diameter is 102 m, the number of rotations within the cyclone is

107

4 Fluidised bed experiments

Figure 4.8: Mounting of the feeder system.

Property

Dimension

Material number
Density
Thermal expansion
Specic heat
Melting point

kg/m3
m /(mK)
kJ/(kg K )
C

Value
2.4816
8430
14.6 (21 - 427 C)
0.444
1354 - 1413

Table 4.5: Physical properties of Inconell 600 [241]

2.4. The cyclone container shows an exit tube, from which the nes
can be removed by a screw. It is also heated to prevent the tars from
condensing within the cyclone, which would eventually block the system.

108

4.5 Experimental setup of the bench-scale gasier

4.5.1.5 Flare
A simple are was used to combust the product gas before leaving
through the duct. It is possible to adjust primary and secondary air
separately. A methane pilot burner secures that the are re-lights whenever blown o by a pressure wave. This happens when coke and tars
are deposited at the wall of the downstream pipes and are suddenly
blown away when the velocity in the pipe has increased suciently.
The pilot burner proved to be very reliable during the tests.

4.5.2 Sampling
The gas was sampled by using the pressurised sampling system presented in section 3.2. The gas stream is divided into two streams: the clean
permanent gas stream and a solvent stream, containing the tars, water
and particles which pass the lter. The gas stream was measured with
a Varian micro GC (gas chromatograph)2 and the wet stream using a
SPECTRO ICP-OES3 .
Directly after the gas exit several sampling ports are positioned (gure 4.9) and . One of them is an isokinetic sampling port .
The gure shows the lid of the reactor . The gas exits in the tubing
passes the knee and runs straight into the cyclone . In order to
achieve isokinetic sampling, the sampling ow must be adopted to the
output ow of the reactor. The velocities at the cross section where the
sampling line opens must be constant. Isokinetic sampling becomes an
important topic when sampling gas which contains particles. Hyperkinetik sampling e. g. would result in a higher particle loading in the
sampling line than in the main line. The variation of the ow velocity
may be 5 % less or 15 % more than the isokinetik velocity [243]. From
latter standard it can be derived, that isokinetic sampling is best positioned in a vertical duct. Using one central sampling tube is enough
for ducts with sizes up to 350 mm in diameter.
The sampling gas runs through a heated porous metal lter (5 m) before entering the sampling system. If isokinetic sampling is established,
the material in the lter can be considered to be equivalent to the one
in the main gas stream.
2 www.varianinc.com
3 www.spectro.com

109

4 Fluidised bed experiments

Figure 4.9: Sampling ports at the gas exit of the plant

A second sampling port was installed to record the axial concentration

proles along the reactor height. The probe was a lance of about 1.7 m
length and 8 mm in diameter. It is inserted from the top of the reactor through a centred inlet gure 4.9. By using a gland the probe
becomes movable in axial direction. Since only the small particles and
permanent gases were recorded, a porous metal lter was installed directly at the tip of the tubing. An additional thermocouple was inserted
at the tip to monitor the temperature alongside the gas prole.

4.5.3 Controlling system

The system is controlled by a PC based system consisting of a PC and
a SPS4 controlling box. The PC is equipped with National Instruments
(NI) LabView. The controlling box contains inlets for pressure, temperature and logic signals and outlets for mass ow controllers (MFCs),
heaters and switches. The overall scheme of the controlling structure
can be seen in the ow chart gure 4.10.

4.5.4 Safety concept

The safety is ensured by limiting certain sensor values and setting an
alarm if those limits are exceeded. In case one or more of the limits
are exceeded the gasication agent stops owing, the feed auger stops
4 Speicher Programmierbare Steuerung

110

4.5 Experimental setup of the bench-scale gasier

running and the nitrogen ow starts streaming somewhat higher than
the minimum uidisation velocity. This ensures that the bed material
and the ash will not agglomerate in the case of cooling. If there is an
electrical blackout the same will happen because, the nitrogen valve is
normally open and the gasication agent MFC is normally closed.
If the pressure in the reactor is to high safety valves [244] will go o
and release product gas from the reactor into the exhaust pipe. If the
pressure in front of the reactor is too high, the plant will shut down
automatically.

Figure 4.10: Flow chart of the bubbling uidised bed

4.5.5 Instrumentation and measurement methods

Several measurement techniques were applied. Most of them are online
and continuously. Some had to be oine since the samples could not be

111

4 Fluidised bed experiments

taken out of the process during the run time. These are bed material,
ash and lter ash.
4.5.5.1 Fluidisation and Inertisation
Three gas mass ow controllers (MFC) from Bronkhorst are used: the
rst one controlling the airow (gasication agent), the second one
controlling the nitrogen purge and the third one controlling the He spike
ow. The last one is used as standard addition in order to obtained the
total gas ow at the exit (see equation (4.13)). Calibrations were done
by means of a Ritter gas meter, which as an accuracy of 0.2 %rel.
4.5.5.2 Temperature
The temperature sensors are type K thermocouples which are standard
for these kind of operations. The accuracy can be expected to be around
0.5 %rel. But care must be taken when the sensor exceeds 600 C. The
material recrystallises and may well show an additional shift of 5 C at
400 C when standard calibration curve is applied [245]. All together
an uncertainty of around 10 C must be accepted when working with
type K thermocouples above 600 C. More accurate but as well more
expensive options are Type N thermocouples or resistance thermometer
(PT) up to 850 C.
Measurement response by radiation could be observed during the heating up of the reactor, but were not evident during the operation of the
gasier due to the good mixing behaviour of the uid bed.
4.5.5.3 Pressure
The pressure is measured by means of relative pressure sensors with a
range of 0-2.5 bar. The pressure is recorded as dierence compared to
the ambience. The accuracy for this sensor is 1 %rel [246].
4.5.5.4 Cooling water
The cooling water ow is measured by a Gems water turbine [247] operating inline. The signal is an impulse for each round which is transformed into an analog 0-20 mA signal. The accuracy of 3 % within the

112

4.5 Experimental setup of the bench-scale gasier

normal range plus the uncertainty of 0.5 % concerning the repeatability.

The standard ow was around 2.5 l/min.
4.5.5.5 Gas analysis
For the measurements of the permanent gases a Varian micro GC was
used [248]. It is equipped with two lines each with two columns (Mol
seive 5 A and PoraPLOT U) and a TCD5 sensor. The measurements
are done redundant on both lines. The columns are calibrated with
mixtures showing an uncertainty of 2 %rel and a standard deviation of
0.2 % at a single point. Besides the main components (N2 , CO2 , CO,
H2 , CH4 ) the colums can detect O2 mainly to detect leakages in the
sampling line, C2 HX since the contribution to the heating value can be
substantial, C3 H6 which can be present in minor amounts, the sulphur
components H2 S and COS and nally He for the He-spike method. The
concentrations are not normalised to 100 %. This is simply due to the
fact, that each components has its own calibration with its own uncertainties and errors. By normalising, all concentrations are changed,
wheras maybe only one concentration is wrong or else there may be a
component which can not be detected.
To check the ammonia concentration a Draeger tubes were used in one
experiment.
4.5.5.6 Tar and water analysis of the gas
The tar is determined gravimetrically for selected experiments by weighing the residue after vaporising the solvent. Since this leads to the
loss of the lighter tars, GC/MS measurements of tars are done for selected samples in one experiment.
For the water content and tar analysis several samples were taken during the experiments and analysed using Karl-Fischer titration.
4.5.5.7 Product gas ow
The product gas ow could be quantied by using the He-spike method. The helium is introduced into the lining of the gasication agent
before it enters the reactor at a constant ow V He . By measuring the
5 TCD: Thermal Conductivity Detector

113

4 Fluidised bed experiments

concentration of helium x He in the gas phase the gas ow V gas can be
calculated with the following formula.
V
V gas = He V He
x He

(4.13)

This method was successfully applied in an additional project during

this thesis, in which the slip stream of methane from a PSA separation
plant was evaluated see appendix .
4.5.5.8 Analysis of inorganic components in the gas
The ICP-OES measurements were conducted in a collaboration with
the work group of Christian Ludwig at PSI. The device is a SPECTRO
ICP-OES located in a truck and thus being able to be placed very
close to the test rig. The ICP-OES is operated with a argon plasma
torch into which the sample is injected continuously by an ultra sonic
vaporiser. The device detects the elemental composition of the sample
with a CCD detector simultaneously.
4.5.5.9 Analysis of solids
The fuel was analysed externally for elemental composition. The water
content was determined by gravimetric drying and the ash content by
incineration following [249].
The remaining bed and hot gas lter nes are taken once after each
experiment and weighed to determine the particle load of the gas. The
nes of the lter are then incinerated and analysed with ICP-OES for
the selected inorganic constituents.
An additional portion is analysed for total organic carbon (toc) to get
the amount of unreacted carbon.

4.5.6 Heat losses of the reactor

Bench-scale reactors for thermal processes are very sensitive to heat
losses, because of their large surface to volume ratio. There can be
several sources, e. g. convection, conduction, radiation or mass bound
energy losses. In gure 4.11 the major sources for heat losses are illustrated. The following calculations are made for a typical experiment,
where the process temperature was 750 C.

114

4.5 Experimental setup of the bench-scale gasier

Figure 4.11: Major heat losses of the bench-scale uidised bed

The cooling water is typically 2.5 l/min with an increase of the water temperature from 29 to 30 C . With a given specic heat of
4.177 kJ/(kg K ) [250] the removed heat is
cooling c p T = 173 W
Q cooling = M

(4.14)

where
Q cooling
cooling
M
cp
T

is the energy ow transported by the cooling

is the mass ow of the water
is the specic heat of water
is the temperature dierence between inlet and outlet

The reactor shield was measured to be 80 C. This temperature leads

to convective losses and losses through radiation. The radiation can be
expected to be very low at this temperature [250].
Q radiation = A1 F1 2e ( T24 T14 ) = 0.42 W

(4.15)

where
Q radiation is the energy ow transported by radiation
A1
is the surface of the shield

115

4 Fluidised bed experiments

F1 = 1
is the fraction of the surface visible to the environment
e
is the emission factor (0.118 for stainless steel [250])

is the Stefan-Boltzmann constant

T1 =25 C

The convection can only be estimated because there are many disturbing items around the reactor, which hinder a proper free convection.
This will be neglected here. The responsible equations were taken from
Bejan and Kraus [251]. The Nusselt correlation of Le Fvre for vertical
cylinders yields a value of:

0.25
4
7GrPr2
4(272 + 315Pr ) L

Qconvection =
+
= 266 W (4.16)
3 5(20 + 21Pr )
35(64 + 63Pr ) D

Where
Q convection

Gr
Pr
L
D

is the energy ow transported by free convection

is the Grashof number
is the Prandtl number
is the length of the body
is the diameter of the body

Additionally there is also a heat loss from the top of the freeboard.
With appropriate equations for natural convection [251] this will be
around 11 W (equation (4.17)).
Nu =

5
0.394Gr0.2 Pr0.25 = 11 W
3

(4.17)

It has to be noted that the natural convection up the shield will aect
the natural convection from the top lid. Since there is no need here to
be more accurate than the given numbers this eect shall be neglected
here.
Altogether, there is a heat loss of around 451 W , which is very large
compared to the size of the reactor (2-5 kW ). For this reason the reactor must be stabilised by electric heaters during the experiments. For
larger reactors this problem diminishes due to its much better surface
to volume ratio and thus power to heat loss ratio.
Finally there is a substantial heat leaving the reactor bound to the gas
ow. The product gas possesses a temperature close to the reactor
temperature. If we consider cooling the gas down from 750 C to 20 C
(using average data of c p = 1.4 kJ/(kg K ), gas = 0.7 kg/m3 ), the sensible
heat coming with the stream is around 0.7 kJ/l ) of gas. For the presented experiments this is roughly 190 W . For the corresponding input
power of around 2.9 kW this is 6.6 % of the energy. It shows another

116

4.5 Experimental setup of the bench-scale gasier

major advantage of integrating the gasier into a combined cycle. This

sensible heat can be recuperated for the bottoming cycle.

4.5.7 General experience

The uidised bed installation ran very well during all experiments.
The de-bridging device in the silo showed an excellent performance. No
bridging occurred during close to 100 h of accumulated operation.
The feed auger proved very reliable. No clogging or blocking occurred. After each test the auger was removed; there were hardly any
signicant depositions visible. Only a thin black layer at the tip of the
auger was evident gure 4.12.

Figure 4.12: Auger after the experiments

The uidisation could be accomplished throughout all experiments

without inducing any deuidisation or slagging of the ash.

The He-spiking of the gasication air to determine the gas ow,

was successfully conducted throughout all experiments.
During all tests it could be observed, that the char is separated from

the bed and oats on top of it. This could be detected by promptly terminating the uidisation and remove layer by layer of the bed starting
from the top.

The tar content of the gas was not measured for each experiment.
But its was low enough that no depositions in the downstream lining
could be observed in any of the tests at all.

Commissioning of the gasier The gasier was rst tested with

crushed wood pellets. The bed material used was silica sand. One of

117

4 Fluidised bed experiments

the experiments is presented in appendix .1. The result was stable

gasication during 5 h of operation. The gas composition was good, the
lower heating value was 6.8 MJ/kg for an air to fuel ratio of 0.22. 1

4.6 Experimental procedures

Graph 4.16 displays three dierent uidisation characteristics at three
dierent temperatures for the same bed material. It shows the pressure
drop over the bed versus the velocity of the uidisation agent (air). The
rst increase of the pressure drop is due to the rising velocity through
the immobile bed of particles. The minimum uidisation velocity is
reached when the particles break loose and start to oat. Then the
pressure drop rises much slower with increasing velocity. At the same
time the bed expands much alike a rotameter.
If the uidisation is accomplished from low to high velocities there will
be a hysteresis at the relaxation point um f . The initial uidisation
velocity seems higher than expected. This eect is based on the fact,
that the initial force to unclench the particles of the xed bed is higher
than the eective force needed to start the uidisation. The relaxation
point is not visible if the measurement is conducted from higher to
lower velocities.
All experiments were conducted using the same procedure:
G Cleaning of the reactor
G Filling in 500 g of the selected bed material
G Filling in an appropriate amount of fuel in the silo for a 5h run
G Heating up the reactor to the process settings with electrical hea-

ters

G Starting the uidisation

G Starting the fuel feed

When the reactor reached its temperature set point, the fuel auto ignited rapidly. The rst ame in the are could be observed already
1 min after starting the fuel auger. The experiment was terminated
after around 5 h by stopping the fuel feeder. The gasication agent
(air) was stopped and a nitrogen purge ow was started in order to
cool down the remaining bed more eciently and keep the remaining
materials from reacting.

118

4.7 Experimental matrix

4.7 Experimental matrix

Table 4.6 lists the parameters varied in the experiments. The axial
prole measurement was conducted for =0.3 at 750 C with alumina.
The characters denote the experiments conducted and will be used as
reference in the discussion below.

0.17
0.20
0.25
0.30
0.35

700 C
Dolimite SiO2
a

b
c

Al2 O3

750 C
Al2 O3

d
e
f

g
h
i6
j

Table 4.6: Experimental matrix for the gasication experiments,

(6) axial prole measurement for this point

Additional experiments were carried out to test the uidisation characteristic of the bed material (section 4.9.1) and the ash melting behaviour
of the grass together with the chosen bed materials (section 4.8.2)

4.8 Fuel characterisation

The fuel was characterised by several methods:
G Water content: Mettler/Toledo infra red dryer once for each ex-

periment [252]

G Major elemental analysis: once for each type of fuel (ETHZ)

G Minor elemental analysis: once for grass (external laboratory)
G Ash content: once applying DIN 1978 No 51719 [249]

Table 4.7 gives the average dry major elemental composition of the
grass used in the experiments. The second line illustrates values derived
from the fuel analysis in section 2. The data is quite comparable to the
average expected composition.
In table 4.8 the average measured composition of some important minor
elements is given. These values too are very comparative to the expected average composition. The data was not acquired for wood. Lead

119

4 Fluidised bed experiments

grass avg. %w dry

grass avg. eDaB %w dry
wood avg. %w dry
wood avg. eDaB %w dry

Ash

43.11
44.88
47.31
49.24

5.66
5.51
6.23
6.14

41.05
40.00
44.44
42.26

1.30
1.64
0.18
0.41

0.12
0.19
0.01
0.07

8.76
7.78
*1.83
1.83

Table 4.7: Major elemental analysis (*assumed from eDaB)

could not be veried in the grass (the detection limit of the method
was 4.6 mg/kg).
g/kg dry
eDaB g/kg dry
mg/kg dry
eDaB mg/kg dry

Cl

Ca

Mg

Na

Si

2.15
2.17
Ba

4.45
6.62
Sr

7.0
6.6
Li

17.3
18.8
V

1.58
2.04
Pb

0.11
0.51
Mo

13.9
9.4

16
29

17
21

2
7

4.8
4.5

Table 4.8: Minor elemental analysis for grass (: below detection limit)

The energy content was not measured but calculated from the elemental
data as proposed by Channiwala and Parikh [107] (equation (4.19)).
The elemental data is inserted as %w. The HHV can be expected to
be accurate within an uncertainty of 3 %rel. The lower heating value
was calculated using the correlation proposed by Oasmaa et al. [100]
(equation (4.19)).
HHV

LHV

349.1 C + 1178.3 H 103.4 O +

(4.18)

100.5 S 15.1 N 21.1 Ash

HHV 0.21813 H

(4.19)

Where
The heating values are given in MJ/kg
The elemental data is given in %w
HHV, MJ/kg
LHV, MJ/kg

17.28
16.05

Table 4.9: Caclulated energy content of grass

The water content of the fuel varied for each experiment. The grass
showed a signicant hygroscopic behaviour, which can be derived from

120

4.8 Fuel characterisation

gure 4.13. The diagram shows the water content of grass dependent
on the date, when the sample was taken. The grass pellets took up
around 3 % of moisture in rst half of the year being within the bag.
This is an important hint for the storage facilities of a larger plant,
where the fuel must be kept up to a year. The grass bags stayed closed
until used. The grass was chaed and stored in a sealed bin until the
experiment was conducted.

Figure 4.13: Change of water content of grass samples during time

4.8.1 Fuel preparation

The grass and wood pellets were delivered by Mhle Scherz AG, CH as
16 mm respectively 6 mm pellets. Since the size of the plant limits the
size of the auger the pellets had to be crushed in advance. This was
done by a cutting mill SM2000 [253]. The matrix was 10 mm square
through which the fuel was shredded. The resulting particles showed
every size from nes to 4 mm. The density of the original pellets were
determined to be 1.3 kg/l for grass and 1.2 kg/l for wood.

Figure 4.14: Fuel pellets as received, left picture: grass 16 mm/ right picture:

wood 6

mm

121

4 Fluidised bed experiments

The fuel was then put into the silo which stayed closed until the experiments started. Wood was only used as reference fuel to test the
uidised bed. No profound analysis of the gas phase was conducted for
the wood experiments.

4.8.2 Ash melting: preliminary microscopic observations

To test the ash melting behaviour of grass in combination with dierent
bed materials, samples of grass were mixed with each bed material.
The mixture was softly freed from volatiles at 400 C during one hour.
Then the mixture was heated up to the nal temperature of 700, 750 or
800 C for another hour. The result was analysed under the microscope
for appearance and mechanical strength.
For all bed materials the resulting ash was weak at 700 C and showed
a rising brittleness with increasing temperature. Figure 4.15 shows an
example of photographs taken from the microscope of the ashes. The
reference sample consisted of ash of pure grass. It showed a signicant
brittleness from around 800 C. Additionally small molten beads could
be recognized, which is rst signal that agglomeration can occur. This
behaviour was comparable with the addition of silica. For the alumina
bed the ash was signicantly weaker and the molten beads much less
obvious, though a few could still be observed. These tests showed that
the gasication of native grass without additives to bind the alkalis
becomes critical above 750 C.

Figure 4.15: Ash melting observations by means of a microscope at 800 C.

122

4.9 Results and discussion

4.9 Results and discussion

4.9.1 Fluidisation
The uidisation of the bed and the fuel was done by the gasication
air directly. The uidisation diagram (gure 4.16) was taken at three
dierent temperatures within the reactor. The data points near zero
are distorted because the MFC7 used for the uidisation was very inaccurate in this area.

30

pressure drop, mbar

25
20
15
20C
400C
700C
umf(20C)

10
5

umf(400C)
umf(700C)

0
0

0.01

0.02

0.03

0.04
0.05
Air velocity, m/s

0.06

0.07

0.08

Figure 4.16: Fluidisation diagram of Al2 O3 with a mean size of 270 m

The minimum uidisation velocity can be calculated with the Ergun

formula (4.20) ([254]).
(1 em f )2 g u m f
(1 em f ) g u2m f
p
= 150
+
1.75
3
3
H
d p
(d p )2
em
em
f
f

(4.20)

where
p
H
ap

e
g
um f
g

is the pressure drop over the height of the bed

is the specic surface area
is the void fraction at the uidisation point
is the gas phase viscosity
is the minimum uidisation velocity
is the density of the gas phase

7 Mass Flow Controller

123

4 Fluidised bed experiments

The pressure drop on the other hand can be replaced by a balance of

forces around a particle which gives the pressure drop that can just lift
the particle (equation (4.21)). The force of the particle trying to fall
and the force of the ow trying to lift the particle are balanced.
p
= (1 em f )(s g ) g
H

(4.21)

For real systems the specic surface area and the void fraction are very
dicult to determine. For this reason the equation was reformulated in
order to reduce the unknown to possibly constant numbers. The result
is given in formula (4.22). Rem f is the Reynolds number at the uidisation point and Ar is the Archimedes number given in formula (4.23).
C1 and C2 are constants which can be taken from literature e. g. Yang
[239] and Basu [127]. The calculated uidisation velocities (from equation (4.24)) are plotted in the diagram as solid vertical lines. They
match the experimental values very nicely. The constants used for the
calculations are C1 = 33.7 and C2 = 0.04. The standard deviation is
reported to be above 30 % [255].
Rem f

Ar

um f =

um f d p g

C12 + C2 Ar C1

g ( p g ) gd3p

(4.23)

d p g

q

C12 + C2 Ar C1

(4.22)

(4.24)

um f decreases with rising temperature as shown in gure 4.16. The

controlling mechanisms are the temperature dependency of the density and the viscosity. For small particles as it is the case for these
experiments the rst part of equation (4.20) becomes relevant above
the second part. From this part it can be seen, that the uidisation
velocity is inversely proportional to the viscosity. Between 100 and
700 C the viscosity approx. doubles and hence the uidisation velocity drops. The diagram also shows very nicely that the dependency
on the temperature gets weaker with increasing temperature.

The bed expansion above the uidisation point is dependent on the velocity and the minimum uidisation velocity of the system [127][recited].
H Hm f
Hm f

124

u um f
um f

(4.25)

4.9 Results and discussion

If the velocity is chosen to high, the bed will entrain. For this reason a
freeboard with an extended diameter is used to decrease the supercial
velocity before the gas exit. The volatilisation of the fuel during the
gasication leads to an increase of the volume ow. The bed expansion
must therefore be expected to be non linear.

4.9.2 General stability of the process

4.9.2.1 Dolomite bed

Dolomite (CaMg[CO3 ]2 ) has a Moh's hardness between 3.54. Compared to other bed materials like sand (hardness 7) or alumina (hardness 9), dolomite appears rather week. In uidised bed gasication the
turbulences in the reactor especially at higher temperatures are very
strong. The experiment with dolomite resulted in a continuous removal
of bed material out of the reactor by entrainment. Usually the pressure
drop during the run time increases slightly because the ash accumulates
in the uidised bed as it can be seen from gure 4.20. Figure 4.17 shows
the pressure drop over the bed during the run time of the experiment.
It decreases substantially, which can only happen if the ow decreases,
the temperature decreases, the particles get smaller or less particles are
in the reactor. Since the temperature eectively increased and the ow
was hold constant only smaller or less particles can be responsible. It
was stated in literature that under certain conditions dolomite becomes
friable [256]. For this reason dolomite was excluded from further tests.
It though might still be interesting as additive to bind alkalis.
4.9.2.2 Silica and alumina bed tests
The main experiments were carried out with silica and alumina bed
material. Simultaneous runs of the complete diagnostic was done for
selected tests only. For the main fraction of the experiments besides
temperature and pressure only micro GC measurements were taken.
The loaded solvent was fractionated and analysed afterwards.
From the gasication of agricultural residues, alkali metals especially
potassium and sodium have been known a long time to form sticky
melts together with SiO2 bed material [257259]. If these melts form
eutectic mixtures, which have the characteristic to solidify at low temperatures, the bed material and y ash is glued together and the ui-

125

800

100

600

75

400

50

200

25

0
12:00

13:00

14:00

15:00
clock time

16:00

17:00

pressure drop, mbar

Bed temperature, C

4 Fluidised bed experiments

0
18:00

Figure 4.17: Pressure and temperature for the dolomite experiment.

disation is terminated. For this reason SiO2 is used as bed material

only up to 700 C. For tests at 750 C, Al2 O3 was used. The ash can
still agglomerate since grass itself contains signicant amounts of silica
and alkalis. But alkali alumino silicates, which can be formed on the
bed material are known to possess very high melting points [260; 258],
which lessens the problem. As long as the amount of bed material is
much more compared to the ash in the reactor agglomeration should
be of minor concern at temperatures up to 800 C.
Figure 4.18 shows an typical example of gas phase, temperature and
pressure readings. The graphs show a section of a run at 750 C with
alumina bed material. The rst graph shows the permanent gas data.
The permanent gas data stops due to the blocking of the sampling
system, which was explained in detail in section 4.5.7.
Figure 4.19 shows an equivalent example of a run with silica at 700 C.
The sampling system was maintained during the time, which shows the
shaded overlay. The gas phase concentrations after the maintenance
was entirely the same. Only C2 H2 shows a decreasing trend, which
is stopped after three hours. The important conclusion is that the
process is stable during the 5 h run for both bed materials. The main
experiments and analysis were conducted for the alumina bed, since it
proved to be the better option.

126

Bed temperature, C

800

400

600

300
pressure drop
temperature

400

200

200

100

0
00:00

0
01:30

00:30
01:00
elapsed time, hh:mm

Pressure drop over the bed, mbar

4.9 Results and discussion

10

Concentration, %vol

CO2
CH4

10

CO
N2
C2H4

10

C2H6
C2H2

Blocking of the sampling system

10
00:00

C3H6

00:30
01:00
elapsed time, hh:mm

01:30

Bed temperature, C

800

400

600

300
pressure drop
temperature

400
200

200
100

0
00:00

01:00

02:00
03:00
elapsed time, hh:mm

04:00

0
05:00

Pressure drop over the bed, mbar

Figure 4.18: Example of a gasication run for grass in a Al2 O3 bed at 750 C.

10
Concentration, %vol

H2
CO2
0

10

10

CH4
CO
N2
C2H4
C2H6
C2H2

10
00:00

C3H6

01:00

Blocking of the sampling system

02:00
03:00
elapsed time, hh:mm

04:00

05:00

Figure 4.19: Example of a gasication run for grass in a SiO2 bed at 700 C.

127

4 Fluidised bed experiments

4.9.2.3 Extended test (10 h)

Additionally to the standard tests a long run lasting 10 h of gasication
was conducted. The temperature and pressure signal is depicted in
gure 4.20. The temperature drops slightly during this run. This is
due to the electrical heaters, which were subsequently reduced as the
reactor wall temperature increased. There was no evidence, that the
process became unstable during this run. It thus can be derived, that
a continuous operation at the given settings is feasible without risking
ash melting problems.
400

600

300
temperature
pressure drop

400
200

200
100

0
00:00

02:00

04:00
06:00
elapsed time, hh:mm

08:00

Pressure drop, mbar

Bed temperature, C

800

0
10:00

Figure 4.20: Temperature and pressure during the 10 h experiment with grass,

alumina bed, 750 C.

The gas composition was checked only at the end of the run and is
listed in table 4.10.
H2

N2

CH4

CO

CO2

C2 H4

C2 H6

C3 H6

10.01

56.89

3.47

8.46

18.58

0.78

0.16

0.23

Table 4.10: Permanent gas concentration at the end of the 10 h run

4.9.3 Axial prole measurements

There was an attempt to analyse the alkali release along the height of
the reactor during the gasication. Based on the experiments with the
single pellet gasier (see section 5), there is a strong evidence, that the
major alkali release is subject to the char gasication, which takes place

128

4.9 Results and discussion

at the top of the uidised bed. The probe was a lance inserted from the
top of the gasier being mobile in axial direction. Any vertical position
could be accessed and the gas composition measured. There was a 5 m
lter at the tip of the probe in order not to remove any bed material
and keep the nes out. The attempt failed, due to problems with the
lter of the probe. During the measurement the lter got more and
more plugged and the sampling gas stream decreased steadily. Though
it was possible to obtain enough gas to feed the micro GC, it was not
enough to obtain a proper sample to analyse the in the ICP-OES for
contaminants.
The permanent gas data is presented in gure 4.22 (dashed lines). Using
such a probe in a uidised bed results in data that is most likely to be
assigned to the dense phase [261]. This is the reason why the concentration above the bed (above 0.9 m) abruptly changes. The dierence
of compositions between the bubble and dense phase has also been a
result from a mathematical approach by Bilodeau et al. [262]. The last
data set at the exit of the gasier and the one at the entrance were
not measured with the probe and can be considered as real gas phase
concentrations. At the entrance the volatiles react with the oxygen
mainly in the rst 30 cm (heater section). Then most of the oxygen is
consumed. From there the change of the gas phase concentration in the
bed is a complex combination of gas diusion between the bubble phase
and the dense phase, char gasication and homogeneous gas phase reactions.
In the rst 60 cm a decreasing CO2 ow combined with an increasing
CO and H2 ow is observed. This component change can be explained
by the Boudouard- and water-gas-reaction, which produce CO and H2
through the reaction of CO2 and H2 O with solid carbon. Both reactions
are endothermal.
The concentration change in the upper part of segment II is possibly due
to the temperature decrease but also to diusion between the bubble
and dense phase.
From the remaining bed after the experiments, it could be concluded
that the char is to a great extend oating on top of the bed. The main
endothermic char gasication thus takes place in the unheated section.
The local mechanisms in a uidised bed gasication including diusion
as well as homogeneous and heterogeneous reactions are not understood
today. One point surely is that such proles for gasication reactors

129

4 Fluidised bed experiments

300

400

500

600

700

Temperature
Flow
H2
CO
CO2
CH4
C2H4
O2

10
15
20
Concentration, %mol and Vgas, lN/min

25

800
140
130
120
110
100
90
80
70
60
50
40
30
20
10
0
30

Reactor height, cm

Temperature, C
200

Figure 4.21: Permanent gas concentration and temperature proles in the

uidised bed

are very rare in the literature for the reason that they are very dicult
to accomplish. But exactly such measurements are the keys to a better
understanding.
Through the He spike method, an estimation of the local product gas
ow can be made. It is plotted in gure 4.22 as stars. Helium diuses
very fast and the dierence between the bubble and the dense phase can
be assumed small. This is conrmed by the prole. It indicates that the
dierence of the concentrations between the two phases is small. The
major increase of the ow takes place in the rst part of the bed. This
corresponds to the volatile part of the fuel. The remaining increase is
likely due to the char gasication.
The last plot in gure 4.22 is the temperature prole. It shows that the
temperature in the bed is very constant. It decreases in the upper bed
and the freeboard because the reactor is not suciently insulated and
there is no stabilising heater in this part. In addition the endothermic
char reactions in segment II are partly responsible for this cooling.

130

4.9 Results and discussion

Temperature, C
300

400

500

600

700

800
140

Temperature
H
2

CO
CO

120
110

C2H4
O2

130

CH

100
90
80
70
60
50

Reactor height, cm

200

40
30
20
10
0.0

0.5

1.0
1.5
2.0
Component flows, lN/min

2.5

3.0

Figure 4.22: Permanent gas ow and temperature proles in the uidised bed

4.9.4 Monitoring the permanent gas data

It is hardly possible to change an isolated parameter without changing
at least some more by doing so. For a constant uidisation both air
and fuel feed must be changed to get a variation of . Though the
nal space velocity will stay constant, the smaller portion of fuel will
lead to a dierent bed expansion behaviour and thus dierent mixing
of the bed. The comparison of datasets from dierent uidised bed
experiments should be compared with care.
Graph 4.23 shows the change of the concentration of the main species.
The concentration of CO, H2 and CH4 increases, whereas the concentration of CO2 stays nearly constant with decreasing air to fuel ratio.
This is an expected behaviour since the decrease of O2 leads to less
combustion products (CO2 , H2 O) and shifts the equilibrium to CO
and H2 . This also leads to a higher char fraction since both O2 and
H2 O are less present. One experiment (encircled) shows unusual high
amounts of hydrogen and CO at = 0.26. This indicates an increased water gas reaction (equation (4.3)). The concentration is stable
for the run of the experiment and no inconsistency could be found in
the micro GC dataset. The obvious dierence of the fuel is 1.5 % less

131

4 Fluidised bed experiments

moisture, which can not account for this signicant dierence. It is

neither explained by the uncertainty of the measurements. There is an
unvalidated uncertainty concerning the gasication air. It was taken
out of the technical pressure grid and the moisture may uctuate due
to outside moisture or technical failures of the condenser. Air at 8 bar
can contain as much as 0.5 %mol of water. This corresponds to about
60 mg/kgf uel . This amount can hardly account for the dierence. There
is not enough data available so far to give a propper explanation for
this behaviour. In contrast these values are barely out of the usual
range (see table 4.12).

molar ratio, % dry

20

H2
CO
CO2

15

CH4
C2H4

10

0
0.2

0.22

0.24

0.26

0.28

0.3

0.32

0.34

Figure 4.23: Change of gas composition versus the air to fuel ratio for alu-

mina bed experiments at 750 C

Graph 4.24 illustrates the same correlation for the tests at 700 C in the
alumina bed. The major dierences are an increased hydrogen concentration and a decreased CO concentration. This tendency corresponds
to the temperature change and thus is an expected behaviour.
The gas production rate is depicted in gure 4.25. The increasing gas
production is primarily a consequence of the nitrogen ow introduced
as part of the higher air ow. To some extend the combustion of hydro
carbons also lead to an increase of the ow.

4.9.5 The carbon balance

In order to evaluate the measured ows of various kinds, the carbon
balance was made for one experiment. Carbon was chosen because it
was the element to be measured with a sucient accuracy (<5 %) in all

132

4.9 Results and discussion

molar ratio, % dry

20

H2
CO
CO2

15

CH4
C2H4

10

0
0.2

0.22

0.24

0.26
,

0.28

0.3

0.32

Figure 4.24: Change of gas composition versus the air to fuel ratio for alu-

Gas production rate, m3gas/kgfuel

mina bed experiments at 700 C

2
750C (Al2O3)

1.8

700C (Al2O3)
700C (SiO )
2

1.6
1.4
1.2
1

0.16

0.18

0.2

0.22

0.24 0.26
,

0.28

0.3

0.32

0.34

Figure 4.25: Change of gas production rate versus for the alumina and silica

bed

relevant streams. The balance could be closed to 96 % as it is depicted

in the Sankey chart 4.26. The result leads to a second conclusion. As
it was said before isokinetic sampling was used to get access to the
nes of the product gas ow. The carbon content of the nes was
usually between 40 and 50 %w. The closure of the balance proves that
isokinetic sampling was conducted sucessfully. The amount of carbon
which was not found was 4.5 % of the carbon inlet ow. This number
is well within the uncertainty of the sampling and measurements.

133

4 Fluidised bed experiments

Figure 4.26: Exemplary Sankey chart for the carbon ows for experiment i

4.9.6 The heating value

It is very important to measure the concentrations of the higher hydrocarbons because they contribute a substantial part to the heating value
and subsequent validation of the gas. Table 4.11 lists the contribution
in percent of the combustible gases for a typical gas composition. It is
fairly impressive that C2 H4 holds a portion of almost 10 % and C3 H6
still a contribution of 4.7 %.
Component
H2
CH4
CO
C2 H4
C2 H6
C3 H6

concentration, %vol

contribution, %

11.0
3.9
10.1
0.8
0.2
0.2

25.62
30.29
27.66
9.60
2.10
4.70

Table 4.11: Contribution of the combustible components to the heating value

The lower heating values for the dierent tests with alumina are plotted
in gure 4.27. For lower temperatures the values decrease because of
a worse carbon conversion. There is a minor uctuation of the values
because the heating value is not only dependent on the air to fuel
ratio and temperature but as well on the uidisation properties. These
settings are somewhat dierent for each of the data sets. The dots,
which are framed by a box e. g. are taken for the same uidisation
settings and same fuel moisture. The encircled data point was taken
for lower moisture and higher uidisation. The data point marked by an
ellipse was measured for lower moisture but same uidisation settings

134

4.9 Results and discussion

than the rst three. The heating values are well within the expected
range and are large enough that the gas can be used even in a mono-fuel
application.
5.5
750C
700C

LHV dry, MJ/m3N

5.0

4.5
4.0
3.5
3.0
0.2

0.22

0.24

0.26

0.28

0.3

0.32

0.34

Figure 4.27: Lower heating value for the dry gas at dierent temperatures for

alumina

The lower heating value can be increased if steam is added to the gasication air. This way less air is used and more char is converted by the
water gas instead of the oxidation reaction. Steam can be extracted
from the HTSG in the IGCC process, there is no need to install an
extra steam generator. The temperature can be increased if the ash
melting problem is controlled for better char conversion.
The LHV of grass is generally lower than for wood. This is mainly due
to the higher carbon content in the dry biomass. A smaller portion
accounts for the process temperature, which is usually higher for wood,
than for grass (see table 4.2).

4.9.7 Tar content and composition

The data plotted in gure 4.28 illustrates the non volatile content of
the solvent, which is usually reported as gravimetric tar. The amount
was determined by vaporising the solvent and weighing the remaining
substance. By this way, it can not be distinguished between non volatile
tars and nes that are in the solvent as well. The lighter tars can not
be measured by this procedure and must be analysed by a GC/MS.
For the single value at = 0.31, which is signicantly higher, a higher
uidisation was used. This decreases the residence time of the gas in

135

4 Fluidised bed experiments

the reactor. In addition the fuel showed a smaller moisture content

(approx. 1.5 % less). This nding is in agreement with van Paasen and
Kiel [209] where a lower fuel moisture resulted in a higher tar content.
Steam produced from the moisture can crack tars.
The lower contents for lower air to fuel ratios may be due to the higher
char inventory. Those could be observed for the mentioned settings. If
the tars combine with the char they will be subject to steam gasication
as the char itself and are subsequently decomposed.

Non volatile content, g/m3N

20
750C
700C

15

10

0
0.2

0.22

0.24

0.26

0.28

0.3

0.32

0.34

Figure 4.28: Non volatile content for dierent temperatures and air to fuel

ratios in the alumina bed

For certain experiments (h-j table 4.6) the tar composition was measured by means of a GC/MS. The tars analysed were chosen from the
chromatogram as depicted in the appendix gures .3. The selection
of the compounds was based on their signicant presence in the chromatogram. The light tars did not change signicantly over the air to
fuel ratio as can be seen from gure 4.29.
Usually the tar concentrations in uidised beds at the given temperatures are expected to be higher [209] (10-20 g/m3 ). It is obviously a
characteristic of the fuel type grass that generally lower tar concentrations can be expected. Even more since most of the common tars are
not converted at 750 C according to van Paasen and Kiel [209]. This
conclusion is in agreement with von Scala [93] who stated, that more
char is produced if more potassium is present at the expense of tars.
This condition is certainly true for grass.

136

4.9 Results and discussion

Figure 4.29: Tar from GC/MS analysis for experiments h-j

4.9.8 Water content

The water content as depicted in gure 4.30 increased with increasing
. For higher air to fuel ratios more steam is formed as a combustion
product. This also corresponds to a lower hydrogen content and less
char inventory, which consumes less steam for the char reactions. No
data was acquired for the experiments at 700 C.

Water content, g/m3N

98
96
94
92
750C

90
0.2

0.22

0.24

0.26
,

0.28

0.3

0.32

Figure 4.30: Water content for dierent air to fuel ratios in the alumina bed

137

4 Fluidised bed experiments

4.9.9 Comparing the gas compositions to literature

Table 4.12 compares a typical gas phase composition to other gasiers
with similar fuels or larger sizes. It is instantly clear, that the product
gas composition is quite comparable including the tar load. The particle
load seems high compared to the Vrnamo plant. Circulating uidised
beds can reintroduce a part of the nes through a cyclone. This is not
possible for bubbling uidised beds. Here a weaker uidisation instead
would lead to a smaller particle load. The lower heating value of the gas
is already good but can surely be improved by optimising the process
parameters. The carbon conversion for = 0.25 is around 90 %.

138

this study

11
10
3.7
18
55
< 0.2
4.6
<4
80
0.01
grass
750
alumina
Turn et al. [169]

11
13
3.9
16
54
< 0.17

< 19

0.01
banagrass
800
*

HNEI
10
13
3
19
55

3.9
<4

0.1
rye grass
630
NA

HTW

Gudenau et al. [3]

(*not published from the composition it could be a type of augite).

Table 4.12: Comparison of the product gas compositions to literature data

Reference

H2 , %vol
CO, %vol
CH4 , %vol
CO2 , %vol
N2 , %vol
NH3 , %vol
LHV, MJ/m3 dry
Gravimetric tar*, g/m3 dry
Fines, g/m3 dry
Size, MW
Fuel
Temperature, C
Bed material
Stahl [41]

11
16
6
16
48
< 0.16
5.5
<5
< 10
18
wood, straw
850
magnesite

Vrnamo

Waldheim [263]

13
17
4
15
52

5
< 1.5

25
wood
850

Arbre

4.9 Results and discussion

139

4 Fluidised bed experiments

4.9.10 Monitoring of the contaminants

In the following chart (4.31) the beginning of the monitoring is depicted
for run j (see table 4.6). There are two phenomena, which occurred that
can both be seen in the graph. The rst one is a phenomenon reasoned
by the hot gas lter. The increasing lter cake of the hot gas lter
leads to a better retention of the contaminants. In this measurement
only K, P, Mg were detectable. The detection limits are given in the
slim graph on the right hand side. The potassium concentration was
detectable only during the rst 20 min; then the concentration went
below the detection limit.

Figure 4.31: ICP-OES monitoring of the product gas at 750 C in an alumina

bed

The second phenomenon is due to the formation of NH4 CO3 H. This

leads to plugging of the lining and distorted the measurement data.
Due to these diculties back up samples were taken and evaluated
oine.
The oine data is presented in table 4.13. The values are all signicant
but close to the detection limit. The data for potassium could not be
evaluated since it was below the detection limit. Though the signal
in gure 4.31 is evidence, that there is potassium at least during the
built up of the lter cake. Afterwards it disappears below the detection
limit. The data for the other elements mentioned earlier were all below

140

4.9 Results and discussion

the detection limit and were not veried in the presented experiment at
all. Though for some other experiments the existence could be shown.
Lambda7
dry gas 7
Na
K
Mg
Ca
P

0.30

g/m3

g/m3

0.21

Turn et al. [179]

44

30

26

10'000
64'000

2'900
19'000

g/m3

11

0.25

6
16
6

3
11
8

g/m3

Table 4.13: Contaminant readings for the gasication of grass in an alumina

bed at 750 C (: below detection limit)

The contaminant concentrations reported by Turn et al. [179] were measured using a sampling port inside the reactor at 725 C, which is why
the concentrations are much higher. Additionally within the reactor,
no substantial lter cake can exist. It has been stated: temperatures
above 650 C the vapour pressure of the alkalis is high enough that an
unacceptable high fraction can pass to the gas turbine [32].
Since the acquired data is so close to the detection limit, it is not possible to derive any trend concerning the parameter settings. A partial
exception is magnesium. There is a trend of the values rising with the
air to fuel ratio. This could be a hint, that during the combustion of
char the volatilisation behaviour dierers from that of char gasication
with steam. But more profound data is needed to evaluate this assumption. This eect would suggest, that the addition of steam could
be a parameter to inuence the volatilisation behaviour of some contaminants.
Table 4.14 compares the gas turbine requirements (see table 1.2) with
the detection limits of the system. The data was calculated by using
the gas to solvent ratio of the sampling system and assuming an air to
fuel ratio for the gas turbine according to section 1.4. It becomes obvious that for that case of the coring conguration the detection limits
are well below the concentrations of proof. This is not the case for the
alkalis sodium and potassium in the mono-fuel conguration. Here the
detection limits are not low enough to proof the given restrictions. All
the other elements though can be veried with the system. It is believed though that with a carefully adopted calibration for each element

141

4 Fluidised bed experiments

14

Mg, g/l solvent

12
10
8
6
4

750C

2
0.2

0.22

0.24

0.26

0.28

0.3

0.32

0.34

Figure 4.32: Magnesium content for dierent air to fuel ratios at 750 C, alu-

mina bed

the detection limits can be tuned and using a longer sampling interval
the raw counts of the ICP-OES will further enhance the detectability of
potassium. From experience it can be told, that the potassium concentrations in the raw gas is usually in the same range as sodium [180; 169].
It may be repeated here, that the given limits are the most restrictive
ones found in the literature review.

K
Na
Pb
V
Ca
Mg

concentration of proof
coring
g/l solvent

concentration of proof
mono-fuel
g/l solvent

181

20

603
301
1205
1205

28
14
56
56

detection limit
sampling train
g/l solvent
92.9
5
9.19
3.2
0.2
0.3

Table 4.14: Comparison of gas turbine limits and detection limits for the co-

ring conguration

The presented results show that, the gas after a hot gas lter at 400 C
is clearly clean enough (in terms of gas turbine contaminants) to supply
a gas turbine in a coring mode, whereas the applied sampling train
does not allow a verication for potassium in the mono-fuel mode. The
sodium concentration alone is already to high to pass the specications.
The result also proves, that hot gas ltration at 400 C does not by

142

4.9 Results and discussion

all means hold back all the inorganic compounds though latter are
expected to be present as condensed matter. Secondary measures must
be involved to reduce the sodium and potassium levels to a sucient
degree for the mono-fuel conguration.

4.9.11 Verication of the hot gas lter

Fraction of fuel input, %mol

The elemental analysis of the nes in the hot gas lter is given in gure 4.33. The lter nes were ashed at 400 C for 9 h. Though the
standard procedure allows 815 C for at least 60 min, the lower temperature was chosen to prevent the volatilisation of inorganic elements like,
alkalis or cadmium, which are known to evaporate long before 815 C.
To compensate for the lower char reactivity at the chosen temperature,
the duration was increased to 9 h. The ash was then cooled down to
150 C in the furnace and down to ambient conditions in an exsiccator.
The samples were then enclosed to prevent the uptake of moisture and
delivered for ICP-OES analysis. The nes consisted of 40-60 % carbon
(rest ash) with increasing carbon content for smaller values of .
200
HGF filter fines
Remaining bed

150
100
50
0

Na

Mg

Ca
P
Elements

Ba

Mo

Figure 4.33: Elemental distribution in the hot gas lter nes and bed after

the test

The graph illustrates nicely that all veried elements were found to
a high fraction in the nes for the given process settings. Only for
potassium a large part was found attached to the bed material. The
uncertainty for this kind of analysis is around 10 %rel by experience.
Since both the fuel content and the HGF content were determined by
ICP-OES analysis this uncertainty becomes 20 %rel. The used alumina

143

4 Fluidised bed experiments

NWa 155 from Sasol shows minor impurities of SiO2 , Fe2 O3 and Na2 O.
Sodium is reported to be below 0.005 % [264]. But especially the sodium
impurities of the bed could have led to the excess of the output. Lead
was neither veried in the grass sample nor in the gas or hot gas lter
ash. The analysis for vanadium yields a much higher value for the
output than for the input stream. One reason for the higher output
concentration of the elements could be the analysis method for the
elemental composition of grass. Applying the standard DIN method
results in the release of a part of those elements into the gas phase
being lost for the mass balance.
This result conrms, that only a very small portion of the contaminants
could have passed the hot gas lter and reached the solvent.
XPS measurements8  which give information about the composition
of the surface atoms of a solid material  conrmed, that about 2.4 %at
of the surface consisted of potassium (see table 4.15). The amounts of
aluminium and oxygen t the main fraction, which is alumina Al2 O3 .
The major part consited of carbon. The measurement does not tell if it
is sticking soot or maybe a carbonate. The potassium could be attached
as alkali alumino silicate such as KAlSiO4 (kalsilite), KAlSi2 O6 (leucite) or alkali silicates such as K2 SiO3 or K2 Si2 O5 [181; 265; 258; 119],
which would be feasible based on the given data.
Atom

surface concentration %at

Al
O
K
Si
Ca
C

21.4 %
29.5 %
2.4 %
4.2 %
1.2 %
40.2 %

Table 4.15: XPS analysis of the surface of the bed material after the expe-

riment.

4.9.12 Note about sulphur and ammonia

As it was stated before, the sampling train does not allow a proper
validation of the sulphur components as well as the ammonia concentration. It became very clear during the experiments, that both are
8 X-ray Photoelectron Spectroscopy

144

4.9 Results and discussion

present in comparably large amounts. Sulphur scrubbers are state of

the art technology and are installed in IGCC power plants from the
beginning to remove H2 S and COS [32]. Ammonia is also an issue in
coal gasication. The Claus kiln is therefore equipped with a catalyst
to convert the nitrogen species NH3 and HCN to N2 [32].

145

Chapter

A novel single pellet gasier MiV

Chapter 5 presents the design and experimental results for a novel single
pellet gasier. Unlike common options, the design of the reactor oers
the opportunity to expose a single solid fuel pellet to conditions very
similar to real gasication, combustion or pyrolysis processes. The characterisation and optimisation of the alkali sensor applied in the experiments is the scope of the PhD thesis of Marco Wellinger from Chemical
Processes and Materials group at PSI. The experiments presented in
section 5.6 were conducted in close collaboration with Marco Wellinger.

5.1 Motivation for this approach

Bench-scale gasiers (2-10 kWth ) are the rst step to demonstration
plants. In terms of controllability (ows, temperature) and detailed
analysis these gasiers are already too large. To understand certain
inuences, such as moisture of the fuel, alkali content or gasication
agent, smaller devices are required (<100 Wth ). With the result of
small reactors the behaviour of gasication reactors can be predicted,
if similar conditions can be created. The main drawback of these small
reactors is the problem to reproduce the exact conditions of the represented process.
Thermogravimetric analysis (TGA) e. g., has been widely used to gain
insight into the volatilisation of all sorts of biomass and materials. The

147

5 A novel single pellet gasier MiV

parameters, which has been varied mostly are heating rate, terminal
temperature and feed gas. It has also been used to predict volatilisation characteristics in biomass gasication processes [266268; 163; 269;
270]. The major drawbacks of TGAs are the limited heating rate of the
system and the small amount of the sample. In biomass gasication the
fuel enters the reactor within seconds, where it experiences a temperature increase from ambient temperature to between 700 and 1000 C.
New TGA devices can be operated at heating rates up to 200 K/min,
which is still hardly comparable to the real system. A literature review reveals that the inuence of the heating rate on the product is
remarkable [89; 270]. This has also been proven for the volatilisation
of alkalis by Keown et al. [271]. Starting from 600 C to 900 C, the
volatilisation of K, Na, Ca and Mg starts to increase strongly for fast
heating rates, whereas for slow heating rates it stays nearly constant.
TGA normally uses very small amounts of material (10-40 mg approx.
200 m nes). Recent results about the elemental distribution for different particle sizes [203] rise doubts, whether the chosen sample and
subsequently the kinetic results are representative. Where entrained
gasiers eectively use nes, uidised bed and xed bed usually use
larger particles of sizes between 1 and 10 cm. The dierent behaviour
of a standard TGA and a macro TGA (larger samples) is conrmed by
Haselbacher [269]. The kinetic behaviour of a larger particle is quite
dierent from a small sample due to diusion limitation. This is obviously a critical point for fuel particles, which follow the shrinking core
mechanism [272; 273]. This mechanism describes the ongoing reaction
within a particle. The reaction takes place along the interface of the
shrinking core leaving the remaining ash shell at constant size.
A few attempts were made to introduce a fuel particle into an already
hot furnace [274276]. The amount still did not exceed 40 mg of material. The introduction of the small amount of fuel positioned in a
sample holder led to substantial thermal delays.
Putting the described experience together, the result of a TGA will
dier from common tests if larger particles would be used and real
heating rates would be achieved. In this thesis a novel single pellet
gasier referred as MiV 1 was developed, which aims to eliminate both
of the two drawbacks. Since large particles (entire pellets2 500 mg)
1 German: Mini Vergaser (English: Mini Gasier)
2 Pellet size: 5x20 mm, density: 1.3 kg/l

148

5.2 Realisation of the MiV

can be used and a real heating rate is realised by letting the particle
drop through a lock within a second. Furthermore, no thermal delay
is introduced by means of additional sample holders. The gasication
agent circulates completely around the single pellet and does not ow
by above the fuel like in common furnaces. Also from this point of
view, the reactor resembles a uidised bed better.
The reactor will be utilised to analyse the alkali emission during the
gasication of grass more profoundly than it is possible with the presented uidised bed gasier. The properties which will be tested are the
water and alkali content of the grass. The absolute alkali content can
be reduced by leaching the fuel in advance. It was shown that leaching
leads to less emission of alkalis during the gasication process [179]. It
has not been evaluated so far, how much of the remaining alkalis would
pass a particle lter and subsequently enter the gas turbine.

5.2 Realisation of the MiV

The design of the reactor is illustrated in gure 5.1. The internal height
is 100 mm, and the internal diameter 16 mm. The reactor consists of
three parts: a lower part , where the pellet is gasied, a middle part
, where the gas exits the reactor and a top part , from where the
pellet is introduced. Into the rst part the grate is inserted. This part
is entirely within the furnace. The gasication agent enters the reactor
through the line below the grate. The middle part is connected to
the lower part by a conical ange, which  under moderate conditions 
is gas tight itself and does not need an additional sealing. Nevertheless,
there is a sealing nut provided in case such is needed at higher pressures.
From the upper reactor the gas can exit through line . This point
is not in the furnace anymore (see also gure 5.2). In this part the
inlet for the thermocouple is positioned. It reaches down through
the reactor to position . The third part is the pellet lock hopper
. The real locking valve is not depicted in the CAD drawing but is
illustrated in gure 5.2. This part houses the pellet as well as the reactor
locking bead and is separated from the reactor and on the other
hand the atmosphere through valves. The reactor can be equipped
with additional liners to study the inuence of the reactor material.
The reactor is made of Inconel matching the material from the uidised bed. Using glass as reactor material was avoided, since in house ex-

149

5 A novel single pellet gasier MiV

Figure 5.1: Design of the MiV 1:2

perience showed, that at high temperatures (>600 C), the glass tends
to adsorb alkalis. The reactor locking bead is a standard bearing ball.
It is magnetic and thus can be removed from its locking position with
a magnetic rod. By this option several pellets (1-3) can be inserted in
one run, without opening the reactor. Due to the design and small size
of the reactor, it is also able to run at higher pressures.

150

5.3 Controlling and safety aspects

5.3 Controlling and safety aspects

The furnace was heated by electrical heaters by means of an in house
built 48V transformer. The transformer was controlled by the very
same LabView software as the sampling system. It incorporates alarm
functions similar to the one in the uidised bed. Additionally, there is
a pressure relief valve that opens above 0.5 bar to avoid high pressures.
This is necessary, since the reactor is provided with compressed air by
means of a mass ow controller. Blocking of the lining would lead to
full grid pressure in the reactor.

5.4 Measurement techniques

The measurement devices for this reactor must be in any case fast
enough to follow the signal. The proposed sampling frequency must
be at least 1 s. Gas chromatography and ICP-OES measurements are
too slow. Only mass spectrometer and surface ionisation measurements
were available and fast enough to keep up with the signal.

5.4.1 Mass spectrometer (MS)

A Thermo Onix mass spectrometer from ProLab [277] was used to monitor the concentration change of the permanent gases (CO2 , H2 , CH4 ,
O2 and N2 ). To analyse CO properly a dierent system is required,
since m/z 28 and 29 also respond to nitrogen. There was a signal during the gasication at m/z 30, where the 30CO isotope can be found,
though the signal was very weak. With the MS measurement it is possible to distinguish between gasication and combustion, which both
take place during the processing of a pellet.

5.4.2 Surface Ionisation Detector (SID)

Surface ionisation technology for analysis goes back to the beginning
of the seventies. The principle of the sensors are based on the high
probability of some alkali metals to get ionised during the desorption
process from the ionising lament [278]. The sensor is especially sensitive to potassium, sodium and caesium at the same time and thus
measures the sum of those [220]. Barium is an element, which also

151

5 A novel single pellet gasier MiV

can be ionised by the lament but the ionisation probability is much

reduced compared to the rst three elements [279]. Furthermore Ba
was not found in the uidised bed gasication analysis, and hence is
neglected. Such sensors have been built several times in the past and
tested successfully [280; 279; 219]. The SID is an in-line sensor giving
the option to connect a second analyser directly after the SID. For instance the SID can be coupled with a MS. This would additionally yield
the information, what kind of alkali component is passing by.
The normal signal of the SID is given in nA and corresponds to the
alkali concentration. The integral of the signal then corresponds to the
sum of all ionised alkalis. The signal depends on the eective volume
ow carrying the alkalis. For this reason the volume ow was kept
constant for all runs. The signal also depends slightly on the bulk
gas composition. In order to reduce this inuence and account for the
high sensitivity of the sensor the gas from the reactor was diluted with
nitrogen. The fraction of sample gas was chosen to be around 8 % of
the total gas stream owing through the SID (see also section 5.5).

5.5 Experimental setup and procedures

The MiV reactor is positioned inside a cylindrical furnace (see gure 5.2),
which can be electrically heated to the desired temperature. The gasication agent (reactor gas) enters from the bottom through a distributor
that at the same time serves as grate for the pellet. The pellet is given
into a lock hopper above the reactor. When the temperature and all
sensors are stable, the pellet is released through the ball valve into the
reactor. The pellet drops through the tubing from ambient conditions
into the hot reactor and thereby experiences similar conditions as if it
would be transported into a gasier. After the pellet has dropped a
metal bead is released to lock the pellet entrance and reduce the dead
volume of the reactor to a minimum. The product gas leaves the reactor
at the top through a heated line in order to prevent the condensation
of tars. Additionally, the product gas is quenched and thereby diluted
by a nitrogen ow at Q1 after leaving the reactor. This is a common
procedure to limit the particle growth [217]. The ow introduced in Q2
was smaller than the ow of the sampling system, and can be adjusted
that around 8 % sample gas from the reactor was used for the analysis.
(A photograph is given in appendix gure .1.) The gas enters the

152

5.5 Experimental setup and procedures

Figure 5.2: Flow chart of the experimental setup

heated SID, which measures the alkali content in the gas. After leaving
the SID, the gas is instantly quenched by a solvent as described in section 3.2. The two phase ow is pressurised and cooled to enforce the
condensation and separation of tars and separation of particles. The

153

5 A novel single pellet gasier MiV

cleaned gas is directed to a MS to measure the concentrations of the

mentioned gases. In addition, the temperature in the centre of the reactor and close vicinity of the pellet is recorded at all times. Similar to
the uidised bed experiments the loaded solvent could be analysed by
means of ICP-OES measurements. Due to the small amount of solvent
and the low concentration of alkalis, these measurements could not be
accomplished satisfyingly. Still, this analysis should be done in future
experiments to quantify the alkali emissions. After the experiments the
grate was removed, the ash recovered and the reactor cleaned.

Fuel preparation: The elemental data of the fuel was presented in

section 4.8. The data is very similar to the values presented in literature. Compared to wood, especially the potassium and silicon but
also magnesium, sulphur and nitrogen concentrations are higher in the
grass (see section 2.7.4). The grass was pelletised by the fuel supplier
and crushed at PSI to produce a suitable pellet for the MiV setup.
In order to inuence the volatilisation behaviour of the alkalis certain
properties can be manipulated. Among those properties are the water
content and the water soluble minerals. These properties were altered
accordingly to the following experimental matrix (table 5.1).
Fuel
grass

Reactor gas
air
N2 , air

Fuel preprocessing

H2 O , %

none
Mocca Express (105 C, 4min)
doped (KNO3 , NaNO3 )
dried (24 h, 105 C)
none

8.8
7.8
8.1
2.1
8.8

Table 5.1: Experimental matrix; H2 O : Water content

Leaching of alkalis: There are many extraction methods to remove

alkalis from the fuel. Leaching was done before by rinsing, spraying
or mechanically enhanced extraction [281283]. At rst leaching as
proposed by Dayton et al. [283] was tried, but it became clear that
soaking the grass for 24 h in water resulted in anaerobic decomposition
of the grass. For this reason a dierent method was tried with excellent
results.
154

5.5 Experimental setup and procedures

A hot water extraction was performed by means of a standard well

known mocca express machine as depicted in gure 5.3. A scheme of
the working principle is illustrated alongside the picture. Though being
a method not commonly used in scientic research, it is a very serious
and ecient extraction method in process engineering. The extraction
takes place at around 105 C when the boiling water is pressed through
the grass by vapour. This temperature is not decomposing the grass
it rather increases the extraction eciency. The process takes about
4 min only. The amount of grass that can be processed in the 3 cup
version was 11.5 g using 144 ml of demin water. The extracted liquid

Eluate
Sieve

Grass
Vapor
Water
Heat (el.)

Figure 5.3: Leaching setup (left: scheme, right: mocca express)

(eluate) can be recovered in the upper chamber, whereas the moist fuel
will stay in the sieve. Only small amounts of nes were dragged up into
the upper chamber. The removed amount of alkalis were determined by
an ICP-OES measurement of the eluate (table 5.2). The grass was dried
after the processing. The amount of leached potassium was 72 %. This
is about the same amount, which is given in literature for other leaching
Element

Amount, %

K
Na

72
21

Ca
Mg
Cl
P
S
Sr

NQ
NQ
NQ
NQ
NQ
NQ

Table 5.2: Extracted elements (NQ: veried; not quantied)

155

5 A novel single pellet gasier MiV

types like rinsing. For our small samples the mocca extraction method
was best suited showing simmilar or even better results within much
shorter time and less eort. The other elements listed in table 5.2 were
not quantied but found in the eluate in signicant concentrations.
At least chlorine is known to be responsible for the volatilisation of
inorganic constituents such as potassium [274].

Doping with alkalis: Doping of the grass was done by soaking the

grass sample with an aqueous solution of KNO3 and NaNO3 at ambient

conditions. The grass was subsequently dried at 40 C assuming the nitrates were entirely adsorbed. The amounts of the alkalis in the nitrate
were chosen at concentrations to double the alkali concentrations in the
used grass.

Drying of the grass: Drying grass completely is hardly achievable

based on its highly hygroscopic behaviour. Drying for 150 minutes

at 105 C reduced the water content to less than 0.5 %. Two pellets
were produced from the dried grass and transported to the reactor.
One pellet was gasied and the other pellet was analysed for its water
content being 4 % again. In a second try the grass was rst pressed
into pellets and then dried. This resulted in only 2 % water content of
the gasied pellet. Compared to a water content of normally 8 % this
was assumed to be low enough to see a dierence in the volatilisation
behaviour.

Pelletising of the grass: After the pretreatments the fuel was weighed and manually pressed into a pellet to a constant volume and density under elevated temperature (80 C) as described in [284]. The density for a commercial grass pellet was measured to be around 1.3 kg/l .
The pellets were produced accordingly. The resulting pellets had a
diameter of 5 mm and a height of 20 mm. This corresponds to a pellet
weighing approx. 500 mg ten times as much as used in a TGA. The
pellet pressing device is depicted in gure 5.4. The resulting pellets
proved to be quite strong.
Sampling of the gas stream: Sampling respectively gas cleaning

was conducted with the pressurised scrubber, exactly like the procedure
for the uidised bed experiments. The solvent was identical.

156

5.6 Results and discussion of the basic behaviour

5
Figure 5.4: Pellet pressing device

5.6 Results and discussion of the basic behaviour

The rst test was conducted in order to determine the slip-stream of the
alkalis through the sampling system. The test was done only for standard grass pellets. Maintaining a constant ow, the SID was positioned
once upstream of and once downstream of the sampling system. Each
time a grass pellet was dropped into the reactor. The dierence of the
signal is assumed to be the part being removed by the sampling system.
The integral was evaluated for the slip as illustrated in equation (5.1)
R
I
(outlet of the scrubber)
Alkali slip = Rt SID
I
t SID (inlet of the scrubber)

(5.1)

Since the SID always showed a tailing, the signal was cropped at around
30 min but only when the signal was below 10 % of its peak value.
Graph 5.5 depicts results for the slip stream. The total retention of
the particles containing alkalis is about 99.9 %. This test was repeated
once to ensure reproducibility. From the mechanistic principle of the
sampling system it can be said, that the fraction that can pass the
system are the particles with sizes presumably between 30 and 100 nm.
This conclusion is based on two phenomena, particles in gas streams
are subject to. Large particles are separated easily based on their large
inertia. Very small particles (<30 nm) are subject to difusion. For long
linings this means that those particles are separated as well. In Hinds
[212] it is described that 1 nm particles will be lost to 97.8 % in a 1 m
tubing for a laminar ow due to difusion. 10 nm particles will be lost
to a degree of 10.8 %, wheras 100 nm particles will only lose 0.6 % due

157

5 A novel single pellet gasier MiV

to difusion. The used lining was 11 m long. Thus it can be assumed,

that all the smallest particles will be removed as well.
Based on this experiment a second conclusion can be drawn. The alkalis, which form the rst peaks in the signal are likely in the discussed
range.

SID signal, nA

300

Reference experiment
(I = 267A s)
Slip stream
(I = 0.199A s)

200

100
0.09% of reference signal

00:00

05:00

10:00
15:00
20:00
Elapsed time, mm:ss

25:00

30:00

Figure 5.5: Measurement of alkali slip-stream through the sampling system

compared to a typical alkali signal during gasication and char

combustion

In gure 5.6 the reference experiment is illustrated. It was conducted

with an untreated grass pellet and air as gasication agent. The upper
graph shows the temperature that was measured in the direct vicinity of
the pellet ( gure 5.1). The middle graph depicts the alkali signal by
means of the current, produced by the ionized potassium and sodium
molecules. In the lower graph the MS intensities for the main species
CO2 , H2 and CH4 are plotted. The existence of CH4 and H2 proves
that after the pellet drops immediate pyrolysis and gasication takes
place. At the same time the temperature drops signicantly due to
the endothermic processes during volatilisation. A small portion of the
temperature drop results from the energy transfer into the pellet. This
was tested by a stainless steel pellet of the same size. The steel pellet
shows a higher specic heat as well as a higher mass and hence should
even enhance this eect. But the temperature drop caused by the
pellet itself is much less signicant. After the pyrolysis and gasication
is nished the char combustion takes place. This can be seen by means
of the temperature, which rises above the original furnace temperature
and the MS signal that only shows CO2 during the combustion phase.
The combustion is considered to be nished, when the temperature
reaches its set point again.

158

5.6 Results and discussion of the basic behaviour

Temperature, C

The alkali signal (second graph) shows two very distinct and fast peaks
followed by a wider shoulder holding most of the volatilised alkali portion. This general characteristic is constant for all tests. Similar results
were obtained by Dayton and Milne [274] who showed that the main alkali compound (KCl) volatilised primarily during the combustion phase
by means of a MS. The fast peak during the pyrolysis phase was not
detected by those experiments.
1000
Reactor temperature

combustion

900
800
700

pyrolysis

300
SID , nA

Collector current ( = 259A s)

I

200
100
0

MS, AU

H2
CO2
CH4

00:00

05:00

10:00
15:00
Elapsed time, mm:ss

20:00

25:00

30:00

Figure 5.6: Test with untreated grass pellet (reference)

The CO2 concentrations take slightly more time to come down after
combustion is nished. This can be explained by combustion of remaining carbon that is more dicult to access. It may not be detectable
by a temperature increase any more. A second explanation is the sampling system tends to blur the concentration changes (see section 3.5).
The alkali signal takes much longer to return to its background level.
The MS measurement shows by using a rough calibration that the CO2
concentration peaks at 19 %, H2 and CH4 at 6 % and 5 % respectively.
This is similar to the concentrations from the uidised bed experiments
just above the fuel feed inlet (gure 4.22), where the pyrolysis takes
place. It thus can be assumed, that the conditions during the pyrolysis
much resemble those in the uidised bed.
In order to evaluate the hypothesis of the two processes pyrolysis phase
versus the combustion phase, further experiments were conducted (-

159

5 A novel single pellet gasier MiV

N2

1000

Air
Combustion

800
Pyrolysis

600
300

SID, nA

Temperature, C

gure 5.7) to separate the two stages. In this case the reactor was rstly
run on pure nitrogen until pyrolysis was over and then the nitrogen ow
was replaced by an equivalent air ow. The graphs show very nicely
that the rst temperature drop and the rst alkali intensity increase can
be allocated to the volatilisation of the fuel, whereas the second part 
showing the much bigger portion of alkali emission  can be connected
to the combustion phase. The second peak (char combustion) holds
92 % of the alkali signal (area).

Reactor temperature
Time, hh:mm

200
100

Collector current
(I = 354A s)

=28
I

0
MS, AU

H2
CO

CH4

00:00

10:00
20:00
30:00
Elapsed time, mm:ss

40:00

50:00

Figure 5.7: Test with untreated grass pellet: pyrolysis - combustion separated

For this test the alkali signal also takes much longer to return to the
background than the other signals. There could be several explanations
for this eect:
G The SID sensor is saturated by the amount or type of the alkali

components. The ionisation of the alkalis takes place bit by bit

until the lament is blank again. The integral of the curve is
equivalent to the overall airborne alkalis.

G The alkalis are deposited in the lining and eventually resuspended.

G It could be a combined deposition of tars and alkalis during the

pyrolysis phase.

160

5.7 Results and discussion of the pretreated grass

The rst suggestion could not be tested with this set up. The approach
would be to increase the dilution by changing the ow at Q2. Dilutions
lower than 4 % of sample gas in nitrogen were technically not possible
with the installed mass ow controllers. Nevertheless it could be veried, that the integral of the signal changes according to the weight of
the pellets introduced. This means that the alkali signal corresponds
to the absolut amount of the alkalis in the pellets.
Resuspension by vaporisation can be excluded because the temperature
in the lining does not exceed 400 C. There are a number of other
reasons why particles detach [212], from which only resuspension by
jets can be relevant. This eect depends on the accessibility of the air
jet to the particle, and the force the jet can apply onto the particle.
Usually the force of a laminar gas stream at 10 m/s can not detach
particles with sizes less than 10 m [212]. But the maximum gas ow
in the lining did not exceed 4 m/s (Re 500). Such a process would also
result in a decreasing alkali signal, whereas the measured signal stays
very constant for some time.
The last thesis was tested by an appropriate experiment, in which the
lining between the reactor and the SID was ushed with air between
the gasication and combustion sequence (gure 5.7). This did not
produce a signicant signal. The combustion was initiated by letting
air through the reactor until the temperature dropped but the SID
signal was still high.The SID did hold its signal even after that the
reactor gas and quench gases were switched o. This proves the tailing
in the SID signal is not produced by depositions in the lining. It can be
concluded from the described test, that the signal characteristic of the
SID must be due to surface phenomena at the lament of the sensor.

5.7 Results and discussion of the pretreated grass

The SID signal responds to the absolute amount of alkalis. A Linear
tendency between the absolute alkali content and alkali emission was
derived from the experiments. Quantication is not possible with the
sensor until the mentioned phenomena can be explanation.

161

5 A novel single pellet gasier MiV

5.7.1 The dried pellet

Dried pellets were tested to analyse the rst intensive peak of the alkali
signal. It was thought to result from the sudden evaporation of the water and entrained alkalis during this step. The rst peak did not change
its shape or amplitude ratio of the rst to the second peak dependent
on the water content. This leads to the conclusion, that the described
phenomenon is not due to the evaporation of water. Figure 5.8 displays the comparison between a standard run (see gure 5.6) and the
test with the dried pellet. The dried pellet emitted less than the normal
pellet. This is rather based on the smaller absolute alkali content of
the pellet not on the emission behaviour of the drier fuel.

SID signal, nA

300

Reference experiment
(I = 267A s)
Dried 2%
(I = 234A s)

200

100
88% of reference signal

00:00

10:00
20:00
Elapsed time, mm:ss

30:00

Figure 5.8: Comparison of dried grass pellet ( = 2 %) with reference pellet

( = 8.8 %)

5.7.2 The leached pellet

The leached pellet emitted about 40 % less alkalis then the reference
(gure 5.9). This is rather surprising, since the extraction removed
72 % of the alkalis from the grass. One reason may be the mechanism
of partial melting as explained by Andersson et al. [280]. For large
particles only the outer layers of the particle melt. This means, that
the particle size distribution has an eect on the eective signal. It is
by all means possible that the leached pellet is more brittle causing a
higher nes entrainment than the natural pellet. Another reason may
be due to the formation of potassium hydroxide and potassium cyanate
as reported by [274]. These compounds are formed if chlorine is not
present in sicient amounts to form chlorides.

162

5.7 Results and discussion of the pretreated grass

SID signal, nA

300

Leached
( = 158A s)
I

Reference experiment
(I = 267A s)

200

100
59% of reference signal

00:00

10:00
20:00
Elapsed time, mm:ss

30:00

Figure 5.9: Comparison of leached grass pellet with reference pellet

5.7.3 The doped pellet

The gasication and combustion of doped grass revealed an increase of
around 80 % alkali emission, though the doping doubled the amount of
potassium and sodium in the grass. But is has to be noted that the
doping was perfomed with alkali nitrate and no additional chlorine was
introduced. As mentioned earlier chlorine is one of the main elements
responsible for the volatilisation of inorganic elements.
600
SID signal, nA

Doped (I = 480A s)
Reference experiment (I = 267A s)

400

180% of reference signal

200

00:00

10:00

20:00
30:00
Elapsed time, mm:ss

40:00

50:00

Figure 5.10: Comparison of doped grass pellet with reference pellet

The additional alkalis seem to volatilise primarily in the combustion

phase. A smaller portion is detected right at the beginning, whereas
the main part adds to the combustion resulting in a much longer tailing.
The peaks at the end of the signal are signal distortions.

163

5 A novel single pellet gasier MiV

Running the leached and doped pellets in the separated gasicationcombustion mode (as in gure 5.7) revealed that the manipulation effected the combustion phase much more than the gasication phase.

5.7.4 Summary of the tests with the pretreated fuel

The results show that leaching the grass as pretreatment will unlikely be
relevant for industrial applications. The inuence on the alkali emission
by leaching aects only the char combustion, which is equally covered
by the hot gas ltration. The results for the doped pellets indicate that
the alkali emission corresponds to the alkali content. The dependency
on chlorine seems to be of minor inuence as it was already found by
Dayton and Milne [274] for biomass combustion.

5.7.5 The inuence of hot gas ltration

A nal set of experiments was performed by introducing a hot gas lter
into the gas line after the reactor exit. The hot gas lter has a pore
size of 5 m and was operated at 400 C. The lter area was very large
compared to the gas volume, so no dynamic inuence of a lter cake
could distort the measurement. The lter was identical with the hot
gas lter used in the uidised bed experiments. The result is presented
in gure 5.11. The response was around 1 % of the reference signal.
The alkalis passing the 5 m lter were found to volatilise during the
pysrolysis and gasication phase. This is in excellent agreement with
the slip-stream, since for both systems only the smallest particles can
pass. Normally a hot gas lter acumulates a lter cake, which results
in a very ecent lter enhancement. In such a case, even less alkalis
would pass.
As it can be seen in gure 5.12, the ash still shows the shape of the
former pellet. The gure shows three gasied pellets. The last one lays
on the top. This means the gasication and subsequent combustion is
following the shrinking core model at a constant particle size [272; 273].
It is also an indication, that the particle size is a parameter that can
not be neglected. From the shape of the ash it can be derived, that
the pellets did not break, or explode when being dropped into the reactor. This is an important issue since the entrainment of mechanically
suspended particles would distort the measurements.

164

5.7 Results and discussion of the pretreated grass

SID signal, nA

300

Reference experiment
(I = 267A s)
Hot gas filtered
(I = 4A s)

200

100

1% of reference signal

00:00

10:00
20:00
Elapsed time, mm:ss

30:00

Figure 5.11: Comparison of the alkali emission with and without hot gas l-

tration at 400 C

Figure 5.12: Pellet before (left) and after (right) gasication and combustion

in the reactor grate

The above described results show two reproducible but unexpected behaviours of the SID sensor: rstly there is a tailing of the alkali signal
and secondly there is a stable plateau during the combustion phase.
Both phenomena can not be explained by means of the conducted experiments, but both are thought to be connected to surface phenomena
on the lament, triggered by too many or too large particles.

165

Chapter

Conclusions

6.1 Fuel review

G The stability of the uidised bed process depends on the ash

melting behaviour, which mainly depends on the formation of

low melting alkali silicates. Besides grass, agricultural residues
and energy crops show similar amounts of silicon and alkalis in
the fuel. The ash deformation and sintering temperature (see
gure 2.14 and 2.15) is comparable to each other. Figure 6.1 displays a ternary plot for the main ash inuencing elements. The
arrows indicate the composition change with increasing ash melting risk based on the formation of the alkali silicates (K2 SiO3
and K2 Si2 O5 ) given by Kosminski et al. [285]. Since the rst
compound is reported to be dominating, grass may be expected
to be the more dicult fuel. Every fuel below the lines have excess silicon, which means the fuel with more alkalis is expected
to show higher risks of ash melting.
Unless a specic fuel shows higher levels of silicon and alkalis
than grass, any of the mentioned solid fuels is expected to behave
stable with the reported settings.

G The review revealed minor amounts of the earth alkalis barium

and strontium. These elements are of similar or higher corrosiveness than the usually mentioned alkalis potassium and sodium.

167

6 Conclusions

K
Wood
Agric. resid.
Energy crops
Grass
Coal

1
0.9

0.1

0.8

0.2

0.7

0.3

0.6

0.4

0.5

0.5

x K2SiO3 0.4
+ (1x) Ca

0.6

0.3

0.7

0.2

0.8

Si

0.1

x K2Si2O5 + (1x) Ca

0.9

0
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Ca

Figure 6.1: Molar ternary diagram of the main bio-ash inuencing elements

They are not restricted by the gas turbine manufacturers but

must be observed as well. The corrosion potential of all relevant
elements must meet the limitation.

6.2 Sampling system

The continuous monitoring of the contaminants required the development of an appropriate sampling system. Such a system was developed
at PSI and optimised in this work.
G The sampling system proved to run very reliable during wood

gasication showing an excellent separation of nes and condensables. It also proved to be able to measure contaminant concentrations in the gas phase continuously in ranges down to g/kg.
This is a major progress in continuous monitoring of contaminants
in product gases from gasication units.

G Using the system in grass gasication resulted in the formation

of NH4 CO3 H, which corresponds to the high ammonia concen-

168

6.3 Fluidised bed gasication

tration in the gas phase and the operation parameters (pressure,

temperature) of the sampling system. Acidication and water
addition of respectively to the solvent improved the situation but
did not prevent the formation. The formation did mainly interfere
with the ICP-OES measurements, whereas the sampling system
could cope with the solid NH4 CO3 H fairly well.

6.3 Fluidised bed gasication

A 5kW bubbling uidised bed gasier was designed and operated on
grass. Temperature, bed material and air to fuel ratio were varied to
discover the gasication behaviour regarding the stability and contaminant emission.
G The uidised bed gasier is by any means very suitable to gasify

grass at slightly lower temperatures than for wood and coal. This
is required due to the lower ash melting point of grass. The temperature can be as high as 750 C, if alumina is used as bed material. For silica sand the temperature should not exceed 700 C,
unless secondary measures are taken to prevent ash agglomeration. Dolomite as sole bed material should be avoided due to its
low material strength and consequent bed material loss.

G The carbon conversion was around 90 %. To reach a better carbon

conversion, secondary air or steam injection should be considered.

The char produced during the volatilisation was found to oat on
top of the uidised bed. The steam injector should be adjusted to
this position. A second possibility could be employing a circulating uidised bed, where most of the particles can be recycled to
the feed. The recycled char would be introduced into an oxygen
rich zone.

G The heating values are good and slightly lower than for wood ga-

sication. This is mainly because of the lower carbon fraction in

the fuel since the product gas shows a lower CO concentration
compared to wood gas. The concentrations of the other permanent gases are similar.

G Despite the lower temperatures in comparison with usual ui-

dised bed gasication the tar concentration is very low. This

corresponds to the generally lower lignin content of grass compared to wood. This is in agreement with DeGroot and Richards

169

6 Conclusions

[92]; von Scala [93] that for biomass with a higher alkali content
less tar but more char can be expected.
G The concentration of nes in the raw gas stream is higher, owing

to the high uidisation, which was chosen to lower the risk of ash
agglomeration. The entrainment can be reduced by lowering the
uidisation.

G The analysis of the used alumina bed by XPS revealed potassium

attachments together with silica and calcium. This indicates that

reactions between the bed material and alkali silicates is possible.

G In spite of the low temperature of the hot gas particle lter

(400 C), the concentration of sodium in the clean gas is too high

for direct application in a mono-fuel power plant. The concentration of potassium could not be veried at suciently low concentrations. The concentration of the other relevant contaminants
(Mg, Ca, Pb, V) are low enough for the direct application.

G After hot gas clean up, the gas with a coring fraction of 10 %

LHV is clean enough to be used without secondary measures for

coring with NG. This is valid unless the combustion air contains
alkalis as it is the case for sites close to the sea.

6.4 Single pellet gasier MiV

A novel reactor was built to process entire pellets of 500 mg compared to
TGA studies, which process about a tenth of this amount. Especially if
the fuel is characterised by a shrinking-core-model during volatilisation
and combustion, the size of the fuel plays an important role. The
reactor was used to examine the gasication and contaminant emission
of a single pellet in more detail.
G The reactor allows heating rates as shown in gasication units,

where the fuel experiences volatilisation within seconds.

G With the reactor it is possible to represent the pyrolysis and gasi-

cation phase during the volatilisation. The volatilised gas shows

a similar composition as the gas from the uidised bed gasication
in the lower part near the feed inlet. The char combustion as the
second phase was conducted with air, whereas the char reactions
in the uidised bed are mainly due to steam and CO2 gasication.
This part would be better simulated by changing the gasication

170

6.4 Single pellet gasier MiV

agent entering the MiV to the corresponding concentrations. This

gas composition can be derived from the axial proles. Since the
volatilising pellet provides exactly the gas composition, which it
would experience when rising in the reactor through the following
volatilising pellet, a back loop of the produced gas into the reactor
could be a good option to simulate real gas conditions.
G With the reactor it is possible to monitor the qualitative alkali

emission from single grass pellets during gasication and subsequent combustion by means of a surface ionisation detector.
First alkali emissions takes place very fast during drying and volatilisation, whereas the main alkali emission takes place during
char combustion. This is in agreement with tests by Dayton and
Milne [274] and Porbatzki [276].

G Additional tests showed that smaller particles are emitted during

the volatilisation than during combustion. Larger particles can be

removed by ltration, whereas small particles pass the lter. This
again shows, that small particles can not be neglected and must
be retained by secondary measures e. g. feeding solid adsorbents
together with the feed.

G Since leaching mainly inuences the alkali emission from the char

combustion, but the hot gas ltration removes this fraction eciently, the eort to leach the grass in advance is most likely not
justied. There is a strong evidence derived from the leaching
experiments and the HGF experiment, that the eort to leach
the grass in advance is most likely not justied. Furthermore
the pellets made of leached grass are less stable during handling
compared to the natural grass.

G The alkali emission primarily corresponds to the alkali content.

The dependency on chlorine seems to be of minor inuence, not

less but rather other alkali species such as KOH must be expected
when chlorine is absent. The manipulation of the alkali content
aects the emission during the char combustion much more the
one during volatilisation.

G Alkali emission characteristics proved to be quite dierent from

standard TGA experiments. The ratio between the alkalis emitted during volatilisation and the alkalis emitted during combustion is lower for the used setup compared to TGA tests [286].

171

6 Conclusions

G The SID showed a phenomenon, which can not be explained by

the conducted tests alone. The signal stayed at the peak level for
much longer time then the pellets needed to fully react (tailing).
Furthermore the signal was constant at this level indicating a
steady state. This behaviour most likely corresponds to surface
physics taking place during the operation.

172

Chapter

Outlook

7
7

7.1 Fluidised bed gasication

G Both alumina and silica are commercially available for uidised

bed applications. Silica is a natural product, whereas alumina

must be produced through e. g. the Bayer-Process. Pure alumina
was used in this study to provide the process with a non silica
bed material showing a high hardness. In real applications alumina of this grade will unlikely be used because of its higher costs
compared to silica. Additionally chemical degradation of the bed
material as well as abrasion must be expected. This leads to the
need to periodically replace a part of the bed material. A native alumina or alumina silicate based bed material e. g. bauxite
or kaolinite that can be transported from nearby, will always be
preferred. The low Moh's hardness (2-3) of the native materials
suggests a pre-treatment like calcination. Calcined kaolinite e. g.
shows an increased Moh's hardness of 6-8 [287]. Pure silica based
materials should be avoided due to increased risks of ash melting.
The important factor when discussing the costs of the bed material, is the distance between the power plant site and the mining
site of the qualied material. For this reason prices depend strongly on the transportation and can only be calculated if those sites
are determined.

173

7 Outlook

G Based on the results it is necessary to test secondary measures

to remove the remaining alkalis from the gas if the gas is applied in a mono-fuel plant. This can be done by introducing
reactive bed materials like bauxite, kaolinite (Al2 Si2 O5 (OH)4 )
or dolomite (natural materials) together with the fuel into the
reactor or by placing a xed bed absorber downstream of the
particle lter. The named materials are known to have binding
eects on alkalis from biomass and coal. A preliminary literature review reveals alkali alumina silicates such as KAlSiO4 as
the major resulting components for aluminium containing aditives [288; 180; 4; 265; 289293]. The addition of dolomite was
reported to form solid MgCa(SiO3 )2 [265]. The removed silicon
increased the ash melting temperature. The additives were introduced to bind either alkalis or silicon into higher melting minerals
such as alkali alumino silicates or alkali oxides. Tests should be
conducted to nd the most suitable for grass.

G Steam injection should be tried to increase the heating value of

the gas and increase the carbon conversion. Steam could be taken
from the steam cycle in the IGCC plant.

G CO2 gasication may be a possible way to increase the overall

eciency, since the future CC power plants will be equipped with

CO2 -sequestration. A partial stream could be looped back to the
gasier.

G If higher lter temperatures than 400 C are required, a dual bed

gasier like the Battelle/Ferco or FICFB type should be considered for grass gasication. In the rst reactor (allothermal) the
pyrolysis and gasication takes place. The bed material and the
char is entrained to the second reactor (exothermal), where the
char is combusted. The heated bed material is entrained to the
rst reactor, where the heat is used for the endothermic pyrolysis.
Since most of the alkalis are released from the char, they would
be permanently removed from the gas turbine cycle.

G Sulphur and ammonia species should be quantied to get informa-

tion about the requirements of the sulphur removal unit. Organic

sulphur species are relevant for catalytic applications of the gas.
Recognition and quantication of those organic sulphur species
are crucial for fuels with a high sulphur content such as grass.

174

7.2 The single pellet gasier MiV

G Prole measurements in gasication units are very rare but reveal

much phenomena. More such measurements should be conducted

to get information about the kinetics in the uidised bed. This
includes steam as well as alkali, ammonia and sulphur proles. It
would much improve the fundamental knowledge needed to model
the uidised bed gasication process.

7.2 The single pellet gasier MiV

G MS analysis should be employed to get further information about

the compounds such as alkali chlorides, hydroxides or cyanides

emitted during the gasication process.

G The behaviour of the gasication should be tested for dierent ga-

sication agents such as steam or CO2 , which both are available

in an IGCC power plant especially with regard to CO2 sequestration.

G Further and more profound identication of the general alkali

emission characteristic obtained from the rst tests is a very important task to be able to link the signal to species or particle
size. It should include MS analysis as well as particles size distributions.

G MiV experiments are suitable to produce data to model the gasi-

cation of a single pellet. The appropriate approach derived from

the experiments would be the shrinking core constant size model
for grass. For wood the approach must also include a shrinking
shell [294].

175

Epilogue
Diese Arbeit wurde durch die freundliche nanzielle Untersttzung des
Axpo Naturstromfonds mglich gemacht. Dafr mchte ich mich bei
Jeanine Oswald und Stefan Roth als Stellvertreter der Axpo bedanken.
Fr die Begleitung meiner Arbeit mchte ich Prof. Alexander Wokaun,
Serge Biollaz und Samuel Stucki meinen Dank ausdrcken. Ebenfalls
mchte ich mich bei Prof. Massimo Morbidelli bedanken, der fr diese
Arbeit das Koreferat bernommen hat.
Fr die Hilfe bei meiner schriftlichen Arbeit geht ein riesiger Dank
an Manuel Damsohn, der die Mglichkeit gefunden hat meine Arbeit
intensiv gegenzulesen. Fr die Fhigkeit meine Arbeit in englisch zu
verfassen mchte ich mich bei Prof. Joe Deans von der University of
Auckland bedanken.
Diverse Menschen haben mir bei dem Aufbau der Wirbelschicht geholfen. Mit brennenden Problemen bezglich der experimentellen Hardware konnte ich Marcel Hottiger immer spontan beaufschlagen, was
mich mehr als einmal gerettet hat. Seine Eigeninitiative und Ideen
bei den Realisierungen trugen immer zu besseren Lsungen bei. Bedanken mchte ich mich auch bei Thomas Marti, der sich immer wieder mit einem versteckten Lcheln  aber geduldig  meine verrcktphantastischen Ideen angehrt hat, von denen wohl nur einige praktischen Sinn inne hatten. Mit seiner Untersttzung konnten alle anlagentechnischen Probleme elegant gelst werden. Ein grosser Dank geht
auch an Peter Hottinger und Hans Regler fr die Hilfe an elektronischen Teilen und die Freizgigkeit, mit der Peter mich an der Anlagensteuerung hat arbeiten lasssen. Erich DeBoni mchte ich danken
fr die Notuntersttzungen, die ich immer bei ihm einholen konnte,
wenn ich nicht mehr weiter wusste. Ein herzliches Dankeschn geht an

177

Jrg Schneebeli fr die lehreiche Zeit und die Untersttzung bei den
Samplingsystemen und dafr, dass ich immer wieder fragen kommen
durfte, wenn ich wieder mal vergessen hatte, warum die Chemie ist wie
sie ist. Die Messkampagne in Luzern wird mir immer lebhaft in Erinnerung bleiben. Fr ihre wertvolle Untersttzung und Hinweise mchte
ich mich herzlich bei Michael Roberts vom GTI und Tom Miles (Technical Consultants, Inc.) wie auch Daniel Chisholm (bioenergylists.org)
bedanken.
Einen besonderen Dank mchte ich Gisela Herlein aussprechen fr ihren
Beistand in harten Zeiten.
Fr die kollegiale Zusammenarbeit in Labor und Kaeepause mchte
ich mich bei Martin Seemann fr die phantastische Zeit beim DggeliBau und mehr, Jan Kopyscinski fr die Brogemeinschaft und sein
enormes Wissen, Marco Wellinger fr gemeinsame Messungen und den
guten Kaee, Martin Schubert fr Diskussionen und Messuntersttzung, Tilman Schildhauer fr die Zeit, die er eigentlich nicht hatte,
Hans Regler und Stefan Bihr fr technische Unterstzung, Jrg Wambach fr Theoretisches in letzter Minute, Albert Schuler fr die ICP
Messungen, Marcelo Rechulski, Urs Rhyner, Martin Rdisueli und dem
ehemaligen LEM-Team einfach fr ihre Anwesenheit bedanken.
Ferner mchte ich einen grossen Dank aussprechen fr die Hilfestellungen, die ich von ausserhalb des Labors und des PSI einfordern konnte.
Hierbei sei speziell erwhnt: Patrick Ruch, Yohannes Ghermay, Salvatore Daniele, Mathias Sauer, Andreas Lscher, Jean-Louis Hersener,
Ralph Stahl, Sylvia Kchli, Peter Fischer, Axel Metzger, Martin Gysel
und Robert Schraner.
Mein grsster Dank jedoch geht an meine Familie, die im letzten Jahr
alles Mgliche auf sich genommen hat, um mir den Freiraum fr die
erfolgreiche Beendigung meiner Dissertation einzurumen.

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199

Appendix

Additional analysis

 Additional analysis

.1 Preliminary test with wood

900

400

750

300
temperature
pressure

600

200

450

300
00:00

100

01:00

02:00
03:00
04:00
elapsed time, hh:mm

Pressure drop, mbar

Bed temperature, C

The two diagrams in gure .1 present an experiment for wood at 800 C

with SiO2 as bed material. The concentration axis of the permanent gases
is logarithmic to give access to the low concentrations of the higher CX HY
species. The test was performed in order to evaluate the newly built uidised
bed test rig. The data is in excellent agreement with the expected data for
uidised bed wood gasication [223]. The test was conducted without any
problems of the feeding mechanism or uidisation. The sampling system
worked ne as well. The lower heating value was 6.8 MJ/kg for an air to fuel
ratio of 0.22. The blank in the permanent gas data occurred due to general
problems with the sampling system.

0
06:00

05:00

Concentration, %vol

10

H2
CO2

10

CH4
CO
N2

10

C2H4
C2H6

10

C2H2
C3H6

10
00:00

01:00

02:00
03:00
04:00
elapsed time, hh:mm

05:00

06:00

Figure .1: Process data for the reference experiment with wood for = 0.22

in a silica bed

II

2008-07-21 16:43

Hauptansicht

100

200

Gert:
NETZSCH STA 449 C
Datei:
Gras_1.ssu
Projekt:
Versuchs-ID: Gras
Datum/Zeit:
04.07.2008 12:44:59
Labor:
PSI
Operator:
RS51
Dateipfad: D:\Gras_1.ssu Bemerkung:

rabe

40

50

60

70

80

90

100

TG /%

TCALZERO.TCX /
30.0/10.0(K/min)/800.0
DTA(/TG) HIGH RG 4 / S

Gras_1, 32,500 mg
--Gras

400
500
600
Temperatur /C

Probe:
Referenz:
Material:
Korrektur-Datei:
Tempkal./Empf. Datei:
Bereich:
Probentr./TC:

300

TG
H2O_1
CO2
CO
CH4

Modus /Messart.:
Segmente:
Tiegel:
Atmosphre:
TG Korr/Messber:

-4

-2

0.8
8

0.2

0.4

0.6

1.0
10

1.2

1.4

14
12

1.6

1.8

16

18

TG / Probe
2/2
DTA/TG crucible Al2O3
---/--- / Ar/16 / Ar, 8 ml/min/--000/5000 mg

[1.2]
[1.2]
[1.2]
[1.2]

[1.2]

CO2 /Import
H2O_1 *10-2 /Import CO /Import

700

[1.2] Gras_1.ssu

.2 TGA for grass

.2 TGA for grass

Figure .2: TGA for a untreated grass sample

.3 GC/MS tar analysis

...

III

Figure .3: GC/MS analysis of light tars: uidised bed experiment at 750 C, =0.26

Additional analysis

IV

Figure .4: GC/MS analysis of light tars: uidised bed experiment at 750 C, =0.21

.3 GC/MS tar analysis

Appendix

Photographs from the set ups

Figure .1: Setup of the MiV experiments

VII

 Photographs from the set ups

Figure .2: Bubbling uidised bed test rig

VIII

Appendix

Methane slip stream in a biogas plant

with PSA operated CO2 sequestration
The methane loss project was realised as a mandate of the BFE under the
contract ID 1017181 . The project name is: Methanverluste bei der BiogasAufbereitung .
The goal was to evaluate the loss of methane during the conditioning of the
biogas from the fermentation process by means of a PSA2 plant. The result
is depicted in gure .1. Around 2.3 % of the methane (inlet) is released into
the environment.

Figure .1: Methane ows to and from the PSA unit

The nal report is online available at the information platform aramis.
1 http://www.aramis.admin.ch/Default.aspx?page=Texte&ProjectID=21120
2 Pressure Swing Adsorption

IX

Index

Index

Symbols
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .97

A
acid treatment
fuel . . . . . . . . . . . . . . . . . . . . . . . 75
aerosol
denition . . . . . . . . . . . . . . . . . . 80
sampling . . . . . . . . . . . . . . . . . . 82
alkali. . . . . . . . . . . . . . . . . . . . . . . . . . . .22
melt . . . . . . . . . . . . . . . . . . . . . . . . 7
alkalialulminosililcates . . . . . . . . . 144
alkalinity number . . . . . . . . . . . . . . . 36
alumina
bed material . . . . . . . . . . . . . 100
experiment . . . . . . . . . . . . . . . 125
aluminium . . . . . . . . . . . . . . . . . . . . . . 46
ammonia . . . . . . . . . . . . . . . . . . . . . . . . 44
ammonium hydrogen carbonate . 88
antimony. . . . . . . . . . . . . . . . . . . . . . . .67
arsenic . . . . . . . . . . . . . . . . . . . . . . . . . . 46
ash
agglomeration . . . . . . . . . . . . . 34
DIN 51730 . . . . . . . . . . . . . . . . 33
fuel . . . . . . . . . . . . . . . . . . . . . . . 32
HGF . . . . . . . . . . . . . . . . . . . . . 143
melting . . . . . . . . . . . . . . . . . . . . 33
melting point . . . . . . . . . . . . . . 33
MiV. . . . . . . . . . . . . . . . . . . . . .164
ash melting
furnace test . . . . . . . . . . . . . . 122
potassium . . . . . . . . . . . . . . . . . 60
silicon . . . . . . . . . . . . . . . . . . . . . 70
ash melting, calcium . . . . . . . . . . . . 50
auger . . . . . . . . . . . . . . . . . . . . . . . . . . 104
image . . . . . . . . . . . . . . . . . . . . 104

B
B-IGCC . . . . . . . . . . . . . . . . . . . . . . . . . . 2

barite . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
barium . . . . . . . . . . . . . . . . . . . . . . . . . . 48
bed material . . . . . . . . . . . . . . . . . . . 100
BFB . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
basic data . . . . . . . . . . . . . . . . 103
uidisation . . . . . . . . . . . . . . . 123
heat loss . . . . . . . . . . . . . . . . . 114
biomass . . . . . . . . . . . . . . . . . . . . . . . . . 17
Boie formula . . . . . . . . . . . . . . . . . . . . 25
boron . . . . . . . . . . . . . . . . . . . . . . . . . . . 47

C
CAA . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
cadmium . . . . . . . . . . . . . . . . . . . . . . . . 50
calcium . . . . . . . . . . . . . . . . . . . . . . . . . 49
photosynthesis. . . . . . . . . . . . .50
carbon . . . . . . . . . . . . . . . . . . . . . . . . . . 40
carbon balance . . . . . . . . . . . . . . . . . 132
carbon conversion . . . . . . . . . . . . . . . 97
carbonisation . . . . . . . . . . . . . . . . . . . 74
char. . . . . . . . . . . . . . . . . . . . . . . . . . . . .92
uidised bed . . . . . . . . . . . . . 117
chlorine . . . . . . . . . . . . . . . . . . . . . . . . . 51
chlorosis
iron . . . . . . . . . . . . . . . . . . . . . . . 56
chromium . . . . . . . . . . . . . . . . . . . . . . . 53
coalication . . . . . . . . . . . . . . . . . . . . . 27
cobalt . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
composition
grass . . . . . . . . . . . . . . . . . . . . . 119
inorganic . . . . . . . . . . . . . . . . . 119
permanent gas . . . . . . . . . . . 138
contaminants, gas phase. . . . . . . . .91
cooling water . . . . . . . . . . . . . . . . . . 112
copper . . . . . . . . . . . . . . . . . . . . . . . . . . 54
corrosion . . . . . . . . . . . . . . . . . . . . . . . 7 f.
critical elements . . . . . . . . . . . 75
sulphidation attack . . . . . . . . . 7
corrosion, barium . . . . . . . . . . . . . . . 48
cost
delivery . . . . . . . . . . . . . . . . . . . 16

XI

Index
grass . . . . . . . . . . . . . . . . . . . . . . 16
harvest . . . . . . . . . . . . . . . . . . . . 16
storage . . . . . . . . . . . . . . . . . . . . 16

D
degradation
grass . . . . . . . . . . . . . . . . . . . . . . 29
pyrolysis . . . . . . . . . . . . . . . . . . 25
density . . . . . . . . . . . . . . . . . . . . . . . . . . 22
deposition
magnesium . . . . . . . . . . . . . . . . 62
phosphorus . . . . . . . . . . . . . . . . 65
dolomite
bed material . . . . . . . . . . . . . 100
experiment . . . . . . . . . . . . . . . 125
drying . . . . . . . . . . . . . . . . . . . . . . . . . . 92

E
eciency
cold gas . . . . . . . . . . . . . . . . . . . 97
hot gas . . . . . . . . . . . . . . . . . . . . 97
elements
essential . . . . . . . . . . . . . . . . . . . 37
nutrients . . . . . . . . . . . . . . . . . . 37
energy
heating value . . . . . . . . . . . . . . 25
photosynthesis. . . . . . . . . . . . .25
energy crops. . . . . . . . . . . . . . . . . . .13 f.
Ergun. . . . . . . . . . . . . . . . . . . . . . . . . .123
erosion . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
eutectics . . . . . . . . . . . . . . . . . . . . . . . 125
experiment
extended . . . . . . . . . . . . . . . . . 128
procedures . . . . . . . . . . . . . . . 118

F
feeding
double jacket . . . . . . . . . . . . . 106
lter cake . . . . . . . . . . . . . . . . . . . . . . 140
nes
denition . . . . . . . . . . . . . . . . . . 80
HGF . . . . . . . . . . . . . . . . . . . . . 143
xed carbon. . . . . . . . . . . . . . . . . . . . .30
uidisation . . . . . . . . . . . . . . . . . . . . . . 99
experiment . . . . . . . . . . . . . . . 118
uidised bed . . . . . . . . . . . . . . . 99, 101
bed expansion . . . . . . . . . . . . 124
reactor . . . . . . . . . . . . . . . . . . . 107
uorine . . . . . . . . . . . . . . . . . . . . . . . . . 55
fouling . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

XII

sulphur . . . . . . . . . . . . . . . . . . . . 45
freeboard . . . . . . . . . . . . . . . . . . . . . . 125
fuel
blending . . . . . . . . . . . . . . . . . . . . 9
bridging . . . . . . . . . . . . . . . . . . 103
doping . . . . . . . . . . . . . . . . . . . 156
drying. . . . . . . . . . . . . . . . . . . .156
feeder . . . . . . . . . . . . . . . . . . . . 104
leaching . . . . . . . . . . . . . . . . . . 156
MiV. . . . . . . . . . . . . . . . . . . . . .154
origin . . . . . . . . . . . . . . . . . . . . 121
pellets . . . . . . . . . . . . . . . 121, 156
pre-treatment . . . . . . . . . . . . . 73
preparation . . . . . . . . . . . . . . 121
storage . . . . . . . . . . . . . . . . . . . 103

G
gas turbine
aero derivative. . . . . . . . . . . . . .9
ow exibility . . . . . . . . . . . . . 10
heavy duty . . . . . . . . . . . . . . . . . 9
requirements . . . . . . . . . . . . . . . 5
gasication . . . . . . . . . . . . . . . . . . . . . . 92
gasier
Battelle/ FERCO . . . . . . . . . 94
Blauer Turm . . . . . . . . . . . . . . 94
downdraft . . . . . . . . . . . . . . . . . 94
entrained ow . . . . . . . . . . . . . 94
xed bed . . . . . . . . . . . . . . . . . . 94
uidised bed . . . . . . . . . . . . . . 94
HTW . . . . . . . . . . . . . . . . . . . . . 98
IGT Renugas . . . . . . . . . . . . . . 98
updraft . . . . . . . . . . . . . . . . . . . . 94
GIS . . . . . . . . . . . . . . . . . . . . . . . . . . 9, 17
grass
availability . . . . . . . . . . . . . . . . 15
cost . . . . . . . . . . . . . . . . . . . . . . . 16
growth . . . . . . . . . . . . . . . . . . . . 16
greenhouse
gas . . . . . . . . . . . . . . . . . . . . . . . . 41
ozone. . . . . . . . . . . . . . . . . . . . . .41

H
He

spike . . . . . . . . . . . . . . . . . . . . . 130
HHV . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
HTSG . . . . . . . . . . . . . . . . . . . . . . . . . 135
hydrogen . . . . . . . . . . . . . . . . . . . . . . . . 42
hydrothermal gasication . . . . . . . 76

Index

IGCC . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
blending . . . . . . . . . . . . . . . . . . . . 3
Buggenum . . . . . . . . . . . . . . . . . . 1
coring . . . . . . . . . . . . . . . . . . . . . 3
Cool Water . . . . . . . . . . . . . . . . . 1
installations . . . . . . . . . . . . . . . . 1
Lnen . . . . . . . . . . . . . . . . . . . . . . 1
mono-fuel . . . . . . . . . . . . . . . . . . 3
Puertollano . . . . . . . . . . . . . . . . . 1
retrot . . . . . . . . . . . . . . . . . . . . . 3
Wabash River . . . . . . . . . . . . . . 1
IGCC-CCS . . . . . . . . . . . . . . . . . . . . . . . 2
impinger
sampling . . . . . . . . . . . . . . . . . . 82
iron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
ISO DIN 51720. . . . . . . . . . . . . . . . . .29

NH4HCO3 . . . . . . . . . . . . . . . . . . . . . 140
nickel . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
nickel carbonyl . . . . . . . . . . . . . . . . . . 64
nitrogen. . . . . . . . . . . . . . . . . . . . . . . . .43
Nuon Magnum . . . . . . . . . . . . . . . . . . . 2
nutrients . . . . . . . . . . . . . . . . . . . . . . . . 39

L
lambda . . . . . . . . . . . . . . . . . . . . . . . . . 97
leaching
alkali . . . . . . . . . . . . . . . . . . . . . . 60
fuel . . . . . . . . . . . . . . . . . . . . . . . 74
lead . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
limits . . . . . . . . . . . . . . . . . . . . . 66
legumes . . . . . . . . . . . . . . . . . . . . . . . . . 43
LHV . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
cellulose . . . . . . . . . . . . . . . . . . . 26
lignin. . . . . . . . . . . . . . . . . . . . . .26
permanent gas . . . . . . . . . . . 134
lignication . . . . . . . . . . . . . . . . . . . . . 21
lignin . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
Lurgi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

M
magnesium . . . . . . . . . . . . . . . . . . . . . . 61
manganese . . . . . . . . . . . . . . . . . . . . . . 62
mass loss . . . . . . . . . . . . . . . . . . . . . . . . 24
mercury . . . . . . . . . . . . . . . . . . . . . . . . . 57
metal dusting
nickel . . . . . . . . . . . . . . . . . . . . . 65
MiV . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
ash . . . . . . . . . . . . . . . . . . . . . . . 164
CAD . . . . . . . . . . . . . . . . . . . . . 149
leaching . . . . . . . . . . . . . . . . . . 154
mocca express . . . . . . . . . . . . . . . . . 156
molybdenum . . . . . . . . . . . . . . . . . . . . 63
MS
MiV. . . . . . . . . . . . . . . . . . . . . .151

oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . 42

P
particles. . . . . . . . . . . . . . . . . . . . . . . . . .8
denition . . . . . . . . . . . . . . . . . . 80
pellet press . . . . . . . . . . . . . . . . . . . . 156
pellets . . . . . . . . . . . . . . . . . . . . . . . . . . 22
periodic system . . . . . . . . . . . . . . . . . 38
permanent gas
denition . . . . . . . . . . . . . . . . . . 80
Petersen column . . . . . . . . . . . . . . . . 82
phosphorous . . . . . . . . . . . . . . . . . . . . 65
plant
growth . . . . . . . . . . . . . . . . . . . . 16
plugging . . . . . . . . . . . . . . . . . . . . . . . . . 8
poisoning
sulphur . . . . . . . . . . . . . . . . . . . . 45
potassium . . . . . . . . . . . . . . . . . . . 37, 58
leaching . . . . . . . . . . . . . . . . . . . 37
potassium silicate . . . . . . . . . . . . . . . 70
pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . 92

R
reaction
CO shift. . . . . . . . . . . . . . . . . . .93
methanation . . . . . . . . . . . . . . . 93
oxidation . . . . . . . . . . . . . . . . . . 93
water gas . . . . . . . . . . . . . . . . . . 93
RWE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

S
safety
emergency. . . . . . . . . . . . . . . .110
sampling . . . . . . . . . . . . . . . . . . . . . . . . 81
isokinetic . . . . . . . . . . . . . . . . . 109
MiV. . . . . . . . . . . . . . . . . . . . . .156
ports . . . . . . . . . . . . . . . . . . . . . 109
prole . . . . . . . . . . . . . . . . . . . . 110
scrubber

XIII

Index
slip-stream . . . . . . . . . . . . . . . 84
step response . . . . . . . . . . . . . . 86
selenium . . . . . . . . . . . . . . . . . . . . . . . . 68
shrinking core . . . . . . . . . . . . . . . . . . 148
SID . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
silica
bed material . . . . . . . . . . . . . 100
experiment . . . . . . . . . . . . . . . 125
silicon. . . . . . . . . . . . . . . . . . . . . . . . . . .68
slip-stream
MiV . . . . . . . . . . . . . . . . . . 84, 157
slurry . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
sodium . . . . . . . . . . . . . . . . . . . . . . . . . . 58
specic costs . . . . . . . . . . . . . . . . . . . . . 9
starch . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
stibium . . . . . . . . . . . . . . . . . . . . . . . . . 67
sulphur. . . . . . . . . . . . . . . . . . . . .44, 144
sulpidation attack
vanadium . . . . . . . . . . . . . . . . . 71

T
tar

denition . . . . . . . . . . . . . . . . . . 79
deposition . . . . . . . . . . . . . 8, 117
tar protocol . . . . . . . . . . . . . . . . . . . . . 82
temperature
prole . . . . . . . . . . . . . . . . . . . . 130
Texcao . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
TGA. . . . . . . . . . . . . . . . . . . . . . . . . . .147
alkali . . . . . . . . . . . . . . . . . . . . . 148
macro . . . . . . . . . . . . . . . . . . . . 148
titanium . . . . . . . . . . . . . . . . . . . . . . . . 70
torrefaction. . . . . . . . . . . . . . . . . .43, 74
transfer coecient . . . . . . . . . . . . . . 60

U
ultimate
analysis . . . . . . . . . . . . . . . . . . 119

V
Vrnamo . . . . . . . . . . . . . . . . . . . . . 2, 27
van Krevelen . . . . . . . . . . . . . . . . . . . . 27
vanadium . . . . . . . . . . . . . . . . . . . . . . . 71
vitrication number . . . . . . . . . . . . . 36
volatile content . . . . . . . . . . . . . . . . 135
volatile matter . . . . . . . . . . . . . . 29, 92
volatility . . . . . . . . . . . . . . . . . . . . . . 30 f.

W
water content . . . . . . . . . . . . . . . . . . 120

XIV

biomass . . . . . . . . . . . . . . . . . . . 28
fuel . . . . . . . . . . . . . . . . . . . . . . 137
wood, gasication. . . . . . . . . . . . . . . .II

X
XPS . . . . . . . . . . . . . . . . . . . . . . . . . . . 144

Z
zinc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
desulpurisation . . . . . . . . . . . . 72