4898 Giannakopoulou Kanellina 2010

Kanellina Giannakopoulou
Development of a low pressure, catalytic process for the

production of biofuels
DISSERTATION
zur Erlangung des akademischen Grades einer
Doktorin der technischen Wissenschaften
erreicht an der
Technischen Universität Graz
Univ.Prof. DI Dr. Hans Schnitzer
Institut für Prozess- und Partikeltechnik
Technische Universität Graz
2010
STATUTORY DECLARATION
I declare that I have authored this thesis independently, that I have not used other than the
declared sources / resources and that I have explicitly marked all material which has been
quoted either literally or by content from the used sources.
…………………………… ………………………………………………..
(date) (signature)
3
Abstract
The need for low fuel prices, energy independence of countries and mitigation of global warming had
as a result the development of biofuel production technologies. The EU has set as a reference target a
5.75% market share for biofuels in 2010. The thermochemical conversion technologies have been
attracting scientific attention, since they can convert a wide variety of biogenic raw materials into liquid
biofuels with desirable properties. The addition of catalysts into the conversion system has a result the
production of biofuels with improved characteristics.
The development of a Catalytic Low Pressure Liquefaction process (in german Katalytische
Niederdruck Verölung – KNV) for the production of biofuels was presented. Low pressure conversion
can give the possibility to better regulate the residence time of produced vapours into the reactor
system, enabling the increase of liquid product yield without the use of high-investment reactors. The
zeolite addition can improve the quality of the liquid product. The yields, the chemical composition, the
elemental composition and the physical properties of the conversion products were presented after
each test.
The co-conversion of rapeseed cake and safflower oil was examined, in the absence of catalysts and
in the presence of three different zeolite catalysts (Fe-ZSM-5, H-ZSM-5 and H-Beta) at 400 °C and 350
°C. The rapeseed cake conversion with two reactor c onfigurations (with or without a vapour upgrading
section) was examined in the absence of catalysts and in the presence of two different zeolite catalysts
(H-ZSM-5 and H-Beta) at 400 °C. The separate conver sion of meat meal C1 and algae was examined
in the presence of the H-ZSM-5 zeolite at 400 °C, w ithout and with a vapour upgrading section,
respectively. The energy balance of the different conversion tests at 400 °C was calculated and
evaluated.
The feasibility study for the upscaling of the KNV laboratory process into a pilot plant, using algae as a
feedstock, was performed. Two Design Layouts were employed: (A) using a gas burner to heat up the
reactor and (B) using an induction generator to heat up the reactor. The fixed investment costs, the
labour costs, the energy and auxiliary material costs as well as the production costs were assessed.
The payback time for each Design Layout was calculated. Both feasibility studies were evaluated.
Keywords
zeolite catalysts; low pressure conversion; co-conversion; rapeseed cake; vegetable oil; biogenic
waste; vapour upgrading; biofuel
5
Kurzfassung
Die Notwendigkeit niedriger Treibstoffpreise, Energie - Unabhängigkeit und Reduktion der
Erderwärmung resultierte in der Entwicklung von Produktionstechnologien für Bio-Treibstoffe. Die EU
hat als Ziel bis 2010 einen Marktanteil von 5,7% des Gesamttreibstoffbedarfes an biogenen Treibstoffe
definiert. Thermochemische Konversionstechnologien zogen die Aufmerksamkeit von
Wissenschaftlern an, da sie eine große Vielzahl an nachwachsenden Rohstoffen zu flüssigen
Treibstoffen umsetzen können, bei Einhaltung der erwünschten Eigenschaften. Durch das Verwenden
von Katalysatoren im Konversionsprozess wurden Biotreibstoffe mit verbesserten Eigenschaften
erhalten.
In der vorliegenden Arbeit wird die Entwicklung einer Katalytischen Niederdruck Verölung KNV für die
Produktion von Bio-Treibstoffen vorgestellt. Niederdruck Verölung kann eine bessere Regulierung der
Verweilzeit von produzierten Dämpfen im Reaktorsystem ermöglichen. Dies ermöglicht eine Erhöhung
der Reaktorausbeute an Flüssigprodukt, ohne dass hochpreisige Reaktoren eingesetzt werden
müssten. Die Beigabe von Zeolit kann die Qualität des Flüssigproduktes verbessern. Zu jedem
Versuch werden die Erträge, chemische Zusammensetzung, atomare Zusammensetzung und
physikalische Eigenschaften dargestellt.
In der Arbeit wurde die geichzeitige Umwandlung von Rapspress-Kuchen und Distelöl untersucht,
wobei einmal keine Katalysatoren, in anderen Versuchen drei verschiedene Zeolith-Katalysatoren (Fe-
ZSM-5, H-ZSM-5 und H-Beta) bei 400 °C und 350 °C ei ngesetzt wurden. Die Umwandlung von
Rapspress-Kuchen bei zwei verschiedenen Reaktor Konfigurationen (mit oder ohne Dampf Reinigung)
wurde einmal ohne Katalysatoren und die anderen Male in Anwesenheit von zwei verschiedenen
Zeolith Katalysatoren (H-ZSM-5 und H-Beta) bei 400 °C untersucht. In getrennten Versuchen wurden
Tiermehl C1 und Algen in Anwesenheit von H-ZSM-5 Zeolith bei 400 ° C untersucht, sowohl mit als
auch ohne Dampf Reinigung. Die Energiebilanz der verschiedenen Umwandlungsversuche bei 400 ° C
wurde berechnet und evaluiert.
Es wurde eine Feasibility-Studie für das Upscaling einer Katalytischen Niederdruck Verölung KNV vom
Labourmaßstab zum Pilot-Plant-Maßstab, unter Verwendung von Algen als Rohmaterial durchgeführt.
Hier wurden zwei Anlagen-Ausführungen verglichen: (A) ein Gasbrenner zur Erhitzung des Reaktors,
(B) ein Induktionsheizgerät zur Erhitzung des Reaktors. Ebenso wurden die Fixkosten für die Anlagen-
Investition, Personalkosten, kosten für Energie und Hilfsstoffe und Produktionskosten abgeschätzt. Die
Amortisaitonszeit für jede Anlagen-Ausführung wurde berechnet. Danach wurden beide Feasibility
Studien verglichen.
6
Schlagwörter
Zeolit Katalysatoren; Niederdruck Konversion; Co-Konversion; Rapskuchen; pflanzliches Öl; Biomüll;
Dampfraffination; Biotreibstoff
7
Acknowledgements
I would like to thank:
Ao. Univ. Prof. Dipl. Ing. Dr.techn. Hans Schnitzer for his trust, by assigning me this research work,
and for his help, support and guidance through my studies at the Institute of Process and Particle
Engineering at the Graz University of Technology.
Ao.Univ. Prof. Dr.phil. Norbert Klempier of the Institute of Organic Chemistry at the Graz University of
Technology for his interest and advice on my research.
Ao.Univ. Prof. Dipl. Ing. Dr.techn. Rudolf Eichinger of the Institute of Paper, Pulp and Fibre Technology
at the Graz University of Technology for his chairmanship during the doctorate inception.
Dipl. Ing. Christoph Brunner for his support through the course of my research work in Graz and all the
people at the offices and laboratory of the Institute of Sustainable Techniques and Systems of
Joanneum Research for their help.
Assistant Professor Dr. Aleksey Vasiliev of the Department of Chemistry at the East Tennessee State
University for his assistance on catalysis issues.
Mag. Dr. Sigurd Schober of the Institute of Organic Chemistry at the Karl Franzens University of Graz
for his help with the elemental analysis, approximate analysis and physicochemical properties analysis
of the products.
Mag. Dr. Christine Latal of the Institute of Applied Geosciences at the Graz University of Technology
for her help with the XRD analysis of the fresh and regenerated catalysts.
The chemical company Sud-Chemie (Germany) for supplying the catalytic materials used for the
experimental tests.
The Local Government of the Municipality of Styria (Austria), which funded this research work.
The scholarship foundation Korgialleneion Athlon (Greece) for the economic support during my studies
at the Graz University of Technology.
My family for the precious support all through the years and my friends Sia and Maria for their
stimulating companionship.
Kanellina Giannakopoulou,
Graz, March 2010
9
Contents 11
Contents
1 INTRODUCTION............................................................................................................................ 23
1.1 Biofuels overview..................................................................................................................... 23
1.1.1 The energy sector today .............................................................................................. 23
1.1.2 Biofuel generations ...................................................................................................... 24
1.1.3 Recent biofuel production ............................................................................................ 26
1.1.4 Biofuel production targets ............................................................................................ 28
1.2 Biofuel incentives .................................................................................................................... 29
1.3 EU vision for biofuels............................................................................................................... 32
2 BIOFUEL PRODUCTION – STATE OF THE ART......................................................................... 35
2.1 Biogenic resources.................................................................................................................. 35
2.1.1 Biomass classification ................................................................................................. 35
2.1.2 Biomass physicochemical composition ....................................................................... 35
2.1.3 Biomass availability...................................................................................................... 35
2.2 Biomass conversion technologies ........................................................................................... 36
2.2.1 Gasification .................................................................................................................. 38
2.2.1.1 Description .............................................................................................................. 38
2.2.1.2 Reactor types .......................................................................................................... 38
2.2.1.3 Reaction mechanisms ............................................................................................. 41
2.2.1.4 Mass and energy efficiency..................................................................................... 42
2.2.2 Pyrolysis....................................................................................................................... 42
2.2.2.1 Description .............................................................................................................. 42

Contents 12
2.2.2.2 Reactor types .......................................................................................................... 43
2.2.3 Liquefaction ................................................................................................................. 49
2.2.3.1 Description .............................................................................................................. 49
2.2.3.2 Reactor types .......................................................................................................... 53
2.2.3.3 Organic liquid carrier effect ..................................................................................... 53
2.2.4 Catalysis in thermochemical conversion processes .................................................... 58
2.2.4.1 Catalytic pyrolysis and catalytic liquefaction reaction mechanisms......................... 60
3 THE DEVELOPED PROCESS (KNV) ............................................................................................ 65
3.1 Motivation / Contribution.......................................................................................................... 65
3.2 The experimental KNV unit and procedure ............................................................................. 65
3.3 Selection of feedstocks ........................................................................................................... 69
3.4 Selection of liquid carrier / solid carrier material...................................................................... 70
3.5 Selection of catalysts............................................................................................................... 71
3.6 Performed tests / Results........................................................................................................ 72
3.6.1 Co-conversion of rapeseed cake and safflower oil...................................................... 72
3.6.1.1 Scientific background .............................................................................................. 72
3.6.1.2 Performed tests ....................................................................................................... 73
3.6.1.3 Phase composition of the reaction mixture ............................................................. 74
3.6.1.4 Chemical composition of the organic phase ........................................................... 75

Contents 13
3.6.1.5 Chemical composition of the aqueous phase ......................................................... 76
3.6.1.6 Elemental composition / Physical properties........................................................... 77
3.6.2 Rapeseed cake conversion with two reactor configurations........................................ 79
3.6.2.2 Performed tests ....................................................................................................... 80
3.6.2.7 Catalyst regeneration and characterization ............................................................. 85
3.6.3 Meat meal C1 and algae conversion ........................................................................... 88
3.6.3.2 Performed tests ....................................................................................................... 88
3.7 Discussion of results ............................................................................................................... 93
3.7.1 Co-conversion of rapeseed cake and safflower oil...................................................... 93

Contents 14
3.7.2 Rapeseed cake conversion with two reactor configurations........................................ 98
3.7.2.3 Chemical composition of the aqueous phase ....................................................... 101
3.7.2.4 Elemental composition / Physical properties......................................................... 102
3.7.2.5 Catalyst regeneration and characterization ........................................................... 102
3.7.3 Meat meal C1 and algae conversion ......................................................................... 103
3.7.3.1 Phase composition of the reaction mixture ........................................................... 103
3.7.3.2 Chemical composition of the organic phase ......................................................... 104
3.7.3.3 Chemical composition of the aqueous phase ....................................................... 104
3.7.3.4 Elemental composition / Physical properties......................................................... 105
3.8 Energy balance...................................................................................................................... 105
4 FEASIBILITY STUDY ................................................................................................................... 109
4.1 Research on the framework .................................................................................................. 109
4.1.1 Policy framework ....................................................................................................... 109
4.1.2 Funding framework .................................................................................................... 110
4.1.3 Technoeconomic framework ..................................................................................... 110
4.1.4 Social framework ....................................................................................................... 112
4.2 Technical design ................................................................................................................... 112
4.2.1 Pre-treatment: algae .................................................................................................. 113
4.2.2 Pre-treatment: catalyst............................................................................................... 114
4.2.3 Conversion................................................................................................................. 115
4.2.4 Regeneration ............................................................................................................. 117

Contents 15
4.2.5 Safety......................................................................................................................... 118
4.2.6 Environment............................................................................................................... 118
4.2.7 Design Layout A......................................................................................................... 119
4.2.8 Design Layout B......................................................................................................... 121
4.3 Cost assessment................................................................................................................... 124
4.3.1 Fixed investment........................................................................................................ 124
4.3.2 Turnover capital ......................................................................................................... 128
4.3.2.1 Labour cost............................................................................................................ 130
4.3.2.2 Energy and auxiliary material cost......................................................................... 132
4.3.2.3 Production cost...................................................................................................... 134
4.4 Economic evaluation ............................................................................................................. 135
5 CONCLUSIONS ........................................................................................................................... 137
6 ISSUES FOR FURTHER RESEARCH......................................................................................... 141
7 LITERATURE ............................................................................................................................... 143
8 ANNEX ......................................................................................................................................... 151
8.1 Biomass database................................................................................................................. 151
8.2 Mass balances of the performed tests .................................................................................. 157
8.2.1 Co-conversion of rapeseed cake and safflower oil.................................................... 157
8.2.2 Rapeseed cake conversion with two reactor configurations...................................... 157
8.3 Detailed composition of the liquid products........................................................................... 158
8.3.1 Co-conversion of rapeseed cake and safflower oil.................................................... 158
8.3.2 Rapeseed cake conversion with two reactor configurations...................................... 160

Contents 16
8.4 Heating values prediction models ......................................................................................... 163
8.5 Sample photos of the liquid fuel samples.............................................................................. 164
8.6 Chromatograms example of the liquid product samples....................................................... 164
8.7 XRD spectrum example of the regenerated catalyst............................................................. 166
8.8 Sample photos of the catalyst before and after regeneration ............................................... 166
8.9 Published papers at scientific journals .................................................................................. 167
8.10 Presentations and public events........................................................................................ 167

Figures 17
Figures
Figure 1-1. Biofuel production in EU since 1993 (2004: EU-25) (Biofuels Research Advisory Council)
............................................................................................................................................................... 27
Figure 1-2. Anticipated future roadmap (Biofuels Research Advisory Council) .................................... 33
Figure 2-1. The main biomass conversion pathways............................................................................ 37
Figure 2-2. Mechanism of cellulose degradation without alkali metals (Huber et al., 2006)................. 47
Figure 2-3. Glucose degradation with alkali metal catalyzed or glycoside rupture pathways (Huber et
al., 2006) ................................................................................................................................................ 48
Figure 2-4. Mechanism of triglycerides pyrolysis (Huber et al., 2006) .................................................. 49
Figure 2-5. Cellulose decomposition pathways in supercritical water (Huber et al., 2006)................... 56
Figure 2-6. Reaction pathways for the catalytic cracking of biomass-derived oxygenates. Note: for
dehydrogenation and decarbonylation reactions, the hydrogen can be produced by hydrogen transfer to
a hydrogen-deficient molecule (Huber and Corma, 2007)..................................................................... 61
Figure 2-7. The conversion of model bio-oil compounds with ZSM-5 (Huber and Corma, 2007) ........ 62
Figure 2-8. Proposed reaction pathway for the cracking of vegetable oils with H-ZSM-5 (Huber and
Corma, 2007)......................................................................................................................................... 63
Figure 2-9. γ-Hydrogen mechanism on the symmetrical ketone and methyl ketone (Leung et al., 1995)
............................................................................................................................................................... 64
Figure 3-1. (a) Reactor, (b) stirring device and (c) vapour condensation section................................. 66
Figure 3-2. The reactor system............................................................................................................. 66
Figure 3-3. Product yields (wt. % on biogenic mixture) of the performed rapeseed cake and safflower
oil co-conversion tests ........................................................................................................................... 74
Figure 3-4. Organic phase composition of the rapeseed cake and safflower oil co-conversion liquid
products ................................................................................................................................................. 75
Figure 3-5. Aqueous phase composition of the rapeseed cake and safflower co-conversion liquid
products ................................................................................................................................................. 76
Figures 18
Figure 3-6. Product yields (wt. % on biogenic mixture) of the performed rapeseed cake conversion
tests using two reactor configurations ................................................................................................... 81
Figure 3-7. Organic phase composition of the rapeseed cake conversion liquid products using two
reactor configurations ............................................................................................................................ 82
Figure 3-8. Aqueous phase composition of the rapeseed cake conversion liquid products using two
reactor configurations ............................................................................................................................ 83
Figure 3-9. XRD patterns of (a) the fresh H-ZSM-5, (b) the regenerated H-ZSM-5 from the reactor and
(c) the regenerated H-ZSM-5 from the vapour upgrading section......................................................... 86
Figure 3-10. XRD patterns of (a) the fresh H-Beta, (b) the regenerated H-Beta from the reactor and (c)
the regenerated H-Beta from the vapour upgrading section.................................................................. 87
Figure 3-11. Product yields (wt. % on biogenic mixture) of the performed separate meat meal C1 and
algae conversion tests ........................................................................................................................... 89
Figure 3-12. Organic phase composition of the separate meat meal C1 and algae conversion liquid
products ................................................................................................................................................. 90
Figure 3-13. Aqueous phase composition of the separate meat meal C1 and algae conversion liquid
products ................................................................................................................................................. 91
Figure 3-14. Mass and energy flows of the KNV laboratory process .................................................. 106
Figure 4-1. KNV pilot plant flowsheet for the Design Layout A ........................................................... 120
Figure 4-2. KNV pilot plant flowsheet for the Design Layout B ........................................................... 123
Figure 8-1. Sample photos of (a) the organic and (b) the aqueous phase ......................................... 164
Figure 8-2. Chromatogram example of the organic phase ................................................................. 164
Figure 8-3. Chromatogram example of the aqueous phase ............................................................... 165
Figure 8-4. XRD spectrum example of the regenerated catalyst........................................................ 166
Figure 8-5. Sample photos of the catalyst (a) before and (b) after regeneration................................ 166
Tables 19
Tables
Table 1-1: Biofuel classification into generations according to the used biogenic feedstock ............... 25
Table 2-1: Biogenic materials classification .......................................................................................... 35
Table 2-2: Overview of the gasification reactor types (FAO, 1986; Henrich and Weirich, 2002; National
Renewable Energy Laboratory; Miccio et al., 2009; Yogi Goswami, 1986; Suna et al., 2009).............. 39
Table 2-3: Overview of the pyrolysis reactor types (Adam et al., 2006; Antonakou et al., 2006a;
Bridgwater 2004; Bridgwater, 2006; BTG World, 2009; Czernik, 2004; Demiral and ensöz, 2008;
Gayubo et al., 2005; Mohan et al., 2006; Pütün et al., 2006; Vitolo et al., 1999)................................... 45
Table 2-4: (a) Hydrogen donor compounds and (b) catalysts used for transfer hydrogenation (Brieger
and Nestrick, 1974) ............................................................................................................................... 55
Table 2-5: Overview of the thermochemical conversion technologies (Bridgwater, 1994; Demirbaş,
2001; Goyal, 2008, Zeevalkink, 2005) ................................................................................................... 57
Table 2-6: Overview of the liquid products obtained via thermochemical conversion technologies
(Bridgwater, 2003; Czernik, 2004; Czernik and Bridgwater, 2004; De Klerk, 2007; Elliott and
Schiefelbein, 1989; Mohan et al., 2006; Schaub, 2005) ........................................................................ 58
Table 2-7: Overview of the main thermocatalytic conversion processes (16th Biomass Conference,
2008; Adam et al., 2006; Aho et al., 2008; Antonakou et al., 2006a; Antonakou et al., 2006b;
Bridgwater, 1994; Davda et al., 2005; Gayubo et al., 2005; Koch, 2005; Mahfud et al., 2007; Pindoria et
al., 1998; Pütün et al., 2006; Spath and Dayton, 2003; Triantafyllidis et al., 2007; Vitolo et al., 1999;
Williams and Nugranad, 2000) .............................................................................................................. 59
Table 3-1: Physicochemical properties overview of the selected solid biogenic materials ................... 70
Table 3-2: Physicochemical properties overview of the safflower oil.................................................... 71
Table 3-3: Physicochemical properties of the zeolites used for the KNV experiments (Süd-Chemie,
2006)...................................................................................................................................................... 72
Table 3-4: Performed tests overview of the rapeseed cake and safflower oil co-conversion............... 73
Table 3-5: Organic phase characteristics of the rapeseed cake and safflower oil co-conversion tests
............................................................................................................................................................... 77
Tables 20
Table 3-6: Aqueous phase characteristics of the rapeseed cake and safflower oil co-conversion tests
............................................................................................................................................................... 77
Table 3-7: Residue characteristics of the rapeseed cake and safflower oil co-conversion tests.......... 78
Table 3-8: Performed tests overview of the rapeseed cake conversion using two reactor configurations
............................................................................................................................................................... 80
Table 3-9: Organic phase characteristics of the rapeseed cake conversion tests using two reactor
configurations ........................................................................................................................................ 84
Table 3-10: Aqueous phase characteristics of the rapeseed cake conversion tests using two reactor
configurations ........................................................................................................................................ 84
Table 3-11: Performed tests overview of the separate meat meal C1 and algae conversion (with
different reactor configurations)............................................................................................................. 89
Table 3-12: Organic phase characteristics of the separate meat meal C1 and algae conversion tests
............................................................................................................................................................... 92
Table 3-13: Aqueous phase characteristics of the separate meat meal C1 and algae conversion tests
............................................................................................................................................................... 92
Table 3-14: Energy consumption and products energy content of the selected performed tests....... 107
Table 3-15: Energy efficiencies of the selected performed tests ........................................................ 107
Table 4-1: Estimated parameters of the algae pre-treatment process ............................................... 114
Table 4-2: Estimated parameters of the catalyst pre-treatment process ............................................ 115
Table 4-3: Estimated parameters of the conversion process ............................................................. 116
Table 4-4: Estimated parameters of the regeneration process........................................................... 117
Table 4-5: Necessary equipment and their characteristics for the Design Layout A .......................... 121
Table 4-6: Necessary equipment and their characteristics for the Design Layout B .......................... 123
Table 4-7: Equipment purchasing cost for the Design Layout A and B .............................................. 125
Table 4-8: Basic cost factors of the fixed investment and their coefficients over the equipment
purchasing cost (Lipowatz-Kremezi, 2003).......................................................................................... 127
Tables 21
Table 4-9: Breakdown of the total production cost (Lipowatz-Kremezi, 2003).................................... 129
Table 4-10: Time-plan for the KNV pilot plant and predicted demand for employees ........................ 131
Table 4-11: Total labour cost calculation ............................................................................................ 132
Table 4-12: Energy cost calculation .................................................................................................... 133
Table 4-13: Analytical cost of the auxiliary materials .......................................................................... 133
Table 4-14: Basic factors of the production cost and their coefficients (Lipowatz-Kremezi, 2003)..... 134
Table 4-15: Sale price of the KNV products........................................................................................ 135
Table 4-16: Money flows and net cash flows for the Design Layout A and B ..................................... 135
Table 4-17: Total return of investment periods for the Design Layouts A and B ................................ 136
Table 8-1: Biomass database ............................................................................................................. 151
Table 8-2: Product yields (wt. % on biogenic mixture) of the performed rapeseed cake and safflower
oil co-conversion tests ......................................................................................................................... 157
Table 8-3: Product yields (wt. % on biogenic mixture) of the performed rapeseed cake conversion
tests using two reactor configurations ................................................................................................. 157
Table 8-4: Product yields (wt. % on biogenic mixture) of the performed separate meat meal C1 and
algae conversion tests ......................................................................................................................... 157
Table 8-5: Organic phase detailed composition of the performed rapeseed cake and safflower oil co-
conversion tests................................................................................................................................... 158
Table 8-6: Aqueous phase detailed composition of the performed rapeseed cake and safflower oil co-
conversion tests................................................................................................................................... 159
Table 8-7: Organic phase detailed composition of the rapeseed cake conversion tests using two
reactor configurations .......................................................................................................................... 160
Table 8-8: Aqueous phase detailed composition of the rapeseed cake conversion tests using two
reactor configurations .......................................................................................................................... 161
Table 8-9: Organic phase detailed composition of the separate meat meal C1 and algae conversion
tests ..................................................................................................................................................... 162
Tables 22
Table 8-10: Aqueous phase detailed composition of the separate meat meal C1 and algae conversion
tests ..................................................................................................................................................... 163
Table 8-11: The heating value prediction model by Boie .................................................................... 163
Chapter 1: Introduction 23
1 INTRODUCTION
1.1 BIOFUELS OVERVIEW
1.1.1 THE ENERGY SECTOR TODAY
For the past decades the energy sector has been facing some major problems.
During the period 2001-2005 the oil dollar price tripled. Although the exchange rate
movements cushioned the effect, Europe saw oil prices more than double. Over the next
twenty to thirty years, the European Union (EU) fossil oil production is expected to decline,
while the transport demand is likely to continue to grow. The world oil demand is also
expected to show strong growth. The global distribution of the known fossil oil reserves will
leave the Middle East Organization of Petroleum Exporting Countries (OPEC) members, as
the main suppliers for this increased demand, although the accelerated exploitation of
Canadian and Venezuelan tar sands could provide up to 3% of the world fossil oil production
by 2010 (Commission of the European Communities, 2006a).
The still available crude oil resources amount cannot be easily estimated, but it is believed to
be gradually decreasing. Countries have been seeking to their energy independence for
economic and political reasons. The environmental effect of the greenhouse gases is
profound today, due to the presence of the extreme meteorological phenomena that take
place around the globe.
In EU-27, almost 1/3 of the final energy was consumed in the transportation sector in the
year 2005 (Directorate General for Energy and Transport, 2008).
Because of its almost complete dependency on fossil oil, transportation accounts for more
than half the fossil oil used in the EU and this share is increasing. The growing demand in
the transportation sector is the main reason for the growth in the overall EU oil consumption
(Commission of the European Communities, 2006a).
In EU-27, transportation was responsible for an estimated 23.4% of all greenhouse gas
emissions that are contributing to global warming. Between 1990 and 2003, when
greenhouse gas emissions in the EU saw an overall reduction, the transportation share grew
by about 24%. The reduction of the greenhouse gas emissions from transportation,
therefore, could contribute significantly to meeting the EU Kyoto targets (Commission of the
European Communities, 2006a).
Plants are abundant biogenic resources that use light, nutrients and CO2 for their growth and
multiplication. Their exploitation for the production of biofuels would have as a result the
creation of a carbon cycle, where the produced CO2 emissions would be re-captured and be
used for the growth of new plants. The emissions level could be initially stabilized, while CO2
mitigation could be finally achieved.
Apart from fossil based liquified petroleum gas (LPG) and compressed natural gas (CNG),
liquid biofuels are currently one of the few possible substitutes for fossil oil based
transportation fuel. They can easily be put on the market now and provide immediate
greenhouse gas reductions. In contrast to fossil oil reserves, which are concentrated in a
relatively small number of geographical regions, the raw material for biofuels can be
produced nearly anywhere on earth. Thus, increasing the share of biofuels in EU
transportation fuels could help to broaden the range of the EU energy suppliers
(Commission of the European Communities, 2006a).
In the EU transportation sector, fossil oil is the main energy source with a 98% contribution
to all transportation fuels. In 2002, alternative motor fuels contributed 2% and biofuels only
0.3%. However, during the last years the contribution of biofuels has increased due to the
implementation of the biofuels directive in several Member States (Commission of the
European Communities, 2006a).
1.1.2 BIOFUEL GENERATIONS
Biofuels can be classified according to the feedstock used during their production process.
The following Table presents the different biofuel generations and the main biofuel types
produced:
Table 1-1: Biofuel classification into generations according to the used biogenic feedstock
st
The 1 generation biofuels have been exploiting feedstocks which are edible for humans,
containing oils, fats, starch and sugar. The most widely produced biofuels of this generation
are bioethanol and biodiesel. They have been used as transportation fuels either alone or in
blends with conventional fuels. Several bioethanol and biodiesel commercial production
plants have been operating around the world. The EU has supported the scientific research
in this area and the penetration of these fuels into the market. Still, the use of these
feedstocks have deprived humans of materials with high nutrient value, bringing up
economic and moral issues on the biofuel market.
The idea of producing biofuels from lignocellulosic materials appeared to provide a solution
to the mentioned problem. As a result, the 2nd generation biofuels emerged. Due to the more
complex chemical structure of these feedstocks, different conversion processes had to be
developed. Increased scientific research, with the support of the EU, has managed to
develop new processes for the conversion of lignocellulosic materials into biofuels that could
be used in engines, turbines or boilers. These conversion processes are still facing some
challenges. Therefore the penetration of the 2nd generation biofuels into the fuel market is
limited for the moment.
Studies on biofuel strategies have shown that the key factors for the establishment of a bio-
based energy economy is (a) the availability of arable land for biomass cultivation and (b) the
rd
productivity rates of different biomass types. The 3 generation biofuels emerged by the
idea to use algae as feedstock, since they demonstrate high productivity rates and no
demand in arable land for their cultivation. On a more general approach, the 3rd generation
biofuels were defined by the use of specially designed/engineered energy crops that would
allow an improved conversion. With the help of biotechnology, plant characteristics could be
altered in a positive way, so that plants with e.g. higher oil/sugar/starch content, lower lignin
content, ability to grow on acidic soil or higher productivity could be produced. In this case,
the produced biofuel types would again be bioethanol, biodiesel, synthetic fuels, pyrolysis
bio-oils, e.t.c. This generation is in the early stages of development and mainly uses the 2nd
generation conversion techniques.
th
Finally, the new idea of developing the 4 generation biofuels has started to grow. As
feedstock, tailor-made plants will be used with enhanced carbon storage ability. This carbon-
nd
rich biomass would then be converted to biofuel using the 2 generation conversion
technologies. The produced emissions from the conversion process will be captured and
then geo-sequestered in suitable fields, where they could be stored for hundreds or
thousands of years. It is soon to predict how this biofuel generation will evolve, but it has
already found supporters from the scientific community.
1.1.3 RECENT BIOFUEL PRODUCTION
The EU produced an estimated 768 million gallons of biofuel in 2004 compared with the US
(United States) biofuel production of 3.4 billion gallons (mostly ethanol). Biodiesel accounted
for nearly 80% of the EU biofuel production. Germany produced over half of the EU
biodiesel. France and Italy are also important biodiesel producers, while Spain is the EU
leading bioethanol producer (Schnepf, 2006).
Tons of Oil Equivalent
Figure 1-1. Biofuel production in EU since 1993 (2004: EU-25) (Biofuels Research
Advisory Council)
The supply of feedstocks is crucial to the success of the EU biofuel strategy, because they
represent the primary cost component in the biofuel production process. The major
feedstock for the EU biodiesel production has been the rapeseed oil, although almost any
vegetable oil or animal fat (including restaurant deep-fry grease) is viable. In 2004, the EU
biodiesel production used about 4.1 million metric tons (MMT) of rapeseed. In 2004, the EU
harvested oilseeds area was estimated 7.5 million hectares (MHA), out of which 60% was
rapeseed, 29% sunflowerseed and 4% soybeans (Schnepf, 2006).
The EU bioethanol is generally produced using a combination of sugar beets and wheat. In
2004, the EU bioethanol production used 1.2 MMT of cereals out of the total EU production
of over 289 MMT of grains and 1 MMT of sugar beets out of 123.5 MMT of the sugar beet
production. In the long run, abundant domestic supplies and production potential for cereals
and sugar beets suggest that bioethanol production likely has greater potential in the EU
than biodiesel does. However, high-production costs of the EU-produced biofuels (primarily
due to high-priced internal feedstocks) in comparison with the fossil fuels remain a major
impediment to the market-based expansion of the EU biofuel production, particularly for
bioethanol. According to the European Commission (EC), the EU-produced biodiesel breaks
even at oil prices of around 60€ ($71.60) per barrel, while bioethanol becomes competitive
with oil prices of about 90€ ($107.37) per barrel. During February 2006, a barrel of oil —
Europe Brent spot price FOB — was quoted at $60.73 per barrel (Schnepf, 2006).
Looking beyond 2010, biofuels could play a more significant role if: (a) oil prices further
increase, (b) agricultural policies reform, (c) new technological breakthroughs take place and
(d) imports from third countries are challenged (Commission of the European Communities,
2006b).
1.1.4 BIOFUEL PRODUCTION TARGETS
The Biofuels Directive has set as “reference value” targets a 2% market share for biofuels in
2005 and a 5.75% share in 2010. For the EU-25, the target would require 18.6 million tons of
oil equivalent (mtoe) of biofuels by 2010 (Commission of the European Communities,
2006b).
The EU-15 Member States are committed to a combined 8% reduction of greenhouse gas
emissions by 2008–12 under the Kyoto Protocol and most new Member States have
individual targets (Commission of the European Communities, 2006a).
The EU Action Plan on energy, adopted by the EU leaders in March 2007, sets out concrete
actions to achieve competitive, sustainable and secure energy system coupled with a major
reduction in greenhouse gas emissions by 2020 (Directorate General for the Environment,
2008). They include:
− cutting energy consumption by 20% compared with business as usual levels through a
major improvement in the energy efficiency of a wide range of appliances and equipment
− reducing greenhouse gas emissions by at least 20% (compared with the 1990 levels) by
2020
− increasing renewable energy sources share of energy consumption to 20% from around
7% in 2007
− raising biofuels share of petrol and diesel to 10% from around just 1% in 2007
− adopting a policy framework to ensure and promote environmentally safe use of carbon
capture and geological storage (CCS) technology. The aim is to deploy the CCS
technology in new fossil-fuel power plants, if possibly by 2020.
1.2 BIOFUEL INCENTIVES
The EC is using both legislation and formal directives to promote biofuel production and use
within the EU (Schnepf, 2006):
1) EU Common Agricultural Policy (CAP)
The EU crop production patterns have been heavily influenced by the CAP, with its high
support prices, planting restrictions, intervention buying, stock management and rigid border
controls. Presently, the CAP includes rules on agricultural land use as well as a special
payment for the production of crops dedicated to biofuels.
2) Blair House Restrictions
The 1992 Blair House Memorandum of Understanding (Blair House Agreement) between the
United States and the EU helped to resolve a mutual dispute over the EU domestic support
programs that impaired the US access to the EU oilseed markets and thus facilitated the
completion of the Uruguay Round Agreement for agriculture. Specifically, the Blair House
Agreement limits the amount of the EU oilseed production for food on non-set-aside land
and for non-food (i.e. industrial or energy) purposes on set-aside land. The set-aside-based
oilseed production is restricted to roughly 0.7 MHA. However, the EC believes that, pursuant
to CAP reforms undertaken in 2003, it is no longer subject to the Blair House limitations on
oilseed production. In 2005, rapeseed production intended for use as biodiesel feedstock
was grown on 1.8 MHA including 0.9 MHA of the set-aside.
3) CAP Land Use Rules
Under the CAP, EU farmers are required to set aside 10% of their land to qualify for other
CAP benefits. Participating farmers receive a set-aside compensation payment. In addition,
EU farmers are allowed to plant oilseeds on the set-aside land (subject to Blair House
Agreement limitations) as long as it is contracted solely for the production of biodiesel or
other industrial products and not sold into either food or feed markets.
4) Energy Crop Payments
In 2003, a new round of CAP reforms established a special aid for energy crops grown on
non-set-aside land. Energy crops — those grown for the production of biofuels or for use as
biomass in the production of electric and thermal energy — were eligible for a premium of
45€ per hectare. To establish a budgetary ceiling on such outlays, the energy payments
were to be restricted to a maximum guaranteed area of 1.5 MHA. If fully implemented on 1.5
MHA, the program would cost 67.5 million. In 2005, an estimated 0.5 MHA received the
energy crop payment.
5) Sugar Sector Reform
On February 20 2006, the EU adopted significant reform measures for its sugar sector,
including a 36% cut in the internal sugar support price, elimination of the intervention system
of sugar purchases and partial sugar production quota buyback. The sugar reforms could
impact biofuel feedstock availability, since they substantially reduce internal sugar beet
production incentives. However, much of the potential decline in sugar production could be
offset by a drop in EU sugar exports, which are restricted to not more than 1.273 MMT
annually (compared with an estimated 7.1 MMT in 2005/06). In addition, two reform
provisions are likely to impact positively the availability of sugar beets as a biofuel feedstock.
First, sugar beet production now qualifies for both set-aside payments when grown as a non-
food crop and for the energy crop aid of 45€ per hectare on non-set-aside area. Second,
sugar used for the production of bioethanol will be excluded from sugar production quotas.
Despite the reforms, the EU internal sugar prices are expected to remain substantially above
international market prices; thus preserving it as an expensive feedstock.
6) EC Directives
In the recent years, the EC has attempted to focus increasing attention on the development
of the EU biofuels sector. Three principal legislative directives, governing biofuels use,
taxation and quality, have been issued recently by the EC to guide Member State
agriculture-based renewable energy production.
7) Biofuels Use Directive
As already stated before, the EC established a goal of deriving at least 2% of EU

transportation fuel from biofuels by the end of 2005, then growing the biofuels share by
0.75% annually until December 31 2010, when it would reach 5.75%. However, the biofuels
goal is not mandatory and individual Member States are free to establish higher standards.
As a result, the degree of participation varies substantially across the EU Member States.
Because the targets are not mandatory, no penalty for non-compliance is involved. However,
Member States are expected to report annually those measures undertaken to aid
compliance on the sales of both total transportation fuel and the share of biofuels. Despite
various State and EU-wide policies designed to support biofuels production, the EU biofuels
goal of 2% by 2005 was not achieved. Instead, it appears that biofuels attained a EU-wide
share of only about 1.4% of transport fuels.
8) Energy Taxation Directive
In 2003, the EU framework for the taxation of energy products and electricity was amended
to allow Member States to grant tax reductions and/or exemptions in favor of renewable
fuels under certain conditions. These tax concessions are considered as state aids, which
may not be implemented without prior authorisation by the Commission. The Commission
assessment has the aim of avoiding undue distortions of competition and is based on the
Community guidelines on state aid for environmental protection. (Commission of the
European Communities, 2006b). To minimize the tax revenue loss for Member States, the
final tax on biofuels intended for transport use may not be less than 50% of the normal
excise duty.
9) Fuel Quality Directive
In 2003, the EU environmental specifications for market fuels were amended to establish
specifications for petrol and diesel. The new specifications encompassed the incorporation
of biofuels. The European Committee for Standardization (CEN) has set limits on biodiesel
blending to no more than a 5% share by volume (or 4.6% in energy terms) for technical
reasons. As a result, this appears to be an issue that the EC will need to resolve to achieve
its goal of a 5.75% share of transportation fuel by 2010.
Present actions at European level (ERA-NET) in the field of biomass cultivation and
utilization aim to further increase the cost-effectiveness of R&D funding through programme
coordination and the initiation of joint activities at national and regional level (Commission of
the European Communities, 2006b).
The proposal for the Seventh Framework Programme (2007–2013) gives priority to biofuel
research to further strengthen the competitiveness of the EU biofuel industry. In the
Cooperation Specific Programme research activities will concentrate mainly on two themes
(i) “Energy”, aiming at bringing down the unit cost of fuels by improving conventional
technologies and developing second-generation biofuels (e.g. Fischer-Tropsch biodiesel,
lignocellulosic ethanol, bio-dimethylether) and (ii) “Food, agriculture and biotechnology”,
applying life sciences and biotechnology to improving biomass production systems. The
concept of biorefineries, aiming at the integral use of the biomass and maximising the cost
effectiveness of the final products, will be a key focus in both themes (Commission of the
European Communities, 2006b).
1.3 EU VISION FOR BIOFUELS
Looking at the near future (2010), a regulated market-based approach that encourages the
development of the EU’s domestic biofuel industry in a balance with imports would bring an
average cost of € 6 billion per year in order to meet the indicative target of the Biofuels
Directive. Relating this to the gross diesel and gasoline consumption in the EU-25 (334
billion litres in 2002), it corresponds to an average increase of the transportation fuel cost of
1.2 to 2.5 euro cents per litre in order to finance the additional biofuel use targeted for 2010.
The uncertain development of oil prices and the cost of biofuel production make it difficult to
quantify the cost to society of reaching the vision for 2030. Preliminary estimates, based on
2005 market prices, suggest that 25% biofuels in road transportation in 2030 could cost an
excess of € 31 billion per year, equivalent to an additional 6.6 euro cents per litre of gasoline
and 8.2 euro cents per litre of diesel.
In this context, the cost of increased biofuel use to society has to be weighed against the
monetary value of the benefits, such as reduced greenhouse gas emissions, diversification
of our energy mix, enhanced security of supply and job creation in rural areas. A
forwardlooking biofuel strategy with a strong focus on research, development and innovation
should be part of a consistent set of research and energy policies which have as their goal a
cleaner and sustainable energy future.
Large-scale deployment of biofuels can be expected by 2020-2030. It is nevertheless

necessary to identify the intermediate steps and the likely timeline for the development of the
new options required for a strong biofuels industry and a significant biofuel use in Europe
(Biofuels Research Advisory Council).
Figure 1-2. Anticipated future roadmap (Biofuels Research Advisory Council)
Liquid biofuels, which are compatible with the current technology, offer the highest potential
for the fast introduction of biofuels on a large scale. The preference for liquid fuels from
biomass does, however, not mean that there is no place for gaseous fuels in this strategy
(Biofuels Research Advisory Council).
Chapter 2: Biofuel Production – State of the Art 35
2 BIOFUEL PRODUCTION – STATE OF THE ART
2.1 BIOGENIC RESOURCES
2.1.1 BIOMASS CLASSIFICATION
The biogenic materials classification is a complicated task due to their variety of physical
characteristics, chemical characteristics and uses.
The following Table gives a biomass resources overview according to their sector of
appearance (e.g. forestry, industry) and their type (e.g. raw material, waste):
Table 2-1: Biogenic materials classification
2.1.2 BIOMASS PHYSICOCHEMICAL COMPOSITION
The physicochemical composition of different biogenic materials may indicate their suitability
as feedstocks for different conversion processes. The biogenic materials can be categorized
into the following clusters: untreated wood, treated wood, grass/plant, straw (including stalks,
cobs, ears), husk/shell/peat, organic residue/product, algae, manure and sludge. A database
with information on their ultimate analysis, biochemical composition, ash content, water
content, higher and lower heating value is presented in the Annex (IEF Joanneum Research;
KF-Uni Graz; Phyllis Biomass Database).
2.1.3 BIOMASS AVAILABILITY
The official data concerning the biomass availability and prices in the EU are limited.
Literature references indicated that in 2006, the EU felling residues were estimated to be
173 Mm3 annually, out of which 63 Mm3 could be technically available for further use. In
addition, 9 Mm3 stumps could be collected out of 78 Mm3 in total. Assuming that 25% of the
excess growth in commercial forests could be cut for energy use, a total wood-for-energy of
140 Mm3 annually could be estimated. These figures include the current use, but do not
include traditional firewood or industrial/secondary wood (EU Experts Workshop, 2006).
In 2006, the harvested roundwood was more costly, but it typically worth 30 € / m3 versus 10
3
€ / m , which was the price for energy wood (EU Experts Workshop, 2006).
3
In 2005, the removal of coniferous roundwood species in EU-25 was 317022 Mm , while the
3
removal of non-coniferous roundwood species was 108671 Mm (Eurostat, 2007).
In 2003, the actual wheat & barley production in EU was 1000 tonnes/region, the straw
production was also 1000 tonnes/region, while the ratio of straw/grain varied from 0.62 to
0.94 (EU Experts Workshop, 2006).
In 2007, the annual selling prices of agricultural products (absolute prices) in EU-27 was in
the range of 15.3-23.5 € / 100 kg of soft wheat, 20.3-33.2 € /100 kg of rape and 22.3-42.0 €
/100 kg of sugar beet (Eurostat, 2008).
In 2007, the total harvested production in EU-27 was 260302 kt of cereals (including rice),
114810 kt of sugar beet, 18128 kt of rapeseed and 4783 kt of sunflower. The harvested
production of the most important cereals was 120253 kt for wheat, 57871 kt for barley,
47532 kt for grain maize, 7992 kt for rye/meslin and 2723 kt for rice (Eurostat, 2008).
2.2 BIOMASS CONVERSION TECHNOLOGIES
Different pathways exist for the conversion of different biomass types. The following graph
presents the main biomass conversion processes (thermochemical, biochemical and
physichemical), their required level of temperature (high, medium, low) and their products:
Figure 2-1. The main biomass conversion pathways
The physichemical biomass conversion consists of processes that focus on the utilization of
oils/fats for the 1st generation biofuels production (e.g. biodiesel). The biochemical biomass
conversion consists of a cluster of processes that use the nature’s media (e.g. enzymes and
microorganisms) for the biogenic feedstocks transformation into the 1st and 2nd generation
biofuels (e.g. ethanol and butanol). It is not within the scope of the present work to focus on
these processes, since they represent a different aspect of the biofuel production in terms of
raw materials and auxiliary media. The thermochemical processes can use a wide variety of
nd rd
raw materials for the production of 2 and 3 generation biofuels with valuable
characteristics.
Gasification, pyrolysis and liquefaction are the three main processes included in the
thermochemical biomass conversion. The main characteristics of these processes are
summarized in the sections below.
2.2.1 GASIFICATION
2.2.1.1 DESCRIPTION
This process requires a high temperature level (>800 °C): therefore in order to increase its
energy efficiency it is not typically designed as a stand-alone process in commercial
applications. Research efforts have been employed in order to develop efficient, low cost
and reliable gasification systems as well as to design their commercialization, particularly for
power generation (Sharma, 2009). Due to the high operating costs, gasification has been
facing economic challenges regarding its upscaling to commercial applications (Lappas,
2008). Its main product is syngas (CO2, H2), which can be used as a gas fuel. Alternatively, it
can be converted into a liquid fuel in a subsequent step, by the Fischer-Tropsch technology
(Bridgwater, 1994). The Fischer-Tropsch process advantage is that it produces liquid
hydrocarbons, which can be used as a transportation fuel. Still, the gasification high
temperature demand and the two-step conversion process requirement for the liquid biofuel
production are factors that lower the mass and energy efficiency of this technology.
2.2.1.2 REACTOR TYPES
Gasifiers are classified according to the way the gasification agent is introduced. There are
three main gasifier types: the updraft, the downdraft and the crossdraft. The choice of one
gasifier type over the other is dictated by the used fuel, its available form, its size, its
moisture content as well as its ash content (Yogi Goswami, 1986). Apart from the three main
gasifier types, additional ones have been developed. Much experimental work has been
done on the fluidized bed biomass gasification using different gasification agents (e.g. air,
pure steam, oxygen/steam and air/steam) (Campoy et al., 2009). Entrained flow gasifiers
have also been developed. In this case, a pulverised solid fuel is mixed with a steam/oxygen
stream and is converted under a turbulent dust flame at high temperatures (>1200 °C) in a
very short time (few seconds) (Henrich and Weirich, 2002). Cyclone gasifiers are a type of
entrained flow reactors, used both as gas cleaners and gasifiers. An overview of the
gasification reactor types is depicted below:
Table 2-2: Overview of the gasification reactor types (FAO, 1986; Henrich and Weirich, 2002; National Renewable Energy Laboratory; Miccio
et al., 2009; Yogi Goswami, 1986; Suna et al., 2009)
Presently most of the existing biomass gasification technologies can not completely satisfy
the industrial application requirements, because of their structural characteristics and the
operational conditions (Suna et al., 2009). Therefore, further research is needed.
2.2.1.3 REACTION MECHANISMS
If the complex biomass material must be reduced to a simplified chemical formula, with very
small amounts of sulfur and nitrogen that are not considered in terms of overall chemistry,
then this formula would be: CH1.4O0.6.
Oxygen-blown gasification can be considered to be an incomplete combustion or partial

oxidation. Gasification using a minimum amount of oxygen can be described by the following
reaction:
CH1.4O0.6 + 0.2 O2 → CO + 0.7 H2
In cases where no oxygen is used, the gasification reaction can be described by the
following reaction:
CH1.4O0.6 → 0.6 CO + 0.4 C + 0.7 H2
This reaction is endothermic and heat is needed for its initialization. The heat is provided by
the oxidation reactions shown above or by indirect heat transfer. Although these ideal
reactions are simple, the actual gasification is more complex. Intermediate compounds, such
as benzene, tars, methane and other light hydrocarbons are formed, that must be further
processed if the syngas is to be used in high efficiency power applications or biofuel
production processes (National Renewable Energy Laboratory).
The water gas shift reaction is a reaction that results in the formation of unwanted CO2, but it
can be used to shift the H2:CO ratio of the incoming syngas:
H2O + CO → H2 + CO2
The Fischer–Tropsch process involves a variety of competing chemical reactions, which lead
to a series of desirable products and by-products. The most important reactions are those
resulting in the formation of alkanes. These can be described by chemical equations of the
following form:
(2n+1) H2 + n CO → CnH(2n+2) + n H2O

The simplest of these (n=1) results in the formation of methane, which is generally
considered an undesirable by-product (particularly when methane is the primary feedstock
used for the syngas production). Process conditions and catalyst composition are usually
chosen to favor higher order reactions (n>1) and thus minimize methane formation. Most of
the alkanes produced tend to be straight-chained, although some branched alkanes are also
formed. In addition to the alkane formation, competing reactions result in the formation of
alkenes as well as alcohols and other oxygenated hydrocarbons.
2.2.1.4 MASS AND ENERGY EFFICIENCY
The gasification energy efficiency can vary according to the used feedstock and the process
characteristics. Assuming optimum conditions, the energy efficiency from wood (with 35%
moisture) to 40 bar syngas (with H2/CO equal to 2) is 81%, calculated based on the Lower
Heating Values (LHVs). If the net electricity production is included (calculated to the primary
energy with 40% efficiency), the overall efficiency is 84%. Alternatively, two options can be
selected to pre-treat biomass before gasification: (a) torrefaction to produce torrefied wood
or (b) fast pyrolysis to produce oil/charvslurry respectively. These combined systems show
lower energy efficiency (overall efficiency is approximately 75%), higher investment costs
and more complexity, but pressurizing and feeding systems become conventional compared
with those of sole gasification (Van der Drift et al., 2004). Efforts should be focused on
minimizing the clean syngas production cost (Spath and Dayton, 2003).
Fischer-Tropsch plants exist in South Africa, Malaysia, New Zealand (Spath and Dayton,
2003) and Germany (Choren, 2008). Shell has been financing the research work of the
company Choren on the Gasification / Fischer-Tropsch combined process. Choren has been
building the world’s first commercial plant in Freiberg, Saxony. The biomass to liquid fuel
(SunDiesel) efficiency of this developed process is reported to be ~20% (Choren, 2008).
2.2.2 PYROLYSIS
2.2.2.1 DESCRIPTION
There are different versions of this process, depending on the used operational parameters:
(1) slow pyrolysis, (2) conventional pyrolysis, (3) flash pyrolysis and (4) fast pyrolysis.
Specific interest is focused on the flash pyrolysis, which can maximize the liquid product
yield (70% wt.). Another pyrolysis version is the vacuum flash pyrolysis: in this case,
conversion is performed under vacuum to limit the secondary decomposition reactions;

therefore, a high oil yield and a low gas yield is accomplished (Zeevalkink, 2005). The
pyrolysis liquids are non-thermodynamically controlled products and optimal residence times
and temperatures are necessary to freeze the desired intermediates. The pyrolysis liquid
(bio-oil) has a high oxygen content, which makes it less attractive as a liquid fuel. This high
oxygen content is responsible for its unusual characteristics, such as water miscibility and
temperature sensitivity. Bio-oil can be used in motors and turbines, while its use as a
transportation fuel requires further upgrading to improve its fuel properties (Huber and
Corma, 2007). Currently, there are two different upgrading methodologies: (a) the modified
conventional bio-oil hydrotreating to a naphtha-like product that can be characterized as
CH2, or (b) the bio-oil zeolite cracking and the highly aromatic product synthesis, which can
be characterized as CH1.2 (Bridgwater, 1994).
At the heart of the fast pyrolysis process is the reactor. Although it probably represents at
most only about 10-15% of the total capital cost of an integrated system, most research and
development projects have focused on the reactor. Increased attention is now being paid to
the liquid quality control and improvement as well as the collection systems improvement.
The rest of the process consists of the biomass reception, storage and handling, the
biomass drying and grinding, the product collection and storage as well as, when relevant,
the liquid upgrading (Bridgwater, 2006).
Different types of pyrolysis reactors exist apart from the simple fixed bed reactor. Bubbling
fluid bed reactors are fluidized bed reactors. Their difference with the circulating fluid bed
reactors is that the char residence time of the latter is almost the same as for vapours and
gases and the char is more attrited, due to higher carrier gas velocities. The ablative
pyrolysis is substantially different in concept from the other fast pyrolysis methods. In all the
other methods, the reaction rate is limited by the heat transfer rate through the biomass
particles, which is why small particles are required. In ablative pyrolysis, heat is transferred
from the hot reactor wall to “melt” wood, that is in contact with it under pressure. The
reaction rate is strongly influenced by the pressure, the biomass relative viscosity and the
heat exchange surface as well as the reactor surface temperature. Entrained flow fast
pyrolysis is in principle a simple technology, but most developments have not been as
successful as had been hoped, mostly because of the poor heat transfer between the hot
gas and the solid particle (Bridgwater, 2006). Screw reactors have been recently developed
for the pyrolysis process. The screw can be single or twin. A fast twin screw flash pyrolysis
reactor has been developed. The objective was to produce a high yield of a transportable
bio-oil/char slurry for subsequent large scale gasification (Bridgwater, 2004). BTG has
developed a rotating cone biomass pyrolysis reactor. This reactor operates with
centrifugation principles and uses sand as an auxiliary medium. Centrifugation drives hot
sand and biomass up the rotating heated cone. Vapours are condensed, the char is burned
and hot sand is re-circulated (Czernik, 2004). A pyrolysis reactors overview is depicted
below:
Table 2-3: Overview of the pyrolysis reactor types (Adam et al., 2006; Antonakou et al.,
2006a; Bridgwater 2004; Bridgwater, 2006; BTG World, 2009; Czernik, 2004; Demiral and
ensöz, 2008; Gayubo et al., 2005; Mohan et al., 2006; Pütün et al., 2006; Vitolo et al.,
1999)
None of the reactor concepts described above, in their present state of development, fully
satisfy the requirements for a promising biofuel production methodology with a reasonably
trouble-free operation, scaling up potential and economically competitive performance
(Mohan et al., 2006). Further research will be necessary to optimize reactor types according
to the different application requirements.
Pure cellulose pyrolysis produces mainly levoglucosan, probably by a mechanism involving

intramolecular condensation and sequential depolymerization of the glycosidic units, as
shown in the following Figure (Huber et al., 2006):
Figure 2-2. Mechanism of cellulose degradation without alkali metals (Huber et al., 2006)
The biomass pyrolysis, at the medium temperature range of 250-700 °C, can produce a
liquid product with the following empirical formula (Bridgwater, 1994):
C6H12O6 → C6H8O4 + 2 H2O
Inorganic impurities present in the biomass play a key role in terms of the bio-oil product
selectivity. The addition of minor amounts of alkali (such as K, Li, Ca) to cellulose shifts the
mechanism (and the final product selectivity) so that glycolaldehyde is the stable reaction
intermediate instead of levoglucosan (Huber et al., 2006).
The exact mechanism where trace quantities of salts and metal ions influence the pyrolysis
course is not known, although a probable mechanism is shown in the following Figure.
Figure 2-3. Glucose degradation with alkali metal catalyzed or glycoside rupture pathways
(Huber et al., 2006)
The pyrolysis behavior of sugars is different than that of cellulose even though they have
similar chemical structures (Huber et al., 2006).
A possible mechanism for the thermal decomposition of soybean oil is shown in the following
Figure. The exact thermal decomposition mechanism is very complex, generating a wide
range of structures (Huber et al., 2006):
Figure 2-4. Mechanism of triglycerides pyrolysis (Huber et al., 2006)
The pyrolysis conversion mass balance is significantly affected by the operational

parameters used during the conversion. Slow pyrolysis favours the charcoal production at
the expense of gas and liquid. The maximum charcoal yield is ~30%. Conventional pyrolysis
produces approximately equal quantities of liquid, gas and charcoal. Flash pyrolysis
maximizes liquid yields (up to 70% wt.), while the fast pyrolysis maximizes gas yields (up to
80% wt.). The energy efficiency data collection of pyrolysis systems is challenging due to the
variety of raw materials and available technologies that result in different numbers. The
pyrolysis has a lower capital cost than liquefaction and many pyrolysis technologies are
currently being used commercially (Huber and Corma, 2007).
2.2.3 LIQUEFACTION
2.2.3.1 DESCRIPTION
This cluster contains a wide variety of processes. We could classify them in two general
categories: (1) the hydrothermal processes, when water is used as a liquid carrier for the
biomass conversion and (2) the solvolysis processes, when organic liquids are used as liquid
carriers (Bridgwater, 1994). High pressure is often applied in liquefaction processes to avoid
the evapouration of the liquid carrier. Therefore, the liquefaction processes

commercialization is quite challenging due to high investment costs (Bridgwater, 1994).
Often, liquefaction appears to produce a liquid product with a lower oxygen content (16%
wt.) than that of pyrolysis liquid (35-40% wt.) (Bridgwater, 1994).
Some characteristic liquefaction technologies are displayed below. All information

concerning the product quality and yields are based on the process developers statements:
HydroThermal Upgrading (HTU):
The HTU process is a hydrothermal liquefaction process that runs at 300-350 °C, at 120-200
bar, with 5-20 min residence time. Different types of dry or wet biomass can be used to
produce 45% wt. of biocrude. The thermal efficiency of the process (ηth = LHVbiocrude output /
(LHVof feed + LHVof used external fuel)) is reported to be ~75% (Naber and Goudriaan).
Aqueous Phase Dehydration/Hydrogenation (APD/H):
This catalytic process can be used to convert biomass-derived oxygenated hydrocarbons

into alkanes, at low temperatures (150-265 °C). Alk anes, ranging from C1 to C6, can be
produced by aqueous-phase dehydration/ hydrogenation (APD/H). Liquid alkanes, ranging
from C7 to C15, can be produced by combining the dehydration/hydrogenation process with
an upstream aldol condensation step to form C–C bonds. The dehydration/hydrogenation
step takes place over a bi-functional catalyst (4 wt.% Pt/SiO2–Al2O3) containing acid and
metal sites in a specially designed four-phase reactor. An aqueous inlet stream containing
the large water-soluble organic reactant, a hexadecane alkane sweep stream and a H2 inlet
gas stream is employed. The hexadecane sweep stream is used to remove the products
from the catalyst as valuable components before they go on further to form coke (Huber et
al., 2006).
NTK-Process (FH Gießen)
This process runs at atmospheric pressure, at a temperature level of 350-400 °C, in the
presence of catalysts and in the absence of oxygen. The process was developed to convert
sewage sludge and meat and bone meal. The products are claimed to be aliphatic
hydrocarbons (C5-C20), carbon residue with minerals, non condensable gases (C1-C4, CO2)
and reaction water with dissolved salts. The condensate is separated via centrifuge into
reaction water, organic liquid and powder (Let, 2007).
B/M-Process (Mueborit)
The main objective of this process was not to produce liquid fuels according to transportation
fuel standards, but to convert biomass into a liquid fuel that could be an alternative to
heating oil or that could be used as raw material for further synthesis. Lignin is converted
into soluble phenol derivatives, the molecular size of cellulose is reduced and the
lignocellulosic bonds are dissolved by using solvolysis. Lignocelluloses are decomposed in a
discontinuous agitating tub with 5 bar overpressure and a temperature below 200 °C in a
potassium carbonate hydrate molten bath. Organic compounds (density: ~1.5 kg/m³) can be
separated from the slurry phase by a column. The final product is a dark brown mixture of
various compounds. The highest energetic yield is in the range of 35-37 MJ/kg. The residual
slurry contains organic and polar substances and is used as a fuel to supply energy for the
process.
BFH-Process (BFH)
This process deals with the conversion of lignocellulosic feedstocks into liquid products by a
thermal pressurized treatment. Different reaction systems, retention times, temperature and
pressure ranges as well as solvents, catalysts and reducing gases were tested. In the most
promising version, the catalytic hydrogenolysis with the use of hydrogen, noble metal
catalyst and carrier oil was used. Within a semi-continuous reaction system of three
connected autoclaves, it is possible to convert wood (100% wt.) and hydrogen (4% wt.) into
36% wt. oil, 25% wt. aqueous phase, 5% wt. charcoal and 38% wt. gaseous products. The
C1-C4 fraction of the occurring gas phase (approx. 17% wt.) is partially treated via the water
gas shift reaction to gain the required hydrogen.
KDV-Process (Dr. Koch, Prof. Willner)
The KDV process (Katalytische Druklose Verölung) is a low pressure, medium temperature
catalytic process that claims to convert biogenic, crude oil-based and other carbonaceous
feedstocks as well as residues into liquid fuels in the range of diesel and gasoline. The
process runs at a temperature level of 290-370 °C a nd at atmospheric pressure or slight

vacuum. The used catalysts are Y-type zeolites (Alphakat, 2007).
The pre-treated feedstock is mixed with the liquid carrier and the catalyst in powder form.
The vapour products leave the reactor continuously and enter a hydrocyclone, where they
are separated from the solid particles. After leaving the cyclone, the gas phase passes a
water-cooled condenser, where the water is separated. Finally, the condensate is led into a
distillation column, where the remaining water is separated from the oil and different oil
fractions are collected. The remaining mixture of the liquid carrier and the solid particles is
heated and pressed, whereby a large part of liquid carrier can be recycled into the process.
The occurring vapours are also fed into the distillation column. The remaining paste is dried
and pressed into pellets, that have a higher energy content than wood chips pellets. The
partially recycled liquid carrier is mixed with new feedstock and enters the reactor again.
Within the existing Alphakat pilot plant set-up (capacity: 500 l/h), a combined heat and power
unit with 230 kW is included. It uses 10% of the produced fuel to provide the process with
electricity and thermal energy. Additionally, the non-condensable gases are mixed with the
combustion air (Behrendt, 2006). The liquid carrier provides a good heat transfer and a
homogenous feedstock heating. A petroleum-based oil (e.g. vacuum gasoil) was used as a
liquid carrier.
Unfortunately, there are no reliable data regarding the mass and energy balances or the
detailed product chemical composition. According to the developers, the biogenic feedstocks
usage leads to an energy efficiency of ~30% (on dry biomass weight) (Behrendt, 2006).
DoS-Process (Prof. Willner)
The DoS process (Direct liquefaction of organic Substances) is a thermochemical process

that converts organic substances into liquid fuels. The conversion takes place under
pressure (80 bar), in the presence of a hydrogen atmosphere and at a moderate
temperature range of 350-500 °C. The setup and syst em layout is similar to the KDV
process described above, but hydrogen is added into the system. In comparison to the KDV
process, the catalysts use is non-compulsory in the DoS process. The used feedstock within
this application is a lignin-rich biomass type, like wood, miscanthus or straw.
The dried and milled biomass is fed into the reactor by a screw conveyor. Within this kind of
extruder, the feedstock is pre-heated and mixed with recycled heavy bio-oil from the reactor.
Before the liquid products are distilled into diesel, gasoline and aqueous fractions, they are
separated from the solid particles and the other gaseous by-products. The heavy oil and
charcoal particles are recycled into the extruder. The other product gases can be used to
provide energy for the process. The solid residue is used together with the aqueous phase to
produce hydrogen, which is consumed within the process. This is accomplished via steam
gasification with a combined CO-conversion. In this way, it is possible to run the process
autarkic in terms of energy and hydrogen demand. The oil yield is ~33% (on dry biomass
weight), which leads to an energy efficiency of ~70%, considering an oil mixture LHV of 40
MJ/kg. In a laboratory scale, the produced charcoal is in a range of 10% wt. of the dry
biomass. It has been stated by the developer that the formation of charcoal can be almost
completely avoided within in a larger scale plant (Willner, 2005; Willner, 2007).
Due to the large variety of liquefaction systems and operational parameters, it is challenging
to make an overview of the used reactor configurations.
2.2.3.3 ORGANIC LIQUID CARRIER EFFECT
The organic liquid carrier used in liquefaction technologies can play a chemical role during
the biomass conversion, apart from its role as a heat transfer medium.
Biomass can be viewed as a hydrogen-deficient molecule when compared with petroleum-

based feedstocks. The maximum theoretical yield of the desired olefin or aromatics is a
function of the effective hydrogen-to-carbon ratio (H/Ceff) of the feed. The H/Ceff ratio is
defined as:
H/Ceff = (H-2O-3N-2S) / C
where H, C, O, N and S correspond to the moles of hydrogen, carbon, oxygen, nitrogen and
sulfur, respectively, that are present in the feed.
A decrease in the H/Ceff ratio of the feed results in a decrease in this yield (Huber and
Corma, 2007).
Decarbonylation and decarboxylation reactions are reactions that produce compounds with a
higher H/Ceff ratio. Aldehydes undergo decarbonylation reactions to produce CO and a
decarbonylated product that has an increased H/Ceff ratio. Acids can undergo
decarboxylation reactions to produce CO2 and a decarboxylated product that has an

increased H/Ceff ratio (Huber and Corma, 2007).
Hydrogenation, hydrogen transfer and decarbonylation are the key reactions that can enrich
the products H/Ceff ratio. Hydrogen transfer reactions occur in the fluid catalytic cracking
(FCC) of petroleum-derived feedstocks. The typical reaction involves a hydrogen donor (e.g.
a naphthene) and a hydrogen acceptor (e.g. an olefin). When only biomass-derived products
are fed into a FCC unit, another hydrogen source is required, if products with enriched H/Ceff
ratio are desired (Huber and Corma, 2007).
It has been reported that hydrogen could be transferred from petroleum feedstocks to
biomass feedstocks during the catalytic cracking of such mixtures (Huber and Corma, 2007).
Hydrogenation reactions usually occur on metal surfaces, where H2 is dissociated and then
undergoes reaction. Metal or metal impurities on a zeolite surface may dissociate H2, which
could then be used for hygrogenation reactions. Alkenes, aromatics, aldehydes and ketones
can be hydrogenated with acid catalysts (Huber and Corma, 2007).
It is also possible to achieve the multiple bonds reduction with the aid of an organic molecule
as the hydrogen donor in the presence of a catalyst. This process is known as catalytic
transfer hydrogenation. The choice of donor is generally determined by its ease of reaction
and availability. The chosen compounds can be hydroaromatics, unsaturated terpenes and
alcohols (Brieger and Nestrick, 1974).
The following Table lists most of the reported hydrogen donors and the used catalysts:
Table 2-4: (a) Hydrogen donor compounds and (b) catalysts used for transfer hydrogenation
(Brieger and Nestrick, 1974)
(a) (b)
The solvents effect on the course of the reaction has been studied in a limited number of
cases. Temperature appears to be a very critical parameter for the catalytic transfer
hydrogenation (Brieger and Nestrick, 1974).
A number of different catalysts have been used during the catalytic transfer hydrogenation
reactions. Comparing the effectiveness of various catalysts, clearly palladium is the most
effective. Under the standardized conditions where palladium is effective, neither platinum
nor rhodium catalysts work (at least at temperatures below 200 °C). The exceptional
palladium role in hydrogen transfer reactions appears to be due to its general mobilizing
action for hydrogen-carbon bonds. Commercially available catalysts are perfectly adequate
for transfer hydrogenation. Catalysts used for homogeneous hydrogenation have also been
used for transfer hydrogenation. Hydrogenolysis frequently accompanies the reduction of

multiple bonds (Brieger and Nestrick, 1974).
The dehydrogenated donors, such as benzene or naphthalene, cause no more problems

than their usual removal with an inert solvent (Brieger and Nestrick, 1974). In the case of the
biofuel production, the hydrogen donor should be of biogenic origin. Additionally, the
dehydrogenated donor should have a chemical composition with a high added value as a
biofuel component, if its removal is undesirable due to economic reasons.
Due to the fact that few publications have focused on the reaction mechanisms of biomass
liquefaction, it was possible to retrieve little information on this. The decomposition pathways
of cellulose and glucose in supercritical water is shown in the following Figure:
Figure 2-5. Cellulose decomposition pathways in supercritical water (Huber et al., 2006)
Hemicellulose undergoes analogous reaction pathways to those shown below (Huber et al.,
2006).
Any available data on the mass and energy efficiency of different liquefaction technologies
are already displayed during the technologies description(see section 2.2.3.1).
An overview of the thermochemical conversion technologies and their characteristic

parameters is depicted in the following Table:
Table 2-5: Overview of the thermochemical conversion technologies (Bridgwater, 1994;

Demirbaş, 2001; Goyal, 2008, Zeevalkink, 2005)
The overview of liquid products and their characteristic parameters obtained via
thermochemical conversion technologies is depicted in the following Table:
Table 2-6: Overview of the liquid products obtained via thermochemical conversion
technologies (Bridgwater, 2003; Czernik, 2004; Czernik and Bridgwater, 2004; De Klerk,
2007; Elliott and Schiefelbein, 1989; Mohan et al., 2006; Schaub, 2005)
2.2.4 CATALYSIS IN THERMOCHEMICAL CONVERSION PROCESSES
The aim of the catalysts use in biomass conversion is to enhance the produced liquids
quality, by lowering the energy barrier for reactions that can produce compounds with high
added value, such as fuels and chemicals.
Catalysts can either be added directly into the reactor for the biomass conversion or they
can be used to upgrade the liquid products. Research work on the catalysts use already
exists and is presently evolving for all thermochemical processes.
Materials that can be used as catalysts are either “natural catalysts”, already integrated into
the biomass feedstock in the form of inorganic components (e.g. K, Na), or “added
catalysts”, added externally into the reaction system. The catalytic material is solid in most
cases, but liquid catalysts could also be used. Solid catalysts can either be natural or
artificial.
An overview of the catalytic materials used in the main thermochemical processes is given
below:
Table 2-7: Overview of the main thermocatalytic conversion processes (16th Biomass
Conference, 2008; Adam et al., 2006; Aho et al., 2008; Antonakou et al., 2006a; Antonakou
et al., 2006b; Bridgwater, 1994; Davda et al., 2005; Gayubo et al., 2005; Koch, 2005;
Mahfud et al., 2007; Pindoria et al., 1998; Pütün et al., 2006; Spath and Dayton, 2003;
Triantafyllidis et al., 2007; Vitolo et al., 1999; Williams and Nugranad, 2000)
Further focus will be given on the catalysis mechanisms of pyrolysis and liquefaction
technologies.
2.2.4.1 CATALYTIC PYROLYSIS AND CATALYTIC LIQUEFACTION REACTION

MECHANISMS
Early zeolite cracking research on biomass derived pyrolysis liquid was carried out in
conventional mono-functional ZSM-5 catalyst (Bridgwater, 1994):
C6H8O4 → 4.6 CH1.2 + 1.4 CO2 + 1.2 H2O
One conjectural way of overcoming the hydrogen deficit is through the modification of the
catalyst to include a shift component, that can generate in-situ hydrogen from product gases
through the water-gas shift reaction. This might be carried out in a bi-functional or multi-
functional catalyst that can operate in a carbon limited environment rather than a hydrogen
limited one (Bridgwater, 1994):
3.6 CO + 3.6 H2O → 3.6 H2 + 3.6 CO2
C6H8O4 + 3.6 H2 → 6 CH1.2 + 4 H2O
Huber and Corma (2007) have suggested that the FCC conversion of oxygenates from
biomass-derived feedstocks mainly occurs through the following five reaction classes (as
described in the following Figure): 1) dehydration reactions, 2) cracking of large oxygenated
molecules to smaller molecules (not shown in the following Figure), 3) hydrogen producing
reactions, 4) hydrogen consuming reactions and 5) production of larger molecules by C-C
bond-forming reactions (such as aldol condensation or Diels– Alder).
Figure 2-6. Reaction pathways for the catalytic cracking of biomass-derived oxygenates.
Note: for dehydrogenation and decarbonylation reactions, the hydrogen can be produced by
hydrogen transfer to a hydrogen-deficient molecule (Huber and Corma, 2007)
In this process, H2 may be produced through steam-reforming, carbohydrates or

hydrocarbons dehydrogenation, water gas shift and decarbonylation of the partially
dehydrated biomass species. These reactions produce CO, CO2 and graphitic coke as well
as hydrogen. The hydrogen produced in these reactions may be consumed in reactions that
increase the products H/Ceff ratio and lead to olefins and alkanes. Hydrogen may be
exchanged directly through hydrogen transfer reactions between two
hydrocarbon/carbohydrates chains or through consecutive dehydrogenation/hydrogenation
processes. Hydrogen-transfer reactions occur on acid sites, while
dehydrogenation/hydrogenation reactions are greatly accelerated by the presence of a
metal. Aromatics are also produced during this process, possibly by Diels–Alder reactions of
partially dehydrated/hydrogenated species. To selectively produce olefins and aromatics, the
dehydration, the hydrogen-forming and the hydrogen-transfer reactions must be properly
balanced by choosing the proper catalysts and reaction conditions (Huber and Corma,
2007).
The reactivity and reaction pathways for some model bio-oil compounds using ZSM-5
catalysts has been studied:
Figure 2-7. The conversion of model bio-oil compounds with ZSM-5 (Huber and Corma,
2007)
These feeds have higher H/Ceff ratios than those of most bio-oils. Nevertheless, these
experiments do teach us some of the chemistry involved, since these molecules would be
important intermediates of the biomass conversion into olefins and aromatics. Different bio-
oils molecules display a significant difference in reactivity and coke formation rates.
Lignin, which consists of polyaromatic oxygenated compounds, is especially challenging to

catalytically convert as a result of its stable (non-reactive) aromatic structure. Phenols, which
have a chemical structure similar to lignin, produce large molecules of coke on ZSM-5
catalysts (Huber and Corma, 2007).
Vegetable oils catalytic cracking and pyrolysis can be used to produce liquid fuels that
contain linear and cyclic paraffins, olefins, aldehydes, ketones and carboxylic acids.
Vegetable oils catalytic cracking involves the vegetable oils pyrolysis in the presence of solid
catalysts that can improve the product yield. Mainly zeolite catalysts have been tested for
this reaction, including H-ZSM-5, Beta zeolite and USY. A reaction pathway for the catalytic
cracking of vegetable oils is shown in the following Figure:
Figure 2-8. Proposed reaction pathway for the cracking of vegetable oils with H-ZSM-5
(Huber and Corma, 2007)
The formation of a symmetrical ketone by the carboxylic acids passing over heated metal
oxides at high temperatures is a well-established reaction (Leung et al., 1995):
2 RCO2H → RCOR + H2O + CO2
It was postulated that the symmetrical ketones generated from the carboxylic acids would
undergo a γ-hydrogen transfer mechanism rearrangement to form methyl ketones and
terminal alkenes. The enol product is very unstable and it can re-arrange to form the methyl
ketone by the process of keto-enol tautomerism. The methyl ketone can also undergo the
same mechanism to further produce 1-decene again and acetone. There is an inverse
relationship between the hydrocarbon yields and the symmetrical ketone yields (Leung et al.,
1995):
Symmetrical / Methyl Ketone
γ – hydrogen transfer
Enolic form 1 – Alkene
Methyl Ketone
i) Diundecyl Ketone, R1 = -(CH2)10CH3 R2 = -(CH2)7CH3
ii) 2-Tridecanone, R1 = -CH3 R2 = -(CH2)7CH3
Figure 2-9. γ-Hydrogen mechanism on the symmetrical ketone and methyl ketone (Leung et
al., 1995)
Chapter 3: The Developed Process (KNV) 65
3 THE DEVELOPED PROCESS (KNV)
3.1 MOTIVATION / CONTRIBUTION
Aim of the laboratory tests was to evaluate the effect of catalysts, liquid/solid carriers and
operational parameters during the conversion of different types of biomass. The name of the
developed process was defined as Catalytic Low Pressure Liquefaction (in german
Katalytische Niederdruck Verölung – KNV), with the term liquefaction used in the sense of
the one-step (direct) production of liquid biofuel. The role of catalysts during the conversion
was studied. The catalytic effect at different points of the conversion process was identified.
Different types of biomass were used in the laboratory tests and their suitability as
feedstocks for the KNV process was evaluated.
3.2 THE EXPERIMENTAL KNV UNIT AND PROCEDURE
3.3.1 Experimental unit
The unit consisted of a batch, stirred, stainless steel reactor (12 L), a vapour cooling section
(reflux cooler), a vacuum pump as well as systems for collecting the liquid and gas samples
and temperature/pressure/energy consumption controllers and recorders. The stirrer is
designed with such a geometry in order to homogenize efficiently liquid/solid or solid/solid
mixtures, giving a circular and upward direction to the components of the mixture. In order to
prevent gases from contaminating the vacuum pump, a cold trap containing liquid nitrogen
was added after the vapour cooling section and before the vacuum pump. In the second
reactor configuration, a fixed bed catalytic vapour upgrading section was added into the
reactor, so that produced vapours could pass through it before they exit the reactor system.
Figure 3-1. (a) Reactor, (b) stirring device and (c) vapour condensation section
The flowsheet of the reactor system is presented below:
Figure 3-2. The reactor system

3.3.2 Experimental procedure
Before each test, the biogenic feedstock was dried (humidity <10% wt.), milled and sieved
(0,500mm-1,000mm). The catalyst was activated in the muffle oven at 500 °C for 1h, in
order to release any water absorbed into its pores.
Non-catalytic and catalytic tests with three different types of catalysts were performed. The
biomass (500 g), the liquid carrier (1 L) or the inert solid carrier (1500 g) and the catalyst (15
g) were mixed and fed into the reactor. In the case when the vapour upgrading section was
used, catalyst (50 g) was also added in the section. The reactant system was sealed and the
oxygen was removed from the system.
The temperature was set and controlled through a temperature control system. During the
experiments, the pressure was controlled and set at slight vacuum (0.9 bar). The final
reaction temperature used for the presented experiments was 350 °C and 400 °C and a
heating rate of ~6 °C/min was used. The parameters of the process were selected to
achieve the highest conversion of biomass to liquid products at relatively mild conditions that
could increase the energy efficiency of the process. The mixture was vigorously stirred
during the test. The produced vapours exited the reactor, due to the slight vacuum applied
into the system. They were condensed at the vapour cooling section and collected in the
liquid products’ flask. The non-condensable gases exited the vapour cooling section and
were trapped in the cold trap. Gases that were non-condensable in the cold trap exited the
system via the vacuum pump and were guided into a gas collection system. The
experimental apparatus was held at the final temperature until no further significant release
of vapours was observed. After the end of the test, the cold trap was isolated from the
system, the liquid nitrogen was removed and the gases were guided into a gas collection
system.
The liquid product contained of two easily separated phases: a lighter organic and a heavier
aqueous phase. The two phases are left to stand still into a decanter and then they are
easily separated due to their different density. Samples of the collected gas, the organic and
the aqueous phases and the residue are sent for physicochemical analysis.
3.3.3 Analysis of products
After the end of the experiment, the liquid products and the residues were weighed, while the
gas products were measured volumetrically. The liquid and gas products were analyzed with
the help of an Agilent 6890N Gas Chromatographer equipped with a 5973 Mass Selective
Detector. The compounds were identified using the Wiley 275 library. For the liquid samples
(organic and aqueous phases), the separation was performed on a HP5-MS column (Agilent
Technologies) with (5% phenyl)methyl-polysiloxane layer (30 m x 0.25 mm i.d. x 0.25 µm film
thickness) with the aid of helium as a carrier gas (0.3 mL/min). The inlet temperature was set
at 240 °C (split ration 20:1) while the oven temper ature started at 40 °C with a gradient of 5
°C/min to 300 °C where the temperature was held for 2 min. The injection volume was 1 µL.
For the gas samples, the separation was performed on a GS-GASPRO column (Agilent
Technologies) (60 m x 0.324 mm i.d.) using helium as a carrier gas (3.3 mL/min). The inlet
temperature was set at 60 °C (split ratio 1:17) whi le the oven temperature was 80 °C for 0.5
min, then increased to 175 °C with a gradient of 25 °C/min, and was held at this temperature
value for 2 min. Afterwards, an increase with a gradient of 25 °C/min followed until 250 °C.
The injection volume was 500 µL (manual injection with a gas tight syringe).
The C and H contents were determined on a Universal CHN Elemental Analyzer Vario El.
The sulfur contents were assessed by UV-fluorescence detection on a Mitsubishi TS-100
Analyzer. Dibutylsulfide in toluene was used for the trace level calibration. Furthermore,
nitrogen determination was performed on the same apparatus but via chemiluminescence
detection. The calibration was performed with pyridine. Finally, the oxide ash was measured
in accordance with DIN EN ISO 6245, after heating a sample at a muffle furnace at 775 °C
for 20–30 min and weighing, then repeating until consecutive weightings differed no more
than 0.5 mg.
The water content in liquid phases was measured by the Karl– Fischer titration on an 808
Titrando (Metrohm AG). The attained data were evaluated with the aid of the Tiamo 1.1
software. The density and viscosity measurements were carried out by the SVM 300
Stabinger Viscometer (Anton Paar Ltd.). The water content in the biomass was determined
by drying at 120 °C for 24 h.
3.3.4 Catalyst regeneration and characterization
The spent zeolites, from both the reactor and the vapour upgrading section, were
regenerated in a muffle oven at 500 °C for 24 h to remove all the coke from the zeolite
structure. The structure and phase purity of the zeolites were studied by X-ray powder
diffraction (XRD). The sample of the regenerated zeolite was milled and the fine powder was
pressed on a sample holder. The main structural components were identified by X-ray
diffraction analysis (Panalytical XPert Pro) in the angle range between 4° and 110° 2 θ CoΚα.
The evaluation of the X-ray diffractograms was performed by means of the Panalytical
Software XPert Highscore Plus and database PDF-2 (Release 2007).
3.3 SELECTION OF FEEDSTOCKS
The present research focused on the utilization of feedstocks with low edible-use, such as
organic wastes and aquatic plants. The following biogenic feedstocks were selected for
experimental testing:
(a) Rapeseed cake: a large amount of rapeseed cake is obtained as a by-product from
rapeseed oil production by the press and extraction method. The properties of the
cake depend on the type of rapeseed plant, for instance canola can be used as
cattle-feed (Özçimen and Karaosmanoğlu, 2004). For other types of rapeseed cake,
their utilization through the production of liquid fuels would increase the total liquid
fuel yield of the biodiesel production. The rapeseed cake used in the performed tests
was obtained via the mechanical cold press extraction method at BioDiesel Kaernten,
in the area of Carinthia, Austria.
(b) Meat meal C1: meat meal is prepared by the organic residues associated with
slaughtering processes and rendering of dead animals. Its composition can vary,
depending on the materials used and their blending. Category C1 comprises of
animal by-products of high health risk, due to infection with communicable illnesses,
viruses or exposure to other pharmaceutical substances. Due to the fact that
pathogenic organisms have been detected to meat meal C1, now it’s usually
incinerated instead of being used as animal feed. Recently, the use of meat meal for
biodiesel production has been allowed. Its use for the production of biofuels and
biochemicals could also be explored. The meat meal C1 used in the performed tests
was supplied by the a waste collection company in Slovenia.
(c) Algae: algae are aquatic plants, which grow in both fresh and salty water and show a
high production rate and high productivity. Algae appear to have a good potential for
their use in biofuel and biochemical production. The algae used in the performed
tests were supplied from Jakobs University in Germany.
The physicochemical properties of the selected materials are presented in the following
Table:
Table 3-1: Physicochemical properties overview of the selected solid biogenic materials
3.4 SELECTION OF LIQUID CARRIER / SOLID CARRIER MATERIAL
During the biomass conversion tests, the carrier material can either act as a heat carrier
or/and as a promoter of chemical reactions to produce liquid products of higher added value.
In the first case, it can stay inert during the biomass conversion, in the second case it will be
consumed during the reaction. If the carrier is in the liquid state, it should have a high boiling
point, since the KNV process runs at slight vacuum. The high temperature range of the KNV
process requires a liquid carrier with low toxicity, low corrosiveness, high flame point and
high thermochemical stability.
For the performed tests, vegetable oils were selected to be tested as liquid carriers, due to
their bio-based nature, in contrast to other used liquid carriers, such as tetralin or vacuum
gasoil. As fatty oil, the linoleic type of safflower oil (rich in esters of polyunsaturated fatty
acids) was used, supplied by the food company Estermann (Austria).
The physicochemical properties of the safflower oil are summarized in the following Table:
Table 3-2: Physicochemical properties overview of the safflower oil
Quartz sand was selected as a solid carrier material, since it consists of >90% SiO2, it is
chemically stable until 2230 °C and it is highly re sistant to attrition. The quarz sand was
supplied by the company Quarzwerke (Austria).
3.5 SELECTION OF CATALYSTS
Three different types of zeolite catalysts were used for the experiments: (1) Fe-ZSM-5
(SiO2/Al2O3 molar ratio: 27), (2) H-ZSM-5 (SiO2/Al2O3 molar ratio: 27) and (3) H-Beta
(SiO2/Al2O3 molar ratio: 25). The catalysts were produced by SüdChemie AG. Their
physicochemical properties are presented in the following Table:
Table 3-3: Physicochemical properties of the zeolites used for the KNV experiments (Süd-
Chemie, 2006)
The three zeolite catalysts possess particular characteristics: H-Beta is an acidic catalyst
with wide pores, H-ZSM-5 has strong acidic properties and small pores and Fe-ZSM-5 is a
mild solid acid containing a transition metal.
Zeolite ZSM-5 catalysts have a strong acidity, high activities and shape selectivities, which
can convert the oxygenated bio-oil to light hydrocarbons C1–C10 by dehydration and
deoxygenation reactions (Williams and Horne, 1995). The effect of shape-selectivity is still
enhanced with the hydrogen exchange in ZSM-5 zeolite with bigger Fe3+ cations. In addition,
the Fe exchanged form of ZSM-5 zeolite has a lower total acidity at the absence of very
strong acidic sites compared with H-ZSM-5 zeolite (Das et al., 1995). The presence of Fe
can promote metal catalyzed reactions, such as hydrogenation. Zeolite Beta catalysts have a
medium acidity and larger pore size than zeolite ZSM-5, which makes easier the access to
active sites, located inside its pores, for large molecules of biomass origin.
3.6 PERFORMED TESTS / RESULTS
3.6.1 CO-CONVERSION OF RAPESEED CAKE AND SAFFLOWER OIL
3.6.1.1 SCIENTIFIC BACKGROUND
Rapeseed oil is one of the most important sources not only for the edible-oil technology, but
also for the biodiesel production. A large rapeseed cake amount is obtained as a by-product
of rapeseed oil production. The increased production of the rapeseed cake as a by-product
reduces its demand. Therefore, it has to be converted efficiently into a high added value
product to help the economics of biodiesel production plants. Safflower oil is a widely used
vegetable oil for edible and non-edible purposes, e.g. biodiesel production.
The catalytic pyrolysis of vegetable oils, used vegetable oils and fatty acids has also been
previously studied. Different types of zeolites had been used, such as ZSM-5, Beta, MCM-
41, SBA-15 and REY (Alencar et al., 1983; Chew and Bhatia, 2008; Huber and Corma,
2007; Leung et al., 1995; Lima et al., 2004). Zeolites demonstrated a very good performance
as solid acid cracking catalysts, owing to their material properties. Results showed that a
gasoline-like or diesel-like fuel could be produced.
All biomass fuels have potential to significantly reduce the import of petroleum products.
Additionally, economies of scale can play a large factor in lowering the product cost.
Therefore, opportunities to co-feed with coal or natural gas systems may be one way to get
renewable fuels into the marketplace, just as co-firing biomass with coal is being done in the
power generation industry (Spath and Dayton, 2003).
The co-processing of these feedstocks is an interesting approach in terms of material

efficiency and economics. Low pressure conversion can give the possibility to better regulate
the residence time of produced vapours into the reactor system, enabling the increase of
liquid product yield without the use of high-investment reactors, e.g. fluidized bed. The
catalyst addition into the reactor system is expected to improve the quality of the liquid
product by promoting the formation of compounds with high added value and less oxygen
content.
3.6.1.2 PERFORMED TESTS
The following tests were performed (set of tests: A):
Table 3-4: Performed tests overview of the rapeseed cake and safflower oil co-conversion
3.6.1.3 PHASE COMPOSITION OF THE REACTION MIXTURE
In each experiment the mixture of the liquid product, the solid residue and the gases was
obtained. The liquid products consisted of two well separated phases: an organic and an
aqueous phase. The relative contents of these phases depended on the process
temperature and the catalyst used:
100%
Percentage of the starting mixture
90%
80%
70%
Organic phase
60%
Aqueous phase
50%
Gas product
40%
Residue
30%
20%
10%
0%
A.1 A.2 A.3 A.4 A.5 A.6 A.7
Test No
Figure 3-3. Product yields (wt. % on biogenic mixture) of the performed rapeseed cake and
safflower oil co-conversion tests
At 400 °C, the non-catalytic run exhibited the high est liquid product yield compared with that
of all catalytic runs. A low gas product yield was formed at the absence of the catalysts.
Deep cracking leads to the formation of gas products.
At both process temperatures, the H-Beta zeolite displayed the lowest residue production
and the highest liquid production, while the Fe-ZSM-5 zeolite presented the highest residue
production and the lowest liquid production. At 350 °C, the liquid phase yield was
significantly decreased. In addition, a considerable residue amount was formed at these
conditions.
At 400 °C, the organic liquid phase yield was the h ighest after the non-catalytic test. For the
catalytic tests, H-Beta resulted in its higher formation. In reference with the aqueous phases,
their yields slightly depended on the catalyst. On the contrary, at 350 °C, the organic phase
yields increased by the following order: Fe-ZSM-5 < H-ZSM-5 < H-Beta, while for the
aqueous phase yield this order was reversed: H-Beta ≃ H-ZSM-5 < Fe-ZSM-5.
At both temperatures, CO2 and light hydrocarbons (C2-C6) were present in the gas phases.
3.6.1.4 CHEMICAL COMPOSITION OF THE ORGANIC PHASE
The chemical composition of the organic phases, gained at different tests, is depicted in the
following Figure. The components are classified into chemical groups according to their
chemical structure. The individual compounds found in organic phases (with their contents)
are listed in Table 8-5 in the Annex.
Figure 3-4. Organic phase composition of the rapeseed cake and safflower oil co-
conversion liquid products
At 400 °C, the non-catalytic conversion of feedstoc k led to low yields of aliphatic
hydrocarbons, being essential components of the fuel. In contrast, the liquid phase, obtained
after the catalytic conversion, became rich on compounds of this group. As to the aromatic
hydrocarbons, the Fe-ZSM-5 zeolite slightly increased their yield, while the H-forms of
zeolites reduced it. The total yield of hydrocarbons (aliphatic and aromatic) was higher for
the Fe-ZSM-5 and H-Beta zeolites (~63%).
As it can be seen in Figure 3-4, the remaining fatty acid contents were the lowest after the
conversion on Fe-ZSM-5 zeolite (~6%). At the same time, the yield of hydrocarbons and
nitriles was the highest.
Conducting the experiments at lower temperature significantly changed the organic phase
composition. The contents of the aliphatic and aromatic hydrocarbons were higher at
significantly reduced amount of fatty acids and nitriles. The summary contents of all
hydrocarbons were higher for the H-ZSM-5 zeolite (~85%). The Fe-ZSM-5 zeolite
demonstrated a higher production of aromatic hydrocarbons. Finally, at this temperature, a

very low amount of nitriles was found in the reaction mixture.
3.6.1.5 CHEMICAL COMPOSITION OF THE AQUEOUS PHASE
The aqueous phase analysis illustrated the presence of the following groups of water-soluble
compounds: carboxylic acids and their derivatives (esters, nitriles), phenols, heterocyclic
compounds, alcohols, aldehydes and ketones (Figure 3-5). Among these products all
catalysts favored the formation of short-chain acids and N-heterocyclic compounds.
Figure 3-5. Aqueous phase composition of the rapeseed cake and safflower co-conversion
liquid products
At 400 °C, the highest yields of short-chain acids were observed at the H-ZSM-5 and H-Beta
zeolites and the lowest at the non-catalytic test. The yield of the phenolic compounds was
higher on the H-ZSM-5 and H-Beta zeolites and very low when Fe-ZSM-5 was applied. The
O-heterocyclic compound production was insignificantly dependent on the absence or
presence of different catalyst type. Finally, comparing the catalytic runs, the N-heterocyclic
compound production was the lowest when the H-ZSM-5 zeolite was used. The distribution
of the water-soluble products by the groups was almost similar at both experimental
temperature values. However, at 350 °C the acid for mation on H-Beta zeolite was
significantly higher than that on other catalysts.
3.6.1.6 ELEMENTAL COMPOSITION / PHYSICAL PROPERTIES
The elemental composition results and the physical properties of the produced organic
phase, aqueous phase and residue are depicted in the following Tables:
Table 3-5: Organic phase characteristics of the rapeseed cake and safflower oil co-
conversion tests
Table 3-6: Aqueous phase characteristics of the rapeseed cake and safflower oil co-
conversion tests
Table 3-7: Residue characteristics of the rapeseed cake and safflower oil co-conversion
tests
Comparing the elemental analysis data, it’s obvious that the organic phase produced on the
H-Beta zeolite demonstrated the lowest oxygen content. Sulfur is another undesirable
component of fuels. Sulfur content in the organic phases was low in comparison with No. 4
fuel oil and No. 6 fuel oil (according to the classification with the U.S. nomenclature) (1.5-
4.0% wt.) (Özçimen and Karaosmanoğlu, 2004). Among the catalysts, at 400 °C the H-Bet a
zeolite provided the lowest sulfur contents.
The water content in all organic phases was low in comparison with that of the pyrolysis bio-
oil (Bridgwater, 1994). At 400 °C, the water conten t decreased by the following order: Fe-
ZSM-5 > H-ZSM-5 > H-Beta. At 350 °C, the water cont ent of the organic phases was
approximately similar on all catalysts. The pH value of organic phases was higher than the
pH of typical wood pyrolysis oil (2-2.5) (Bridgwater, 1994), making it easier to handle due to
reduced corrosion effect.
The produced organic phases possessed higher Higher Heating Values (HHV) than pyrolysis
and liquefaction oils (19.3 and 30-35 MJ/kg respectively) (Bridgwater 1994; Naber et al.,
2002). At 350 °C, the densities and viscosities of the organic phases were similar to that of
diesel (~0.85 g ml-1 and 2-4.5 cSt respectively).
As shown in Table 3-7, at 400 °C, the HHV of residu es decreased by the following order:
non-catalytic > Fe-ZSM-5 > H-ZSM-5 ≃ H-Beta. At 350 °C, the HHV of residues from all
tests was similar.
3.6.2 RAPESEED CAKE CONVERSION WITH TWO REACTOR

CONFIGURATIONS
The catalytic upgrading of bio-oils can be performed in situ in specially designed reactor
systems, by mixing the biogenic feedstocks with the catalysts (Adam et al., 2006; Aho et al.,
2008; Antonakou et al., 2006a; Antonakou et al., 2006b; Demiral and Şensöz, 2008; Pütün et
al., 2006; Williams and Nugranad, 2000; Zhang et al., 2009). Alternatively, it can be
performed in series with the thermochemical process (Gayubo et al., 2005; Vitolo et al.,
1999; Vitolo et al., 2001), by evapourating the produced bio-oil and bringing it in contact with
the upgrading catalyst, including a costly vapour condensation/re-evapouration step.
The presence of a significant water amount in the liquid products can affect the structure and
acidic properties of the zeolite catalysts. The hydrothermal treatment of ZSM-5 and Beta
zeolites causes the migration of tetrahedral framework Al to extraframework positions, where
it is positively charged (Cejka et al., 1995; Fan et al., 2006; Kuehl and Timken, 2000). As a
result, new strong Lewis acid sites are formed in the material, while the number of Brønsted
acid sites is reduced (Fan et al., 2006). The extraframework Al is active in coke formation
(Cejka et al., 1995). The accumulation of extraframework Al at the outer surface of zeolite
crystals reduces the material pore size. Therefore, steric hindrances are created during
catalytic reactions (Fan et al., 2006). It has been reported that the number of stronger acid
sites of ZSM-5 zeolites decreased in increasing steaming time (Masuda et al., 1998). The
steamed ZSM-5 zeolites do not appear to have a degraded crystalline structure compared
with the parent material (Cejka et al., 1995; Fan et al., 2006). The Beta zeolite contains a
substantial concentration of lattice defects (Kuehl and Timken, 2000). When the Beta zeolite
is steamed, the micropore structure remains intact. However, the intense steaming of the
Beta zeolite creates clefts or mesopores in zeolite crystallites, shortening the diffusion
pathways to the framework active sites (Van Bokhoven et al., 2002).
The subsequent citric acid treatment of the ZSM-5 zeolite can have as an effect the zeolite
realumination. Unlike ZSM-5, the Beta zeolite can be realuminated by citric acid without prior
steaming (Fan et al., 2006). It has also been reported that octahedrally coordinated Al
species of the Beta zeolite can reversibly convert to tetrahedral Al sites upon reaction with
NH3 gas (Kuehl and Timken, 2000). When Beta zeolite is steamed and then treated with
NH3, the octahedral Al reverts to tetrahedral, but part of the fine structure is lost. It indicates
a loss or ordering around some of the Al atoms and the formation of an amorphous phase,
probably silica-alumina (Van Bokhoven et al., 2002).
In the case of the ZSM-5 zeolite, a considerable portion of Lewis acid sites is in pseudo-
tetrahedral symmetry. In the case of the Beta zeolite, the Lewis acid sites are predominantly
in octahedral symmetry, probably due to the larger pore volume of the Beta zeolite, allowing
enough space for the coordination of Al with three water molecules (Kuehl and Timken,
2000).
The following tests were performed (set of tests: B):
Table 3-8: Performed tests overview of the rapeseed cake conversion using two reactor
configurations
In each experiment the mixture of the organic liquid phase, the aqueous liquid phase, the
solid residue and the gases were obtained. The liquid products consisted of two well
separated phases: an organic and an aqueous phase. The relative contents of these phases
depended on the reactor configuration and the used catalyst (Figure 3-6).
Percentage of the starting mixture 100%

90%
80%
70%
Organic phase
60%
Aqueous phase
50%
Gas product
40%
Residue
30%
20%
10%
0%
B.1 B.2 B.3 B.4 B.5
Test No
Figure 3-6. Product yields (wt. % on biogenic mixture) of the performed rapeseed cake
conversion tests using two reactor configurations
The liquid product yields decreased by the following order: non catalytic ≃ H-Beta > H-ZSM-
5 > H-Beta (upgr.) > H-ZSM-5 (upgr.). As it has already been mentioned, the catalytic
biomass conversion tests usually result in a lower liquid product yield compared with non-
catalytic one.
In the absence of the vapour upgrading section, the H-ZSM-5 zeolite showed better catalytic
activity, since it produced less residue and more gas products than the H-Beta zeolite.
However, in the presence of the vapour upgrading section, the H-Beta zeolite was more
active than H-ZSM-5, gaining the lowest residue yield and the highest gas product yield.
The organic phase production increased by the following order: H-ZSM-5 (upgr.) > H-Beta >
H-ZSM-5 > non catalytic > H-Beta (upgr.).
CO2 and light hydrocarbons (C2-C6) were present in the gas phases.
following Figure. The components are classified into chemical groups according to their
chemical structure. The individual compounds found in organic phases (with their contents)
are listed in Table 8-7 in the Annex.
45,00% 400°C, no catalyst

40,00% 400°C, H-ZSM-5
400°C, H-Beta
Relative percentage
35,00% 400°C, H-ZSM-5, vapour upgr.

30,00% 400°C, H-Beta, vapour upgr.
25,00%
20,00%
15,00%
10,00%
5,00%
0,00%
Aliphatic HC Aromatic HC Phenols Acids Esters Nitrils N- Amides
Heterocyclic
compounds
Group of compounds
Figure 3-7. Organic phase composition of the rapeseed cake conversion liquid products
using two reactor configurations
As shown in Figure 3-7, the major organic phase components were carboxylic acids and
their derivatives: esters, amides and nitriles. The acid yields on the H-Beta zeolite were
higher than on H-ZSM-5. In the presence of the vapour upgrading section their yields
increased. In contrast, the ester and nitrile yields decreased with the vapour upgrading
section. The ester and nitrile production was maximized at the non-catalytic test. The yields
of amides, that are the intermediate products of acid conversion into nitriles, are almost
independent on the catalyst. The presence of the vapour upgrading section slightly reduced
their yields.
Hydrocarbons are another large group of compounds. Their maximum yield was attained on
the H-ZSM-5 zeolite and a slightly reduced yield on the H-Beta zeolite. The use of the
vapour upgrading section with both catalysts reduced the aliphatic and aromatic hydrocarbon
yields. In all cases, the aliphatic hydrocarbon production prevailed over the aromatic ones.
The H-Beta zeolite was less active in the phenol production than H-ZSM-5 zeolite. The use
of H-ZSM-5 zeolite and the vapour upgrading section reduced the phenol yield. No clear
dependence was found between the vapour upgrading and the N-heterocyclic compound
yields.
The aqueous phase analysis showed the presence of the following groups of water-soluble
compounds: phenols, heterocyclic compounds, alcohols and ketones (Figure 3-8).
90,00% 400°C
400°C, H-ZSM-5
80,00%
400°C, H-Beta
Relative percentage
70,00% 400°C, H-ZSM-5, vapour upgr.

60,00% 400°C, H-Beta, vapour upgr.
50,00%
40,00%
30,00%
20,00%
10,00%
0,00%
Phenols Ketones Alcohols O-Heterocyclic N-Heterocyclic
compounds compounds
Group of compounds
Figure 3-8. Aqueous phase composition of the rapeseed cake conversion liquid products
The major group of water-soluble compounds was N-heterocyclic compounds (mainly

pyridinol isomers and pyrrole). Their yield was maximized when H-ZSM-5 zeolite was used.
The non-catalytic test also produced a high N-heterocyclic compound yield. In the presence
of the vapour upgrading section their yields decreased.
The O-heterocyclic compound production (furan derivatives) was significantly low, while the
use of the vapour upgrading section increased its yield. The phenol yields were
approximately similar in all tests, except when the H-ZSM-5 zeolite was used in the presence
of the vapour upgrading section. Ketones were mainly formed on the H-Beta zeolite, while
the vapour upgrading section increased their production. The formation of small amounts of
alcohols was observed in two tests only.
The results of the elemental composition and the physical properties of the produced organic
and aqueous phase are depicted in the following Tables:
Table 3-9: Organic phase characteristics of the rapeseed cake conversion tests using two
reactor configurations
Table 3-10: Aqueous phase characteristics of the rapeseed cake conversion tests using two
reactor configurations
Comparing the elemental analysis data, it is shown that the organic phases produced in the
presence of the H-ZSM-5 zeolite showed similar hydrogen and oxygen content with the non-
catalytic test. The use of the H-Beta zeolite increased the oxygen content of the organic
phase and reduced the carbon content. The vapour upgrading section significantly reduced
the carbon contents of the organic phases. Sulfur is one undesirable component of fuels.
The sulfur content in the organic phases was low in comparison with fuel oils (sulfur content
No. 4 fuel oil and No. 6 fuel oil (according to the classification with the U.S. nomenclature)
was reported 1.5-4.0% wt. (Özçimen and Karaosmanoğlu, 2004)).
The pH value of the organic phases was in the basic region and it was considerably higher
than the pH value of typical wood pyrolysis oil (2-2.5) (Bridgwater, 1994).
The produced organic phases possessed higher HHV than pyrolysis oils and similar to
liquefaction oils (19.3 and 30-35 MJ/kg respectively) (Bridgwater, 1994; Naber et al., 2002).
The organic phase HHV increased by the following order: H-ZSM-5 > non-catalytic > H-ZSM-
5 (upgr.) > H-Beta > H-Beta (upgr.). The organic phase density was slightly higher than that
-1
of diesel (~0.85 g ml ).
3.6.2.7 CATALYST REGENERATION AND CHARACTERIZATION
The X-Ray diffractograms of the fresh and regenerated zeolites from both the reactor and
the upgrading section are depicted in Figure 3-9 for the H-ZSM-5 zeolite and in Figure 3-10
for the H-Beta zeolite.
Figure 3-9. XRD patterns of (a) the fresh H-ZSM-5, (b) the regenerated H-ZSM-5 from the
reactor and (c) the regenerated H-ZSM-5 from the vapour upgrading section
Figure 3-10. XRD patterns of (a) the fresh H-Beta, (b) the regenerated H-Beta from the
reactor and (c) the regenerated H-Beta from the vapour upgrading section
In Figure 3-9, the diffractogram comparison of the fresh and regenerated H-ZSM-5 zeolite
from the reactor showed obvious similarities. The differences between the two
diffractograms indicated the presence of a second phase. The peak heights in the
diffractogram of the regenerated sample were lower than for the primary material, which
indicated a lower degree of crystallinity. On the contrary, the regenerated H-ZSM-5 zeolite
from the vapour upgrading section showed an XRD pattern very similar to the fresh one,
which proved its successful regeneration.
In Figure 3-10, the regenerated sample of the H-Beta zeolite from the reactor had a
completely different mineralogical composition than that of the fresh material. Mineral
phases like quartz could be identified. A broad peak at 9.01° 2 θ could point to a very low
portion of the H-Beta zeolite. H-Beta zeolite was the main component in the diffractogram of
the regenerated material from the vapour upgrading section, although some differences to
the primary material were visible, especially at angles greater than 55° 2 θ. This indicated a
change in the crystalline structure of the material.
3.6.3 MEAT MEAL C1 AND ALGAE CONVERSION
Apart from edible feedstocks that have been used for biofuel production (e.g. oils/fats,
starch, sugar), focus has been given in non-edible biogenic sources. Presently, meat meal
C1 is mainly incinerated, because it is considered to be a high health risk material. If meat
meal C1 is utilized in a different way, products with higher added-value may yield. Algae has
been gathering increased attention as a feedstock for biofuel production, due to the fact that
its chemical composition can be regulated according to the used cultivation conditions as
well as its increased productivity in non-arable land. Both biogenic materials have been
selected as feedstocks for the KNV process in order to explore their conversion into biofuels.
The following tests were performed (set of tests: C):

Table 3-11: Performed tests overview of the separate meat meal C1 and algae conversion
(with different reactor configurations)
Test C.1 was performed in the absence of the vapour upgrading section, while test C.2 was
performed in the presence of the vapour upgrading section. For test C.1, 250 g of the
starting feedstock was used instead of 500 g, which was the standard quantity of solid
feedstock for the previous experiments. The reason for this was the nature of meat meal C1,
which created thin powder during the experiments. The lower the quantity of starting meat
meal C1, the lower the quantity of the produced thin powder. Consequently, blockages in the
piping network of the system could be avoided.
In each experiment the mixture of the organic liquid phase, the aqueous liquid phase, the
solid residue and the gases were obtained. The liquid products consisted of two well
separated phases: an organic and an aqueous phase. The relative contents of these phases
depended on the feedstock and reactor configuration (Figure 3-11).
100%
Percentage of the starting mixture
90%
80%
70%
Organic phase
60%
Aqueous phase
50%
Gas product
40% Residue
30%
20%
10%
0%
C.1 C.2
Test No
Figure 3-11. Product yields (wt. % on biogenic mixture) of the performed separate meat
meal C1 and algae conversion tests
The meat meal C1 conversion demonstrated a significantly high residue production (~51%),
while the gas production prevailed over the liquid production. The ratio of organic to liquid
product was approximately 1:1.
Algae in the presence of the vapour upgrading section and H-ZSM-5 zeolite gave a higher
liquid production and a lower residue production compared with the rapeseed cake test,
using the same parameters. The organic phase yield was also maximized when the algae
was used.
CO2 and light hydrocarbons (C2-C6) were present in the gas phases.
following Figure:
Organic phase
80,00% meat meal C1, H-ZSM-5

70,00%
Relative percentage
algae, H-ZSM-5, vapor upgr.

60,00%
50,00%
40,00%
30,00%
20,00%
10,00%
0,00%
Aliphatic HC Aromatic HC Phenols Acids Esters Nitrils N- Amides
Heterocyclic
compounds
Group of compounds
Figure 3-12. Organic phase composition of the separate meat meal C1 and algae
Meat meal C1 conversion, with H-ZSM-5 zeolite in the absence of a vapour upgrading
section, produced a higher yield of hydrocarbons (aliphatic and aromatic: ~32%) compared
with the rapeseed cake conversion (~23%). The amide and nitril production was increased
when meat meal C1 was used (~40%) compared with that of rapeseed cake (~30%) at the
expense of acids (~6% and ~20% respectively). The N-heterocyclic compound yield of meat
meal C1 (~15%) was higher than that of rapeseed cake (~5%), while a small quantitiy of
phenols was present in the organic phase.
The catalytic conversion of algae in the presence of H-ZSM-5 zeolite and the vapour
upgrading section resulted in the production of an organic phase with a higher content of
hydrocarbons (~75%, aliphatic and aromatic hydrocarbons) compared with the rapeseed
cake test. Limited production of acids and nitrils was demonstrated, while no phenols, N-
heterocyclic compounds and amides were present.
The aqueous phase contained phenols, ketones, O-heterocyclic compounds and N-

heterocyclic compounds:
Aqueous phase
100,00% meat meal C1, H-ZSM-5

90,00%
algae, H-ZSM-5, vapor upgr.
Relative percentage
80,00%
70,00%
60,00%
50,00%
40,00%
30,00%
20,00%
10,00%
0,00%
Phenols Ketones O-Heterocyclic N-Heterocyclic
compounds compounds
Group of compounds
Figure 3-13. Aqueous phase composition of the separate meat meal C1 and algae
Both feedstocks favored the significant formation of N-heterocyclic compounds. Algae and
rapeseed cake in the presence of H-ZSM-5 and the vapour upgrading section, gave equal
contents of N-heterocyclic compound. Algae demonstrated a higher production of ketons
and O-heterocyclic compounds than rapeseed cake. In the case of meat meal C1, phenols
were distributed between organic and aqueous phases.
The results of the elemental composition and the physical properties of the produced organic
and aqueous phase are depicted in the following Tables:
Table 3-12: Organic phase characteristics of the separate meat meal C1 and algae
conversion tests
Table 3-13: Aqueous phase characteristics of the separate meat meal C1 and algae
conversion tests
Comparing the elemental analysis data, it is shown that the organic phase produced during
the algae conversion had a lower oxygen content as well as a higher carbon and hydrogen
content compared with that of meat meal C1. The organic phase of meat meal C1 had a
higher oxygen and a lower carbon content than that of rapeseed cake.
The sulfur content in the organic phases was low in comparison with No. 4 fuel oil and No. 6
fuel oil (according to the classification with the U.S. nomenclature) (1.5-4.0% wt.) (Özçimen
and Karaosmanoğlu, 2004).
The pH value of the organic phases was in the basic region and it was considerably higher
than the pH value of typical wood pyrolysis oil (2–2.5) (Bridgwater, 1994).
The produced organic phases showed lower oxygen content than pyrolysis oils (30-37% wt.)
(Naber et al., 2002; Bridgwater 1994). The density of the algal organic phase was slightly
higher than that of diesel (~0.85 g ml-1).
The produced organic phases possessed higher HHV than pyrolysis oils (19.3 MJ/kg). The
organic phase of the algae conversion possessed similar HHV to liquefaction oils (30-35
MJ/kg) (Bridgwater, 1994). Algae produced the organic product with the highest HHV
compared with that of rapeseed cake and meat meal C1 conversion tests.
3.7 DISCUSSION OF RESULTS
At 400 °C, the addition of zeolite catalyst to the feedstock significantly affected the phase
composition of the product mixture. This is expected due to the catalyzing effect of zeolite in
cracking and other acid-catalyzed reactions, leading to intensive formation of compounds
with lower molecular weight.
At both process temperatures, the structural characteristics of the H-Beta zeolite were
responsible for the lower production of residues and the higher production of liquids. The
pore size of this zeolite is large enough (7.7 Å) to provide access of bulky molecules to its
strong acidic sites and to perform their cracking to smaller molecules. The H-ZSM-5 zeolite
has stronger acidic sites than H-Beta (Hegde et al., 1989), but smaller pores (5.6 Å). Thus,
the cracking ability of this catalyst is limited by its shape-selectivity that reduced the liquid
product and gas yield. In contrast, the activity in polymerization (leading to coke formation)
does not require very strong catalyst acidity and remains high. As a result, the solid residue
yield increased.
The effect of shape-selectivity is still enhanced with the hydrogen exchange in ZSM-5 zeolite
with bigger Fe3+ cations. In addition, the Fe exchanged form of ZSM-5 zeolite has a lower
total acidity at the absence of very strong acidic sites compared with H-ZSM-5 zeolite (Das
et al., 1995). In the presence of Fe-ZSM-5 zeolite, the rate of reactions proceeding on strong
acidic sites was still lower than on H-ZSM-5 zeolite, while polymerization and coking became
the predominant processes.
The same relative behavior of the catalysts was observed at both process temperatures.
However, the liquid product yield at 350 °C was sig nificantly lower, while the main conversion
product was solid residue. As it is known, the acid-catalyzed polymerization reactions
(responsible for coking) easily proceed at lower temperature, while cracking requires much
harder conditions.
At 350 °C, the significant reduction of the liquid product yield and the residue increase could
be explained by the reduced zeolite catalytic activity at lower temperature. But more
probably, safflower oil was not completely hydrolyzed to fatty acids at this temperature and
the liquid oil intensively polymerized on the acidic sites of zeolites.
At 350 °C, the higher aqueous phase and the lower o rganic phase yield on the Fe-ZSM-5
zeolite could be explained by the enhanced activity of Fe-ZSM-5 in oxidative
dehydrogenation that produces more water and water-soluble heterocyclic and other highly
oxygenated compounds.
The biofuel is mainly composed of water-insoluble substances that form the organic phase of
liquid products. The quality of a liquid biofuel can be estimated by the presence of
compounds that are also present in conventional petroleum fuels. Therefore, the presence of
aliphatic and aromatic hydrocarbons enhances the quality of a liquid biofuel. The presence
of phenolic compounds can also be beneficial, since in conventional fuels limited quantities
of oxygenated compounds, such as alcohols and ethers, are added to increase the anti-
knocking behavior (Stournas et al., 2000). The increased presence of carbonyl compounds
(acids, esters, ketones, aldehydes) in a liquid biofuel reduces its quality. The low pH values
makes difficult its application in engines due to corrosion, while the increased oxygen
content reduces its heating value and alters its physical properties, e.g. volatility. Finally, the
increased concentration of nitrogen containing compounds is lowering the biofuel quality,
since NOx emissions are released during the fuel combustion. Still, nitrogen containing
compounds, such as alkylesters of nitric acid are used as additives in order to increase the
cetane number of diesel (Stournas et al., 2000).
The catalytic and non-catalytic conversion of fatty oil and biomass involves a large variety of
individual reactions. The most important of them are cracking/alkylation,
hydrogenization/dehydrogenization and hydration/dehydration. Other types of reactions

(heterocyclization, esterification, etc.) can also occur. These reaction rates are significantly
affected by the presence of a catalyst and its characteristics, such as acidity, pore size and
chemical composition. Thus, the catalysts with stronger acidic sites increase the rate of
reactions proceeding with an ionic mechanism (cracking, alkylation); small pore size
catalysts are more selective in the smaller molecule formation, while the metal-containing
zeolites catalyze reactions with a radical mechanism (hydrogenization and
dehydrogenization).
At 400 °C, H-ZSM-5 and H-Beta zeolites produced mor e light hydrocarbons (alkanes and
olefins C7-C14) in comparison with Fe-ZSM-5 zeolite. The products of cracking of heavier
hydrocarbons (C15-C17) were light hydrocarbons. Heavier hydrocarbon yields respectively
reduced on the H-forms of zeolites. The Fe-ZSM-5 zeolite had a significantly lower cracking
ability that resulted in higher contents of heavier hydrocarbons in the product mixture. The
absence of light olefins on this catalyst can be explained by its hydrogenating ability due to
the presence of transition metal cations. Another important characteristic of the Fe-ZSM-5
zeolite is its activity in aliphatic hydrocarbon aromatization. The yield of aromatic
hydrocarbons on this catalyst is twice higher than on H-forms of zeolites. In particular,
tridecylbenzene was formed only on this catalyst.
Another large group of the organic phase components is fatty acids. They were obtained at
the high-temperature hydrolysis of safflower oil. As these compounds are primary products
of the process, the acid content in the reaction mixture depends on their further conversion
to other compounds. Nitriles are produced from carboxylic acids in the presence of ammonia
and a dehydration catalyst (Denton and Bishop, 1953). The highest yield of fatty acids (and
respectively, the lowest yield of hydrocarbons and nitriles) was found on the H-ZSM-5
zeolite. Based on these data it can be concluded that the fatty acid conversion requires the
presence of metal in the catalyst, while acidic site strength is not very important. In addition,
the zeolite pore size plays a significant role in its ability to catalyze the acid conversion due
to steric hindrances.
At 400 °C, the cracking processes prevailed over al kylation for all zeolite catalysts: the
alkylphenols amount was very low, especially on strongly acidic H-forms of zeolites. In
particular, dodecylphenol formed during the non-catalytic conversion was not detected in the
reaction mixture after all the catalytic experiments. As it was expected, the fatty oil
conversion into hydrocarbons was the lowest at the non-catalytic test due to the absence of
acidic sites necessary for cracking. However, at these conditions fatty acids were still able to
transform into nitriles. Also, the non-catalytic test favored the fatty acid esterification.
At 350 °C, the strong acidity of the H-ZSM-5 zeolit e became a more important factor of its
activity than the steric limitations caused by its smaller pore size. At 350 °C, the less acidic
H-Beta and Fe-ZSM-5 zeolites appeared less active.
Comparing the zeolite catalytic activity, it should be taken into account that all liquid product
yields decreased considerably at this temperature. Thus, a relative degree of catalyst
deactivation can be estimated.
The Fe-ZSM-5 zeolite showed increased dehydrogenation and aromatization ability, leading
to higher aromatic hydrocarbon and olefin yield compared with the H-forms of zeolites. In
contrast to H-forms of zeolites, its alkylation ability predominates over cracking (Choudhary
et al., 1999) that resulted in the formation of substituted benzenes. The limited diffusion of
long-chain olefins to the active sites, due to the shape-selectivity effect, led to the formation
only of alkylbenzenes with shorter alkyl groups (up to C9) on this catalyst.
Due to the insufficient cracking ability of Fe-ZSM-5 zeolite, the gained liquid phase contained
a significant amount of unreacted linoleic acid. In the case of the more acidic H-ZSM-5
zeolite, linoleic acid was completely converted to other compounds.
The very low amount of nitriles found in the product mixture may be caused by the
insufficient formation of ammonia at the low-temperature biomass cracking. The relative
nitrile yields correlate with the catalysts cracking ability.
The biomass conversion processes offer the possibility for the production not only of biofuel
but also of biochemicals. In particular, the aqueous phase could be utilized for the extraction
of chemical compounds with high added value. For example, nitrogen containing compounds
can be used in a variety of applications in pharmaceutical, plastic and food industry
(Higashio and Shoji, 2004). Additionally, oxygen containing compounds can be used for the
production of bio-polymers and other chemicals (Bridgwater, 1994).
The highest yields of short-chain acids (mainly acetic and propanoic) were observed on H-
ZSM-5 and H-Beta zeolites. As they are primary products of fatty acid and O-heterocyclic
compound cracking, it was expected that the catalysts with stronger acidic sites would favor
their formation. In contrast, the short-chain acid yield at the non-catalytic test was minimized.
Phenolic compounds are the typical lignin cracking products. Their yields were higher at use
of highly acidic H-ZSM-5 and H-Beta catalysts. The Fe-ZSM-5 zeolite did not show sufficient
cracking ability and, therefore, phenol yield was twice lower than that on H-forms of zeolites.
It should be noted that the Fe-ZSM-5 zeolite did not produce any diols.
O-heterocyclic compounds were formed during the carbohydrate dehydration.

Carbohydrates are decomposition products of polysaccharides. The O-heterocyclic
compound yields slightly depended on the presence of a catalyst, since the cellulose and
hemicellulose dehydration easily proceeded even at the absence of a catalyst. The lower O-
heterocyclic compound yield on the Fe-ZSM-5 zeolite can be explained by their catalytic
conversion to other compounds (such as N-heterocyclic compounds or ketones) on metal-
containing zeolite (for example via furan–pyrrole ring-exchange, Hatada et al., 1974). As a
result, the yields of products that belong to these two groups on the Fe-ZSM-5 zeolite are
the highest among all catalysts.
The N-heterocyclic compound formation can occur due to the reaction of ammonia with O-
heterocyclic compounds, as well as at the direct decomposition of biomass components. The
H-ZSM-5 zeolite led to their lower yield, probably due to its higher cracking ability that favors
further conversion of N-heterocyclic compounds to smaller molecules.
As shown in Figure 3-5, the higher acid formation on the H-Beta zeolite clearly proves that
the effect of shape-selectivity at lower temperature plays a critical role in the conversion of
large molecules of fatty acids and O-heterocyclic compounds. The low Fe-ZSM-5 zeolite
acidity and its small pore size were responsible for the reduced acid yield when this catalyst
was used.
The profile of the catalyst activity in the formation of phenols, ketones, alcohols and N-
heterocyclic compounds at 350 °C was the same as at 400 °C.
The oxygen content is an important characteristic of the biofuel. As deoxygenation occurs

during the fatty oil and biomass cracking, it was expected that catalysts with high acidity
would produce an organic phase with lower oxygen content, like H-Beta zeolite in this case.
The lower deoxygenation ability of the H-ZSM-5 zeolite was attributed to its smaller pore size
that restricted the access of large substrate molecules to its active sites. The weaker acidity
of the Fe-ZSM-5 zeolite further reduced the deoxygenating ability of this catalyst. The
produced organic phases showed a lower oxygen content than pyrolysis and liquefaction oils
(30-37% wt. and 10-18% wt. respectively) (Bridgwater 1994; Naber et al., 2002).
At 400 °C, the water contents correlate with the de oxygenation degree of the organic phase:
the mixture gained on the H-Beta zeolite has the lowest oxygen and, respectively, water
content. In contrast, the Fe-ZSM-5 zeolite resulted in the formation of more oxygenated
organic phase, containing a higher water amount. Evidently, highly oxygenated compounds
in the organic phase are polar and absorb the water, forming complexes with water
molecules.
The pH values depend on the carboxylic acid and phenols concentration in the mixture.
Since the mixture obtained at 350 °C contained less fatty acids, its pH value was still higher
than that the organic phase obtained at 400 °C.
The quality of a fuel is characterized by its HHV. This depends on the deoxygenation
degree: the high oxygen content of a fuel reduces its HHV. Thus, the organic phase HHV
obtained at 400 °C follows the same order as their oxygen content: Fe-ZSM-5 < non-catalytic
< H-ZSM-5 < H-Beta. The same correlation between HHV and oxygen content was observed
for the organic phases obtained at 350 °C.
Not only the presence of oxygen but also the ash content affects the HHV of residues. While
ash amount in the liquid phase is insignificant, for the residues it plays a notable role,
reducing their HHV. At 400 °C, the HHV decreased in the following order: non-catalytic > Fe-
ZSM-5 > H-ZSM-5 ≃ H-Beta. For the first three experiments it correlated with the oxygen
content, but in the case of the H-Beta zeolite, the HHV was significantly lower than expected
due to the high ash content.

CONFIGURATIONS
The addition of a zeolite catalyst to the feedstock considerably affected the phase
composition of the product mixture. Both zeolites catalyzed the lignin and polysaccharide
cracking of the biomass. Another reaction catalyzed by zeolites was the polymerization of
formed unsaturated compounds, which could result in the solid residue production. The
relative rate of these reactions depended on the zeolite structural and acidic properties.
Thus, the strongly acidic H-ZSM-5 zeolite possessed a higher activity in cracking, which led
to the intensive formation of compounds with lower molecular weight. As a result, the gas
product yield increased, while the amount of formed residue was lower in comparison with
that of the H-Beta catalyst. In contrast to cracking, polymerization reactions (leading to the
coke formation) do not require very strong acidic sites on the catalyst. Therefore, the H-Beta
zeolite favored coking. Both zeolites did not show a notable difference in the liquid product
yield.
The recycled condensed vapours got again in contact with the catalyst inside the biogenic
mixture. In the case when the vapour upgrading section was added into the system, the
recycled condensed vapours got in contact with the catalyst in the vapour upgrading section.
In the presence of the vapour upgrading section, the biomass conversion to non-
condensable gases should have increased, while the liquid product and coke formation
should have decreased. The higher activity of H-Beta zeolite in the vapour upgrading section
was attributed to the creation of clefts or mesopores in the zeolite crystallites by
hydrothermal treatment. As a result, the diffusion pathways, leading to the active sites inside
the pores, were shortened and the site availability was considerably increased (Van
Bokhoven et al., 2002).
On the contrary, the hydrothermal treatment of the H-ZSM-5 zeolite resulted in the
dealumination of the material, which led to the micropore blockage of the material, making
active sites inaccessible for reactants (Fan et al., 2006). This was evident from the reduced
liquid and gas yields, while the coke formation increased. It has been reported that
hydrothermal dealumination followed by subsequent citric acid treatment can have as an
effect the realumination of the zeolite. In our case, the realumination of the H-ZSM-5 zeolite
could have been possible in the presence of carboxylic acids. Still, based on the obtained
data it seemed that it had a minor effect in the presented results, probably due to the weaker
acidity of fatty acids in comparison with citric acid.
The organic phase production was increased by the following order: HZSM-5 (upgr.) > H-
Beta > H-ZSM-5 > non catalytic > H-Beta (upgr.). The lowest water-insoluble compound yield
was observed on the H-Beta zeolite with the vapour upgrading section. This might be caused
by the deep catalytic cracking of biomass into gas and liquid products with low molecular
weight. In the case of the H-ZSM-5 zeolite with the vapour upgrading section, the lower
activity of the vapour-treated catalyst slowed the biomass deep cracking, increasing the
organic product yield.
Biofuel is mainly composed of water-insoluble substances that form the organic phase of
liquid products. The main groups of compounds produced by the rapeseed cake conversion
were fatty acids and their derivatives: esters, amides and nitriles. The fatty acids were
formed by the high temperature hydrolysis of fatty oils. As these compounds (mainly oleic
acid) were the primary products of the process, the acid contents in reaction mixtures
depended on their further conversion to other compounds. The HZSM-5 zeolite showed
higher activity in the fatty acid conversion, due to the presence of strong acidic sites that
favored cracking to hydrocarbons, their esterification and transformation to nitriles through
the intermediate amide formation. The amides were formed by the reaction of acids with
amines or ammonia. The further conversion to nitriles requires the presence of a dehydration
catalyst of acidic nature (Denton and Bishop, 1953). The conversion of fatty acids to amides
and nitriles is a reversible process. As we can see from experimental data, the presence of a
catalyst shifts the equilibrium to acids while non-catalytic conversion results in higher
contents of nitriles.
Yields of nitriles also depend on cracking ability of the catalyst. The HZSM-5 zeolite provided
a higher fatty acid cracking degree to hydrocarbons that reduced the nitrile yields in
comparison with the H-Beta zeolite. In contrast, the less acidic H-Beta zeolite did not favor
the fatty acid cracking, resulting in its further conversion into nitriles. Amides are the
intermediate compounds in the nitrile formation, thus, their yields depended on the relative
rate of both acid amidation and amide dehydration. The insufficient Brønsted acidity of the
hydrothermally treated catalysts in the vapour upgrading section resulted in an increased
amount of unreacted acids and a reduced production of esters and nitriles.
Hydrocarbons are valuable components of bio-oils and can improve their fuel properties.
Hydrocarbon yields depended on the zeolite acidity and correlated with the fatty acid
conversion. The most acidic H-ZSM-5 zeolite provided the highest aliphatic hydrocarbon
yields (C8-C17). This catalyst also enhanced the aromatic hydrocarbon production due to its
aromatization ability, as it’s known from other references (Williams and Nugranad, 2000;
Chew and Bhatia, 2008). It is evident that the presence of the upgrading section reduced the
aliphatic hydrocarbon yields.
Two other groups of compounds were present in both organic and aqueous phases. Phenols
were products of lignin decomposition, and N-heterocyclic compounds formed from amines
and ammonia that was released during the decomposition of proteins. Pyrrole was primarily
formed and then it partially converted to indole, which is a product of cycloaddition. These
two compounds readily polymerized in the presence of acids. Thus, their relative contents in
the reaction mixture depended on the catalyst polymerizing ability.
The presence of phenolic compounds can also be beneficial, since limited presence of
oxygenated compounds can improve the anti-knocking behaviour of conventional fuels
(Stournas et al., 2000). The phenol yield was maximized when the HZSM-5 zeolite was used
in the presence of the vapour upgrading section, since steric hindrances on this zeolite
prevented their further decomposition.
Carbonyl and N-containing compounds reduce the quality of biofuels. Thus, the low pH
values of acid-rich oils results in metal corrosion; increased oxygen content reduces the
biofuel HHV and alters its physical properties, e.g. volatility; and N-containing compounds
are responsible for NOx emissions during fuel combustion. They must be eliminated from
bio-oils at its further conversion to biofuel. However, nitrogen containing compounds, such
as alkylesters of nitric acid are used as additives in order to increase the diesel cetane
number (Stournas et al., 2000).
In spite of the low rapeseed cake nitrogen content, N-containing compounds were the major
components of the aqueous phase due to their solubility in water. The main nitrogen source
was rapeseed cake proteins that thermally decomposed during the process. The aminoacid
content in dry rapeseed cake (mainly arginine, lysine, methionine, cysteine, threonine and
tryptiphan) usually varies between the range of 7-9% wt. (Leming and Lember, 2005). As it
has been reported, the main routes of aminoacids decomposition are decarboxylation and
deamination (Klingler et al., 2007; Peterson et al., 2008). In the performed tests, the
produced ammonia and lower amines further reacted with other compounds of the reaction
mixture. The highest N-heterocyclic compound yields were reached when the H-ZSM-5
zeolite was used, due to the presence of strong acidic sites involved in the reactions of
natural substance decomposition. In formation of N-heterocyclic compounds at non-catalytic
test carboxylic acids of the reaction mixture may play the role of a catalyst.
O-heterocyclic compounds (mainly furan-2-methanol) were formed from carbohydrates,

which are products of the polysaccharide decomposition (Karagöz et al., 2005; Román-
Leshkov et al., 2007). Their yields slightly depended on the presence of a catalyst, since
cellulose and hemicellulose dehydration easily proceeded even at non-catalytic conditions.
The vapour upgrading section increased the O-heterocyclic compound yields, probably due
to slowing their further destruction into low molecular weight products.
Phenols and their derivatives (including methoxyaromatic compounds) are products of lignin
decomposition (Karagöz et al., 2005). Compounds of this group are distributed between
organic and aqueous phases. Their total yields were approximately similar for all tests,
except from the vapour upgraded H-ZSM-5 zeolite. The higher phenolic compound yield on
this catalyst could be explained by the additional formation of phenols from O-heterocyclic
compounds. Thus, 4-methyl-2,6-di-tert-butylphenol was formed from both lignin and

cellulose (Karagöz et al., 2005).
Alcohols and ketones are other products of the carbohydrate degradation. They formed
mainly on the H-Beta zeolite, because its wide pores provided higher accessibility of the
reacting molecules to the active sites.
The pH value of both the organic and aqueous phase was in the basic region (≥7). The
highest pH was observed in the liquid products gained after the biomass conversion with H-
ZSM-5 zeolite in the presence of the vapour upgrading section. This correlated with the high
nitrogen content of both organic and aqueous phases. This effect could be attributed to the
presence of dissolved ammonia and/or lower amines formed during the protein
decomposition. Their further conversion to less basic compounds was restricted by the
blocking of zeolite pores by the extraframework aluminum.
When H-ZSM-5 zeolite was used, the oxygen content of the organic phases was similar to
that of the non-catalytic test. Additionally, when H-Beta zeolite was used, the oxygen content
of the organic phases was higher than that of the non-catalytic test. In contrast, the total
oxygen content of the liquid products of all catalytic tests, except from Test 5, was lower than
that of the non-catalytic test (63.24%, 61.90%, 62.64%, 56.02%, and 65.60% respectively).
The high activity of zeolite H-Beta, in the presence of the vapour upgrading section, had as a
result the maximum total water production compared with all other tests. Therefore, the total
oxygen content in the liquid product was higher than in the case of the non-catalytic run.
The HHV of organic phases correlates with their elemental composition. The H-ZSM-5
zeolite provided the highest degree of deoxygenation. Thus, the mixture obtained on this
catalyst had the highest (C+H)/O ratio, providing the highest HHV. The high oxygen content
of the organic phase, gained with the H-Beta zeolite and the vapour upgrading section,
resulted in a reduced HHV.
3.7.2.5 CATALYST REGENERATION AND CHARACTERIZATION
The regeneration by thermal treatment has as a result changes in the acidic and structural
properties of the zeolite catalysts. The number of Lewis acid sites increase at the expense of
Brønsted acidity. The thermal treatment affects the structural characteristics of the materials,
causing their partial amorphization or formation of new crystalline phases.
The spent catalysts from the reactor were contaminated by the highly viscous residue,
product of the conversion process, making their efficient regeneration more difficult. During
the thermal treatment, the high coke concentration on the catalytic material could have led to
local overheating and disruption of the crystalline structure.
As XRD results showed, the regeneration of the spent catalyst from the vapour upgrading
section was more successful than from the reactor. Thus, the H-ZSM-5 zeolite from the
vapour upgrading section showed improved regeneration ability. As it was already
mentioned, the steam treatment of zeolites results in their partial dealumination and,
respectively, increases their Si/Al ratio. The crystalline structures of highly siliceous zeolites
are more stable against acids and thermal treatment. As it is shown from X-Ray
diffractograms of the fresh and regenerated H-ZSM-5 zeolite, the crystallinity loss of this
catalyst was insignificant. However, the activity of stabilized zeolite was lower due to the
reduced framework aluminum content and the increased steric hindrances.
In the case of the H-Beta zeolite, its stability was very low even in the vapour upgrading
section. In contrast to the H-ZSM-5 zeolite, the reduced peaks in X-Ray diffractogram of H-
Beta showed its notable amorphization. As to the H-Beta catalyst from the reactor, its
crystalline structure was completely destroyed.
Meat meal contains an increased amount of inorganic components compared with other
feedstocks. Biomass thermochemical conversion is expected to be catalyzed by small ash
amounts. Higher ash amounts are assumed to have a negative influence on the biomass
conversion, therefore this could explain the low liquid product yield during the meat meal
conversion under the selected operational conditions.
The significantly low residue production during the algae conversion could be attributed to
the reduced lignin content of the raw material. The significantly high liquid production could
be explained by the increased oil content of the algae. The oil content of the feedstock also
resulted in a maximized organic phase yield compared with the rapeseed cake test.
The hydrocarbon production (aliphatic and aromatic) was higher for the meat meal C1 than
for the rapeseed cake, due to the higher fat content of meat meal C1 compared with the oil
content of rapeseed cake. The acids in the meat meal organic phase were further converted
into amides and nitrils. This could be attributed to the increased protein content of the meat
meal C1 compared with that of rapeseed cake, which could promote the ammonia addition.
The increased protein content of the meat meal could explain the increased N-heterocyclic
compound yield compared with that of rapeseed cake.
The significant oil content of the algae resulted in an important production of aliphatic and
aromatic hydrocarbons, which are important components for biofuel production. The
presence of H-ZSM-5 zeolite in the reaction mixture and in the vapour upgrading section
promoted decarboxylation and cracking reactions and resulted in a wide carbon chain length
(C8-C17). The nitril production prevailed over the amide production, since the H-ZSM-5
zeolite resulted in more intensive acid dehydration. The reduced lignin content of algae
resulted in a reduced production of phenols in the organic and aqueous phase.
N-heterocyclic compounds are the major components of aqueous phase for both feedstocks,
due to their solubility in water. The main source of nitrogen is the feedstock proteins that
thermally decomposed at the process conditions. The higher yield of N-heterocyclic
compounds was reached when meat meal C1 was converted, due to its increased protein
content compared with that of rapeseed cake.
Phenols could be products of the lignin or protein decomposition. In the case of meat meal
C1, compounds of this group are distributed between the organic and aqueous phases. The
reduced lignin content of the algae resulted in a reduced phenol production during the
conversion test.
Algae consists of carbohydrates, that were converted into O-heterocyclic compounds and
ketons. The O-heterocyclic compounds formed during the meat meal C1 conversion could
be formed during the protein decomposition.
The pH value of both the organic and aqueous phases was in the basic region (≥7), which
correlated with their high nitrogen content. This effect could be attributed to the presence of
dissolved ammonia and/or lower amines, formed during the protein decomposition.
The HHV of a product correlates with its elemental composition. Thus, the organic phase of
the algae conversion had the highest (C + H)/O ratio, providing the highest HHV compared
with that of the other performed tests. Meat meal C1 showed a lower HHV compared with
rapeseed cake conversion with H-ZSM-5 zeolite in the absence of the vapour upgrading
section.
The algae produced an organic phase with a lower water content than the respective organic
phase from the rapeseed cake conversion. The lower oxygen content of algae and its
increased oil content had a beneficial effect in the final organic product, resulting in less
water content of both organic and aqueous phases.
The meat meal C1 produced more water in the organic product compared with that of the
rapeseed cake conversion. That could explain the increased solubility of N-heterocyclic
compounds in the organic phase when the meat meal C1 was converted.
3.8 ENERGY BALANCE
The mass and energy flows of the KNV laboratory scale process are depicted in the Figure
below:
Figure 3-14. Mass and energy flows of the KNV laboratory process
Sieving was performed manually during the laboratory tests preparation.
The energy balance of the following tests, performed at 400 °C, was calculated: (1) the co-
conversion of rapeseed cake and safflower oil with H-ZSM-5 zeolite [A.3], (2) the separate
rapeseed cake conversion with H-ZSM-5 zeolite [B.2], (3) the separate rapeseed cake
conversion with H-ZSM-5 zeolite in the presence of the vapour upgrading section [B.4], (4)
the meat meal C1 conversion with H-ZSM-5 zeolite [C.1] and (5) the algae conversion with
H-ZSM-5 zeolite in the presence of the vapour upgrading section [C.2].
The energy balance calculation of the KNV laboratory process was based on the higher
heating values of the feedstock and products as well as the energy consumption during the
biomass pre-treatment, catalyst activation and the catalytic conversion step. Devices for
measuring the energy consumption were used during the test performance. The higher
heating values of feedstocks and products were calculated by the prediction model
developed by Boie, based on their elementary composition (see Annex). The total energy
efficiency of the KNV laboratory process was calculated as the ratio of the useful energy
(energy content of products) divided by the energy consumed (energy content of feedstocks,
heat and electricity). The total energy efficiency of the process (from feedstock to biofuel
production) could be increased by using the gas product of the KNV conversion to generate
heat for the reactor.
The energy consumption during the selected KNV laboratory tests and the energy content of
the products are presented in the following Table:
Table 3-14: Energy consumption and products energy content of the selected performed
tests
Due to the low material quantity, the energy required for the feedstock milling and the
catalyst activation was equal for all experiments. The co-conversion test resulted in organic,
gas and residue products with significant energy contents. The organic product of the algae
conversion had a high energy content compared with separate rapeseed cake conversions
and meat meal C1 conversion.
The energy efficiencies of the selected KNV laboratory tests are presented in the Table
below:
Table 3-15: Energy efficiencies of the selected performed tests

Both the total energy efficiency and the total energy efficiency with heat generation of the
performed tests increased by the following order: C.1 < C.2 < B.4 < B.2 < A.3. The higher
the energy content of the gas product, the higher the difference between the total energy
efficiency and the total energy efficiency with heat generation.
The co-conversion test showed significantly higher energy efficiency compared with all other
tests. This could be attributed to the high energy content of its KNV products. Comparing the
two separate rapeseed cake conversion tests, the gas produced in the absence of the
vapour upgrading section had an increased energy content, which resulted in an increased
energy efficiency of this test. The algae drying required a significant amount of thermal
energy. Although its products energy contents were similar to those of the separate
rapeseed cake conversion in the presence of the vapour upgrading section, the energy
efficiency of this test was significantly reduced.
Chapter 4: Feasibility Study 109
4 FEASIBILITY STUDY
This chapter will present the results of the feasibility study for the upscaling of the KNV
laboratory process into a KNV pilot plant.
To perform the feasibility study the following steps were followed: (1) research on the
framework of the concept by identifying the present conditions concerning the policy,
funding, technoeconomic and social framework, (2) performance of the technical design, (3)
performance of the cost assessment and (4) performance of the economical evaluation.
The feasibility study for the pilot plant is condition-specific, in terms of raw materials,
auxiliaries and process design. For this study, algae were selected as a raw material and the
use of a vapour upgrading section was selected for the reactor set-up of the pilot plant.
4.1 RESEARCH ON THE FRAMEWORK
4.1.1 POLICY FRAMEWORK
According to the latest greenhouse gas emissions inventory of the Federal Environmental
Agency, Austria emitted 78.96 million tons CO2-equivalent in the Kyoto base year 1990. This
value covers all greenhouse gases within the scope of the Kyoto Protocol. For Austria, the
13% reduction of greenhouse gases in the Kyoto commitment period 2008-2012 translates
into a target value of about 68.69 million tons CO2-equivalent. Compared with the 1990
figures, this is a reduction by 10.27 million tons CO2-equivalent. The Austrian industry and
transportation sectors are responsible for half of the energy consumption (European
Technology Platform for Zero Emission Fossil Fuel Power Plants, 2009).
On 4 November 2004, the Biofuel Directive was transposed into Austrian national law with an
amendment to the Fuel Ordinance. This amendment stipulates that all companies that put
fuels in circulation (e.g. Österreichischen Mineralölverwaltung (OMV)) must, from 1 October
2005, replace 2.5% of the total fuel energy by biofuels. From 2007 this percentage will
increase to 4.3% and in 2008 the target of 5.75%, as stipulated in the Directive, will have to
be achieved. Together with the amendment to the Fuel Ordinance, the Mineral Oil Act has
been revised. Accordingly, tax concessions will be granted for fuels with a biofuel share of at
least 4.4%. However, to be able to profit from the tax concessions, the fuel must also be
sulphur-free (less than 10 mg sulphur per kg of fuel) (Environmental Agency Austria, 2009).
As shown from all the above, the european and local policy framework in Austria promotes
the production and use of biofuels across the country.
4.1.2 FUNDING FRAMEWORK
The EU focus on the biofuel penetration in the energy market has forced country-members
to establish funding and economic incentives for biofuel production companies. On a
national level, these incentives differ from country to country, but usually follow two
directions: (a) state funding in the form of loan with favourable terms for an important part of
the total investment (up to 80%) and/or (b) tax exemption up to 100% of the profits. The rest
of the money for the total investment has to be supplied by private investors.
On an international level, the Austrian Ministry of Transport, Innovation and Technology has
been running the programme IV2Splus – “Intelligent Transport Systems and Services plus”.
This programme focuses on expanding the excellence in research and development (R&D)
through stronger international embedding of successfully established national R&D
competences, with the goal of increased integration of these competences into international,
industrial, value-creation chains (Austrian Federal Ministry for Transport, Innovation and
Technology, 2009).
Either of these two options could supply the necessary funding for the erection and operation
of a biofuel pilot plant in Austria.
4.1.3 TECHNOECONOMIC FRAMEWORK
As it was presented earlier in the results of Chapter 3, the use of algae as feedstock for the
KNV process appears to have a good potential, due to its high liquid product yield, the high
abundance of aliphatic hydrocarbons and the low oxygen content of the organic phase.
The algae cultivation system advantages lie: (a) on their high productivity potential, (b) on
the ability to use otherwise unsuitable water and land resources, (c) on the ability to integrate
waste treatment and (d) on the enhanced fuel production per area, compared with that of
other biomass sources. Many of the approximately 50000 algal species can grow in brackish
and saltwater. This means that the algae technology will not put additional demand on
freshwater supplies needed for domestic, industrial and agricultural use. The ocean will
become the ultimate sink for the anthropogenic CO2. The unique ability of algae to grow in
saline water means that we can target areas of a country which are coastal arid and/or in
which saline groundwater supplies prevent any other useful application of water or land
resources. The goal is to mitigate CO2 into energy and/or to permanently sequester the
biomass (and thus the CO2) with the production of biofuels and biochemicals (Thomsen,
2008).
The organic product of the KNV pilot plant has to be post-treated to meet fuel standards
before it is sold in the liquid fuel market. This could be done in conventional refineries, that
are already equipped with the infrastructure for such treatments (e.g. desulphurization).
Additionally, the aqueous product of the KNV pilot plant could be sold as raw material to
chemical companies for the production of biochemicals.
The future global demand of biofuels is estimated to be approximately 250 billion liters by
2020, based on a scenario that looks at volume based targets that different regions may put
in place by 2020 and how these targets might be met if 2nd generation biofuels are available
(E4tech, 2008). This means that the successful development and scaling up of a biofuel
production technology can be sold around the world and bring profit to the inventors.
The location selection for the erection of the pilot plant is very important, since it has
significant effect, not only on the economic stability of the investment plan, but also on the
natural and social environment. Algae require high amounts of CO2 during their cultivation.
Therefore, the location of the algal bioreactor close to a CO2 source, such as a power plant
or plants which produce high amount of exhaust gases (e.g. cement industry), can be
advantageous in terms of resource economy.
The main utility power plants in Austria are (European Technology Platform for Zero
Emission Fossil Fuel Power Plants, 2009):
• EVN AG
• Verbund Austria Thermal Power GmbH & Co KG
• Wienstrom GmbH
• Energie AG Oberösterreich
• Linz Strom.
Energie AG, in Upper Austria, has shown interest in cooperating on a project for the
industrial production of algal biomass, using CO2 directly from the power plant emissions.
The algae production site should be located close to the facilities of the Energie AG for the
direct utilization of the CO2 emissions. The KNV pilot plant should also be erected close to
the algal biomass production area to avoid costly transportation of the raw material to the
pilot plant location. This area appears to have sufficient infrastructure for plant erection and
operation (road network, access to raw and auxiliary materials, labour resources), because it
is close to the plant facilities of the Energie AG. Since the produced biofuel, which has
higher bulk density than the algal feedstock, has to be sent to a conventional refinery for
post-treatment, it could be transferred to the local installations of Rohöl-Aufsuchungs AG

(RAG) in Gampern (Upper Austria) and then be transported either by pipeline or via railway
tank cars to the Schwechat refinery of OMV (Rohöl-Aufsuchungs AG, 2009).
4.1.4 SOCIAL FRAMEWORK
The last years, there has been increased awareness of the public opinion concerning the
global environmental problems and the greenhouse gas emissions. Locals have been
experiencing weather extremes around the year, which affect the agricultural and fauna
balances and cause environmental distructions, such as floods and droughts. Measures and
investment plans aiming to reduce emissions in an area where an intensive air-polluting
plant is located will be welcomed by local authorities and residents.
4.2 TECHNICAL DESIGN
The technical design of the KNV pilot plant was the key step of the feasibility study, since
this was the core, based on which the cost assessment and the economic evaluation of the
investment plan were designed. The larger size of the pilot plant compared with that of the
laboratory unit provided the possibility for design changes, to assure higher material and
energy efficiency.
In principal, the technical design should be based on simplicity, efficiency, sustainability and
safety. Additionally, the design should provide flexibility for future changes, depending on the
optimization requirements and/or future demands of the process. The selected equipment
has to be reliable, economic and safe. The cost of operation and maintenance should not be
high, the emissions should be controllable and the energy consumption should be
minimized. The use of continuous operation equipment could decrease the labour costs,
since there will be no demand for repeated loading and unloading of materials, but the
investment costs would increase.
The KNV pilot plant would be operating in series with the algae production site close to
Energie AG. The area of the algae production pilot plant was planned to be 10000 m2.
Smaller algae production areas would create challenges in the profitability of the investment
plan for the erection and operation of the KNV pilot plant. The algae productivity can vary
according to the bioreactor design. The maximum productivity reported in literature reference
3
was 1.5 kg dry algae/m /d (Sanchez Miron et al., 1999) and for this study, this productivity
3
was used. Assuming an algal reactor volume of 10000 m , that would yield 15000 kg dry
algae/d, which would then be sent to the KNV pilot plant for conversion.
4.2.1 PRE-TREATMENT: ALGAE
Harvested algae have to be pre-treated before they reach the conversion reactor. The pre-
treatment procedure includes a drying process, a size reduction process and a screening
process. As demonstrated in the laboratory scale tests, the desirable humidity level of the
reactor feedstock was <10% and the desirable size fraction was 0.500-1.000 mm.
There is a wide variety of dryers, such as tray dryers, screen-conveyor dryers, tower dryers,
rotary dyers, screw conveyor dryers, fluid bed dryers, spray dryers, thin film dryers and drum
dryers. The algae consist of an important amount of humidity. Depending on the algae
harvesting method, the harvested algae may be in the form of a thick paste or even in the
form of a highly concentrated solution. The types that appear to be suitable for the specific
application of the KNV pilot plant are: (1) the screw conveyor dryer (suitable for pasty
materials), (2) the drum dryer (suitable for pasty materials and solutions). Spray dryers and
thin film dryers could also be used. But in the first case, this equipment is complicated and it
does not have a high efficiency when it is used only as dryer (efficiency is increased when it
is also used as an evaporator, crystallizer, size reduction unit and grader). In the second
case, this equipment is relatively expensive and has a relatively low surface for thermal
treatment (McCabe, 2001).
The comminuting equipment is classified into crushers, grinders, ultrafine grinders and
cutters. Primary crushers can process big pieces of minerals (e.g. from mines) and break
them into pieces of 150-200 mm size. A secondary crusher can reduce the size of these
particles to 6 mm. Grinders can produce particles up to 74 µm, while ultrafine grinders 1-50
µm. During the laboratory experiments, the wet algae paste was fed into a batch laboratory
dryer and the dried paste was in the form of big pieces (~150 mm) of strong thick texture.
The size of these pieces indicated that it would be necessary to combine a secondary
crusher and a grinder in series to produce algae particles with 1 mm maximum diameter.
Different types of crushers exist, such as jaw crushers, gyratory crushers and roll crushers.
Roll crushers are secondary crushers that can give a product with 1-12 mm particle size.
Additionally, different types of grinders exist, such as hammer mills, impactors, rolling-
compression machines and attrition mills. Very often the comminuting process takes place in
a closed system, where a comminuting equipment and a separator are connected in such a
way that larger size particles are recycled. In this case, energy has to be spent on the
operation of transporters and separators, but the reduction in the energy consumption of
closed systems in comparison with that of open systems can reach up to 25%. The energy
cost is a very important point during comminuting processes, therefore it is important to
select the most suitable equipment and the parameters that can regulate this cost. The size
reduction is one of the less energy efficiency processes, since less than 1% of the provided
energy is used for the new surface production. The rest is consumed during equipment
operation and as heat losses (McCabe, 2001).
The estimated parameters of the algae pre-treatment process are summarized in the
following Table:
Table 4-1: Estimated parameters of the algae pre-treatment process
4.2.2 PRE-TREATMENT: CATALYST
The catalyst has to be activated by calcination at 500 °C for 1 h in an oven, before it is used
during the conversion. During the laboratory tests, catalyst in powder form was mixed with
the algae and was fed into the reactor. Additionally, catalyst in extruded form was added in
the vapour upgrading section. The diameter of the extruded catalyst used in the laboratory
tests was 2 mm. The regeneration of the catalyst in powder form was difficult, due to the fact
that the used catalyst was mixed with the residue. After regeneration, the residue produced
ash in powder form. The separation of the regenerated catalyst from the ash was very
challenging. Therefore, it was decided that catalyst in extruded form would be mixed with the
algal feedstock in the KNV pilot plant. The catalyst collection and regeneration are very
important, since the operational costs can be significantly reduced via catalyst recycling. The
extruded catalyst employment was expected to enhance the transport phenomena in the
reactor. Consequently, a 100% increase in the catalyst quantity was utilized and mixed with
the algae. As a result, the catalyst in the reactor will be equal to 6% wt. of the algae, instead
of 3% wt. that was used during the laboratory tests.
The estimated parameters of the catalyst pre-treatment process are summarized in the
following Table:
Table 4-2: Estimated parameters of the catalyst pre-treatment process
4.2.3 CONVERSION
The algae, the catalyst and the solid heat carrier were mixed before they entered the reactor.
The dry solid material mixing requires more energy than the mixing of liquids. Unlike the
liquid material mixing, where a completely homogenized liquid phase can be produced, the
solid material mixing produces two or more easily distinctive phases. They are considered
“well mixed” when the ratio of the mixed particles are in the range of a specified value,
defined by the engineers. There are four types of mixers suitable for dry solid particles: (a)
ribbon blenders, (b) internal screw mixers, (c) tumbling mixers and (d) impact wheels. The
internal screw mixers mix in a slower rate than the ribbon blenders, but the energy
consumption is lower (McCabe, 2001).
The reactor is the main component of the conversion system. The biomass conversion is an
endothermic process. For this reason, the heat transfer towards the reactor has to be
efficient. The heat can be transferred conventionally, via convection from the heating
medium and via conduction through the walls of the reactor. Alternatively, the heat can be
transferred via induction. Two different design layouts were examined: (i) Design Layout A:
with conventional reactor heating and (ii) Design Layout B: with induction reactor heating.
In both design layouts, the reactor of the pilot plant would be a continuous, horizontal,
rotating, single screw reactor. Along the edge of the helix, sharp scrapers would be attached
and would be touching the reactor shell. In this way, the inner surface of the reactor shell
could be “cleaned” during the operation by carrying away the produced charcoal. The
accumulation of this highly viscous charcoal residue would be responsible for regular
maintenance. The residence time of the reactor could be regulated by the screw pitch and
the rotation speed of the screw. A double screw could be used instead of a single, but the
wear rate and solid attrition would be increased in this case. This effect is not desirable,
since after regeneration the separation of the catalyst and the solid heat carrier from the
charcoal ash would be more difficult, due to the fine particle size of the materials. The
reactor would be divided into a pre-heating section (~200 °C) and the actual conversion
section (400 °C) to increase the heat transfer rate . Due to the optimized engineering of the
pilot plant, the mass balance could reach the following yields: (1) organic phase: 45%, (2)
aqueous phase: 25%, (3) gas product: 15%, (4) residue: 15%. An opening at the bottom end
of the tubular reactor would lead the residue to a collection tank. At the upper end of the
tubular reactor, an opening would lead the gases and vapours at the vapour upgrading
section, via the application of vacuum. The vapour upgrading section would be a vertical
tubular reactor, where the catalyst pellets would be placed in a fixed bed. Due to the limited
catalytic activity, a second vapour upgrading section would be placed in parallel with the first.
When the catalytic activity would be significantly reduced, the first section would be isolated
and the second section would be connected in series with the reactor and vice versa.
The estimated parameters of the conversion process are summarized in the following Table:
Table 4-3: Estimated parameters of the conversion process
After the vapour upgrading section, a condenser would be applied to condense the mixture
of organic and aqueous vapours from ~360 °C to ~70 °C. The condensation rate of these
vapours would be significantly reduced, since non-condensable gases would also be present
in the mixture. The condensers suitable for such applications should be placed vertically
instead of horizontally. Vapours should be condensed inside the tubes, while the cooling
medium should flow inside the shell (McCabe, 2001).
The non-condensable gases would exit the system via the vacuum pump. Due to the fact
that slight vacuum would be used during the operation (0.9 bar absolute pressure) a side
channel blower could be utilized, since its purchasing cost would be significantly lower
compared with other types of vacuum pumps.
All three products of the conversion process would be collected in storage tanks. The gas
product would be collected in a volumetric tank. The mixture of condensed vapours (liquid
product) would be collected in a vessel and be left to rest. The different density of the liquid
compounds would create two immiscible phases which could then be easily separated. Each
phase (organic and aqueous) would be put in different storage tanks.
4.2.4 REGENERATION
The regeneration of the reactor residue and the vapour upgrading catalyst would be
performed in the same oven used for the catalyst activation process. Both materials would
be regenerated at 500 °C for 16 h. During the regen eration process, all organic depositions
would be oxidized in a controllable way, by regulating the atmosphere and temperature of
the regeneration chamber. The charcoal oxidation is an exothermic reaction, which requires
significant amount of thermal energy at the reaction offset. It was assumed that the
regeneration efficiency of the reactor catalyst could be 70% and it could be used for 15
additional times. The regeneration efficiency of the vapour upgrading catalyst could be 100%
and it could be used for 15 additional times.
After the residue regeneration, the mixture of the solid heat carrier, the algal ash and the
catalyst would exit the oven. This mixture would be guided to the screening equipment to
separate the fractions of powder (<0.5 mm), solid heat carrier (0.5-2.0 mm) and catalyst
(>2.0 mm). Due to increased attrition forces inside the screw reactor during operation, some
material losses would be expected, because of a size reduction that would lead to powder
formation. These losses were considered negligible for the present calculations.
The estimated parameters of the regeneration process are summarized in the following
Table:
Table 4-4: Estimated parameters of the regeneration process

4.2.5 SAFETY
Industries that deal with powders, liquids and gases that can create explosive mixtures in the
atmosphere must take necessary measures to avoid such incidents. The EN 1137 regulation
demands that such risks should be eliminated or minimized using three principles: (i)
prevention by avoiding explosive atmospheres, (ii) prevention by avoiding effective ignition
sources and (iii) protection by limiting the effects of explosions (Riskman, 2009).
The ATEX application directive affects a vast number of companies, such as those which
process seeds, feedstuff or wood, use coating machinery or produce fireworks or biogas
(Grontmijcarlbro, 2009). For powders, the probability of ignition, especially from electrostatic
discharges, has to be examined. Consideration must be given to the movement of material
after drying, where fine dust can be produced by attrition. Dust collectors can become high
risk areas for fire or explosion. For liquids/gases, their handling and use as fuels requires
Hazardous Area Classification and Basis of Safety definition according to the latest
European Standards. Often a large number of wastes (e.g. ash) are flammable and their
disposal must be handled with the necessary safety measures (Chilworth Global, 2009). The
minimization of ignition sources in closed areas where materials are handled is a common
practice for preventing fires and explosions. Several process equipment types are classified
according to the ATEX directive for the conditions under which they can operate safely. An
increase in their ATEX classification is followed by an increase in their purchasing cost.
The ATEX directive advises that the affected workplaces must implement an extended
workplace assessment, reviewing the potentially explosive areas in the company and
comprising, among other things, a full-scale safety analysis, a risk assessment and
personnel training plans (Grontmijcarlbro, 2009). As expected, such studies increase the
investment cost for the erection of a pilot plant, but are still necessary for the safe operation
of the production site. For the present calculations, the cost of performing such studies was
considered negligible for reasons of simplicity.
4.2.6 ENVIRONMENT
The removal of solid particles dispersed in gases (e.g. flue gases) is very important and
crucial in environmental technology. The gas emissions from production plants transfer
particles towards the atmosphere, which originate either from combustion or from the
production processes that take place. Cyclones and electrofilters are very often used,
especially in industries that are significant producers of gas streams containing solid
particles, such as the cement industry, the industry of inorganic acids and metallurgies. Due
to the high investment cost of this equipment, for the present calculations on the KNV pilot
plant it was assumed that the produced fume gases contain a low amount of solid particles.
4.2.7 DESIGN LAYOUT A
For the Design Layout A, the reactor would be made out of stainless steel. A burner would
be used to heat up the activation/regeneration oven (500 °C) and the reactor (400 °C). The
burner would be able to operate with two different types of gas fuels: (a) with natural gas
from the grid and (b) with the gas product of the algae KNV conversion. The gas product
would contain corrosive compounds (e.g. H2S), therefore the burner might require more
frequent maintenance. The gas burner would have a thermal capacity of 8000 kW. Double
walled equipment (reactor, oven) would be used, since their content (algae, catalyst) should
not be in direct contact with the flue gases.
The proposed flowsheet of the KNV pilot plant for the algae conversion into liquid biofuel is
presented in the following Figure. The mass flow of the materials (algae, solid heat carrier,
catalyst) is marked in black, the flow of the auxiliary utilities (electricity, flue gases, air,
cooling water) is marked in colour, the storage vessels are marked with patterned fill and the
processes that require heat are marked with dashed red lines.
Figure 4-1. KNV pilot plant flowsheet for the Design Layout A
The list of the necessary equipment and their characteristics is presented in the following
Table:
Table 4-5: Necessary equipment and their characteristics for the Design Layout A
4.2.8 DESIGN LAYOUT B
For the Design Layout B, the reactor would be made out of non-metal material that could
stand high temperatures, such as ceramic. The reactor would be heated up by using an
induction generator, which would be creating an induction field around the screw reactor.
The induction heating system would consist of the following components: the induction
generator, the heating coil and the heat exchanger for the cooling medium, which would be
cooling water in this case. The cooling medium would be pumped in a closed circuit. The
heat exchanger could be air/water or water/water. For this application, a water/water heat
exchanger could be used. Metal spheres (4 mm) would be added inside this reactor to
directly heat up the loaded feedstock, rather than the walls of the reactor. In this way, the
temperature profile inside the feedstock would be more homogeneous and local overheating
would be avoided. Still, it is expected that the investment cost of an induction heating system
would be higher than that of a conventional heating system.
The proposed flowsheet of the KNV pilot plant for the algae conversion into liquid biofuel is
presented in the following Figure. The mass flow of the materials (algae, solid heat carrier,
catalyst) is marked in black, the flow of the auxiliary utilities (electricity, flue gases, air,
cooling water) is marked in colour, the storage vessels are marked with patterned fill and the
processes that require heat are marked with dashed red lines:
Figure 4-2. KNV pilot plant flowsheet for the Design Layout B
The list of the necessary equipment and their characteristics is presented in the following
Table:
Table 4-6: Necessary equipment and their characteristics for the Design Layout B
4.3 COST ASSESSMENT
For the cost assessment, a Preliminary Estimate was performed. Such estimates are usually
used to assist the decision making process and to integrate an investment plan to the
budget of a company. A variety of information was needed, such as mass and energy
balances, a list of necessary equipment, a pilot plant layout and a pilot plant location. Some
of the investment elements (piping, insulation, electrical, e.t.c.) were estimated as a
percentage of the basic equipment cost, but others were analytically calculated (i.e.
equipment). The possibility of error in such estimates is less than ±20% (Lipowatz-Kremezi,
2003).
The total investment for the erection and operation of the pilot plant consists of two main
components: the fixed investment and the turnover capital. The fixed investment is the
required amount of money needed for the construction of the main and auxiliary installations
of a plant. The turnover capital is the necessary amount of money needed to cover the
operational expenses of the plant (Lipowatz-Kremezi, 2003).
4.3.1 FIXED INVESTMENT
The equipment investment cost is a key element of the fixed investment, based on which the
total fixed investment cost can be calculated. When referring to the equipment investment
cost, there is a distinction between the purchasing cost, the delivery cost and the installation
cost. In the present calculations, the delivery cost was integrated into the purchasing cost.
The installation cost can be calculated as a percentage of the purchasing cost (Lipowatz-
Kremezi, 2003).
The equipment purchasing cost for both Design Layouts are depicted in the following Table:
Table 4-7: Equipment purchasing cost for the Design Layout A and B
The fixed investment includes a series of direct or indirect costs. Different methodologies
can be used for the calculation of the total fixed investment cost. For the present study, the
Lang methodology was applied. According to this, the total fixed investment cost can be
calculated as (Lipowatz-Kremezi, 2003):
CF = [ CE + ( ΣfjCE) ] fI
where CF: the fixed investment cost for the plant
CE: the purchasing cost for all the plant equipment
fj: a coefficient per cost category to estimate the cost of piping, monitoring/control,
electrical installation, building, land preparation, auxiliary installations and land
investment
fI: a coefficient to estimate the indirect costs (design and supervision, construction
labour costs, contractor costs, unexpected expenses)
The equation above can be written in the following form:
CF = fL CE
where fL = [1 + ( Σfj) ] fI , is the Lang coefficient
The calculation of the Lang coefficient was performed for solid/fluid processing of a pilot
plant, with medium scale automated control, mostly located in an indoor construction, without
important additions in auxiliary intallations, on the grounds that the KNV pilot plant will be
closely located to the Energie AG plant. The following Table presents the basic cost factors
of the fixed investment, their estimated coefficients according to the Lang methodology and
their actuall cost in Euros (Lipowatz-Kremezi, 2003):
Table 4-8: Basic cost factors of the fixed investment and their coefficients over the equipment purchasing cost (Lipowatz-Kremezi, 2003)
As expected, the fixed investment of the Design Layout B was significantly higher than that
of the Design Layout A (almost twice as high).
4.3.2 TURNOVER CAPITAL
For the calculation of the operational cost (production cost), the activity degree of the plant
should be defined. In every plant the operation is stopped for some days per year for repair
and/or maintenance. Consequently, the activity degree rarely exceeds the level of 90-95%.
The mean activity degree in industry is approximately 80% (Lipowatz-Kremezi, 2003).
The breakdown of the total production cost is presented below:

Table 4-9: Breakdown of the total production cost (Lipowatz-Kremezi, 2003)

The added labour costs include dues, holiday bonus, day-off allowance and participation to
profits. For the present calculation, the administration expenses were included as overhead
charges in the hourly rate of engineers and technicians. It was assumed that the research
and development expenses would be covered by Joanneum Research. The sales expenses
were assumed to be insignificant, since the product could be sold to selected parties. Due to
the fact that the pilot plant would be located close to the Energie AG plant, the process cost
expenses could be minimized, as these provisions could be supplied by the nearby plant
facility. Finally, it was assumed that the cost of the raw material would be insignificant, since
the environmental regulations for the reduction of the CO2 emmissions would motivate the
establishment of a co-operation deal between the power plant and the KNV pilot plant.
Analyzing the production cost of a big number of chemical plants, different researchers have
set forward simple or more complex models for the production cost calculation, using the
cost of five basic parameters: the raw materials, the direct labour, the energy, the fixed
investment and the sales expenses. The direct and indirect production expenses can be
expressed as parts of these five basic parameters.
4.3.2.1 LABOUR COST
For the calculation of the labour cost, it was important to estimate the number of technicians
and engineers per shift. The following scheme illustrates the time-plan for the processes of
the KNV pilot plant and the predicted demand for employees (technicians and engineers)
during the plant operation:
Table 4-10: Time-plan for the KNV pilot plant and predicted demand for employees
It was assessed that the production of the KNV pilot plant would be stopped for 34 h/w to
perform maintenance (80% degree of production activity), while the laboratory analysis of
the products would require 16 h/w. It was assumed that the pilot plant would be operating 24
h/d, 7 d/w. The continuous operation of the plant would correspond to 8760 working h/y.
Every working team would cover 40 h/w * 52 weeks/y = 2080 h/y. As a result, 8769 / 2080 =
4.21 working teams would be requested. Considering that each employee would require 4
weeks/y for holidays, every working team would cover 1920 h/y, consequently 8769 / 1920 =
4.56 working teams would be needed. Due to the existence of public holidays and the
absence of employees from work due to medical reasons, it was decided that 5 working
teams would be necessary, working 36.5 working h/week. Each employee would be
receiving 14 salaries per year. The added labour costs (dues, holiday bonus) were estimated
as 25% of the total labour cost calculation.
The following Table depicts the calculation of the total labour cost:
Table 4-11: Total labour cost calculation
The labour cost was equal for both Design Layouts.
4.3.2.2 ENERGY AND AUXILIARY MATERIAL COST
The energy costs of both Design Layouts are displayed in the following Table:
Table 4-12: Energy cost calculation
The natural gas consumption is higher in the Design Layout A, but the electricity
consumption is higher in the Design Layout B. The differences in their unit prices result in
higher energy cost for the Design Layout A in comparison with the Design Layout B.
The analytical cost calculations of the auxiliary materials used in both Design Layouts are
illustrated in the following Table:
Table 4-13: Analytical cost of the auxiliary materials
The cost of the catalytic material was the same for both Design Layouts. The increased
demand for cooling water in induction heating systems was responsible for the higher
cooling water cost for the Design Layout B. Because the equipment purchasing cost and the
fixed investment cost for the Design Layout B were higher, the repair/maintenance and
laboratory cost was increased. As a consequence, the total cost of the auxiliary materials
was higher for the Design Layout B.
The unit price of the catalyst is a key factor for the feasibility of the KNV pilot plant. The cost
of the synthetic zeolite can reach the price of 45000 €/t. For the present calculations, the unit
price of the catalyst was 4500 €/t. Such a decrease in the price could be achieved by
changing supplier or by changing the catalytic material. The use of a natural catalyst or a
non-patented synthetic one with a lower production cost could be a possible alternative.
4.3.2.3 PRODUCTION COST
The following Table lists the basic factors of the production cost and their coefficients for the
KNV pilot plant (Lipowatz-Kremezi, 2003):
Table 4-14: Basic factors of the production cost and their coefficients (Lipowatz-Kremezi,
2003)
The cost of supervision, maintanace and laboratory was already calculated in the labour
cost. The cost of auxiliary materials was not calculated according to this model, but
separately for reasons of accuracy. For the present calculations, it was assumed that there
were no rights expenses, no rent expenses, no general expenses, no research and
development expenses, no sales expenses and low uncertainty level for unexpected
expenses.
In the present calculations, the production cost was significantly affected by the energy
costs. The production cost for the Design Layout A was higher than that for the Design
Layout B.
4.4 ECONOMIC EVALUATION
For the economic evaluation of the two investment plans (Design Layout A and Design
Layout B) the cash flows and the return of the investment periods (payback times) were
calculated. The investment plan with the shorter payback time would be selected as the most
beneficial one.
The KNV pilot plant would be making profit by selling: (a) the organic phase as biofuel to
refineries for further post-treatment, (b) the aqueous phase as raw material to biochemical
industries, (c) the ash produced by the residue regeneration as inorganic material (filler) to
cement industries and (d) the algae powder produced by the size reduction processes as
material for further use (e.g. animal feed). The sale price (in contrast to retail price) for these
materials are presented at the Table below:
Table 4-15: Sale price of the KNV products
The money flows and the net cash flows for both Design Layouts are presented in the
following Table:
Table 4-16: Money flows and net cash flows for the Design Layout A and B
It was assumed that 75% of the fixed investment would be funded by the government in the
form of loan with favourable terms (rate of return: 3%) to promote the penetration of biofuels
into the Austrian market. The rest 25% of the fixed investment would be funded by private
investors (rate of return: 10%).
It was assumed that the private investor would require 10 y of payback time for the Design
Layout A and 15 y of payback time for the Design Layout B. The payback time for the bank
loan and the total payback time for the whole investment are displayed in the Table below:
Table 4-17: Total return of investment periods for the Design Layouts A and B
The payback time of the bank loan for the Design Layout A (24 y) was significantly lower
than that of the Design Layout B (44 y). The increased purchasing cost of the induction
heating systems resulted in a higher fixed investment cost. The operational cost was lower,
but not low enough to prove the Design Layout B more profitable. A change in the energy
prices (electricity, natural gas) could significantly affect the results. Both Design Layouts
were expected to have the same product yields. The present calculations, based on the
specific selected parameters, demonstrated that the Design Layout A was more profitable.
The biofuel prices are subject to variation, according to the biofuel demand and the
conventional petroleum prices. If these factors increase, then the biofuel prices will also raise
and the investment plans will appear more profitable. Biofuel industries require the support
of funding and other actions on national or EU level to penetrate into the fuel market.
Chapter 5: Conclusions 137
5 CONCLUSIONS
The low pressure catalytic co-conversion of safflower oil and rapeseed cake seems to be an
interesting thermochemical process for the manufacture of transportation fuels and
biochemicals. The catalyst addition to the biomass conversion system reduced the liquid
phase yield and significantly changed its composition. The product mixture properties and
composition depended on the process temperature and the catalyst used.
The liquid phase yields at 350 °C were low, while t he main product was solid residue. Thus,
this temperature is not recommended for biomass conversion. However, increasing the
temperature to 400 °C significantly reduced coking and resulted in higher organic liquid
phase yield.
The liquid phase characteristics varied by the use of different catalysts. The Fe-ZSM-5
zeolite did not show high cracking and deoxygenating ability. In its presence, a very low
amount of lower hydrocarbons (C7-C15) formed. The organic liquid phase obtained on this
catalyst was rich in oxygen and had a lower HHV.
The H-ZSM-5 zeolite possesses a better cracking activity, producing an organic liquid phase
with a significantly lower oxygen content. However, the catalytic properties of this zeolite
were restricted by the shape-selectivity effect, preventing the access of big molecules to its
active sites. As a result, a significant part of the fatty acids remained unreacted.
The best results were gained on the H-Beta zeolite that possesses sufficiently strong acidic
sites at absence of steric hindrances. Thus, the degree of biomass polymer and fatty acid
conversion was the highest on this catalyst. The organic liquid product revealed lower
oxygenated compound content and, respectively, the highest HHV. Comparing the results
obtained on all catalysts, it was concluded that the H-Beta zeolite can be recommended to
be applied in the co-conversion of vegetable oil and solid biomass to biofuel. The gained
organic products were similar to fossil fuels by some important characteristics (HHV, density,
viscosity), while other characteristics were even improved (such as sulfur content).
Compared with other biofuels, i.e. pyrolysis oil or liquefaction oil, the gained organic products
showed improved characteristics (HHV, density, viscosity, pH).
The produced aqueous phase contained chemical compounds, such as O- and

Nheterocyclic compounds, that can be a valuable source of biochemicals.
The characteristics of the biofuel produced by the low pressure, catalytic conversion of
rapeseed cake depended on the catalyst type and the presence of the vapour upgrading
section. The addition of catalysts in the conversion system reduced the liquid phase yield
compared with the non-catalytic test.
The organic liquid phases gained at the rapeseed cake conversion on H-ZSM-5 zeolite had a
better quality than those produced when H-Beta zeolite was used. They had lower oxygen
contents and higher HHV. The H-ZSM-5 zeolite possessed higher activity in cracking,
producing a higher amount of aliphatic and aromatic hydrocarbons. The presence of the
vapour upgrading section with this catalyst did not affect significantly the chemical
composition; however, it resulted in an increased organic liquid phase yield. Thus, the use of
the vapour upgrading section in the reactor with H-ZSM-5 zeolite favored an increased
production of biofuel, which could be used in different liquid fuel applications.
The produced aqueous phase contained chemical compounds, such as O- and N-

heterocyclic compounds, that can be a valuable source of biochemicals.
The biofuel characteristics of the low pressure, catalytic conversion of meat meal C1, with H-
ZSM-5 zeolite at the absence of the vapour upgrading section, were different than those of
the rapeseed cake conversion using the same parameters. The increased meat meal C1 ash
content had as a result the residue increase. The organic phase consisted of increased
amounts of valuable biofuel components, such as aliphatic and aromatic hydrocarbons. Still,
the organic phase of the rapeseed cake conversion had a better quality, demonstrating a
higher HHV and a lower water content.
The low pressure, catalytic conversion of algae, with H-ZSM-5 zeolite in the presence of the
vapour upgrading section, resulted in a significantly increased biofuel yield compared with
that of the rapeseed cake conversion test. The organic phase consisted of an increased
amount of hydrocarbons (aliphatic and aromatic) and had a higher HHV than that of
rapeseed cake as well as a density similar to diesel. Thus, the organic phase of the algae
conversion had a better quality than the organic phase of the rapeseed cake conversion.
The produced aqueous phases of both meat meal C1 and algae conversion tests contained
chemical compounds (e.g. N-heterocyclic compounds) that can be a valuable source of
biochemicals.
The energy efficiency of the selected KNV laboratory tests, using H-ZSM-5 zeolite, increased
by the following order: [meat meal C1 conversion] < [algae conversion] < [rapeseed cake
conversion with vapour upgrading section] < [rapeseed cake conversion without vapour
upgrading section] < [safflower oil and rapeseed cake co-conversion].
The increased products energy content of the co-conversion test resulted in a rise in its
energy efficiency. On the contrary, the energy efficiency of the meat meal conversion was
low. The increased energy content of the produced gas from the rapeseed cake conversion,
in the absence of the vapour upgrading section, was responsible for the increased energy
efficiency of this test, compared with that when the vapour upgrading section was present.
Feedstocks with a significant humidity amount (e.g. algae) show an increased thermal
energy demand for drying. As a result, the energy efficiency of their conversion is
significantly lower compared with other tests.
The present feasibility studies calculations, based on the selected parameters, proved
Design Layout A (with a conventional gas burner) more profitable than Design Layout B (with
an induction heating system).
The technology selection significantly affected the fixed investment costs, while it had a
negligible effect on the labour costs. The production costs depended on the used energy/fuel
and its present unit prices. Any changes in these prices could significantly affect the
production costs. The high catalyst price was also a key factor. The investment plan could
only be profitable when a lower unit price and efficient catalyst regeneration was ensured. An
increase in the conventional petroleum price could result in an increase in the produced
biofuel price. That could make the investment plan for the erection of the KNV pilot plant
more profitable. Still, biofuel industries need strategic and funding support on a national or
EU level. In this way, the biofuel penetration into the fuel market will be possible.
Chapter 6: Issues for further Research 141
6 ISSUES FOR FURTHER RESEARCH

Based on the results of the present work, the following issues for further research are
suggested:
- the performance of laboratory tests using higher temperature (> 400 °C) and higher
vacuum (< 0.9 bar), in order to explore their effect on the KNV conversion of different
feedstocks
- the performance of algae conversion tests with the H-Beta catalyst in the presence and
absence of the vapour upgrading section, in order to clarify the catalytic effect on the
products
- the performance of meat meal C1 conversion tests with H-ZSM-5 in the presence of the
vapour upgrading section and with H-Beta catalyst in the presence and absence of the
vapour upgrading section, in order to clarify the catalytic effect on the products
- the application of different separation technologies for the removal of compounds from the
organic phases, which should not be present in biofuels
- the application of different separation technologies for isolating valuable compounds of the
aqueous phases
- the performance of a market study for the utilization of the aqueous phases as a source of
biochemicals
- the performance of laboratory tests with other promising catalytic materials (natural or
synthetic ones) for the KNV conversion of biogenic feedstocks into biofuels
Chapter 7: Literature 143
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Chapter 8: Annex 151
8 ANNEX
8.1 BIOMASS DATABASE
Table 8-1: Biomass database

8.2 MASS BALANCES OF THE PERFORMED TESTS
Table 8-2: Product yields (wt. % on biogenic mixture) of the performed rapeseed cake and

CONFIGURATIONS
Table 8-3: Product yields (wt. % on biogenic mixture) of the performed rapeseed cake
conversion tests using two reactor configurations
Table 8-4: Product yields (wt. % on biogenic mixture) of the performed separate meat meal
C1 and algae conversion tests
8.3 DETAILED COMPOSITION OF THE LIQUID PRODUCTS
Table 8-5: Organic phase detailed composition of the performed rapeseed cake and
Table 8-6: Aqueous phase detailed composition of the performed rapeseed cake and

CONFIGURATIONS
Table 8-7: Organic phase detailed composition of the rapeseed cake conversion tests using
two reactor configurations
Table 8-8: Aqueous phase detailed composition of the rapeseed cake conversion tests
Table 8-9: Organic phase detailed composition of the separate meat meal C1 and algae
conversion tests
Table 8-10: Aqueous phase detailed composition of the separate meat meal C1 and algae
conversion tests
8.4 HEATING VALUES PREDICTION MODELS
Table 8-11: The heating value prediction model by Boie

8.5 SAMPLE PHOTOS OF THE LIQUID FUEL SAMPLES
Figure 8-1. Sample photos of (a) the organic and (b) the aqueous phase
8.6 CHROMATOGRAMS EXAMPLE OF THE LIQUID PRODUCT

SAMPLES
Figure 8-2. Chromatogram example of the organic phase

Figure 8-3. Chromatogram example of the aqueous phase

8.7 XRD SPECTRUM EXAMPLE OF THE REGENERATED

CATALYST
Figure 8-4. XRD spectrum example of the regenerated catalyst
8.8 SAMPLE PHOTOS OF THE CATALYST BEFORE AND AFTER

REGENERATION
Figure 8-5. Sample photos of the catalyst (a) before and (b) after regeneration
8.9 PUBLISHED PAPERS AT SCIENTIFIC JOURNALS

1. Giannakopoulou, K., Lukas, M., Vasiliev, A., Brunner, C., Schnitzer, H., 2009, Low
pressure co-conversion of biogenic waste (rapeseed cake) and vegetable oil, Bioresource
Technology, doi:10.1016/j.biortech.2009.12.032
2. Giannakopoulou, K., Lukas, M., Vasiliev, A., Brunner, C., Schnitzer, H., 2010, Conversion
of rapeseed cake into bio-oils in a batch reactor: effect of catalytic vapour upgrading,
Microporous and Mesoporous Materials 128, 126-135
8.10 PRESENTATIONS AND PUBLIC EVENTS
The results of this study were presented at the following conferences/public events:
1. 16th Biomass Conference and Exhibition, 1-6/6/2008, Valencia, Spain
2. Advances in Energy Studies, 6th Biennial International Workshop, 29/6-2/7/2008, Graz,

Austria
3. National IEA Bioenergy Workshop, 9/9/2008, Vienna, Austria
4. 4th International Symposium on the Environment, AT.IN.E.R., 21-24/5/2009, Athens,

Greece
KANELLINA GIANNAKOPOULOU
Personal
Information
Date of birth 15/02/1982
Marital status Single
Address Sarkoudinou 109, 11744, Athens, Greece
Tel. +30 210 9013772
+30 6938 416492
E-mail [email protected]; [email protected]
Profile Highly motivated individual, with leadership, organizing, and problem-solving

skills. With good technical background in chemical engineering issues. Compe-
tent in observing, comparing, analyzing and planning. Able to cooperate and
communicate efficiently with others. Decisive and hard-working.
Education
Dates Oct. 2006 – March. 2010
PhD thesis: “Development of a low pressure, catalytic process for the

production of biofuels”, Graz University of Technology, Graz, Austria
Design of the catalytic process, construction of a laboratory-scale testing facility,

performance of systematic tests with different feedstocks and catalysts, prepa-
ration of a feasibility study for the upscaling of the developed process.
Dates Oct. 1999 – Feb. 2005
Diploma in Chemical Engineering, National Technical University of Athens,

Athens, Greece
Focus on Process Analysis and Design. The Diploma Thesis included research
and experimental work about the “Use of cerium catalysts for the Water-Gas
Shift reaction”.
Professional
experience
Dates Jul. 2005 – Dec. 2005
Internship at Joanneum Research, at the Institute of Sustainable Tech-

niques and Systems, Graz, Austria
Research work in the field of synthetic fuels, solar thermal energy, energy effi-
ciency and market research for the development of new products.
Dates Sept. 2003 – Oct. 2003
Internship at the Department of Operations, Engineering and HSSE of

Shell-Gas, Aspropyrgos, Greece
Familiarization with the safety rules and technical specifications of constructing

domestic / industrial LPG facilities and of the delivering / storage / distribution of
LPG.
Dates Apr. 2003 – May 2003 and Oct. 2004 – Dec. 2004
Member of the research team “Development and Application of Quality

Control Systems at Fuels Stations in Greece” ELIN Fuels in co-operation
with the National Technical University of Athens, Athens, Greece
Sampling of liquid fuels from fuel stations in West Peloponnese and quality test-
ing at the Laboratory of Fuels and Lubricants of the National Technical Univer-
sity of Athens.
Languages
Greek Native speaker
English Excellent skills:
(1) Certificate of Proficiency in English, Cambridge University, Dec. 2000
(2) Qualification of Adequacy for the English Language, Greek Ministry of Edu-
cation
German Intermediate speaking and writing skills
Computer Microsoft Office (Word, Excel, Powerpoint, Visio), Photoshop, Mathcad, Matlab,
Skills Fortran
Seminars Creativity Techniques (2008),
Innovation for Sustainability in Industry (2008),
Ecological Process Evaluation (2007),
Renewable Resources-Production Technologies (2007),
Production Integrated Environmental Protection (2007)
at the Graz University of Technology, Graz, Austria.
Renewable Energy Resources (2006)
at the Halmstad University, Falkenberg, Sweden
Interests Special interest in arts: ballet (10 years), traditional greek dance (4 years), opera
singing (3 years), music, theatre, cinema. Also, travelling and psychology.
Publications
Scientific (1) K. Giannakopoulou, M. Lukas, A. Vasiliev, C. Brunner, H. Schnitzer, “Low

Journals pressure co-conversion of biogenic waste (rapeseed cake) and vegetable
oil”, Bioresource Technology, , doi:10.1016/j.biortech.2009.12.032
(2) K. Giannakopoulou, M. Lukas, A. Vasiliev, C. Brunner, H. Schnitzer, “Con-

version of rapeseed cake into bio-oils in a batch reactor: effect of catalytic
vapor upgrading”, Microporous and Mesoporous Materials 128 (2010) 126-
135
Conferences (1) K. Giannakopoulou, M. Lukas, S. Scober, M. Mittelbach, B. Slawitsch, H.

Boechzelt, C. Brunner, H. Schnitzer, “Low pressure, catalytic depolymeriza-
tion of biogenic feedstocks”, 16th Biomass Conference and Exhibition, 1-
6/6/2008, Valencia, Spain
(2) K. Giannakopoulou, M. Lukas, S. Scober, M. Mittelbach, B. Slawitsch, H.

Boechzelt, C. Brunner, H. Schnitzer, “Development of a Low Pressure,
Catalytic, Direct Liquefaction Process for the Conversion of Biogenic Mate-
rials into Liquid Fuels”, Advances in Energy Studies, 6th Biennial Interna-
tional Workshop, 29/6-2/7/2008, Graz, Austria
(3) K. Giannakopoulou, C. Brunner, “Low Pressure, Catalytic Conversion of Bio-

genic Feedstocks”, National IEA Bioenergy Workshop, 9/9/2008, Vienna,
Austria
(4) K. Giannakopoulou, C. Brunner, H. Schnitzer, “Low Pressure, Catalytic Con-

version of Biogenic Materials into Liquid Biofuels: Effect of Zeolite Cata-
lysts”, 4th International Symposium on the Environment, 21-24/5/2009, Ath-
ens, Greece
rd
Conferences (1) 3 Panhellenic Conference of Chemical Engineering, NATIONAL
Attended TECHNICAL UNIVERSITY OF ATHENS, 31/5-2/6/2001, Athens, Greece
(2) “Waste utilization in favor of Humans”, FESTIVAL FOITHSH, 22-23/11/2003,

Athens, Greece
(3) Biofuel Marketplace International Workshop and Stakeholder Event,

INTELLIGENT ENERGY EUROPE, 9/3/2006, Budapest, Hungary
(4) Environmental Management Accounting and Cleaner Production

(EMAN/CP), GRAZ UNIVERSITY OF TECHNOLOGY, 26/4/2006, Graz,
Austria
(5) World Biofuel Markets, GREEN POWER CONFERENCES, 12-14/3/2008,

Brussels, Belgium
(6) 16th Biomass Conference and Exhibition, ETA-Florence Renewable Ener-

gies, 1-6/6/2008, Valencia, Spain
(7) Advances in Energy Studies, 6th Biennial International Workshop, GRAZ

UNIVERSITY OF TECHNOLOGY, 29/6-2/7/2008, Graz, Austria
(8) National IEA Bioenergy Workshop, IEA AUSTRIA, 9/9/2008, Vienna, Austria
(9) “Moving towards a future with Renewable Energy Sources”, GREEK

WOMAN’S ENGINEERING ASSOCIATION, 4/3/2009, Athens, Greece
(10) “Improvement of the Energy Efficiency in Industry, Buildings, Transporta-

tion”, GREEK WOMAN’S ENGINEERING ASSOCIATION, 5/3/2009, Ath-
ens, Greece
(11) 4th International Symposium on the Environment, AT.IN.E.R., 21-

24/5/2009, Athens, Greece
Associations (1) Member of T.E.E. (Technical Chamber of Greece)
(2) Member of E.D.E.M. (Greek Woman’s Engineering Association)
(3) Member of AT.IN.E.R. (The Athens Institute for Education and Research)
Scholarships (1) From “Korgialleneion Athlon” for support during the PhD studies, 10/2006-
9/2009
(2) From I.K.Y. (State Scholarships Foundations) for high academic achieve-
ment, 10/1999-6/2000

4898 Giannakopoulou Kanellina 2010

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4898 Giannakopoulou Kanellina 2010

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Kanellina Giannakopoulou

Development of a low pressure, catalytic process for the

zur Erlangung des akademischen Grades einer

Doktorin der technischen Wissenschaften

Technischen Universität Graz

Univ.Prof. DI Dr. Hans Schnitzer

Institut für Prozess- und Partikeltechnik

Technische Universität Graz

Graz, March 2010

1.1 Biofuels overview..................................................................................................................... 23

1.1.1 The energy sector today .............................................................................................. 23

1.1.2 Biofuel generations ...................................................................................................... 24

1.1.3 Recent biofuel production ............................................................................................ 26

1.1.4 Biofuel production targets ............................................................................................ 28

1.2 Biofuel incentives .................................................................................................................... 29

1.3 EU vision for biofuels............................................................................................................... 32

2 BIOFUEL PRODUCTION – STATE OF THE ART......................................................................... 35

2.1 Biogenic resources.................................................................................................................. 35

2.1.1 Biomass classification ................................................................................................. 35

2.1.2 Biomass physicochemical composition ....................................................................... 35

2.1.3 Biomass availability...................................................................................................... 35

2.2 Biomass conversion technologies ........................................................................................... 36

2.2.1 Gasification .................................................................................................................. 38

2.2.1.1 Description .............................................................................................................. 38

2.2.1.2 Reactor types .......................................................................................................... 38

2.2.1.3 Reaction mechanisms ............................................................................................. 41

2.2.1.4 Mass and energy efficiency..................................................................................... 42

2.2.2.1 Description .............................................................................................................. 42

2.2.2.2 Reactor types .......................................................................................................... 43

2.2.2.3 Reaction mechanisms ............................................................................................. 46

2.2.2.4 Mass and energy efficiency..................................................................................... 49

2.2.3 Liquefaction ................................................................................................................. 49

2.2.3.1 Description .............................................................................................................. 49

2.2.3.2 Reactor types .......................................................................................................... 53

2.2.3.3 Organic liquid carrier effect ..................................................................................... 53

2.2.3.4 Reaction mechanisms ............................................................................................. 56

2.2.3.5 Mass and energy efficiency..................................................................................... 57

2.2.4 Catalysis in thermochemical conversion processes .................................................... 58

2.2.4.1 Catalytic pyrolysis and catalytic liquefaction reaction mechanisms......................... 60

3 THE DEVELOPED PROCESS (KNV) ............................................................................................ 65

3.1 Motivation / Contribution.......................................................................................................... 65

3.2 The experimental KNV unit and procedure ............................................................................. 65

3.3 Selection of feedstocks ........................................................................................................... 69

3.4 Selection of liquid carrier / solid carrier material...................................................................... 70

3.5 Selection of catalysts............................................................................................................... 71

3.6 Performed tests / Results........................................................................................................ 72

3.6.1 Co-conversion of rapeseed cake and safflower oil...................................................... 72

3.6.1.1 Scientific background .............................................................................................. 72

3.6.1.2 Performed tests ....................................................................................................... 73

3.6.1.3 Phase composition of the reaction mixture ............................................................. 74

3.6.1.4 Chemical composition of the organic phase ........................................................... 75

3.6.1.5 Chemical composition of the aqueous phase ......................................................... 76

3.6.1.6 Elemental composition / Physical properties........................................................... 77

3.6.2 Rapeseed cake conversion with two reactor configurations........................................ 79

3.6.2.1 Scientific background .............................................................................................. 79

3.6.2.2 Performed tests ....................................................................................................... 80

3.6.2.3 Phase composition of the reaction mixture ............................................................. 80

3.6.2.4 Chemical composition of the organic phase ........................................................... 81

3.6.2.5 Chemical composition of the aqueous phase ......................................................... 83