Faculty of Bioscience Engineering

Academic year 2013 2014

The role of alkali and earth alkaline metals as

intrinsic catalysts in the fast pyrolysis of biomass
constituents

Jens Huyghe
Promotors:

Prof. dr. ir. Frederik Ronsse

Prof. dr. ir. Wolter Prins

Tutor: Ir. Jop Vercruysse

Masters dissertation submitted in partial fulfillment of the requirements

for the degree of Master in Bioscience Engineering: Chemistry and
Bioprocess Technology

II

De auteur en de promotoren geven de toelating deze scriptie voor consultatie beschikbaar te

stellen en delen ervan te kopiren voor persoonlijk gebruik.
Elk ander gebruik valt onder de beperkingen van het auteursrecht, in het bijzonder met
betrekking tot de verplichting uitdrukkelijk de bron te vermelden bij het aanhalen van
resultaten uit deze scriptie.
The author and the promotors give the permission to use this thesis for consultation and to
copy parts of it for personal use.
Every other use is subject to the copyright laws, more specifically the source must be
extensively specified when using the results from this thesis.

Gent, 6 juni 2014,

De promotoren,

Prof. dr. ir. Frederik Ronsse

De auteur,

Prof. dr. ir. Wolter Prins

Jens Huyghe

III

IV

PREFACE
Ik sluit mijn studies aan de faculteit bio-ingenieurswetenschappen af met deze masterproef,
waar ik de voorbije tien maanden intensief aan heb gewerkt. Hierbij heb ik hulp gekregen van
verschillende personen die ik graag even wil bedanken.
Mijn eerste dankwoord gaat naar mijn promotor, Prof. dr. ir. Frederik Ronsse. Graag wil ik
hem bedanken om mij de kans te geven deel uit te maken van de vakgroep
Biosysteemtechniek. Ik kon steeds bij hem terecht met al mijn vragen en met zijn raad tijdens
onze regelmatige bijeenkomsten zorgde hij ervoor dat ik door de bomen het bos bleef zien.
Vervolgens wil ik graag mijn tutor Jop Vercruysse bedanken, met wie ik het zowel op
persoonlijk als professioneel vlak goed kon vinden. Hij stond steeds klaar om me te helpen
bij de micropyrolyse experimenten en om mijn geschreven werk na te kijken.
Ook Andries Poupaert, mijn medethesisstudent, wil ik bedanken voor de vlotte
samenwerking en het studeerwerk dat hij me bespaarde dankzij zijn uitleg over statistische
analyses.
Het laatste dankwoord wil ik richten aan mijn ouders die me de kans hebben gegeven om
deze mooi studies te volbrengen. Hun vertrouwen en steun hebben me steeds veel deugd
gedaan.

Jens Huyghe
Gent, juni 2014

VI

SAMENVATTING
Bio-olie als product van snelle pyrolyse biedt een groot potentieel als bron voor de productie
van chemicalin of zelfs als vervanger voor fossiele brandstoffen. Het voorbije decennium is
veel onderzoek gevoerd naar de mechanismen en de kinetiek van snelle pyrolyse van
biomassa en de vele mogelijkheden die de uiteindelijke producten kunnen leveren. In deze
masterproef werd het effect van natuurlijk voorkomende anorganische elementen onderzocht
op de snelle pyrolyse van de twee hoofdbestanddelen van biomassa, namelijk lignine en
cellulose. Zouten van kalium en calcium werden gebruikt als vertegenwoordigers van
respectievelijk de alkali-en aardalkalimetalen, terwijl een HZSM-achtige zeoliet aangewend
werd om het katalytisch effect van de intrinsieke anorganische componenten te kunnen
vergelijken met dit van een extern toegevoegde katalysator. Voor dit onderzoek werd de
techniek van micropyrolyse, gekoppeld met gaschromatografie en massaspectrometrie,
toegepast. Dit is een zeer nuttige manier omdat via deze techniek een onderscheid kan
gemaakt worden tussen primaire en secundaire afbraakreacties. Om de primaire reacties te
onderzoeken werden de katalysatoren gemengd met afwisselend lignine en cellulose voor ze
samen gepyrolyseerd werden (in-bed katalyse). Anderzijds werden de secundaire reacties
bestudeerd door de katalysator in een reactor na de pyrolysereactor te plaatsen, waar het de
dampen katalyseert (ex-bed katalyse). Eerst werden cellulose en lignine gepyrolyseerd bij
verschillende temperaturen om een onderscheid te maken in de degradatiemechanismen en
de optimale pyrolysetemperatuur vast te stellen. Een temperatuur van 500C werd gekozen
om de verdere experimenten uit te voeren aangezien bij deze temperatuur de opbrengst aan
bio-olie maximaal is. Vervolgens werden katalytische experimenten uitgevoerd met de twee
hoofdbestanddelen van biomassa gempregneerd met acetaat, citraat en chloride zouten van
kalium en calcium. Algemeen wordt aangenomen dat alkali-en aardalkalimetalen de primaire
afbraak van cellulose benvloeden. Zij worden beschouwd als inhibitoren van het breken van
de glycosidebindingen tussen de glucose units, wat leidt tot fragmentatie en dus een hogere
opbrengst van laagmoleculaire componenten. Dit effect werd bevestigd door onze resultaten.
Ook de daling in geproduceerd levoglucosaan bevestigt deze theorie. Een ander interessant
resultaat is het vermogen van calcium om de opbrengst van waardevolle chemicalin zoals
furfural en 5-hydroxymethylfurfural te verhogen. Het katalytisch effect op lignine was minder
intens. Er werd een kleine toename van de niet-gemethoxyleerde fenolische componenten
en aromaten waargenomen, wat wijst op een katalytisch effect op de demethoxylering.
Vervolgens werd ook ontdekt dat dezelfde katalytische invloeden zoals beschreven voor inbed katalyse werden teruggevonden in de resultaten van de ex-bed experimenten. Dit geeft
aan dat alkali- en aardalkalimetalen levoglucosaan en andere anhydrosuikers kunnen
destabilizeren en fragmenteren in componenten met een laag moleculair gewicht. Het effect
van de HZSM-5 katalysator was volledig verschillend dan de effecten geobserveerd bij de
experimenten met alkali- en aardalkalimetalen. HZSM-5 heeft een grotere invloed op de
secundaire reacties en zal vooral cyclisatiereacties leidend tot aromaten promoten.

VII

VIII

ABSTRACT
Fast pyrolysis bio-oils have huge potential as a source for the production of chemicals or
even as a replacement fossil fuels. Last decade lots of scientists studied the mechanisms
and kinetics of biomass fast pyrolysis and the possibilities the final products offer. In this
masterthesis the effect of naturally occurring inorganics on the fast pyrolysis of the two main
biomass constituents, lignin and cellulose, is investigated. Salts of potassium and calcium
were used as representatives for respectively the alkali and earth alkaline metals, while a
HZSM-like zeolite was used to compare the catalytic effect of intrinsic inorganics with those
of extrinsic added catalysts. Therefore micropyrolysis coupled to gas chromatography and
mass spectrometry is applied as a useful approach because a distinction can be made
between primary and secondary thermal degradation reactions. Therefore the catalyst is
respectively mixed with the biomass compound (in-bed catalysis) and placed in a reactor
downstream the pyrolysis reactor where it catalyzes pyrolysis vapors (ex-bed catalysis).
First cellulose and lignin were pyrolyzed at different temperatures to differentiate thermal
degradation mechanisms and to define a proper pyrolysis temperature for the catalytic
experiments. A temperature of approximately 500C was chosen to execute the experiments
since it is the optimal temperature for maximizing the bio-oil yield. Next catalytic pyrolysis
experiments were conducted with cellulose and lignin impregnated with the acetate, citrate
and chloride salts of potassium and calcium. It is generally accepted that alkali and alkaline
earth metals have an influence on the primary decomposition of cellulose. They are
considered as inhibitors for glycosidic bond breakage, leading to a higher yield of low
molecular weight oxygenates. This effect was confirmed by our results, together with a
significant decrease in levoglucosan production. An interesting result is the potential of
calcium to increase the yield of furfural and 5-hydroxymethylfurfural, both valuable platform
chemicals. The catalytic effect on lignin was less intense, but a small increase in nonmethoxylated phenolic species and aromatics was observed, which indicates a catalytic
effect on the demethoxylation reaction. Furthermore it was interesting to discover that the
same catalytic influences as described for in-bed catalysis were also found back in ex-bed
catalysis. This indicates that alkali and earth alkaline metals are able to destabilize and
fragment levoglucosan and other anhydrosugars into low molecular weight compounds. The
effect of the HZSM-5 catalyst was totally different than this observed by the salts. The effect
of in-bed and ex-bed catalysis with HZSM-5 was similar with respect to the pyrolysis vapor
constituents formed, which proves that HZSM-5 merely acts on the secondary decomposition
of the already formed primary vapour constituents.

IX

TABLE OF CONTENTS
Preface.................................................................................................................................. V
Samenvatting ...................................................................................................................... VII
Abstract ................................................................................................................................ IX
List of Figures..................................................................................................................... XIII
List of Tables ....................................................................................................................... XV
Introduction ........................................................................................................................... 1
Literature research ................................................................................................................ 3
1.

First and second generation biofuels .......................................................................... 3

2.

What is biomass ......................................................................................................... 4

2.1 Cellulose .................................................................................................................. 5
2.2 Lignin ....................................................................................................................... 6
2.3 Hemicellulose ........................................................................................................... 6
2.4 Extractives ................................................................................................................ 7
2.5 Ash ........................................................................................................................... 7

3.

Conversion of biomass ............................................................................................... 8

3.1 Thermochemical conversion ..................................................................................... 8

4.

Bio-oil ........................................................................................................................12
4.1 Applications .............................................................................................................14

5.

Decomposition mechanisms of biomass constituents in fast pyrolysis .......................15

5.1 Cellulose .................................................................................................................15
5.2 Lignin ......................................................................................................................17
5.3 Hemicellulose ..........................................................................................................18

6.

Catalytic upgrading ....................................................................................................19

6.1 Influence of alkali and alkaline earth metals ............................................................20

Objective ..............................................................................................................................23
Materials and methods .........................................................................................................25
1.

Sample preparation ...................................................................................................25

2.

Micropyrolysis experiments (pyGC-MS) .....................................................................25

3.

Catalytic pyrolysis experiments (pyGC-MS) ...............................................................26

4.

GC-MS data processing.............................................................................................28

Results and discussion .........................................................................................................29

1.

Temperature effect ....................................................................................................29

1.1 Cellulose .................................................................................................................29
XI

1.2 Lignin ......................................................................................................................32

2.

Alkali and earth alkaline metal catalysis .....................................................................37

2.1 In-bed catalysis .......................................................................................................37
2.2 Ex-bed catalysis ......................................................................................................44

3.

Zeolite catalysis .........................................................................................................49

3.1 Cellulose .................................................................................................................49
3.2 Lignin ......................................................................................................................52

Conclusions..........................................................................................................................55
Recommendations for further research ................................................................................57
References ...........................................................................................................................59
Appendix ..............................................................................................................................65
1.

List of pyrolysis products............................................................................................65

XII

LIST OF FIGURES
Figure 1: Technology pathways to transform biomass into biofuel. 4
Figure 2: Cellulose structure
5
Figure 3: Non-, mono- and dimethoxylated monoligols in lignin
6
Figure 4: Main constituents hemicellulose.
7
Figure 5: Influence of temperature on product distribution..
11
Figure 6: Biomass mass loss in function of temperature.
15
Figure 7: Proposed models for the degradation of cellulose 16
Figure 8: Mechanism for levoglucosan formation proposed by ponder et al. 17
Figure 9: Reactions associated with the catalytic upgrading of bio-oils.. 19
Figure 10: Cellulose degradation mechanism in presence of inorganics 21
Figure 11: Micropyrolysis setup at the department of bioscience engineering. 25
Figure 12: Reaction tube packed with catalyst. 27
Figure 13: Overview of the frontier micropyrolyzer. 27
Figure 14: TIC chromatogram of pure cellulose (Avicell) micropyrolysis of approx. 0.5 mg at
(upper) 300C, (middle) 400C and (bottom) 500C..
29
Figure 15: Relative amount of oxygenated compounds, furans/pyrans and anhydrosugars in
function of pyrolysis temperature in pygcms 31
Figure 16: relative amount produced of the 6 most important cellulose pyrolysis degradation
products. Levoglucosan (LG) and 1,6-Anhydro--d-galactofuranose (agf) are examined on
the left axis, Hydroxymethylfurfural (hmf), levoglucosenone (lgo), furfural (FF) and
hydroxyacetaldehyde (ha) on the right axis. 32
Figure 17: TIC chromatogram of lignin micropyrolysis of approx. 0.5 mg at (upper) 300C,
(middle) 400C and (bottom) 500C.. 33
Figure 18: Relative amount of low molecular weight compounds, phenolas and aromatics in
function of temperature in pygcms. 34
Figure 19: Total peak area per mg sample calculated from the gas chromatographic analysis
of lignin and cellulose pyrolysis products in pygcms.. 35
Figure 20: Amount of non, mono and dimethoxylated phenols produced during lignin
pyrolysis in function of temperature in pygcms 36
Figure 21: Amount produced of twelve most important products of lignin pyrolysis in function
of temperature in pygcms 37
Figure 22: Classification of pyrolysis products of cellulose samples impregnated with various
concentrations of potassium citrate in pygcms at 500c. 38
Figure 23: Classification of pyrolysis products of cellulose samples impregnated with various
concentrations of Calcium citrate in pygcms at 500C 39
Figure 24: Effect of different salts on five main cellulose pyrolysis products. 42
Figure 25: Relative amount of low molecular weight compounds, phenols and aromatics
during 500C lignin pyrolyis in function of added cacl2 concentration.. 43
Figure 26: Amount of non, mono and dimethoxylated phenols produced during 500C lignin
pyrolysis in function of the added metal concentration 43
Figure 27: Effect of different salts on main lignin 500C pyrolysis products 44
Figure 28: Classification of pyrolysis products of cellulose at 500C after vapour phase
catalysis with kcl and cacl2 in pygcms . 46
Figure 29: TIC total peak area per mg sample of the pyrolysis products of cellulose in in- en
ex-bed catalyzed mode 47
XIII

Figure 30: tic total peak area per mg sample of the pyrolysis products of both cellulose and
lignin in non-catalyzed and in in- and ex-bed catalyzed mode
48
Figure 31: effect of different levels of hzsm-5 on the main cellulose 500C pyrolysis products
in pygcms. levoglucosan (lg) is examined on the left axis; toluene, furfural (ff), 2,3-anhydro-dgalactosan and hydroxyacetaldehyde (haa) on the right axis.....
50
Figure 32: Absolute amount of cellulose pyrolysis products detected by the gc/ms in terms of
total peak area
50
Figure 33: Absolute amount of lignin pyrolysis products detected by the gc/ms in terms of
total peak area
52

XIV

LIST OF TABLES
Table 1: Elemental composition for different kinds of biomass 8
Table 2: Differences between conventional, fast and flash pyrolysis.
9
Table 3: Physical properties of bio-oil and heavy fuel oil.
12
Table 4: Characteristics of bio-oil.. 14
Table 5: Gas chromatographic analysis of pyrolysis products from cellulose at 500C. The
products determined at 300C are indicated with a star, those with one or more stars are
found at 400C.. 30
Table 6: Gas chromatographic analysis of pyrolysis products from lignin at 500C. the
products indicated with at least one star are also found in the distribution at 400C, the
products with only one star are those determined at 300C.. 33
Table 7: Relative amount (TIC relative abundance) of the main cellulose 500c pyrolysis
products after vapor phase upgrading .. 46
Table 8: Relative amount of the main lignin pyrolysis products after vapor phase
upgrading 48
Table 9: Gas chromatographic analysis of 500C pyrolysis products from lignin catalyzed
with hszm-5 in ex-bed mode 51

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XVI

INTRODUCTION
The use of biomass as a source of renewable energy has become very important because of
the large opportunities it offers to solve environmental problems. Together with the living
standards the world population is increasing, which forces us to find alternatives to satisfy the
growing energy demand without contributing to the greenhouse effect originating from the
use of fossil fuels. The high and fluctuating prices of oil and the desire of countries to be
independent in their energy supply are economic reasons to justify the use of renewable
resources. The declining reserves of fossil fuels and the abundant availability of biomass
worldwide, coupled with the concerns about nuclear energy, are additional driving forces to
investigate the opportunities of biomass-derived energy. The most interesting advantage of
the use of biomass is the fact that there is no net contribution to the atmospheric CO 2, one of
the most important gases causing global warming. Since the growing concerns about the
well-known greenhouse effect, scientists are attracted to study the possibilities of bio-energy
and in this way reducing the emissions of CO2.1 The European Union has decided that by
2020 a minimum of 20% of the consumed energy must be derived from renewable resources
and furthermore they have set an obligatory target of 10% for biofuels2. These targets are
ambitious if you know that in 2010 only 12.4% of the energy was renewable. Belgium didnt
even reach 5%. Biomass is with 67% by far the most important source of renewable energy3.
Its particularly interesting because at this moment its the only renewable resource of liquid
transportation fuel. Fast pyrolysis is receiving attention as one of the most promising
processes to obtain bio-oil. During this process, the biomass constituents are thermally
cracked into numerous smaller components, which can be classified according to their
physical appearance at room temperature: liquid bio-oil, solid char and non-condensable
gases. Although a lot of research has been done during the last decades to improve the
quality of the bio-oil, still some problems exist in terms of viscosity, acidity, aging etc. Thats
why knowledge about its chemical composition and consequently about possible ways to
improve bio-oil quality is of utmost importance. Biomass contains some natural catalysts
which can affect the pyrolysis process. Previous work has demonstrated the catalytic effect
of inorganic compounds and alkali metals and alkaline earth metals in particular. They have
a significant influence on the yield and composition of pyrolysis liquids as they catalyze
specific pyrolysis reactions. Hence the main purpose of this master thesis is the investigation
of the catalytic effect of alkali and alkaline earth metals on the primary and secondary
pyrolysis reactions of the major biomass constituents cellulose and lignin.

LITERATURE RESEARCH
1. FIRST AND SECOND GENERATION BIOFUELS
The use of fossil fuels and the subsequent CO2 production can be decreased by applying
biofuels from renewable resources since the CO2 released by burning the biofuel is the same
amount that has been stored by the plant using photosynthesis. A distinction can be made
between biofuels of the first and the second generation. First generation biofuels are made
from sugar, stark or vegetable oils and are already commercially produced: over 100 billion
liters of the three main types (biodiesel, ethanol and biogas) are annually produced from
crops as sugarcane, corn, soy and palm4. But there are growing concerns about these
technologies. Because of the growing number of people in the world dealing with food
scarcity, it seems unethical to use food crops as energy crops or to even use productive land
for growing energy crops. Skeptics also mention the impact on the biodiversity and the cost
inefficiency of e.g. biodiesel.
A better solution can be offered by biofuels produced with lignocellulosic biomass, the so
called biofuels of the second generation. These lignocellulosic materials (e.g. switch grass,
miscanthus, poplar and agricultural wastes) have generated a lot of attention as they are
cheap and abundant and the plants dont compete with food crops. However they still might
compete in land use if production increases. Although its a very promising path to
investigate, at present it isnt cost effective due to some technical obstructions. More
investigation and development is required to identify the ideal characteristics of the feedstock
and especially to improve the pre-treatment methods for opening up the matrix of cellulose,
hemicellulose and lignin5 6.
As can be seen in Figure 1, a lot of different pathways originating from various types of
biomass to a wide range of biofuels exist. One of the most promising and nowadays most
studied processes is pyrolysis. Pyrolysis is a thermochemical decomposition process of
organic material at elevated temperatures without the addition of oxygen7. A substantial
variety of biomass can be used to produce bio-oil through pyrolysis. The most important
feedstock in North-America and Europe are forest residues as bark, sawdust and shavings.
In the rest of the world agricultural residues and sugar cane bagasse are feedstocks of
choice. Nevertheless still plenty of lignocellulosic biomass sources have the potential to be
pyrolyzed, including bagasse, rice hulls, rice straw, peanut hulls, switchgrass, wheat straw
and wood8.

FIGURE 5: TECHNOLOGY PATHWAYS TO TRANSFORM BIOMASS INTO BIOFUEL9

Lately the capability of algae as a feedstock for bio-fuel production has also been
investigated. This expansion of research area is logical since 70% of the earth surface is
covered by water. The results are hopeful since algae species that produce valuable
carbohydrates instead of lipids as their reserves were discovered9. If the crop harvest and
treatment is upgraded, we can refer to the algae fuel production as the third generation of
biofuels.

2. WHAT IS BIOMASS
The renewable energy directive (2009/28/EC) of the European parliament gives us the
following definition of biomass: "Biomass means the biodegradable fraction of products,
wastes and residues from biological origin from agriculture (including vegetable and animal
substances), forestry and related industries including fisheries and aquaculture, as well as
the biodegradable fraction of industrial and municipal waste"10. Biomass contains a lot of
energy, stored as chemical bonds which are formed through photosynthesis. In this process,
water and carbon dioxide from the air are converted into energy-rich carbohydrates using
solar energy.
Lignocellulosic biomass is essentially composed of cellulose, hemicelluloses, lignin,
extractives and minerals. The exact composition depends on various characteristics
4

including the plant species, type of plant tissue, growth stage and growing conditions.
Usually, in woody biomass, a distinction is made between hardwood and softwood because
the properties of both groups are different, but even within these groups a large diversity is
observed11. These terms are quite misleading because hardwoods are not necessarily harder
or stronger, the terms just refer to the type of tree. The wood from conifers (gymnosperms),
trees with needle-like leaves, is usually called softwood while hardwoods comprise the
broad-leaved trees (angiosperms). These last mentioned are at most deciduous, but in more
tropical climates evergreen broad-leaved trees appear12.

2.1 CELLULOSE
D-glucose polysaccharide is the most important structural component in lignocellulosic
biomass and contributes to approximately 40-45% of the plants dry weight. As a cell wall
component, the main function is to protect, stabilize and give structure to the plant. The
glucopyranose units are linked by -1,4-glycosydic bonds. Two adjacent glucose units are
rotated 180 to eachother and are defined as the disaccharide cellobiose 13. The degree of
polymerization DP is used to express the chain length, which can have a value from 800 to
10 000 according to the plant species. Every glucose subunit contains three hydroxyl groups
with a high reactivity when positioned in the equatorial plane. This is the basis for intra -and
extracellular hydrogen bonds, which promote the formation of a partially crystalline structure
and which give cellulose a multitude of different fiber structures and morphologies14. The
parallel aligned cellulose polymers form microfibrils, these in turn assemble as fibrils and
finally cellulose fibres are built from the fibrils. The non-uniformity of the cellulose fiber, with
amorphous regions on the one hand and regions of very high crystallinity on the other hand,
is the reason for the interesting opposing properties of cellulose such as stiffness and rigidity,
but also flexibility. The strong hydrogen bonds strengthen the structure and makes the
cellulose insoluble in most solvents 1.

FIGURE 6: CELLULOSE STRUCTURE15

2.2 LIGNIN
Lignin is the second most abundant organic polymer in plants. Only vascular plants are
lignified but the amount of lignin present can differ a lot in plants. Woody species contain 20
to 40 wt.% lignin, while the content in aquatic and herbaceous species is less. The main
function of lignin is to give strength to the cell wall of vascular tissues, specialized for liquid
transport and mechanical strength. They also connect the cellulose fibers and hemicellulose.
The structural integrity of the cell wall is increased to such an extent that the plants get the
opportunity to grow upright15. Lignin is very heterogenic, has an extremely complex three
dimensional structure and consists of random connected substructures of monolignol
monomers which differ in their degree of methoxylation, namely p-coumaryl, coniferyl and
sinapyl alcohol. These monolignols are synthesized from phenylalanine in a multistep
proces16. In general, softwoods consist of guaiacyl lignin (with mainly coniferyl alcohol units)
and hardwoods are composed of guaiacyl-syringyl lignin (with both coniferyl and synapyl
units). In both cases, p-hydroxyphenyl (from p-coumaryl alcohol) appears in small
quantities17.In guaiacyl lignin of softwood, about 20-25% of the guaiacyl units are linked with
a stable 5-5 carbon linkage, while in hardwood this percentage doesnt exceed 10%. This is
because of the additional methoxygroup at carbon 5 of syringyl monomers in hardwoord. But
the most widespread links are -O-4 ether bonds. At last it can also bind with other
components like hemicelluloses, glycoproteins or tannins18. As a result of the random linkage
the polymers are retained to form crystalline structures. They have a high atomic mass, but
its very difficult to determine the degree of polymerization due to the irregularity of the
structure.

FIGURE 7: NON-, MONO- AND DIMETHOXYLATED MONOLIGOLS IN LIGNIN

2.3 HEMICELLULOSE
In contrast with the homopolymer cellulose, which is strong and partially crystalline,
hemicellulose is a branched heteropolysaccharide with little strength and amorphous
structure. Also the degree of polymerization is up to 100 times lower. Moreover its qualified
as an alkali soluble material, where cellulose is insoluble2. Due to the short chain length, in
addition with the high rate of hydrogen bonds, they are capable of absorbing huge quantities
6

of water. Hemicellulose exists of a highly substituted chain of sugar monomers, as there are
pentoses (-d-xylose, -l-arabinose), hexoses (-d-mannose, -d-glucose, -d-galactose)
and uronic acids (-d-glucuronic, -d-4-O-methylgalacturonic and -d-galacturonic acids).
Occasionaly other sugars such as -l-rhamnose and -l-fucose can be found in small
quantities19. Xylans and glucomannans are the most abundant hemicelluloses and theyre
typically separated into 6 main classes: glucoronoxylans, galactoglucomannans,
arabinoglucuronoxylans, xyloglucans and arabinoxylans and complex heteroxylans19.

FIGURE 8: MAIN CONSTITUENTS HEMICELLULOSE

2.4 EXTRACTIVES
Extractives are the organic compounds besides the polymeric parts of the cell wall and can
be extracted by hot water or organic solvents. Primary metabolites like sugars, fats, amino
acids and carboxylic acids are always present, but also more complex secondary metabolites
such as phytosterols, terpenes and phenolic compounds can be found. The functionality is
diverse, for example fats are an energy source for the cells, while terpenoids and phenolic
compounds are protecting against microbiological invasion. Other components are important
for odor and color. Especially bark contains a lot of these extractives20.

2.5 ASH
The alkali and alkaline earth metals are the most significant metals present in the ash, with
calcium being the most abundant, followed by potassium and magnesium. They are
incorporated in salts as carbonates, sulfates, silicates, oxalates and phosphates. In most
plants, these metals only make up approximately 1% of the dry wood weight, but they can
have a significant effect on the product distribution of biomass pyrolysis. Thats why its
important to take into consideration the exact amount of each metal present. The elemental
compositions of some biomass materials are shown in Table 1. Only trace amounts of heavy
metals are found20. Its important to realize that the ash content in fast growing energy crops
or in plants growing on contaminated soils can be significantly higher.
7

TABLE 2: ELEMENTAL COMPOSITION FOR DIFFERENT KINDS OF BIOMASS 22

3. CONVERSION OF BIOMASS
Energy can be produced from biomass by chemical, biological or thermal treatment and the
choice of an appropriate method depends on the biomass feedstock, the desired endproduct, economic conditions etc. Power and heat generation, transportation fuels and
chemicals are three main products which can be derived from biomass. The thermochemical
conversion processes, which are becoming very important nowadays, apply heat (and
eventually catalysts and pressure) to convert a broad range of biomass into these products.
The four most important methods (combustion, gasification, liquefaction and pyrolysis) will be
described further, pyrolysis in particular. Fermentation for the production of ethanol and
anaerobic digestion for the production of biogas (mainly containing methane and carbon
dioxide) are the best known biological conversion methods. A well-known chemical treatment
on the other hand is the trans-esterification of several specific kinds of biomass (e.g.
rapeseed oil) to produce bio-diesel21.

3.1 THERMOCHEMICAL CONVERSION

3.1.1C OMBUSTION
The most straightforward thermal conversion process is to completely oxidize the biomass by
combustion, providing heat which can be applied in heating systems or in steam production
for electricity generation. There are a couple of restrictions for the biomass when used as a
feedstock for combustion. First of all the water content has to be lower than 60 %. In addition
constituents apart from C, H and O should be avoided since they are associated with ash,
deposits and corrosion. Combustion of herbaceous biomass is not favorable because it
contains usually higher amounts of N, S, K and Cl, promoting higher emissions of NOx and
polluting particulates. Wood is better suited to the requirements for combustion. The process
itself involves drying, devolatilization, gasification, char combustion and gas-phase
8

oxidation22. High air pollution and low energy yield have forced to shift to other degradation
processes.

3.1.2 G ASIFICATION
Gasification is just as combustion an exothermal process that partially oxidizes the solid fuel
(biomass) at temperatures in a range from 800 to even 1700C into a gaseous fuel named
producer gas. The main constituents of this gas are CO and H2, together with smaller
amounts of CO2, CH4 and N2. For an engine driven by a fuel gas, gasification is the
suggested conversion method. The obtained gas can also be used as a fuel gas for
combustion to provide heat, but the most efficient concept is the biomass integrated
gasification/combined cycle heat and power generation, where the produced gas is
converted in a turbine to obtain electricity. Further treatment of the gas by Fischer-Tropsch
process is a more recent application where methanol or other liquid hydrocarbons are
synthesized 6.

3.1.3 P YROLYSIS
Pyrolysis is derived from the Greek words pyro (fire) and lysis (decomposition). Its a
thermal decomposition process in the absence of oxygen that converts biomass into solid,
liquid and gaseous products. The process has been used for ages to produce charcoal and
in ancient Egypt it has been used to acquire tar for caulking boats.23 Earlier the preferred
product was solid char and the term pyrolysis referred to carbonization.8 But the capability of
pyrolysis to produce liquids from biomass has attracted more and more attention in recent
years because these bio-oils could be profitable thanks to their advantages in storage,
transport and wide range of applications24. At the end of the 20th century scientists
discovered that through fast pyrolysis the yield of liquid products can be increased, simply by
adjusting some process parameters in the conventional slow pyrolysis process25. Fast
pyrolysis, as a novel technology, was born, where a liquid yield as high as 72% can be
reached when the feedstock is heated rapidly and also the produced vapors are condensed
as fast as possible. The terms slow and fast are quite arbitrary as there are no precise
definitions of involved heating rates or times8. The process conditions of slow pyrolysis are
less extreme than those applied in the fast pyrolysis process, where liquid yield is
maximized. Flash pyrolysis is a type of fast pyrolysis where even higher temperatures are
used with smaller residence times. As a result the main products formed are gaseous,
therefore this method approaches gasification. A short overview of the differences is given in
Table 2 26.
TABLE 2: DIFFERENCES BETWEEN CONVENTIONAL, FAST AND FLASH PYROLYSIS28

3.1.3.1 F EED PREPARATION

Two important treatment operations of the feed have to be done to accomplish an effective
heat transfer and a smooth performance of the pyrolysis reactor. Both the biomass moisture
content and particle size should be reduced. In a fluidized bed pyrolysis reactor for example,
particles in a range of 2-6 mm are required to achieve a proper heat transfer and
consequently, to achieve sufficiently high reaction rates. Prior to grinding, the biomass
should be dried to a moisture content below 15 wt.%, as water has an adverse effect on the
bio-oil properties such as pH, viscosity, stability and corrosiveness27. It has been proven that
a drying temperature exceeding 200C decreases the bio-oil yield. The drying time on the
other hand has no impact on the liquid product quality28.

3.1.3.2 P YROLYSIS PROCESS

Primary pyrolysis reactions start when the used feedstock is heated and volatiles are
released from the particles while char is formed. A chain reaction is started by the hot
volatiles which heat up the remained unpyrolyzed biomass and the volatilization is
maintained. In competition with the volatilizing pyrolysis reactions, some of the volatiles
condense in contact with colder parts of the biomass and produce tar. Depending on
temperature, pressure and residence time, other reactions such as thermal decomposition,
dehydrations, radical recombinations and water gas shift reactions are possible8.
Short residence time and a controlled temperature of 500C are necessary to maximize the
oil yield and reduce the further degradation of the vapors. This formation of low molecular
weight compounds and gases is called secondary cracking and takes place at temperatures
exceeding 500C. Fast condensation is required to eliminate these reactions. Condensation
can be realized by rapid cooling while aerosols can coagulate and agglomerate. Using a cold
trap is the easiest solution, but this method can cause liquid fractioning and even blockage of
piping in the condenser system because of the preferential deposition of highly viscous,
lignin derived components. Quenching of the vapors in product oil or in an immiscible
hydrocarbon is the generally accepted method. Electrostatic precipitation is widely applied at
smaller scales (up to pilot plant)29. Nevertheless eliminating all secondary decomposition
reactions is impossible because char particles contaminating the vapors need to be excluded
prior to condensation in a cyclone or another hot vapor filtration device, prolonging the
residence time.
At temperatures below 400C, decomposition reactions on the char take place. This
phenomenon can appear on the surface of the particles when the vapor residence time is too
long, but particularly takes place inside the larger particles. During pyrolysis, the particles are
vaporized more and more inwards, leaving behind char layers at the outside. The produced
vapors diffuse slower out of the particle and are subjected to condensation and
decomposition as the vapors are diffusing through the outer char layers30. Char also
contributes to a higher concentration of polycyclic aromatic hydrocarbons (PAHs), which are
atmospheric pollutants27. So for an optimal bio-oil yield, an efficient char removal is required.
The conventional method of char removal is by cyclones, although the smallest particles
cant be held back and when they collect in the pyrolysis liquid they have a negative
influence on the oil stability resulting in the problem of aging. Alternative approaches are
being developed, such as in-bed vapor filtration and rotary particle separation, but they tend
10

to create filter clogging problems due to the complex interactions between char and pyrolysis
liquid and the subsequent formation of a gel-like phase29. Another issue is the liquid yield
reduction by 10 to 20% because of the catalytic cracking by the char accumulation on the
filter surface 24.
3.1.3.3 P YROLYSIS PRODUCTS
The yield of the products can be influenced by changing the temperature, since different
reactions occur at different temperatures. Figure 5 shows an overview of the yield of each
product fraction as a function of temperature. The moisture content is an additional important
factor in the product distribution as it accounts for water condensation in the liquid fraction,
hereby extracting water-soluble compounds from the gaseous phase and in this way
decreasing gas fractions31.
At higher temperatures the large molecules in char and tar are cracked to smaller, gaseous
molecules. Consequently, the yield of the char can be maximized at a low temperature and
low heating rate. The majority of the solid char left after biomass pyrolysis results from lignin
and hemicellulose degradation. If pyrolysis is complete, char exists nearly completely of
carbon, since the hydrogen and oxygen fractions have been removed from the biomass
feedstock. Other heteroatoms as N, S and P, which affect the properties of bio-char, can be
found as incorporations in aromatic rings, their degree of incorporation depending on the
pyrolysis conditions and feedstock type32. Also the biomass mineral fraction is retained in the
char.

FIGURE 5: INFLUENCE OF TEMPERATURE ON PRODUCT DISTRIBUTION29

Liquid products are gaseous when collected at pyrolysis temperature but are condensed at
room temperature to a dark brown viscous liquid. Liquid products from biomass pyrolysis are
discussed in more detail in the next paragraph.

11

The main constituents of the produced gas, after removal of the condensable pyrolysis
vapors, are H2, CO, CO2, H2O, N2 and light hydrocarbons as CH4, C2H4, C2H6 etc33. H2
production originates from the further cracking of hydrocarbons at higher temperatures, while
CO and CO2 originate from the decarbonylation and decarboxylation of oxygenated
compounds. Extreme conditions such as temperatures exceeding 1200C ensure complete
cracking of the volatiles, only leaving H2 and CO. During pyrolysis these temperatures are
never reached and therefore the gas contains more components, as mentioned before. The
pyrolysis-gas is called producer gas and can be cleaned to syngas, an equimolar mixture of
H2 and CO. Pure syngas can be used for power generation, for the production of
transportation fuels including methanol and FT-diesel (through Fischer-Tropsch synthesis)
and for synthesis of chemicals such as ammonia (for fertilizers) and hydrogen (used in
refineries). The main application of producer gas on the other hand is found in power and
heat generation by combustion. It isnt recommended for more advanced applications
because only 50% of the energetic value of the producer gas is derived from the syngas
components CO and H2. Only for the production of synthetic natural gas (SNG) the use of
production gas is desirable because in this case the presence of CH4 is beneficial for
achieving a high yield 34.

4. BIO-OIL
Bio-oil is the liquid fraction obtained after condensation of the pyrolysis vapor phase. This
dark brown organic liquid is often referred to by many other names, like bio-crude-oil (BCO),
bio-fuel, liquid wood, liquid smoke, wood distillates, pyrolysis oil, pyrolytic oil etc. It is a
complex mixture that contains highly oxygenated products but the elemental composition
resembles that of the biomass it has been derived from29 7. In Table 3 the major differences
between pyrolysis bio-oil and conventional heavy fuel oil are given.
TABLE 3: PHYSICAL PROPERTIES OF BIO-OIL AND HEAVY FUEL OIL7

More than 300 components can be identified in bio-oil and most of them possess oxygen,
leading to an oxygen content of approximately 35-40 wt.%. The high oxygen level is the key
reason for the differences in properties between bio-oil and conventional hydrocarbon fuels,
but the percentage can be adjusted by changing the pyrolysis conditions. Severe conditions
(high temperature, long residence time and high heating rate) favor the formation of
12

secondary reactions and hence decrease the bio-oil yield, but the remaining organic liquid
contains less oxygen7. Reducing the oxygen content is an important purpose, knowing that it
causes the bio-oil to have a heating value which approaches only more or less 50% of the
heating value of conventional fuel oils. The many polar groups present also give rise to poor
chemical stability of bio-oil and high boiling points and viscosities30.
Water in bio-oil originates either from the moisture present in the initial feedstock, or it is
produced by dehydration reactions during the pyrolysis process. So the water content in the
bio-oil varies from 15 to 30 wt.%, depending on the biomass used and pyrolysis severity.
Thanks to the numerous polar compounds derived from carbohydrate decomposition, water
is in this concentration miscible with the oligomers resulting from lignin conversion. On the
one hand water is desirable because it reduces the viscosity (advantageous for combustion)
and it leads to lower NOx production and a more uniform temperature profile in diesel
engines. On the other hand with increasing water content the heating value and the
combustion rate reduces significantly35 24.
Because of the wide range of feedstock and process conditions, the viscosity can vary from
25 cP up to even 1000 cP at 40C. But with higher temperatures the viscosity reduces
rapidly, unlike conventional fuels of which the viscosity decreases a lot slower under the
same conditions. Not only by water but also by mixing with other polar solvents like methanol
and acetone the viscosity can be reduced drastically7. Finally the increase of viscosity with
time is referred to as aging. This phenomenon is caused by formation of larger molecules by
condensation reactions among the bio-oil components36.
Another disadvantage of bio-oil is the high level of corrosiveness due to organic acids,
particularly formic acid and acetic acid, causing a very low pH of 2-3. As a result, the bio-oil
can affect construction materials as aluminum and carbon steel. At high temperatures and
with high water contents the oil is even more corrosive37.
At last, the combustion behavior of bio-oils is very unique. Due to the high amount of
nonvolatile species, significant energy is needed for ignition. The combustion of an oil droplet
begins with evaporation of water after which vaporization of light compounds and liquidphase pyrolysis of the heavier fraction occurs. This phase is characterized by some unique
processes such as swelling, shrinking and micro-explosions. After this phase, the initial blue
flame of quiescent burning is followed by a bright yellow flame with increased size. The last
step is the solid residual char burnout, with formation of cenosphere-like particles. Petroleum
oil only shows a quiescent, sooty burning after ignition38 39. An overview of the bio-oil
characteristics is given in Table 4.

13

TABLE 4: CHARACTERISTICS OF BIO-OIL29

4.1 APPLICATIONS
Compared to gases and solids, liquid products are far easier to transport which is of major
importance in for example combustion equipment. Poor volatility, coking, high viscosity,
corrosiveness and the variability of its composition are factors which have limited the number
of bio-oil applications. However, lots of efforts have been made on the development of
pyrolysis oil and still many challenges are left, but progression has been made and plenty of
organizations are succeeding in giving bio-oil a place on the market.
Furnaces and boilers are usually less efficient than engines and turbines for heat and power
generation, but the huge variety of fuels that can be used in the former gives them a major
advantage. So bio-oil too has received interest to be used for example as a boiler fuel in
district heating, although a better quality and price is required to make this economically
feasible. The use as combustion fuel in diesel engines on the other hand is also being
investigated but until today a lot of difficulties exist with typical bio-oil properties such as its
difficult ignition and corrosiveness7. These characteristics are also the major drawbacks in
the use of pyrolysis liquids in turbines, however, with a proper accommodation of the
turbines, electricity generation is possible.
Bio-oil doesnt seem to be interesting for transportation fuels due to high viscosity and
corrosiveness, low stability and so on, but some of these properties can be improved by
numerous upgrading processes such as mixing with conventional fuels, deoxygenation by
hydrotreating or catalytic vapor cracking etc. The most promising application in this area is
the use as a source of hydrogen for a variety of petrochemical processes such as
hydrocracking and hydrogenation.
Production of a whole range of chemicals derived from bio-oil is also possible, but separation
techniques are very complex and most of these chemicals are now already being produced
14

from coal, natural gas or crude oil at a much lower cost. However some typical and unique
pyrolysis chemicals such as glycolaldehyde and levoglucosan can be more easily isolated
and are derived from bio-oil with an acceptable yield.
In summary, bio-oil shows lots of opportunities but the challenges to be overcome are the
high cost, the lack of standards, the unavailability of materials, incompatibility with
conventional fuels and the lack of familiarity to the user7.

5. DECOMPOSITION MECHANISMS OF BIOMASS CONSTITUENTS IN FAST

PYROLYSIS
Pyrolysis processes are very complex because there are a lot of variables to be considered.
Biomass has a very complicated structure and a large number of products are created
through thousands of different physical and chemical transformations during the process.
Since the first kinetic model of cellulose pyrolysis developed in 1960 by Broidos group 40,
many extensive studies have exposed new insights in the different pathways and reactions.
Only later the pyrolysis of the other two important biomass components, lignin and
hemicellulose, were described. Figure 6 shows an overview of the mass loss rate for the
three biopolymers41.

FIGURE 6: BIOMASS MASS LOSS IN FUNCTION OF TEMPERATURE44

5.1 CELLULOSE
Cellulose pyrolysis already starts at temperatures as low as 150C. At this low temperature a
charred residue is formed and a very low yield of liquids is achieved. Depolymerization takes
place, besides the free radical formation and water elimination. Plenty of carbonyl, carboxyl
and hydroperoxide groups are formed as well, together with a small amount of gaseous
species as carbon monoxide and carbon dioxide. Once above 300C, lots of new reactions
are introduced which contribute to the formation of a liquid product42. The maximum weight
loss rate was reached between 315 and 400C. This single step-multiple reaction type
behavior was later described by an improved kinetic model by Shafizadeh43 who proposed
15

the formation of an intermediate species called activated cellulose, a reactive component

resulting from depolymerization, from which two major pathways start: further
depolymerization through the 1-4 glycosydic bond scission and fragmentation of the
glucose rings, also known as ring-scission. The most typical compounds formed during
depolymerization of cellulose are levoglucosan and other anhydrosugars, furans, anhydrooligosaccharides, pyrans and cyclopentanones. The glucose units mainly exist as pyranoses,
however lots of furan derivatives such as 5-hydroxymethyl furfural (HMF) are formed due to
the fact that these species are more stable and also kinetically favored. On the other hand
the more endothermic ring-scission reaction provides mainly linear alcohols and carbonyls,
such as hydroxyacetaldehyde and acetol, esters and others. The first proposed models do
not take secondary reactions into account, so later on a modified Shafizadeh-Broido model
was developed, according to which the primary products were produced by three competing
reactions, after which secondary char and gases were produced from the vapors43.

FIGURE 7: PROPOSED MODELS FOR THE DEGRADATION OF CELLULOSE

Levoglucosan is by far the principal cellulose pyrolysis product. A mechanism for

levoglucosan formation was proposed by Ponder et al.44 as shown in Figure 8. Heterolytic
cleavage of glycosidic bonds leads to a glycosyl cation, which subsequently transforms into
an intermediate containing a terminal 1,6-anhydopyranose. A further cleavage of the
glycosidic bond results in a levoglucosan unit accompanied by a depolymerized unit26. A
study on the fundamental degradation mechanism of cellulose has shown that levoglucosan
is stable at 500C, which allows to exclude complex levoglucosan degradation reactions
when explaining the product distribution of cellulose pyrolysis. This result also confirms the

16

modified model of Shafizadeh, stating that competitive reactions rather than sequential
degradation account for the formed species.

FIGURE 8: MECHANISM FOR LEVOGLUCOSAN FORMATION PROPOSED BY PONDER ET AL.47

5.2 LIGNIN
Lignin is the thermally most stable compound of biomass due to its complicated, highly
branched three-dimensional structure. Therefore its degradation is also the least understood,
its strongly influenced by plenty of parameters as temperature, biomass source and heating
rate. The high quantities of lignin residues available worldwide however have caused major
interest in its thermal behavior and in its potential to serve as a source for valuable
chemicals.
The temperature range over which lignin decomposes is wide because of the variety of
chemical bonds linking the aromatics, all with their own thermal stability and thus other
degradation temperatures. Low molecular weight products are produced by the cleavage of
the several functional groups, while at higher temperatures complete rearrangements of the
backbone occur, producing char and a series of volatile species. Also radical formation and
initially self-condensation occur, but the latter is inhibited by phenolic species leading to a
mass distribution equilibrium. Coniferous lignin is the most stable and accordingly causes the
17

highest char yield. Lignin pyrolysis starts around the relatively low temperature of 200C, but
the main degradation processes occur at higher temperatures, with the formation of aromatic
hydrocarbons, (hydroxy)phenolics and guaiacyl-and syringyl-type components. Between 275
and 350C, the lignin monomers are cleaved, while demethylation of the dimethoxygroups
occurs at 350-450C, hereby increasing the conversion rate of phenols into pyrocatechols.
No demethylation or demethoxylation occurs at lower temperatures, so the substitutes from
the resulting phenols arent changed and the substitution pattern of the native lignin can be
analyzed. The faster the heating rate, the greater the amount of hydrocarbons and alkylphenol derivatives, while lower heating rates gives components with high oxygen ratios.
Unsaturated products (e.g. styrene, vanillin and eugenol) are formed during dehydration of
lignin, together with the production of substantial amounts of water. A temperature of 230C
induces the formation of CO, followed by other condensable gases such as CH4. At 500C
the main non-condensable gas produced is H2, released by rearrangements and
condensations of the aromatic rings. The further decomposition at temperatures exceeding
600C are called secondary reactions and they comprise the decomposition of the formed
intermediates to char and gases. The decomposition reactions of the strongest bonds such
as the oxygen functional groups at even higher temperatures are referred to as tertiary
reactions, producing more H2 and CO.
Lignin and cellulose have a mutual effect when theyre pyrolyzed together. Lignin favours the
formation of low molecular weight products from cellulose, leading to a decreased char yield,
while cellulose also reduces the char formation from lignin by inhibiting secondary char
formation.

5.3 HEMICELLULOSE
The varying properties and high complexity of hemicellulose are the primary reasons why the
mechanisms and kinetics of its thermal degradation are largely unexplored. A huge variety of
linkages and branches are present, depending on the species, the tissue location and even
the tissue age45. Due to their interaction witch cellulose and lignin, hemicellulose is very
difficult to obtain and as a result many studies used xylan or 4-O-methyl-D-glucurono-D-xylan
as a model compound to study pyrolysis behavior. Nevertheless hemicellulose consists of a
set of different polysaccharides which may have different properties. Unlike cellulose,
hemicellulose lacks crystallinity, the amorphous structure causes the hemicellulose to be less
thermally stable42. So thermal decomposition starts at a slightly higher temperature, namely
180C, but the greatest mass loss is reached at 280-340C, which is lower than cellulose
decomposition. At lower temperatures, dehydration and decomposition of the side chains,
which are very easy to remove are the most important processes, followed by breakage of
the glycosidic, C-C, C-O and C-H bonds of the individual sugars, depolymerization,
decarboxylation and decarbonylation. The non-condensable volatiles mainly consists of CO2,
CH4,CO, H2, C2H2, C2H4, and C2H6. CO2 is predominant in the early stages of pyrolysis (low
temperatures), but since its concentration decreases with temperature, H2 and CH4 become
more significant above 750C. The liquid products can be classified in following groups:
furans, cyclopentanes, alcohols, saturated fatty acids, cyclohexanes and aromatics. Between
300 and 600C, particularly oxygen compounds with low molecular weight (alcohols,
anhydrosugars), cyclopentanes, simple aromatics and fatty acids are formed, while the
pyrolysis at temperatures exceeding 800C yields specially phenolic and polynuclear
18

aromatic compounds. The components produced in the early stages can also experience
condensation, hereby generating complex aromatic compounds such as benzofuran and
indene. Generally, the char yield of hemicellulose pyrolysis is larger than the one from
cellulose pyrolysis19.

6. C ATALYTIC UPGRADING
The study of catalyzed biomass pyrolysis is becoming very popular, because of its huge
potential for modifying the pyrolysis products in order to provide a more efficient pathway for
chemical production or to improve the bio-oil quality. The main purpose for the latter is
producing a liquid transportation fuel from biomass that is able to replace fossil fuels, which
is essentially achieved by the removal of oxygen. By adding catalysts to the pyrolysis
process,
reactions
such
as
decarbonylation,
decarboxylation,
hydrocracking,
hydrodeoxygenation, and hydrogenation are enhanced. An overview of these different types
of reactions can be seen in Figure 946. The bio-oil properties are improved since oxygenated
compounds are removed via H2O and CO2, making the oil less corrosive. Furthermore these
cracking reactions lead to a lighter, less viscous product and also the heating value of the
bio-oil is increased thanks to the formation of more valuable components resembling
petrochemical products. Numerous types of catalyst applications, each responsible for
another product distribution, have been studied in order to improve pyrolysis productivity.
They can be classified according to their application: one possibility is to mix the catalyst with
the biomass before being fed to the reactor, but if a more intense contact with vapor, solids
and char is needed they can also be fed directly to the reactor. The catalysis occurs in the
reactor and thats why it is called in-bed catalysis. Another option is to locate them in a
secondary reactor downstream of the actual pyrolysis reactor, the so-called ex-bed
catalysis27. In-bed catalysts mainly influence the primary reactions while the ex-bed catalysts
affect the secondary reactions (vapor phase upgrading).

FIGURE 9: REACTIONS ASSOCIATED WITH THE CATALYTIC UPGRADING OF BIO-OILS49

19

Its very important to take into account that biomass itself contains components to which
catalytic effects can be ascribed. Common inorganics such as Na, K, Ca, Mg and silica have
been proven to alter the behavior of cellulose and lignin during thermal degradation. So when
the pyrolysis of biomass with additional catalysts is studied, a good understanding of the
effect of naturally occurring inorganics is essential47.
The two most important routes for bio-oil upgrading separated from the pyrolysis reactor are
hydrodeoxygenation and zeolite cracking. Hydrodeoxygenation is a catalytic hydrotreatment
of the bio-oil under high pressure in the presence of hydrogen or hydrogen and carbon
monoxide. Occasionally other hydrogen donor solvents are used. Sulfide/oxide and transition
metal catalysts are applied to promote the carbon-oxygen bond cleavage with hydrogen.
Nowadays cracking catalysts such as zeolites are receiving more interest since they operate
at atmospheric pressure and in the absence of hydrogen47. Zeolites are microporous
minerals with a complex three-dimensional structure and varying elemental composition. The
pore size and acidity of the zeolite are the main parameters which affect the reactivity. The
most widely applied zeolite, HZSM-5, is an aluminosilicate composed of several pentasil
units (eight five-membered rings). Its acidity depends on the Si/Al ratio; a low ratio indicates
high acidity, which provides a better adsorption of the oxy-compounds. A drawback of using
these catalysts is the formation of high amounts of coke, which deposit on the catalyst
surface and block the pores in this way, making the catalyst less reactive. To minimize
depositions and promote the desired cracking reactions, zeolites with a correct pore size and
well defined number of acidic reaction sites should be used46.

6.1 INFLUENCE OF ALKALI AND ALKALINE EARTH METALS

The last two decades studies already have proven that high amounts of inorganic
compounds present in the biomass alter the product distribution and chemical speciation of
the bio-oil. More and more interest is focused on the effect of alkali and alkaline earth metals
(AAEM), since there is observed that especially these species have a strong catalytic activity.
Raveendran et al.48 studied the effect of deashing on pyrolysis product distribution of twelve
types of biomass. In all cases the liquid yield increased in expense of the gas yield.
Varheghyi et al.49 used thermogravimetric analysis (TGA) to investigate the influence of
mineral matter on the mass loss rate in function of the temperature. They found that the
biomass decomposition already started at a lower temperature in presence of greater
amounts of inorganics. The study demonstrated also the accelerated secondary
decomposition resulting in a broad range of smaller products. Various studies made use of
TGA when studying the effect of metals on biomass pyrolysis, but this technique is not
capable to produce the same high heating rates as applied in fast pyrolysis, which is a
serious drawback. Obtained results from these studies could be wrong since lower heating
rates favor the production of char26. The investigation of the effect of indigenous or added
inorganics on biomass pyrolysis focused on the classification of the product yields in terms of
char, liquids and gases, while only a few studies investigated the chemical speciation as a
result of pyrolysis reactions. Piskorz et al.50 pyrolyzed demineralized biomass in a fluidized
bed reactor and discovered an increase in the yield of anhydrosugars. He suggested two
possible mechanisms for cellulose pyrolysis depending on the presence of mineral matter.
Depolymerization leading to levoglucosan and other anhydrosugars is the main mechanism
20

in demineralized biomass, while the presence of inorganics favors the fragmentation to low
molecular weight products. He reported that the C-O bond in glucose monomers is less
stable than the C-C bonds and consequently the two-, three- and four-carbon fragments
could be produced directly from cellulose in competition with levoglucosan formation. Eom et
al.51 and Nowakowski et al.52 confirmed that these ring-opening reactions are catalyzed by
potassium in particular. Figure 10 shows the suggested mechanism in presence of
inorganics, while Figure 8 represents the cellulose degradation pathway in absence of
inorganics.

FIGURE 10: CELLULOSE DEGRADATION MECHANISM IN PRESENCE OF INORGANICS28

Patwardhan et al.53 pyrolyzed different glucose-based carbohydrates to investigate the

thermal degradation mechanisms and exposed numerous competitive degradation pathways
which are dependent on temperature and concentration of inorganic species. Other authors54
55
indicate sodium and potassium as the strongest catalysts (stronger then calcium). The
anion counterpart also seems to play a significant role in the catalytic effect.54 Shimada et
al.56 confirmed that the production of low molecular weight compounds was increased by
AAEMs. In general the investigated salts induced the production of low molecular weight
species because the Ca2+ and K+ kations induced homolytic fission of glucose rings. The
complexity of these reactions has been proved by isotopic labeling studies. In the case of
glycerine up to four competing fragmentation reactions were proposed depending on the
presence of acid or basic catalysts. The degree of polymerization of the applied cellulose
also has a major influence on the type of reaction57.
The pathway for the effect of AAEMs on cellulose is better understood than for lignin.
Although Galgano et al.58 reported an increase in total phenols, which are typical degradation
products of lignin. The presence of NaOH increased guaiacol and cresol production, while
KOH increased the formation of phenol and isoeugenol. Kleen et al.59 reported that sodium
has a beneficial effect on demethoxylation, demethylation and dehydration reactions, hereby
significantly changing the pyrolysis product distribution. Interestingly, the results of lignin
decomposition are modified by AAEMs in a comparable way, but more investigation is
required to clarify the complete mechanism60.

21

22

OBJECTIVE
The objective of this masterthesis is to investigate the effect of alkali and earth alkaline
metals on the fast pyrolysis of biomass constituents. Previous work has shown the catalytic
influence of char on the thermal degradation of biomass, but less is known about the
complex mechanisms behind this process. Furthermore the pyrolysis products are generally
classified in tar, char and gas but this kind of classification does not give information about
the different chemical species formed. A better understanding of the exact catalytic role of
the naturally occurring minerals on the chemical speciation can be achieved by using
micropyrolysis-GC/MS as analysis technique. Through pyrolyzing biomass constituents, with
focus on cellulose and lignin, mixed with various salts in different concentrations a better
insight in their effect on the final product distribution is received. Micropyrolysis together with
gas chromatography and mass spectrometry is for this purpose a very useful approach
because a distinction can be made between primary and secondary reactions. The complex
nature of pyrolysis reactions has led to a lack of distinguishing primary and secondary
reactions. However the residence time of vapors in the micropyrolyzer does not exceed 20
ms, which makes it possible to exclude the main secondary reactions. This allows us to study
the catalytic influence of metals on the primary reactions by mixing them with the biomass
samples before dropping them in the micropyrolyzer oven. On the other hand, by placing a
secondary reactor containing metals fixed in a bed downstream of the pyrolysis reactor, also
the effect on secondary reactions can be analysed.

23

24

MATERIALS AND METHODS

1. SAMPLE PREPARATION
Avicel microcrystalline cellulose, purchased from EMC Biopolymer was used to run the
pyrolysis experiments. This commercially available cellulose is derived from fibrous plants
and is already partially depolymerized. Lignin was purchased from SigmaAldrich as alkali
lignin, separated from cellulose by the Kraft process. Five catalysts (CaCl2, calcium citrate,
calcium acetate, potassium citrate and potassium acetate) were also purchased from SigmaAldrich as a powder, while for KCl a 3 M solution from VWR international company was
applied. The last catalyst used was a non-commercial, spray-dried heterogeneous ZSM-5
based catalyst, modified for enhanced mesoporosity and was supplied by Delft Solid
Solutions (Delft, The Netherlands). Cellulose and lignin samples doped with these catalysts
were prepared for in-bed catalytic pyrolysis. Impregnation was used in order to achieve a
good mixing of cellulose and lignin with the catalysts. Samples with different concentrations
(ranging from 0.1 to 22 wt.%) were prepared by impregnation. The precisely weighed amount
of salt was dissolved in 25 ml deionized water and 2.5 g of cellulose was dispersed in this
solution. The well-mixed slurry obtained by good stirring for 2 hours was put in an oven at
110C to dry overnight. Approximately 0.5 mg of these samples were pyrolyzed and each
experiment was run in duplicate or triplicate.

2. MICROPYROLYSIS EXPERIMENTS (PYGC-MS)

The micro-pyrolysis set-up used to perform the fast pyrolysis experiments is shown in Figure
11. It consists of a micro-pyrolysis unit (FrontierLab Multi-shot pyrolyser EGA/PY-3030D)
connected to a gas chromatograph and a mass spectrometer (Thermo Fisher Scientific
Trace GC Ultra and Thermo ISQ MS). Xcalibur data processing software was used for the
final product identification and integration.

FIGURE 11: MICROPYROLYSIS SETUP AT THE DEPARTMENT OF BIOSCIENCE ENGINEERING

25

A more detailed illustration of the micro-pyrolysis unit is given in Figure 13. It consists of a
sampler and a quartz pyrolysis tube that can be preheated by a furnace to the desired
temperature (500C). Furthermore a heated interface (350C) and deactivated needle (which
is directly inserted into the GC injector) can be distinguished.
Sample cups of deactivated stainless steel were loaded with approximately 500 g of the
finely ground lignin or cellulose sample. Roughly 2 mg of inert quartz wool was added on top
to prevent loss of sample material during transportation of the cup and particularly during the
free fall through the reactor tube. A Mettler Toledo microbalance with a sensitivity of 0.001
mg was used to weigh the cups accurately before they were dropped into the quartz
pyrolysis tube. The cup falls freely into the preheated furnace by gravity in a very short time
period of approximately 12-20 ms. In that way the sample is heated at a heating rate
exceeding 2000C/s, hereby ensuring fast pyrolysis. Its difficult to determine the yield of
liquids and solids by using micropyrolysis. Initially it was tried to estimate the amount of char
produced by weighing the cup before and after pyrolysis, but some loss of quartz wool during
the process is inevitable which leads to an underestimation of the produced amount of char.
But the gas chromatographic analysis results allowed us to determinate the different volatile
pyrolysis products. All of these experiments were conducted at least two times to confirm the
reproducibility of the tests.
Helium gas was used as the carrier gas to sweep all the produced vapours directly into the
GC. A split/splitless injection port with a split ratio of 1:100 was used to achieve a constant
helium gas flow of 1 ml/min in the capillary column, knowing that the original gas flow was
100 ml/min. The injection temperature was 300C. A Restek capillary column (Rtx-1707, 60m
L x 0.25 mm I.D. x 0.25 m df) with a stationary phase consisting of a crossbond 14%
cyanopropylphenyl and 86% dimethyl polysiloxane was used to separate the injected
pyrolysis vapours. The GC oven temperature started with a 3 min. hold at 40C, followed by
heating to 280C at a heating rate of 5C/min. Finally the temperature was held constant for
1 min. After separation on the column, the species are broken down in the mass
spectrometer for further analysis.

3. C ATALYTIC PYROLYSIS EXPERIMENTS (PYGC-MS)

Catalytic experiments were performed in both in-bed and ex-bed mode in a Tandem
Pyrolyzer. The in-bed mode experiments only require one reactor (Frontier single -reactor)
since the catalyst is mixed with the biomass constituents prior to dropping the cup in the
pyrolyzer, while for ex-bed mode a secondary tube furnace needs to be mounted
downstream of the pyrolysis reactor (Frontier tandem -reactor). In this way the vapors
produced by regular pyrolysis are contacted with the catalyst. The secondary reactor
contains a quick-change quartz catalyst reaction tube with an inner diameter of 5 mm of
which the temperature can be independently controlled, separate from the primary reactor.
The reaction tube is packed with the catalyst as shown in Figure 12. The usable vertical
length of the catalyst bed is 40 mm. This leads to a catalyst amount of approximately 5 mg
which is placed in the tube between small amounts of quartz wool and two coil springs to
26

prevent the catalyst from shifting in case of sudden pressure changes. The catalysts used
were the same in both in-and ex-bed mode (see sample preparation).

FIGURE 12: REACTION TUBE PACKED WITH CATALYST61

FIGURE 13: OVERVIEW OF THE FRONTIER MICROPYROLYZER61

27

4. GC-MS DATA PROCESSING

The peak areas were derived from the total ion current (TIC) chromatograms, which are
found in the quality browser of the Xcalibur software. The peaks represent the relative
abundance (the peak area of one component divided by the sum of all the individual peak
areas) of the detected components. The software allows us to perform an integration of the
peaks, applying restrictions as baseline window (set to 200) and area to noise factor (set to
100) to reduce the integration of the huge number of small peaks that arise in the spectra
due to noise. All components with a relative abundance greater than 0.09% were quantified
and identified. The identification of the individual components was performed by using the
National Institute of Standards and Technology (NIST) MS library. Subsequently the detected
and quantified compounds were grouped according to their chemical functionality (a
distinction was made in the following groups: carbon dioxide, aliphatic hydrocarbons,
aromatic hydrocarbons, alcohols, ketones, aldehydes, ethers, carboxylic acids, furans and
pyrans, phenolics and methoxylated benzenes, sugars, N-compounds and others). In
addition the phenolic species were grouped according to their degree of methoxylation (non-,
mono and dimethoxylated species). The most abundant components of each sample where
studied and compared to determine differences between the catalysts chemical activities.
These differences were highlighted with statistical analysis using SPSS software. Since its
hard to determine normality or homoscedasticity of a small group of data (only three values
coming from the repetitions of every sample), non-parametric tests were used to verify
significant differences. The Wilcoxon rank-sum was applied for comparing two populations,
while the Kruskal-Wallis test was used when more than two populations needed to be
compared.

28

RESULTS AND DISCUSSION

At first lignin and cellulose were pyrolyzed non-catalytically at different pyrolysis
temperatures to differentiate thermal degradation mechanisms and to define a proper
pyrolysis temperature for the catalytic experiments. This prior investigation was necessary to
study the effect of the catalysts on the first mentioned degradation reactions of both biomass
constituents. In the second part an overview is given of the catalytic effect of five different
potassium and calcium salts and the non-commercial HZSM-5 zeolite. A distinction was
made between their effect on primary and secondary reactions by comparing the pyrolysis
products from both in-bed and ex-bed catalysis.

1. TEMPERATURE EFFECT
1.1 CELLULOSE
Pure cellulose was pyrolyzed at 300C, 400C and 500C. Figure 14 shows their respective
chromatograms. The decomposition products from the pyrolysis of pure cellulose at 500C
are given in Table 5. These 47 identified products make up to approximately 96% of the total
peak area in the TIC chromatogram. At 300C and 400C respectively only 13 and 22
products could be distinguished respectively. The products determined at 300C are
indicated with a star in Table 5, those with one or more stars are found at 400C.

FIGURE 14: TIC CHROMATOGRAM OF PURE CELLULOSE (AVICELL) MICROPYROLYSIS OF APPROX. 0.5 MG AT
(UPPER) 300C, (MIDDLE) 400C AND (BOTTOM) 500C

29

TABLE 5: GAS CHROMATOGRAPHIC ANALYSIS OF PYROLYSIS PRODUCTS FROM CELLULOSE AT 500C. THE
PRODUCTS DETERMINED AT 300C ARE INDICATED WITH A STAR, THOSE WITH ONE OR MORE STARS ARE FOUND
AT 400C
Iupac name

Apex RT

TIC Peak
Area %

Iupac name

Carbon dioxide*

4,65

1,29

Cyclohexanol, 2,3-dimethyl-

Ethane

4,77

0,46

Acetaldehyde

5,13

Furan

Apex RT

TIC Peak
Area %

26

0,16

Maltol

26,36

0,05

0,11

2-Hydroxy-gamma-butyrolactone

26,44

0,06

5,66

0,07

Cyclopentanecarboxaldehyde

27,2

0,06

2-Propenal

5,98

0,04

2,3-dihydro-3,5-dihydroxy-6-methyl-4H-Pyran-4-one

27,7

0,08

Acetic anhydride*

6,26

0,58

Levoglucosenone**

27,93

0,18

2,3-Butanedione

7,86

0,08

3,5-Dihydroxy-2-methyl 4H-Pyran-4-one*

28,28

0,18

Hydroxyacetaldehyde*

9,06

0,76

2-Pentanol, 5-(2-propynyloxy)-**

30,43

0,45

Acetic acid

10,28

0,05

2H-Pyran-3(4H)-one, dihydro-6-methyl-

30,56

0,08

1-Hydroxy-2-propanone

11,41

0,17

2,3-Anhydro-d-galactosan

30,69

0,12

2(5H)-Furanone*

15,76

0,25

2,3-Anhydro-d-mannosan*

30,88

0,21

3-furfuraldehyde

15,88

0,05

1,4:3,6-Dianhydro--d-glucopyranose**

31,19

0,42

Methylpyruvaat*

16,32

0,20

2,4;3,5-Dimethylene-l-iditol*

31,78

0,21

Furfural*

16,86

0,42

5-hydroxymethylfurfural**

32,81

0,44

5-Methyl-2(3H)-furanone

18,28

0,05

4-Cyclopentene-1,3-diol

32,95

0,07

dihydro-4-hydroxy-2(3H)-furanone*

20,12

0,27

2-Butene-1,4-diol**

33,95

0,12

1,2-Cyclopentanedione*

20,42

0,21

2-Hydroxy-2-methyl-Butanedioic acid

34,84

0,14

5-Methylfurfural

21,36

0,10

Methyl--d-ribofuranoside**

35,08

0,56

23,53

0,22

Levoglucosan**

42,16

79,71

25,02

0,35

1,6-Anhydro--d-galactofuranose**

44,9

8,66

1,2-Cyclopentanedione, 3-methyl2,5-Dimethyl-4-hydroxy-3(2H)furanone*

Figure 15 shows the relative yield of the three main groups of products (low molecular weight
oxygenates, furans/pyrans and anhydrosugars) formed in function of the temperature. It is
clear that depolymerization reactions, leading to anhydrosugars and levoglucosan in
particular (mechanism is shown in Figure 8), are the most important, but at elevated
temperatures, i.e. from 400C on, the formation of oxygenated compounds and furan/pyran
derivatives becomes more significant since they are produced by endothermic glucose ringscission reactions. Regarding the results in Figure 15, attention has to be paid to the fact that
the absolute amount of anhydrosugars still increased from 5.97*1010 to 4.03*1012 TIC (in
peak area per mg cellulose sampled), which indicates that the polymeric structure of
cellulose is more degraded into monomers at higher temperatures.

30

TIC relative abundance (peak area %)

100
90
80
70
60
50

300C

40

400C

30

500C

20
10
0
Oxygenated
compounds

Furans / Pyran Anhydrosugars

FIGURE 15: RELATIVE AMOUNT OF OXYGENATED COMPOUNDS, FURANS/PYRANS AND ANHYDROSUGARS IN

FUNCTION OF PYROLYSIS TEMPERATURE IN PYGCMS

Levoglucosan (1,6-anhydro--D-glucopyranose, LG) has been demonstrated to be the major

product formed during cellulose pyrolysis26 61. As can be seen in Table 5, the yield of 79.70%
at 500C confirms this theory. 1,6-Anhydro--d-galactofuranose is the second most abundant
species formed (8.67%). The formation of this levoglucosan-isomer requires more energy,
leading to smaller yields which increase at higher temperatures62. Other products are formed
in much lower amounts, those most valuable for chemical production are shown in Figure 16.
One of them is levoglucosenone, but its amount reduces from 1.24% to 0.18% with
increasing temperature because it rapidly polymerizes. Levoglucosenone is an interesting
product since it contains easily modifiable functional groups, which can be very useful in the
production of several chemicals63. The amounts of hydroxyacetaldehyde and furfural also
increase significantly, while the amount of 5-hydroxymethylfurfural, a compound derived from
the dehydration of certain sugars, increases from 0.24% at 300C to 0.51% at 400C, but
remains constant at higher temperatures. This can be explained by the growing share of
furfural, which is a degradation product of hydroxymethylfurfural63.

31

1,6

80

1,4

70

1,2

60

50
0,8
40
0,6

30

0,4

20

0,2

10
0

0
300C

400C

TIC relative abundance (peak area %),

except LG and HA

TIC relative abundance (peak area %)

90

LG
AGF
HMF
LGO
FF
HA

500C

FIGURE 16: RELATIVE AMOUNT PRODUCED OF THE 6 MOST IMPORTANT CELLULOSE PYROLYSIS DEGRADATION
PRODUCTS. LEVOGLUCOSAN (LG) AND 1,6-ANHYDRO--D-GALACTOFURANOSE (AGF) ARE EXAMINED ON THE
LEFT AXIS, HYDROXYMETHYLFURFURAL (HMF), LEVOGLUCOSENONE (LGO), FURFURAL (FF) AND
HYDROXYACETALDEHYDE (HA) ON THE RIGHT AXIS.

Pathwardan26 et al. stated earlier that levoglucosan does not degrade at temperatures under
600C in a micropyrolysis set-up. It is also very volatile, so it degradation can be minimized
by applying short residence times and rapid cooling. Statistical analysis proved that at a 5%
significance level the variation in levoglucosan at three temperatures (shown in Figure 16) is
negligible, which confirms these findings. As such it can be assumed that other pyrolysis
products were produced from an active intermediate species (i.e. a cellulose-derived
precursor prior to the formation of levoglucosan) instead of from further degradation of
levoglucosan.

1.2 LIGNIN
The same experiment was also applied to lignin, the second main constituent of biomass.
The product distribution of lignin pyrolysis can differ significantly among the various types of
biomass. The pyrolyzed lignin in the following experiments was extracted from an unknown
plant species. The obtained chromatograms at three different temperatures are shown in
Figure 17, while the product distribution analyzed at 500C is shown in Table 6. Once more
the products indicated with at least one star are also found in the distribution at 400C, the
products with only one star are those determined at 300C.

32

FIGURE 17: TIC CHROMATOGRAM OF LIGNIN MICROPYROLYSIS OF APPROX. 0.5 MG AT (UPPER) 300C, (MIDDLE)
400C AND (BOTTOM) 500C

TABLE 6: GAS CHROMATOGRAPHIC ANALYSIS OF PYROLYSIS PRODUCTS FROM LIGNIN AT 500C. THE PRODUCTS
INDICATED WITH AT LEAST ONE STAR ARE ALSO FOUND IN THE DISTRIBUTION AT 400C, THE PRODUCTS WITH
ONLY ONE STAR ARE THOSE DETERMINED AT 300C.
Iupac name

Apex RT

Area %

Iupac name

Apex RT

Area %

Carbon dioxide*

4,9

8,25

2-methoxy-3-(2-propenyl)-phenol*

32,48

1,26

Methanethiol*

5,38

2,02

2-methoxy-4-propyl-phenol*

32,54

0,73

Methanol**

5,57

2,07

Catechol

33,01

0,35

Dimethyl sulfide

6,2

0,12

2,6-dimethoxy-Phenol, 2,6-dimethoxy-

33,2

0,32

Acetic acid

10,43

0,38

Benzene, 4-ethenyl-1,2-dimethoxy-

33,65

0,32

1-Hydroxy-2-Propanone

11,56

0,14

Phenol, 2-methoxy-4-(1-propenyl)-**

33,89

1,29

Toluene

11,75

0,22

4-(2-propenyl)-phenol

34,56

0,14

Benzene, 1-methoxy-4-methyl-

21,18

0,19

Phenol, 2-methoxy-4-(1-propenyl)-, (Z)**

35,2

6,29

2-Cyclopenten-1-one, 3-ethyl-2-hydroxy-

24,03

0,20

2-Methoxy-4-formylphenol**

35,85

1,78

Phenol*

24,5

2,20

1-(4-Hydroxybenzylidene)acetone

36,14

0,16

Guaiacol*

25,16

19,58

4-propylguaiacol

37,25

0,45

2-methyl-phenol

25,9

0,90

1-(4-hydroxy-3-methoxyphenyl)-ethanone*

37,77

1,78

1,2-dimethoxy-benzene

26,01

0,22

1,2-Dimethoxy-4-n-propylbenzene

38,04

0,31

4-methyl-phenol

26,92

0,74

Guaiacylaceton*

38,95

1,74

3-methyl-phenol

26,98

0,79

4-(2-Hydroxyethyl)-2-methoxyphenol

39,13

0,28

3-Methylguaiacol

27,14

1,56

4-ethoxy-3-methoxy-Benzaldehyde

39,64

0,32

4-Methylguaiacol*

28,06

7,57

Homovanillic acid*

41,66

5,46

Cyclopropyl carbinol*

28,32

0,42

4-((1E)-3-Hydroxy-1-propenyl)-2-methoxyphenol

42,25

0,47

3,4-Dimethoxytoluene**

28,54

1,12

2,3-dimethoxy-Naphthalene

43,47

0,29

4-ethylguaiacol

29,27

0,54

2-Acetyl-6-methoxynaphthalene

44,18

0,27

2-Methoxy-4-vinylphenol*

31,9

11,99

3-(4-hydroxy-3-methoxyphenyl)-2-Propenal*

44,52

0,79

4-ethenyl-1,2-dimethoxy -benzene**

32,34

0,38

3,5-Dimethoxy-4-methylbenzoic acid**

44,65

0,40

33

TIC relative abundance (peak area %)

Figure 18 shows that the product distribution of lignin pyrolysis products is totally different
than the one from cellulose pyrolysis. The main products here are phenolic derivatives, low
molecular weight species and aromatic species, while oxygenated species, furans and
anhydrosugars account for the majority of the cellulose pyrolysis products and were not
found in the pyrolytic spectrum of lignin.

100
90
80
70
60
50
40
30
20
10
0
Low molecular
weight
compounds
300C

Phenols

400C

Aromatics

500C

FIGURE 18: RELATIVE AMOUNT OF LOW MOLECULAR WEIGHT COMPOUNDS, PHENOLAS AND AROMATICS IN
FUNCTION OF TEMPERATURE IN PYGCMS

Figure 19 proves that the pyrolysis behavior is very different among these two constituents.
The amount of pyrolyzed products detected and analyzed by the GC/MS, expressed in peak
area per mg of the pyrolyzed constituent, increases in the case of lignin from 4.98*109 at
300C to 2.02*1010 at 500C, while for cellulose pyrolysis a smaller increase (from 6.21*1010
to 6.31*1010 ) is noticed between 300C and 400C, after which it becomes stable (effect is
not significant). The total quantity of products analyzed (in the TIC chromatogram) is
approximately twelve times higher for cellulose at 300C compared to lignin and still three
times higher at 500C. This means that cellulose is totally decomposed at 400C while at
500C it is further degraded in smaller components. This result is confirmed by Figure 15 and
was also demonstrated by Yang et al.64, who studied the mass loss rates during pyrolysis of
lignin and cellulose using thermogravimetric analysis (TGA). The weight loss for cellulose
pyrolysis was focused at a temperature range between 315-400C, with a maximum rate at
355C. At 400C nearly all cellulose was pyrolyzed. The thermal decomposition of lignin
seemed to be much more difficult, it continued over an extremely wide range. From 100 to
900C decomposition occurred, but at a much lower mass loss rate (6.5 wt.%/C for cellulose
against 0.14 wt.%/C for lignin). The char residue was significantly higher for lignin. This
effect is due to their difference in chemical structure. The wide temperature range of
34

degradation of lignin can be explained by the variety of chemical bonds with different
stabilities linking the aromatic moieties, as mentioned before in the literature research.

8E+10

TIC total peak area/mg

7E+10
6E+10
5E+10
4E+10

Cellulose

3E+10

Lignine

2E+10
1E+10
0
300C

400C

500C

FIGURE 19: TOTAL PEAK AREA PER MG SAMPLE CALCULATED FROM THE GAS CHROMATOGRAPHIC ANALYSIS
OF LIGNIN AND CELLULOSE PYROLYSIS PRODUCTS IN PYGCMS

The absolute amount of phenol derivatives and methoxylated aromatics increases with
temperature (from 4.65*109 to 1.66*1010 TIC) but their relative importance diminishes (from
93.4 to 82.6%) due to two competing pathways: one the hand, these phenolic compounds
could polymerize into heavy lignin oligomers and finally char accompanied with the
production of non-condensable gases. On the other hand, the unstable phenolic compounds
are also subjected to demethoxylation reactions leading to aromatics. Small components
such as acetic acid and hydroxypropane are just observed at 500C. Figure 20 shows a
breakdown of the phenolic species of lignin pyrolysis into non, mono and dimethoxylated
species, which are assumed to be the respective degradation products of coumaryl, coniferyl
and sinapyl units of the lignin structure, as described earlier. Monomethoxylated compounds
(or guaiacol derivatives) represent the largest fraction (up to 97,5 % at 300C). Nevertheless
this ratio depends on the wood type from which the lignin is derived since softwood lignins
produce mainly guaiacols and hardwood lignins gives equal amounts of guaiacols and
syringols.65 The lignin used in our experiments is for this reason clearly extracted from
softwood. With increasing temperature the relative amount of guaiacol derivatives reduces
from 97.5% to 86.0% in favor of non methoxylated species. Starting from 400C, these
compounds become significant (1.75% at 400C and 7.23% at 500C). This is a result of the
demethylation of the methoxygroups which takes place between 350 and 400C according to
Murwanashyaka et al.66. On the other hand an increase of syringol derivatives with
temperature (from 2.1 to 5.8%) was observed. The higher yields of components as phenols,
catechols and syringol derivatives were also described by Petrocelli at al.67.

35

TIC relative abundance (peak area %)

120
100
80
300C
60

400C
500C

40
20
0
NON

MONO

DI

FIGURE 20: AMOUNT OF NON, MONO AND DIMETHOXYLATED PHENOLS PRODUCED DURING LIGNIN PYROLYSIS IN
FUNCTION OF TEMPERATURE IN PYGCMS

Figure 21 summarizes the tendency of the twelve most common compounds in function of
the applied temperature. Most of these are indeed guaiacols derivatives. Unsaturated
compounds such as isoeugenol and vinylguaiacol are just as vanillin formed during the early
stages of pyrolysis by dehydration of lignin. During this process also a substantial amount of
water is produced68. These components are relatively unstable and rapidly degrade at higher
temperatures, which is very clear for vinylguaiacol (from 21.4 to 11.9%). Methylguaiacol and
ethylguaiacol are also already formed at temperatures between 200 and 300C by the
degradation of the propanod side chain of lignin41. Guaiacol, vinylguaiacol, isoeugenol,
vanillin, acetylguiacol, guaiacylaceton and homovanillic acid are all monomethoxylated and
their relative share decreases at increasing temperature due to the earlier mentioned
demethoxylation reaction. Their decrease can also be explained by the induced
rearrangements of the functional groups at higher temperatures, leading to a bigger amount
of char and heavier products such as polyaromatics.

36

TIC relative abundance (peak area %)

30
25
20
15
300C
10
5

400C
500C

FIGURE 21: AMOUNT PRODUCED OF TWELVE MOST IMPORTANT PRODUCTS OF LIGNIN PYROLYSIS IN FUNCTION
OF TEMPERATURE IN PYGCMS

2. ALKALI AND EARTH ALKALINE METAL CATALYSIS

2.1 IN-BED CATALYSIS
As alkali and earth alkaline metals are naturally occurring compounds in whole biomass, the
aim is to investigate whether these mineral compounds could act catalytically on primary
pyrolysis reactions of biomass, and whether their effect is detrimental or beneficial in
biomass pyrolysis.
For the in-bed catalysis experiments three different potassium and calcium salts were
chosen. Patwardhan et al.26, who observed the effect of different metals on cellulose
pyrolysis and classified them by their effect on levoglucosan reduction, showed that
potassium and calcium are respectively the alkali and alkaline earth metal with the largest
impact. In this study the chlorides, acetates and citrates of both metals were applied to also
investigate the effect of the anion and the catalysts were mixed with lignin and cellulose in at
least three different concentrations. The metal concentrations were kept low (between 0.05
and 22 wt.%) in order to resemble natural occurring metal concentrations in lignocellulosic
biomass. To reduce the variation in reproducibility for impregnated samples due to
heterogeneity and the use of very small catalyst amounts (in the order of micrograms),
experiments were run in triplicate. Zaror et al.69 also reported effects such as fibre swelling
and matrix modification after mixing wood with alkaline and neutral salts, which means
attention has to be paid on the pyrolytic behavior of this pretreatment. Previous studies70
describe the optimal pyrolysis temperature for maximizing the bio-oil yield in a range of 475525C, so a temperature of 500C was chosen to execute the catalytic fast pyrolysis
experiments. This was also confirmed by the results in the previous section.

37

2.1.1 C ELLULOSE
The first conclusion that can be made is that similar decomposition products are identified in
pure cellulose and samples with added salt catalysts, but their relative yields differ. Between
73 and 120 products were identified, accounting for approximately 90% of the total peak area
in all chromatograms. The first step of the volatile production during cellulose pyrolysis is
generally the generation of anhydrosugars and levoglucosan in particular, which is confirmed
by the graph in Figure 22, where the products are classified into different categories
according to their chemical appearance. When the amount of anhydrosugars is 90.05% of all
pyrolysis products for pure cellulose, this remains only 17.62% at samples containing 2.5
wt.% potassium citrate. The presence of a very small amount of salt was already found to
have an adverse effect on levoglucosan production. Pathwardan et al.26 suggested that the
added salts lower the levoglucosan degradation temperature, so it isnt stable anymore at
500C. Another hypothesis is that inorganics only interact with the formation of levoglucosan
and do not have an effect on its secondary degradation. Therefore a comparison should be
made with the ex-bed experiments. The decrease of anhydrosugars was accompanied by a
considerable increase in low molecular weight species including hydroxyacetaldehyde (from
0.78% to 8.52%), acetic acid (from 0.04 to 0.37%) and formic acid (with a maximum for the
initial loading of 0.02 wt.%). The ratio of other ring-open cracked species as alcohols,
ketones, aldehydes, ethers, carboxylic acids and aliphatics also increased significantly.
These species result from the direct separation from glucose units, or from the
decomposition of levoglucosan and other earlier formed anhydrosugars.

TIC relative abundance (peak area %)

100%
90%

Sugars

80%

Phenols

70%

Furans / Pyran

60%

Carboxylic
acids/esters
Ethers

50%
40%
30%

Aldehydes
Ketones

20%
Alcohols
10%
0%

Aliphatic
CO2

FIGURE 22: CLASSIFICATION OF PYROLYSIS PRODUCTS OF CELLULOSE SAMPLES IMPREGNATED WITH VARIOUS
CONCENTRATIONS OF POTASSIUM CITRATE IN PYGCMS AT 500C

38

TIC relative abundance (peak area %)

Figure 23 shows the pyrolysis products of samples impregnated with calcium citrate,
subdivided conform the classification shown earlier. A first important difference with
potassium catalysis is the smaller decline in levoglucosan yield. Still 63.94% of
anhydrosugars, of which 54.7% was levoglucosan, remained when 2 wt.% calcium citrate
was present in the cellulose sample. In contrast the amount of the low molecular weight
species increased. Only a quantity as small as 0.05 wt.% was required to drastically
influence the yield of ketones, alcohols, aldehydes, furan derivatives and carboxylic acids.
Nevertheless compared with potassium citrate the catalytic effect of calcium citrate is less
dependent on the concentration of added salt. Only a significant difference was observed
between the amounts of ethers, with a yield increasing from 0.45 to 3.34%, and alcohols,
with maximum yield of 2.53% at 0.05 wt.% of catalyst after which it declined again. The other
categories didnt show a significant difference when the catalyst loading exceeded 0.05 wt.%.
100%
90%
80%
70%

Anhydrosugars
Phenols

60%

Furans / Pyran

50%

Carboxylic acids/esters

40%

Ethers

30%

Aldehydes

20%

Ketones

10%

Alcohols

0%

Aliphatic

FIGURE 23: CLASSIFICATION OF PYROLYSIS PRODUCTS OF CELLULOSE SAMPLES IMPREGNATED WITH VARIOUS
CONCENTRATIONS OF CALCIUM CITRATE IN PYGCMS AT 500C

The impact of different potassium and calcium salts on five main cellulose pyrolysis products
is shown in Figure 24. Levoglucosan, hydroxymethylfurfural, furfural, hydroxyacetaldehyde
and acetol are chosen to study the reaction mechanisms of catalytic fast pyrolysis. The
reduction of levoglucosan is generally used as a parameter to interpret the catalytic strength
of the applied salts. The graphs on the left side show the effect of potassium salts, the ones
on the right side represent the influence of calcium salts.
From the results it is obvious that potassium combined with acetate yields the lowest amount
of levoglucosan. By doping a gram of cellulose with 0.005 mmoles of potassium acetate the
levoglucosan yield diminished from 79.7% to 8.2%. No further effect on levoglucosan was
noted when higher catalyst concentrations were applied. On the contrary, a minimal amount
39

of potassium acetate enhanced the formation of furfural, hydroxyacetaldehyde and acetol.

The hydroxymethylfurfural yield wasnt significantly influenced by this organic salt.
A remarkable result is the increase of hydroxymethylfurfural when cellulose is doped with
citrate as counterion for potassium. It initially increased drastically, but decreased again
when more than 0.0007 mmol potassiumcitrate per gram cellulose was added. For
levoglucosan, furfural and hydroxyacetaldehyde the effect was similar to that of potassium
acetate. Only in the case of acetol a significant difference (p=0.041<0.05) could be detected
between both organic salts. When potassium acetate was present in a small concentration
of 0.005 mmol per gram cellulose the acetol yield increased to 8.3%, while the increase in
the presence of citrate was less steep (to 7.2% when even 0.08 mmol per gram was added).
Hereby it is necessary to mention that the organic anions can also degrade and in this way
influence the amounts of low molecular weight cellulose degradation products, but the added
concentrations are too low to have a significant effect. Acetate in particular will not contribute
to the formation of for example acetol, since acetol contains three carbons and acetate only
two.
At last the influence of KCl was found less severe in the case of levoglucosan yield
degradation and the increase of acetol. The effect on hydroxyacetaldehyde and furfural is
similar, but a far stronger impact on hydroxymethylfurfural is observed. The yield rises from
0.44% to 2.93% when 0.37 mmol KCl/g cellulose is present. Higher concentrations of KCl
seem to induce a decline in its yield, but this effect is not significant (p=0.083>0.05).
When looking at the calcium salts, for none of the five studied components a significant
difference was found between the citrate and acetate salt. A correlation between the
increase of furfural and the similar decrease in hydroxymethylfurfural can be assumed, but
cannot be proven statistically. Although its important to mention that the used nonparametric statistical tests arent as strong in determining differences as parametric ones.
Both the calcium citrate and acetate show similar trends as discussed for potassium citrate
and acetate, but the effect of calcium is less severe: the levoglucosan yield degraded only to
approximately 58%, while the increase in hydroxyacetaldehyde and acetol were respectively
about two and four times smaller than accomplished with the potassium organic salts.
The yield of both small oxygenates followed a remarkable trend in case of calcium chloride:
after a steep increase at the initial metal loading of 0.002 mmol/g cellulose a decline from
1.97 to 1.2% was observed at higher calcium concentrations. The amount of
hydroxyacetaldehyde even diminished to 1.64% at a loading rate of 0.22 mmol/g cellulose
after a maximum of 6.22 % in presence of only 0.002 mmol/g cellulose. This is consistent
with previously reported studies51, but more investigation is needed to elucidate the correct
mechanisms.
Finally, calcium chloride is most effective of all tested catalysts in production of furfural and
hydroxymethylfurfural. Their yields increased respectively from 0.04 and 0.44% to 3.3 and
6.2% in presence of 0.22 mmol/g cellulose. This is in accordance with our expectations since
calcium is known to promote dehydration reactions51.

40

LEVOGLUCOSAN
KAc

KCit

CaCl2

TIC relative abundance (peak area %)

TIC relative abundance (peak area %)

KCl
90
80
70

60
50
40
30
20

10
0

0,05

0,1

0,15

0,2

0,25

0,3

0,35

CaAc

CaCit

90
80
70

60
50
40
30
20

10
0

0,4

0,05

0,1

0,15

0,2

0,25

mmol/g cellulose

mmol/g cellulose

HYDROXYMETHYLFURFURAL
7

TIC relative abundance (peak area %)

TIC relative abundance (peak area %)

4
3,5
3

2,5
2
1,5
1
0,5
0

0,1

0,2

0,3

0,4

6
5

4
3
2
1
0
0

0,05

0,1

0,15

mmol/g cellulose

0,2

0,25

mmol/g cellulose

TIC relative abundance (peak area %)

TIC relative abundance (peak area %)

FURFURAL
2
1,8
1,6
1,4
1,2
1
0,8
0,6
0,4
0,2
0
0

0,1

0,2

0,3

0,4

3,5
3
2,5
2

1,5
1
0,5
0
0

mmol/g cellulose

0,05

0,1

0,15

0,2

0,25

mmol/g cellulose

HYDROXYACETALDEHYDE
TIC relative abundance (peak area %)

TIC relative abundance (peak area %)

12

10
8

6
4

2
0
0

0,05

0,1

0,15

0,2

0,25

0,3

0,35

0,4

mmol/g cellulose

ACETOL

6
5
4

3
2
1
0
0

0,05

0,1

0,15

0,2

0,25

mmol/g cellulose

41

TIC relative abundance (peak area %)

10
8
6
4
2
0
0

0,05

0,1

0,15

0,2

0,25

0,3

0,35

0,4

TIC relative abundance (peak area %)

ACETOL

12

3
2,5
2
1,5
1
0,5
0
0

0,05

0,1

0,15

mmol/g cellulose

0,2

0,25

mmol/g cellulose

FIGURE 24: EFFECT OF DIFFERENT SALTS ON FIVE MAIN CELLULOSE PYROLYSIS PRODUCTS

According to Nowakowski et al.52 at least a duplication of the amount of char is produced

during potassium-catalyzed pyrolysis. Although it was impossible to measure directly the
amount of char produced, it could be estimated indirectly by comparing the magnitude of the
total peak area per mg cellulose pyrolyzed. The overall peak area decreases from 6.27*10 10
for pure cellulose to 2.7*1010 for a sample impregnated with 2.5 wt.% which indicates an
increase in the char production71. However this could also indicate an increase in noncondensable gases which cannot be detected by the GC.

2.1.2 L IGNIN
In accordance with the tests on cellulose, similar samples were prepared to figure out the
influence of calcium and potassium on the thermal degradation of lignin. Less is known about
the precise mechanisms of catalytic degradation of lignin, since most of the studies so far
were focused on cellulose. In general, the differences in product distribution after pyrolysis of
lignin with added salts are a lot smaller than those of salt-enriched cellulose. The catalytic
effect is less intense and for this reason, samples with higher weight percentages (up to 10
wt.%) were prepared and analyzed.
The relative amount of the low molecular weight species, phenolics and aromatics is given in
Figure 25. Phenolic derivatives and methoxylated aromatics are the main pyrolytic products
of pure lignin, but their amount decreased with increasing metal content (from 81.7% for pure
lignin to 62.3% for a 0.9 mmol CaCl2/g lignin sample) while the share of aromatics increased.

42

TIC relative abundance (peak area %)

90
80
70
60
50
40
30
20
10
0
low molecular
weight
compounds
lignin

0,23 mmol

phenolics

aromatics

0,45 mmol

0,9 mmol

FIGURE 25: RELATIVE AMOUNT OF LOW MOLECULAR WEIGHT COMPOUNDS, PHENOLS AND AROMATICS DURING
500C LIGNIN PYROLYIS IN FUNCTION OF ADDED CACL2 CONCENTRATION

As can be seen in Figure 26 an increase in potassium or calcium content causes an increase

in the formation of non-methoxylated phenols. The percentage of non-methoxylated phenol
derivatives shifts from 7.43% for pure lignin to 13.84% for a 0.9 mmol CaCl2/g cellulose
sample and to 10.61% for a 1.34 mmol KCl/g cellulose sample. In contrast the amount of
monomethoxylated species diminishes in presence of metal catalysts. Demethoxylation of
guaiacyl units is the main route of phenol formation, from which can be derived that
potassium and calcium have a significant influence on this reaction2. The influence on
demethoxylation is confirmed by the small increase in phenol with increasing metal content.
100
90

peak area %

Peak area %

80
70
60
50
40
30
20
10

100
90
80
70
60
50
40
30
20
10
0
NON

0
NON

MONO

DI

MONO

DI

Lignin

0,007 mmol KCl

0,34 mmol KCl

Lignin

0,23 mmol CaCl2

0,14 mmol KCl

0,45 mmol CaCl2

0,9 mmol CaCl2

1,34 mmol KCl

FIGURE 26: AMOUNT OF NON, MONO AND DIMETHOXYLATED PHENOLS PRODUCED DURING 500C LIGNIN
PYROLYSIS IN FUNCTION OF THE ADDED METAL CONCENTRATION

43

3
2,5
2
1,5
1
0,5
0

0,5

CaCl2

TIC relative abundance (peak area %)

TIC relative abundance (peak area %)

Phenol

0,5

KCl

0,4

0,3

0,2

0,1

0
0,5

CaCl2

KCl

Guaiacol

20
16

12
8

4
0
0

0,5

1,5

mmol/ g lignin

CaCl2

mmol/g lignin

Catechol

24

1,5

TIC relative abundance (peak area %)

TIC relative abundance (peak area %)

Figure 27 shows the amount of the most abundant components formed after pyrolysis of
lignin in the presence of potassium and calcium chloride. The effect of potassium chloride on
the formation of phenol, guaiacol and 4-vinylguaiacol is quite remarkable. An initial decrease
in their yields was followed by a steady increase at higher potassium concentrations. These
results are in conflict with those published before. Eom et al.51 reported an increase in
guaiacol and 4-vinylguaiacol with increasing potassium contents. The beneficial effect on the
demethoxylation reaction was also proven by the substantial increase in catechol. Calcium
on the other hand seems to be detrimental for guaiacol and its derivatives, although previous
studies report only a minimal effect of calcium on the product distribution of lignin pyrolysis in
contrast to potassium. For the other components its not possible to conclude whether the
small differences are a result of a catalytic effect or the uncertain reproducibility.

12

1,5

mmol/g lignin

KCl

4-Vinylguaiacol

10
8
6
4
2
0

0,5

CaCl2

KCl

1,5

mmol/ g lignin

FIGURE 27: EFFECT OF DIFFERENT SALTS ON MAIN LIGNIN 500C PYROLYSIS PRODUCTS

2.2 EX-BED CATALYSIS

In general it is difficult to investigate the difference between primary and secondary
degradation reactions due to the close coupling of both processes. But thanks to the short
residence times in the micropyrolysis reactor, secondary reactions can be inhibited which
44

allowed us to investigate the effect of alkali and alkaline metals on primary reactions through
mixing them with lignin and cellulose (i.e. in-bed catalysis). A secondary reactor was used to
study the effect of catalysts on the secondary degradation reactions (ex-bed catalysis). The
temperature of the secondary reactor was kept at 500C as well. An excessive amount of
potassium chloride and calcium chloride were placed alternately in the secondary reactor to
catalyze the cracking reaction of the primary pyrolysis products (vapors). A comparison with
the results of in-bed catalysis allows us to differentiate the catalytic effects on primary and
secondary reactions.

2.2.1 C ELLULOSE
Figure 28 shows the classification of cellulose pyrolysis products when the produced gases
are pushed through a catalytic bed of potassium chloride or calcium chloride. The bed
contains about 5 mg of catalyst. The residence time of the pyrolysis vapors is longer which
makes the secondary degradation of levoglucosan and other primary vapor-phase
compounds possible. The decline in the yield of sugars was accompanied by an increase in
low molecular weight species, especially ketones, aldehydes, and furan derivatives. This
result is similar to that of in-bed catalysis, although the effect seems to be less effective in
terms of levoglucosan yield. More than 67% of the identified products are sugars, while even
very small quantities of potassium chloride were able to reduce the sugar content to 17%
when mixed with cellulose before pyrolysis. Calcium on the other hand seems to have a
stronger effect on secondary cracking since only 40.8% of sugars remain, which is far less
than the yield of 67.8% after potassium catalysis. One had to keep in mind that the effect can
be due to the differences in particle size of the packed bed catalyst and the related residence
time. The particles of both catalysts did not have the same size distribution, which leads to
another specific surface area for each bed. For both catalysts, the same packed bed was
used three times.

45

TIC relative abundance (peak area %)

100%
90%

Sugars

80%

Phenols

70%

Furans / Pyran

60%

Carboxylic acids/esters

50%

Ethers

40%

Aldehydes
Ketones

30%

Alcohols
20%

Aliphatic

10%

CO2

0%
cellulose

KCl

CaCl2

FIGURE 28: CLASSIFICATION OF PYROLYSIS PRODUCTS OF CELLULOSE AT 500C AFTER VAPOUR PHASE
CATALYSIS WITH KCL AND CACL2 IN PYGCMS

The main products of ex-bed catalyzed cellulose pyrolysis are shown in Table 7. These are
the same as detected after in-bed catalyzed pyrolysis, but their relative yields are
significantly different for some compounds. For calcium chloride the yield of
hydroxymethylfurancarboxaldehyde is much smaller (0.8% with respect to 6.2%) in an exbed setup, while the yield of acetol and acetic anhydride is respectively four and two times
higher compared to their yield in in-bed catalysis. In the case of the potassium chloride
experiment the yields of the low molecular weight species are multiple times larger for in-bed
catalysis, which indicates a more intensive degradation. Nevertheless, the generally
accepted hypothesis that alkali and alkaline earth metals only interact in the primary
degradation of cellulose into anhydrosugars is not entirely correct26: a limited catalytic effect
in the vapor phase could be demonstrated wherein the vapor-phase anhydrosugars, in their
turn, are broken down into smaller oxygenated compounds through heterogenous catalysis,
which also has been suggested by Ronsse et al.72

TABLE 7: RELATIVE AMOUNT (TIC RELATIVE ABUNDANCE) OF THE MAIN CELLULOSE 500C PYROLYSIS
PRODUCTS AFTER VAPOR PHASE UPGRADING

Iupac name

Cellulose

Cellulose + KCl

Cellulose + CaCl2

Carbon dioxide

1,29

6,91

8,30

Ethane

0,46

1,70

3,60

Acetic anhydride

0,58

2,14

5,00

Hydroxyacetaldehyde

0,76

1,25

0,44

Acetic acid

0,05

0,51

0,80

Acetol

0,17

1,69

2,68

Furfural

0,42

1,69

3,63

46

1,2-Cyclopentanedione

0,21

1,26

2,68

3,4-Anhydro-d-galactosan

0,12

1,81

0,68

2,3-Anhydro-d-mannosan

0,21

2,82

1,23

5-(Hydroxymethyl)-2-furancarboxaldehyde

0,44

0,71

0,80

79,71

50,80

30,63

8,66

6,35

3,19

Levoglucosan
1,6-Anhydro--d-galactofuranose

It is hard to quantify the differences between in-and ex-bed catalysis because in in-bed mode
various small concentrations were applied, while in ex-bed mode an excess in catalysts was
used. The differences in relative yield are small, which is a remarkable result since one
usually related the catalytic effect of alkali and earth alkaline metals only to the primary
degradations reactions. Figure 29 shows the absolute amounts of different types of products
formed. Knowing that non-catalyzed cellulose pyrolysis produces 200 times more
anhydrosugars than ex-bed catalyzed pyrolysis, one can conclude that there is also a similar
catalytic effect on secondary degradation reactions.

1,6E+10

TIC total peak area/mg

1,4E+10
1,2E+10
1E+10
8E+09
6E+09
4E+09
2E+09
0

ex-bed

in-bed

FIGURE 29: TIC TOTAL PEAK AREA PER MG SAMPLE OF THE PYROLYSIS PRODUCTS OF CELLULOSE IN IN- EN EXBED CATALYZED MODE

2.2.2 L IGNIN
The fixed bed reactor of potassium and calcium salts mounted downstream the first pyrolysis
reactor doesnt have a remarkable impact on the yield of the stable products from the thermal
degradation of lignin. Table 8 shows the relative amounts produced of the main lignin
47

pyrolysis products before and after going through the bed, but no significant differences
could be determined. When the 76 identified compounds are classified according to their
chemical structure, a decrease of phenolic species from 83% to respectively 76 and 74,5%
was observed in favor of aromatics, aliphatics and CO2 although this cant be proven
statistically.
TABLE 8: RELATIVE AMOUNT OF THE MAIN LIGNIN PYROLYSIS PRODUCTS AFTER VAPOR PHASE UPGRADING

Iupac name

lignin

Lignin + KCl

Lignin + CaCl2

Carbon dioxide

9,28

10,40

7,66

Phenol

2,45

2,60

2,32

16,79

17,55

18,87

4-Methylguaiacol

7,27

7,45

8,20

4-Ethylguaiacol

4,50

4,63

4,70

4-Vinylguaiacol

9,53

8,62

10,01

Iso-eugenol

5,84

5,43

6,03

Homovanillic acid

4,70

3,95

5,21

Guaiacol

Figure 30 shows that the type of catalysis also has a significant influence on the total product
yield. The TIC total peak area is given and for cellulose a significant decrease is observed for
ex-bed catalysis products. The effect is also noticed when even a small amount of 0.05 wt.%
CaCl2 was added to the in-bed samples. The degradation is more intense when catalyzed
and therefore more non condensable gases, which cannot be detected by the GC/MS, are
produced. The influence on lignin is much less severe, no significant differences are
observed between the three experiment types.
8E+10

TIC total peak area/mg

7E+10
6E+10
5E+10
4E+10

cellulose

3E+10

lignin

2E+10
1E+10
0
pure

CaCl2 ex-bed

0,05 wt.%
CaCl2

FIGURE 30: TIC TOTAL PEAK AREA PER MG SAMPLE OF THE PYROLYSIS PRODUCTS OF BOTH CELLULOSE AND
LIGNIN IN NON-CATALYZED AND IN IN- AND EX-BED CATALYZED MODE

48

3. ZEOLITE CATALYSIS
In the previous section, some of the alkali and earth alkaline metals, naturally abundant in
lignocellulosic biomass have been tested with respect to their catalytic activity towards
primary and secondary pyrolysis decomposition reactions using pyGCMS methodology.
These naturally occurring catalysts are also referred to as intrinsic. In this section, an
example will be worked out of a so-called extrinsic catalyst, i.e. a synthetic added catalyst
and studied using the same methodology with pyGCMS.
A non-commercial HZSM-5 like catalyst was chosen to investigate in in-bed and ex-bed
mode because this type of zeolite has already been confirmed as very effective in decreasing
the oxygen-containing products and even more in producing aromatic hydrocarbons during
biomass pyrolysis, resulting in a more stable pyrolysis oil product with properties that are
more compatible for cofeeding in a petrochemical refinery for fuels and chemicals
production73.

3.1 CELLULOSE
3.1.1 I N - BED CATALYSIS
The product distribution of cellulose pyrolysis mixed with HZSM-5 in three different
concentrations (5, 10 and 20 wt.%) differed with those obtained by metal catalysis. Figure 31
shows the yield of five important species formed during catalyzed pyrolysis.
The
levoglucosan yield was decreased from 79.7 to 69.3% when 5 wt.% of catalyst was present
and did not vary significantly when the catalyst concentration was increased. Yields of other
anhydrosugars such as 2,3-anhydro-d-mannosan, 1,4:3,6-dianhydro--d-glucopyranose, 1,6anhydro--d-galactofuranose and 2,3-anhydro-d-galactosan (from 0.12 to 1.03%) were
slightly increased. These cyclic products are obtained by transglycosylation, dehydration and
cyclization reactions. In contrast, the presence of zeolites induced a steady decline in the
formation of hydroxyacetaldehyde from 0.48 to 0.21%, which was also observed by Azeez et
al.74. From this can be assumed that this zeolite induces ring-closure (aromatization)
reactions.

49

1,40

80

1,20

70
1,00
60
0,80

50
40

0,60

30
0,40
20
0,20

10
0

TIC relative abundance (peak area %)

TIC relative abundance (peak area %)

90

LG
Toluene
FF
2,3-Anhydro-dgalactosan
HAA

0,00
0

10

15

20

25
% HZSM-5

FIGURE 31: EFFECT OF DIFFERENT LEVELS OF HZSM-5 ON THE MAIN CELLULOSE 500C PYROLYSIS PRODUCTS IN
PYGCMS. LEVOGLUCOSAN (LG) IS EXAMINED ON THE LEFT AXIS; TOLUENE, FURFURAL (FF), 2,3-ANHYDRO-DGALACTOSAN AND HYDROXYACETALDEHYDE (HAA) ON THE RIGHT AXIS.

Furthermore no aromatics were identified in pure cellulose pyrolysis, while in HZSM-5

catalysed pyrolysis compounds as toluene and p-xylene were detected. Their share also
increased at higher zeolite concentrations (respectively up to 0.29 and 0.20%). It is generally
known that zeolites catalyse the formation of aromatics in their pores. In terms of total peak
area one can conclude that the product yield is a lot lower in ex-bed catalysis, as can be
seen in Figure 32.

TIC abundance (peak area)

9E+10
8E+10
7E+10
6E+10
5E+10
4E+10
3E+10
2E+10
1E+10
0
Pure
cellulose

5 wt.%
ZSM-5

10 wt.%
ZSM-5

20 wt.%
ZSM-5

Ex-bed

FIGURE 32: ABSOLUTE AMOUNT OF CELLULOSE PYROLYSIS PRODUCTS DETECTED BY THE GC/MS IN TERMS OF
TOTAL PEAK AREA

50

3.1.2 E X - BED CATALYSIS

A totally different product distribution is obtained after ex-bed catalysis with the HZSM-5
catalyst compared to metal catalysis, as can be seen in Table 9. The catalytic processes on
the zeolite surface described earlier for in-bed catalysis are intensified when placing the
catalyst in a reactor downstream the pyrolysis oven, leading to products such as styrene,
benzenes and naphtalenes which were yet not identified in cellulose pyrolysis. Furthermore
other common small oxygenates such as hydroxyacetaldehyde and acetol cannot be
identified anymore.

TABLE 9: GAS CHROMATOGRAPHIC ANALYSIS OF 500C PYROLYSIS PRODUCTS FROM LIGNIN CATALYZED WITH
HSZM-5 IN EX-BED MODE
IUPAC name

Apex RT

Peak area %

IUPAC name

Apex RT

Peak area %

Carbon dioxide

6,22

3,44

Benzene, 2-propenyl-

22,16

0,39

Propene

6,29

2,51

Benzene, 1-propynyl-

23,06

2,16

2-Butene

6,48

1,09 Benzene, (1-methylenepropyl)-

25,21

0,17

Furan

7,36

1,05 Phenol

25,6

0,43

Acetone

7,86

0,32 Benzene, 1-butynyl-

26,13

0,46

Acetic anhydride

8,08

0,91 Naphthalene, 1,2-dihydro

26,51

0,26

Acetonitrile

8,56

0,16 Naphthalene

27,87

4,32

Furan, 2-methyl-

8,78

0,57 Naphthalene, 1-methyl-

30,87

2,04

Methyl vinyl ketone

9,73

0,16 2-Pentanol, 5-(2-propynyloxy)-

31,45

0,28

Benzene

10,18

2,78 2,3-Anhydro-d-galactosan

31,71

0,37

Toluene

13,15

5,52 2,3-Anhydro-d-mannosan

31,88

0,70

Ethylbenzene

16,17

0,18 1,4:3,6-Dianhydro--d-glucopyranose

32,2

0,48

p-Xylene

16,42

2,15 Naphthalene, 2,6-dimethyl-

33,67

0,82

2(5H)-Furanone

17,38

0,78 -D-Glucopyranose, 1,6-anhydro-

41,89

56,80

Styrene

17,7

0,51 Anthracene

43,72

0,23

2-Cyclopenten-1-one

18,3

0,89 1,6-Anhydro--d-galactofuranose

45,01

6,59

Benzocyclobuten-1(2H)-one

21,83

0,47

The results correspond to those obtained by Liang et al. who studied the catalytic effect of
HZSM-5 on pyrolysis75. This zeolite is known to enhance dehydration, transglycolysation and
cyclization reactions, hereby removing oxygen as water, CO and CO2. The increase of mono, di- and even poly-aromatics confirm this statement. In this case the fraction of small
molecular products is given by small aliphatic products as propene, 2-butene and furan-like
species. Liang et al. also made notice of the inhibition of both furfural and
hydroxymethylfurfural formation, which is consistent with our results since their amount was
too small to be discovered in the ex-bed HZSM-5 catalyzed experiments. Levoglucosan was
also further degraded by secondary reactions, since a relative yield of only 56.8% remained,
while this was more than 71% for in-bed catalysis.

51

3.2 LIGNIN
Lignin was mixed with 5, 10 and 20 wt.% of HZSM-5. The catalytic effect on the product
distribution of lignin is less severe if compared with the influence it exerts on cellulose.
HZSM-5 is known to catalyze the formation of aromatics, but since the pyrolysis of pure lignin
already produces lots of aromatic species and the catalyst is added in small amounts (up to
20 wt.%), no large differences in the relative product distribution can be observed. Yet the
amount of mono-aromatic species is increased from 1.78 to 4.61%. The methoxylated
aromatics and phenolics on the other hand are classified in a separate category and here a
small decrease (from 81.84 to 75.61%) was noted, which is most likely caused by the
catalyzed deoxygenation reactions on the zeolite surface74. For this reason also yield of
alcohols (from 2.47 to 1.93%) and carboxylic acids and esters (from 0.52 to 0.31%) reduced.
There are furthermore no relative differences between the different classes. On the other
hand a large difference was observed between the absolute amounts of detected products,
as can be seen in Figure 33. In a sample containing 10 wt.% of the zeolite, the total peak
area of the TIC chromatogram is three times larger than in the case of pure lignin pyrolysis.
Nevertheless the product yield decreased when 20 wt.% of zeolite is added to the lignin.
Mullen et al. also found that depolymerization of lignin is more intense when mixed with
HZSM-5, which is confirmed by our results76. The elevated yields of small aliphatic species
(from 0.07 to 0.28%), which used to link the lignin monomers, is another proof of the catalytic
effect on depolymerization.
8E+10

TIC abundance (peak area)

7E+10
6E+10
5E+10
4E+10
3E+10
2E+10
1E+10
0
Pure lignin

5 wt.% ZSM-5 10 wt.% ZSM-520 wt.% ZSM-5

Ex-bed

FIGURE 33: ABSOLUTE AMOUNT OF LIGNIN PYROLYSIS PRODUCTS DETECTED BY THE GC/MS IN TERMS OF TOTAL
PEAK AREA

The effect of HZSM-5 on lignin was very limited on the relative distribution in in-bed mode
and also in ex-bed mode the catalytic impact was not as drastic as on cellulose. The amount
of non-methoxylated phenolics increased from 8.7 to 11.1%, while the total yield of phenolics
decreased from 83.5% to 73.3% in favor of mono-aromatics and aliphatic species. As
expected also a decrease in low molecular weight oxygenates and an increase in di- and
52

polyaromatics was observed. Figure 32 also shows that the absolute amount of lignin
pyrolysis products decreased, in contrast to the in-bed experiments. This is a result of the
high amount of products held back by the zeolite bed, which could visually be confirmed from
the bed since it turned black due to coke deposition. The low yield of products from ex-bed
catalysis can also be explained by the dilution of pyrolytic vapors by the helium carrier gas
because there is too much time between pyrolysis and catalysis (secondary reactions) in this
setup, resulting in a lower efficiency of the catalyst.

53

54

CONCLUSIONS
The effect of various potassium and calcium salts on lignin and cellulose pyrolysis was
investigated in both in-and ex-bed mode to distinguish their catalytic effect on primary and
secondary degradation reactions. It has been found that both metals have a significant
influence on the pyrolysis product distribution. They induced a decrease in the absolute
amount pyrolysis products formed, accompanied by an increase of non-condensable gases
and char.
The most severe effect was observed in the yield of levoglucosan and other anhydrosugars,
the primary thermal degradation products of cellulose. Potassium citrate reduced the
levoglucosan yield even to 8.2%. In in-bed mode, calcium was found to be less powerful in
levoglucosan reduction, but it had the strongest impact in ex-bed mode. In terms of
levoglucosan degradation, acetate seems to be the anion with the strongest impact. In
general acetate and citrate followed the same trends as the chloride anion, but they are more
efficient when it comes to 5-hydroxymethylfurfural and acetol production.
The yields of low molecular weight pyrolytic products of cellulose such as
hydroxyacetaldehyde, acetic acid and acetol enhanced in the presence of even very small
amounts of catalyst. An interesting result is the potential of calcium to increase the yield of
furfural and 5-hydroxymethylfurfural, which are considered to be valuable platform chemicals.
On the other hand the amount of 5-hydroxymethylfurfural reduced in ex-bed mode, from
which one can conclude that calcium promotes the primary formation of 5hydroxymethylfurfural.
It is commonly accepted that alkali and alkaline earth metals (AAEM), as well as certain
anions, could interfere in the primary decomposition of cellulose. More specifically, cellulose
decomposes according to two competing mechanisms, i.e. glycosidic bond breakage leading
to levoglucosan and ring scission yielding low molecular weight oxygenates. AAEMs are
believed to inhibit the glycosidic bond breakage, thus leading to increased production of
lighter oxygenates at the expense of levoglucosan formation. The results of the in-bed
catalytic experiments with cellulose seem to corroborate this hypothesis. However, the
experiments using the same AAEMs in ex-bed mode demonstrated similar production of
light oxygenates, which clearly indicates that levoglucosan is destabilized by AAEMs in the
vapour phase and thus (at least partially) contradicting the well-established hypothesis of
AAEM interaction in primary cellulose decomposition.
Methoxylated phenolics and aromatic species are the main lignin pyrolysis products. The
effect of calcium and potassium on lignin pyrolysis was found to be far less intense
compared with their influence on cellulose degradation. The increase of non-methoxylated
phenolic species and aromatics indicates a catalytic effect on the demethoxylation reaction.
The production of aromatics, though in small quantities, when performing Ca-catalyzed lignin
pyrolysis is also noteworthy.

55

As an example of extrinsic catalysis, HZSM-5 was studied in both in-bed and ex-bed mode
for both cellulose and lignin. The catalytic effect of the extrinsic zeolite HZSM-5 is totally
different than the effect of the earlier discussed intrinsic alkali and earth alkaline metals. The
increasing amounts of aromatics as toluene proves that HZSM-5 induces ring-closure
reactions. The formation of oxygenated species such as furfural and hydroxymethylfurfural
was inhibited, which confirms the theory that HZSM-5 removes oxygen as water, CO and
CO2.
The effect of in-bed and ex-bed catalysis with HZSM-5 was similar with respect to the
pyrolysis vapor constituents formed, which proves that HZSM-5 merely acts on the
secondary decomposition of the already formed primary vapour constituents. This conclusion
was somehow expected, as HZSM-5 particles are relatively large (100 m) and hence, the
primary vapors have to diffuse out of the reacting biomass particles and onto the surface
(and into the pores) of the catalyst particles.

56

RECOMMENDATIONS FOR FURTHER RESEARCH

There is still a lot of research necessary to elucidate the complex reaction mechanisms of
biomass pyrolysis and the influence of natural occurring alkali and earth alkali metals. In this
masterthesis only two metals were discussed, but biomass contains also significant amounts
of other inorganics from which the catalytic influence can be investigated.
The investigation could also be continued with the pyrolysis of hemicellulose, the third model
compound of biomass. Furthermore also real biomass should be pyrolyzed to study the
effects of the three different model compounds on the final product distribution.
Various parameters can be changed during micropyrolysis, including the pyrolysis
temperature, the added concentration of the catalyst and the counteranions of the applied
cations. It was clear from current investigation that all of these parameters have a significant
influence on the pyrolysis mechanism. Particularly concentration effects are interesting to
investigate. Adding an excessive amount of the catalyst to the samples in in-bed mode can
help to make a better, more quantitative comparison with the results of the ex-bed
experiments.
Sample preparation can also alter the final pyrolysis product distribution. Different methods of
lignin and cellulose extraction can lead to model compounds with other properties, which is
definitely interesting to investigate. Its also possible that remaining naturally alkali and earth
alkaline metals can interfere with the extrinsic added catalysts, like HZSM-5. This could also
be tested using pyGCMS.
At last it is also required to scale up the experiments. It is only by producing real bio-oil and
studying its properties and product distribution that our findings from the micropyrolysis
experiments can be confirmed. Biomass pyrolysis is a very complex area which is
extensively studied last decade, but still a lot of research is required to benefit optimally from
its opportunities.

57

58

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64

APPENDIX
1. LIST OF PYROLYSIS PRODUCTS

Acetic acid
1,6-anhydro-alpha-d-galactofuranose

Acetic anhydride
2,3-anhydro-alpha-d-galactosan

Acetol
2,3-anhydro-d-mannosan

1,4:3,6-dianhydro-alpha-d-galactosan
Acetylguaiacol

65

Benzene

Furan

Catechol

Furfural

Glycerine
Cyclopentanedione

Guaiacol
Ethylguaiacol

Formic acid

66

Guaiacylaceton

Isoeugenol

Hydroxyacetaldehyde
Levoglucosan

Hydroxymethylfurfural

Levoglucosenone

Homovanillic acid
Methylguaiacol

Hydroxypropane
Naphtalene

67

Phenol

Styrene

Syringol

Vanillin

Vinylguaiacol

68