CATALYTIC PYROLYSIS OF BIOMASS FOR IMPROVED

LIQUID FUEL QUALITY

D Meier - Project Co-ordinator, BFH-Institute for Wood Chemistry, DE
MI Crespo Rodriguez - University of Santiago de Compostela, SP
AV Bridgwater - Aston University, UK
P Nakos - Sapemus - ARI, DE-GR
D di Blasi - Naples University, IT
W Prins - Twente University, NL
J Alonso - Union Fenosa, SP,
M Samolada - CPERI, GR
Contract JOR CT95-0081
PUBLISHABLE FINAL REPORT
January 1996 to June 1998
Research funded in part by
THE EUROPEAN COMMISSION
in the framework of the
Non Nuclear Energy Programme
Joule III
1
Abstract
The project covered five different research areas:
1. catalytic pyrolysis and improvement of pilot plants,
2. liquid modification,
3. incorporation of bio-oil into wood adhesives,
4. modelling, and
5. development of analytical methods.
Work
The main part of the work comprised the use and evaluation of catalysts in fast pyrolysis aimed at improving the
quality of the liquids in terms of stability. More than 50 catalysts were tested in screen experiments using micro-
scale and bench-scale fast pyrolysis apparatus. Four modes of operation were used: co-feeding the catalyst
together with the biomass, replacing the sand fluid bed with a catalytic one (in bed), including catalysts in the
primary reactor (ex bed) and close-coupling catalysts in a secondary reactor. Commercial FCC catalyst was also
tested in a circulating fluidized bed and a rotating cone reactor showing that the catalyst was too active leading to
reduced oil and increased gas yields.
The experiments revealed that thermally expanded slate, a cheap construction material, gave the best
quality liquids as measured by initial viscosity, stability and water content. Therefore, larger scale experiments
were conducted with this type of material using lab-scale and pilot plant scale fluid bed reactors and a rotating
cone reactor. The results show that the results from the laboratory could be transferred. However, difficulties in
the fluid bed reactors were observed due to the different fluidization behaviour of slate. Substantial technical
improvements of the pilot plants with fluid bed reactor and rotating cone reactor could be made in the course of
the project.
Both oxidants and anti-oxidants have been used for liquid modification. The addition of a 10%
wt
/
wt
aqueous solution phenol was found to result in the best quality pyrolysis liquid. This chemically modified
pyrolysis liquid was more stable and had a lower water content than regular pyrolysis liquid.
A process has been tested for the use of biomass pyrolysis liquid product as a partial substitute for
formaldehyde-based resins in the production of composite panel. The technology was proven at the lab scale.
The pyrolysis oil can be used as such to replace up to 20% of the UF/PF binder in composite board production
with no significant impairment of the board strength properties.
A new experimental system has been developed to investigate the fast pyrolysis kinetics of solid fuels,
in the absence of heat and mass transfer limitations. A model has been formulated for the fluid-bed flash
pyrolysis of biofuels with and without the presence of catalyst particles. A closed-form solution has been
obtained for the tar profiles along a spherical catalyst particle, as a result of intra- and extra-particle diffusion and
chemical reactions. The dynamics of tar vapors as they enter a packed bed reactor have been mathematically
described. Furthermore, a model has been developed for the ablative pyrolysis of wood particles. Finally, an
existing kinetic model was adopted to predict the distribution of primary products in fluidized bed and rotating
cone reactors.
Several analytical methods have been modified and developed. The most important ones are the
determination of carbonyl groups by oximation, the evaluation of whole liquids by FTIR, and the assessment of
stability by use of the Aston Viscosity Index.
Conclusions
The use of catalysts in fast pyrolysis is a suitable measure to improve the stability of liquids with respect to
viscosity and water content. The understanding of the catalysts behaviour in fast pyrolysis is not yet understood.
Selectivity, reactivity and specificity have still to be investigated. Models for various fast pyrolysis reactor
configurations were developed and allow the prediction of the yields of the three main products oil, gas, and
char. However, the performance of the models should be further improved.
One of the most important result from the project was the addition of crude pyrolysis liquids to adhesives to
substitute expensive phenol in resin formulations.
Exploitation intentions
As both the fluid bed reactor and the rotating cone reactor were improved within this project the
commercialization of these technologies is being intended, basically to further improve the plants and to produce
more oil for energetic and chemical applications.
The use of bio.oil in adhesives will be further persued in future EU-projects as short term commercial solutions
can be expected.
2
1 Partnership
Table 1 The partners and names / addresses in the EC project JOR CT95-0081
Name Address Contact Person
BFH, Institute for Wood
Chemistry
D-21027 Hamburg, GER D. Meier tel.: +49 40 73962-517
fax: +49 40 73962-502
email:
dmeier@aixh0501.holz.uni-
hamburg.de
Aston University Birmingham B47ET, UK A.V. Bridgwater tel.: + 44 121 359 3611
fax: + 44 121-359 6814
e-mail:
A.V.Bridgwater@aston.ac.uk
Twente University P.O.Box 217
7500 AE Enschede, NL
W. Prins tel.: +31 53 4892891
fax: + 31 53 489 4774
e-mail: W.Prins@ct.utwente.nl
Sapemus Chemie GmbH /
Adhesives Research Institute
Ltd.
Sofouli 88
GR-55131 Kalamaria
Thessaloniki, GR
P. Nakos tel.: + 30 31 424 167
fax: + 30 31 424 149
e-mail: panakos@ari.gr
CPERI P.O.Box 361
57001 Thermi Thessaloniki,
GR
M. Samolada tel.: + 30 31 498 146
fax: + 30 31 498 180
e-mail:
samolada@alexandros.cperi.forth.
gr
Union Fenosa Ingeneria Piquer 7 28039 Madrid, SP J. Alonso tel.: + 34 91 384 71 00
fax: + 34 91 384 71 99
e-mail: gen@ufisa.es
Napoli University P.le V. Tecchio, 80125
Napoli, IT
C. di Blasi tel.: + 39 081 768-2232
fax: + 39 081 2391 800
e-mail: diblasi@unina.it
University Santiago de
Compostela
Avda. de las Ciencias s/n
ES-15706 Santiago de
Compostela, SP
I. Cresp tel.: + 34 981 56 31 00
fax: + 34 981 59 50 12
e-mail: eqisacre@usc.es
3
2 Objectives
The use of pyrolysis liquid, has been limited by a belief that the quality is inadequate for
commercial applications. Pyrolysis liquid, known as bio-oil, is relatively unstable and changes
with time. Bio-oil can have a high viscosity, is acidic and can separate into two or three
phases under certain circumstances. These negative characteristics increase with high
temperature, long storage times and exposure to air and light.
Therefore, the project main objective is to explore catalytic and chemical modification of the
fast pyrolysis process and the pyrolysis liquids it produces, to improve the liquid properties
and characteristics and thus make them more amenable to utilisation.
The results from laboratory studies should be transfered to two existing pilot plants in of
which the operation had to be improved.
Two other objectives were formulated: (1) modelling of fast pyrolysis processes and reactors
and (2) the application of whole bio-oil in adhesive formulation for wood panels.
3 Technical Description
3.1 Catalytic Pyrolysis and I mprovement of Pilot Plants
Experiments with catalysts were performed at different scales and with different reactors:
3.1.1 Micro scale pyrolysis
Catalysts were tested in a commercial analytical pyrolysis equipment (CDS Pyroprobe) which
consists of a controller and a resistively heated platinum coil probe. The probe is directly
coupled to a gas chromatograph which is equipped either with a mass spectrometer or a flame
ionization detector. After pyrolysis under well defined conditions the vapors are directly
swept onto the cold column and separated, identified and if possible qunatified. The
resulting chromatograms were compared against blank runs to assess the catalytic activity.
Both in-bed and ex-bed modes were tested with the micro-scale unit which is shown in Figure
1.
Interface 200C
Pyrolysis tube
with heating coil
Carrier gas:
He
Split injector
to Capillar GC (GC/MS)
inert glass wool
Liner
(wood) sample
and Catalyst
in heating coil
Figure 1 Schematic of the micro-scale pyrolysis unit for catalyst sreeening
4
3.1.2 Bench-scale pyrolysis
For these experiments mainly small fluid-bed reactors were used with a capacity of 100-
200 g/h. Most of the bench-scale runs were conducted with a commercial fluid-bed reactor
consisting of a continuous fedding system for small particles, the reactor with cyclone and
charpot, cooling device and electrostatic precipitator to collect non-condensables
aerosols.Four modes of operation were used: co-feeding the catalyst together with the
biomass, replacing the sand fluid bed with a catalytic one (in bed), including catalysts in the
primary reactor (ex bed) and close-coupling catalysts in a secondary reactor. A typical reactor
configuration is presented in Figure 2.
Nitrogen
Biomass
FEEDER
FURNACE
CYCLONE
AND
CHAR POT
WATER
CONDENSER
ELECTROSTATI C
PRECI PI TATOR
COTTON
WOOL
FILTER
Product Gas to
Meter,
Sampling and
Vent
Mai n
Liquid
Product
Water In
Wat er Out
FLUI D BED
REACTOR
Aqueous
Secondary
Product
DRY I CE
CONDENSER
Figure 2 Typical fluid bed reactor configuration for bench scale experiments
3.1.3 Lab-scale pyrolysis
These experiments were performed in larger fluidized bed reactors with a capacity of 1 and 5
kg/h. A drawing with the description of the latter is presented in Figure 3.
1
2
3
4
5
6 7 8
9
10
11
12
1 silo
2 vibration conveyor
3 screw feeder
4 fluidized bed reactor
5 cyclone
6 heat exchanger
7 intensive cooler
8 electrostatic precipitator
9 flair
10 compressor
11 gas preheater 1
12 gas preheater 2
13 overflow container
charcoal
gas
oil
gas circulation
500 C
13
Figure 3 Typical fluidized bed plant (5kg/h) for lab-scale experiments
5
3.1.4 Pilot plant scale pyrolysis
Two pilot plants, each with a capacity of processing 200 kg/h of biomass, were used for these
experiments: a fluid bed reactor and a rotating cone reactor. A picture of the rotating cone is
presented in Figure 4.
Figure 4 Photograph of the pilot plant rotating cone: the inner space with the rotating cone
3.2 Liquid modification
Liquid modification has been done by mixing various solvents and other reagents to the
pyrolysis liquid. This is an easy procedure and requires no specific technical apparatus.
Furthermore, the formation of methyl-aryl-ethers (MAE) has been tested with phenol as
model compound to give anisol in a catalytic test unit shown in Figure 5.
Steam unit 200
N
2
TIC
TIC
TIC
TI
FIC
N
2
PI
Vent
Vent
Volumetric
cylinder
G.C. Analysis
7
8
9
3
5
6
TIC
P.C.
Simulated
Distillation
Leco Coke Analysis
1
2
F
2
F
1
FIC
Gases
G.C.
Liquids
101
104
103
102
102
FIC
102
101
1.Liquid Feedstock
2.Syringe Pump
3.Feed Injector
4.Steam Injector
5.Catalyst Bed
6.Reactor Furnace
7.Cold Liquid Bath
8.Liquid Product Receiver
9.Gas Collection System
PI
101
PI
Vent
4
101
BIOMASS UNIT 100 BIOMASS UNIT 100
Figure 5 Fixed bed reactor system for chemical modification experiments
6
3.3 I ncorporation of bio-oil into wood adhesives
A literature search in the field of utilisation of the biomass pyrolysis oil (bio-oil) in the
production of resins for the wood panel industry, was carried out. The references found were
limited and relatively new. In any case, a positive trend for the application of pyrolytic oil in
such a field was identified.
In a preliminary series of lab scale trials, pyrolysis oil produced from eucalyptus biomass was
tested for its standard properties (e.g. pH value, solids content) and potential to substitute or
upgrade the performance of Urea-Formaldehyde (UF) resin in the production of
particleboards. To optimise the parameters of bio-oil application, the incorporation of pine
bio-oil into a UF resin during synthesis was tried out. The best resin formulation thus obtained
was applied in lab scale particleboard production.
3.4 Modelling
For the assessment of the computer models, an experimental system has been designed and
constructed which allows biomass pyrolysis to be carried out under fast heating conditions.
Weight loss and temperature of the sample are continuously recorded and these data are used
to formulate semi-global reaction mechanisms and to estimate the related kinetic constants. In
order to compare the data obtained from the innovative experimental system here developed,
a first set of measurements has been carried out for cellulose and, successively, a second set
of tests has been conducted for beech wood, the feedstock of interest in this project. The
system combines the characteristics of pyrolysis tube reactors and the classic thermoanalyzer
systems. A schematic drawing is presented in Figure 6.
Reflectors
Lamps
Heated zone
Quartz
reactor
A
radiative heater
sample
precision
balance
thermocouple
B
gas out
15 cm
quartz reactor
2.5 cm
2.6 cm
Figure 6 Schematic picture of the cross section of the radiant furnace (A) and of the reactor
(B)
3.5 Development of analytical methods
Well-known techniques have been introduced, to analyse the oil on basis of its physical (e.g.
density, viscosity) and chemical (pH, CHN, and H
2
O contents) properties. Additional
methods were developed to investigate the oils composition with respect to main compounds
like acids, aldehydes and ketones, as well as many others. These parameters will be used in
comparing the oils derived at different operating conditions (reactor type, operating
temperature, feedstock rate etc.) or in the oils derived from various catalysts. In Table 2.1 the
various analysis techniques applied are summarised.
7
Table 2 Analysis methods used
materials Analyses
wood moisture content
pyrolysis gas overall volume with gas meter
separation and quantification by gas chromatography
pyrolysis oil Fourier transform infrared spectroscopy (FTIR)*
UV-spectroscopy*
gas chromatography-flame ionization detection (GC-FID)
identification of single products by gas chromatography-mass
spectrometry (GC-MS)
elemental analysis
water determination by Karl-Fischer titration
acid number by titration*
methanol determination by head space GC (HS GC)*
viscosities with capillary and falling ball viscosimeters*
determination of carbonyl groups by oximation*
pour point
ash content
ethanol insolubles
char Elemental analysis
Methods with an asterisk were newly developed.
4 Results and Conclusions
4.1 Catalytic pyrolysis
In total 71 catalysts (single or mixtures) were tested in over 250 test runs using the analytical
pyrolysis-GC/MS and GC/FID system at IWC and a micro fixed bed reactor system at
CPERI. Conclusions of the screening tests were drawn from the gaschromatograms and from
the spectra of the MS. Screening of the catalysts intended to be used in catalytic pyrolysis,
aims to:
reduce the number of catalysts used in larger experimentation,
ascertain which would be the best catalyst to use,
indicate which chemicals should be analysed for in the product pyrolysis liquids.
Several categories of catalysts were included in the experiments:
1. zeolites
2. FCC
3. Silica
4. Alumina
5. Iron/Chromium
6. Sodium
7. Magnesium
8. Cerium
8
The following conclusion can be drawn from the results:
analytical pyrolysis in combination with GC/FID or MS is a valuable tool for screening
experiments. A qualitative result can be obtained and the basic feature of a catalyst can be
observed. However, quantitative results cannot be obtained. Therefore, tests at larger
scale are necessary for a better evaluation of catalysts. Furthermore, the screening method
only monitors the volatile products whereas larger scale experiments with complete oil
collection can lead to more substantial results.
cracking is observed mainly for carbohydrate derived compounds. Lignin derived
compounds are more stable against catalysts.
the amount of gas is increased.
the number of arising components is reduced.
the amount of some components is reduced (e.g. acetic acid).
no distinct differences could be seen between In-bed and Ex-bed experiments.
the results from pyrolysis GC-MS which were not clear enough to evaluate the effect of a
catalyst
Y-zeolite is expected to give best oil quality as a wider variety of chemicals are produced
HZSM-5 completely converts carbonyls into furans and hydrocarbons
Iron/chromium gives less water formation
zeolites mostly decrease the amount of carbohydrate derived vapours
Zinc, magnesium and cerium and showed almost no effect on the vapours composition
Catalysts have been incorporated into the fast pyrolysis process in four modes of operation:
co-feeding catalyst with biomass; replacing the inert sand fluid bed with a catalytic one;
including catalysts close-coupled in this primary reactor and close-coupling catalysts in a
secondary reactor. The following results were obtained with catalytic pyrolysis in bench
scale:
The slate fluid bed gave the best quality pyrolysis liquid as measured by initial viscosity,
stability and water content. The maximum organic yield using slate was similar to that using
inert sand and found to be at 475C, lower than that of the original pyrolysis process when
using inert sand as the fluidising medium. (Aston)
Experiments with co-feeding and in-bed gave the highest oil yields and lowest viscosities. A
mordonite zeolitic catalyst yielded more than 80 % of an oil and exhibited at the same time a
reasonable viscosity of 15 cSt (BFH-IWC).
Furthermore, the mordonite oil contained only 1.7 mol/kg of carbonyl groups whereas the
other pyrolysis liquids were in the range of 3-5 (BFH-IWC).
However, due to more cracking the water content of the oils increased to 30 %. This
corroborates also the findings from CPERI who found that a zeolite type catalyst converted
most of the carbonly groups but leads also to more water formation. This is a positive effect
as this type of functional groups is prone to further chemical reactions which may lead to the
undesired instability. (BFH-IWC).
Also a commercial Y-zeolite gave high oil yields and low viscosities when fed in the co-feed
mode (BFH-IWC).
Thermally expanded slate, first discovered and used at BFH-IWC, gave a low water content
around 10 % and yields in the range of 74 %. The carbonyl content is around 4 mole/kg. Slate
9
is a very inexpensive natural material and must not necessarily recovered. The particle size
can be controlled and this makes it a good candidate for a catalysts in fast pyrolysis as this
technology should not require expensive upgrading methods (BFH-IWC).
With alumina, magnesium and sodium the oil yields decreased drastically to 54-63 % and
were not considered as suitable catalysts (BFH-IWC).
Catalytic experiments with nickel, slate, Octavision, and -alumina were performed in the
fluid bed at conditions where the non-catalysed runs showed optimum values for the oil yield,
while using beech wood as the feedstock. The yield trends of catalytic pyrolysis were in line
with those of the non-catalysed runs, although the absolute values differed of course
significantly. The decrease in the oil yield was mainly due to the increase in the non-
condensable gases (Twente).
Oil yields for the -alumina catalyst were also notably lower than for the non-catalysed runs,
while the gas yields were somewhat higher. Furthermore, the water content of the produced
oil was much higher (the water content of the CT oil was over 65 wt.%) (Twente).
For the nickel and the slate materials, yields and water contents were comparable with those
of the sand-derived oils. However, the viscosity of the condensation train oil is significantly
lower. It should be noticed also that the oils from the electrostatic precipitator are in this case
less viscous. Unfortunately the viscosity of the EP oil could not be measured (Twente)
The Octavision FCC catalyst has been shown to deactivate quite rapidly during the
experiment. After a sufficient long period, the catalyst seems to become almost inert towards
the cracking reaction, resulting in a bio-oil type resembling the sand derived oil. The oil
derived from the slate is similar to the oil derived from sand. Slate offers a good starting point
as the catalyst to be used for the RCR experiments (Twente).
It was found that the liquid yield is reduced in all catalytic runs made with a fixed bed reactor.
No major differences in the distribution of product yields was detected by changing the
operation mode, in-bed versus ex-bed (CPERI).
Comparing in-bed and ex-bed GC/MS results, it is evident that in-bed catalysis produces less
heavier compounds than ex-bed An unexpected lower water content of the liquid was
measured in slate pyrolysis. This result is reasonable, considering the fact that in the in-bed
mode the primary pyrolysis vapours are in a direct contact with the catalyst, while in the ex-
bed mode spend some time under thermal cracking conditions, where secondary reactions and
polymerisation might occur. Coke is enhanced in the ex-bed mode (CPERI).
Catalytic biomass pyrolysis runs in the fixed bed reactor gave comparable trends concerning
the catalysts evaluation with those obtained using the synthetic bio-oil mixture of model
compounds (CPERI).
Screening at CPERI was performed with a solution of model. The results showed that HZSM-
5 had the largest effect on the product distribution. All carbonyl groups of the synthetic bio-
oil were destroyed and converted to furans and hydrocarbons. It can be concluded that the
model compounds approach is a useful and easy approach for catalysts evaluation, without
any interference of any faults coming from the pyrolysis reaction (CPERI).
10
Lab-scale and pilot plant scale experiments with slate gave some difficulties in fluidization
due to the lower density of slate compared with sand. More research should be done to
determine optimum conditions for slate as fluidizing material. However, the oils obtained
were comparable to those produced at bench scale. (BDH-IWC, FENOSA).
FCC and slate were tested as catalysts in the rotating cone. Again, the results were quite
similar to those obtained in the catalytic fluid bed experiments. The catalytic effect of FCC
appeared to be much too strong, while the slate had a very moderate effect. While applying
the latter catalyst, a less viscous oil was obtained with a slightly lower amount of polymeric
components. A noteworthy result for FCC was the strongly improved mixing behaviour,
which could be observed from the fact that almost no char was collected in the cyclone after
the reactor (Twente).
4.2 Catalyst regeneration
Heating in a furnace was applied to burn off the coke deposits. Scanning Electron Microscope
(SEM) was used to view catalysts used, and the char or coke produced from running the
pyrolysis apparatus. The final location in the apparatus of the catalyst following pyrolysis
may also be ascertained by examining product char samples for catalyst. The SEM technique
can also be used to evaluate the degree of regeneration achieved (Aston).
It is recommended that the optimum time for regeneration is less than twenty-four hours, to
avoid damage to the surface, and greater than one hour (in the region of two hours) to remove
all the coke (Aston).
When thermally expanded slate is used as the fluidising medium, coke appears to build up
around the pores rather than blocking or covering them. The surface is therefore more smooth
after regeneration when the coke has been burned off (Aston).
Coke deposited on the catalyst was burned (600
o
C for 10 hr) and the regenerated catalyst was
characterised in terms of BET surface area and XRD analysis. Mesoporous materials are not
stable catalysts, because they are very sensitive to the presence of water in the reaction
system. They become more amorphous after pretreatment reaction and regeneration (CPERI).
The obtained product yields using the regenerated catalysts are comparable to those obtained
using the fresh samples. XRD results indicate that the same phases are present in the
regenerated catalysts and the fresh samples, while BET support the fact of the complete
regeneration of the catalysts CPERI).
Characterisation of both the FCC type catalyst and the olefin plus used in catalytic biomass
pyrolysis in the FCC unit indicate that the catalyst remains unchanged after regeneration in
the regenerator reactor of the unit. Catalysts regeneration can be effectively realised after their
use in catalytic biomass pyrolysis (CPERI).
All catalysts after the experiments were black and the particles covered with coke. This coke
formation leeds to a deactivation after a certain run time. A change of oil quality in our lab-
scale runs could not be detected (BFH-IWC).
Regeneration was done in a funace at 650C over night. After the treatment the black colour
disappeared as the coke was completely oxidized. In conclusion it can be stated that simple
11
oxidation can be used to clean the catalyst from coke. The subsequent use of regenerated
catalyst did not lead to a decease in oil yield (BFH-IWC).
After each catalytic flash pyrolysis experiment, the catalyst material was regenerated by
feeding air to the fluidised bed. In this way the carbon deposited on the catalyst could be burnt
off. For three of the applied catalysts this procedure appeared to have no influence on the
activity in any following pyrolysis experiment. However particle sintering was observed for
Nickel, which resulted in an irreversible deactivation of the catalyst (Twente).
4.3 Liquid modification
Solvents such as alcohols, acetone, ethyl acetate, phenol, and glycerol were added. The
addition of all solvents that were able to be measured, produced more stable liquids compared
to the blank runs (Aston).
Water also produces a comparatively stable liquid, but this is done with detriment to the final
water content. Unlike water, phenol addition actually reduces the water content of the liquid
compared to the blank pyrolysis liquid (Aston).
Chemicals have also been added to the pyrolysis liquid, after production, to try to remove the
source of polymerisation, as an alternative method of stabilisation. Both oxidants and anti-
oxidants have been used. The addition of a 10wt.% aqueous solution phenol was found to
result in the best quality pyrolysis liquid, measured by water content and the Aston Viscosity
Index AVI (Aston).
The catalytic methylation of biomass pyrolysis vapours was studied to investigate the chance
of the selective direct conversion of the phenolic compounds to methyl aryl ethers (MAEs),
either inside the pyrolysis reactor or just at the reactor exit prior the liquid products
condensation. Unfortunately, the procedure indicated that it cannot be realized in a direct step,
because of the high reactor exit temperature. It is believed that entirely new catalysts, than
those usually applied to the methylation of phenolic compounds, should be developed
CPERI).
4.4 Production of Adhesives
The following results were obtained from project research work (SAPEMUS):
A positive trend for the application of pyrolytic oil in the production of resins for the wood
panel industry was identified through a literature survey.
Lab particleboards were produced by substituting up to 25% of the UF binder with eucalyptus
or pine bio-oil. Lab plywood was produced by substituting up to 20% of the PF binder with
pine bio-oil.
A synthesis procedure was modified in the lab for the production of PF resins (resoles) by
partial substitution of the phenol needed with bio-oil. The performance of these resins was
tested in the production of lab particleboards.
A synthesis procedure was modified in the lab for the production of UF resins by partial
substitution of the resin solids with bio-oil. The performance of these resins was tested in the
production of lab particleboards.
12
Lab particleboards were produced by substituting 20% of the UF binder with pine bio-oil and
without adding any resin curing agent.
The bio-oil samples of UNION FENOSA, Inst. for Wood Chemistry and Univ. Of TWENTE
were incorporated in PF resins during synthesis. The efficiency of the resins was tested by
measuring standard properties and by producing lab scale particleboards.

From the results the following conclusions were thus drawn:
The pyrolysis oil can be used as such to replace up to 20% of the UF/PF binder in
composite board production with no significant impairment of the board strength
properties.
The partial substitution of resin raw materials by bio-oil in UF/PF systems provides
sufficient reactive binders for particleboard production.
The use of bio-oil as a hardener for UF systems is not considered advantageous.
The UF/PF resins substituted/modified by bio-oil have low formaldehyde emission,
irrespective of the high formaldehyde content used.
The performance of a specific bio-oil sample depends on the wood raw material and the
pyrolysis conditions applied.
Summarising, the use of the bio-oil as a UF/PF resin replacement in the production of
composite panels was proven possible, however the price of such a material should be
attractive and the supply guaranteed, to initiate industrial application. The performance of the
bio-oil resins could be improved if the aldehyde and/or phenolic fraction of the oil was
increased. The dark colour of bio-oil, however, prevents its use in the production of resins for
decorative applications (e.g. decorative paper/veneer impregnation).
4.5 Modelling
The predictions of several semi-global mechanisms, which take into account the formation of
char, tar and gas, have been compared for the primary pyrolysis of cellulose and wood, under
chemical reaction control. The cellulose mechanisms examined are: 1) the Broido mechanism
with two different sets of kinetic constants, the Shafizadeh mechanism and a modified
Broido-Shafizadeh mechanism with two sets of kinetic constants. For wood, a mechanism
which combines the contributions of cellulose, hemicellulose (xylan) and lignin is considered,
where char and volatiles (tar and gas) formations compete. The widely used three-reaction
mechanism, leading to the formation of char, tar and gas, is also examined, with four sets of
kinetic constants (including those estimated in this project). Product yields and conversion
times are evaluated as the temperature and the heating rate are varied (Naples).
It has been found that, while differences in the simulations of cellulose pyrolysis are only
quantitative, both qualitative and quantitative differences are established for wood.
Furthermore, only the kinetics determined in this project can describe correctly the
dependence of product yields on temperature under fast heating (Naples).
A model has been formulated for the fluid-bed flash pyrolysis of biofuels with and without
the presence of catalyst particles. The hydrodynamics of the bed are described by empirical
relations, widely used in the literature (Naples).
13
A detailed particle model was coupled with the reactor model to take into account intra-
particle processes. The models describe changes in the mass concentration of biomass, char,
gas and tar, due to primary particle degradation and secondary extra-particle reactions
(thermal cracking and catalytic conversion), and temperature. The effects have been
investigated of the volumetric inert gas flow rate, the biomass mass flow rate and the furnace
temperature on the product yields. It is shown that a maximum in the tar yields exists for
intermediate reaction temperatures and sufficiently short volatile residence times (Naples).
Simulation results reproduce well the experimental observation for cellulose and, when the
kinetic mechanism formulated in this project is used, also for wood. Simulations indicate that
intra-particle secondary reactions are negligible, though spatial temperature gradients can be
high at the most severe conditions (Naples).
A closed-form solution has been obtained for the tar profiles along a spherical catalyst
particle, as a result of intra- and extra-particle diffusion and chemical reactions (Naples).
AQ model has been developed which describes the combustion of coke deposited on the
surface of catalyst particles under fluidized-bed conditions, based on the assumption of a
continuous perfectly stirred reactor. Numerical simulations have been made by varying the
thermal and fluid-dynamic conditions of the bed as well as the rate of catalyst supply. They
indicate that oxygen diffusion across the catalyst particle plays a controlling role (Naples).
The dynamics of tar vapors as they enter a packed bed reactor have been mathematically
described. The reaction rate shows the usual Arrhenius dependence on temperature and is first
order in the mass concentration of tar (Naples).
A model has been developed for the ablative pyrolysis of wood particles. Pyrolysis is
described by a semi-global, multi-step mechanism, consisting of solid depolymerization,
followed by two competing pathways leading to vapor (liquid) formation (high temperatures)
or to gas and char formation (low temperatures). Depolymerized wood is a molten phase
intermediate.
Only for temperatures above 823K and heat transfer coefficients above 0.05 cal/cm
2
sK the
process presents the typical features of ablative pyrolysis. For these conditions, product yields
show only a weak dependence on the wall temperature. Indeed, there is almost complete
conversion to volatiles (80-87 percent on a dry wood basis) (Naples).
The thickness of the molten layer, which remains constant for the whole duration of the
conversion, becomes successively thicker as the wall temperature is decreased, with a
corresponding decrease in the ablation rate. The predictions of ablative pyrolysis show good
quantitative agreement with single particle and reactor experiments in relation to ablation rate,
thickness of the molten layer and product distribution (Naples)
A reactor model has been developed including the primary wood decomposition reactions as
well as the cracking of primary and secondary tars. It allows the calculation of the product
distribution as a function of the operation temperature and the hot vapour residence time.
Primary kinetics are shown to determine the ultimate product distribution (Twente)
14
The maximum oil yield obtainable appears to depend only on the pyrolysis temperature,
because heat transfer limitations and intra-particle cracking of the produced vapours do not
occur for the fine wood particle considered (Twente).
Cracking of the hot vapours elsewhere in the reactor and its connection to the condensation
section may occur depending on their residence time in the hot sections. If the degree of
cracking remains limited to below 25%, the type of gas mixing (ranging from plug flow to
ideally mixed) becomes irrelevant. In that case a detailed knowledge of the flow pattern in the
transfer tubes and cyclones is not required; the only parameter needed is the average vapour
residence time (Twente).
The predictions of a simplified model are in reasonable agreement with the measured data for
sand and slate as a heat carrier or catalyst material. Any observed deviations can be explained
by the uncertainties in the average hot vapour residence times (Twente).
It has been learned from the modelling that in future flash pyrolysis operation, the residence
times should be reduced to below one second to approach the maximal possible oil yield. On
the other hand, the temperature in the transfer line to the condensation section should be well
selected. Too high temperatures will induce excessive cracking of the desired products, while
too low temperatures may cause undesired condensation and clogging. The optimal
temperature for heat tracing must be determined experimentally, and will usually be found
around 675 K (Twente).
4.6 Development of analysis methods
Several methods were applied, adopted, improved and developed:
Gases: In total 16 different gases were analyzed using two methods:
1. Micro- GC CP 2002 (CHROMPACK) with two TCDs on Hayesep and mol sieve
columns and
2. GC 439 A, CHROMPACK, with FID and alumina PLOT column coated with KCl. All
components were quantified based on calibration mixtures.
CO, CO
2
, methane, nitrogen, hydrogen and other gases up to C
2
were determined with the
TCD. Other gases were analyzed in a GC equipped with FID. Methane (CH
4
), ethane (C
2
H
6
),
ethene (C
2
H
4
), ethine (C
2
H
2
), propane (C
3
H
8
), propene (C
3
H
6
), n - butane (C
4
H
10
), iso butane
(C
4
H
10
), as well as cis -, trans - and iso - butene (C
3
H
8
) were qunatified based appropriate
calibration mixtures (BFH-IWC).
Liquids: Liquid samples were qualitatively measured on a GC/MS system. A special mass
spectra library was used and further expanded within the project for the identification of
compounds. For quantification 41 different mixtures were prepared with the most important
components. The individual compounds were calibrated and determinded using the internal
standard method (BFH-IWC).
From the chromatograms peaks were grouped into the following categories:
1. carbohydrate derived products
2. lignin derived products
3. carbonly products
4. hydroxyl products
5. furane products
6. acetic acid
15
7. levoglucosan
Thus, the volatile part from all oils could be directly compared in order to monitor changes
caused by catalysts. Up to 40 % of the pyrolysis oil could be separated by GC and three
quaters from that part could be qunatified (BFH-IWC).
FTIR Spectroscopy: All FTIR spectra were recorded on a BIO-RAD Typ FTS-40 instrument
with absrbance technique. The liquid samples were placed between two Irtran II plates (ZnSe)
with a thickness layer of ca. 20 m. A scanning rate of 32 was chosen and a spectral
resolution of 4. The selected measuring range was between 4000 and 700 cm
1
wavenumbers.
With the help of te BIORAD software all spectra were baseline corrected and normalized to
the vibrations of teh aromatic ring whih is between 1520 and 1500 cm
1
(BFH-IWC).
A new evaluation method for pyrolysis liquids using FTIR spectra was developed. The
spectra were subdivided into 11 sectors of which 7 are in the fingerprint region. Division was
based on different signals coming from various finctional groups of the oil constituents. The
integrated areas of the sectors were compared beween the different oils in order to monitor
changes caused by pyrolysis conditions (BFH-IWC).
It is an advantage of the FTIR method, that no sample preparation is needed. It is very quick
and during the analyis, the whole oil and not a fraction is being measured. Problems arise with
the interpretation of the spectra. A skilled person is needed for spectra manipulation and to
draw the right conclusions (BFH-IWC).
UV Spectrometry:UV spectrometry was applied with whole pyrolysis mixtures. The
information content of the spectra is not very high. The differences between the oils were not
very pronounced as mostly the absobance of lignin is monitored by UV. It seems that the
chemical nature of the pyrolytic lignin, which is dissolved in the pyrolysis liquid, does not
change very much. By comparing the absorbance at 279 nm differences of carbonyl contents
can be measured (BFH-IWC).
Carbonyl Groups: The quantitative determination of the carbonyl groups was performed
through oximation. The carbonyl groups are oximated through hydroxylaminhydrochlorid
(HAHCl).The addition of pyridin ensures te complete oximation. After the reaction the free
acid in the form of pyridinhydrochlorid is determined through titratin with NaOH.and is a
direct measure for the amount of reacted carbonyl groups (first transition point of the titraton
curve). The unreacted rest of hydroxylaminhydrochlorid can be determined through titration
with NaOH (BFH-IWC).
The method is working correctly as controlled with standards. However, skilled persons are
needed and some further research work is needed. The results from the wet chemical
determination do not in all cases correspond with those measured by FTIR and GC (BFH-
IWC).
Capillary viscometry was used to establish the Aston Viscosity Index (AVI). It uses raised
temperaturesfor 24 h to accelerate ageing of the pyrolysis liquid and to therefore asses liquid
stability. It was developed following a study of the effect of storage temperature on pyrolysis
liquid viscosity. Three temperatures, 25, 50 and 75 C were used to store pyrolysis liquid for
viscosity and water content testing. It was found that pyrolysis liquid was most stable with
respect to viscosity when stored at 25 C. This temperature was chosen as the reference
16
temperature at which all liquid would be tested. A direct comparison could therefore be made
between liquids stored at different temperatures. The lower the number is, the more stable the
pyrolysis liquid. A zero result indicates no viscosity change. Its advantage is that only 48
hours is required for a test, rather than prolonged ageing tests (Aston).
4.7 I mprovement of pilot plant
The fast pyrolysis plant located in Meirama, Galicia, Spain and operated by FENOSA was
improved. The following technical changes have been made:
New mechanical feeding system to the pyrolyser based on the first design of the
system installed during the operation.
Cleaning and substitution of some filters, with new implementation of screen filters
before the cyclone.
Modifications of the collection system, including cleaning and checking the shock
cooler.
Modification of the lower flange of the reactorin order to avoid leaking and
clogging.
Modification of the drain system with the incorporation of new tanks in order to
improve the recovery of different oil fractions at the condensing or draining points.
17
5 Exploitation plans and anticipated benefits
The project led to new results both in a scientific area and technical area. The results
concerning the scientific area are mainly derived from the work packages catalyst screening,
modelling, and analysis methods, namely FTIR, GC and the Aston Viscosity Index. These
results have been and will be published in scientific journals and presented at international
conferences. The whole scientific community may use the results as new tools for the
characterization of bio-oils. Thanks to the PyNe Network the results can easily be distributed
to all members within Europe and the IEA members in USA and Canada.
The technical progress is mainly due to the discovery of slate which is an interesting,
inexpensive material with moderate catalytic activity, so that overall yields are not affected. It
is planned in future work to perform more tests with larger scale experiments.
The most important finding was the suitabiliy of pyrolysis liquids to be a substitute for phenol
in resins used as adhesives in panel manufacture. First results were already published as a
contribution to the PyNe Newsletter. There is a lot of potential in this field and further
research is required. The use of bio-oil in adhesives will provide the wood panel industry with
more environmentally friendly and less costly resins.