Renewable Energy 35 (2010) 232–242

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Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Fundamentals, kinetics and endothermicity of the biomass pyrolysis reaction

Manon Van de Velden !, Jan Baeyens a, b, *, Anke Brems c, Bart Janssens c, Raf Dewil c, d
a
Department of Chemical Engineering, University College London, London, United Kingdom
b
School of Engineering, University of Warwick, Coventry, United Kingdom
c
Department of Chemical Engineering, Katholieke Universiteit Leuven, Campus De Nayer, Sint-Katelijne-Waver, Belgium
d
Chemical and Biochemical Process Technology and Control Section, Department of Chemical Engineering, Katholieke Universiteit Leuven, Heverlee, Belgium

a r t i c l e i n f o a b s t r a c t

Article history: The paper reviews the pyrolysis of biomass constituents and possible secondary reactions. Biomass
Received 14 December 2008 pyrolysis yields mostly liquid and solid fuel, easy to store and transport.
Accepted 22 April 2009 Relevant working conditions for experiments and large-scale operation are: (i) biomass parti-
Available online 4 June 2009
cles < 200 mm, (ii) a particle heating rate of at least about 80 K min1 and (iii) a reactor environment
where the internal resistance to heat penetration is smaller than the external resistance to heat transfer
Keywords:
(Biot-number, Bi < 1).
Biomass
The circumstances of TGA and DSC experiments meet these requirements and fully determine the
Pyrolysis
Kinetics reaction kinetics and endothermicity of the pyrolysis reaction. The reaction rate constant and the heat of
Heat of pyrolysis reaction are essential parameters in the design of a pyrolysis reactor. For most of the biomass species
Experimental and operating conditions tested, the first order reaction rate constant is large and >0.5 s1. The heat of reaction ranges from 207 to
434 kJ kg1. All results tie in with literature data, although the reader is cautioned in using literature data
since experiments were not always performed under relevant testing conditions.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction
Energy from biomass is recognised as the renewable energy
source with the highest potential towards sustainable development
in the near future [1–3]. Biomass provides already 14% of the
world’s primary energy production [4], but is largely squandered by
inefficient use and unsustainable exploitation. To exploit the full
potential of this energy source, new approaches and modern
technologies are needed.
Biomass includes all organic matter that is available on
a renewable basis: energy crops and all kinds of organic wastes.
Now and in the near future waste products from agriculture and
forestry, easy and cheap to collect, will dominate as source for bio-
energy. In the European Union wood waste accounts for 94% of the
currently used biomass for energy [5]. In the medium and long
term, residues from agriculture and forestry, and energy crops will
respectively further develop the bio-energy industry [5,6].
Solid biofuels have a low energy density, which limits the
commercial applications to locations close to the place of
* Corresponding author at: School of Engineering, University of Warwick,
Coventry, CV4.7.AL, United Kingdom. Tel.: þ32 16 532834; fax: þ32 16 538729.
E-mail address: baeyens.j@gmail.com (J. Baeyens).
!
Started the research but died accidentally in 2007.
production. One way to solve this problem is the conversion of the
feedstock into liquid fuel. These liquids have a higher energy
density (Table 1) and are easy to store and to transport.
The two most important methods to convert biomass into liquid
fuel are (i) the biochemical conversion by the enzymatic activity of
micro-organisms (to e.g. ethanol) and (ii) the thermochemical
conversion by heat or oxidation. The biochemical conversion
requires a feedstock that contains sugars or carbohydrates and
a water content in excess of 40%. The thermochemical methods are
best suited for dry biomass (moisture content < 10%) which is rich
in lignin (this substance is less suited for biochemical conversion
since it is hardly broken down by enzymatic activity), such as wood
and agricultural wastes. Three main routes exist to thermochemi-
cally convert biomass in energy: combustion, gasification and
pyrolysis [8] (Fig. 1).
This paper targets pyrolysis as conversion technology because of
its efficient energy production and the important advantage that
mainly liquid fuels and solid char are formed, both easy to store and
to transport. Pyrolysis oil moreover contains various chemicals
with specific high-quality and added-value applications [2]. The
expectations for pyrolysis in general, and for bio-oil in particular,
are hence considerable [2,3].
Pyrolysis is the thermal decomposition in the complete absence
of an oxidizing agent (air or oxygen), or with such a limited supply

0960-1481/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.renene.2009.04.019
 M. Van de Velden et al. / Renewable Energy 35 (2010) 232–242 233

List of abbreviations t Time (s)

T Temperature (K)
A Pre-exponential factor of the Arrhenius equation (s1) X Fractional conversion (–)
am Specific surface of a particle per unit weight (m2 kg1) Bi Biot-number (–)
C Reaction heat (J kg1) b Heating rate (K s1)
cp Specific heat capacity (J kg1 K1) r Density (kg m3)
d Diameter (m) s Time for total reaction (s)
D Thermal diffusivity of biomass particle (m2 s1)
E Energy (J) Subscripts
Ea Activation energy (J mol1) 0 Initial
h Heat transfer coefficient (W m2 K1) N End
DHr Reaction heat of pyrolysis (J kg1) B, b Biomass
k Global, apparent (action rate constant (s1)) g Gas phase
kp Heat conductivity of the particle (W m1 K1) in Input
kr Intrinsic or chemical reaction rate constant (s1) c Core of the particle
kht Rate of heat penetration (s1) min Minimum
m Mass (kg) s Surrounding
Q Heat (J) p Particle
R Universal gas constant (8,31 J mol1 K1) out Output
r Radial position in a particle with radius R (m)

that combustion or gasification do not occur to any appreciable
extent. The proportion of products formed is strongly dependent on
the reaction temperature and time, and on the heating rate. In
comparison to gasification, pyrolysis occurs at relatively low
temperatures (673–873 K). High temperatures and long residence
times promote the formation of gas, while low temperatures and
long residence times promote the formation of char. Optimum to
produce oils are medium temperatures and short residence times,
and thus high heating rates [9].
Fast pyrolysis occurs in seconds only, so reaction kinetics, phase
transitions, heat and mass transfer play important roles. It is
therefore critical to subject the biomass particles immediately to
the optimum reaction temperature and to limit their exposure to
lower temperatures, because this will promote the undesired
formation of char. One way to do this is to use small particles in
a fluidized bed, as will be described later. Another possibility is to
transfer the heat very quickly but only to the surface of the particle,
as applied in ablative pyrolysis.
The pyrolysis process produces mainly vapours and char. It is
essential to separate the char from the vapour as quickly as possible
to prevent side reactions, since char acts as a cracking catalyst. Char
particles are recovered by a gas–solid separation technique (mostly
cyclones). After cooling and condensation, a brown, low viscosity
liquid is obtained with a heating value about half that of conven-
tional fuels.
To achieve high oil yields the process parameters are to be
accurately controlled. The essential parameters include [2,7]:
 a very fast heating and heat transfer to the reaction surface;
 a reaction temperature around 773 K and temperatures of the
vapour phase of 673–723 K;
 short residence times, for vapours less than 2 s;
 a fast char separation and cooling of the vapours, to avoid
secondary cracking.
The main product, bio-oil, is obtained with a maximum yield of
60–70 wt% (dry matter), together with char and gas [9]. These by-
products can be burnt externally (to dry the biomass, in co-
combustion etc.) or in the process, to supply the endothermic
reaction heat of pyrolysis. Char in itself has a heating value
(z30 MJ kg1) [2,3,8] comparable to petroleum cokes (‘‘petcoke’’),
and can externally be valorised. The moisture content of the
pyrolysis feedstock shall not exceed 10 wt% to limit the water
content of the bio-oil.
The heart of the fast pyrolysis process is the reactor. Although it
probably represents only 10–15% of the total capital cost of an
integrated system, almost all research and development are
focused on the reactor, since subsequent techniques (separation,
condensation etc.) are known as physical and chemical processes.
Also the rest of the process (biomass reception, storage, handling,
drying and milling, product storage and possible product upgrad-
ing) applies known techniques [2].
Within the common pyrolysis reactor designs, mostly fluidized
beds are applied, operated in either bubbling or circulating mode:
these systems can meet the basic requirements to achieve high oil
yields i.e. short residence time, fast heat transfer and fast separation
of vapour and char. The technological strength and the market
attractiveness (Fig. 2) show that the circulating fluidized bed (CFB)
has the highest commercial potential. The expected breakthrough
of the CFB is conditioned by a better understanding of the hydro-
dynamics (flow regimes, residence time) and reaction kinetics of
the biomass pyrolysis at different heating rates [10].

Table 1 pyrolysis bio-oil storage chemicals

Bulk density, mean heating value and energy density of biomass and thermo-
chemically derived fuels [7].
gasification fuel gas turbine
Energy carrier Bulk density Heating value Energy density
electricity
(kg m3) (GJ t1) (GJ m3)
engine or CHP
Straw w100 20 2
Sawdust w400 15 6 combustion heat boiler
pyrolysis oil w1200 17 20.4
char w300 30 9
Fig. 1. Alternative thermochemical conversions of biomass [2].
234 M. Van de Velden et al. / Renewable Energy 35 (2010) 232–242
Fig. 2. Status of the pyrolysis reactors [7].
The production of bio-oil by pyrolysis is a technology on the
edge between development and demonstration. The most impor-
tant technological issues that remain to be solved before large-scale
use becomes possible, are related to the complex kinetics and
reactor hydrodynamics [10]. The study of the basic kinetics is the
priority of the present research, which intends to make an exper-
imental and theoretical contribution to the development of pyrol-
ysis. It therefore concentrates on the determination of (i) the
operating conditions required in relevant experimental research
and large-scale pyrolysis of biomass; (ii) the kinetic constants of
biomass pyrolysis; and (iii) the reaction heat of biomass pyrolysis
and other thermal parameters required in the heat balance of the
pyrolysis reactor.
2. Biomass pyrolysis reactions
Biomass mainly consists of three components: 30–60% cellulose,
20–35% hemicellulose (polysaccharides) and 15–30% lignin
(a polymer of methoxy substituted cyclic organics), together with
some resins and minerals. Pyrolysis of biomass is very complex due
to the diversity, the heterogeneity and the limited thermal stability
of some of the components. Pyrolysis of biomass yields about the
products expected from the pyrolysis of its three constituent
components separately, despite synergetic effects [11]. The study of
the individual components thus forms the basis of the expected
reaction pathways and determines the occurring primary and
secondary reactions. The order of these reactions, the reaction rate
and the yields depend on parameters such as heating rate,
temperature, pre-treatment, catalytic effects etc. [2,10,12,13]. The
study of the reactions and the effect of the parameters are of critical
importance to drive the reactions to high yields of the desired
products and to avoid side reactions.
2.1. Cellulose
Cellulose, (C6H12O5)n, is the main component of plant cell walls
and consists of anhydroglucose units, connected by glycoside
bonds. Of all lignocellulotic components, the thermal decomposi-
tion of cellulose is mostly investigated and best understood. The
Waterloo-mechanism (Fig. 3) [14] is widely accepted to represent
the reaction pathway, yielding the expected products and defining
the effect of temperature and heating rate.
fragmentation
cellulose active cellulose
(low degree of
depolymerisation
polymerisation)
dehydration
Fig. 3. The primary decomposition of cellulose according to the Waterloo-mechanism [14].
The three competitive primary reactions are (i) the fragmenta-
tion to hydroxyacetaldehyde and other carbonyls, acids and alco-
hols; (ii) the depolymerisation to levoglucosan and other primary
anhydrosugars; and (iii) the dehydration to char, gases and water.
Dehydration dominates at low temperatures (<623 K) and slow
heating rates. At higher temperatures, depolymerisation and frag-
mentation are dominant. Depolymerisation dominates at temper-
atures between 573 and 723 K, while fragmentation has its
optimum at around 873 K. However, inorganic species such as
cations, bases, acids and salts can have a major impact on these
reactions [15,16]. The selectivity of cellulose for fragmentation and
depolymerisation can be as high as 70–80 wt% [17].
2.2. Hemicellulose
Hemicellulose binds the cellulose microfibrils of the cell wall. It
varies in structure and composition (mainly xylan) and has a low
thermal stability [18,19,20]. It is decomposed in a way similar to
cellulose: by dehydration at low temperatures (<553 K) and
depolymerisation at higher temperatures [15]. Dehydration yields
anhydride fragments, water soluble acids, char, gases and water,
while depolymerisation yields volatile organics, levoglucosan and
other anhydrohexoses, levoglucosenone and furans [18]. Here too,
inorganic impurities cause fragmentation effects, but xylan is
specifically sensitive for cations, because of its ion exchange sites.
2.3. Lignin
Lignin is the strengthening component of the cell wall and is
mainly present in woody biomass [19]. It is a polymer of hydroxy
and methoxy substituted propyl phenol units [18]. The very
complex structure depends on the plant species and due to its
structural diversity, pyrolysis yields various products (such as
catechols, vanillins, aromatic carbonhydrates). At low temperatures
(<773 K) dehydration dominates, while at higher temperatures
a diversity of lignine monomers is formed. Above 973 K the
monomers are decomposed and enter the vapour phase. Lignin is
thermally more stable than cellulose and hemicellulose and yields
more char and a higher fraction of aromatic compounds [15,19].
In a pyrolysis reactor the biomass is subjected to the whole
temperature range and therefore all reactions mentioned above
occur to some degree, in function of the heating rate of the whole
biomass particle, and thus of the heat transfer and particle
diameter.
2.4. Secondary reactions
Secondary reactions can occur in the vapour phase or between
vapour and solid phase to form mostly gas. This will considerably
reduce the desired oil yield [21,22]. Two secondary reactions are of
importance for pyrolysis: cracking (>973 K) and the water–gas shift
reaction (<1083 K): H2O þ CO 4 H2 þ CO2. These secondary reac-
tions are however limited at temperatures below 923 K, residence
times <2 s for the gases and vapours and when char is quickly
carbonylcompounds,
e.g. hydroxyacetaldehydes,
acids and alcohols
anhydrosugars,
e.g. levoglucosan
char, gases and water
 M. Van de Velden et al. / Renewable Energy 35 (2010) 232–242
separated. These are the working conditions for commercial
pyrolysis. Reforming, carbon–steam and carbon–carbon dioxide
conversions are negligible under these conditions [14].
The global pyrolysis mechanism of biomass is mainly based on
the pyrolysis of cellulose, although results are similar for wood and
other biomass species [10,11]. The Waterloo concept of Fig. 4 is
recognised to represent the global mechanism.
3. Materials and methods
3.1. Biomass samples
The specific biomass species were selected because of previous
literature references, or because of their potential in Europe:
spruce, pine, poplar, eucalyptus, sawdust, sewage sludge, straw and
the non-harvested stalks and leaves of sunflower and corn. The
samples were crushed and dried for over 2 h at 105  C and again
30 min just before thermal processing.
3.2. The kinetic constants of biomass pyrolysis
The kinetic constants of the pyrolysis of biomass are determined
by thermogravimetric analysis. A Hi-res TGA 2950 Thermogravi-
metric Analyzer was used at atmospheric pressure with a nitrogen
flow of 50 ml min1. The TGA scale was made of platinum and the
weight was registered every 0.5 s with an accuracy of 0.001 mg.
Following the discussion which is presented in Section 4, all
experiments were performed at 100 K min1 and were repeated at
least three times. Calculations use the average results, with a stan-
dard deviation of maximum 5%. The resulting TGA-profiles plot the
weight loss in function of the temperature.
3.3. Reaction heat
A DSC Q10 with Refrigerated Cooling System operating within
a temperature range from 183 to 823 K was used to measure the
heat requirement of the biomass pyrolysis reaction. The experi-
ments were performed from 313 to 823 K, under atmospheric
pressure and with nitrogen supplied at 50 ml min1. The DSC scales
were aluminium and were not reused. The DSC was calibrated
regularly with indium as reference material. The obtained DSC
curves give the heat flux (W g1) in function of the temperature or
in function of the time (constant DT/Dt ¼ 10 K min1).
3.4. Specific heat of the biomass
The specific heat capacity of sawdust, corn residue and poplar
were determined at 25  C using a calorimeter (Leybold Heraeus).
The temperature increase of n-hexane was measured after addition
of preheated biomass.
Fig. 4. The biomass pyrolysis concept of the University of Waterloo [23].
235
4. Results and discussion
4.1. The required operating conditions for relevant experimental
research and large-scale pyrolysis of biomass
4.1.1. Specific operating conditions
The specific working conditions essential to achieve maximal oil
yields have already been described in the introduction of this paper
and include a reaction temperature around 773 K, temperatures in
the vapour phase around 673–723 K; a high heating rate and high
heat transfer at the reaction surface; a short residence time, for
vapours less than 2 s and a rapid cooling of the vapours and
separation of the char, to avoid secondary cracking.
Essential for the fast decomposition and high oil yields is the fast
heating of the biomass particle. Slow pyrolysis decreases the oil yield
considerably in favour of gas and char. Moreover long residence times
favour secondary cracking of the oil. Short residence times, rapid
cooling of the oil and rapid separation of the char are hence required.
This fast heating of the whole biomass particle to a uniform
temperature requires a high heat transfer. If the heat supply would
be insufficient, important thermal gradients would occur leading to
slow pyrolysis and/or incomplete reactions in the core of the
particle. Smaller particles have a larger specific surface and are
more mobile within the reactor mass, which enhances the heat
transfer. Also, temperature gradients in small particles are expected
to be negligible, as will be shown below.
When choosing the experimental and large-scale parameters,
the thermal characteristics of the biomass, the reaction kinetics and
the heat transfer will have to be jointly considered. Some basic
principles of the reaction kinetics and conversion of solid particles,
of heat transfer in powder reactors and of heat penetration inside
the particle allow to determine these conditions in anticipation,
which makes it possible to program the experiments in a relevant
and effective way. This analysis allows at the same time to critically
evaluate the literature data: research has not always been per-
formed under these optimum conditions (for example [12]), with
results that could lead to wrong conclusions.
Recommendations concerning the computational aspects of
kinetic analyses were made in a series of articles [24–28], where
both one-step/multi-step kinetic schemes and parallel/consecutive
reactions are considered. Analysis of the data hereafter by the
method of Flynn, Wall and Ozawa reported in [24] demonstrates
that the biomass pyrolysis can be considered as a one-step reaction,
thus simplifying the treatment, but nevertheless requiring an
assessment at different heating rates. The analysis of the effect of
heating rate is presented below.
4.1.2. The influence of temperature gradients in the biomass particle
Fast pyrolysis and its associated maximum oil yield can only be
achieved by fast and uniform heating of the biomass particles. To
meet these targets, avoiding thermal gradients in and around the
particle is very important. Application of the basic principles of
both heat transfer to the particle and of heat conduction within the
particle, allows to determine the required working conditions.
The temperature uniformity throughout the biomass particles can
be determined by the heat conduction law of Fourier, here applied in
non-stationary regime and for the simple case of a spherical particle:
! !
vT kp v2 T 2 vT v2 T 2 vT
¼ þ ¼ D þ (1)
vt rp cp vr2 r vr vr 2 r vr
with kp: heat conductivity of the biomass at temperature T
(W m1 K1), cp: specific heat capacity of biomass at temperature T
(J kg1 K1), rp: density of the biomass (kg m3), D: thermal diffu-
sivity of the particle (m2 s1).
236 M. Van de Velden et al. / Renewable Energy 35 (2010) 232–242
The solutions of this unsteady thermal condition are simple
when easy boundary conditions can be applied, as will be used
further in the text. Solutions are very difficult or impossible for
complex boundary conditions and/or bodies of irregular shape. The
general solutions are therefore commonly expressed by a dimen-
sional analysis. For a sphere of radius r, initially at temperature T0
and suddenly exposed to surroundings at Ts, the temperature
distribution, at any time t and position x, is given by:
 
Ts  T hr t x
¼ f ; D 2;
Ts  T0 kp r r
with h: external heat transfer coefficient at surface of sphere
(W m2 K1).
Since it is important to know the evolution of the temperature in
the core of the sphere (Tc at x ¼ 0) and introducing the Biot-number
( ¼ (r/kp)/(1/h)) reduces equation (2) to:
 
T s Tc t
¼ f Bi; D 2
Ts  T0 r
For large (Bi / N) or very small (Bi / 0) values of the Biot-
number, solutions are graphically given by Carslaw and Jaeger [29].
For applications of biomass particles in a fluidized bed, Biot-
numbers are intermediate (Bi ¼ 0.2–1, see further in the text) and
extreme conditions do not apply. For these intermediate values of
the Biot-number, results are presented by Heisler [30] in the form
of charts, expressing (Ts  Tc)/(Ts  T0) in terms of Dt/r2 (the Fourier-
number) with 1/Bi as parameter. Illustrative application of the chart
is given in Table 2, with characteristic properties of sawdust at
773 K, i.e. kp ¼ 0.15 W m1 K1 [31], cp ¼ 1150 J kg1 K1 and
rp ¼ 700 kg m3, and for an average fluidized bed heat transfer
coefficient at the surface of the sphere i.e. 500 W m2 K1.
Since fast pyrolysis requires the reaction to take place within 2–
2.5 s, it is clear that only very small particles will meet the
conditions of fast heating to a uniform temperature. In this case,
particle sizes above 200 mm diameter (radius 100 mm) already take
0.38 s to warm up, i.e. nearly 15% of the proposed reaction time of
2–2.5 s, thus starting to jeopardize the ideal condition of fast
pyrolysis.
According to the previous calculations, it can be assumed that
the heating rate throughout the particle is uniform when heating
very small particles (200 mm) at a rate b (K s1): simplified
boundary conditions can hence be applied to Eq. (1), i.e. vT=vt ¼ b
for r ¼ 0 to R( ¼ dp/2) and vT=vr ¼ 0 for r ¼ 0 (in the core).
The solution is given by Carslaw and Jaeger [29] as:
DTmax ¼ ðTR  Tc Þ ¼ bd2p =ð24DÞ
with TR: T at the surface of the particle (at r ¼ R) (K), Tc: T in the
core of the particle (at r ¼ 0) (K).
Table 2
Time required for the core of a spherical saw dust particle to nearly (99%) reach the
temperature of the surroundings (773 K) where the particle is suddenly submerged
in.
r (mm) Bi-number Dt/r2
50 0.17 13
100 0.34 7 0.38
200 0.67 5 1.08
400 1.33 2.2
It is assumed that a condition where the core temperature has reached 99% of the
temperature of the surroundings (Ts z 773 K) meets conditions of uniform
temperature T throughout the sphere (i.e. Tc z 0.99 Ts). The initial T of the sphere is
293 K and D z 1.86  107 m2 s1.
Eq. (4) can be applied for various values of b and with e.g. the
characteristic properties of sawdust mentioned above. The results
are a set of curves in function of the diameter as shown in Fig. 5.
These calculations show that the temperature differences
between the biomass surface and core are very limited, certainly
when considering that the surrounding temperature is 773 K and
that the heating rate will vary between minimally 1.5 K s1 in a TGA
(thermogravimetic analysis) experiment, to a few hundred K s1 in
a bubbling or circulating fluidized bed.
To obtain a fast heating of the whole particle, it is appropriate
(2)
thus to use small biomass particles (e.g. <200 mm for saw dust) and
no significant thermal gradient will occur in these small particles:
the core and the surface of the biomass particle will behave both
thermally and kinetically in a similar way.
4.1.3. The influence of heat transfer to the biomass particles
Fast pyrolysis requires a fast heat transfer to the biomass. This
heat transfer is conditioned by the degree of gas and solid turbu-
(3) lence achieved in the reactor [32,33]. The heat transfer coefficient
depends on the gas–solid contacting mode. It ranges from
10 W m2 K1 for a static bed, to 50–100 W m2 K1 in a fixed bed
with forced gas circulation (as in TGA), and several hundreds of
W m2 K1 for bubbling and circulating fluidized beds. This
explains why the fluidized beds are specifically considered as top
technologies for biomass conversions. The heat transfer coefficient
in a CFB can be estimated from the results of Kobro and Brereton
[34]. In a CFB operating with 100 mm sand as bed material at
a recommended gas velocity of 5 m s1 and a solid circulation rate
of 200 kg m2 s1, the convective heat transfer coefficient is
620 W m2 K1.
Since not only external convection but also internal conduction
is important, the overall picture is expressed by the Biot-number,
which represents the internal resistance to heat penetration
divided by external resistance to heat transfer and is written as
follows:
r=kp
Bi ¼
1=h
For the 200 mm sawdust particle (r ¼ 100 mm) at 773 K, the
values are as follows:
h ¼ 300 W m2 K1 Bi ¼ 100  106  300=0:15 ¼ 0:2
h ¼ 500 W m2 K1 Bi ¼ 100  106  500=0:15 ¼ 0:33
(4) h ¼ 700 W m2 K1 Bi ¼ 100  106  700=0:15 ¼ 0:47
t (s)
0.017
2.2
Fig. 5. Maximum temperature difference (DTmax) between the surface and core of the
sawdust particle in function of the particle diameter at different heating rates (b).
 M. Van de Velden et al. / Renewable Energy 35 (2010) 232–242
The Biot-number is <1 in all cases, implying that the external
resistance associated with convectional heat transfer largely domi-
nates. Bi is only >1 for coarse particles and/or too high values of h. This
result confirms Fig. 5 where increasing DTmax values are noticed with
increasing b values (achieved at high convection heat transfer rates).
4.2. The selection parameters for the conversion of biomass
in a powder reactor
4.2.1. The kinetic expression for the conversion of an individual
biomass particle
Occurring reactions during pyrolysis are endothermic, as will be
further determined from DSC (differential scanning calorimetry)
measurements. As illustrated in Fig. 4, pyrolysis of biomass prog-
resses along a reaction path with primary and secondary reactions,
each reaction with its specific expression for the rate of product
formation [35,36]. The present paper considers the overall
decomposition rate of the biomass particle only, expressed by a first
order reaction. The overall reaction rate constant, k, is however the
sum of the reaction rate constants of the parallel primary reactions.
The experimental data moreover enable the reader to apply a more
complex kinetic assessment, if so desired. In the present
Fig. 6. Time for complete conversion as function of the biomass particle size for (a) sawdust, (b) eucalyptus.
237
assessment, the kinetics are expressed by a continuous reaction
mechanism for the small particles under consideration: the
temperature distribution across the small particle is quasi-uniform
so that the pyrolysis reaction proceeds at the same rate everywhere
throughout. The slowest step in the process is the heat transfer
through the external film around the particle. For small particles,
the time needed to reach a certain conversion (including complete
conversion) increases therefore in a way that is approximately
linear with the particle size dp [33]. For relatively large particles, the
internal heat conduction resistance is larger, leading to tempera-
ture gradients inside the particle, as mentioned above. The rate of
pyrolysis is now limited by the slower heat conduction process,
whereby the time needed to reach a particular (or full) conversion
increases as d2p. This distinction is demonstrated in Fig. 6 where the
time of complete conversion, as determined from TGA experiments,
is illustrated for sieved biomass fractions of sawdust (0–200 mm)
and eucalyptus (0–600 mm).
The continuous reaction model can hence certainly be used for
the description of the conversion of smaller biomass particles,
expressed for a first order reaction as:
1  X ¼ expðktÞ (5)
238 M. Van de Velden et al. / Renewable Energy 35 (2010) 232–242

The apparent and measured rate constant, k, should be Table 4

expressed in terms of the rate of heat penetration (kht) and the The total heat requirements for pyrolysis.

intrinsic or chemical reaction rate constant (kr) [33,37–39]: The total heat requirement Heat requirement for pyrolysis (J g1)
for pyrolysis sample
1=k ¼ 1=kr þ 1=kht (6)
pruce 342
with kht: rate of heat penetration, equal to ham/cp (s1), h: heat eucalyptus 400
transfer coefficient from reactor bulk to the particle (W m2 K1), poplar 207
sawdust 434
am: specific surface area of the particle per unit weight (m2 kg1),
corn 267
cp: specific heat capacity of the particle (J kg1 K1). sunflower 292
Heat transfer limitations are negligible in operations achieving straw 375
a high value of kht and reaction rates are then kinetically sewage sludge 385
controlled only (k z kr) if additionally the internal heat conduction
resistance is negligible (small particles). Experiments should
therefore be preferably performed under such conditions. Such (see Section 4.2.4). The required heat of reaction is hence C.m0 (J).
high values of kht and thus of h can only be obtained in bubbling or The heat balance then results in equation (8a).
circulating fluidized beds. Since the use of small particles is
required and the residence time needs to accurately controllable, m0 cp bt  0:7m0 XC (8a)
the circulating fluidized bed is the most appropriate reactor for
biomass pyrolysis. Inserting the value of t from Eq. (5), the general equation (8b) is
As will be shown in the experimental results in further sections, obtained.
the reaction rate constant is a strong function of the temperature,
cp b lnð1  XÞ=k  0:7XC (8b)
and follows the Arrhenius equation (7). The activation energy has
a constant but different value for each specific biomass. or

k ¼ A expðEa =RTÞ (7) k  cp b lnð1  XÞ=ð0:7CXÞ (8c)

Table 3 compares kht and k for a few target samples, whereby This equation can thus be applied to any values of conversion
equation (6) is used to determine the error on k if no heat transfer (X). In the present research, overall values of k are measured, i.e. at
limitations are accounted for. The error is insignificant, even at high nearly complete conversion of the biomass (Table 4). Equation (8c)
temperatures, indicating that virtually no external heat transfer is hence applied using these experimental k values and a conver-
limitations are present under the experimental conditions used. sion of 95% is assumed to be the measure of complete pyrolysis.
Equation (8c) is then reduced to:
4.2.2. The influence of the heating rate in TGA experiments
The external heating rate b (K s1) can be programmed in TGA k  4:5cp b=C (8d)
experiments, and literature data are available for b values between
It should be noted that for very low conversions (X / 0) a more
0.033 K s1 and 1.67 K s1. Experimental values of k vary signifi-
restrictive condition on k is obtained since the initial reaction rate is
cantly, even for a single biomass species. The influence of the
highest. This condition of very small conversions will however not
heating rate is of paramount importance since the heat transferred
be applied in the present treatment since only overall k values are
must be sufficient to supply the total endothermal heat of reaction
known.
(C, J kg1). A too low heating rate (low value of b) will retard the
This approach was tested using the TGA results of Section 4.2.3
pyrolysis reaction and will yield an apparently lower value of the
below, obtained at different heat supply rates and for various
reaction rate constant. The anticipated definition of the required
biomass species. Illustration for spruce is given in Fig. 7, which
minimum b value can prevent faulty experiments and related
clearly indicates that relevant k values can only be obtained if
experimental data.
During TGA-pyrolysis, reactions take place between approx. 473
b exceeds 80 K min1. Application of Eq. (8d) at an average 573 K,
with a cp of 1.08 kJ kg1 K1 (at 573 K) and with the experimentally
and 673 K (average 573 K). The relationship between sufficient heat
determined C values (Table 4) demonstrates that the theoretical
supply and reaction yield can be expressed in terms of kinetic and
value of b should exceed 79 K min1, in line with the experimental
thermal data, as determined below. The first order kinetics relate
findings.
conversion (X), reaction rate constant (k) and time (t), according to
Similar calculations were performed for the different biomass
expression (5). Since the heat supplied should at any time and for
species, using the experimentally determined char yield and C
any conversion X exceed the heat consumed, a heat balance can be
made. The heat supplied during the reaction equals m0cpbt (J),
with m0 the initial amount of biomass (kg). The char yield is on
0,025
average 30 wt%. Heat requirements (C) were measured by DSC
0,02

0,015
k (s-1)

Table 3
Effect of the heat penetration upon the reaction rate constant (k).
0,01

T (K) Saw dust (85 mm) Eucalyptus (37.5 mm) Corn (50 mm) 0,005
k kht error on k kht error on k kht error on
kr (%) kr (%) kr (%) 0
0 20 40 60 80 100 120 140
573 0.01 5.88 0.2 0.01 26.67 0.05 0.02 24.00 0.1
673 0.12 5.47 2.1 0.21 24.81 0.8 0.27 22.33 1.2 heating rate (K min-1)
773 0.68 5.12 11.8 1.52 23.19 6.1 1.59 20.87 7.1
Fig. 7. The effect of the heating rate upon the reaction rate constant for spruce.
 M. Van de Velden et al. / Renewable Energy 35 (2010) 232–242 239

Table 5 biomass and represents 25–35 wt%, with the exception of corn with
Required minimum heating rates for an accurate measurement of the reaction rate only 10 wt% residue, and sunflower and sewage sludge, where the
constant.
char fraction is significantly higher. The high ash content of sewage
Biomass k at 573 K (s1) bmin (K min1) sludge is related to its well-known high content of minerals. The
spruce 0.0200 79 results correspond fairly with previous literature data, i.e. 21% char
eucalyptus 0.0138 64 for spruce [40], 30% for straw [40,41] and on average between 19
poplar 0.0116 28
and 26% [42].
sawdust 0.0111 56
corn 0.0242 75 From the dynamic TGA experiments, the reaction rate constant k
sunflower 0.0856 289 can be determined by Eqs. (9)–(11), as used in e.g. [10–12,43].
straw 0.0350 152  
sewage sludge 0.0067 30 dXðtÞ=dt ¼ k Xp  XðtÞ (9)

with
values. A heating rate b of 80 K min1 is sufficient to meet the
required reaction heat (Table 5) for most biomass species. All XðtÞ ¼ ðm0  mðtÞÞ=m0 (10)
experiments were therefore performed at 100 K min1. To accu-
rately measure the kinetics, heating rates should exceed Xp ¼ ðm0  mN Þ=m0 (11)
100 K min1 for sunflower residue and straw.
with m0: initial weight of biomass (at t ¼ 0) (mg), mN : residual
The previous calculations demonstrate that literature data
weight of biomass after the reaction (mg), m(t): weight of biomass
obtained at lower heating rates (e.g. [12]) should be considered
at time t during the experiment (mg).
with caution and should not be compared to results obtained under
As the weight of the sample is continuously registered, X and Xp
relevant conditions.
are known parameters and the reaction rate constant can be
derived from Eq. (9) at every moment. Because of the known
4.2.3. Kinetic analysis
temperature profiles of the TGA (known DT/Dt), the reaction rate
The obtained TGA-profile plots, shown in Fig. 8, are similar for
constant is also known as a function of the temperature. The
all tested biomass samples. The results show that pyrolysis occurs
Arrhenius Equation (7) can be applied after transformation and
in the temperature range between 473 and 673 K, depending on the
plotting of the results as ln(k) versus 1/T. The activation energy and
type of biomass. This observed temperature range was also found in
the pre-exponential factor can be derived from respectively the
literature data [10,12,40].
slope and the intersection of the obtained straight line with the
It is obvious that the pyrolysis reaction produces a solid residue
ln(k)-axis.
or char, noticed by a final limited loss of weight per unit of time.
Results for the different biomass species at b ¼ 100 K min1 are
This char consists of minerals and the organic coking-residue of the
illustrated in Fig. 9 and summarised in Table 6, together with some
literature data.

a -2
0,0015 0,0016 0,0017 0,0018 0,0019 0,002
-3

-4
lnk

-5

-6

-7
1/T (K-1)
spruce eucalyptus poplar sawdust

b -2
0,0015 0,0016 0,0017 0,0018 0,0019 0,002
-3

-4
lnk

-5

-6

-7
1/T (K-1)
corn sun flower straw sewage sludge

Fig. 9. Temperature dependency of the rate constant of biomass pyrolysis at a heating

Fig. 8. TGA plots for (a) spruce, eucalyptus, poplar and sawdust, and (b) corn, rate of 100 K min1 for (a) spruce, eucalyptus, poplar and sawdust, and (b) corn,
sunflower, straw and sewage sludge. sunflower, straw and sewage sludge.
240 M. Van de Velden et al. / Renewable Energy 35 (2010) 232–242

Table 6 Table 7
Kinetic constants from own experiments and literature. Specific heat at 298 K.

Sample Ea (kJ mol1) A (s1) at 100 k (s1) Sample cp (kJ kg1 K1)
K min1 at 773 K Poplar 1.2
Own Spruce 68.4 3.47  104 0.824 Sawdust 1
experiments Eucalyptus 86.4 1.06  106 1.52 Corn residue 0.9
Poplar 54.1 1.00  103 0.219
Sawdust 75.8 9.12  104 0.684
Corn 77.0 2.55  105 1.59 (the optimum T in pyrolysis reactors) are included in Table 6.
Sunflower 63.9 2.48  104 1.19 Literature data should be used with caution: although data for k, A
Straw 76.3 3.16  105 2.21 and Ea are given, both the method and procedure used, and the
Sewage 45.3 8.95  101 0.078
sludge
heating rates are generally not included. It is however clear that the
Ea values are in the range of those of the biomass components at
Thurner and Oak 106.5 2.47  106 0.156
their respective wt%: 195–213 kJ mol1 for cellulose, 105–
Mann [43]
Gorton and Hard wood 89.52 1.48  10 6
1.31 111 kJ mol1 for hemicellulose and 34–65 kJ mol1 for lignin [47],
Knight [44] each present in biomass for around respectively 45, 30 and 25%.
4
Nunn et al. [45] Gum tree, 69.1 3.64  10 0.775 Moreover, it should be mentioned that the k values, with the
hard wood exception of poplar and sludge, exceed 0.5 s1 corresponding to
Reina et al. [12] Forest wood 95.4 2.40  105 0.0852
Di Blasi and Beech 95.4 2.4  105 0.156
a fast reaction of the biomass. A high conversion can thus be ach-
Branca [46] ieved in short reaction times so that the possible occurrence of side
reactions is limited.

4.2.4. Thermal analysis

The activation energy of a specific biomass is nearly constant
The thermal parameters are necessary to formulate the heat
(and representative for the biomass type) at different heating rates
balance of the pyrolysis reaction. Since pyrolysis, as every cracking
(Fig. 10), as can be seen from the parallel ln(k) versus 1/T lines.
reaction, is an endothermic reaction, the reaction heat is to be
Fig. 10 shows however that the pre-exponential factors, and thus
supplied indirectly (heat exchangers) or directly (e.g. by preheating
the reaction rate constant depend on the heating rate. When the
the bed material or the fluidization gas). Usually the combustion of
heating rate increases, the pre-exponential factor A (and thus k)
pyrolysis gas supplies the required heat (C, J g1) and the
increases first quickly to then reach a maximum value: at low
combustion gases form the oxygen-free carrier gas. The heat
heating rates insufficient reaction heat is supplied for the endo-
required to pyrolyse biomass contains two components (Eq. (2)):
thermic reaction, as was previously discussed. Although the
the heat required to heat the biomass to the temperature at which
obtained k values are nearly constant when obtained at high
heating rates (b) during the TGA experiments, the b values are still
of the order of 1–2 K s1 only (due to TGA limitations). In fast
pyrolysis, biomass particles are subjected to heating rates in excess
of 100 K s1. Section 4.2.2. discussed the influence of the heating
rate on the biomass conversion in view of balancing the heat supply
rate with both the heat required for pyrolysis and progress of
conversion. This balance is met at b w 1–2 K s1. Heating rates in
excess of 100 K s1 can only be examined in pyrolysis reactors such
as fluidized beds. This study is ongoing at present, where the batch
pyrolysis of biomass is studied. Results will be reported in the near
future and are essential to evaluate the possible extrapolation of
the current data and kinetic expressions to systems with a fast
heating rate.
From these A and Ea values, the rate constant of the pyrolysis
reaction can be calculated at any temperature, and values at 500  C

-2
0,0015 0,0016 0,0017 0,0018
-2,5
-3
-3,5
-4
lnk

-4,5
-5
-5,5
-6
-6,5
1/T (K-1)
-1
50 K min 80 K min-1 100 K min-1 120 K min-1

Fig. 10. Temperature dependency of the reaction rate of the pyrolysis of spruce at Fig. 11. DSC curves (10 K min1) for (a) spruce, eucalyptus, poplar and sawdust, and (b)
different heating rates. corn, sunflower, straw, sewage sludge.
 M. Van de Velden et al. / Renewable Energy 35 (2010) 232–242
Fig. 12. Heat requirement for pyrolysis in function of the temperature for (a) spruce,
eucalyptus, sawdust, poplar, and (b) corn, sunflower, straw, sewage sludge.
pyrolysis occurs and the heat required for the endothermic pyrol-
ysis as such. Hence the required heat can be written as follows:
C ¼ mb cp;b ðTr  T0 Þ þ mb DHr (12)
The temperature at which pyrolysis occurs, the specific heat
capacity cp and the reaction heat DHr (J g1) required for the
pyrolysis itself were experimentally investigated and will be dis-
cussed hereafter.
The specific heat capacity cp (J g1 K1) of the biomass samples
under scrutiny is presented in Table 7. Since cp values increase with
increasing temperature, the value at 500  C will be about 15%
higher than the experimental value at 298 K. Results are close to
literature data, which at 773 K vary between 1.1 kJ kg1 K1 [48] to
1.2 kJ kg1 K1 [49].
The obtained DSC curves, giving the heat flux (W g1) in func-
tion of the temperature or in function of the time (constant DT/
Dt ¼ 10 K min1) are shown in Fig. 11.
The DSC curves show that the heating process is clearly in the
domain of heat requirement, which confirms the endothermic
character of pyrolysis. Integration of these heat fluxes over time
(Eq. (13)) gives the total heat requirement C (J g1) as a function of
the temperature (Fig. 12). This includes the heat required for
heating the biomass as well as the heat for the pyrolysis reaction.
The endothermic peak at about 100  C, due to the evaporation of
residual water, was eliminated before integration. When the
pyrolysis is completed, the heat requirement decreases. Declining
values before the end of the reaction and beyond the normal
temperature range of pyrolysis can be explained by the occurrence
of secondary reactions (e.g. the aggregation of the char).
Zt   eastern region experience. FAO – Food and Agricultural Organization of the
dC dT dT
¼ cp þ DHr /C ¼ cp þ DHr dt (13)
dt dt dt
0 10.12.08].
241
The calculated heat requirements for pyrolysis of the tested
biomass species are presented in Table 4. These values are the
average of three experiments, with a deviation of approximately
6%. The end temperature of pyrolysis was obtained from the TGA
experiments.
The results are in the same order of magnitude of literature data:
500 kJ kg1 for straw [38], 400–450 kJ kg1 for cellulose [41,50],
235 kJ kg1 [51] and 418 kJ kg1 [52] for unspecified wood and 120–
360 kJ kg1 for various wood species [42].
5. Conclusions
Energy from biomass is recognised as the renewable energy
source with the highest potential in the near future. Within the
thermochemical conversion techniques, pyrolysis offers major
advantages through yielding mostly liquid and solid fuel, easy to
store and transport.
Although the operating conditions for a maximum oil yield are
well-known, the kinetics of the biomass conversion need to be
determined. The paper considered (i) the required working
conditions for relevant experimental research; (ii) the thermogra-
vimetric measurement of the kinetic constants and (iii) the reaction
heat of the biomass pyrolysis.
A review of the pyrolysis of the main constituents of biomass i.e.
cellulose, hemicellulose and lignin, and of the possible secondary
reactions stresses the value of the biomass pyrolysis concept of the
University of Waterloo.
To program experiments in a relevant and effective way, and to
critically assess previous literature results, it was demonstrated
that tests should be carried out (i) with biomass particles smaller
than approx. 200 mm and (ii) in a reaction environment where the
particle heating rate is about 80 K min1 and where the internal
resistance to heat penetration is smaller than the external resis-
tance to heat transfer (expressed in the condition of Biot-number,
Bi < 1).
TGA and DSC experiments on a wide variety of biomass particles
determine respectively the reaction kinetics and the Arrhenius
dependency, and the endothermicity of the reaction. For most of
the biomass species, the reaction rate constant is >0.5 s1, corre-
sponding with a fast reaction. The endothermic heat of reaction
ranges from 207 to 434 kJ kg1. These results tie in with literature
data, although the reader is cautioned in the use of literature data
since experiments were often performed at non-representative
testing conditions.
Both kinetic and thermal data are essential in the design of
pyrolysis reactor, determining respectively the required residence
time and the amount of heat to be supplied to the reactor. Their use
will be illustrated in a further paper where the design strategy of
a 10 MW (bio-oil) pyrolyser is presented.
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