Fuel 90 (2011) 2301–2314

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Validation of a numerical approach to model pyrolysis of biomass and assessment

of kinetic data
Bernhard Peters
Université du Luxembourg, Faculté des Sciences, de la Technologie et de la Communication, Campus Kirchberg, 6, rue Coudenhove-Kalergi L-1359, Luxembourg, Luxembourg

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

Article history: The objective of this contribution is to introduce a numerical approach that predicts pyrolysis of various
Received 23 November 2010 biomasses under various boundary conditions such as particle geometry and heating rate. Hence, the
Received in revised form 25 January 2011 approach is applicable to numerical tools that help exploiting further the potential of biomass as an
Accepted 2 February 2011
energy resource. Furthermore, it is intended to represent the general trend of state of the art in model
Available online 16 February 2011
developments. The presented model itself is based on one-dimensional and transient differential conser-
vation equations for mass, momentum, species and energy. In order to account for a variety of reaction
Keywords:
schemes a formulation based on the Arrhenius equation including intrinsic modelling is chosen. It is
Pyrolysis
Modelling
believed to represent the majority of kinetic pyrolysis data derived from experiments. Applying this sin-
Discrete Particle Method (DPM) gle numerical approach to predict pyrolysis under varying experimental conditions for different materials
always revealed good agreement with measurements.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction ethylene) and aromatic tars. Weighting between both product

As decomposition during devolatilization and pyrolysis is a very
complicated and complex process, dependent also on heat transfer
by convection and radiation; some tentative first models were
based on a global one-dimensional energy balance. These one-step
models decompose the organic fuel into volatiles and coke with a
fixed char yield.
An initial review on numerical approaches to model pyrolysis
may be found in an articles of Peters [1]. Since then researchers
gained more kinetic data for different materials through experi-
ments, while modelling is largely based on lumped parameter
models or differential conservation equations. However, more
effects such as secondary reactions are taken into account.
During the pyrolysis, especially of wood, secondary reactions
may occur at rising temperatures. Di Blasi and Russo [2] assumed
two competing secondary reactions. Tar may be decomposed into
lighter gases or polymerised into coke in exothermic reactions.
The activation energies of the primary reactions are based on the
data given by Thurner and Mann [3]. Both secondary reactions only
differ in the frequency factor, and therefore, always take place
simultaneously. The pyrolysis model developed by Di Blasi and
Russo [2] was employed by Miller and Bellan [4] for their one-
dimensional model. The frequency factors of the primary reactions
are corrected according to Thurner and Mann [3].
Chan et al. [5] used a pyrolysis model of three primary reactions
and one secondary reaction. The products of the secondary tar
reaction are divided into light gases (carbon monoxide, ethane,
E-mail address: bernhard.peters@uni.lu
groups depends on the boundary conditions. The kinetic data are
determined from experiments with pine wood. Based on the data
given by Chan et al. [5], Grønli [6] studied the extension of a
parallel reaction as a secondary tar reaction in addition to other
models. Tar is converted into (light) gases in an exothermic
reaction. Agreement with the experimental data is satisfactory.
As in the single-step pyrolysis model, the gases are regarded to
be a mixture of carbon monoxide CO and carbon dioxide CO2, while
the tars are considered to be benzene.
Abbassi et al. [7] investigated into pyrolysis of biomass both
experimentally and numerically. The reactor was divided into
three zones that were treated as perfectly stirred reactors. Tar as
a major product of pyrolysis was assumed to crack into methane
CH4, carbon monoxide CO, carbon dioxide CO2 and hydrogen H2,
determined by an Arrhenius expression. The model was validated
with measurements and was used to control plant operation.
Similar experiments were carried out by Skodras et al. [8] to
characterise the degradation behaviour of residue-derived fuels.
Biomass and plastics are considered the main components present
in residue derived fuels (RDF), and thus, determine thermal
degradation by mass-weighted rates of cellulose, hemicellulose,
lignin and polyethylene as major components of the fuel. Measure-
ments confirmed this behaviour and showed that interactions
between the main components are negligible. Rattea et al. [9]
predicted pyrolysis of wood waste by a model approach developed
earlier by Peters [10] and proved that this approach may also be
employed to large wood particles. The latter approach has also
been used by Sadhukhan et al. [11] for large wood particles and
they emphasised that intra-particle convection is important.

0016-2361/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2011.02.003
2302 B. Peters / Fuel 90 (2011) 2301–2314
Nomenclature
Physical symbols
c concentration, mol/m3
cp specific heat, kJ/kg K
C Forchheimer constant, –
D diffusion coefficient, m2/s
Ea activation energy, J/mol
f correlation factor, –
H reaction enthalpy, kJ/kmol
k pre-exponential factor, –
k permeability, m2
M molar mass, kg/kmol
L length, m
n geometry factor, –
q_ 00 specific heat flow, W/m2
Q heat source, kJ
Q_ volumetric flow rate, m3/s
r radius, m
R gas constant, J/mol K
Dupont et al. [12] performed biomass pyrolysis also in an en-
trained flow reactor under high temperatures from 1073 to
1273 K and high heat fluxes (10–100 kW/m2). Their experimental
results were compared to predictions of the kinetic mechanism
of Ranzi et al. [13] and encouraged design and understanding of
industrial gasifiers.
The influence of temperature and heating rate on pyrolysis of
pine between a temperature of 300 and 720 °C and heating rates
from 5 to 80 K/min were investigated by Williams and Besler
[14]. Their findings showed that wood decomposes mainly to va-
pour H2O, carbon dioxide CO2 and carbon monoxide CO at lower
temperatures (200–400 °C) and to hydrogen H2, water vapour
H2O, oil and hydrocarbon gases with reduced concentrations of
CO and CO2 at higher temperatures. Similar experiments were car-
ried out by Jakab et al. [15]. Correlations revealed that the terminal
CH2OH decomposes into water and formaldehyde whereas the
scission of methoxyl groups form both methane and methanol.
Due to the complexity of detailed kinetic mechanisms of gasifica-
tion, pyrolysis, partial oxidation and combustion of hydrocarbon
mixtures Ranzi et al. [16] presented a method to lump both a large
number of components and reactions into a limited set of indepen-
dent elementary kinetic parameters.
Similar experiments have been carried out by Tonbul [17], who
determined the degradation kinetics of pistachio shells through
thermogravimetry at different heating rates of 5, 10, 15 and
20 °C/min up to 800 °C. Collura et al. [18] evaluated the kinetics
of Miscanthus grass by thermogravimetry. The kinetic parameters
determined agree with findings of other researchers in particular
those of Müller-Hagedorn et al. [19]. Xiua et al. [20] used an en-
trained flow reactor to estimate the kinetic parameters for fast
pyrolysis of corn stalk. The parameters found agree with a previous
study of pulverised corn stalk, and thus, allow a scale-up of the re-
sults to entrained-flow reactor concepts.
As pyrolysis of biomass produces a gas that contains methane
and a large amount of tar Valin et al. [21] investigated into the con-
version of typical biomass pyrolysis gas into a methane rich gas. In
order to reach a conversion rate of 90%, the gas has to be heated to
at least 1650 K at a residence time of 2 s.
Kinetic data for the pyrolysis of styrene–butadiene was also
determined by Grieco et al. [22]. Experiments and modelling re-
vealed that the heating rate and sample size have a small influence
on char and tar production whereas the yield of noncondensable
Re Reynolds number, –
S mass source, kg/m3 s
t time, s
T temperature, K
v velocity, m/s
Y mass fraction, –
Greek symbols
a heat transfer coefficient, W/m2 K
b mass transfer coefficient, m/s
 porosity, –
g effectiveness factor, –
k heat conductivity, W/m2 K
l dynamic viscosity, kg/m s
x_ reaction rate, mol/m3 s
q density, kg/m3
r Boltzmann constant, J/K
s tortuosity, –
gases may vary to a large extent. Olazar et al. [23] derived kinetic
data for pyrolysis of tyres from experiments in a temperature
range between 425 and 610 °C. Predictions obtained by a novel
model agreed well with measurements.
Bech et al. [24] dealt with a novel design of a pyrolysis centri-
fuge reactor that produces liquid fuel from biomass. The organic
material is pressed against the wall through centrifugal forces,
and thus, experiences heat transfer and subsequent decomposi-
tion. A pseudo-surface reaction model predicts the yields stem-
ming from flash pyrolysis satisfactorily.
Golovano et al. [25] analysed firing and smoldering of peat by
an analytical approach. Solving the differential conservation equa-
tions for mass and energy yielded the peat smoldering velocity that
was in good agreement with experiments.
Chiarioni et al. [26] developed a steady-state model including
two continuous phases for air and solid to describe a pyrolysis
reactor for automotive shredder residue (ASR). They predicted re-
sults showing the influence of temperature.
Kausley and Pandit [27] developed a one-dimensional and un-
steady model to describe the combustion behaviour of a domestic
stove. The model includes the processes of moisture evaporation,
devolatilization, pyrolysis and homogeneous and heterogeneous
combustion reactions. As a validated model it predicts the influ-
ence of flow rate of air, moisture content, and the density of fuel
on the ignition front velocity and the fuel burn rate.
Pyrolysis and combustion of oil palm stone and palm kernel
cake in fixed-bed reactors were investigated by Razuan et al.
[28]. Experiments showed that higher air flow rates caused an in-
creased combustion rate. The FLIC code [29] was used to simulate
the combustion process and its results were in good agreement
with measurements.
Razvan et al. [30] developed a two-dimensional continuous
model to describe pyrolysis of wood. The reactor was discretised
into elements of which its state was represented by thermody-
namic properties such as temperature, gas composition and trans-
fer conditions at a node. The thermodynamic state at each node
was determined by models for heat transfer, drying, thermochem-
ical decomposition of biomass and transport. Similar efforts were
undertaken by Saravanakumar et al. [31] and Saravanakumar
et al. [32] who undertook an experimental investigation and mod-
elling study of long stick wood gasification in a top lit updraft fixed
bed gasifier. From the analysis of measurements they concluded
 B. Peters / Fuel 90 (2011) 2301–2314
that a top lit updraft gasifier is more suited to long stick wood as
feed than a conventional updraft gasifier. Tinaut et al. [33] devel-
oped a one-dimensional continuum model to describe a downdraft
fixed bed gasifier. After validation of the model through an exper-
imental set-up of a downdraft gasifier, the authors claimed that the
model may be employed as a design tool. Furthermore, it may be
applied to estimate performance and pollutant emissions of an en-
gine fuelled with the gas composition predicted. Simsek et al. [34]
coupled CFD and Discrete Element Method (DEM) to simulate grate
firing systems. Motion of particles was predicted by Newton’s sec-
ond law, whereas conversion of particles is taken into account by a
lumped parameter model. The solid phase of the particles was
coupled to the primary air by heat and mass transfer. The predicted
results showed qualitatively reasonable results, whereby the devi-
ations may be attributed to the rather coarse resolution of particle
conversion.
Papadikis et al. [35–37] studied the effect of size of biomass on
pyrolysis exposed to fluidised bed of sand with the size of the sand
particles being 400 lm. Smaller (350 lm) and larger (550 lm)
sized biomass particles were mixed with the sand particles. Con-
ductive heat transfer between the fluidised bed and the larger bio-
mass particles was considered and was neglected for smaller
biomass particles. The simulations were performed using an Eule-
rian model of the FLUENT software for the gas as nitrogen and flu-
idised phase. The sand was treated as a continuum and the solid
phase model was based on a radial distribution function and a
granular temperature. The coupling between the continuous and
discrete phases was developed as a user-defined function in
FLUENT and based essentially on the particle drag force in the con-
tinuum. The heat transfer along the particle radius was calculated
by solving the heat diffusion equation for an isotropic particle. It
has been found that different heat transfer mechanisms are in-
volved for particles of different sizes, resulting in different heat
transfer coefficients. The temperature gradients inside the particles
could be neglected due to small Biot numbers. According to the
study, smaller particles yielded better results for fast pyrolysis
applications, because they are better entrained in the bed during
degradation. Furthermore, smaller sized particles reduced the ef-
fect of secondary reactions resulting in higher yields of biofuels.
Domazetis et al. [38] carried out experiments on gasification of
low-rank coals catalysed by iron species and developed a model
describing gasification. Molecular modelling explained that vapour
molecules chemi-adsorb onto an active [Fe–C] group, followed by
reactions that yield hydrogen H2 and carbon monoxide CO. It
caused a higher than expected hydrogen H2 yield.
In order to predict devolatilisation and combustion of coal
Pallares et al. [39] combined the CFD software CFX with the package
FG-DVC that predict the rate of the volatile release and the compo-
sition of key species linked to the resulting macro-porous and mi-
cro-porous structure of the char. Predicted results were compared
with plant measurements and showed reasonable agreement. Mod-
elling of pyrolysis of coal–biomass blends was undertaken by Sad-
hukhan et al. [40] to explain the co-pyrolysis behaviour of lignite
coal–biomass blends. An analysis of mass loss history of blends
showed that any synergetic effects were not present. The latter con-
clusion was contradicted by Park et al. [41] who carried out exper-
imentally co-pyrolysis of a sawdust and coal blend. It has been
observed that the volatile yield is higher than those of the sum of
sawdust and coal individually. Depending on the blending ratio
gas products increased by 39% and the calorific value of the product
gas increased up to 68%. A different behaviour was observed during
pyrolysis of Elbistan lignite under atmospheric pressure by Ozbas
[42]. Experiments were carried out under non-isothermal condi-
tions with a heating rate of 10 °C/min under nitrogen atmosphere
up to 900 °C. Pyrolysis rates and characteristic peak temperatures
were attributed to different pyrolysis regions and thermogravimet-
2303
ric (TG/DTG) and differential thermal analysis (DTA) yielded appar-
ent activation energies and Arrhenius constants that varied to a
large extent. Kinetic data for the pyrolysis of coal according to the
particle size was derived by Duz et al. [43] with thermal gravimetric
(TG/DTG) experiments at an ambient temperature to 800.0 °C un-
der a nitrogen atmosphere at a heating rate of 10.0 K/min. Depend-
ing on the particle size of the coal samples, the mean activation
energy values varied between 49.1 and 84.6 kJ/mol.
Zhou et al. [44] reported from experimental findings that atten-
uation of incident radiation by pyrolysis volatiles of pine or PMMA
amounts to 6–14%. A review of approaches to model gasification of
agricultural residues in air is given by Nemtsov and Zabaniotou
[45] For a further complementary review of literature on pyrolysis
the reader is referred to Kersten [46] and Wang et al. [47].
Models employed so far by different authors differ in complex-
ity to a large extent. Therefore, the current approach aims at deriv-
ing a single model that takes into account various aspects
mentioned-above including resolution and reaction kinetics. The
quality of the model is assessed through prediction of thermal
degradation of a number of materials under strongly differing
experimental conditions. All the predictions are compared to
measurements.
2. Numerical model
A discrete particle may be considered to consist of different
phases as summarised below:
 gas
 liquid
 solid
 inert
whereby local thermal equilibrium between the phases is
assumed. It is based on the assessment of the ratio of heat trans-
fer by conduction to the rate of heat transfer by convection
expressed by the Peclet number as described by Peters [48] and
Kansa et al. [49]. The gas phase represents the porous structure,
e.g. porosity of a particle and is assumed to behave as an ideal
gas. According to Man and Byeong [50] one-dimensional differen-
tial conservation equations for mass, momentum and energy are
sufficiently accurate. Transport through diffusion has to be aug-
mented by convection as stated by Rattea et al. [9] and Chan
et al. [51]. In general, the inertial terms of the momentum equa-
tion is negligible due to a small pore diameter and a low Reynolds
number [49]. However, for generality and at no additional
expenses, the inertial terms are taken into account by the current
formulation. The importance of a transient behaviour is stressed
by Lee et al. [52,53].
Each of the phases may undergo various conversion based on
both homogeneous and heterogeneous reactions whereby
the products may experience a phase change such as encountered
during drying, i.e. evaporation. The need for more elaborate models
of heterogeneous reactions was pointed out by Chapman [54]. In
addition, intrinsic rate modelling is applied to the current model
to capture accurately the nature of various reaction process as
pointed out by Rogers et al. [55] and Hellwig [56].
Thus, the Discrete Particle Model (DPM) offers a high level of
detailed information, and therefore, is assumed to omit empirical
correlations, which makes it independent of particular experimen-
tal conditions for both a single particle and a packed bed of parti-
cles. Such a model covers a larger spectrum of validity than an
integral approach and considerably contributes to the detailed
understanding of the process [57–59]. Hence, processes of thermal
2304 B. Peters / Fuel 90 (2011) 2301–2314

@ qi;g 1 @  n  1 @  D  X l
i;eff @ qi;g
conversion are described by a set of one-dimensional and transient
differential conservation equations applied to the solid, liquid and þ n r ~v g qi;g ¼ n rn þ x_ k;i ð3Þ
@t r @r r @r M i @r k¼1
gaseous phase, whereby the solid and liquid species are considered
as immobile. The predictions include major properties such as
where qi,g and x _ k;i are partial density of gaseous specie i and a reac-
temperature and species distribution inside a particle. Thus, a
tion source. A contribution of the Knudsen diffusion is neglected
description by conservation equations does not bound the
due to an approximate value of pore diameters of 50:0 lm and a
reactions to a finite temperature range, so that they take place
pressure of approximately 1.0 bar, so that only molecular diffusion
simultaneously, or to a reaction mode, such as a reacting- or a
in the pores is taken into account [6,61]. As a result of the averaging
shrinking-core mode. In detail, the following assumptions are
process and the influence of tortuosity s on the diffusion, an effec-
made to describe conversion of a particle
tive and local diffusion coefficient is derived as follows [62,63]:
 a particle consists of a solid, inert and a gaseous porous phase
that may be accompanied by a liquid phase;
P
Di;eff ¼ Di ð4Þ
 thermal equilibrium between gaseous, liquid, inert and solid
s
phases inside a particle;
where P is the porosity of the particle and the molecular diffusion
 particle geometry represented by slab, cylinder or sphere;
coefficients Di are taken from the equivalent ones of the appropriate
 description by one-dimensional and transient differential
species in air. However, measurements of effective diffusion coeffi-
conservation equations for mass, momentum, species and
cients already include the effect of tortuosity, so that it is not re-
energy;
quired to account for it by Eq. (4) and the value of tortuosity s is
 convective and diffusive transport in the gas phase, i.e. porous
set to 1 for the current study. Diffusivity is further effected by con-
space through Darcy flow;
version through a change in porosity, that is taken into account by
 spatially resolved transport properties for diffusion and conduc-
Eq. (4) through the evolution of porosity in time and space.
tion inside a particle depending on local composition;
Similarly, conservation for both liquid and solid species writes
 thermal conversion described by homogeneous, heterogeneous
as follows
and intrinsic rate modelling;
 gas phase as a mixture obeying the equation of state;
 regressing surface of a particle during mainly combustion and @ qi;liquid X l
¼ x_ k;i;liquid ð5Þ
gasification processes. @t k¼1

@ qi;solid X l
2.1. Conservation of mass ¼ x_ k;i;solid ð6Þ
@t k¼1
Conservation of mass for the porous gas phase writes as
follows: where the right-hand side comprises all reactions k involving a spe-
@q 1 @  n  cie i, each of which is characterised by specific kinetic parameters
 gþ n v g ¼ Smass
r qg ~ ð1Þ [64–67]. Due to intrinsic rate modelling of the current approach,
@t r @r
where , q, ~v and Smass denote porosity of the particle, gas density, reaction regimes [48] of a shrinking- and a reacting-core mode
velocity and mass sources due to a transfer between the solid/liquid are distinguished. Depending on the rate-limiting process, the
phase to the gas phase and its reactions, respectively. Due to a gen- depletion of solid material therefore results in either a decreasing
eral formulation of the conservation equation with the independent particle density or a reduction of particle size [48,68]. The latter
variable r as a characteristic dimension the geometrical domain can causes a decreasing height of a reacting bed.
be considered as an infinite plate (n = 0), infinite cylinder (n = 1) or The distribution of porosity  and specific inner surface S are
sphere (n = 2). determined by the following equations

2.2. Conservation of momentum

@  Ms
¼ x_ s ð7Þ
Transport of gaseous species within the porous space of a parti- @t qs d
cle is approximated by a Darcy flow. An analysis of orders of the
relevant terms yields [60], that convective terms are negligible @S 1  o
and consequently the effect of friction is described by the Darcy
¼ x_ s ð8Þ
@t cos
and Forchheiner correlation. Hence, the following balance of linear
momentum is applied:
where Ms, cs, x _ s and d denote the molecular weight, concentration
of solid material, reaction rate of solid material and characteristic
vg
@ qg ~ @p l
 ¼  ~ v g  C qg ~
v g j~
vgj ð2Þ pore length, respectively [68,69]. The superscript ‘‘o’’ stands for ini-
@t @r k tial values of the appropriate variable.

where p, l, k and C stand for pressure, viscosity, permeability and

Forchheimer coefficient, respectively. In general, the inertial terms Table 1
may be neglected, however, are kept within the present formula- Properties of spruce wood.
tion. The solution of the continuity and momentum equation fur- Property Value
nishes a gas velocity within the porous part of the particle.
Density q 450:0 kg=m3
Specific heat cp ð1500:0 þ TÞ J=kg K
2.3. Conservation of species Conductivity kspruce 0:35 W=m K
Conductivity kmchar 0:1 W=m K
Porosity  0.68
Convection in conjunction with diffusive transport describes
Pore diameter dp 50:0  10:06 m
the distribution of gaseous species i in the porous particle versus
Tortuosity s 1.0
time and space as follows:
 B. Peters / Fuel 90 (2011) 2301–2314 2305

2.4. Conservation of energy @T

 keff j ¼ aðT R  T 1 Þ þ q_ rad þ q_ cond ð12Þ
@r R 
Due to a negligible heat capacity of the gas phase compared to @ci 
 Di;eff  ¼ bi ðci;R  ci;1 Þ ð13Þ
the liquid, inert and solid phase conservation of energy includes @r R
solids and liquids only (local thermal equilibrium):
where T1, ci,1, a and b denote ambient gas temperature, concentra-
  tion of specie i, heat and mass transfer coefficients, respectively.
P
k
@ qi cp;i T   X l Due to the outflow m _ g of volatiles and steam from the particle the
i¼1 1 @ @T
¼ n
rn keff þ x_ k Hk ð9Þ Stefan correction is introduced into the transfer coefficients, which
@t r @r @r k¼1 are estimated as follows [70]:
The locally varying conductivity keff is evaluated as [6] _ g =qg
m
b¼ ; ð14Þ
X
k _ g =qg b0 Þ  1
expðm
keff ¼ P kg þ ni ki;solid þ krad ð10Þ
m_ g cp;g
i¼1 a¼ _ g cp;g =a0 Þ  1
; ð15Þ
expðm
which takes into account heat transfer by conduction in the
gas, solid, liquid and radiation in the pore. The latter is approxi- where a0 and b0 denote the transfer coefficients for a vanishing
mated as convective flux over the particle surface.

X
k
i;solid
krad ¼ ni r 4:0 T 3
i¼1
1  i;solid
where , r and T stand for porosity, Boltzmann constant and tem-
perature, respectively. The solid mass fraction xi in Eqs. (10) and
(11) determines the contribution of respective and available solid
mass to the overall conductivity and radiative transfer, and thus, re-
flects the effect of varying mass fractions during conversion. The
source term on the right-hand side represents heat release or con-
sumption due to chemical reactions.
2.5. Initial and boundary conditions
In order to complete the mathematical formulation of the prob-
lem, initial and boundary conditions must be provided. A wide
range of experimental work has already been carried out in this
field and appropriate laws in terms of Nusselt and Sherwood
numbers are well established for different geometries and flow
conditions. Good compilations can be found in [57,70–74]. The fol-
lowing boundary conditions for mass and heat transfer of a particle
are applied:
3. Results
ð11Þ
Validated results from predictions obtained by the current
numerical approach mentioned above are presented within the
current section. Thereby a large variety of different applications
and materials was emphasised. Hence, the latter include wood
samples such as spruce, beech, pine, casuarina, cellulose and lignin,
that were pyrolysed under different sizes and heating conditions.
Furthermore, reaction schemes of varying complexity describing
pyrolysis were employed. It is believed that the selected validation
data covers the range of engineering relevant applications, and
thus, proves that the model presented may be viewed as a
general approach to describe pyrolysis under a large variety of
conditions.
3.1. Pyrolysis of spruce wood
Grønli [6] carried out pyrolysis experiments of spruce cylinders,
of which one of the circular side surfaces was exposed to a radia-
tive flux of 80.0 kW and 130.0 kW, respectively. During an experi-
ment the temperatures at five different positions (L = 1, 4, 8, 12,

Fig. 1. Comparison between measured and predicted interior temperatures during pyrolysis of a cylindrical spruce wood sample at a radiative heat flux of 80.0 kW/m2.
2306 B. Peters / Fuel 90 (2011) 2301–2314

Fig. 2. Temperature profile during pyrolysis of spruce at a radiative flux of 80.0

kW/m2.
Fig. 4. Char profile during pyrolysis of spruce at a radiative flux of 80.0 kW/m2.

Fig. 3. Wood profile during pyrolysis of spruce at a radiative flux of 80.0 kW/m2. Fig. 5. Porosity profile during pyrolysis of spruce at a radiative flux of 80.0 kW/m2.

and 24 mm) along the cylinder axis were recorded. Several exper- evaluated, and thus, yielded a measure for experimental uncer-
iments under identical conditions were carried out, so that mini- tainty related to the unavoidably inhomogeneous wood samples.
mum and maximum temperatures at different positions were Thus, an improvement of predictions within the experimental er-

Fig. 6. Comparison between measured and predicted interior temperatures during pyrolysis of a cylindrical spruce wood sample at a radiative heat flux of 130.0 kW/m2.
 B. Peters / Fuel 90 (2011) 2301–2314 2307

ror is not necessary. A detailed description of the experimental set-

up and pyrolysis model is found with Grønli [6].
The properties of spruce wood employed are listed in the fol-
lowing Table 1.
Fig. 1 depicts a comparison between the measured temperature
and the predictions at different locations within the sample. In
general, the temperature profiles attain the exponential character-
istics of heat conducted within a solid material [75]. The measured
maximum and minimum temperatures indicate differences of
more than 100.0 K during its evolution for the temperatures
measured closest to the sample surface. However, these differences
reduce to 30–50 K for inner locations of temperature measure-
ments. The predicted transient temperature profiles at the five
locations fall mostly between the maximum and minimum
measured temperature profiles, and thus, agree well with the
experiments.
Fig. 8. Wood profile during pyrolysis of spruce at a radiative flux of 130.0 kW/m2.
Figs. 2–4 show the spatial and temporal temperature, wood
and char profiles during pyrolysis, respectively. The temperature
profile depicts a smooth increase versus time and space, and
thus, represents conduction within the initial wood sample that
is continuously converted into char. Depletion of the former is
depicted in Fig. 3, that indicates a separation between an unre-
acted core of still available spruce and a outer region, where
spruce is already entirely converted into char. These characteris-
tics agree with the temperature profiles in Fig. 2, that a signifi-
cantly large part of the inner particle is hardly heated up, and
therefore, no conversion has taken place within the investigated
time interval.
Consequently, a similar distinction into an unreacted core and a
reacted outer region is observed in Fig. 4, that shows the distribu-
tion of char versus time an and space. Within the outer region char
is formed, that is followed by a transition region where both spruce
and char co-exist.
Morphological changes in particular porosity are depicted in
Fig. 5 during pyrolysis of a sample at a radiative flux of 80.0
Fig. 9. Char profile during pyrolysis of spruce at a radiative flux of 130.0 kW/m2.
kW/m2. During pyrolysis spruce wood is converted into charred
material with its characteristic porosity. Thus, porosity increases
from 0.68 of spruce wood to 0.9 of char whereby the evolution
in time and space is determined by the characteristic conversion Fig. 7 depicts the evolution of temperature in time and space for
rates. The latter depend on available spruce wood and a particle subject to an external heat flux of 130.0 kW. Similarly to
temperature. Fig. 2 the temperature profile is dominated by the conductive heat
The following Fig. 6 depicts the evolution of temperature at five transfer inside a particle. The following Figs. 8 and 9 show the pro-
different interior position as mentioned above under a radiative files of wood and char in time and space during pyrolysis. The
heat flux of 130.0 kW. In general, the same characteristics as for rather sharp gradients indicate a conversion front propagating
the case of a radiative flux of 80.0 kW for both experimental data through the particle and separating it into a reacted outer and
and predictions appear. Due to a higher heat flux, maximum steady unreacted inner region.
state temperatures reach a level of 1200.0 K, and consequently, Concluding, temperature differences of several hundred de-
larger amounts of spruce have been pyrolysed. grees occur within the sample under the conditions investigated.
These findings indicate that, in addition to a reaction-limited re-
gime, a heat transfer-limited regime exits for large wood parti-
cles. Therefore, global approaches based on an average
temperature do not estimate the behaviour accurately and are
bound to fail.

Table 2
Properties of beechwood.

Property Value
Density q 750:0 kg=m3
Specific heat cp 2551:3 J=kg K
Conductivity kbeech 0:1256 W=m K
Conductivity kmchar 0:1 W=m K
Porosity  0.64
Pore diameter dp 50:0  10:06 m
Fig. 7. Temperature profile during pyrolysis of spruce at a radiative flux of Tortuosity s 1.0
130.0 kW/m2.
2308 B. Peters / Fuel 90 (2011) 2301–2314

3.2. Pyrolysis of beechwood 3.3. Pyrolysis of pine wood

While the previous section emphasised radiative heating condi-
tions, the following results of beech pyrolysis depend on convec-
tive heating and size parameters. Bruch [76] investigated the
influence of the sample diameter and heating temperatures. The
latter were set to 643, 743 and 843 K and the particle diameter
was varied between 8, 12, 17 mm. Relevant beechwood properties
are given in the following Table 2.
The kinetic pyrolysis developed by Balci et al. [77] ðA ¼ 1:35
109 1=s; Ea ¼ 123:1 kJ=mol; Dh ¼ 4500 kJ=kgÞ was employed.
Fig. 10b depicts the mass loss of beech versus time for different
particle sizes. The start of pyrolysis is indicated by a negligible
mass loss, and hereafter, pyrolysis proceeds with an almost con-
stant rate until a final yield of 25% is reached. Similar results
are obtained for a variation of the heating temperature shown in
Fig. 10b. A comparison between measurements and predicted re-
sults shows good agreement, taking into account experimental
uncertainties as mentioned in the previous section. Both parame-
ter, particle size and heating rate, were condensed into an empiri-
cal equation by Petek [78] in the following form
Over the last decades several models to describe pyrolysis were
developed. These approaches distinguish each other by a degree of
complexity [79]. Therefore, predictions of a one-step and a reaction
scheme including secondary tar reactions are compared. Relevant
properties of pine are given in the following Table 3 [80]:
The reaction schemes for pyrolysis employed were those of
Grønli [6]. A one-step model decomposes pine into char and gas,
whereas the second model including secondary reactions has tar
as an additional product of decomposition, of which gas is formed
in a secondary reaction. The following Fig. 10 depicts the predic-
tions obtained by the pyrolysis models in conjunction with exper-
imental data.
The one-step model agrees well with the experimental data
reaching a final conversion of 72%. Although the reaction scheme
with secondary tar reactions predicts satisfactorily the onset of
Table 3
Properties of pine wood.

m0:54 Property Value

t 95 ¼ 5:4  104 1:39
ð16Þ Density q
T 470:0 kg=m3
Specific heat cp 1733:0 J=kg K
to express the characteristic reaction time t95 at which 95% mass Conductivity kpine 0:2 W=m K
reduction was achieved. Within this equation, mass m and temper- Conductivity kmchar 0:1 W=m K
Porosity  0.68
ature T are to be inserted as [g] and [°C], respectively. The character-
Pore diameter dp 50:0  10:06 m
istic reaction time t95 was also extracted from the results predicted Tortuosity s 1.0
and compared satisfactorily to Eq. (16), which is shown in Fig. 10b.

Fig. 10. Conversion during pyrolysis of pine.

 B. Peters / Fuel 90 (2011) 2301–2314 2309

Fig. 10 (continued)

pyrolysis, deviations increase during the final stage of pyrolysis temperatures obtained with the present model are compared to
leading to a char yield of 8%. cylindrical (D = 20 mm, L = 100 mm) and spherical samples of
20 mm in diameter at bulk temperatures of 320 °C and 410 °C.
The dimensions of the cylindrical samples were chosen under the
3.4. Pyrolysis of casuarina wood
condition that a one-dimensional analysis was feasible.
Figs. 11 and 12 depict residual mass fraction and centre temper-
Sadhukhan et al. [11] carried out experimental investigations
ature during pyrolysis of casuarina at a heating temperature of
for large cylindrical and spherical casuarina wood in an electrically
320 °C. Although a cylindrical sample offers a larger surface to heat
heated furnace under inert conditions. The properties of casuarina
transfer, the spherical particle heats up at a higher rate due to its
are listed in the following Table 4.
reduced thermal capacity compared to the cylindrical wooden
A simple reaction scheme of Koufopanos et al. [81] was applied
particle as shown in Fig. 12. Hence, the spherical particle under-
to describe primary pyrolysis, that decomposes biomass into char,
goes degradation with a steeper profile than the cylinder depicted
volatiles and gases. Primary volatiles are not released instanta-
in Fig. 11. However, both particle geometries show satisfactory
neously to the ambient for large particles due to transport
agreement with measurements.
limitations, e.g. residence time. Therefore, char and primary vola-
Figs. 13 and 14 show similar trends at a bulk temperature of
tiles interact and undergo a secondary reaction to form secondary
410 °C and agree well with experimental findings for both residual
char and volatiles. Predictions of residual mass fraction and centre
mass fraction and centre temperature. Furthermore, both measure-
Table 4 ments and predictions indicate that large particles in general expe-
Properties of casuarina wood. rience significant temperature gradients that have to be taken into
Property Value account by respective transport equations of the numerical ap-
proach for pyrolysis.
Density q 682:0 kg=m3
Specific heat cp 212:05 þ 4:85T J=kg K
Conductivity kcasuarina 0:0481 þ 0:0003T W=m K 3.5. Pyrolysis of cellulose
Conductivity kmchar 0:1 W=m K
Porosity  0.68
Whereas the applications of the previous sections have em-
Pore diameter dp 50:0  10:06 m
ployed pyrolysis models of different complexity with lumped
Tortuosity s 1.0
product species, Ranzi et al. [13,12] developed a detailed reaction
2310 B. Peters / Fuel 90 (2011) 2301–2314

Fig. 11. Residual mass fraction during pyrolysis of casuarina at a heating temperature of 320 °C.

Fig. 12. Centre temperature during pyrolysis of casuarina at a heating temperature of 320 °C.

mechanism including a variety of different product species. The
mechanism is based on degradation of cellulose, hemi-cellulose
and lignin, of which biomass is composed. Thus, pyrolysis of bio-
mass may be predicted by pyrolysis of these constituents. There-
fore, degradation of cellulose of which material properties are
listed in Table 5 [82] is also employed with the current model.
Experiments were carried out by Milosavljevic and Suuberg [83]
with heating rates of 100.0 °C/min and 1000.0 °C/min, respectively.
The detailed pyrolysis model of Ranzi et al. [13,12] was employed
to validate the current numerical approach. Its predictions are
shown in Fig. 15 and compared to experimental data. Predicted
results agree well with measured residual mass fractions of cellu-
lose for both experiments with heating rates of 100.0 °C/min and
1000.0 °C/min, respectively. Both measurements and predictions
indicate a final char yield of 8%. Although, deviations may be
attributed to experimental uncertainty, the current reaction mech-
anism, detailed though, is still to be considered as an approxima-
tion to a rather complex degradation process of cellulose. Hence,
deviations stem also from an insufficient representation of the
entire process. However, it is believed that an approach similar
to the current scheme is sufficient to represent engineering appli-
cations with a required accuracy.
3.6. Pyrolysis of lignin
Pyrolysis of lignin was described by a detailed reaction
mechanism developed by Ranzi et al. [13,12], that includes various
product species. These reactions were employed to predict pyroly-
sis of lignin with its properties listed in Table 6.
Predictions obtained were compared to experimental data of
Jakab et al. [15], who conducted experiments with a heating rate
of 20.0 °C/min and is depicted in the following Fig. 16. Good agree-
ment between measured and predicted residual mass fraction was
obtained including a final char yield of 30%.
 B. Peters / Fuel 90 (2011) 2301–2314 2311

Fig. 13. Residual mass fraction during pyrolysis of casuarina at a heating temperature of 410 °C.

Fig. 14. Centre temperature during pyrolysis of casuarina at a heating temperature of 410 °C.

4. Summary equations for mass, momentum, species and energy. These conser-
vation equation are coupled with reaction schemes ranging from
The current numerical approach employs a detailed model single one-step reactions to multiple reaction system to describe
based on one-dimensional and transient differential conservation degradation of various biomass. Kinetic data of respective reactions

Table 5 Table 6
Properties of cellulose. Properties of lignin.

Property Value Property Value

Density q 650:0 kg=m3 Density q 650:0 kg=m3
Specific heat cp 2333:0 J=kg K Specific heat cp 2300:0 J=kg K
Conductivity kpine 0:1256 W=m K Conductivity kpine 0:1256 W=m K
Conductivity kchar 0:1 W=m K Conductivity kchar 0:1 W=m K
Porosity  0.7 Porosity  0.7
Pore diameter dp 50:0  10:06 m Pore diameter dp 50:0  10:06 m
Tortuosity s 1.0 Tortuosity s 1.0
2312 B. Peters / Fuel 90 (2011) 2301–2314
Fig. 15. Pyrolysis of cellulose with a heating rate of 100.0 °C/min and 1000.0 °C/min.
Fig. 16. Pyrolysis of lignin with a heating rate of 20.0 °C/min.
were taken from literature derived from dust samples within the
kinetically controlled regime. Boundary conditions, e.g. heating
rates as prevailed during the experiments were applied without
further empirical correlations to predict pyrolysis of a large range
of biomass particles of different sizes and materials. Predictions
obtained from the present numerical approach yielded good
agreement with experimental data without exception. Thus, the
resolution in time and space of the current model proved to be well
suited to describe pyrolysis. Furthermore, kinetic data from litera-
ture with sufficient accuracy, preferably obtained in the kinetically
controlled regime, is quite suitable to be employed with a detailed
pyrolysis model to describe pyrolysis of biomass. Hence, numerical
approximations with a lower degree of accuracy are bound to fail
or have to include further empirical correlations, that compensate
for a loss of accuracy. Since, the model proved to be applicable un-
der various boundary conditions and materials, it is well suited to
predict degradation of engineering applications such as fixed bed,
fluidized bed, rotary kiln or grate systems. The focus of further re-
search will be concentrated on the application of the numerical
tool particularly in forward or backward acting grate systems.
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