Biomass and Bioenergy 22 (2002) 41–53

Modeling thermally thick pyrolysis of wood

Kenneth M. Brydena; ∗ , Kenneth W. Raglandb , Christopher J. Rutlandb
a Department of Mechanical Engineering, Iowa State University, Ames, IA 50011-2161, USA
b Department of Mechanical Engineering, University of Wisconsin-Madison, Madison, WI 53706, USA

Received 21 September 2001; accepted 21 September 2001

Abstract
A general model of the pyrolysis of a wood slab is presented and validated with a set of heat release data. The model is
applied to particle half-thicknesses from 5
m to 5 cm, temperatures from 800 to 2000 K, and moisture contents from 0%
to 30%. Internal temperatures, pyrolysis rates and yields of tar, hydrocarbons and char are presented. Four pyrolysis regimes
are identi2ed, depending on external temperature and particle size: thermally thin—kinetically limited, thermally thin—heat
transfer limited, thermally thick, and thermal wave regimes.
c 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Modeling; Wood; Pyrolysis; Fire

1. Introduction contents with or without external combustion. In this

Understanding the mechanisms and rates of wood
combustion is important for modeling building 2res
and for designing wood stoves, furnaces, and boilers.
Fires in buildings involve large wood slabs. Stoves
typically use stick wood and small logs. Furnaces
and boilers are designed for sawdust, woodchips,
chunkwood, or logs. Modeling combustion of these
wood fuels involves applying chemical kinetics, heat
transfer, and mass transfer to drying, pyrolysis, char,
and external gas phase processes. A detailed computa-
tional model of wood combustion has been developed
and validated by Bryden [1]. This wood combustion
model handles the full range of sizes and moisture
∗ Corresponding author. Tel.: +1-515-294-3891; fax: +1-515-
294-3261.
E-mail address: kmbryden@iastate.edu (K.M. Bryden).
paper, this model has been utilized to examine the
eAect of wood size, moisture content, and temperature
on the rate of pyrolysis, and formation of tar, volatiles,
and char.
2. Background
Several researchers have developed detailed numer-
ical models of wood pyrolysis [2–11]. In general, these
models include gas Bow within the particle in con-
junction with gas phase continuity, solid phase con-
tinuity, and energy conservation within the particle.
Multiple, competing two-step reactions are used to
model pyrolysis. The primary assumptions of these
models are one-dimensional heat and mass trans-
port and local thermal equilibrium between the solid
and the gaseous species. In general, several areas of
concern in wood pyrolysis are not modeled. These

0961-9534/02/$ - see front matter  c 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 9 6 1 - 9 5 3 4 ( 0 1 ) 0 0 0 6 0 - 5
42 K.M. Bryden et al. / Biomass and Bioenergy 22 (2002) 41–53

Nomenclature

A pre-exponential frequency factor  dynamic viscosity

dp eAective pore diameter  density
ė rate of chemical energy release ˜ uncorrected density (see, Ref. [1])
E activation energy  Stefan–Boltzman constant
f shrinkage factor !˙ i mass rate of production of species i per
G mass Bux unit volume
h heat transfer coeHcient
Ihk heat of reaction for reaction k Dimensionless numbers
Ih0i heat of formation of species i Bi Biot number
i internal energy Py
second (external) pyrolysis number
k rate constant
Lc characteristic length Subscripts
p pressure C char
Q external radiative heat Bux cond conduction
R universal gas constant dry dry
t time eA eAective
T temperature g gas
Wi molecular weight of species i L light hydrocarbons
X speci2c gravity M moisture
Yi mass fraction of species i pyr pyrolysis
r recondensation
Greek letters rad radiation
 void fraction T tar
 reaction progress variable V water vapor
 permeability W wood
’ emissivity ∞ background
 thermal conductivity

include char shrinkage, diAusive transport of volatile
species within the solid matrix, recondensation of
volatile species, and char combustion and gasi2cation.
A one-dimensional model for dry wood with char
shrinkage [4] and several one-dimensional models of
wet wood pyrolysis [7–11] have been presented.
The kinetics of wood pyrolysis have been modeled
by a number of researchers, and several reviews of this
area have been completed [12,13]. The most complete
wood pyrolysis models currently available use mul-
tiple, competing two-step reactions. The most com-
mon primary reaction scheme is wood pyrolyzing to
tar, gas, and char [11,14 –18]. By using the secondary
reactions, product yield becomes a function of tem-
perature, heating rate, and residence time within the
particle. In her review Di Blasi [13] recommends the
use of two secondary reactions in which tar cracking to
lighter gases and tar repolymerization to char is mod-
eled. This pyrolysis scheme is utilized in this paper.
In general, the primary pyrolysis reaction rates are
represented with an Arrhenius-type temperature de-
pendence and 2rst-order dependence with respect to
the mass of the unreacted wood. Chan, Kelbon, and
Krieger [11] present kinetic rate parameters for ther-
mally thick combustion in which the pressure wave
within the particle is not modeled and the resistance
to Bow within the particle was assumed to be neg-
ligible. Nunn et al. [16] present experimental-based
kinetic rate parameters which are for the overall de-
composition of gas. Similarly, Koufopanos et al. [15]
 K.M. Bryden et al. / Biomass and Bioenergy 22 (2002) 41–53
have presented kinetics parameters for gas and tar as
a group. Thurner and Mann [18] present parameters
for decomposition to tar, gas, and char based on par-
ticles small enough that mass transfer and secondary
reactions are negligible. In this study, the parameters
of Thurner and Mann [18] are used for the tar, gas,
and char reactions. Secondary vapor phase decompo-
sition of tar is generally modeled in the literature as
a homogeneous process proportional to the tar den-
sity with an Arrhenius-type temperature dependence
[13,19 –23]. Lede et al. [24] note the wide acceptance
of the tar-to-gas kinetic rate parameters of Liden et al.
[19], which have been used by Di Blasi [13] to model
pyrolysis under a wide range of conditions. Limited
information is available on the tar-to-char reaction.
Di Blasi [13] has estimated this reaction to proceed at
1
40 th the rate of the tar-to-gas reaction.
Moisture has a signi2cant impact on the overall
biomass combustion process, including changing the
pyrolysis products and increasing the overall combus-
tion time. Experimental studies (e.g. [26 –28]) provide
temperature as a function of time within the wood un-
der thermally thick combustion conditions. In these
experiments, the wood at a particular location rises
from ambient temperature to a plateau within a few
◦
degrees of 100 C and then continues to rise. In dry
wood there is little or no drying plateau, and as mois-
ture content increases, the span of this plateau in-
creases. Currently, there are four basic ways to model
the drying of wood under combustion heat Buxes. The
simplest of these is an energy balance in which the
drying front is assumed to be in2nitely thin and an
◦
energy sink at 100 C accounts for the heat of vapor-
ization [8–10]. A second method [11] models drying
of wood as an additional chemical reaction using an
Arrhenius expression. A third method [2] uses an al-
gebraic expression for temperature as a function of
moisture content to describe equilibrium moisture con-
tent in wood in an atmosphere of superheated steam.
A fourth method, the diAusion model, is based on re-
search and numerical modeling of low temperature
◦
(¡ 200 C) drying of wood [25]. The movement of
unbound water and gas within the wood is modeled
using a modi2ed form of Darcy’s law, and bound wa-
ter movement is modeled using a diAusion expression.
Evaporation is driven both by the saturation pressure
of the liquid water and the partial pressure of the water
vapor [7].
43
Each of the drying models has its advantages and
disadvantages, and none has a clear advantage over the
others. The energy balance model is simple and easy
to implement numerically. Its primary disadvantage is
that the drying zone is reduced to an in2nitely thin
moving surface and may not model drying and pyrol-
ysis of small particles where the thickness of the dry-
ing zone is not negligible compared to the thickness
of the material. The kinetic scheme has two primary
advantages. The numerical results match the experi-
mental results in that temperature rises continuously
into and out of a drying plateau, and the scheme can
be implemented as one more Arrhenius-type relation-
ship in a numerical code that handles many of these.
The primary disadvantage of using an Arrhenius re-
lationship for drying is that many diAering physical
phenomena are lumped into a single expression. Addi-
tionally, only one-way coupling is maintained between
the drying rate and pressure evolution. In the algebraic
model [2] no drying of the wood occurs at tempera-
◦
tures ¡ 100 C. The algebraic expression is only appli-
cable to relatively dry materials with moisture contents
¡ 14%. Moisture content above this limit is handled
in the same manner as the thermal model of drying.
Additionally, it is unlikely that equilibrium moisture
conditions exist within wet wood exposed to combus-
tion level Buxes. The diAusion model accounts for both
drying and recondensation within the wood, however,
the parameters have been experimentally veri2ed only
for low temperature wood drying and not for combus-
tion heat Buxes. Recondensation is accounted for by
assuming that the partial pressure of the water vapor
is equal to its equilibrium pressure. Additionally, the
pressure wave is tightly coupled to the drying rate.
Because of this, areas that are not addressed in current
models such as cracking and the multi-dimensional
aspects of water movement that impact the pressure
wave can have signi2cant impact on the drying rate,
recondensation, and temperature pro2le.
3. Description of the mathematical model
A wet wood slab of thickness L, subjected on
one surface to a radiant heat Bux is modeled. The
one-dimensional wood slab is a porous solid, and the
void volume is initially 2lled with humid air. Exter-
nal heat transfer by radiation is assumed to be much
44 K.M. Bryden et al. / Biomass and Bioenergy 22 (2002) 41–53

Table 1
Parameters used for drying, recondensation, and pyrolysis reactions

Reaction A E Ref. Heat of reaction Ref.

(s−1 ) (kJ mol−1 ) (MJ kg−1 )

Pyrolysis reactions
1 k
Wood →gas 1:44 × 104 88.6 18 −0:42 [3]
k2
Wood →tar 4:13 × 106 112.7 18 −0:42 [3]
3 k
Wood →char 7:38 × 105 106.5 18 −0:42 [3]
k4
Tar →gas 4:28 × 106 107.5 19 0.04 [19]
k5
Tar →char 1 × 105 107.5 13 0.04 [19]

Process A E Ref. Heat of reaction Ref.

(s−1 ) (kJ mol−1 ) (MJ kg−1 )
Drying
6 k
Moisture→water vapour 5:13 × 1010 88 1,11 −2:44 [32]

Process k7 Ref. Heat of reaction Ref.

(cm−1 ) (MJ kg−1 )
Recondensation
7 k
Water vapour →moisture 125 1 2.44 [32]
dGV ◦
!˙ r = − = k7 G V ; T ¡ 95 C
where dx ◦
!˙ r = 0; T ¿ 95 C

greater than that by convection. The radiant Bux is
incident on the slab from a 2xed temperature external
source. As the slab is heated, the energy required
to dry the wet wood and the diAering eAective con-
ductivities between the unreacted, wet wood and the
char result in a thermal wave with steep temperature
and species gradients. Material properties (e.g., void
fraction, permeability, thermal conductivity, speci2c
heat), volume occupied by the solid, pressure, and
temperature all continuously change with time. Py-
rolysis of wood to gas, tar, and char; and secondary
pyrolysis reactions decomposing tar to gas and char
form a two-step, 2ve-reaction model for pyrolysis.
The complete set of reaction parameters for drying,
pyrolysis, and recondensation is given in Table 1.
Wood drying, pyrolysis, and combustion consist of
two separate domains, a porous solid and an external
gas phase with the surface of the char providing the
interface between these two domains. As the surface
is heated, the wood is 2rst dried and then pyrolyzed
by radiant and convective heat transfer. A small
portion of the pyrolysis gases and water vapor are
convected inward, while the greater portion of py-
rolysis gases and water vapor pass through the char,
providing blowing at the surface. The pyrolysis gases
may react with oxygen within the boundary layer
to form a Bame zone that feeds back energy to the
surface. In this paper, radiant energy from external
surfaces dominates, and an inert external gas is as-
sumed. The solid phase equation set used to describe
drying and wood pyrolysis within the solid matrix
is based on the diAerential conservation equations of
mass, species, and energy (Table 2).
This equation set is derived using the following
assumptions: (1) wood is a one-dimensional porous
reacting media with a well-de2ned surface free of
cracking; (2) gas and solid are in local thermal equilib-
rium; (3) diAusive transport of species within the pores
is negligible; (4) the inertial terms within the mo-
mentum balance equation are negligible, and the
Bow can be described using Darcy Bow; and (5) the
shrinkage occurs only in the radial direction. The 2rst
assumption must be applied with care. Although this
is a common assumption, there are few real cases
 K.M. Bryden et al. / Biomass and Bioenergy 22 (2002) 41–53 45

Table 2
Summary of the equations used to model solid phase pyrolysis of wood

Conservation of wood @˜W =@t = !˙ W

Conservation of char @˜C =@t = !˙ C

Conservation of moisture @˜M =@t = !˙ M




@ fp @ p  @p !˙ V !˙ L !˙ T
Pressure evolution +f =R + +
@t T @y T  @y WV WL WT

Conservation of tar @(fYT g )=@t + f@(YT Gg )=@y = !˙ T

Conservation of water vapor @(fYV g )=@t + f@(YV Gg )=@ = !˙ V

Conservation of pyrolysis gases @(fg )=@t + f@Gg =@y = !˙ g


@(˜W iW + ˜C iC + ˜M iM ) @((YL hL + YT hT + YV hV )g u) @ @T 
Conservation of energy +f =f eA + Ih0i !˙ i
@t @y @y @y

Rate of production of wood !˙ W = − (k1 + k2 + k3 )˜W

Rate of production of char !˙ C = k3 ˜W + fk5 T

Rate of production of moisture !˙ M = − k6 ˜M + k7 GV

Rate of production of tar !˙ T = k1 ˜W − f(k4 + k5 )YT g

Rate of production of vapor !˙ V = k6 ˜M − k7 GV

Rate of production of gas !˙ g = (k1 + k2 )˜W − fk5 T + k6 M − k7 GV

Heat release rate ė = k1 ˜W Ih1 + k2 ˜W Ih2 + k3 ˜W Ih3 + fk4 YT g Ih4
+fk5 YT g Ih5 + (k6 ˜M − k7 GV )Ih6

where this can be fully justi2ed. Thermal and trans- where

port properties are strongly dependent on orientation. ◦
!˙ dry = 0; T ¡ 95 C;
Even so, signi2cant insight can be gained by consid- (1)
◦
ering a one-dimensional model. !˙ dry = k6 ˜M ; T ¿ 95 C:
Assumption two is reasonable based on the Peclet
number [11,29]. By similar discussion it can be shown Chan et al. [11] suggest rate parameters for dry-
that diAusive transport of species within the wood ing of A6 = 5:13 × 106 s−1 and E6 = 88 kJ mol−1 .
pores is negligible [11]. Assumption four is reason- Using these parameters results in a drying plateau at a
able based on the small Reynolds number (¡ 0:01) higher temperature than expected for thermally thick
resulting from the small diameter of the wood pores wood combustion. In this work, the pre-exponential
[29]. Assumption 2ve is based on the assumption of a frequency was adjusted by multiplying A6 above by
◦

one-dimensional media. Derivation of the solid phase 104 to provide a drying plateau between 100 C and
◦

equations with shrinkage is presented in Ref. [1]. 120 C.

In this work drying is modeled using an Arrhenius- Recondensation of the water vapor within the un-
type expression. reacted wood is modeled by assuming that within the
cooler, unreacted regions of the wood, the water va-
k
Moisture →6 water vapor; por exists in a supersaturated state and is condensed
46 K.M. Bryden et al. / Biomass and Bioenergy 22 (2002) 41–53

at a rate proportional to the mass Bux of water vapor. values and correlations used for the physical param-
k
eters are presented in Table 3. The number of grid
Water vapor →7 moisture; points is chosen to provide good spatial resolution of
the steep temperature and species gradients encoun-
where tered. To achieve this, the number of grid points is
!˙ r = − dGV =d x = k7 GV ; T ¡ 95 C
◦
varied depending on the thickness of the wood and
◦
(2) the pyrolysis conditions. The number of grid points
!˙ r = 0; T ¿ 95 C: for the solid phase ranged from 21 to 1201. The time
steps for the solid phase are chosen to ensure stability
The proportionality constant is chosen by comparison
and accuracy of the solution. The time steps ranged
with the experimental results. A recondensation factor
from 1 × 10−4 to 1 s. Details of the numerical model
of 125 cm−1 is used in all cases [1].
are given in Ref. [1].

4. Numerical model
The conservation equations for the solid domain are
solved using second-order accurate 2nite diAerencing.
A moving boundary incorporates both char shrink-
age and surface recession due to char combustion and
gasi2cation. The diAerenced equations developed are
implemented in a Fortran-based computer code. The
5. Validation of the model
The model was validated using the experimental
work of Tran and White [27]. In these experiments
wood blocks, built by gluing strips of wood together
to form 15 cm ×15 cm ×6:4 cm blocks, were exposed
on one of the 15 cm × 15 cm sides in air to a radiant

Table 3
Values and correlations of physical parameters used in the model

Property Correlation=value Ref.

Void fraction  = 1 − (W + C )=1500 − M =1000 [34]

Permeability  = W + (1 − )C where  = mW =mW; 0

W = 1 × 10−2 darcys [1]
C = 1 darcys [1]

Thermal conductivity eA = cond + rad

rad = =(1 − )’p dp 4T 3 [35]
’p = 0:9 Assumed
cond = M + W + (1 − )C
W = 0:200X + 0:0238 (W m−1 K −1 ) [33]
M = X (0:0040M ) (W m−1 K −1 ) [33]
C = 0:105 W m−1 K −1 [36]

Speci2c heat cW = 0:003867(T − 273:2) + 0:1031 (kJ kg−1 K −1 ) [37]

cC = 1:39 + 0:00036T (kJ kg−1 K −1 ) [38]
cpyr = 2:4 kJ kg−1 K −1 [1]
cM = 4:18 kJ kg−1 K −1 [32]

Molecular weight WV = 18 × 10−2 kg mol−1 [32]

WL = 26 × 10−2 kg mol−1 [1]
WV = 110 × 10−2 kg mol−1 [1]

Dynamic viscosity  = 4:847 × 10−7 T 0:64487 (kg m−1 s−1 ) [1,32]

 K.M. Bryden et al. / Biomass and Bioenergy 22 (2002) 41–53 47

1.5
Southern Pine
1.0

0.5

0.0
20 30 40 50 60

Char Rate (mm min )

1.5

-1
Basswood
1.0

0.5

0.0
20 30 40 50 60
1.5
Red Oak
1.0
Fig. 1. Internal temperature history of 64 mm thick red oak exposed 0.5
on one surface to a 38 kW m−2 radiant heat Bux;—model results,
the shaded area is the range of experimental results from Ref. [27]. 0.0
20 30 40 50 60
-2
Heat Flux (kW m )

Fig. 2. Average charring rate as a function of the radiant heat Bux

heat Bux. The dominant direction of the heat Bux was
tangential to the annual rings. Temperatures were mea-
sured as a function of time at 6, 12, 18, 24, and 36 mm
from the surface. The char depth was assumed to cor-
◦
respond to a temperature of 300 C. When the tem-
perature at the thermocouple 36 mm from the surface
◦
reached 300 C, the experiment was stopped and the
average charring rate determined. The radiant Bux re-
ported accounted for the increase in the temperature
of the heating environment and reradiation back to the
sample due to the Bames.
The measured and modeled internal temperatures
as a function of time for test locations within a wood
slab are shown in Fig. 1. The temperature at a location
rises 2rst to the drying plateau and then rises smoothly
through the pyrolysis zone. When completely charred,
the temperature rise slows down and the temperature
through the char layer tends toward a steady state tem-
perature pro2le between the hot surface and the cold
unreacted core. As shown, the model matches well
with the drying plateau, the 2nal temperatures, and the
overall temperature pro2le. The temperature pro2le of
the model slightly leads the experimental data until
a depth of 36 mm where the model lags the experi-
mental data. It is suspected that this occurs because
cracking of the solid matrix increases with time, thus
increasing the conduction rate within the particle. This
eAect is not included in the model.
The average charring rate as a function of heat Bux
for red oak, basswood, and southern pine is shown in
for wood in air; —, model results; •, measurements of Ref. [27].
Fig. 2. The density, moisture content, and char shrink-
age coeHcients used in the model are those reported
by Tran and White [27] and are given in Table 4.
The primary diAerences between these three woods
are density and the char shrinkage. The less dense the
wood, the smaller the mass of water to vaporize and
the smaller the mass of wood to heat and pyrolyze,
which results in faster charring rates. As the heat Bux
rises, the char shrinkage decreases due to less time
at temperature, resulting in increased char thicknesses
insulating the unreacted core from the Bux, raising
the surface temperature, and increasing the convective
heat loss. As a consequence, the rise in the charring
rate tends to Batten as the radiant heat Bux increases.
As shown, the match between the model and the exper-
imental data is good, even though generalized wood
pyrolysis kinetics are used in the model.
6. Modeling results
The numerical model was used to examine the
impact of moisture content and particle size on the
wood pyrolysis rate and regime. Generally, based on
transient conduction within the wood particle, wood
pyrolysis has been divided into two separate regimes,
thermally thin and thermally thick. Within the
48 K.M. Bryden et al. / Biomass and Bioenergy 22 (2002) 41–53
Table 4
Wood properties used in the model
Species Density Ref.
(g cm−3 )
Basswood 420 27
Poplar 504 28
Red oak 660 27
Southern pine 508 27
thermally thin regime, pyrolysis is divided into kineti-
cally controlled pyrolysis and heat transfer controlled
pyrolysis based on the time scales of the thermally
thin combustion and pyrolysis kinetics [30]. Based on
the modeling results, it is suggested that in addition
to thermally thin and thermally thick, a third regime
be added—the thermal wave regime.
The pyrolysis cases discussed here are for a 2xed
background temperature that provides a radiant Bux
that dominates the heat transfer to the particle. Oxygen
levels in the freestream are set to 0% with no gas phase
or external char reactions. The half-thicknesses exam-
ined range from 50
m to 5 cm. Background tempera-
tures range from 800 to 2000 K, and moisture contents
range from 0% to 30%. This covers a wide range of
wood combustion interests, including 2res with rela-
tively low temperatures; combustion of large particles,
such as wood chunks or logs in a 2xed bed at high
temperature; wood chip gasi2cation and combustion;
and suspension burning.
The Biot number, based on the conductivity of dry
wood and modi2ed to account for radiant heat transfer,
can be used to assess the relative rates of internal and
external heat transfer.
Bi = hrad Lc =;
where
hrad = ’(Ts + T∞ )(Ts2 + T∞
2
):
The surface temperature, Ts , is not known indepen-
dently from the model and varies during pyrolysis
in most cases; therefore, it is assumed to be equal
to background temperature. This overestimates hrad ;
to account for this, hrad is divided by a factor of 2.
This approximation places hrad within about 25% of
the actual value and therefore does not signi2cantly
Shrinkage factor Ref. Shrinkage factor Ref.
(drying) (pyrolysis)
0.934 33 0:354 + 0:003Q [27]
0.954 33 0.672 [28]
0.956 33 0:446 + 0:005Q [27]
0.958 33 0:402 + 0:003Q [27]
impact the interpretation of the Biot number. In tran-
sient conduction the error associated with the lumped
capacitance method (thermally thin assumption) is
small if Bi ¡ 0:1 [31]. For the case of solid particle
drying, Ragland and Borman [32] recommend that the
particle be considered to be thermally thin if Bi ¡ 0:2.
Based on a review of the model output, the higher
limit of Bi ¡ 0:2 is appropriate. This results in maxi-
mum temperature diAerence across the particle during
pyrolysis of about 30 –35 K. In this case, the pyroly-
sis rate obtained from using the average temperature
varies by ¡ 10% from the pyrolysis rate obtained con-
sidering the temperature gradient. This is reasonable
based on the available kinetics and physical properties.
Since moisture increases the conductivity of wood, the
Biot number increases as the particle dries. Because
of this, the limiting Bi number for thermally thin py-
rolysis occurs after the wood is dried, and hence the
wood particle size limit for thermally thin combustion
is independent of the moisture content.
In thermally thin pyrolysis of a thin wood slab
exposed to relatively low temperature (e.g. 50
m
half-thickness and 800 K), the resistance to heat trans-
fer within the particle is small compared to the exter-
nal heat transfer. Drying and pyrolysis occur in series
(3) (Fig. 3). Moisture content and particle size do
not aAect the pyrolysis rate. At 2000 K, a 15
m
half-thickness (30
m thick) is the largest size for a
(4) wood slab that the thermally thin assumption is valid.
This size limit increases to 250
m half-thickness as
the temperature decreases to 800 K. For wood par-
ticles that can be treated as cylinders the thermally
thin limit is a diameter of 60
m and 1 mm at 2000
and 800 K, respectively. For wood particles that can
be treated as spheres the thermally thin limit is a
diameter of 90
m and 1:5 mm at 2000 and 800 K,
respectively.
 K.M. Bryden et al. / Biomass and Bioenergy 22 (2002) 41–53 49

0.25 0.020
Total
Mass Flux (kg m s )

0.20
-2 -1

0.015

Mass Flux (kg m s )

-2 -1
Tar Total
0.15 Tar
0.010
Water Vapor
0.10
Light Hydrocarbons
+ Tar
0.005
0.05
Water

0.00 0.000
0.0 0.1 0.2 0.3 0.4 0 50 100 150
Time (s) Time (s)

Fig. 3. Mass Bux vs. time for poplar with a 50
m half-thickness Fig. 5. Mass Bux vs. time for poplar with a 0:5 cm half-thickness
and 30% moisture exposed to an 800 K radiant temperature Bux and 20% moisture exposed to a 1000 K radiant temperature.
in nitrogen.

0.07

Mass Flux (kg m s )

700 2 -1 0.06
Original distance from the centerline
600 0.05

500 0.5 cm 0.04

Temperature ( C)

Water vapor
o

400 0.4 cm 0.03

0.3 cm Light Hydrocarbons
Total
300 0.2 cm 0.02

200 0.1 cm 0.01

100
0 Time (s)
0 50 100
Time (s)
Fig. 4. Internal temperatures vs. time for poplar with a 0:5 cm
half-thickness and 20% moisture exposed to a 1000 K radiant
temperature.
In thermally thick pyrolysis (e.g. 0:5 cm half-
thickness and 1000 K) the relative rates of internal
and external heat transfer are similar. Throughout the
drying and pyrolysis process there is a temperature
gradient across the particle and at a given location
there is a transient temperature plateau due to drying
(Fig. 4). The drying and pyrolysis zones in the par-
ticle overlap only slightly (Fig. 5). As a result, the
moisture content has limited impact on the product
yield. In contrast, particle size does aAect the product
yield by increasing the holdup time in the particle and
the temperature of the tars and pyrolysis gases within
the particle.
Tar
0.00
0 100 200 300 400
150 200
Fig. 6. Mass Bux vs. time for poplar with a 2 cm half-thickness
and 30% moisture exposed to a 1500 K radiant temperature in
nitrogen.
With a relatively large particle and high background
temperatures (e.g. 2 cm half-thickness and 1500 K) a
thermal pyrolysis wave results (Fig. 6). The internal
rate of heat transfer is slow relative to the external
rate of heat transfer, and there is a large temperature
gradient across the particle. At a given location there
is a transient temperature plateau due to drying. How-
ever, in contrast to the thermally thick mode, pyroly-
sis and drying occur simultaneously throughout most
of the pyrolysis. A thermal wave, which dries and py-
rolizes the particle as it moves through the particle,
is established and moves to the center of the particle.
The temperature within the pyrolized char region rises
quickly compared to the non-reacted moist wood core
because of the smaller heat capacity of the char. This
50 K.M. Bryden et al. / Biomass and Bioenergy 22 (2002) 41–53
diAerence in heat capacity, combined with the energy
required to dry the wood, thins the drying and pyroly-
sis regions and brings them relatively close together.
No current guidelines are available for the divi-
sion between the thermally thick and thermal wave
regimes. For the purposes of this study, the pyrolysis
wave regime was determined to be when at least 20%
of the solid core is still undried and at least 20% of
the wood has been pyrolyzed. This de2nition ensures
that drying and pyrolysis occur simultaneously for a
signi2cant portion of the combustion process. As the
char layer thickens, the heat transfer rate into the un-
reacted core slows down, and the drying and pyrolysis
rates gradually slow down (Fig. 6). After the particle
is dried, the temperature of the core rises quickly and
the small portion of the remaining wood is rapidly py-
rolized. Product yield is a function of both moisture
content and particle thickness. Higher moisture con-
tent lowers the temperature of the pyrolysis region and
the temperature within the char, thus reducing the rate
of secondary reactions. This increases the tar yield and
decreases the light hydrocarbon yield. As particle size
increases, the char layer thickens, providing more time
for secondary reactions and decreasing the tar yield.
This division between the thermally thick and the
pyrolysis wave regime occurs at Bi ≈ 10 based on
the conductivity of the dry wood. This limit is a weak
function of particle size and moisture content increas-
ing from Bi = 8 for 1 mm particles with 20% moisture
to Bi = 15 for 4 cm particles with 0.1% moisture. To
understand why this limit is a function of the Bi num-
ber, remember that the transient non-dimensionalized
temperature pro2le in a homogeneous, non-reacting
plane wall is a function of the Bi number [31]. As the
Biot number increases the temperature drop across the
particle increases. In moist wood the aAect is accen-
tuated by the energy required to dry the particle and
the change in material properties as the wood is py-
rolyzed to char. The moisture slows the inward move-
ment of the thermal wave while the lower density of
the char allows the temperature pro2les within the char
to respond more quickly than the temperature pro2les
within the unreacted wood. As a consequence, in large
wood particles the pyrolysis and drying zones are ad-
jacent to each other and driven by a thermal wave.
The impact of particle size, temperature, and mois-
ture content on pyrolysis product yield is summarized
in Fig. 7. As shown, the yields of tar and light hydro-
1.0
Product Yield (mass fraction)
0.8
1500 K 2000 K
Tars
0.6
800 K 1000 K
0.4
2000 K
0.2 1000 K
1500 K
Light HC
0.0 800 K
0.03 0.1 1 10 30
Half-Thickness (mm)
Fig. 7. Pyrolysis product yields vs. thickness for poplar parti-
cles exposed to various radiant temperatures and moisture levels
of—0% and, - - - 30%.
carbons are inversely coupled, while the char yield re-
mains relatively constant. For small particles tar yield
increases as a function of temperature from about 60%
at 800 K to about 74% at 2000 K. Conversely, light
hydrocarbon yield decreases as a function of tempera-
ture from about 10% at 800 K to about 5% at 2000 K.
As particle size increases, the secondary reactions
reduce the tar yield and increase the light hydrocarbon
yield. The impact of the secondary reactions increases
with temperature. At 800 K the tar yield is reduced by
about one-third from approximately 60% for 50
m
particles to 40% for 3 cm particles, while the light
hydrocarbon yield is increased by about three times
from approximately 10% for 50
m particles to 30%
for 3 cm particles. At 2000 K the tar yield is reduced
by about 90% from about 74% for 50
m particles to
about 6% at 3 cm, and the light hydrocarbon yield is
increased by about 12 times from about 5% for 50
m
particles to about 60% at 3 cm. At high temperatures,
product yield is a weak function of moisture content.
At higher moisture contents the temperature in the
char layer is slightly reduced, reducing the rate of the
secondary reactions.
Pyrolysis time as a function of particle size, tem-
perature, and moisture content is summarized in
Fig. 8. As shown, the impact of moisture content on
the total pyrolysis time is small compared to increases
in pyrolysis times due to changes in background
temperature and particle thickness. As the parti-
cle becomes thinner at 800 K, the overall pyrolysis
 K.M. Bryden et al. / Biomass and Bioenergy 22 (2002) 41–53 51

10
4
thermally thin, kinetically controlled combustion can
800 K
1000 K
be assumed within the region Bi ¡ 0:2 and Py
¿ 5.
Additionally, within a furnace or 2re environment the
3
10
1500 K
2
Py' = 5 2000 K assumption of Py
¿ 5 may be able to be relaxed at
10 higher temperatures. However, particle sizes smaller
Region 1
1
800 K
than 1
m are required to reach this regime at temper-
Time (s)

10
Region 4
10
0
Region 2
-1
10 Bi = 10
Region 3
-2
Bi = 0.2
10
-3
10
0.01 0.1 1 10
Half-Thickness (mm)
Fig. 8. Pyrolysis time vs. half-thickness for poplar particles exposed
to various radiant temperatures and moisture levels of—0% and,
- - - 30%. Region 1 is the kinetically limited, thermally thin
pyrolysis regime, Region 2 the heat transfer limited, thermally thin
pyrolysis regime, Region 3 the thermally thick pyrolysis regime,
Region 4 the thermal wave pyrolysis regime.
time tends towards a constant time independent of
moisture content or thickness. This is expected; in
this region the particle is thermally thin and kineti-
cally controlled. As temperature increases, this region
is reached at smaller and smaller particle sizes be-
cause the rate of pyrolysis increases exponentially as
the temperature rises, requiring higher external heat
transfer rates to reach the kinetically limited region.
The relative rates of external heating and pyrolysis
can be assessed by considering the external pyrolysis
number, Py
. The second or external pyrolysis number
is
Py
= hrad =(kpyr W cW d):
The thin dotted lines represent the pyrolysis time
for an in2nitely thin, kinetically controlled particle.
The diAerence between the thin dotted line and the
solid line at the same temperature can then be seen
as the error associated with the in2nitely thin, ki-
netically controlled assumption at various particle
half-thicknesses. Pyle and Zaror [30] recommend a
limit of Py
¿ 10 for the thermally thin, kinetically
controlled regime. As shown, the error in pyrolysis
times at Py
= 5 is ¡ 25% at 800 K. At higher temper-
atures this error is signi2cantly smaller. Based on this,
atures of 1500 K or higher. As shown, most pyrolysis
1000 K within high temperature environments occurs in the
thermally thick and pyrolysis wave regimes.
Fig. 8 provides insight to a number of practical
systems. For example, consider co-2ring very 2nely
1500 K
chipped wood with coal. Assume Bat particles 0:2×2×
10 mm in size. The half-thickness of the characteristic
100 length is 0:1 mm and typical background temperatures
are between 1500 and 2000 K placing the pyrolysis
in the thermally thick regime. Moisture content of the
feed stock will not aAect the pyrolysis gas yield and
will have a limited impact on the pyrolysis time. Con-
sider wood gasi2cation of poplar chips. Typical wood
chip sizes are in the range of 0:3 × 1:5 × 3 cm, the
half-thickness of the characteristic length is 1:5 mm.
Using a background temperature of 1000 K, the py-
rolysis occurs in the thermally thick regime. Changes
in moisture content will impact pyrolysis time but not
the product yield. Both stick wood pyrolysis and 2res
involve very thick particles (half-thickness ¿ 2 cm)
and are in the thermal wave regime. In the case of 2res,
the thermal wave is so evident that pyrolysis rates are
given in cm s−1 [33].
7. Conclusions
Results from a detailed computational model show
that the pyrolysis rate of wood depends primarily
on radiant surface temperature and particle size, and
(6)
secondarily on particle moisture. Predicted pyrol-
ysis times ranged from 10 ms for small particles
at 2000 K to 80 min for large particles at 800 K.
Yields of tar and light hydrocarbons depend on par-
ticle size and temperature and are inversely coupled,
while the char yield remains relatively constant. Four
pyrolysis regimes are denoted: (1) thermally thin—
kinetically limited, Bi ¡ 0:2 and second Py
¿ 5;
(2) thermally thin—heat transfer limited, Bi ¡ 0:2
and Py
¡ 5; (3) thermally thick, 0:2 ¡ Bi ¡ 10; and
(4) the thermal wave regime, Bi ¿ 10. Most practical
applications are in regimes 3 or 4.
52 K.M. Bryden et al. / Biomass and Bioenergy 22 (2002) 41–53
Acknowledgements
The authors wish to thank Robert White of the US
Forest Service Forest Products Laboratory in Madison,
WI, for sharing his detailed experimental results.
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