Combustion and Flame 156 (2009) 1503–1513
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Combustion and Flame
journal homepage: www. elsevier.com/loc ate/combustﬂame
A model for the oxidative pyrolysis of wood
Chris Lautenberger * , Carlos FernandezPello
Department of Mechanical Engineering, University of California, Berkeley, Berkeley, CA 94720, USA
article info
Article history:
Received 26 January 2008 Received in revised form 8 April 2009 Accepted 8 April 2009 Available online 20 May 2009
Keywords:
Wood
Pyrolysis
Oxidative pyrolysis
Charring
Char oxidation
abstract
A generalized pyrolysis model (Gpyro) is applied to simulate the oxidative pyrolysis of white pine slabs irradiated under nonﬂaming conditions. Conservation equations for gaseous and solid mass, energy, spe cies, and gaseous momentum (Darcy’s law approximation) inside the decomposing solid are solved to calculate proﬁles of temperature, mass fractions, and pressure inside the decomposing wood. The con densed phase consists of four species, and the gas that ﬁlls the voids inside the decomposing solid con sists of seven species. Four heterogeneous (gas/solid) reactions and two homogeneous (gas/gas) reactions are included. Diffusion of oxygen from the ambient into the decomposing solid and its effect on local reactions occurring therein is explicitly modeled. A genetic algorithm is used to extract the required material properties from experimental data at 25 kW/m ^{2} and 40 kW/m ^{2} irradiance and ambient oxygen concentrations of 0%, 10.5% and 21% by volume. Optimized model calculations for mass loss rate, surface temperature, and indepth temperatures reproduce well the experimental data, including the experimen tally observed increase in temperature and mass loss rate with increasing oxygen concentration. 2009 Published by Elsevier Inc. on behalf of The Combustion Institute.
1. Introduction
During a compartment ﬁre, combustible solids may be exposed to oxygen concentrations ranging from the ambient value (nor mally 21%) to near zero when a surface is covered by a diffusion ﬂame. The presence or absence of oxygen can affect solid materials’ decomposition kinetics and thermodynamics to different degrees. For example, the thermal stability of polymethylmethacrylate (PMMA) is relatively insensitive to oxygen [1] when compared with polypropylene (PP) and polyethylene (PE) which both show
a 
marked decrease in thermal stability as oxygen concentration 
is 
increased [2] . During wood pyrolysis in an inert environment, 
the volatile formation process is endothermic [3] , but in oxidative
environments such as air, oxidative reactions occurring near the surface are exothermic and can lead to visible glowing. The effect of oxygen concentration on decomposition rates in thermogravimetric experiments has been widely investigated, and models for oxygensensitive decomposition have been devel oped [4,5] . However, there are negligible gradients of temperature and species concentrations in thermogravimetric experiments, and the oxygen concentration that the degrading sample ‘‘feels” is approximated as the ambient value. Consequently, zerodimen sional models based on transient ordinary differential equations can be applied. In comparison, signiﬁcant gradients of temperature and species are usually present during the pyrolysis of a solid fuel slab (for
* Corresponding author. Fax: +1 510 642 1850. Email address: clauten@me.berkeley.edu (C. Lautenberger).
example, in a Cone Calorimeter experiment). Near the exposed sur face, oxygen concentrations may approach ambient values; how ever, there may be little or no oxygen present indepth. Due to these spatial variations in temperature and species concentrations, which can only be simulated by solving partial differential equa tions, modeling oxidative pyrolysis of a solid fuel slab is more com plex than simulating a zerodimensional thermogravimetric experiment. Despite the potentially signiﬁcant effect of oxidative pyrolysis on a material’s overall reaction to ﬁre, modeling the effect of oxy gen concentration on the decomposition of a thermally stimulated solid fuel slab has been infrequently explored. Reaction kinetics and thermodynamics of polymer oxidative pyrolysis have been di rectly related to the freestream oxygen concentration [6,7] . Although many models have been presented for the pyrolysis of wood slabs, rarely are exothermic oxidative reactions explicitly considered. Shen et al. [8] modeled the pyrolysis of several differ ent species of wet wood using three parallel reactions. Although they simulated Cone Calorimeter experiments conducted in air, all three reactions were modeled as endothermic, so oxidative pyrolysis was not explicitly considered. Oxidative pyrolysis of wood has been simulated by including the effect of exothermic reactions in the exposed face boundary condition [9,10], but oxida tive reactions do not necessarily occur only immediately at the ex posed surface. This paper presents a comprehensive model for the oxidative pyrolysis of a wood slab. A novel feature is that conservation equa tions are solved for each gaseous species inside the decomposing wood. Rather than relating reaction kinetics and thermodynamics
00102180/$  see front matter 2009 Published by Elsevier Inc. on behalf of The Combustion Institute.
doi:10.1016/j.combustﬂame.2009.04.001
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C. Lautenberger, C. FernandezPello / Combustion and Flame 156 (2009) 1503–1513
Nomenclature 

Letters 

A 

b 
exponent in Eq. (15) 
B 

c 
speciﬁc heat capacity 
E 
activation energy 
h 
enthalpy 
h _{c} 

_ 
condensed phase species A (reactant)
condensed phase species B (product)
convective heat transfer coefﬁcient
j ^{0}^{0} 
diffusive mass ﬂux 

k 
thermal conductivity 

K 
number of heterogeneous reactions or permeability 

‘ 
index of homogeneous gas phase reaction 

L 
number of homogeneous gas phase reactions 

_ m ^{0}^{0} 
mass ﬂux 

M 
molecular weight or number of condensed phase spe cies 

N 
number of gaseous species 

n 
exponent (reaction order, O _{2} sensitivity, property tem perature dependence) 

p 
exponent in Eq. (15) 

P 
pressure 

q 
exponent in Eq. (15) 

_ q ^{0}^{0} 
heat ﬂux 

_ 
Q ^{0}^{0}^{0}
heat
generation per unit volume
R 
universal gas constant 
t 
time 
T 
temperature 
X 
volume fraction 
y 
yield 
Y 
mass fraction 
z 
distance 
Z 
preexponential factor 
Greek symbols
c 
radiative conductivity parameter 
d 
thickness or Kronecker delta 
e 
emissivity 
j 
radiative absorption coefﬁcient 
m 
viscosity ( l / q ) or reaction stoichiometry coefﬁcient (Eq. (8) ) 
q 
bulk density in a vacuum 
w 
porosity 
_ x ^{0}^{0}^{0} 
reaction rate 
Subscripts 

0 
initial 
1 
ambient 
R 
see Eq. (9) 
ash 
ash 
char 
char 
cop 
char oxidation products 
d 
destruction 
dw 
dry wood 
e 
external 
f 
formation 
g 
gaseous 
H _{2} O 
water vapor 
i 
condensed phase species i 
j 
gaseous species j 
k 
reaction index 
‘ 
homogeneous reaction index 
op 
oxidative pyrolysate 
O _{2} 
oxygen 
r 
radiative or reference 
s 
solid 
s–g 
solid to gas 
sol 
solid 
tp 
thermal pyrolysate 
v 
volatiles 
vol 
volatiles 
ww 
wet wood 
Superscripts
^{}
at time t
to the freestream oxygen concentration, they are related to the lo cal oxygen concentration inside the pore space of the decomposing wood. This is made possible by estimating the diffusion rate of oxy gen from the ambient into the pores of a decomposing wood slab where it may participate in oxidative pyrolysis. Both heteroge neous (gas/solid) and homogeneous (gas/gas) reactions inside the decomposing solid are considered. The model’s predictive capabil ities are assessed by comparing its calculations to experimental data for the oxidative pyrolysis of white pine [11,12] .
2. Formulation of generalized charring pyrolysis model
The modeling presented in this paper is a speciﬁc application of Gpyro, an opensource generalized pyrolysis model developed by the authors [13–15]. Although this model is described in detail elsewhere [13–15], the main equations are presented here for completeness.
2.1. Governing equations
A slab of thermally decomposing wood is modeled as consisting of a condensed phase (wood, char, and ash) coupled to a gas phase (oxygen, nitrogen, water vapor, pyrolysate, etc.). The gas phase outside of the decomposing wood slab (the exterior ambient) is
not modeled, so any discussion of the gas phase refers to the gases inside the pores or voids that form in decomposing wood. The fol lowing assumptions are invoked:
Onedimensional behavior. Each condensed phase species has welldeﬁned properties: bulk density, speciﬁc heat capacity, effective thermal conductivity, emissivity, permeability, porosity ð w _{i} ¼ 1 q _{i} = q _{s} _{0} _{;} _{i} Þ . Thermal conductivity and speciﬁc heat capacity of each con densed phase species vary as k ð T Þ ¼ k _{0} ð T = T _{r} Þ ^{n} ^{k} and c ð T Þ ¼ c _{0} ð T = T _{r} Þ ^{n} ^{c} where T _{r} is a reference temperature, k _{0} and c _{0} are the values of k and c at T _{r} , and the exponents n _{k} and n _{c} spec ify whether k and c (respectively) increase or decrease with temperature. Radiation heat transfer across pores is accounted for by adding a contribution to the effective thermal conductivity that increases as T ^{3} , i.e. k _{r} _{,} _{i} = c _{i} r T ^{3} . Averaged properties appearing in the conservation equations (denoted by overbars) are calculated by appropriate mass or vol ume weightings. All gaseous species have equal diffusion coefﬁcients and speciﬁc heat capacities (independent of temperature). Darcian pressuredriven ﬂow through porous media (Stokes ﬂow).
C. Lautenberger, C. FernandezPello / Combustion and Flame 156 (2009) 1503–1513
1505
Unit Schmidt number ( m = D ). Gas phase and condensed phase are in thermal equilibrium. No shrinkage or swelling (volume change) occurs.
The conservation equations that result from these assumptions are given as Eqs. (1)–(7) :
Condensed phase mass conservation:
@
q
@ t ^{¼} ^{}
_
000
_{f}_{g}
x
ð 1Þ
Condensed phase species conservation:
@ ð
qY
i
Þ
@
t
^{¼}
_
x
000
fi ^{}
_
_{x}
000
_{d}_{i}
Gas phase mass conservation:
@
q
g
w
_
_{m}
^{þ} ^{@} @ z ^{¼}
00
@ t
_
000
_{f}_{g}
x
Gas phase species conservation:
@
q
g
wY _{j}
þ ^{@}
_
m
00
Y j
@
t
@ z
@
_
j
00
j
^{¼} ^{} @ z ^{þ}
_
x
000
fj ^{}
_
_{x}
000
_{d}_{j}
ð 2Þ
ð
3Þ
ð 4Þ
Condensed phase energy conservation:
@ ð hÞ
q
@
t
¼ ^{@} @ z ^{}
_{q}
_
00
_
Q
K
000
s — g ^{þ} X
k¼1
_
Q
M
000
s ; k ^{þ} X
i¼1
_
x
000
fi ^{}
_
_{x}
000
di
h _{i}
ð 5Þ
Gas phase energy conservation:
T _{g} ¼ T ð thermal equilibriumÞ
Gas phase momentum conservation (assumes Darcian ﬂow):
M
@
P
@ t RT _{g}
w ¼ ^{@}
@
z
K @ P
m
@
z
þ
_
000
_{f}_{g}
x
ð
6Þ
ð 7Þ
In Eq. (4), the diffusive mass ﬂux is calculated from Fick’s law as
_
. Note that Y _{i} is the mass of con
from Fourier’s law as q ^{0}^{0} ¼
densed phase species i divided by the total mass of all condensed
phase species, and Y _{j} is the mass of gaseous species j divided by
the mass of all gaseous species. Similarly,
_{d}_{i} is the destruction rate of con
densed phase species i . The analogous gas phase quantities are
and
(4) is obtained from Chapman–Enskog theory [16]. Eq. (3) is not
_{d}_{j} . The temperaturedependent diffusion coefﬁcient D in Eq.
of condensed phase species i , and
is the formation rate
, and in Eq. (5) the conductive heat ﬂux is calculated
j _{j} ¼
00
wq _{g} D ^{@} ^{Y} ^{j}
z
@
_
_{k} @ T
z
@
_
_{x} 000
_ 000
x fi
_ 000
x fj
_
_{x}
000
explicitly solved, but it is used to form Eq. (7) after substituting
the ideal gas law ð q _{g} ¼ _{R}_{T} _{g} Þ and Darcy’s law ð m ^{0}^{0} ¼
_
P
M
2.2. Reactions and source terms
K @ P
m
@
z
Þ
.
There are K heterogeneous (solid/gas) reactions, and individual condensed phase reactions are indicated by the index k . Heteroge neous reaction k converts condensed phase species A _{k} to con densed phase species B _{k} plus gases:
N
N
1 kg A _{k} þ ^{X} _{j} _{;} _{k} kg gas j ! m _{B} _{;} _{k} kg B _{k} þ ^{X} _{k} kg gas j
m
^{0}
00
m
j
;
j
¼1
j
¼1
m B ; k ¼ q B ^{k}
A k
^{q}
0
m _{j} _{;} _{k} ¼
ð1 m _{B}_{;} _{k} Þ minð y _{s}_{;} _{j} _{;} _{k} ; 0Þ
00
j
;
m
_{k}
¼ ð1 m _{B} _{;} _{k} Þ maxðy _{s} _{;}_{j} _{;} _{k} ; 0Þ
ð8a Þ
ð8b Þ
ð 8cÞ
ð 8dÞ
Here, y _{s} _{,} _{j} _{,} _{k} is a userspeciﬁed N by K ‘‘species yield matrix” that establishes the values of m _{j} _{;} _{k} and m _{k} . Its entries are positive for the
0
00
j
;
formation of gaseous species and negative for the consumption of gaseous species. The destruction rate of condensed phase species A _{k} by reaction k is calculated as:
_
_{x}
_
_{x}
000
dA _{k} ^{¼}
000
dA _{k} ^{¼}
q Y _{A} _{k}
R ! n
q Y _{A} _{k}
k
q Y _{A} _{k}
^{} _{R} Z _{k} exp RT ^{E} ^{k} ð for n _{O} _{2} _{;} _{k} ¼ 0Þ
q Y _{A} _{k}
R ! n k
q Y _{A} _{k}
q Y _{A} _{k}
R
h
1
þ Y _{O} _{2}
exp RT ^{E} ^{k} ð for n _{O} _{2} _{;} _{k} –0Þ
^{} ^{n} O _{2} ; k 1
i
Z k
ð
q
Y
i
Þ _{R} ð
qY _{i}
^{Þ}^{j} t ¼0 ^{þ} Z t
0
_
000
fi
x
ð sÞ ds
ð9aÞ
ð9bÞ
ð9cÞ
In Eq. (9), the parameter n _{O} _{2} _{;} _{k} controls a reaction’s oxygen sensitiv ity, and the oxygen mass fraction ð Y _{O} _{2} Þ is the local value inside the decomposing solid determined by solution of Eq. (4). Combining Eqs. (8) and (9) , it can be seen that the volumetric
formation rate of condensed phase species B _{k} by reaction k is:
_
x
000
_{f}_{B} _{k} ¼ m B ; k
_
_{x}
000
dA _{k} ^{¼} q B ^{k}
A k
^{q}
_
_{x}
000
_{d}_{A} _{k}
ð 10Þ
Similarly, the formation rate of all gases due to consumption of con
densed phase species A _{k} by reaction k is:
_{f}_{g} _{k} ¼ 1 m
_
x
000
B; k
_
_{x}
000
_{d}_{A} _{k} ¼
k !
1 ^{q} ^{B} ^{k}
q
A
_
_{x}
000
_{d}_{A} _{k}
ð 11Þ
It also follows from Eqs. (8) and (9) that the formation and destruc tion rates of gaseous species j by reaction k are:
_
x
_
_{x}
_{k} ¼ m
000
fj ;
000
dj ; k ^{¼} ^{m} j ; k
00
j
; k
0
_{x} 000 dA _{k} ^{¼}
x
_
_{x} 000
dA _{k} ^{¼} ^{}
_
x
_
_
000
fg ; k ^{m}^{a}^{x} ^{y} s; j ; k ^{;} ^{0}
^{}
000
fg ; k ^{m}^{i}^{n} ^{y} s ; j ; k ^{;} ^{0}
^{}
ð12aÞ
ð12bÞ
The volumetric rate of heat release or absorption to the solid phase due to reaction k is calculated as:
_
Q
000
s ; k ^{¼} ^{}
x
_
000
_{f}_{B} _{k} ^{D}^{H} sol; k ^{}
_
x
000
_{f}_{g} _{k} DH _{v} _{o}_{l} _{;} _{k}
ð 13Þ
where D H _{s}_{o}_{l} _{,} _{k} and D H _{v}_{o}_{l} _{,} _{k} are the heats of reaction associated
respectively with the formation of condensed phase species and
gas phase species by reaction k . Homogeneous gas phase reactions inside the pores of the decomposing wood are also considered. Just as there are K con densed phase reactions and individual condensed phase reactions
are indicated by the index k , there are L homogeneous gas phase
reactions and individual reactions are indicated by the index ‘ . Each homogeneous gas phase reaction ‘ converts two gas phase reactants ( A _{‘} and B _{‘} ) to gaseous products. The stoichiometry of homogeneous gas phase reactions is ex pressed on a mass basis:
N
1 kg A _{‘} y _{g} _{;} _{B} _{‘} _{;}_{‘} kg B _{‘} ! ^{X} max
j ¼1
^{y} g ; j ;‘ ^{;} ^{0}
^{} kg gas j
ð 14Þ
In Eq. (14), y _{g} _{,} _{j} _{,} _{‘} is the userspeciﬁed N by L ‘‘homogeneous gaseous
species yield matrix”, analogous to the gaseous species yield matrix (y _{s} _{,} _{j} _{,} _{k} ) discussed earlier with reference to heterogeneous reactions. The physical meaning of the entries in y _{g} _{,} _{j} _{,} _{‘} is the mass of gaseous species j produced by reaction ‘ (for positive entries) or consumed by reaction ‘ (for negative entries) per unit mass of gaseous species A _{‘} consumed. Eq. (14) has been written assuming that y _{g} _{;} _{A} _{‘} _{;}_{‘} ¼ 1, i.e. the reaction is normalized to 1 kg of gaseous species A _{‘} . The reaction rate of the ‘ th homogeneous gas phase reaction is
the destruction rate of gas phase species A _{‘} :
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C. Lautenberger, C. FernandezPello / Combustion and Flame 156 (2009) 1503–1513
_
_{x}
_{d}_{A} _{‘} ¼ ½A _{‘} ^{p} ^{‘} ½ B _{‘} ^{q} ^{‘} T ^{b} ^{‘} Z _{‘} w exp ^{E} ^{‘}
000
RT _{g}
ð15 Þ
In Eq. (15), [ A ] denotes the molar gas phase concentration of gas eous species A :
½ A ¼ ^{q} ^{g} ^{Y} ^{A}
M
A
ð16 Þ
The creation or destruction of gaseous species j by homogeneous gaseous reaction ‘ is calculated from the homogeneous gaseous spe cies yield matrix (y _{g} _{,} _{j} _{,} _{‘} ) as:
_
x
000
g ; j ;‘ ^{¼}
_
_{x}
000
_{d}_{A} _{‘} ^{y} g ; j ;‘
^{ð}^{1}^{7} ^{Þ}
The volumetric rate of heat release to the gas phase by homoge neous gaseous reaction ‘ is:
_
Q
000
g ;‘ ^{¼} ^{}
_
_{x}
000
_{d}_{A} _{‘} DH _{‘}
ð18 Þ
where D H _{‘} is the heat of reaction associated with homogeneous gas phase reaction ‘ . Since multiple reactions (both heterogeneous and homoge neous) occur, the source terms appearing in the governing equa tions must be determined by summing over all reactions. The total formation rate of all gases from the condensed phase is:
K
fg ^{¼} X
_
x
000
k ¼1
_
000
_{f}_{g} _{k}
x
ð19 Þ
Similarly, the total formation/destruction rates of condensed phase species i and gas phase species j are obtained as:
_
_{x}
000
di
_
000
fi
x
^{¼}
¼
K
X
k
K
^{X}
¼1
k
¼1
d
d
i; A _{k}
i; B _{k}
_
_{x}
000
_{d}_{A} _{k}
_
000
_{f}_{B} _{k}
x
where d _{i}_{;} _{A} _{k} ¼
where d _{i}_{;} _{B} _{k} ¼
1
0
1
0
if
i ¼ A _{k}
if i–A _{k}
if i ¼ B _{k} if i –B _{k}
ð20a Þ
ð
20bÞ
_
_{x}
000
dj
_
000
fj
x
^{¼}
¼
K
X
k
K
^{X}
¼1
k
¼1
L
_
_{x}
000
dj; k ^{} X
¼1
L
‘
_
x
000
fj; k ^{þ} X
‘
¼1
min
max
_
x
000
g ; j ;‘ ^{;} ^{0}
_
x
000
g ; j;‘ ^{;} ^{0}
ð
21aÞ
ð21b Þ
_
The source term Q _{—} _{g} appearing in the condensed phase energy conservation equation is the volumetric rate of heat transfer from
the condensed phase to the gas phase:
000
s
_
Q
000
s— g ^{¼}
m ^{0}^{0} c pg
_
@
T
@
z
L
_
^{X} Q _{;}_{‘}
000
g
‘
¼1
ð22 Þ
Due to the assumption of thermal equilibrium between the gaseous
and the condensed phases (Eq. (6)), any heat release due to homo geneous gas phase reactions (Eq. (18)) is added to the condensed
_
phase energy conservation equation via Q _{—} _{g} . In a ‘‘two tempera
ture” model where thermal equilibrium between the condensed phase and the gas phase is not assumed, the heat release due to homogeneous gas phase reactions (right most term in Eq. (22)) would be added to the source term appearing in the conservation of gas phase energy equation.
000
s
2.3. Solution methodology
When discretized, the above equations yield a system of cou pled algebraic equations that are solved numerically. The recom mendations of Patankar [17] are followed closely. Due to the nonlinearity introduced by the source terms and temperature dependent thermophysical properties, a fullyimplicit formulation is adopted for solution of all equations. The condensed phase
energy conservation equation, gas phase species conservation equation, and gas phase momentum conservation equation are solved using a computationally efﬁcient tridiagonal matrix algo rithm (TDMA). The condensed phase mass and condensed phase species conservation equations are solved with a customized fully implicit solver that uses relaxation to prevent divergence. Source terms are split into positive and negative components to ensure physically realistic results and prevent negative mass fractions or densities from occurring [17] . Newton iteration is used to extract the temperature from the weighted enthalpy and the condensed phase species mass fractions. Additional details are given in Ref. [15] . Initial and boundary conditions are presented in Section 3.2 .
3. Simulating white pine oxidative pyrolysis
In this section, the charring pyrolysis model presented above in general form is applied to simulate the oxidative pyrolysis of white pine slabs irradiated under nonﬂaming conditions. Model calcula tions are compared with the experimental data of Ohlemiller et al. [11,12] who studied the effects of ambient oxygen concentration on the nonﬂaming gasiﬁcation of irradiated white pine slabs. In the experiments, white pine cubes 3.8 cm on edge (initial density of 380 kg/m ^{3} and moisture content of 5% by mass) were irradiated at 25 kW/m ^{2} and 40 kW/m ^{2} in oxygen concentrations of 0%, 10.5%, and 21% (normal air) by volume. Fig. 1 illustrates some of the key measurements that make this set of experiments particularly interesting from a modeling per spective. Fig. 1 a shows that in the 40 kW/m ^{2} experiments, the mass loss rate measured in air is approximately double that measured in
Time (s)
Time (s)
Fig. 1. Experimentally observed [12] effect of oxygen concentration on the surface temperature and mass loss rate of white pine irradiated at 40 kW/m ^{2} . (a) Mass loss rate; (b) Temperature
C. Lautenberger, C. FernandezPello / Combustion and Flame 156 (2009) 1503–1513
1507
nitrogen. The effect of oxidative exothermic reactions is also evi dent in Fig. 1 b, where it can be seen that the surface temperature of the sample tested in air was approximately 150 C greater than that of the sample tested in nitrogen. In addition to the mass loss rate and surface temperature measurements shown in Fig. 1 , in depth thermocouple temperature measurements are also reported [12] .
3.1. Modeling approach
The model described in Section 2 is presented in general form, meaning that it could potentially be used to simulate many differ ent charring materials or experimental conﬁgurations. What differ entiates one material or experiment from another is the material’s thermophysical properties and reaction mechanism (sometimes called material properties) as well as the initial and boundary con ditions that describe the experimental conditions. Postulating a ba sic modeling approach (number of species to track, reaction mechanism, physics to include in the simulation) and then deter mining the required model input parameters is one of the most challenging aspects of pyrolysis modeling. In this work, genetic algorithm optimization [18,19] is used to extract the required in put parameters from the experimental data at 25 kW/m ^{2} and 40 kW/m ^{2} irradiance. In the modeling approach applied here, white pine is simulated as consisting of four condensed phase species, numbered as fol lows: (1) wet wood, (2) dry wood, (3) char, and (4) ash. The bulk density of each species is constant, but thermal conductivities and speciﬁc heat capacities are temperature dependent. Each spe cies has a different surface emissivity to account for blackening of the wood as it chars. All condensed phase species are opaque (no diathermancy) and radiation heat transfer across pores is ac counted for in the char and ash species (which have high porosi ties). Permeability of all species is held ﬁxed at 10 ^{} ^{1}^{0} m ^{2} because scoping simulations indicated that permeability had a negligible effect on the calculated mass loss rate and temperature proﬁles (the experimental measurements against which the model calcula tions are judged). In addition to the four condensed phase species, seven gaseous species are tracked: (1) thermal pyrolysate, (2) nitrogen, (3) water vapor, (4) oxygen, (5) oxidative pyrolysate, (6) char oxidation prod ucts, and (7) pyrolysate oxidation products. It is assumed that all species have identical speciﬁc heat capacities (1100 J/kg K) and equal mass diffusivities. As mentioned earlier, unit Schmidt num ber ( m = D ) and thermal equilibrium between the condensed and gaseous phases are assumed. Four condensed phase (heterogeneous) reactions are consid ered. Reaction 1 converts wet wood to dry wood and water vapor. Reaction 2 is the anaerobic conversion of dry wood to char plus thermal pyrolysate. Reaction 3 also converts dry wood to char, but consumes oxygen in the process to produce oxidative pyroly sate. Finally, reaction 4 converts char to ash, consuming oxygen in the process, and produces char oxidation products. This reaction mechanism is summarized as:
wet wood ! m _{d}_{w} dry wood
ð 23: 2Þ
dry wood þ m _{O} _{2} _{d}_{w} O _{2} ! m _{c}_{h}_{a}_{r} char þ m _{o}_{p} oxidative pyrolysate ð 23: 3Þ
char þ m _{O} _{2} _{c}_{h}_{a}_{r} O _{2} ! m _{a}_{s}_{h} ash þ m _{c}_{o}_{p} char oxidation products ð 23: 4Þ
dry wood ! m _{c}_{h}_{a}_{r} char þ m _{t}_{p} thermal pyrolysate
ð 23: 1Þ
þ
m _{H} _{2} _{O} H _{2} O
The ﬁrst (drying) reaction is modeled after Atreya [20]. Per Eq. (8), the m coefﬁcients in Eq. (23) are related to bulk density ratios and the heterogeneous gaseous species yield matrix discussed ear lier, e.g. m dw = q dw /q ww and m op = (1 q char /q ww ) y s ,5,3 . Two homogeneous (gas/gas) reactions are also considered. They are oxidation of thermal pyrolysate to form pyrolysate oxidation
products, and oxidation of oxidative pyrolysate to form pyrolysate oxidation products:
thermal pyrolysate y _{g} _{;} _{4}_{;} _{1} O _{2} ! y _{g} _{;} _{7}_{;} _{1} pyrolysate oxidation products
ð24 : 1Þ
oxidative pyrolysate y _{g} _{;}_{4}_{;} _{2} O _{2} ! y _{g} _{;} _{7}_{;} _{2} pyrolysate oxidation products
ð24 : 2Þ
In Eq. (24), y _{g} _{,} _{j} _{,} _{‘} is the homogeneous gaseous species yield matrix discussed earlier. The reaction mechanism in Eqs. (23) and (24) differs from the conventional modeling approach wherein char oxidation is viewed as a heterogeneous process occurring at (or near) the surface of a decomposing solid [9,10]. In the present work, oxidative exother mic reactions, including both heterogeneous reactions (Eqs. (23.3) and (23.4)) and homogeneous gas/gas reactions (Eqs. (24.1) and (24.2) ), are permitted to occur indepth. Considerable simpliﬁcations are inherent in the reaction mech anisms embodied in Eqs. (23) and (24) . Gaseous ‘‘virtual” or ‘‘sur rogate” species are used to represent complex gas mixtures. For example, a single gaseous species called ‘‘char oxidation products” is used to represent the gases that form via heterogeneous char oxidation (Eq. (23.4)). In reality, these gases may include a mixture of CO, CO _{2} , H _{2} O, unburned hydrocarbons, etc., but since very little is known about the actual composition of these gases, they are tracked in the model by a single surrogate species. Another approx imation stems from the simultaneous formation of ‘‘char” by the thermal pyrolysis of dry wood (Eq. (23.2)) and the oxidation of dry wood (Eq. (23.3)). In reality, the chemical composition of char formed by thermal pyrolysis of wood is not expected to be the same as that formed by oxidation of the wood. However, the com plexity of the above mechanism is increased signiﬁcantly if a sec ond char species (such as oxidative char) is added. Similarly, thermal pyrolysate (which forms in the absence of oxygen from the pyrolysis of dry wood) and oxidative pyrolysate (which forms by the oxidation of dry wood) are chemically distinct mixtures of species that are tracked by a single surrogate species. Thus, it is expected that their combustion products would be dif ferent. However, it can be seen from Eqs. (24.1) and (24.2) that the oxidation of both species produces pyrolysate oxidation prod ucts. Again, this approximation is invoked to reduce the number of species that must be tracked.
3.2. Initial and boundary conditions representing experimental conﬁguration
Initial and boundary conditions are speciﬁed to simulate the experiments described in Ref. [12] . The initial temperature, pres sure, gaseous species mass fractions, and condensed phase species are initially uniform throughout the thickness of the solid:
M
ð q DzÞ ^{} j _{t} _{¼}_{0} ¼ q _{0} Dz _{0} ¼ ^{X} ðX _{i}_{0} q _{i}_{0} Þ Dz _{0}
i¼1
ð
q Y _{i}
M
DzÞ ^{} j _{t} _{¼}_{0} ¼ q _{0} Y _{i}_{0} Dz _{0} ¼ ^{X} ðX _{i}_{0} q _{i}_{0} ÞY _{i}_{0} Dz _{0}
i¼1
j
Y
_{} _{t} _{¼}_{0} ¼ Y _{j} _{0}
^{T} ^{} ^{j} t ¼0
^{¼}
^{T} 0 ^{)}
M
h ^{} ^{} ^{} t ¼0 ^{¼} X
i¼1
ð Y
h ðT
i0 i0
0
Þ Þ
P ^{} j _{t} _{¼}_{0} ¼ P _{1}
ð
25Þ
ð 26Þ
ð 27Þ
ð
ð
28Þ
29Þ
In Eqs. (25) and (26), X _{i} _{0} (and Y _{i} _{0} ) are 1.0 for wet wood and 0.0 for all other condensed phase species. T _{0} in Eq. (28) is 300 K. The initial gaseous mass fractions (Eq. (27)) are 1.0 for thermal pyrolysate and 0.0 for all other gaseous species. The ambient pressure (Eq. (29)) is 101,300 Pa.
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C. Lautenberger, C. FernandezPello / Combustion and Flame 156 (2009) 1503–1513
Table 1 Condensed phase parameters for white pine simulations.
i Name 
k _{0} (W/m K) 
n _{k} (–) 
q _{0} (kg/m ^{3} ) 
n _{q} (–) 
c _{0} (J/kg K) 
n _{c} (–) 
e (–) 
j (m ^{} ^{1} ) 
c (m) 
K (m ^{2} ) 
q _{s} _{0} (kg/m ^{3} ) 
1 wet wood 
0.186 
0.185 
380 
0 
1764 
0.406 
0.757 
1 
0 
1 10 ^{} ^{1}^{0} 1 10 ^{} ^{1}^{0} 1 10 ^{} ^{1}^{0} 1 10 ^{} ^{1}^{0} 
390 
2 dry wood 
0.176 
0.594 
360 
0 
1664 
0.660 
0.759 
1 
0 
390 

3 char 
0.065 
0.435 
73.0 
0 
1219 
0.283 
0.957 
1 
3.3 10 ^{} ^{3} 6.4 10 ^{} ^{3} 
390 

4 ash 
0.058 
0.353 
5.7 
0 
1244 
0.315 
0.955 
1 
390 

Table 2 Reaction parameters for white pine simulations. 

k From 
To 
v (–) 
D H _{s}_{o}_{l} (J/kg) 
D H _{v}_{o}_{l} (J/kg) 
Z (s ^{} ^{1} ) 
E (kJ/mol) 
n (–) 
n _{O} _{2} (–) 

1 wet wood 
dry wood 
1 
0 
2.41 10 ^{6} 5.33 10 ^{5} 9.94 10 ^{5} 3.77 10 ^{7} 
4.29 10 ^{3} 3.29 10 ^{9} 6.00 10 ^{9} 9.79 10 ^{1}^{3} 
43.8 
0.99 
0 

2 dry wood 
char 
1 
0 
135.0 
4.78 
0 

3 dry wood 
char 
1 
0 
124.2 
4.99 
1.16 

4 char 
ash 
1 
0 
192.4 
1.86 
1.04 
Table 3 Gaseous yields for white pine simulations. Only nonzero yields are shown.
j 
k 

12 
3 
4 

1 
(thermal pyrolysate) 
1 

2 
(nitrogen) 

3 
(water vapor) 
1 

4 
(oxygen) 
0.1 
2.0 

5 
(oxidative pyrolysate) 
1.1 

6 
(char oxidation products) 
3.0 

7 
(pyrolysate oxidation products) 
No boundary conditions are needed for the condensed phase species or mass conservation equations because the condensed phase species and mass conservation equations in each cell reduce to ﬁrst order transient ordinary differential equations with source terms attributed to species formation and destruction, i.e. there are no convective or diffusive terms in Eqs. (1) and (2). The boundary conditions on the condensed phase energy equa tion are:
_{k} @ T
@
z
^{} z ¼0
_{k} @ T
@
z
^{} z¼d
¼
_
e
_{q}
00
e
¼ h c d
h _{c} ð T j _{z} _{¼}_{0} T _{1} Þ er T ^{4}
^{} z¼0 ^{} ^{T} 4
1
T j _{z} _{¼}_{d} T _{1} ^{}
ð30a Þ
ð 30bÞ
In Eq. (30),
experiment being simulated, h _{c} _{d} is 10 W/m ^{2} K, T _{1} is 300 K, and h _{c}
is the frontface convective heat transfer coefﬁcient. The effect of blowing on the latter is estimated with a Couette approximation
e is the externallyapplied radiative heat ﬂux in the
_
_{q}
00
[21]:
h _{c} ¼
_
_{m}
00
_{0} c pg
exp
_
_{m}
00
_{0} c pg = h c ; nb
_{} _{1}
ð30c Þ
Here, h _{c} _{,} _{n}_{b} (the front face heat transfer coefﬁcient with no blowing)
_{0} is the calculated mass ﬂux of gases at the exposed
is 10 W/m ^{2} K,
surface (z = 0), and c _{p}_{g} is 1100 J/kg K. The boundary conditions on the pressure evolution equation are such that the pressure at the front face is set to the ambient value.
_
_{m}
00
Table 4 Homogeneous gaseous reaction parameters for white pine simulations.
The pressure gradient at the back face is set to give a zero mass ﬂux (impermeable approximation) per Darcy’s law:
P j _{z}_{¼}_{0} ¼ P _{1}
ð31aÞ
@
P
@
z
^{} z ¼d
¼ 0
ð 31bÞ
Eq. (4) (gas phase species conservation) requires two boundary con ditions for each gaseous species j. The back face ( z = d ) is assumed impermeable so there is no ﬂow of volatiles across the back face:
@ Y _{j}
@
z
^{} z ¼d
¼ 0
ð32aÞ
The diffusive mass ﬂux of gaseous species into or out of the decom posing solid at the front face is approximated as:
wq _{g} D ^{@} ^{Y} ^{j}
@
z
^{} z ¼0
^{h} ^{c}
c
pg
1
Y
j
Y _{j} ^{}
^{} z ¼0
where Y
1 is the ambient mass fraction of gaseous species j.
j
ð 32bÞ
3.3. Simulation of nitrogen experiments
Even with the approximations noted in Section 3.1 , almost 50
model input parameters (kinetics coefﬁcients, thermophysical properties, etc.) must be determined. Consequently, model input parameters are estimated from the experimental data in two sep arate steps. First, genetic algorithm optimization [18,19] is used in conjunction with the experimental data obtained under nitrogen to estimate values of input parameters that do not involve oxygen (oxidative reactions and species formed by oxidative reactions are not considered). Next, these parameters are held constant while the remaining parameters are determined by genetic algo rithm optimization from the experimental data obtained in oxida tive atmospheres. The model input parameters determined by genetic algorithm optimization (used in all calculations reported in this paper) are listed in Tables 1–5 . In the ﬁrst stage of the model input parameter estimation pro cess, only heterogeneous reactions that do not involve oxygen (Eqs. (23.1) and (23.2) ) affect the calculations. Ash is not formed in the simulations since it is produced only through an oxidative reaction
l Reactant 1 
Reactant 2 
p (–) 
q (–) 
b (–) 
Z (kg m ^{2} /(mole ^{2} s)) 
E (kJ/mol) 
D H (J/kg) 
1 thermal pyrolysate 
oxygen 
1.0 
1.0 
0.0 
2.01 10 ^{9} 2.09 10 ^{9} 
162.7 
1.88 10 ^{7} 1.73 10 ^{7} 
2 oxidative pyrolysate 
oxygen 
1.0 
1.0 
0.0 
161.3 
C. Lautenberger, C. FernandezPello / Combustion and Flame 156 (2009) 1503–1513
1509
Table 5 Homogeneous gaseous yields for white pine simulations. Only nonzero yields are shown.
j 
l 

1 
2 

1 
(thermal pyrolysate) 
1.0 

2 
(nitrogen) 

3 
(water vapor) 

4 
(oxygen) 
1.6 
1.5 
5 
(oxidative pyrolysate) 
1.0 

6 
(char oxidation products) 

7 
(pyrolysate oxidation products) 
2.6 
2.5 
(Eq. (23.4)). Similarly, the homogeneous gas phase reactions both consume oxygen, so they do not occur in the nitrogen simulations. Any model input parameters associated with these reactions (or the species they produce) have no effect on the nitrogen simula tions and can be excluded from the ﬁrst step of the property esti mation process. Fig. 2 compares the measured and calculated temperatures and mass loss rate under nitrogen at 40 kW/m ^{2} . The calculated surface temperature is slightly higher than the experimental data, but the calculated temperatures at depths of 5 mm and 10 mm match the experimental data well. The mass loss rate is also well predicted, except that the peak mass loss rate is slightly underpredicted and occurs 30 s earlier than in the experiment. Fig. 3 compares the measured and modeled mass loss rate at 25 kW/m ^{2} irradiance under nitrogen. It can be seen that the shapes
Time (s)
Fig. 3. Comparison of modeled mass loss rate and experimental data for pyrolysis of white pine at 25 kW/m ^{2} irradiance in nitrogen.
of the curves are qualitatively similar, but the calculated peak mass loss rate is overpredicted and occurs approximately 2 min earlier in the model than in the experiment. Discrepancies between the model calculations and the experimental data at this lower heat ﬂux level may be attributed to the simpliﬁed reaction mechanism and decomposition kinetics used here. At lower heat ﬂux levels, temperatures are lower and decomposition kinetics play a more signiﬁcant role than at higher heat ﬂux levels where mass loss
Time (s)
Time (s)
Fig. 2. Comparison of model calculations using optimized input parameters and experimental data for pyrolysis of white pine at 40 kW/m ^{2} irradiance in nitrogen. (a) Temperature; (b) mass loss rate.
Time (s)
Time (s)
Fig. 4. Comparison of experimentally measured [12] and modeled temperatures at several depths below the surface of white pine irradiated at 40 kW/m ^{2} in oxidative atmospheres. (a) 10.5% O _{2} atmosphere; (b) 21% O _{2} atmosphere.
1510
C. Lautenberger, C. FernandezPello / Combustion and Flame 156 (2009) 1503–1513
Time (s)
Time (s)
Fig. 5. Comparison of experimentally measured [12] and modeled mass loss rate of white pine at 40 kW/m ^{2} irradiance in oxidative atmospheres. (a) 10.5% O _{2} atmosphere; (b) 21% O _{2} atmosphere.
rates are controlled primarily by a heat balance. Thus, slight inac curacies in the decomposition kinetics may lead to larger discrep ancies between the model calculations and experimental data at lower heat ﬂux levels.
3.4. Simulation of oxidative experiments
The second stage of the property estimation process involves oxidative atmospheres (10.5% O _{2} and 21% O _{2} by volume). Model in
put parameters determined from the nitrogen experiments are held constant, and genetic algorithm optimization is used to ex tract additional parameters from the oxidative experimental data. A comparison of the experimental measurements [12] and the optimized model calculations in oxidative environments at 40 kW/m ^{2} irradiance is given in Figs. 4 and 5 . Fig. 4 compares the modeled temperatures with experimental data at oxygen concen trations of 10.5% and 21%. The increase in temperature with ambi ent oxygen concentration is captured because the combined exothermicity of the heterogeneous and homogeneous reactions causes the temperature to increase as the ambient oxygen concen tration is increased. Fig. 5 compares the calculated mass loss rate with analogous experimental data (40 kW/m ^{2} irradiance, 10.5% and 21% O _{2} ). Qual itatively, the calculated shape of the mass loss rate curve is similar to the experimental data. Quantitatively, calculated mass loss rates are underpredicted after the initial peak. This may be due to an underprediction of the char oxidation rate, or perhaps the onset of another reaction that is not included in the simpliﬁed reaction mechanism (Eq. (23) ). Figs. 6 and 7 compare model calculations and experimental data [12] under oxidative conditions at 25 kW/m ^{2} irradiance. It can be seen from Fig. 6 that the temperature calculated at four different locations in the decomposing pine slab is usually within 50 C of the experimental data for the duration of the experiment. When one considers the uncertainty in the experimental measurements, this is considered a good ﬁt.
Time (s)
Time (s)
Fig. 6. Comparison of experimentally measured [12] and modeled temperatures at several depths below the surface of white pine irradiated at 25 kW/m ^{2} in 10.5% O _{2} atmosphere.
Time (s)
Fig. 7. Comparison of experimentally measured [12] and modeled mass loss rate of white pine at 25 kW/m ^{2} irradiance in oxidative atmospheres. (a) 10.5% O _{2} atmosphere; (b) 21% O _{2} atmosphere.
C. Lautenberger, C. FernandezPello / Combustion and Flame 156 (2009) 1503–1513
1511
A comparison of the measured and modeled mass loss rates
(25 kW/m ^{2} , 10.5% O _{2} , and 21% O _{2} ) is shown in Fig. 7 . The general
shapes of the curves are well represented by the model, but there are some quantitative differences. Again, when one considers the experimental uncertainty and the complexity of the problem, this is considered a good ﬁt.
3.5. Comparison of optimized thermal properties with literature data
In the present study, temperaturedependent speciﬁc heat capacities and thermal conductivities are used for each condensed phase species. Figs. 8 and 9 compare the optimized thermal properties determined by genetic algorithm optimization in the present work with the data of Yang et al. [22] as well as thermal property correlations for generic wood compiled in Ref. [13] . In Figs. 8 and 9 , generic wood property correlations reported in Ref. [13] are denoted ‘‘literature (generic)” and values used by Yang
et al. [22] to simulate the pyrolysis of white pine are denoted ‘‘lit erature (white pine)”.
In Fig. 8 a, the speciﬁc heat capacity of wet wood and dry wood
are compared with the available literature data. It can be seen that the speciﬁc heat capacity of dry wood as determined by the genetic algorithm falls between the available literature data. The speciﬁc heat capacity of wet wood used in these calculations is close to the literature data. Fig. 8 b shows the speciﬁc heat capacity of char as optimized by the genetic algorithm falls between the available literature data. Fig. 9 gives similar plots for thermal conductivity. It can be seen from Fig. 9 a that the thermal conductivity of both wet wood and
Temperature (°C)
Fig. 8. Comparison of temperaturedependent speciﬁc heat capacity determined by genetic algorithm optimization with literature data. (a) Virgin wood; (b) Char.
Temperature (°C)
Fig. 9. Comparison of temperaturedependent thermal conductivity determined by genetic algorithm optimization with literature data. (a) Virgin wood; (b) Char.
dry wood optimized by the genetic algorithm is approximately a factor of two higher than the generic wood literature data, but matches the white pine literature data within 20%. Interestingly, Fig. 9 a shows the opposite trend for wood char. That is, the thermal conductivity optimized by the genetic algorithm matches the gen eric wood literature data, but is only 20–50% that of the white pine literature data.
4. Discussion
The simulations described above include both heterogeneous and homogeneous oxidative reactions, but char oxidation is con ventionally viewed as a heterogeneous process. Consequently, it is not clear whether the homogeneous reactions included in the present simulations are realistic. The effect of these homogeneous reactions on the simulation results was assessed by running calcu lations with only heterogeneous reactions, only homogeneous reactions, both types of reactions, and neither type of reaction. The results are shown in Fig. 10 . Comparing the surface tempera ture in Fig. 10 a for the case where both types of reactions occur with the case where only heterogeneous reactions occur, it can be seen that the homogeneous reactions start to have an effect as the surface temperature approaches 600 C. In order to determine whether it is feasible that homogeneous gas phase reactions could start to have an appreciable effect at temperatures near 600 C, the characteristic time scale of homoge neous gas phase combustion reactions must be compared with the gas phase residence time in the hot char layer. If these time scales are of the same order of magnitude, it is conceivable that
1512
C. Lautenberger, C. FernandezPello / Combustion and Flame 156 (2009) 1503–1513
Time (s)
Time (s)
Fig. 10. Calculated effect of heterogeneous and homogeneous reactions on oxida tive pyrolysis of white pine at 40 kW/m ^{2} irradiance and 21% O _{2} . Text in ﬁgures indicates reactions included in simulations. (a) Surface temperature; (b) mass loss rate.
homogeneous gas phase combustion reactions could occur as com bustible volatiles generated indepth ﬂow through the hot char layer and react with oxygen that is diffusing inward from the ambi ent. The order of magnitude of the volatiles’ velocity near the sur face is 10 mm/s. Consequently, the residence time in the char layer, assuming it has a thickness of 5 mm, is approximately 0.5 s. Although lowtemperature gas phase combustion chemistry is not well understood, experimental data [23] suggests the spon taneous ignition delay time of a lean propane/air premixture at 670 C (the lowest temperature at which data were reported) is approximately 0.2 s. Thus, at temperatures above 600 C, the gas phase combustion time scale could approach the residence time in a heated char layer. Consequently, it seems plausible that in oxi dative environments, homogenous gas phase reactions could occur inside the pores or voids of a thermally stimulated solid and con tribute to the overall heat release. However, no ﬁrm conclusions can yet be drawn, and future work in this area is encouraged to help unravel the physical mechanism of oxidative pyrolysis, in par ticular whether or not homogeneous gas phase reactions occur. The present simulations include a simple Couette model for blowing (see Eq. (30c) ) that, while probably better than not accounting for blowing at all, may not accurately represent oxygen diffusion through the natural convection boundary layer in the experiments. The calculated surface temperature and mass loss rate for the 21% O _{2} case are shown in Fig. 11 with and without blowing. It can be seen that the surface temperature is higher when blowing is disabled due to greater diffusion of oxygen to the surface. Blowing also has an appreciable effect on the calcu
Time (s)
Time (s)
Fig. 11. Calculated effect of blowing on white pine oxidative pyrolysis at 40 kW/m ^{2} irradiance and 21% O _{2} . (a) Surface temperature; (b) mass loss rate.
lated peak mass loss rate. Boonmee and Quintiere [9] used the clas sical stagnant layer model (sometimes called the Stefan problem) to account for the effect of blowing through a Spalding mass trans fer number ( B number).
5. Concluding remarks
A model for the oxidative pyrolysis of wood is presented and demonstrated by simulating the nonﬂaming gasiﬁcation of white pine slabs irradiated at 25 kW/m ^{2} and 40 kW/m ^{2} in atmospheres having 0% O _{2} , 10.5% O _{2} , and 21% O _{2} by volume (balance nitrogen). Diffusion of gaseous oxygen from the ambient into the porous char layer and its effect on oxidative reactions occurring within the decomposing solid is explicitly modeled. Both heterogeneous (gas/solid) and homogeneous (gas/gas) oxidative reactions are con sidered. A novel feature of the model is that it includes the capabil ity to automatically adjust to changes in environmental conditions (in particular, reduction in the oxygen concentration that a surface feels due to blowing, immersion in an oxygenvitiated upper layer, or the presence of a nearby diffusion ﬂame). Model calculations are compared to experimental oxidative pyrolysis data [12] for mass loss rate, surface temperature, and indepth temperature with gen erally good agreement. Due to the relatively large number of species and reactions in cluded in the modeling approach (four condensed phase species, seven gas phase species, four heterogeneous reactions, and two homogeneous reactions) almost 50 model input parameters (ther mal properties, reaction coefﬁcients, etc.) must be determined. Ge netic algorithm optimization [18,19] is used to estimate the required input parameters from available experimental data. Tem
C. Lautenberger, C. FernandezPello / Combustion and Flame 156 (2009) 1503–1513
1513
peraturedependent speciﬁc heat capacities and thermal conduc tivity estimated by genetic algorithm optimization are compared to literature data (generic wood properties [13] and properties from an earlier pyrolysis modeling study of white pine [22] ). It was found that the speciﬁc heat capacity for wet wood, dry wood, and char falls between literature values for generic wood and spe ciﬁc data for white pine. However, the optimized values of thermal conductivity for wet wood and dry wood are slightly higher than analogous literature data. The thermal conductivity of char is close to one literature value, but it is considerably lower than another literature value. Although no ﬁrm conclusions can be drawn, the authors believe that the optimized model input parameters deter mined by genetic algorithm can be treated as material properties, meaning that they should be independent of environmental condi tions (applied heat ﬂux, oxygen concentration, etc.).
Acknowledgments
This work was supported by the National Science Foundation under Grant 0730556 and the NASA Graduate Student Researcher Program under Grant NNC04HA08H.
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