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231
A simplified model of the pyrolysis of charring materials is analyzed. The effects of moisture are neglected, and the
heat of pyrolysis is assumed equal to zero. Four stages of pyrolysis are obtained: (i) inert heating, (ii) initial pyrolysis,
(iii) thin char, and (iv) thick char. Formulas for the volatile mass efflux, m, are obtained in stages (ii), (iii), and (iv);
m = 0 in the first stage. The calculations indicate that the surface temperature controls the volatile production rate in
the initial pyrolysis stages (the kinetically controlled regime), while the temperature gradient controls the volatile
production rate in the thick char stage (the diffusion-controlled regime). Comparisons of the calculated results with
numerical computations are made for the volatile mass efflux, the surface temperature, and the density.
I. I N T R O D U C T I O N
Wood and other cellulosic materials constitute a
substantial fraction of the fuel load in many
building fires, and are increasingly being utilized
as renewable sources of energy. Thus, it is
important to understand their behavior under hightemperature burning conditions. When heated
sufficiently these materials eventually undergo
thermal decomposition, producing combustible
gases (volatiles), water vapor, and char. Quantities that are of particular importance in the field of
fire research are the evolution rate of the volatile
gases and the surface temperature of the pyrolyzing sample. Knowledge of these quantities is
required in both the ignition and growth stages of
the fire.
A substantial amount of experimental and theoretical work on the pyrolysis of thermally thick
samples of wood and cellulosic materials has
already been done. The recent experimental work
is reviewed in [1], and will not be considered
further here. The previous theoretical studies can
generally be divided into two groups: (1) detailed
numerical studies that attempt to provide a comprehensive description of wood pyrolysis by ineluding as many physical processes as possible and
Copyright 1987 by The Combustion Institute
Published by Elsevier Science Publishing Co., Inc.
52 Vanderbilt Avenue, New York, NY 10017
0010-2180/87/$03.50
232
~-
~4.
o.
H(Ts-T=)
....
/
-xa#_
I////////I
F-H(T-T.)
,.,
~dT
-E'/RT
,4
.A
p--p,., T=T.
Fig. 1. The physical configuration. The dimensional governing equations and boundary
conditions are also shown.
233
0 _ Inert _ l T r a n s i t i o n
r h e a t i n g l - regime
_ _i Thin
- I - - ] char
Thick
char
?
"
Fig. 2. A qualitative plot of the volatile mass flux, rh, versus time, /', indicating the separate
ties, such as condensation temperatures as functions of pressure, are unknown; therefore, the
calculation of their influence is impossible.
The second assumption is that the chemical
processes occurring in the decomposition of
" d r y " wood to char can be modeled by a single,
one-step rate equation containing three fixed parameters, the char density, the preexponential
factor, and the activation energy. This assumption
is an idealization of the actual process since wood
decomposes in a complex manner, producing
hundreds of compounds. However, there is presently much controversy concerning its precise
nature (even for pure cellulose, see, e.g., [9, 10]),
and no generally accepted reaction pathway, analogous to those used to model gas-phase reactions,
has yet been developed. Thus, since the physical
parameters appearing in the one-step rate equation
have direct physical meaning, and since much of
the recent experimental work has been devoted to
their measurement [11], it is felt that use of the
one-step scheme is appropriate.
The third assumption is that the heat of pyrolysis term, Q, which appears in the equation for
conservation of energy, is negligible. As discussed
in Ref. [4], there is much confusion concerning Q.
Reported values vary between 180 cal/g (endothermic) and - 4 5 0 0 cal/g (exothermic). The
exothermicity apparently arises from secondary
234
Energy:
P at
cgx P
Op
Decomposition:
--= -A(p-6)e
Ot
Mass:
am
ap
ax
at '
(1)
'
-E/r,
(2)
(3)
- P ~xx (0, t ) = 1 - r ( T s -
1).
III. ANALYSIS
There are four distinct stages of pyrolysis that
will be considered in the limit of high activation
energy, E ~ ~ . The important features of each
are illustrated qualitatively in Figs. 3a-3d. In the
inert heating stage the density is constant, because
Ts < Tp is always satisfied (Fig. 3a). The initial
pyrolysis stage contains the preliminary effects of
chemical reaction. A narrow reaction zone develops near the surface, in which 6 < p < 1 and
Tp < Ts < Tc (Fig. 3b). When Ts passes through
To, a thin char layer forms at the surface (Fig. 3c).
In this stage the conditions satisfied by p and Tare
p = ~, Ts -> Tc in the char layer, and t5 < p < 1,
Tp < T < Tc in the pyrolysis zone preceding it.
The temporal and spatial matching of these three
regimes is easily achieved because they fall in the
initial, or kinetically controlled, pyrolysis regime.
The thick char stage, however, represents the long
time behavior of the system (Fig. 3d). Here, the
surface temperature approaches its maximum
value, Tmax = 1 + 1 / r , obtained from the second
of Eqs. (4) by putting a T s / S x = 0. Temporal
matching of the solution in this stage to that in the
kinetically controlled regime is very difficult,
because the time t appears only as a parameter in
the equations.
Here, T = T/~**,p = ~ / ~ , x = / [ / S =
05=/~)7~**/P], and t = /'/? [? = 2/&=] were
used for nondimensionalization. The four nondimensional parameters appearing in Eqs. (1)-(4)
are E = /~//~7~ and A = A?, the nondimen-
235
Ts<TO
p= T=
pT
{a)
ps=pf - -klye
. ---x
\
"Is:,.Tp
(b)
Ts>Tc
Ts'Tmax
Tc
layerzone
Tc 4._.-----Reaction
"z'& I
p= T
(c)
p=,T=
(d)
Fig. 3. The four pyrolysis regimes: (a) the inert-heating stage, in which no reaction occurs
and the density is constant, (b) the transition from inert heating to charring conditions, (c) the
thin-char regime, in which Ts > To, and (d) the thick-char regime.
where
TI = 1 +
a=(-OTi/OX)x=o=er2tp
1[
erfc
X erfc I"v~+
- e rx+r2t
(5)
Tp-ax+b(t-tp)+...,
(6)
and
OT
-- -
ax
erfc(r4~p),
(8)
t=tp
1
ra,
(9)
(10)
b = (OTx/at)x=o -
t=tp N~tp
and
1
A (1 - 6 ) e - E / T 1 ('t).
Ot
- a + b [ x + I'( t - tp)] + " " ,
(7)
236
Asymptotic evaluation of the resulting integral
over t in the limit E ~ oo leads to
Op = 1
A(1 - 5 )
- e-E/Tp.
bE/Tp 2
(I 1)
(i)
0t
0x ~
~\~-x
(ii)
Ox
'
ro
(iii)
O0
(l-o)
-O-~(O't)=
p
(iv)
O(x, 0 ) = 1 ,
( OT,'~ FO
\-~X/---'O
019= _D(p_5)e_(E/Tp2)[ax_b(t_tp)_Ol
Ot
(13)
~'= (aE/Tp2)x,
(ii)
r=(bE/Tp2)(t-tp)+lnDo;
Do =D/(bE/Tp2),
(14)
0 = Oo/(E/Tp 2) + o [(E/To2)-I].
(15)
237
PYROLYSIS M O D E L OF C H A R R I N G M A T E R I A L S
By substituting Eqs. (14) and (15) into Eqs.
(12), (6), and (7), and noting that the initial
conditions (12iv) apply at t = tp (i.e., at z = In
Do), one obtains the following lowest order
equations;
(i)
p -~/=~,
(ii)
0p
--=
Or
- ( p - 6)eo +T-r,
(iii)
OOo
1-O(0, r)
- (0, ~-)=
(iv)
p(~', In Do) = 1,
~"
(16)
p(0, r)
Oo(~', In Do)
i o -OoOt- d x .
m= -
=00(0% r)=0.
By introducing the similarity variable
s=r-~=(bE/Tp2)(t-tp)+lnDo-~,
C o ( s ) = is_~
p(u----3--du,
(18)
(ii)
do
--=q,
ds
p(So) = 1,
q
- - ~--,
ds ( p - ~) p
dq
q2
q(so) = - (1 - a)eSo,
b iv do d s = b [ l - p ( 0 ,
a -=ds
a
(17)
. b. i. Oo ds
a o Or
r)].
(20)
m= --
o -~T
d~ - - e "
a
(o-6)eo-~
b
=- (1- 6)e',
d~
(21)
-"
e - el Tp +(bE/Tp2)(t -
tp),
(22)
( a E / T p 2)
m -
A(1-6)
T~2
e-E/rs,
(23)
( - OT/Ox)s E
(19)
I N D R E K S. W I C H M A N and A R V I N D A T R E Y A
238
e#
2.0
LO-
1.5 l
p,
O,
-1.0
.5
..5
=0.6
~:o
2'0
/b
'
'/o
-
JlO
2.'o
~'in the
t l.O5"
.5"
(24)
1.0
.5
(25)
aE/Tp2
(26)
as
239
00
--=
0re
Oo
TC.AR = TI +E/Tp--------5= TI
I t(l-p(u))/o(u)]
-~
du
(27)
E / Tp2
By substituting T = T c ~ a + if' into the decomposition equation, and expanding for small x and
small t - t~, one obtains the lowest order equation
[compare Eq. (13)],
-(O-6)e
*o+,c-l~.
(31)
mmax
dx = - - -
--
A ( 1 - - 6 ) e-E/rc I ' ( 0 - 6 )
-- a~E/Tc
------2
O._O=
p - A e - E/rc(p _ 6 )e_(E/Tc2)[acX_bc(t_tc)_ ~ l,
Ot
(28)
where [compare Eqs. (8) and (9)]
(i)
a c = ( -- OTCHAR/OX)x=
0
I=t c
(ii)
bc =
(33)
(29)
By defining the stretched variables
~ = (a~E/T~2)x,
F Ae-E/Tc ]
(ii)
(iii)
~I, =
(E/Tc 2)
P-6
11-6= - ( l + k - ~ x ) e-~X/aX
~Io
(32)
--
I=fC
(i)
e - t~ d~c.
a~
1
(OTcHAR/Ot)x=O
d~c
+ o [(E/T~z) - ~],
_l '
(30)
1-6
= 1 - [ 1 + kc ~'~]e-kcr,
(34)
where
4.3 a
k c - 3 . 1 ac
Tp/
"
(35)
240
~2
A(1-~)
1 + kc,/ ( - a T / O x ) s
kc
mmax - -
TcEe-e/rc'
t=t c
(36)
which should be compared with Eq. (23) for
functional dependence of m on T.
111.4. T h e T h i c k - C h a r
Stage
III.4.1.
In this stage the reaction zone is assumed infinitesimally thin with respect to the length scale L,
while the surface temperature is assumed close to
its maximum value, given by Eqs. (4) when a T/Ox
= 0:
Ts,max= 1 + 1/F.
(37)
Zone
0 = ( E / T c 2 ) ( T - To)
and
S = - ( E / T c 2) [ x - Xc(t)],
(40)
~-~ p ~
--0,
(41)
dxR
m = (1 - ~) - - ~ = (1 - 5) OR,
(38)
Decomposition:
where OR = dxR/dt is the velocity of the reaction
layer. To solve for m, the reaction zone must be
studied in detail. This leads to jump conditions on
ap
- - = - (p - 6 ) K ( t ) e - , (42)
aS
where
Ae-E/Tc
(43)
K(t) = (E/Tc)2(dxc/dt) ,
%hot
' "
,~-7 . . . . . . . . .t
2" "
"////////v'/I/////////////f/////////4
" ......
.....
"T
dt
"
R~tion Layer
O--' - 0%
p ~ I.
p-*~
(44)
VJ~in Wood
O = g (t)
Fig. 6. Mass balance across the reaction layer, giving m = (l
- it)oR. Also shown are the boundary conditions on Eqs. (41)
and (42) in the stretched S-coordinate system.
O--+oo,
iso o(z, t) ,
(45)
241
lim S = - oo.
(48)
and
= ( ~ 6 6 ) g( t),
(46)
do
(i)
~-~=q,
p(S--, - oo) = 1,
(ii)
dq - - - qZ ~ g ( t ) - q,
dS 0 - 6
o
q ( S ~ - oo) - (1 - 6 ) K ( t ) e gins.
(47)
g( t) = J/'ftt,
(49)
(50)
J = erf(F/x/-6)
and F is determined from the transcendental
equation
e_F2[(l/6)_l I
erfc F
1 To- 1
e r f ( F / x / 6 ) - x / 6 Tm~x- Tc "
(51)
F=
T-I/"
(52)
242
K(t)
t.O
A5
K(t
q(t)),
5.5
AS(t)
I
1.5
Fig. 7. The reaction-zone thickness, AS, as a function t wz, indicating that AS -- t v2. The
functions K(t) and g(t), used in the calculation of AS, are also plotted against t j/2.
viz.,
m=
(1-tS) F
(53)
IV. N U M E R I C A L COMPUTATIONS:
COMPARISON AND DISCUSSION
Equations (1)-(4) were also integrated numerically
with an iterated Crank-Nicolson scheme [2].
Shown in Fig. 8, for the case (,4, E, ~, r ) =
(10 n, 40, 0.3, 0.4) is the resulting m versus t plot
and its comparison to the predictions of Eqs. (20),
(22), and (23). The mass flux rises until p = ~ at
the surface, and decreases monotonically thereafter. By using pp = 0.99 the parameters shown in
Table 1 can be calculated. The m versus t profiles
of Eqs. (22) and (23) approximate the exponential
rise of m well for small t - tp. However, they rise
much faster as t - tp increases, since reactant
depletion has been neglected. The estimate for m
given by Eq. (20) is also an overprediction;
although reactant depletion has been included, the
asymptotic formulation uses the linearized Arrhenius exponent, ( - E / T p ) + ( E / T p 2 ) ( T Tp),
which for T > Tp is always less than its actual
PYROLYSIS
MODEL
OF CHARRING
243
MATERIALS
A(/-,~
bE
/.6
.5.
~m= ~[/_,,~o,r)l
.5
LO
L5
Fig. 8. The mass flux m versus t for the case A = 10 n , E = 4 0 , 6 = 0.3, a n d F = 0.4.
Shown are the numerical evaluation of Eqs. (1)-(4), the asymptotic predictions of Eqs. (22)
and (23), and the numerically evaluated mass-flux profile of Eq. (20). The numerical
computations give tp = 0.27, tc = 0.69, and rnmax = 0.825. The best-fit curve, m = 0 . 5 2 / ~ ,
is plotted in the thick-char regime. The point rn~x, evaluated from Eq. (36), is also shown.
TABLE
Calculation of Parameter Values for Each Heating Stage, for the Case A = 10 u, E = 40, 6 = 0.3, l" = 0.4 (Where Possible,
Comparisons Are Made between Calculated and Computed Values, and Percent Difference Is Shown)
Heating
Stage
Inert
Initial pyrolysis
Thin char
Quantity
Tp
tp
a
Calculated
Value
Source
1.5
0.27
0.80
0.76
F__.qs. (8)-(1 l)
Eqs. (8)-(11)
F.q. (8)
Eq. (9)
s*
tc
rn,~,
Ax
0.6
0.61
0.66
0.22
Fig. 4
Eq. (24)
Eq. (25)
Eq. (26)
a~
2.58
b~
2.16
1.76
Eqs.
used
Eqs.
used
Eqs.
(8), (29i);
tc = 0.7
(9), (29ii);
tc = 0.7
(5), (15),
Numerical
Value
Percent Difference
[(~NUM -- t~CALC)/~NUM)] X 100
-----
--
---
-0.7
0.825
--
-13
20
--
--
--
--
--
1.97
i0
--
--
0.825
12
-0.52/~-
-62
--
( 1 8 ) , at t = 0 . 6 1
Thick char
kc
0.74
mmax
0.73
F
m
0.27
0.2/x/t
244
I N D R E K S. W I C H M A N and A R V I N D A T R E Y A
/////
m,
*" .5.
t,
. . . . .
.27
.5
tO
L5
Fig. 9. Surface temperature and density profiles for the case of Fig. 8. The asymptotic
estimates of p~ and Ts, obtained in Sections III.1 and II1.2 are also shown (---). The inert
temperature profile is shown as Tt( . . . . . ). Note that Tmax = 1 + r - ~ = 3.5.
Examination of Fig. 10b shows that the temperature profile across the reaction zone (denoted as
the region within hatchmarks) becomes less steep
as the reaction zone propagates into the sample.
This and the above discussion suggest that the m
versus t behavior is controlled primarily by aT~
Ox. From Section 111.4, the substitution of Eq. (49)
for g ( t ) into Eq. (46) shows that the jump in 07"/
@x across the reaction zone decreases as t -~/2.
From Eq. (53), m oc t-1/2, which follows the
same time dependence. Therefore, the volatile
mass flux in the thick char stage depends on the
diffusion of thermal energy into and out of the
reaction zone, which is controlled by the local
temperature gradient.
By contrast, the mass flux in the initial pyrolysis
stage is controlled primarily by the instantaneous
surface temperature, Ts(t) [see Eq. (23)]. The
functional dependence of m on Ts is much
stronger than its dependence on ( - @ T / O x ) s .
Consequently the initial pyrolysis stage is referred
to as the kinetically controlled pyrolysis stage [4].
V. S U M M A R Y A N D C O N C L U S I O N S
The model equations for the pyrolysis of a
charring material were analyzed in four distinct
PYROLYSIS
MODEL
OF CHARRING
MATERIALS
245
t= . 2
t.O,
2.C
1.5
.01
.02
- x - .03=
.04
.05
Fig. lOa
0 ......
o.b5
0 '/
0 '2
~
03
"
Fig. 10b
n-.54
7/.83
]~
mL= A (n - 8) e -E/ T
L 3.
2.
o.1
o.'5
'
,.b
X
,,
"~
Fig. 10c
Fig. 10. Numerically calculated [from Eqs. (1)-(4)] profiles of p, T, and mL = (p -- ~i) e x p ( - E / T ) as
functions o f x and t, for the case A = l 0 n, E = 40, ~ = 0.3, 1" = 0.5. Note that the m a x i m u m of rn
occurs when t = 0.8 (i.e., when p~ = ~5 = 0.3 is first attained). The wavelike character of pyrolysis in the
transition stage is evident from (a). The m a x i m a of mL for t = 0.8 and t = 1.0 occur when p = 0.55.
Therefore, mL and p are n o t functions of T alone.
246
ac
b
bc
Cp
D
Do
E
g(t)
K(t)
kc
L
m
r~
q
r~ = m / ( b / a )
q = da/ds, see Eqs. (19)
heat source term; Q = 0 is used here
Qs
nondimensional net heat flux into surface
/~
ideal gas constant
s
similarity variable, s = r - ~"
so
s evaluated at t = tp, So = In Do - ~"
S
stretched spatial coordinate in thick-char
regime, see Eq. (40)
AS
reaction-zone thickness
s*
value o f s for which m = mmax;S* depends
on 8 [see Fig. 5]
t
nondimensional time, t = f/
T
nondimensional temperature, T = 7~/f'~
TCnAR nondimensional solution for T up to charring time
OR
nondimensional reaction-zone propagation
velocity, OR = dXR/dt
XR
nondimensional reaction-zone location
Greek
&
r
8
~x
0
PYROLYSIS M O D E L O F C H A R R I N G M A T E R I A L S
P
?
xI,
nondimensional density, p = ~ / ~
Stefan-Boltzmann constant
characteristic time, ? = /S2/&~,
nondimensional temperature correction in
the thin-char stage
Subscripts
c
H
I
max
o
p
s
w
oo
char
hot-char
inert
maximum
lowest-order approximation
pyrolysis
surface
unburnt-wood
ambient
Superscripts
dimensional quantity
average
247
REFERENCES
1.