Combustion and Flare,,- 261

A Reviiew cf Kinetics Data for the

Pyrolysis of Wood
and Related Substances
A. F. Roberts
Ministry of Technohlgy, Salbty in Mines Research Establishment. Field Laboratories, H,', put Hill. Buxton.
Derbyshire, England

A considerable variation exists in published values of the kinetics constants for the pyrolysis of wood and its constituent
substances. This paper discusses the factors affecting the pyrolysis process--contposition etTeets, catalysis and
uutocatalysls, effects due to the physical structure of wood. and effects due to ch~lnges in experimental eondition~.
It is convenient to consider the kinetics data in two groups: those derived from experiments with small samples, in which,
experimental condltiotls could be closely controlled, and those derived from experiments with large samples, which relate
more closely to the behavior 9f wood in practical situations.
The data from small samples showed two distinct types of behavior. In some e~tses the pyrolysis appeared to proceed
with an acti~tation energy of 56 kcal mole- 1 and in others with an activation energy of 30 kcal mole- t The deta suggest
that pyrolysis may proceed entirely by either of these routes or by a combination of them. The choice of route may be
dictated by apparently in~.;gnificantfactors, such as the method of preparation of the sample or the size of the sample.
The data I'rom large samples are consistent with the view that pyrolysis proceeds with an activation energy of
30 kcal mole- J and that the pre-exponential factor may vary considerably because of a comb~natlon of structural and
autocatalytic effects. The lowest value derived for the pre-exponential factor for large samples is approximately the same as
the value derived f~r small samples. The factors considered enable the available data to be arranged in a reasonably logical
pattern, from which conclusions may be drawn as to the appropriate values for kinetics consta'ats to be used in particular
situations.

1. Introduction fairly m i n o r c h a n g e s in heating c o n d i t i o n s or

M a n y i n v e s t i g a t i o n s have been reported in
w h i c h d a t a o n the pyrolysis o f w o o d a n d related
s u b s t a n c e s have been an aly zed in t e rms o f a n
overall reaction kinetics scheme. A l t h o u g h any
o n e i n v e s t i g a t i o n will generally p r o d u c e a ki-
netics s c h e m e w h i c h satisfactorily represents a
p a r t i c u l a r set o f data, the variation of rate
c o n s t a n t s d e t e r m i n e d f r o m different investiga-
t i o n s is considerable. T h e pyrolysis of w o o d
involves a c o m p l e x series o f reactions, a n d
s a m p l e c o m p o s i t i o n , for example, m a y affect
n o t o n l y the rate of reaction b u t also ll~e actual
c o u r s e o f the reactions.
Since overall reaction kinetics schemes have
been used successfully to describe the behavior
o f p y r o l y z i n g wo~:,d in a variety o f circumstances,
there is justification for a s s u m i n g that their use
represents a useful a p p r o a c h to the problem.
a l t h o u g h o n e rende red c o m p l e x by the variety
o f factors whi c h m a y affect the pyrolysis

Comht~stitm & dlaow, t4, 26I+272 (197t))

~.~ Crox~nCopyright 19fi9
Published by American ElsevierPublishingCompany. Inc.
262
process. A range of practical problems is as-
sociated with the pyrolysis of wood--the be-
havior of wood in a fire, the self-heating of
cellulosic materials, ihe role of inorganic salts
as fire retardants for timber, for example. The
main purposes of this paper are to assess the
extent to which the accurate studies of the
pyralysis of small samples of wood and its
constituents can be compared with the studies
of the pyrolysis of wood in bulk and to discuss.
for the solution of practical problems, the fac-
tors affecting the choice of a reaction kinetics
scheme to describe the behavior of wood in
bulk.
It has been suggested by Essenhigh [1] that
the use of a reaction kinetics scheme to explain
wood pyrolysis is inappropriate because it
implies that such pyrolysis takes place through-
out the wood volume at a rate dependent on the
local temperature, whereas pyrolysis should be
represented as a process occurring at a surface
which moves into the wood. However. there is
evidence from X-ray measurements [2] and
from heat generation measurements [3"1 tiaat
reaction can take place th.roughout the volume
of pyrolyzing cellulosic cylinders, so that the
use of reaction kinetics cannot be discounted.
Under some conditions there will be a virtual
discontinuity between reacted and tmreacted
substance when wood is being pyrolyzed, but
this can still be consistent with control of the
process by kinetic considerations.
2. Kinetics Equations
The following equations (or wlriations of them)
have been widely used to analyse data on wood
pyrolysis :
?p/gt = (p - pj,)K (I)
and K = k exp ( - E / R T ) (2)
where p =toeal density of pyrolyzing material
at time t. p~, = final density of pyrolyzing ma-
terial at time ~'J, K = reaction rate constant,
A. F. Roberts
k = pre-exponential factor, E = apparent ac-
tication energy, R = gas constant, and T = ab-
solute temperature.
The kinetics data are usually summarized in
terms of k and E, but in the present discussion
sets of data will be compared graphically by
plotting In K against 1/ T ow:r the range of tem-
peratures covered by the particular set of ex-
periments. This method of comparison will be
used for two reasons. (1) It is the reaction rate
constant as such which is of interest in predicting
the rate of weight loss of a pyrolyzing material,
rather than the separate values of k and E.
(2) If two sets of data have similar values of K
in a particular temperature range but the
measured variations of K with T show some-
what different trends, the correlation of K with
T by means of Eq. 2 and the presentation of the
data in terms of E and k would tend to obscure
the agreement which existed.
3. Factors Affecting the Interpretation
of Data
Some information is obtained from data on the
self-heating of wood, interpreted in terms of
thermal explosion theory. Equation I represents
a first-order reaction, whereas the thermal ex-
plosion theories generally assume a zero-order
reaction. The differences involved are usually
small since self-heating analyses are generally
concerned only with the initial stages of the
process of pyrolysis. The effects of reactant
consumption in analyses of this type have been
discussed by Thomas [4].
Several investigations of the pyrolysis of
cellulose 1"5-7] have yielded data in which the
initial stages of the pyrolysis did not follow a
first-order reaction law, although the later stages
did. Tang's [5] data follow a zero-order r'eac-
tion law Ibr the first 2-30/0 of weight Ins:;" the
data of Lipska and Parker [6] show a lapid
initial drop in weight of about 6 ° , Ibllowed by
a zero-order weight loss period accounting lbr
Kinetics Data for Pyrolysisof Wood
about 50°/o of the weight loss; the data of
Madorsky et al. [7] show the rate of weight loss
rising to a maximum at about 20% weight loss,
before decreasing according to a first-order
law; Akita's [8] data, on the other hand, follow
a first-order reactioll law throughout. In cases
of this kind the data relevant to the first-order
period are quoted, so that all data can be com-
pared on the same basis, that is, of a first-order
reaction scheme.
Experiments on the self-heating of wood yield
pre-exponenfial factors equivalent to kP(.i or to
kq, where q is the heat of cxothermic reactions
per unit mass of reactants. In assessing the data
from such experiments, a value ofq = 86 cal g - t
has been used to calculate k, as values close to
this have been reported by several authors
[3, 9 - I I ] . However. the heat of reaction is
another quantity liable to considerable varia-
tion, and values in the range 30-J,00 cat g - t
have been reported [3, 12-13]. The calculated
values of K based on self-heating data are in
doubt to this extent.
A difficulty exists in the use of Eq. I to inter-
pret data, since different authors ~lt|ribute dif-
ferent values to the term pj.. In some cases
where the total weight loss is not large, p/ is
taken to be zero [14.]. In static thermogravi-
metric analyses [15] p¢ is obtained from the
final sample weight after heating at a constant
temperature, whereas in dynamic thermogravi-
metric analyses [5] p/is obtained from the final
sample weight after heating over a range of
temperatures terminating at a high value. Thus.
for a static T G A p/ will be a function of the
temperature of the experiment, whereas foF a
dynamic T G A it will not. In general, two anal-
y,~;es (one static and one dynamic) giving the
same values for Op/?t at the same values of p
and T will not lead to the same values ['or the
rate constant. However, for tee ,~ratures in
excess of 300'°C, 'the effects of this ,Afference are
probabty unimportant. As this is the region ot"
interest in the present paper, such effects will
be neglected.
263
The use of density changes as a measure of
reaction rate in Eq. I implies that the products
of pyrolysis are discharged from the solid
system at the time of formation. However, as
discussed by Martin [16], this represents a
limiting case, since some products may be
formed at one temperature that are nol expelled
fi'om the wood until a higher tempcralLure. The
data of Lipska and Parker [6] on the pyrolysis
of cellulose show that intermediate compounds
accumulate in the solid residue du,ring pyrolysis.
so that the kinetics of the conversion of cellulose
differs from the apparent kinetics based on the
overall weight loss.
4. F a c t o r s A f f e c t i n g the P y r o l y s i s
Process
Composition
Wood is composed mainly of cellulose (c. 50°/o),
hemicellulose (c. 25 °/o), and lignin (c. 25°/o), the
proportions ot' these constituents varying to
some extent between species. Bro'~ne [17] has
stated. "The yield of products when wood has
been completely pyrolyzed is about what would
be obtained by pyrolyzing separately the prop-
ortional amounts of the major wood con-
stituents . . . . The hemicellulose is said to de-
compose first, largely between 200 and 260'.C,
followed by the cellulose at 240 to 350C and
finally by the lignin at 280 to 50,~)"C." Akita [8"]
has treated the kinetics of wood pyrolysis in a
similar way by applying a first-oi'der kinetics
equation to the pyrolysis of each contponent
separately and summing the result. He Ibund
good agreement between the measured weight
variation of a sal.fple of Japanese cypress at
320'C and the variation predicted by the above
means, assuming the wood to be composed of
5t3% cellulose, 30°/~ hemicellulose, and 20f~/.
lignin. At 320~'C. the wood sample lost 70~'/o of
its initial weight, but iignin alone lost only
400/0 of its initial weight, so that the contribu-
tion of lignin to the total weight loss was only
8 % and the calculated curve would therefore be
 264
insensitive to the assumed kinetics of the lignin
pyrolysis.
The kinetics o f the pyrolysis of wood com-
ponents have been studied by Stature [14],
Akita [8], and Tang [5]; some of their findings
are summarized m Table 1. The data for hemi-
Ks-t
cellulose support Browne's statement that this
is the most reactive of the wood constituents,
while the data of' Stature [14] and Tang [5]
support the statement that lignin is the least
reactive of the wood eonstituer~ts. Akita's [8]
data showing lignin to be more reactive than
cellulose are at variance with this statement.
Table 1. Ratios of Reaction Rate Constants of Woo-' Con-
stituents
Temperature, Hemi-
Author °C cellulose Cellulose Lignin
Stature 150 4 1 0,5
Akita 320 I0 I 1.6
Tang 320 I 0.25
Tang 350 I 0.06
Some effects that may be caused by the greater
reactivity of hemicellulose are apparent in dat:t
from experiments with wood. Tang's [5] data.
from dynamic TGA's, show wood to have a
greater reaction rate constant than cellulase
at temperatures up to 315°C (at which temper-
ature the wood had lost 400/0 of its initial
weight, cornpared to 200/0 for cellulose). Akita's
[8] data, from static YGA's. show an initial
, stage in the pyrolysis of wood with a higher
reaction rate constant than the htter stages.
Some support for Tang's data [5] on the,"
kinetics of lignin pyrolysis, which are plotted
in Fig. I. may be inferred from two studies with
samples of wood, Tirmey [I 8], when compu tin~
weight losses of lxeated wooden dowels, found
it necessary ~,~ introduce a "'breakpoint" into
the computations to obtain satisfactory agree-
ment with experimental weight records. In the
first stage of the computation he used E = 30
kcal mole- J and /¢ ~ 6.107-7,10 B s - t ; the re-
A. F. Roberts
lO'l
I0.2
i0-4
1.2 1,4 1.6 I,B 2.0 2.2 2.4
L ~ (°Kl-1
Figure I. Kinetics dat~ for the pyrolysis of lignin.Curve I.
Akita's data for lignin. Curve 2, Tang's data for lignin,
Curve 3, upper limit of Tinney's data for a second stage in
the pyrolysis of wood. Data of Roberts for wood samples
previously heated to constant weightat lower temperatures
are shown by x,
lationship of these values to others obtained for
the pyrolysis of cellulose is discussed in Section
5. In the second stage, he used E = 37-43 kea[
m o l e - t and k =4.10B-2.109 s - L The change
was made with P/Po~½ or ½. Values of K.
calculated with E = 37 kcal mole ~t and k =
2.109 s - t (i.e., the upper limit of Tinney's range
of values for the second stage ofwood pyrolysis),
are plotted in Fig, 1 over the relevant temper-
ature range. There are obvious differences in
ac~,ivation energy between Tinney's data and
tho,.e of Tang, but a measure of agreement
exists between the rate constants for lignin and
for the second stage of wood pyrolysis in this
temperature range.
Iv has been reported [5] that lignin yields
4 5 % solid residue when heated to constant
we;,ght whereas cellulose yields 15°/o. As a
rough guide, a wood containing 24°]0 lignin
init.ielly would yield 220/0 solid residue (H°]o
each from lignin and cellulose) and 78% vo)atile
products (I 3 °/o from lignin, 65 n/o from cellulose).
Tinney's "breakpoint" of P/Po~½ therefore
Kinetics Data tbr Pyrolysisof Wood 265
corresponds numerically to the completion of
cellulose pyrolysis.
The author (previously unpublished work)
obtained some data on l-ram-thick wood sam-
ples in static TGA's, which were carried out in tO-1
stages (see Fig. 1). Each sample was heated to
approximately constant weight at ot~e temper-
ature: the furnace temperature was then raised
to another level and further weight loss measure-
ments were made. At the time, file data seemed
inconsistent with other information, but in the I
light of "Fang's work it appears likely that
r 0 "~
heating the samples in stages allowed the cel- 1.2 1.4 f.6 1.8 2.0 2.2 2.4
lulose pyrolysis to go to completion at the lower I~.0 (oK).1
furnace temperatures, so that lignin pyrolysis
was studied at the higher furnace temperatures. Figure 2. Data of Murty and Blaekshear for tile l~yrolysis of
Data at furnace temperatures less than 320°C a cylinder of cdlulose. E:~chline represents mc~,sureraents
made of a radius r. Radius of cylinder = a.
(not included in Fig. 1) correspond to other data Line r/a Line i'/a
for the pyrolysis of celhtlose. The data given in I 0 5 0.57
Fig. 1 show good agreement with Tang's data 2 I).14 6 0,71
3 0.29 7 0.86
for the pyrolysis of lignin. 4 0.43 8 1,00

Antocataiytic Effects radial permeability, Therefore products from

Murty and Blackshear [2] have presented reac-
tion kinetics data obtained from experiments on
cylinders prepared by pressing filter paper clip-
pings into a mold to a density of 0.6 kg I -~.
Density changes during the heating of these
cylinders were computed from radiographs of
the cylinders so that local reaction rates could
be derived. The data of Murty and Blackshear,
shown in Fig. 2, were obtained in a single ex-
periment from measurements taken at different
radii. The major feature of these data is the great
increase in reaction rate constant at a particular
temperature on passing from the surface te the
center of the specimen, Or, illustrating the same
tiling in another way, a reaction rate eonstaat of
10- ' s - t is achieved at 337°C at the surfitce but
at 150°C at the axis of the specimen. It seems
reasonable to regard this phenomenon as an
autoeatalytic effect.
Because of their method of preparation, the
cellulose cylinders would have a relatively high
the pyrolysis of the ~urface layers would be able
to diffuse toward the cente - of the specimen
without difficulty.
In Fig. 2 a region is apparent in which K =
0.2 s- t over a range of temperatures and radii,
This effect has been attributed by Murty and
Blackshear [2] to the evaporation of an ac-
cumulation of liquid products. It does not
occur in the outer regions of the cylindrical
specimens.
Stamm [14] has described experiments in
which the rate of reaction was increased when
products were not free to escape, an effect that
could also be autocatalytic. Variations in reac-
tion rate caused by the addition of small percen-
tages of inorganic ,'ahs to wood or cellulose have
been described by Tang [5] and by Broido
[19]. Broido found the pyrolysis of cellulose to
be sensitive to as little as 0.15°/0 of inorganic
matter. Tang measured a 10-" increase in reac-
tion rate at a particular temperat,~re when 2 %
266
of monobasic ammonium phosphate was added
to wood. Tang's data show the effect of ;~tor-
ganic salts on the pyrolysis of lignin to be rela-
tively small, and it may well be that autocatalytic
effects are also small for the pyrolysis of lignin.
The Effects of the Physical Structure of Wood
The well-defined grain structure of wood may
be expected to have an effect on IIhe effusion of
volatile products from pyrolyzing wood. The
permeability of a species of wood varies con-
siderably with the direction of flow considered:
for European beech [20], for example, the
longitudinal permeability to air at 20~C (i.e.,
for flow parallel to the grain of the wood) is
0.13 m z s- a a t m - t whereas the average lateral
permeability (i.e.. for flow perpendicular to the
grain) is 2.5.10 -~' m" s-~ arm -~, the ratio of
these two permeabilities being 5.2.10 "~:1.
If one considers the flow of a gas with the
physi~:al properties of air at 20°C (si'ace the
physical properties of the products of wood
pyrolysis are not known) through a sample of
beech at a rate of 10 g m - -' s- t (a practical rate
~or volatile evolution), tb." following pressure
gradients would be created:
For longitudinal flow, pressure gradient
=6.10 -5 arm m m - t
For lateral flow, pressure gradient
= 3 a t m mm - I
These estimated pressure gradients suggest
that a longitudinal mass flux of the above order
could occur in beech . ithout an 7 changes in
structure. A lateral m,tss flux of this order,
however~ would have, : be prect, ded by a marked
breakdown in the wood's structure, giving rise
to a greatly increased lateral permeability.
Measurements have been made of the pres-
s:ares at the axes of heated wooden cylinders the
"rods of which were sealed so that the products el"
th~ pyrolysis were constrained to flow laterally.
Tinne7 [18] measured a maximum pressure of
A. F. Roberts
0.14 atm at a ~ocal temperature of 330°C in one
experiment, and 0.29 atm at a local temperature
of 280°C. The present author (previously un-
published work) measured a maximum pres-
sure of 0,28 atm at a local temperature of 320°C.
In each case the pressure dropped fairly rapidly
from its maximum value at a time when struc-
tural changes could be observed and the rate of
weight loss was high. These maximum pres-
sures correspond to pressure gradients of the
order of 0.1 arm m m -1. In another experiment
with a heated wooden cylinder 1"3], in which the
maximum temperature achieved was 285°C, a
maximum rate of product evolutien of 0.8 g m - 2
s - I was achieved without any macroscopic
structural changes, such as fissuring. According
to the above estimate, such a rate would have
required a pressure gradient of 0.24 atm m m - t
if no change in permeability had taken place.
Either microscopic degradation of the wood
structure, giving rise to breakdown ofcell walls.
or acltivated diffusion of the products could act
to reduce the pressure gradients.
A:tempts have been made to follow the varia-
tion in the resistance to flow of wood specimens
undergoing pyrolysis (present author, previously
unpublished work), by inserting a number of
pressure .~Jppings in a block of wood and passing
a small flow of nitrogen through the block as it
was heated. These experiments showed a fairly
rapid decrease in resistance to flow at a mean
temperature of 308~C. The variations in this
temperature were fairly large, the standard
deviation of the measurements being 30°C.
The longitudinal permeability of wood is a
physical property which varies widely between
species. A range of at least 106:1 has been re-
ported [20]. Experiments have been reported
[21-22] in which samples of wood with similar
densities but widely different longitudinal per-
meabilities were subjected to similar beating
ccnditions. The rate of weight loss was foand to
vary, even with the edges of the sa.npl:s sealed,
so that structural effects may have an influence
on the observed kinetics of pyrolyzing wood.
Kinetics Data Ibr Pyrolysisof Wood 267
The Effects of the Pressure at Which 10-0
Pyrolysis Takes Place
10-1
Madorsky et al. [7] pyr~iyzed 6-rag samples of
cellulose at a pressure of 1.3.10 -8 atm and at 1
atm in nitrogen [23]. "['hey observed no varia- Ks -i I0":~
tion in the rate o ; wetght loss of the samples~ lO-:~
although at I atm the yield of lighter fractions
(condensable at 25°C) was increased at the ex-
pense of the yield of tars, compared to the low- ,o-'
10"s 2
I
pressure experiments. The authors sugd,est that 1.2 1.4 1.6 1.8 2.0 2.2 2,4
the initial pyrolysis is unaffected by pressure
and that at low pressures the tar molecules
escape without undergoing further reaction, Figun 3. Ktlleticsdatafor smallsamplesof woodor cellulose,
whereas at 1 atm their residence time in the Line Author
furnace is sufficient for secondary decomposi- I Tang(initialstages) 5
2 Stature 14
tion to occur. 3 Kujiraland Akahlra 24
In experiments with beech samples 1.2 mm 4 Akita 8
thick, Akita 18] observed a higher reaction rate 5 Madorsky.Hart, and Straus 7
6 Lipskaand Parker 6
at a pressure of I atm than at 2.7.10- 3 atm. At a 7 Tangtfinalslagcs) 5
temperature of 350~'C the ratio of reaction rate
constants was 2.3: I. The amount of solid residue
formed was also higher at a given temperature samples less than 1.5 mm thick were used, are
in the experiments at 1 atm. A related observa- plotted in Fig, 3. One of the sets of data was ob-
tion showed an increase of 15°/'0 in the reaction tained from wood (line 2): the rest. from cel-
rate consiant of a 2.4-ram specimen, compared lulose (paper or cotton). Becau~v of their tightly
with a 1.2-mm specimen at d'e same temperature controlled experimental conditions and ac-
and at a pressure of l atm. These data suggest curacy of measurement, these investigations
that, at a pressure of I atm. the residence time give reasonably reliable values for rate con-
o~ the products within the wood sample is suf- stunts.
ficient for autoeatalysis to occur, thereby in- It is clear that the dat'g in Fig. 3 may be
creasing the reaction rate by an amount which divided into two sets, those giving an activa-
is dependent ~n residence time. tion energy of approximately 30 kcul mole- t
and those giving an activation energy of ap-
The Effect e~ Wood Type on the Observed proximately 50 kcal mole -'1. In the first set the
Kinetics of Pyrolysis data of Tang [5] (initial slages). Akha [8].
I~ experiments at a pressure of 2.7.10 -a atm Stamm [14], and Kujirai and Akahira [24] can
with nine different species of wood Akita [8] all be represented reasonably well by E = 3 0
observed a range of rate ~.onstants of 2.8-- kcal mole-1 and k = 7.107 s - I over the tem-
8.3.10 -3 s -1 at a temperature of 350°C. with perature range 230-400"C. (This line is not
some variation in the apparent activation energy. shown on Fig. 3 because of overcrowding.)The
data in this set relate to all stages in the pyrolysis
5. Kine*ics D a t a of cellulose, from initiation to completion, so
Kinetics Data from Small Samples that it would appear that pyrolysis can proceed
Data from a number o1~investigations, in which entirely by this route. One systematic variation
small samples of finely divided material or which is apparent within this set is in Akita's
268 A. F. Roberts
data, which give E = 36 kcal mole- t at temper- Tats explanation appears to be consistent
a~ures up to 340°C and E = 25 kcal mole "a at with the mechanism for the pyrolysis of cellulose
higher temperatures for both wood and cel- suggested b~:,Kilzer and I~roido [26]. They sug-
lulose. gest competition between a depolymerization
In the second set the d~.ta of Madorsky et al. of cellulose and a dehydration of the cellulose
[7], Lipska and Parker [6], and Tang [5] (final followed by further decomposition of the "de-
stages) can be represented reasonably well by hydrocellulose," with the latter set of reactions
/?= 56 kcal mole- t and k = 4.1017 S- t OVCIthe liable to cata~ysi.~ by inorganic intpurities.
temperature range 275-360°C. None of these Studies of the thermal degradatioL~ of various
data relates to the initial 20°/0 weight loss in polymers, made by Anderson and Freeman [7].
cellulose, as Tang found the first 200/0 of weight have given values of E of 60-67 kcal mole- a for
loss to follow a first-order reaction law but with the main reaction, which is attributed to ran".om
E = 35 keal m o l e - t and the other investiga- rupture of carbon-carbon bonds in the polymer.
tions found that the first 20% of weight loss did a process requiring 66.2 kcal mole- ~. It there-
not follow a first=order reaction law. However, fore seems possible that the reaction ofcdlulose
with this limitation, the data relate to ~:11¢ f t h e with E = 56 kcal mole- t is a depolymerization
remaining stages of cellulose pyrolysis through and the reaction with E = 30 kcal mole- t is the
to completion. catalyst-sensitive decomposition discussed by
A two-stage mechanism for the pyrolysis of Kilzer and Broido [26].
wood or cellulose has often been discussed
[5,8.25], with a high-activation-energy reac- K i n e t i c s D a t a f r o m L a r g e Samples
tion and a low-activation-energy reaction pro- Dam from a number of investigations in which
ceeding simultaneously control passing from lar,(~e samples of material t > 10 ram) were used
the latter to the former with increasing temper-
ature. Although such a mechanism is suggested
by Tang's data, the other data suggest that ~o., __~_~ ~ 3 L
pyrolysis may also proceed throughout by either
one of these reactions, with no transition from
one to the other. Apparently the factors affect-
ing the choice of route by which the pyrolysis I 0 "a
proceeds must be minor ones since the variation
in experimental conditions is not large, A pos-
sible difference between the two sets of condi-
tions is that all of the high-activation-energy data 1.2 I,d t,6 1.8 2.0 2.2 2,4
were obtained in conditions offering the lowest I0~ (OK).I
probability of catalytic or autocata]ytic reac- Fig~ure 4. Kinetics data from experiments with Iarl.,esamples
tions occurring, that is, with wood specimens of wood or cellulose,
0.14 mm thick or with highly purified cellulose. Line Auth'or Rel.
This suggest that the pyrolysis of cellulose will I Var!ous 10. 2829
proceed with E = 5 6 kcal nJ',le -~ when the 2 Robertsand CIoagh ( T < 300 'C) 3
3 MurtyandBlackshear(r/a=0.86) 2
pyrolysis is unaffected by naturally eccurring 4 Tinney(upper limit) 18
inorganic salts or by autocatalysis, bet that a 5 MurtyandBla,:kshear(r/a= 1.0) 2
minol de~,ree of interference by such agencies 6 Robert and Clough (T > 300 C) 3
7 Tinney(lower limit/ 18
will cause the pyrolysis to proceed with E = 30 8 Bamford,Crank, and Malan 9
kcal mole- t. A Representationof lines 1-4 on Fig, 3
KineticsData for Pyrolysisor Wood
are plotted in Fig. 4. As would be expected, the
data for large samples are much more scattered
thal~ those for small samples
Data from three sets of self heating experi-
ments [10,28-29"] are closdy grouped and are
represented by a single line (~ine 1) in Fig. 4. To
this set may be added the ~ata obtained by
Murty and Blackshear [2"]relat:ng to the portion
oftheir cylindrical specimen at a radius of 0.86 ×
(total radius of specim,,n) (line 3) and the data
obtained by Roberts and Clough ['3] in an ex-
periment with a cylinder of wood in which tlae
temperature did not ex.:eed 285°C (line 2). This
set of data may be represented reasonably well
by E = 2 6 kcal mole -l, k = 1.2.108 s -I. The
conditions for all these experiments favor a
moderate degree of zLnlocatalysis. The self-
heating experiments were conducted mainly with
finely divided material, permitting the relatively
free movemem: of products within the mass of
the sample, as with the samples of Murty and
Blackshear [2]. The inclusion of the data from
an experiment with solid wood suggests that,
before the structural failure of the wood in the
temperature region 300-320'~C. the pressure
generated within the sample by the gaseous
products of pyrolysis acts to force some prod-
ucts of pyrolysis deeper into the sample (per-
pendicular to the grain direction) as well as to
force products out of the sample. This effect
promotes autocatalysis within the sample; the
effect of this atttocatalysis in increasing the rate
of reaction is far more significant than any re-
duction in weight loss caused by the wood struc-
ture restricting the free efflux of pyrolysis
products.
A second set of data may be seen for temper-
a~ures in excess of 320°C. In the first stage of his
computations, Tinuey ['18"] used values of
E = 3 0 kcal mole -~ and k = 6.10~-7.5.10 s s -~
to represent his data. In Fig. 4, lines 7 and 4
correspond to the lower and the upper limits
of k. The range of ralLe constants covered by
these values also includes the data of Murty and
Blac~'ohear [2] (for the: surface regions of their
269
sample) (line 5)i~nd of Roberts and Ck.ugh [3],
(in the temperalture range considered) (line 6),
while the data of Bamford et al. [9] (line 8) lie
slightly below this range. Line A, :'e~resenting
the kinetics data from small samples ~vith E =
30 kcal mole- 1 and k = 7.10 s- ~, 1~,".,near the
lower limit of Tinney's range of values, showing
that kinetics data from small samples can be
relevant to the pyrolysis of large samples,
although the reaction rate constants may be
increased by a factor of up to 12 by autocataly:,is
and other disturbing inSuences. There is r,o
evidence, in the d;tta obtained fr~ t. large sam-
pl as, of activation energies appreciabb, in excess
of 30 kcal mole- ~ (except, for the second stage
of Tinney's [18] computatin.ls, wl'.~ch has been
discussed previously). This set of data may be
regarded as rep~'esentir~ the kinetics ef pyrel-
ysis of the :ellulose in wood over the tempera-
ture rao,~e 250-50ff~C when the type of mineral
salt normally found in wood is present and only
minor autocatabtic or catalytic effects occur.
In general, in pyrolyzing wood there would be
a number of regions dominated by different
reaction kinetics. The innermost region, with a
temperature of 310C or less, would consist of
moderately autocatalyzed reaction proceeding
in the way discussed for the first set of data in
~his section. From 310°C to about 360-400":C.
there would be a region in which the pyrolysis
of cellulose went to completion, as in the second
set of data, At higher tempcratur,,'s, there would
be a region in which the pyrolysis oflignia went
to completion, and a region in which no further
pyrolysis occurred.
In experiments with cylinders of wood, the
volumes occupied by !bese regions would be
constantly changing. Initially the whole sample
would be in the low-temperature region, and
then this region would shrink in size to bc re-
placed by the others. It is interesting to compare
the data of Roberts and CIough [3] and tho';e
of Tinney [18] in these terms. In experiments
with an average rate of temperature rise of
20"C min- ~and with the assumption of a single
270
reaction scheme throughout the period of the
experiment, Roberts and Clough [3] obtained
an apparent activation energy o f 15 keal mole - :
over ',h, temperature range 300-450°C, and
their daL appear to link the two sets of data
discussed abeve (line 6). It seems possible that, in
these experiments, the continual variation in
the s!ze of t:ic vari-~us regions gave overall
weight ioss k;netics which shifted continuously
from thou." "Jr the lowest temperature region to
those of ~he t:ighcr temperature regions, yielding
a low value of apoarent activation energy. In
Tinney's ~,.r8] e..pedments, however, with rates
of temperature rise of 200°C rain- t the lowest
temperature regk, n was passed through fairly
quickly and so it did not have the same in-
fluence, while the "isc of two different sets of
kinetic data at every point meant that the first
set gave a better estimate of the kinetic data
for the pyrolysis of cellulose.
The data of Murty and Blackshear ~2] for
the surface regions of cellulose cylinders |hll
near the uppec limit of Tinney's [18] range of
values for wood. sugge,ning a continuing auto-
catalytic effect. The data of Bamford ctal. [9]
come somewhat below the lower limit of Tin-
ney's range of values, but their comparison be-
tween calculated and experimental temperatures
is rather lfinited. It may be that this discrepancy
in the kinetms data is not significam.
6. Discussion
The available data on the kinetics of the
pyrolysis of wood and its constituents lead to
the fpllowing conclusions:
1. The use of a first-order reaction scheme to
describe the weight loss variations of pyrolyzing
wood has well-established theoretical disad-
vantages, because many reactions whose effects
have to be represented in terms o f an overall
reaction ar~'~occurring simuhaueously, and be-
cause the less of weight is not the only criterion
of the degree of advancement of the pyrolysis
reactions. Nevertheless, this practice does as.-
A. F. Roberts
sist in the interpretation of data and provides
consisteut terms of re~erence by which different
sets of da~'a may be compared.
2. Celi~lose, hemicellulose, and iignin, the
major constitueuts of wood, have quite dif-
ferent reaction 'dncdcs, hemicellulose being the
m,.~st reactive constituent and lignin the least.
l~ wood, the pyrolysis of cellulose and bemi-
cellulose (which together represent about 7 ;°/o
of the initial weight) wdl pxoceed to completion
before the pyrolysis of lignin reaches a very
ad'.'anced stage.
3. The course of the pyrolysis reactions in
cellulose, arid the pyrolysis rates, are extremely
sensitive to catalytic and autocatalytic effects.
Under idealized conditions with carefully pur-
ified cellulose, pyrolysis may proceed entirely
by a reaction with E = 56 kcal mole-~. How-
ever, traces of other materials may protnote an
alternative reaction with E = 30 kcal m o l e - 1
and pyrolysis may proceed either entirely by this
rnute or by a combination of tile two . ~ ~tes.
In large samples only the latter reaction has
been observed.
4. The pyrolysis rates of lignin are enn:para-
tively insensitive to the addition of intorganic
salts: it seems likely that autoeatalysis also is
not a significant effect in the pyrolysis of lignin.
5. Experiments with small samples of material
give kinetic data which are also valid in large
oamples under some conditions, although in
large samples the effects of autocatalysis, secon-
dary reactions, and physical structure may cause
import':nt modifications of the kinetics ob-
served.
6. The physical structure of wood imposes a
considerable restraint on the moveraent of
products of pyrolysis at low tet0peratares, but
this restraint largely disappears in the temper-
ature range 300-320°C. Below this temperature
range, products may be forced further into the
wood as well as being expelled from the heated
surface, by the pressures which devel,)p: this
process increases the effects of autocatalysis.
Above this temperature range, products flow in
Kinetics Data for Pyrolysisof Wood
the direction of least resistance, away from the
unreaeted wood, aad autocatalysis is less im-
portant.
7. A fully developed pyrolysis wave advancing
into a block of wood can be subdivided into the
following regions (in order of increasing tem-
perature):
(a) A region in which the wood structure is
virtually intact, and autocatal;,sis of the
pyrolysis of the most reactive constituents
is occurring.
(b) A region in which failure of the wood
structure !.as occurred, the effects of
autocatal3,sis are ~educed, and pyrolysis
of the most reactive constituents is oc-
curring.
(c) A region in which the pyrolys;s ofcellulose
and hemicellulose is complete and the
pyrolysis of lignin is dominant.
(d) A region in which all the wood has been
pyrolyzed to char. Secondar,, reactions
between volatiles generated further into
the wood and the char residue may be
occurring.
This subdivision of the pyrolysis wave into
reg!ons foilows from a consideration of the
available kinetics data. I t has points of similarity
to a previous description by Martin 125].
8. The choice of suitable reaction kinetics to
use in dealing with a problem involving the
pyrolysis of wood will depend heavily on the
nature of the problem. The ignition of the wood
will be controlled by the behavior of the most
reactive comp¢:nents, whereas the time required
to eor, iplete pyrolysis at a given temperature
will be controlled by the behavior of the least
reactive component. Processes involving the
slow heating of wood to a temperature of 300'~C
will greatly increase the importance of attto-
catalysis, and the kinetics of the pyrolysis will
then be highly dependent on circumstances.
Processes involving the rapid heating of wood
to a temperature of 300'~C will reduce the im-
portance of autocatalysis, and in this case
values of E of 30 kca, mole- J and of k of
271
7.107 s- I, derived from experiments wilh small
samples, should give values of K representing
a lower limit to the likely range of values. The
actual values of K may exceed this lower limit
by a factor of up' to 12. depending on circum-
stances. Tang's [5] values for the kinetics of
the pyrolysis of lignin appear to be the most
reliable,
9. Studies of the reaction kinetics of ~olid
wood using cylindrical samples suffer from the
disadvantage that the degree of autocatalys4~ in
the i,~nermost region will be time dependenl and
hence the reaction kinetics observed will not be
of general applicability. In experiments with
plane-heated surfac~s, there is a greatec proba-
bility that the autocatalyzed regior will achieve
steady conditions. It is to be expec,'et ~ ILhatthe
kinetics observed will depend o,1 the direction
of propagation of the pyrolysis wave relative to
the grain of the wood, as products can diffuse
vet3' much more easily along the grain, thereby
increasing the autocatalytic'effects.
~0. A major research need in this area is the
study of the reaction kinetics of wood ht situ by
a technique, such as radiography, capable of
giving local weight variations along an iso-
thermal surface. By this means, the reaction
ki,~etics of each region could be studied sep-
arately and the effects of wtriations in heating
rate. permeability, etc.. assessed.
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