542 Ind. Eng. Chem. Res.

1997, 36, 542-552

An Experimental Investigation of Heat-Transfer Limitations in the

Flash Pyrolysis of Cellulose
Mario Lanzetta, Colomba Di Blasi,* and Federico Buonanno
Dipartimento di Ingegneria Chimica, Universitá degli Studi Napoli Federico II,
P.le V. Tecchio, 80125 Napoli, Italy

A new experimental system is presented to investigate the fast pyrolysis of solid fuels, in the
absence of heat- and mass-transfer limitations. It consists of an electrically heated furnace,
where a thin layer of powdered solid is exposed, on both sides, to radiative heating. A PID
temperature controller is programmed for two different working conditions: the usual constant
furnace temperature (A) and a constant sample temperature (B). Cellulose pyrolysis is
investigated in the temperature range 523-699 K. It is shown that significant heat-transfer
limitations cannot be avoided with the modality A, unless very slow heating rates, as in the
classical TGA systems, are applied. In the modality B (global heating rates 19-56 K/s), the
independence of the char yields from the sample thickness, for values of this below a critical
value, indicates negligible spatial temperature gradients and activity of intraparticle secondary
reactions of primary vapors. External heat-transfer limitations, due mainly to endothermic
reaction energetics, are also avoided through proper variation in the intensity of the external
radiative heat flux. Consequently, conversion occurs under exactly determined temperature
conditions. A cold helium flow carries away from the reaction environment volatile products so
that the activity of extra-bed secondary reactions is hindered as well. Cellulose weight loss and
temperature curves are applied to evaluate the global degradation kinetics and to study the
influences of heat- and mass-transfer limitations.

Introduction and mass transfer and rather narrow ranges of (low)

Pyrolysis of lignocellulosic materials is important in
the fields of energy recovery, through thermochemical
conversion, and fire safety science (Di Blasi (1993)). In
general, for convective/radiative heating (Di Blasi (1994,
1996a,b)), pyrolysis can occur in a chemically controlled
regime (negligible intraparticle spatial gradients of
temperature and no temperature differences between
particle and reacting environment) or in a heat-transfer-
controlled regime. In the heat-transfer-controlled re-
gime, two further cases (Di Blasi (1996c)) can be
observed: (1) internal heat-transfer control (thermally
thick regime) with very large spatial gradients along
the particle, and (2) external heat-transfer control
(thermally thin regime) with no spatial gradients along
the particle, though the temperature may continue to
change with time, depending on the heat-transfer rate
from reactor to particle. Heat-transfer conditions de-
termine the selectivity of primary solid degradation
reactions and thus the characteristics of pyrolysis. It
is known (Scott et al. (1988)) that slow solid heating
rates lead to comparable amounts of char, gas, and
liquid products (slow-conventional pyrolysis), whereas
solid char formation is almost completely hindered
under very fast heating rates (flash pyrolysis) and
reduced volatile residence times (Antal et al. (1990)). It
should also be mentioned that a special case of flash
pyrolysis is achieved in the ablative regime (Lede et al.
(1985), Di Blasi (1996d)), where heat transfer from
reactor to particle occurs by direct contact.
The knowledge of the chemical kinetics of pyrolytic
solid degradation is an important step in the optimal
design and operation of chemical reactors. However,
kinetic investigations, mainly for the fast heating rates
of flash pyrolysis, suffer from large limitations in heat
* Corresponding author. Telephone: 39-81-7682232. Fax:
39-81-2391800.
S0888-5885(96)00551-9 CCC: $14.00
temperature conditions (Antal (1982, 1985), Varhegyi
et al. (1994), Antal and Varhegyi (1995)). In most cases,
the sample (reaction) temperature is not known, given
the significant differences with the controlled system
and the lags in the measuring devices (Narayan and
Antal (1996)). Intra- and extraparticle mass-transfer
limitations also exert a strong influence on the extent
and selectivity of secondary reactions of vapors evolved
from primary solid degradation. Indeed, primary py-
rolysis volatiles may undergo cracking and repolymer-
ization in the hot charred particle and/or the reacting
environment.
Most of the studies on the thermal decomposition of
organic polymers have been carried out by means of
thermogravimetric analysis (TGA). Generally, associ-
ated with this methodology, there are several shortcom-
ings (Agrawal and McCluskey (1983)): (1) uncertainties
in temperature measurement, (2) slow heating rates
(usually below 2 K/s) and (3) difficulties in product
recovery, so that the kinetic analyses are based only on
weight loss curves. In particular, to avoid increases in
the mechanical inertia of the sample pan and to obtain
accurate and sensitive weight measurements, the ther-
mocouple is never in contact with the degrading sample.
Consequently, the reaction temperature is not exactly
known.
Tube furnaces, which allow faster heating rates (up
to 5-10 K/s), have also been proposed (Bradbury et al.
(1979), Thurner and Mann (1981), Agrawal and Mc-
Cluskey (1983)). In this case, products and weight loss
are recorded at selected times, through experiment
repetition, to draw the curves of interest. However, this
procedure is much more tedious than that of TGA
analyses, and again only the furnace temperature is
controlled. Therefore, in some cases, the reaction tem-
perature is significantly lower than that of the heating
system, usually taken as the reaction temperature (see,
for instance, Bradbury et al. (1979)).
© 1997 American Chemical Society
 Ind. Eng. Chem. Res., Vol. 36, No. 3, 1997 543
As the rates of solid heating and degradation are
made faster, the characteristic times of measuring
devices become comparatively too slow, so that accurate
continuous monitoring of the variables of interest turns
in a rather hard task. These problems are well pointed
out in the fast TGA system developed by Antal and co-
workers (Tabatabaie-Raissi et al., 1989), where high
radiative heat fluxes are applied to pyrolyze cellulose
under conditions similar to those of solar environments.
Usually, only final product yields, as functions of the
final reaction temperature, are obtained from experi-
mental systems characterized by very fast nominal
heating rates (up to 10 000 K/s). Also, it should be noted
that, given the very high heat-transfer rates, though the
temperature of the (inert) heating system is well
controlled, significant differences between this and that
of the reacting samples and large intraparticle gradients
are expected. These systems include screen heaters (for
instance, Lewellen et al. (1976), Hajaligol et al. (1982)),
shock tubes (Ozturk and Merklin (1995)), and Curie-
point pyrolyzers (Wanzl (1994)). In the first case, a
stainless steel mesh screen, suspended between massive
brass electrodes, is rapidly heated to the desired tem-
perature. In the shock tube, the propagation of a planar
shock, through a low-pressure gas, results in an almost
step increase in temperature and pressure. The Curie-
point technique is based on the electric current produced
by a conductor introduced in a high-frequency magnetic
field.
Finally, bench-scale, fluid-bed reactors are also used
(for instance, Lipska and Parker (1966), Barooah and
Long (1976)) to measure the total condensable and gas
yields and reaction time on the dependence of the
pyrolysis temperature and to evaluate reaction kinetics.
Shortcomings are related to the difficult determination
of the yields of char (mixed with the granular solid heat
carrier) and, again, to significant heat and mass transfer
limitations.
In this study, a new experimental system is presented
to investigate the pyrolysis of lignocellulosic materials
under heating rates significantly faster than those used Figure 1. Schematic of the experimental system: (A) general,
(B) cross view of the heating chamber, (C) sample holder.
in TGA systems, while continuous, accurate monitoring
of sample temperature and weight is still carried out.
The most innovative aspect of the experimental ap- and gas. The system is a combination of the pyrolysis
paratus consists of the control of the sample tempera- tube used in previous experiments (Madorsky et al.
ture, after conditions for negligible spatial gradients of (1956), Bradbury et al. (1979), Thurner and Mann
temperature are established (thermally thin regime). (1981), Agrawal and McCluskey (1983), Cullis et al.
The externally applied heat flux is used as the adjust- (1983)) and the fast TGA thermoanalyzer developed by
able variable. In this way, heat-transfer limitations are Antal and his group (Tabatabaie-Raissi et al., 1989).
eliminated. Furthermore, intra- and extraparticle sec- Parts A-C of Figure 1 schematically represent the main
ondary reaction activity is minimized by reducing the characteristics of the experimental apparatus. It con-
volatile residence times (thin sample size and inert flow sists of (1) a radiant heating chamber, (2) a quartz reac-
gas). Cellulose is chosen as fuel because, notwithstand- tor, (3) a PID temperature controller, (4) an inert gas
ing the numerous investigations already available (see feeding system, (5) an acquisition data set (PC and re-
reviews by Antal (1982, 1985), Antal and Varhegyi lated accessories), (6) a precision balance, and (7) a col-
(1995), Milosavljevic and Suuberg (1995)), a still large lection system for condensable and noncondensable
uncertainty is shown on conditions and kinetics of flash products of solid pyrolysis.
pyrolysis. The heating system is a radiant chamber, manufac-
tured by Research Inc. The heating elements are
Experimental System tubular quartz infrared lamps with a tungsten wire
filament that emits radiant energy in proportion to the
An experimental system has been designed and applied voltage. Four elliptical, polished aluminum,
constructed to investigate solid pyrolysis under reduced water-cooled reflectors (Figure 1B) focus the high-
limitations of heat and mass transport, so that informa- density infrared energy, emitted by lamps, onto a
tion on the chemical kinetics (semiglobal mechanisms cylindrically shaped target area, whose diameter is 6.5
and data) can be obtained. The system allows for the × 10-2 m. The length of the heated zone is 6.02 × 10-2
continuous monitoring of sample and system tempera- m, delimited on both sides by two inert zones of about
ture and weight and for the collection of products, the same length. The radiant flux is uniform over 80%
lumped into three main classes: solid char, liquid tar, of the chamber length. The maximum temperature,
544 Ind. Eng. Chem. Res., Vol. 36, No. 3, 1997
2500 K, is achieved within 3 s, resulting in rather fast
reactor heating rates. To avoid interaction between the
volatile pyrolysis products and the lamps, a quartz tube
(i.d. 6 × 10-2 m and length 20 × 10-2 m), transparent
to infrared radiation, is located inside the furnace and
used as a reaction chamber. A powdered solid sample
is exposed to thermal radiation by means of a 325
stainless steel mesh screen (4.2 × 10-2 m large and 5.5
× 10-2 m long; Figure 1C), whose sides are wrapped on
two steel rods. Accurate temperature measurements,
under different heating conditions, have been made to
define the uniform temperature zone (this corresponds
to an extention of about 2.6 × 10-2 m, in the direction
of the reactor axis, and 2 × 10-2 m, along the other).
The sample is located at the center of the radiant
chamber and is radiatively heated on both the upper
and bottom sides, this in contact with the sample holder
(Figure 1C). Aluminum supports directly connect the
sample holder to a precision balance (Mettler-Toledo
AT400) with an accuracy of order 0.1 mg and a time
constant of 0.2-0.4 s.
The temperature of the reacting solid is measured by
a thin (0.1 mm bead) chromel-alumel thermocouple in
direct physical contact with the powdered sample layer
(Figure 1C). As pyrolysis takes place, the thermocouple
bead moves according to shrinking rate, and, depending
on the final solid residual yield, at the completion of the
process, it may touch the surface of the sample holder.
The measured temperature coincides with the sample
temperature only if the conversion process occurs in a
thermally thin regime, that is, if a uniform profile is
established along the sample thickness. Therefore,
conditions for conversion in a thermally thin regime
should be first determined. The procedure applied in
this study is based on the well-known dependence of
the residual solid yield on the reaction temperature
(primary char) and the intraparticle residence times of
primary volatile products (secondary char). Indeed, as
the temperatures of the primary degradation are in-
creased (Shafizadeh et al. (1979), Bradbury et al. (1979))
or the residence times of primary vapors inside the
reacting particle are made shorter (Antal et al. (1990)),
the char yields decrease. Thus, for chosen heating
conditions, the sample thickness is decreased until the
solid residual yield becomes constant.
The radiant heater is made to work according to two
modalities, here indicated as A and B, which correspond
to the emission of a constant flux and to the attainment
of a certain temperature with an assigned rate, respec-
tively. The modality A, which is the easier one, also
corresponds to a constant temperature of the emitters,
after short transients whose duration is successively
reduced as the intensity of the radiation is increased.
The heating modality B can be implemented to impose
a certain time evolution of a temperature, which can
be that of the emitters or the specimen, by varying the
intensity of the radiant flux. In this study, the con-
trolled variable is the temperature of the sample
surface, after sample sizes for conversion in a thermally
thin regime are determined. The manipulated variable
is the electric voltage applied to the furnace or, in other
words, the intensity of the radiative heat flux Qe.
In the absence of spatial gradients along the sample
layer, the dynamics of cellulose degradation, for the
heating modality A, are well described by means of the
mathematical model for a thermally thin regime re-
ported by Di Blasi (1996c) (assumptions are listed in
the same reference). In particular, the time evolution
of the sample temperature, T, for the computational
domain consisting of the half-thickness layer, τ, can be
described as:
σS(TL4 - T4)
∂T
(Fscs + cgFg) ) Qr + (1)
∂t V
where Qr and Fc are dependent on temperature and
chemical composition. Also, the emissivity may not be
constant, with further effects on the external heat-
transfer rate. Thus, eq 1 should be formulated and
solved in conjunction with chemical species conservation
equations (Di Blasi (1996c)). In the modality A, Qe )
σSTL4 is constant and the temperature evolution is
thus the result (eq 1) of the effects of both the external
(constant) heating and the variations in the enthalpy
and properties caused by chemical reactions.
From the mathematical point of view, eq 1 and the
control equations are applied to determine how Qe
should be varied, in order to achieve a chosen sample
temperature evolution in the modality B. According to
the classical theory of chemical process control (Seborg
et al. (1989)), eq 1 is linearized, expressed in terms of
deviation variables, transformed in the Laplace domain
and coupled to a PID controller. In the experiments,
the first step deals with a trial and error procedure
applied to the empty sample holder for a first estimate
of the PID controller parameters. Then, prior to each
run, these are adjusted for the presence of the sample
to be pyrolyzed, again with some trial and error tests,
so that the maximum heating rate can be achieved, with
no deviation from the chosen reaction temperature.
A continuous flow of helium is applied to establish
an inert environment and to reduce the residence time
of vapors inside the reaction chamber. It is distributed
at the entrance of the quartz reactor, at a distance of
about 6 × 10-2 m from the sample holder. This is an
important point. It is generally retained that, under
conditions of radiative heating (Tabatabaie-Raissi et al.
(1989)), secondary reactions are promptly quenched
because, as soon as volatile products are released from
the hot reacting solid, they encounter a zone where the
temperature is rather low (apart from a narrow gas
layer, adjacent to the solid surface, which is heated by
conduction). However, it is important to reduce the
residence time of volatile pyrolysis products in the
radiant chamber, because it is also well known (Di Blasi
et al. (1991)) that they can absorb some of the incident
radiation and thus attain temperatures sufficiently high
for secondary reactions to become active. The continu-
ous flow gives rise to very low concentrations of volatiles
in the reaction chamber (for the worst case, that is, the
highest temperatures, it is estimated that the ratio
between volatiles and inert is about 1/1000 mol), thus
keeping gas-phase absorption of radiation to a mini-
mum. Furthermore, helium is preferred to argon, given
the higher diffusion coefficient (a factor of about 3) of
the high molecular weight volatiles (Varhegyi et al.
(1994)). The flow of inert gas, at ambient temperature,
is also used to cool the residual char, left after complete
solid devolatilization.
Usually, two runs are required to measure the weight
loss. In the first, the weight loss curve of the degrading
sample is obtained. The second run is carried out to
record the so-called “blank” curve, which takes into
account the effects of spurious weight changes due to
temperature effects in the gas phase surrounding the
sample while degrading (Tabatabaie-Raissi et al. (1989)).
 Ind. Eng. Chem. Res., Vol. 36, No. 3, 1997 545
This curve, obtained with the sample holder left in the
position of the first test and with the final char yield, is
then used to correct the weight loss curve. These cor-
rections are, at the higher temperatures, on the order
of 50% with respect to the measured sample weight. In
order to verify the correctness of the procedure, after
each run, the final char yield is also weighed and com-
pared with that previously determined. Given the rela-
tively large sample mass (20-8 mg) and the very thin
thermocouple, the close contact of this with the sample
does not affect the mechanical inertia of the system and
simultaneous accurate measurements of temperature
and weight are obtained. An acquisition data system,
based on a PC and the software LabView (National Figure 2. Solid mass fraction as function of time (τ ) 50 µm) for
Instruments), allows for continuous monitoring (0.4-1 different system temperatures (heating modality A).
s) and storage of temperature and weight loss values.
In this study no extensive investigation on the
dependence of product yields on reaction conditions has
been carried out, as the analysis is focused mainly on
the effects of heat-transfer limitations. However, a
product collection system is being applied, consisting of
a condenser (a 10 × 10-2 m long tube filled in with glass
wool) and a plastic bag for gaseous products.
Results
Thermal degradation of thin cellulosic layers is car-
ried out according to the heating modalities A and B,
by varying the intensity of the radiative heat flux and
the final temperature of the sample, respectively. The
influence of intrabed temperature gradients on the
conversion process (apparent kinetics) is investigated,
by varying the sample thickness. Conditions leading
to a true isothermal process, controlled by (intrinsic)
chemical kinetics, are determined. In all cases, com-
mercial cellulose with lengths of the fibers in the range
20-150 µm (Sigma Aldrich), predried for about 10 h at
a temperature of 388 K, is degraded. Cellulose is chosen
as fuel, given its importance in the field of biomass
thermochemical conversion and the still uncertain
behavior under flash pyrolysis conditions. The helium
flow, at ambient temperature, is equal to 8 × 10-4 m3/
min, which, given a cross section of the quartz reactor
of 28 × 10-4 m2, gives rise to velocities of about 30 ×
10-2 m/min. No variations in the degradation process
are seen with larger mass flow rates (factors of 2-3). Figure 3. Time-temperature curves for cellulose (solid lines) and
Cellulose Degradation under Constant Radia- char (dashed lines) (A) for two different system temperatures (Tf
tive Heat Flux (Heating Modality A). Tests have ) 577 and 633 K) and τ ) 50 µm (heating modality A) and (B) for
been conducted, according to the heating modality A, two different sample half-thicknesses (τ ) 100 and 44 µm) and Tf
for about 10 mg of cellulose powder, uniformly distrib- ) 633 K (heating modality A).
uted along the uniform temperature zone of the sample
holder, to give τ ) 50 µm. As will be shown later, this Examples of the weight loss curves (the solid residual,
sample thickness corresponds, for moderate reaction W, including char and cellulose, expressed as a fraction
temperatures, to conversion in a thermally thin regime. of the initial sample mass, M0) are reported, for system
The steady temperature value, Tf, here indicated as the temperatures in the range 543-622 K, in Figure 2. As
“system temperature”, is used to characterize the dif- expected, preheating times, before significant weight
ferent tests and has been varied in the range 543-699 loss, become successively shorter and the amounts of
K, through different values of Qe. For the sample solid, left as charred residual, decrease as the intensity
thickness given above, the cellulose heating rate (re- of the radiative heat flux (or the system temperature)
ferred to the sample surface and before significant is increased.
weight loss) varies from about 12 to 54 K/s as the system Associated with weight loss curves, the temperature
temperature is varied. As will appear from the experi- of cellulose (recorded in the course of degradation) and
ments, external heat-transfer limitations can hardly be char mass fraction (recorded together with the blank
avoided with this heating modality, so that it is not curve) are available. These can be used to get informa-
applicable to study the intrinsic kinetics of degradation. tion on the thermal history of the sample. Examples of
However, some results have been obtained which can the (char and cellulose) temperature curves are plotted
be of interest from the practical point of view, that is, in Figure 3A,B, for two different system temperatures
in relation to pyrolysis units, where biomass particles (Tf ) 577 and 633 K) and τ ) 50 µm (A) and for two
are exposed to a certain reactor temperature. Also, different sample sizes (τ ) 100 and 40 µm) and Tf )
comparison with previous analyses can be carried out. 633 K (B). In all cases, a region exists where the sample
546 Ind. Eng. Chem. Res., Vol. 36, No. 3, 1997
temperatures are significantly lower than those of the
char. The difference becomes successively larger as the
system temperature or the sample thickness is in-
creased. The lower cellulose temperature, measured
during the process transients, is due to reaction ener-
getics and, in principle, larger medium thermal capacity.
Concerning this last point, it should be noted that the
reduction in the effective sample capacity is rather
large, given that, even at the lowest temperature, a
reduction in the sample weight of about 75% is mea-
sured. However, given that, in all cases, for tempera-
tures below 500 K no significant difference is seen
between cellulose and char, it can be assumed that the
role played by thermal capacity is less important than
that of the endothermicity of pyrolysis reactions (tar
formation).
As expected, the temperature difference becomes
successively smaller as time increases, because the
reaction process approaches completion and the two
media tend to be the same. Also, a plateau in the
cellulose time-temperature curve is clearly seen, as-
sociated with the onset of high rates of solid degrada-
tion, for Tf g 600 K. It becomes successively more
evident as the system temperature or the sample
thickness is increased. In fact, given the exponential
increase of the reaction rate with temperature, the heat
requirements by the endothermic degradation also
become more stringent, as Tf or the amount of solid to
be pyrolyzed (sample thickness) are increased.
Under mild heating conditions, (Tf < 580 K), both
cellulose and char slowly approach the steady final
conditions and a period (whose duration is, at least, 1/3
of the total conversion time) is seen where the two
temperatures become equal. The period where the two
temperatures are equal is reached only for conversion
levels of about 90% for 580 K < Tf e 600 K. Finally,
for Tf > 600 K, cellulose always degrades at tempera-
tures significantly lower than those of the system,
though they remain almost constant for most of the
devolatilization. It should be noted that this behavior
has been observed also for very thin sample layers,
indicating that external heat-transfer limitations are
very high and cannot be overcome under constant
heating conditions and temperatures above 600 K,
which give rise to rather fast sample heating rates. This
behavior was already observed in previous experimental
studies (Antal et al. (1980), Bradbury et al. (1979)) and
is the thermal lag due to the endothermicity of cellulose
degradation (high temperatures), well described in the
theories proposed by Di Blasi (1996c) and Narayan and
Antal (1996). Convective outflow of volatiles also affects
the sample heating rate. As the devolatilization rate
(and the flow velocity) increases with temperature, it
has been observed that such a contribution becomes
successively more important as more severe conversion
conditions are considered (Di Blasi (1994, 1996c)).
The maximum temperature difference (between char
and reacting cellulose), ∆Tm, and two sample temper-
atures, T1 and T2, corresponding to ∆T ) 50%∆Tm and
∆T ) ∆Tm, respectively, are reported in Figure 4 as
functions of the system temperature. The temperature
T1, which can be taken as representative of the onset
of significant rates of solid degradation, increases almost
linearly with the system temperature (apart from the
very low values). On the other hand, T2, which can be
taken as representative of the temperature of the
completion of the degradation process, also shows an
almost linear increase with the system temperature for
Figure 4. Maximum temperature difference between cellulose
and char, ∆Tm, and cellulose temperature for ∆T ) 50%∆Tm, T1,
and for ∆T ) ∆Tm, T2, as functions of the system temperature (τ
) 50 µm, heating modality A).
values of this below 600 K. However, for larger values,
the rate of increase is successively reduced and a
tendency toward a constant value of about 600 K
appears. Apart from low Tf values (e580 K), ∆Tm
continuously increase with Tf, at a rate that becomes
faster for values of this above 600 K, as a consequence
of the trend previously observed in T2. It should be
noted that the temperature difference may become as
high as 30 K.
Results presented in Figure 4 indicate that, for
assigned external thermal conditions (radiation), such
as in chemical reactors, the effective reaction temper-
ature can hardly be brought above a certain critical level
of about 600 K. Increasing the sample heating rate,
through reactor temperature, reduces the duration of
the first stage of degradation, which occurs below 600
K and on average the reaction temperature increases.
However, given the endothermicity of the degradation
process and the successively faster reaction rates, the
increase in the effective reaction temperature of cel-
lulose is successively reduced and hardly goes above 600
K, with this heating modality. According to eq 1 and
extensive computations (Di Blasi (1996c), Narayan and
Antal (1996)), an almost constant temperature is at-
tained at the fast heating rates because of a balance
between the requirements of endothermic pyrolysis and
the external heat supply. Also, the occurrence of
pyrolysis during the time-temperature plateau may
explain why the thermal conversion of cellulosic materi-
als has been interpreted as a fusion process. In par-
ticular, for contact (ablative) pyrolysis of wood (Lede at
al. (1985)), a “wood fusion temperature”, equal to 738
K, has been introduced. This value is significantly
higher than the limit observed in this study for cellulose,
but the different chemical behavior between the two
solids and the difference in the external heat-transfer
rates (much larger in the case of ablative pyrolysis) may
justify the difference.
The significant differences between cellulose and
system temperature for a large part (low temperatures)
or for the whole duration of the degradation process
(high temperatures and/or heating rates) make ques-
tionable the use of the data (weight loss and product
yields) obtained according to the heating modality A for
the formulation of kinetic models and the estimation of
kinetic data, since conversion occurs under heat-transfer
control. Heat-transfer limitations for modality A can
be reduced only for slow heating rates, such as those
usually applied in the slow TGA systems which, of
course, are not directly applicable for flash pyrolysis.
Also, very thin sample thickness (or small mass) ap-

Figure 5. Solid mass fraction for solid residence times, ts, equal
to 300 s (Tr ) 573 K) and 10 s (Tr ) 623 K) as a function of the
sample half-thickness (heating modality B).
pears to cause a reduction in the heat-transfer limita-
tions, but this approach is again effective only for
relatively slow heating rates.
Cellulose Degradation under Controlled Sample
Temperature (Heating Modality B). The analysis
of the thermal degradation data, obtained through
modality A, has shown that it is possible to avoid heat-
transfer limitations only for very thin samples and slow
heating rates (low system temperatures). In the heating
modality B the temperature of the sample is the result
of a control process. If the proper size of the sample is
chosen to avoid intrabed gradients, a proper selection
of control parameters allows degradation to be carried
out under exactly known temperature conditions. There-
fore, some preliminary tests have been conducted to
determine the conditions giving rise to a conversion in
a thermally thin regime for modality B. It should be
pointed out that, in relation to intrabed heat- and mass-
transfer limitations, the sample thickness, not the
sample mass, is the key parameter. Consequently, an
important point is to determine, before all, the size of
the sample thickness which does not give rise to
significant spatial gradients of temperature (primary
degradation at different temperatures) and volatile
residence times (activity of secondary reactions). As
previously illustrated, the char yields are taken as a
measure of the importance of these processes. In
particular, conditions of char yields not dependent on
the sample thickness correspond to negligible effects on
primary degradation of intrabed transport phenomena
and secondary reactions. Given that intrabed space
gradients and secondary reaction rates are expected to
increase as heating conditions are made more severe,
two reaction temperatures have been considered, 573
and 623 K.
Tests have been conducted, according to the heating
modality B (examples of the heating curves will be given
in the following), by decreasing the thickness of the
cellulose layer from about 200 µm. The solid residence
times are 300 (low temperature) and 10 s (high tem-
perature). After this time, the power is turned off, and
the sample is promptly moved into a cold zone under a
continuous helium flow. The solid residual, expressed
as a fraction of the initial sample mass, is reported as
a function of the sample half-thickness in Figure 5. As
expected, it initially decreases with the sample size,
because of the increase in the average reaction temper-
ature and the decrease in the volatile residence times,
and then tends to a constant value.
The attainment of a constant value of the char yield
corresponds to conversion in a thermally thin regime.
Ind. Eng. Chem. Res., Vol. 36, No. 3, 1997 547
Figure 6. Temperature-time curves of the cellulose sample
during the initial stage of the process for the heating modality B
(τ ) 50 µm).
Indeed, the char yield does not depend on the sample
thickness only when solid degradation occurs at the
same temperature, independently of the spatial position,
that is, no spatial temperature gradients exist. More-
over, these conditions also indicate that intrabed sec-
ondary charring reactions do not occur to a significant
extent. For cellulose and for the chosen heating condi-
tions, the transition from a thermally thick to a ther-
mally thin regime occurs for sample half-thicknesses
slightly increasing with the temperature, that is, τ )
70 µm (Tr ) 573 K) and τ ) 60 µm (Tr ) 623 K),
respectively. Therefore, conversion of samples with
half-thicknesses below 60 µm and reaction temperatures
below 623 K can be assumed to occur in a thermally
thin regime.
Examples of the time history of the cellulose temper-
ature, for the initial stage of the process, are shown in
Figure 6. These have been obtained for different set
points (reaction temperatures) and τ ) 50 µm (about
10 mg of cellulose powder). After the first stage of linear
increase (heating rates from 40 to 78 K/s for the
temperature range considered), a constant (reaction)
temperature, Tr, is more slowly attained (the time
needed to attain this value is indicated as heating time,
th) and maintained for the whole duration of the process,
with no overshoot in practice. The global heating rates,
for the attainment of the reaction temperature, vary
from about 19 to 56 K/s. For the whole range of reaction
temperatures tested, the endothermicity of degradation
reactions is well compensated by increased external heat
supply. Consequently, no plateau is seen in the time-
temperature curve, even when fast degradation rates
are achieved. Therefore, compared to the curves of
Figure 3, weight loss curves obtained with the heating
modality B show shorter degradation times (Figure 7)
for comparable values of Tf (system temperature of the
modality A) and Tr (the reaction temperature of modal-
ity B).
The weight loss curves of Figure 7 are obtained under
isothermal sample conditions, apart from the very
beginning of the process. Figure 8 reports the ratio
between the conversion time, tc, and the heating time,
th, and the solid mass fraction at t ) th as functions of
the reaction temperature. For Tr e 607 K, the conver-
sion time is significantly longer than the sample heating
time (factors in the range 1000-16), and the conversion
level achieved in relation to the heating period is also
small (0.001-22%) (the factors become 5 and 40%,
respectively, for Tr ) 623 K).
Effects of Intrabed Resistances. In order to
understand the influence of intrabed heat- and mass-
548 Ind. Eng. Chem. Res., Vol. 36, No. 3, 1997
Figure 7. Solid mass fraction as a function of time for different
sample temperatures (τ ) 50 µm, heating modality B).
Figure 8. Ratio of the conversion to the heating time, tc/th, and
solid mass fraction for t ) th, as functions of the reaction
temperature (τ ) 50 µm, heating modality B).
Figure 9. Final char mass fraction as a function of temperature
for the heating modality B (τ ) 50 and 100 µm) and the heating
modality A (τ ) 50 µm). For comparison purposes, literature data
are also enclosed.
transfer resistances on the conversion process, the final
char yields (the solid residual left on the sample holder)
are examined on the dependence of the heating condi-
tions, through Figure 9. The temperature range con-
sidered is 523-630 K, where the upper limit is dictated
by the accuracy of the weighing instrument, that cannot
detect char yields below 1% of the initial cellulose mass.
For comparison purposes and in relation to the temper-
ature range of interest, not only data obtained for τ )
50 µm (modality A and B) and τ ) 100 µm (modality B)
but also some literature data on isothermal cellulose
degradation are enclosed, obtained through fluid-bed
reactors (Lipska and Parker (1966), Barooah and Long
(1976)), a vacuum tube furnace (Shafizadeh et al.
(1979)), and a vacuum TGA system (Ramiah (1970))
(these data are obtained under known external temper-
ature conditions (modality A)).
The trend shown by Figure 9 is in qualitative agree-
ment with the previous literature on the pyrolysis of
cellulose. In other words, the solid residual increases
as the effective reaction temperature decreases (from
modality B to A) or the cellulose layer is made thicker
for the same heating modality (B). Extrapolation of the
measured data for values of the char yield below 1%
shows that cellulose degradation, under radiative heat-
ing, occurs with no char formation for Tr ) 625 K or Tr
) 630 K as the sample layer thickness is increased
(modality B) or for Tf ) 640 K (modality A).
At first glance, it appears that, for temperatures in
the range 523-560 K, the measured char yields are
comparable with those given by Lipska and Parker
(1966), though, in this case, the particle sizes (762 µm)
are much larger than the sample thicknesses used in
the present experiments. This is understandable be-
cause at slow heating rates (low temperatures) a kinetic
regime can be more easily established (Di Blasi (1996c))
or, in other words, the degradation process is so slow
that heat transfer limitations do not impact the results
(Varhegyi et al. (1994)). In general, in all cases, the char
yields measured are lower that those reported in the
literature. For instance, at high temperatures, a com-
parison with the data by Shafizadeh et al. (1979) shows
values lower by factors from 3 to 8. Also, it is worth
observing that the average sample heating rates,
achieved in this study, should be faster than those
typical of fluid-bed flash pyrolysis (Scott et al. (1988)),
given that, in this case, negligible char yields have been
found only for Tf g 900 K (data from this study are not
included in Figure 9, because they are available only
for Tf g 700 K). On the other hand, negligible char
yields have been reported by Lewellen et al. (1976) for
very fast heating rates (400-10 000 K/s). It can be
understood that these results are due to significant
intra- and extraparticle (bed) heat- and mass-transfer
effects, given the much larger sample sizes used in
previous studies, namely, 595 µm (Scott et al. (1988)),
200 µm (Shafizadeh et al. (1979)), and 420-700 µm
(Barooah and Long (1976)), the different external heat-
transfer mechanisms, or the different solid and volatile
residence times.
Therefore, the analysis of the weight loss curves,
measured in this study, can give information on the
kinetic mechanism and data of cellulose flash pyrolysis
(modality B, τ ) 50 µm). Another consideration can be
made in relation to the effective reaction temperature
of modality A (plausibly in the range of temperatures
T1-T2, introduced in Figure 4) and the final solid
residual yields (Figure 9). It appears that, with the
heating modality A and for the range of heating condi-
tions considered in this study, a very small part of the
reaction, if any, occurs at sample temperatures above
600 K. On the other hand, for system temperatures
above 630 K the char yields are of the order of 1%.
Therefore, in terms of primary degradation, significant
char formation can be avoided if a temperature of 600
K is achieved within a relatively short time. However,
it should be stressed that the limit temperature of 600
K is typical of the experimental conditions achieved in
this study (very low heat- and mass-transfer resis-
tances).
Global Kinetics. For the heating modality B, the
process can be divided into two stages: the first is
dynamic, that is, the system or sample temperature
increases to the desired isothermal point, and the second
is the true isothermal stage, that is, the temperature is
 Ind. Eng. Chem. Res., Vol. 36, No. 3, 1997 549
kept at the constant value attained before. In general, K2M0 -Kt
the isothermal approach of the pyrolysis process can be MT ) MT∞ - e (9)
K
considered valid if (1) there is a negligible weight loss
in the first stage and (2) the duration of the first K1νCM0 -Kt
unsteady stage is a small fraction of the whole time MC ) MC∞ - e (10)
needed for the thermal degradation of the sample. In K
fact, in general, one of the disadvantages of the static The final tar yield, MT∞, can be obtained from eq 9
approach is that there is an excessive weight loss before written for t ) 0 as:
pyrolysis temperature is reached and, of course, the
higher the temperature, the greater the weight loss K2M0
(Ramiah (1970)). MT∞ (11)
It has been shown (Figures 5 and 8, τ ) 50 µm and K
heating modality B) that, for large part of the temper-
Furthermore, the total solid mass (char and cellulose),
ature range investigated, the above assumptions are
W, can be obtained from eqs 8 and 10 as:
verified. Thus, a pure kinetic, isothermal theory is

( )
proposed. Of course, this theory is not applicable for K1νC -Kt
the heating modality A. The kinetics of primary cel- W ) W∞ + M0 1 - e (12)
lulose degradation are described through a semiglobal K
mechanism:
where W∞ is the final solid residual and can be obtained
K1 νCCHAR + νGGAS
from eq 10 written for t ) 0:

CELLULOSE K2 (a1–a2) K1νC

W∞ ) M0 (13)
TAR K

This is a modified version of the well-known Broido- An alternative formulation of eq 12 is thus

Shafizadeh scheme (Broido and Weinstein (1971), Brad-
bury et al. (1979)) for cellulose pyrolysis and takes into
W - W∞
P) ) e-Kt (12′)
account the competitive formations of tar (high temper- M0 - W∞
ature) and linked char and gas (low temperature). The
formation of the “active” cellulose with a reduced degree Figure 10 shows the plots of ln(P) versus time, for the
of polymerization, preceding devolatilization, has been weight loss curves reported in Figure 7 (heating modal-
recently shown not to be controlling (Varhegyi et al. ity A, τ ) 50 µm). It should be noted that the final char
(1994)), and thus it has been dropped from the kinetic yields for Tr ) 614 and 623 K are those extrapolated
model. Moreover, though different orders at different from Figure 9, given their very low values and the
stages of the reaction have been suggested (Milosavljevic limited accuracy of the weighing system. The slope of
and Suuberg (1995)), the assumption of first-order the straight lines is the kinetic constant, K, for the
kinetics is usually retained valid in engineering ap- different temperatures. Clearly, in accordance with
plications (Agrawal (1988)). Varhegyi et al. (1994), the process of weight loss can be
The kinetic equations for the pyrolysis scheme (a1- described by a simple first-order reaction.
a2) are expressed as: The usual Arrhenius plot (Figure 11) and a least-
squares analysis give the activation energy and the
∂MS preexponential factor of the global degradation kinetics.
) -KMS (2) The solid line describes the process in the temperature
∂t
range 523-623 K by one set of kinetic data: E ) 214.5
∂MT kJ/mol, A ) 1.2 × 1017 s-1, with a standard deviation
) K2MS (3) equal to 6%. Again, these data are very close to those
∂t
reported by Varhegyi et al. (1994), who analyzed the
∂MC slow dynamics of the thermal degradation of small
) νCK1MS (4) (0.5-2 mg) cellulose samples. It is interesting to note
∂t that, notwithstanding the highly different experimental
systems and heating conditions, the absence of signifi-
First-order rates are expressed as: cant heat- and mass-transfer limitations leads to com-
parable values of the kinetic data. As expected, the
Ki ) Aie-Ei/(RT), i ) 1, 2 (5) presence of significant intraparticle effects and unmet
heat demands (Antal and Varhegyi (1995)) gives rise
and, from mass conservation: to a process described by a lower activation energy (for
543 K e Tr e 623 K, E ) 191.8 kJ/mol for τ ) 100 µm
K ) K1 + K2 (6) against 200.6 kJ/mol for τ ) 50 µm).
The kinetic data for the rates of tar and the linked
Integration of eqs 2-4 (the subscript ∞ is used to char and gas formation can also be estimated by means
indicate the final yields) with conditions (Agrawal of eqs 8 and 15, if the stoichiometric coefficient νC is
(1988)): known. Alternatively eqs 8 and 11 together with the
measurements of the final tar yields can be used.
MS(0) ) M0, MT(∞) ) MT∞, MC(∞) ) MC∞ (7) Though volatile products have not been collected and
thus the final tar and gas yields (and νC) are not known,
gives an estimation of the kinetic data of the two competitive
reactions has been made on the basis of literature values
MS ) M0e-Kt (8) for νC. The results obtained for νC ) 0.35 (Bradbury et
550 Ind. Eng. Chem. Res., Vol. 36, No. 3, 1997
Figure 10. Plots of ln(P) versus time (reduction in the scale as
in Figure 7) for several reaction temperatures (τ ) 50 µm, heating
modality B).
Figure 11. Arrhenius plots for the global degradation rate, K,
the reaction rates of tar (K2) and linked char and gas (K1)
formation, obtained with the heating modality B for τ ) 50 µm.
al. (1979)) are also enclosed in Figure 11. The activation
energy of tar formation is significantly higher (225.1 kJ/
mol, standard deviation 5%) than that of char and gas
formation (158.3 kJ/mol, standard deviation 9%), con-
firming, in agreement with the Broido-Shafizadeh
mechanism, that cellulose degradation occurs according
two competitive pathways, the low temperatures leading
to char formation and the high temperatures to tar
formation. The appearance of a single smooth curve of
weight loss indicates that the transition from the char-
dominating to the tar-dominating reaction is gradual
(Agrawal (1988)). Again, kinetic data for tar and char
formation are in the range of those previously deter-
mined (Bradbury et al. (1979), Agrawal (1988), Arse-
neau (1988), Varhegyi et al. (1994)).
In a recent study (Milosavljevic and Suuberg (1995))
a rough classification of global cellulose kinetics has
been made on the dependence of the thermal conditions.
For rapid heating to temperatures above 600 K, activa-
tion energies are seen to be in the range 140-155 kJ/
mol, while slow heating to temperatures below 600 K
appears to give rise to larger values (about 218 kJ/mol).
Therefore, kinetic constants have also been estimated,
taking the reaction temperature of 600 K as the bound-
ary between two different kinetics (curves are not
reported to avoid crowding). Again, this interpretation
gives data in the same range of those reported in the
above reference, that is, E ) 220.5 kJ/mol (A ) 3.47 ×
1017 s-1) for 523 K e Tr e 600 K and E ) 143.2 kJ/mol
(A ) 3.77 × 1010 s-1) for 600 K e Tr e 623 K. However,
standard deviations, equal to 13% and and 10%, respec-
tively, are higher. On the other hand, a comparison
between the model predictions through only one set of
data (E ) 214.5 kJ/mol, A ) 1.2 × 1017 s-1) and the
Figure 12. Experimental (symbols) and simulated (dashed lines,
one set of kinetic data) solid mass fraction versus time for τ ) 50
µm (heating modality B).
experimental weight loss curves shows very good agree-
ment, confirming the validity of the kinetic scheme and
data proposed (Figure 12). On the contrary, the evalu-
ation of the difference between the measured solid mass
fraction and the predictions, based on the two sets of
kinetic constants, shows rather large values at both low
and high temperatures.
The results presented in this study show that for both
the heating modalities A and B, that is, with and
without significant heat-transfer limitations, cellulose
degradation hardly occurs for temperatures above 600
K. In the first case, the increase in the external heat-
transfer rate does not change significantly the temper-
ature of the reacting cellulose, which is cooled by the
endothermic evolution of volatiles, so that the process
is controlled by heat-transfer (Bradbury et al. (1979),
Antal and Varhegyi (1995)). In the second case, for high
temperatures, the process becomes very fast and com-
plete sample devolatilization is seen for Tr ) 625 K. It
is likely that heat- and mass-transfer limitations are
responsible for the decrease in the activation energy as
the temperature is increased and for weight loss re-
ported at temperatures much higher than it actually
occurs (Antal and Varhegyi (1995)). Consequently, the
temperatures reported for negligible char formation are
also higher.
Some considerations are also needed about the initial
processes which alter the substrate but cause only minor
changes in the weight, described through the formation
of “anhydrocellulose” (Broido and Weinstein (1971)) or
“active cellulose” (Bradbury et al. (1979)) (loss of water
and reduction in the degree of polymerization). The
descriptions of these processes do not appear necessary
for the prediction of the global degradation kinetics in
the kinetic regime, as observed by Varhegyi et al. (1994)
and confirmed by this study. However, changes in the
physical properties (i.e., melting) can be important in
practical situations, where conversion is the result of a
strong interaction between chemical and physical pro-
cesses such as in the case of ablative pyrolysis. Assum-
ing that the rate of active cellulose formation is propor-
tional to 1/ti, where ti is the time needed to attain the
maximum rate of weight loss (Bradbury et al. (1979)),
the following kinetic data are obtained: E ) 250.5 kJ/
mol, A ) 1.8 × 1021 s-1. These are again comparable
to those reported by Bradbury et al. (1979).
Conclusions
A new experimental system has been developed to
investigate the kinetics of the thermal degradation of
solids under reduced heat- and mass-transfer limita-

tions. The system, which is based on radiative heat
transfer, allows for the continuous monitoring of the
sample temperature and weight, while the heating rates
are much faster than those usually encountered in
thermogravimetric analyses.
Experiments have been carried out for cellulose, taken
as representative of biomass fuels, with two different
heating modalities. The first modality (A) consists of
the sample degradation made to occur under known
system temperatures, as in most of the previous studies.
It is shown that external heat-transfer limitations,
which become progressively more important as the
reaction conditions are made more severe, cannot be
avoided for system temperatures above 600 K. Fur-
thermore, for this and higher values, it is confirmed that
most of the pyrolytic degradation occurs for effective
reaction temperatures below 600 K, with negligible char
formation. As a consequence of reduced mass transport
limitations, the char yields are significantly lower than
those reported in the literature for temperatures in the
range 543-630 K.
The second heating modality (B) represents the most
innovative aspect of the study. It is based on the control
of the sample temperature, using the applied radiative
heat flux as the manipulated variable, in order to
eliminate external heat-transfer limitations. The pro-
cess is two-stage. In the first, the sample is rapidly
brought to the chosen sample temperature (set point),
while in the second the temperature is maintained at
the chosen value. The global heating rate has been
varied from about 19 to 56 K/s for cellulose setpoints in
the range 523-623 K. Sample half-thicknesses below
60 µm guarantee the absence of intrabed temperature
gradients and activity of secondary charring reactions.
Therefore, the process is made to occur under known
thermal conditions and reduced heat- and mass-transfer
limitations.
Cellulose weight loss curves have been interpreted in
terms of a single-step process (consisting of two com-
petitive reactions leading to tar and linked gas and char
formation), and the estimated kinetic data are in
agreement with previous studies conducted under ki-
netic control.
Acknowledgment
The research was funded in part by the European
Commission in the framework of the Non Nuclear
Energy Programme (JOULE III), Contract JOR3-CT95-
0081.
Nomenclature
A ) preexponential factor
c ) specific heat
E ) activation energy
M ) mass
MC∞ ) final solid char mass
M0 ) initial cellulose mass
Qe ) radiative heat flux
Qr ) enthalpy variation due to chemical reactions
S ) heat-exposed surface
Tf ) system temperature
TL ) lamp temperature
Tr ) (final) sample temperature
tc ) conversion time
th ) heating time
ts ) solid residence time
V ) sample volume
W ) solid residual (including char and cellulose)
Ind. Eng. Chem. Res., Vol. 36, No. 3, 1997 551
 ) emissivity
F ) density
σ ) Stephan-Boltzmann constant
τ ) bed half-thickness
ν ) stoichiometric coefficient
Subscripts
C ) char
g ) gas/vapor phase
S ) cellulose
T ) tar
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Received for review September 9, 1996
Revised manuscript received November 19, 1996
Accepted November 20, 1996X
IE960551R
X
Abstract published in Advance ACS Abstracts, January 15,
1997.