ARTICLE IN PRESS

Progress in Energy and Combustion Science 34 (2008) 47–90

www.elsevier.com/locate/pecs

Modeling chemical and physical processes of wood and

biomass pyrolysis
Colomba Di Blasi
Dipartimento di Ingegneria Chimica, Università degli Studi di Napoli ‘‘Federico II’’, P.le V. Tecchio, 80125 Napoli, Italy
Received 5 February 2005; accepted 7 December 2006
Available online 23 April 2007

Abstract

This review reports the state of the art in modeling chemical and physical processes of wood and biomass pyrolysis. Chemical kinetics
are critically discussed in relation to primary reactions, described by one- and multi-component (or one- and multi-stage) mechanisms,
and secondary reactions of tar cracking and polymerization. A mention is also made of distributed activation energy models and detailed
mechanisms which try to take into account the formation of single gaseous or liquid (tar) species. Different approaches used in the
transport models are presented at both the level of single particle and reactor, together with the main achievements of numerical
simulations. Finally, critical issues which require further investigation are indicated.
r 2007 Elsevier Ltd. All rights reserved.

Keywords: Pyrolysis; Wood; Biomass; Chemical kinetics; Transport models

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
2. Chemical kinetics of biomass pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
2.1. Measurements of primary pyrolysis rates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
2.2. One-component mechanisms of primary pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.3. Multi-component devolatilization mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
2.4. Multi-component mechanisms of primary pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
2.5. Secondary reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
2.6. Outline of multi-step mechanisms of cellulose pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
2.7. Distributed activation energy (DAE) models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
2.8. Conclusions and further developments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
3. Transport models of biomass particle pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
3.1. Transport models with volumetric decomposition rates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
3.2. Intra-particle transport phenomena. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3.3. External heat transfer coefficients . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3.4. Extra-particle processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.5. Unreacted-core-shrinking models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.6. Simulation results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
3.7. Experimental validation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
3.8. Empirical correlations and apparent kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
3.9. Conclusions and further developments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81

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E-mail address: diblasi@unina.it

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doi:10.1016/j.pecs.2006.12.001
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48 C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90

4. Models of pyrolysis reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82

4.1. Fixed-bed reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
4.2. Fast pyrolysis reactors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
4.3. Conclusions and further developments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84

1. Introduction types of wood, this contribution can reach about 30% of

Sustainable heat and power generation from biomass are
at the center of scientific and industrial interest owing to
the increasing awareness about the continuous diminution
in the availability of fossil fuels and the higher sensibility
toward environment preservation from pollutants gener-
ated by conventional energetic systems. Biomass is a term
for all organic material that stems from plants [1], with
wood as the main representative. From the chemical point
of view, it is a composite material, constituted by a mixture
of hemicellulose, cellulose, lignin and extractives [1–5], with
proportion and chemical structure affected by variety.
Inorganic matter (ash) is also part of the biomass
composition, with a content ranging from less than 1%
in wood to 15% in herbaceous biomass and feedstocks [6]
and up to 25% in some agricultural residues [7]. Potassium,
calcium, sodium, silicon, phosphorus and magnesium are
the main ash constituents [8–11]. Chlorine is also found in
significant concentrations in herbaceous biomass [10,11].
The classification techniques developed for coal, that is,
proximate and ultimate analyses, are also applied for the
characterization of biomass fuels. These are generally low
in carbon (roughly between 40% and 50% on dry, ash-free
basis) and high in volatile matter and oxygen [1,12,13],
which result in low calorific values. A significant advantage
of biomass with respect to coal is that the contents of
nitrogen and especially sulfur are low.
From the physical point of view, biomass presents a
complex structure, accurately characterized for hardwoods
and softwoods [3], which gives rise to anisotropic proper-
ties [14–16]. In this case, the thermal conductivity across
and tangential to the grain direction is approximately one-
third that along the grain, whereas the permeability to gas
flow across the wood grain is much lower (up to a factor of
104) than that along the other two directions. Moreover,
for conditions of practical interest, biomass always present
a non-negligible content of moisture. In freshly harvested
wood, moisture can exist in three forms: water vapor in the
pores, capillary or free (liquid) water in the pores and
hygroscopic or bound water in the solid structure [16]. The
water vapor can be assumed to be in the same potential
energy state as it would exist outside the solid. Neglecting
the capillary-water attractive force, the same assumption
holds for capillary water. The bound water consists of
water molecules absorbed into the cellulose molecule by
hydrogen bounding at the hydroxyl locations. When all
available sites are occupied with water molecules, the
medium is at the fiber saturation point (FSP). For many
the dry weight.
Pyrolysis, consisting of solid thermal degradation in the
absence of oxidizing agents, is a possible thermochemical
conversion route, resulting in the production of a huge
number of chemical compounds. However, for engineering
applications, reaction products are often lumped into three
groups: permanent gases, a pyrolytic liquid (bio-oil/tar)
and char [17], or simply into volatiles and char. They result
from both primary decomposition of the solid fuel and
secondary reactions of volatile condensable organic pro-
ducts into low-molecular weight gases and char, as they are
transported through the particle and the reaction environ-
ment. Numerous factors affect the pyrolysis rate and the
yields, composition and properties of the product classes.
Temperature, pressure and heating rate are the chief
operating parameters. In addition, biomass properties
(chemical composition, ash content and composition,
particle size and shape, density, moisture content, etc.)
also play an important role.
Permanent gases comprise CO2, CO, CH4 and lower
amounts of H2 and C2 hydrocarbons (for instance, see
[18–29]). The composition of the liquid is highly dependent
on the severity of the thermal treatment, that is,
temperature and residence of the tar vapors in the hot
reaction environment [30–37], and the presence of char
[38]. Primary vapors (oxygenates) are associated with
reaction temperatures below 673–773 K, followed by
hydrocarbon or secondary tars for temperatures up to
1123 K and aromatic or tertiary tars above 1123–1273 K.
The composition increases in the order of mixed oxyge-
nated compounds, phenolic eters, alkyl phenolycs, hether-
ocyclic ethers, polyaromatic hydrocarbons (PAH), and
large PAH [30,31]. Liquid products also contain an
appreciable proportion of water originated from both the
moisture content of the solid fuel and the decomposition
reactions.
Reviews are available on the operating conditions and
the reactor configurations which maximize the yields of
condensable products [39–43] or char [38,44,45] from
biomass pyrolysis. In the former case, the conversion
process is indicated as fast pyrolysis and, after cooling and
condensation, bio-oil is obtained. This is a renewable fuel,
which can be easily stored and transported and can also be
used for the production of chemicals [46]. Following the
definition of fast pyrolysis given in [43], specific for the
maximization of the liquid products, the following condi-
tions should be met: (a) high heating and heat transfer rates
at the reaction zone, (b) primary conversion temperature of
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C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
about 770 K and vapor phase temperature of 670–730 K,
(c) short residence time of products in the vapor phase
(below 2 s), (d) rapid cooling of the vapor-phase products
to obtain pyrolysis liquid. Elimination of points (c) and (d),
through an increased activity of secondary reactions of tar
vapors, favor the formation of gaseous (cracking) and/or
solid (polymerization) species. Conversely, the elimination
of point (a) is the key feature for the so-called conventional
(or slow) pyrolysis, which produce comparable yields of the
three lumped classes of products.
The char product is useful as a renewable fuel or for
other applications, such as metal reductant, soil amender
and the production of activated carbon and biocarbon
electrodes [38]. As a measure of the efficiency of the
carbonization process of a given feedstock, a comparison is
suggested between the fixed-carbon yield of char and the
theoretical yield of carbon, predicted by thermochemical
equilibrium calculations. Slow heating rates coupled with a
low-temperature peak, high pressures (also in the presence
of relatively high heating rates, typically 1–2 K/s) and long
residence times of the vapor phase products within the
reaction environment are indicated [38] as the chief
conditions for maximizing the yields of this product.
Despite the low values, a key constraint in the thermal
conversion of biomass arises from the presence of nitrogen.
Nitrogen containing species, released during biomass
pyrolysis, include [47] hydrogen cyanide (HCN), ammonia
(NH3) and isocyanuric acid (HNCO). The first two
compounds are quantitatively more important and their
relative share is affected by the thermal conditions
established during conversion (temperature and particle
size) and the fuel type [47,48]. At low temperatures, a large
portion of the nitrogen is retained in the char and NH3 is
the main gaseous nitrogeneous species. At high tempera-
tures, more nitrogen is released in the gas phase with HCN
becoming the most important product. Hence, two main
routes have been identified: one leading to NH3 and char
nitrogen and the other leading to volatile cyclic amides
which, following cracking, give rise to HCN and HNCO.
High amounts of inorganic constituents, especially
potassium, in some residues and herbaceous biomass often
contribute to adverse impact on the different elements of the
conversion systems through fouling, slagging and, in the
case of fluidized-bed reactors, bed agglomeration [49].
Chlorine is a facilitator of alkali volatilization and, like
sulfur, is an important contributor to corrosion, metal
wastage and pollution [49]. It is not possible [50,51] to
separate the chlorine products into either the char residue or
the volatile products during pyrolysis. Indeed, for some
herbaceous biomass and residues, about 20–50% is released
at temperatures between 573 and 673 K, whereas about
30–60% is still retained by the char up to temperatures of
1173 K [50]. Water washing (leaching) is a mean to eliminate
alkali metals from herbaceous biomass, thus improving the
behavior during thermal treatments [10,52].
Technical enhancements in the contribution of biomass
to commercial energy needs are focused on improving both
49
the efficiency and environmental impacts of conversion
processes. Large-scale development and optimization
require mathematical modeling which, allowing quantita-
tive representation of various phenomena, is a powerful
tool for process design, prediction of reactor performances,
understanding of pollutants evolution, analysis of process
transients and examination of strategies for effective
control. Thermo-chemical conversion of biomass in prac-
tical systems results from a strong interaction between
chemical and physical processes at the levels of both the
single particle and the reaction environment. Thus, in this
review the current state of the art of wood and biomass
pyrolysis models is analyzed in relation first to chemical
kinetics and then to transport phenomena. It is worth
noting that a large part of the models and results reviewed
here may also be of interest in fire safety science where
pyrolysis of lignocellulosic fuels is an important step for the
initiation and growth of both forest and building fires.
2. Chemical kinetics of biomass pyrolysis
Pyrolysis kinetics, coupled with the description of
transport phenomena, produce advanced computational
tools for the design and optimization of chemical reactors
applied for thermochemical conversion of wood and
biomass. Also, the knowledge of the fuel reactivity is
needed for the formulation of simple design and scaling
rules. Several reviews on the chemical kinetics of ligno-
cellulosic materials are already available, which include
those of Refs. [17,53–59]. In this section, after a brief
presentation of the problems encountered in carrying out
measurements of weight loss under a pure kinetic control,
the literature results on the chemical kinetics of wood and
biomass are reviewed, giving special consideration to work
recently published or not previously examined. Wood/
biomass components are not explicitly considered, apart
from a brief outline of the most recent findings about
cellulose pyrolysis, with special emphasis on the formation
rates of the main decomposition products. It should be
mentioned that the mechanisms and kinetic constants for
the decomposition of xylan (representative of hardwood
hemicelluloses) and lignin are summarized in the literature
review reported in the studies [60,61], respectively.
2.1. Measurements of primary pyrolysis rates
On an indicative basis, in thermogravimetry (slow
heating rates for a sufficiently small mass of the sample,
so that a kinetic control is established), primary degrada-
tion of biomass starts at about 500 K, fast rates are
attained at about 573 K and the process is practically
terminated at 700–750 K [55,62,63]. Weight loss results
from the activity of numerous reactions. Therefore,
thermogravimetric curves, measured for dynamic or static
(isothermal) conditions, are useful simply for the formula-
tion of global or semi-global mechanisms, which can
include the effects of reaction parameters and sample
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50 C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
properties. Several studies (for instance, see [64–67])
suggest that primary decomposition rates of biomass can
be modeled taking into account the thermal behavior of the
main components and their relative contribution in the
chemical composition. For heating rates at sufficiently slow
or moderate temperatures, several zones appear in the
weight loss curves, which can be associated with com-
ponent dynamics. Indeed, hemicelluloses decompose at
498–598 K, cellulose at 598–648 K, whereas lignin decom-
poses gradually over the temperature range of 523–773 K
[63]. As the heating rate is increased, given that the range of
the degradation temperatures of components is relatively
narrow, the different peaks in the degradation rate tend to
merge and the characteristic process temperatures tend to
become progressively higher. Furthermore, if temperatures
are sufficiently high, significant degradation rates are
simultaneously attained by all the components.
The term ‘‘pseudo-component’’ is more appropriate as it
is impossible to avoid overlap between the different
components in the measured weight loss curves. In other
words, although for each zone a main contributor can be
identified as hemicellulose, cellulose and lignin, respec-
tively, the simultaneous participation of the other compo-
nents cannot be avoided with an extent that depends on the
biomass characteristics and the severity of the conversion
conditions. On the other hand, results obtained from the
analysis of single components cannot be directly applied to
biomass because of chemical and physical alterations
introduced in the separation procedure, the impossibility
to reproduce component interactions and the presence of
ash [55,67]. Ash constituents, especially potassium, sodium
and calcium, act as catalysts for the decomposition process
and favor char formation [52,68]. As chlorine and
potassium in biomass are water soluble, they can largely
be removed through leaching, thus mitigating their impact
on the high-temperature conversion devices [10,11]. In
reality, water or mild acid washing also introduce
significant modifications in the biomass decomposition
characteristics [52,69–73]. In particular, this procedure is
effective for separating and sharpening the peaks of the
rate curves, thus facilitating, for instance, in situ investiga-
tion of cellulose and hemicellulose decomposition kinetics.
An increase in reaction temperature and amount of volatile
products is also observed.
Despite the numerous weight loss measurements available
in the literature, a systematic classification of biomass fuels,
based on thermogravimetric analysis, and general mechan-
isms to interpret such measurements are not available.
Indeed, the differences in the experimental apparatus and
conditions and the lack of reference materials make this task
extremely difficult. Quantitative differences between ther-
mogravimetric characteristics are caused by several factors
which, in addition to the wood or biomass species, include,
even for the same sample, the geographical origin, the age or
the specific part of the plant [3,73].
A difficulty in kinetic analysis also exists in separating
the effects of chemistry and transport phenomena. One of
the key points, in relation to intrusion of heat and mass
transfer processes in kinetic analysis, is the sample size/
mass during pyrolysis which cause spatial gradients of
temperature (a process taking place under non-negligible
effects of internal heat transfer) or significant differences of
temperatures between the sample and the controlling
thermocouple, especially when these are not in close
contact (non-negligible external heat transfer resistance).
The latter is the most common case given that, in the
experiments motivated by kinetic analysis, usually the
sample mass is small and the rate/temperature of heating is
kept at low levels. Owing to sample thermal inertia and/or
reaction energetics, significant differences, often indicated
as ‘‘thermal lag’’ [74], may be established between the
sample and the controlling (external) thermocouple. These
effects, extensively discussed in previous reviews [53,55],
are quite high for cellulose [72,74–78] as a consequence of
the strong endothermicity of the decomposition process
when pressures are low and mass transfer resistance
negligible. The most visible effects of such a drawback
are a shift of the mass loss peak to higher temperatures and
an increase in the yields of char as the sample mass is
augmented.
In contrast with the pyrolysis of cellulose, the sample
mass is shown to have a negligible influence on the position
of the maximum rate of mass loss and the yield of char for
straw and washed straw [72]. This result is likely to hold
also for other biomasses and stems mainly from lower
effects of reaction energetics. Several studies [79–82] clearly
show that exothermicity in biomass pyrolysis is associated
with the formation of char. It can be understood that,
owing to the higher yields of char generated from biomass
in comparison with cellulose, the positive and negative
effects in the reaction heats tend to become nearly
equivalent.
Char is generated from both primary and secondary
reactions [38]. In the latter case, it is a coke derived from
the decomposition of organic vapors (tars) on the
carbonaceous solid, which acts as a catalyst. Beneficial
effects are reported of both prolonged vapor-phase
residence times and increased concentrations of vapors
on the carbonization chemistry [80]. Under pressure, tarry
vapors have a smaller specific volume, so that their intra-
particle residence time is prolonged, favoring their decom-
position, as they escape the biomass particle. Also the
concentration (partial pressure) of tarry vapors is higher,
thus increasing the decomposition reaction rate. Hence,
pressure and flow rate [80] and, in general, mass transfer
limitations [80,81] are key parameters for both the yields of
char and the exothermicity of the pyrolysis process. Indeed,
a linear relation between heat of pyrolysis reactions and
char yields is found [80–82]. In quantitative terms, for the
exothermic formation of char, values are reported of 3.6
[80], 2 [81] and 3.5–3.8 [82] kJ/g of char formed. The
reactions forming tar precursors are estimated to be nearly
thermo neutral [81] and the main enthalpy sink is
attributed to tar evaporation [80,81], which is favored by
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C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
low pressures and high flow rates. The endothermicity of
tar formation is estimated to be comprised between 0.9 and
1.3 kJ/g of tar formed [82]. Finally, it should also be noted
that, for the conditions of thermal analysis, the processes of
lignin and cellulose decomposition are considered [83–85]
to be globally exothermic and endothermic, respectively.
Another important aspect to be taken into account,
when investigating primary decomposition, is that the
effects of secondary reactions should be kept at a
minimum. Although it is not always possible to separate
the activity of the two classes of reactions, small size/mass
of the sample is highly advisable because of the consequent
reduction in the residence times of the vapor phase
products in the hot reaction environment. A further
key parameter in this matter is the reaction temperature
which, to limit the activity of secondary reactions of tar
cracking, should be maintained at least below 773 K
[18–22,27,28,30].
When coupled with the description of transport phe-
nomena, chemical kinetics should be able to predict: (1)
conversion time, and (2) product distribution, as the
operating conditions are varied. Associated with these
global parameters, details about the degradation dynamics
are also obtained. A simplified description of primary
decomposition processes, usually adopted for isothermal
conditions or fast heating rates, is based on a one-
component (or one-stage) reaction process. In this case,
weight loss curves are often associated with additional
measurements concerning the yields of the three product
classes, in order to evaluate the related formation rates.
Multi-component (or multi-stage) reaction mechanisms are
also proposed where each reaction takes into account the
dynamics of several zones or pseudo-components in the
measured curves of weight loss. Devolatilization reactions
are essentially considered, with only a very few exceptions
where both devolatilization and charring are included. The
kinetic models make use of an Arrhenius dependence on
temperature, thus introducing the parameters activation
energy and pre-exponential factor, and a linear or power-
law dependence on the component mass fraction, which
may lead to additional parameters (the exponents).
Contrary to the case of coal, models based on a Gaussian
distribution of activation energies are scarce. A mention
should also be made of isolated applications of peculiar
models, not discussed in detail here, which include the
deactivation model proposed in [86] for beech wood and a
few agricultural residues, the use of artificial neural
network methods for cellulose and lignin decomposition
[87] and other treatments as discussed in [58].
2.2. One-component mechanisms of primary pyrolysis
As already observed, biomass weight loss curves,
obtained under dynamic or isothermal conditions, present
different reaction zones mainly corresponding to compo-
nent decomposition, which tend to merge as the heating
conditions become more severe. Hence, when fast heating
51
rates or high temperatures are established, the majority of
kinetic mechanisms consists of a single or three parallel
reactions for the formation of the main product classes
(one-stage or one-component mechanisms) following the
proposal by Shafizadeh and Chin [88] for wood (Fig. 1).
The separate formation rates of different product classes
introduced by the reaction mechanism of Fig. 1 may be
questionable from the point of view of analytical chemistry
[53,54]. However, as previously observed [17,89,90], the
comparable activation energies of the three reactions do
not allow the selectivity to be displaced toward only one of
the products. For negligible activity of secondary reactions,
product distribution from cellulose pyrolysis carried out at
atmospheric pressure (in accordance with the mechanism
proposed by Bradbury et al. [91]) indicates that both char
and gas yields decrease as the reaction temperature is
increased (that is, their formation is linked) whereas, in
primary wood pyrolysis, both liquid and gas yields
continuously increase at the expense of char [18–22,
27,29]. It can be postulated that, during fast heating, given
that holocellulose is converted mainly into liquids, the
other two product classes (gases and char) are mainly due
to lignin degradation. Hence, at low temperatures, on a
global basis, there is a competition between liquid
(holocellulose degradation) and char (lignin degradation)
formation, with the former becoming successively more
favored. At high temperatures, gas formation rates tend to
increase, owing to the predominance of devolatilization
(versus charring) rates of lignin decomposition.
Table 1 and Fig. 2 present a summary of the one-
component mechanisms of wood/biomass pyrolysis pro-
posed on the basis of experiments carried out under
isothermal or fast heating rate conditions. At a first glance,
it appears that the activation energy of the global reaction
rate (k) presents widely variable values, roughly comprised
between 56 and 174 kJ/mol. This can be the result of the
different heating conditions established in the experimental
devices, which include tube furnaces, entrained and fluid
bed reactors, screen heaters, drop tubes and classical
thermogravimetry, the different sample characteristics (size
or mass and wood/biomass variety) and the mathematical
treatment of the experimental data.
A more careful examination of the data, taking into
account the temperature range investigated, produces to
the following main groups:
(a1) high-temperature data (up to 1400 K) with
E ¼ 69–91 kJ/mol [93,94,98];
(a2) low-temperature data (below 700–800 K) with
E ¼ 56–106 kJ/mol [92,95,96,99];
Fig. 1. One-component mechanism of primary wood pyrolysis proposed
by Shafizadeh and Chin [88] (activation energies are expressed as cal/mol).
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52 C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90

Table 1
Kinetic constants for one-component mechanisms of wood/biomass pyrolysis (same data as in Fig. 1)

Author (Ref.) Feedstock Experimental Tr Reaction mechanism Kinetic constants: E (kJ/mol),

(variety, size, mass) system A (s1)

Thurner and Oak, 650 mm Isothermal tube 573–673 K dY k ¼ 2.47  106 exp(106.5/RT)
¼  kY
Mann [92] furnace dt kL+kG ¼ 1.73  106 exp(106.5/RT)
k ¼ kC þ k G þ k L kC ¼ 7.4  105 exp(106.5/RT)
kL ¼ 4.12  106 exp(112.7/RT)
kG ¼ 1.43  104 exp(88.6/RT)

Gorton and Hardwood, Isothermal 677–822 K dY k ¼ 1.483  106 exp(89.52/RT)

¼ kY
Knight [93] 300–350 mm entrained-flow dt
reactor

Ward and Wild cherry Isothermal tube 538–593 K dY k ¼ 11.9  1011 exp(173.7/RT)
¼  kðY  Y C1 Þ
Brashlaw [64] furnace dt
Y C1 ¼ 0:25  0:30

Nunn et al. [94] Sweet gum, Screen heater 600–1400 K dY V kL+kG ¼ 33.38  104 exp(69/RT)
¼ kðY V1  Y V Þ
hardwood, (1000 K/min) dt
45–88 mm, 100 mg Y V1 ¼ 0:93

Chan et al. [14] — — — dY kC ¼ 1.08  107 exp(121/RT)

¼  kY
dt kT ¼ 2  108 exp(133/RT)
k ¼ kC þ k T þ kG þ kW kG ¼ 1.3  108 exp(140/RT)
kW ¼ 5.13  106 exp(92.1/RT)

Font et al. [95] Almond shells, Pyroprobe 100 733–878 K dY k ¼ 1.885  106 exp(108/RT)
¼ kY
300–500 mm, 2 mg dt kC ¼ 2.98  103 exp(73/RT)
kL ¼ 5.85  106 exp(119/RT)
kG ¼ 1.52  107 exp(139/RT)

Samolada and Fir wood, Isothermal batch 673–773 K dY V kG+kL ¼ 2.40  104exp(94/RT)
¼ kðY V1  Y V Þ
Vasalos [96] 300–425 mm, 2 g fluid-bed dt
Y V 1 ¼ 0:005

Wagenaar et al. Pine, 100–125 mm TGA 553–673 K dY k ¼ 1.4  1010 exp(150/RT)

¼  kY
[97] Drop tube 773–873 K dt kC ¼ 3.05  107 exp(125/RT)
k ¼ kC þ k G þ k L kL ¼ 9.28  109 exp(149/RT)
kG ¼ 1.11  1011 exp(177/RT)

Reina et al. [98] Forest waste, Isothermal TGA 498–598 K dY k ¼ 7.68  107 exp(124.87/RT)
¼ kðY  Y C1 Þ; Y C1 ffi 0:25
p1000 mm, 25 mg dt

973–1173 K dY k ¼ 6.33  102 exp(91.53/RT)

¼ kðY  Y C1 Þ; Y C1 p0:15
dt

Di Blasi and Beech, o80 mm, 9 mg Tube furnace 573–708 K dY (a) k ¼ 2.4  105 exp(95.4/RT)
¼ kY
Branca [99] dt (b) k ¼ 4.4  109 exp(141/RT)
kL+kG ¼ 1.5  1010 exp(149/RT)
kC ¼ 3.3  106 exp(112/RT)
kG ¼ 4.4  109 exp(153/RT)
kL ¼ 1.1  1010 exp(148/RT)

(a3) low-temperature data (below 700–800 K)
E ¼ 125–174 kJ/mol [64,97–99].
In the presence of non-negligible heat and mass transfer
limitations, the analysis and interpretation of measure-
ments traduce in apparent kinetics, characterized by
activation energies much lower than the true values and
with lower rates than those determined in classical thermo-
gravimetry [55]. This appears to be the case of the kinetic
constants estimated by means of the high-temperature data
of the group a1 (for instance, screen heaters or entrained
bed reactors), which may be affected by significant heat/
mass transfer intrusions. The kinetic models of Refs.
[93,94] are essentially proposed as correlations for specific

C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
2 80
0 [93]
[97]
[95]
-2
[94] [99b]
-4
ln k
[92]
-6 [96]
[99a]
-8
-10
-12
1.00 1.20 1.40 1.60
1000/T [K-1]
Fig. 2. Arrhenius plot for the global decomposition rate of wood/biomass
based on one-component mechanisms (see Table 1 for kinetic parameter
values).
experiments. The actual particle temperatures are unknown
in [93], whereas screen heater measurements [94] are
affected by significant practical problems [100]. In this
apparatus, it is difficult to achieve a good control of the
sample temperature, the recorded value is strongly affected
by thermocouple positioning and the effects of reaction
energetics are not taken into account. Finally, the low
values of the kinetic constant predicted with the model of
Ref. [98] in the high-temperature range (973–1173 K, not
shown) can again be due to a lack of kinetic control.
The impossibility to get high temperatures without going
through the low-temperature region also excludes a change
in the reaction mechanism. These considerations lead Antal
[54] to write that ‘‘accurate estimates of high-temperature
biomass pyrolysis reaction rates can be best obtained by
extrapolating low-temperature kinetic data applicable to
the reaction pathways of interest at high temperatures’’.
However, it can be noted that, for low-temperature data,
both a low-activation energy group (a2) and a high-
activation energy group (a3) of kinetic constants exist.
In order to estimate the global rate constant, k, for the
isothermal process described by the three reactions of
Fig. 1, two different treatments can be used [99], though
assuming in both cases that only the central part of the
weight loss curves, the most important from the quantita-
tive point of view, has to be described. That is, the mass
conservation equations can be integrated over the entire
duration (time) of the process, or specifically over the time
corresponding to the central part of the weight loss curve.
In fact, zones with different slopes in the Arrhenius plot
make evident the existence of several sequential reaction
steps. Then, the usual Arrhenius plot and a least-square
analysis give the activation energy and the pre-exponential
factor of the global pyrolysis kinetics. It is found [99] that
two sets of kinetic constants can be obtained (Table 1:
E ¼ 95.4 kJ/mol (model a), and E ¼ 141.2 kJ/mol (model
b)) for the same group of isothermal experiments. Fig. 2
ARTICLE IN PRESS
53
Ref.
[14]
; [64]
60 ; [92]
Char Yield [wt%]
; [97]
; [98]
40 ; [99]
20
[98]
[64]
0
1.80 2.00 525 575 625 675 725
T [K]
Fig. 3. Predicted (lines) and measured (symbols) of char yields on
dependence of the reaction temperature (kinetic control and one-
component mechanisms).
shows that both sets are comprised in the range of
literature values. The kinetic constants of the model of
Ref. [99] (model a) and those of Refs. [92,96] are roughly
the same. The kinetic constants are also roughly the same
for the model of Ref. [99] (model b)) and those of Refs.
[97,98] (Ref. [98] for a temperature range of 498–598, forest
waste).
The results of Ref. [99] for the models (a) and (b), plotted
in Fig. 2, indicate that the mathematical treatment of the
central part of the same weight loss curves affects
significantly the activation energies. At low temperatures,
the model (a) predicts degradation rates faster than those
of the model (b) but fails to predict the fast increase of the
wood degradation rate with temperature, which is due
mainly to the activity of components in the central part of
the isothermal weight loss curves. Hence, the model (b) and
those of group a3, introduced above, appear to be more
appropriate than the model (a) (and those of group a2) for
predicting the behavior of chemical reactors in practical
applications.
The kinetic constants, plotted in Fig. 2, are inversely
proportional to the characteristic (chemical) times of wood
pyrolysis. If product yields are among the desired model
outputs, the kinetics for the formation rates of the different
product classes should be estimated. For isothermal data,
this requires the knowledge of the corresponding yields for
each reaction stage of the mechanism [89,99]. Given that
accurate measurements of the volatile fractions cannot be
accomplished for the small sample quantity used in
thermogravimetric analysis, and laboratory scale reactors
only allow the total final yields of products to be obtained,
alternative formulations are difficult to accomplish with
respect to a one-component mechanism of wood or
biomass primary degradation including the product
formation rates such as in the proposal of Fig. 1.
The kinetic constants for the formation rates of char, gas
and liquids (or for volatiles and char), where available, are

54 C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
100
80
Liquid
Yields [wt%]
60
Ref.
40
20
Gas
0 experiments are generally carried out by means of classical
525 575 625 675
T [K]
Fig. 4. Predicted liquid and gas yields on dependence of the reaction
temperature (kinetic control and one-component mechanisms).
also listed in Table 1. The corresponding predictions of the
product yields for wood/biomass, obtained under kinetic
conditions and following [99], are summarized in Fig. 3
(char) and Fig. 4 (gas and liquids) where, for completeness,
the experimental data are also included. In all cases, the
measured char yields decrease as the temperature is
increased. Good agreement (Fig. 3) is observed between
predictions and measurements [64,98,99] for low tempera-
tures. The Thurner and Mann [92] mechanism does not
reproduce the experimental trends even from the qualita-
tive point of view, whereas quantitative differences are high
between the other mechanisms. In particular, only the
kinetic constants of Refs. [97,99] predict a strong influence
of temperature (quantitative differences are probably due
to the use of softwood and hardwoods, respectively). In
other cases, the char yields remain high (20–30%).
Consequently, the related kinetics are not applicable for
fast pyrolysis, where typical char yields are below 15%.
For liquid and gas formation, differences between
kinetics (Fig. 4) exist from both the qualitative and the
quantitative point of view. Kinetic constants of Refs.
[14,99], in qualitative agreement with experimental mea-
surements (for instance, [18–22,25–29]), indicate that both
liquid and gas yields increase with temperature. The gas
yields attain about the same values, but liquid yields are
higher in [99] (lower char yield). The other two sets of data
do not give predictions in qualitative agreement with
experimental observation. Indeed, the gas [92] or the liquid
[97] yields decrease as the temperature is increased (though,
in the latter case, this is hardly evident).
It is difficult to explain the differences between the
proposed kinetics, but the use of thick particles [92] clearly
gives rise to heat and mass transfer limitations, which
appear as high char yields. Other critical aspects are the
very narrow range of temperatures investigated, the
evaluation of product yields at high temperature [97],
when secondary reaction activity is not negligible, and the
absence of temperature measurement/control [92,97].
ARTICLE IN PRESS
Finally, the results may be affected by the wood or
biomass species (for instance, at low temperatures, very
high yields of char are predicted [90] in the case of almond
shells [95]).
2.3. Multi-component devolatilization mechanisms
[14]
[92] The majority of multi-component mechanisms simply
[97] consist of devolatilization reactions, which can be applied
[99] to predict only the rate of weight loss, provided that the
total amount of matter to be released in the gas/vapor
phase is already known (assigned or measured). Dynamic
725 thermogravimetry. The most used mechanisms usually
comprise parallel reactions (Fig. 5) for the decomposition
of the volatile fractions of pseudo-components, although
consecutive reactions can also be applied [101], owing to
significant overlap between the different evolution times. In
the former case, each pseudo-component, whose volatile
fraction is among the model parameters, acts as if there
were no interactions. The number of pseudo-components
or zones, in the majority of the cases, is three and again
coincides with hemicellulose, cellulose and lignin (three-
component devolatilization mechanisms). In a few cases,
the contribution of extractives or more than one reaction
stage in the decomposition of components, especially
hemicellulose and lignin, are also taken into account.
An important aspect is represented by the mathematical
treatment of the experimental data to formulate reaction
mechanisms and to estimate the related kinetic parameters.
The use is recommended [59,101] of differential (versus
integral) measurements because the details of the devola-
tilization process are better shown. Furthermore, linear
forms of the mass conservation equations, usually com-
bined with analytical methods for the evaluation of the
kinetic constants, may present serious drawbacks deriving
from data manipulation and applicability limited to single
measurements [59]. Instead, numerical solutions of the
conservation equations coupled with minimization meth-
ods of objective functions, adequately defined, are advised
[57,59].
The three-component mechanism with linear or non-
linear dependence on species concentrations, for the
volatile fractions of the pseudo-components hemicellulose,
cellulose and lignin, is widely applied [55,57,69,70,
73,102–109] to describe dynamic thermogravimetric curves
of wood/biomass devolatilization. In several cases
[55,57,69,73,104,105,107] dynamic measurements and the
corresponding kinetic analyses examine one heating rate
only, generally below 10 K/min. Process simulations show
that the pseudo-components hemicellulose and cellulose
decompose independently of one another, the former
Fig. 5. Multi-component devolatilization mechanisms (Ci is the volatile
fraction of the ith pseudo-component).
 ARTICLE IN PRESS
C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
1.0
0.8
-dY/dt x 103 [s-1]
cellulose
0.6 hemicellulose
0.4
0.2 lignin
0.0
400 500 600 700
T [K]
Fig. 6. Comparison between the observed (symbols) and simulated
differential curves (solid line) for beech wood heated at 5 K/min, by
means of a three-component devolatilization model (parameters estimated
for a single heating rate [107]). Lines with various styles denote the
predicted volatile evolution from the different pseudo-components.
associated with the shoulder and the latter with the peak of
the rate curves, whereas the lignin pseudo-component
decomposes slowly over a very broad range of tempera-
tures. An example is provided in Fig. 6, for beech wood
and a heating rate of 5 K/min [107]. The agreement
between the kinetic parameters, estimated by means of
differential curves, is acceptable. Activation energies vary
between 80 and 116 kJ/mol for hemicellulose, 195–286 kJ/
mol for cellulose, and 18–65 kJ/mol for lignin. Further-
more, the component contributions, expressed as percent
of the total mass fraction, are roughly 20–30% for
hemicellulose, 28–38% for cellulose and 10–15% for lignin.
They are obtained as a result of the optimization procedure
(based on total mass conservation, the complement to 100
is represented by char).
Compared with the case of one-component reaction
mechanisms, the use of classical thermogravimetric systems
with very slow heating rates and the application of
numerical methods for parameter estimations certainly
contribute to reduce the differences between the estimated
values of the kinetic constants. The effects of the highly
heterogeneous material, however, still remain and general
mechanisms with a wide range of applicability are not
available. Attempts in this direction are the results
presented in [107], in relation to nine wood species whose
chemical composition is comprised within the widest range
indicated for the hardwood and softwood categories, and
in [73] for chestnut, which presents large deviations in the
chemical composition compared with standard hardwood
categories. It is reported that, at least for one slow heating
rate, the same set of activation energies can be applied in all
cases. The differences in the characteristic reaction
temperatures and the yields of char between species are
taken into account by pre-exponential factors and stoichio-
metric coefficients. However, in the case of chestnut, the
accuracy in the predictions is acceptable only for engineer-
55
ing applications. The same considerations apply for the
effects of sample geographical origin and pretreatments
(hot water or acetone extraction) [73].
When the kinetic constants are estimated by means of
one experiment only, compensation effects [110,111] are
not avoided, that is, the possibility of different couples of
pre-exponential factor and activation energy to describe
reasonably well the same weight loss curve. Indeed, only
one set of data can predict the behavior of the material at
several heating rates, consisting of the displacement of the
weight loss curves toward successively shorter times for
thermal conditions successively more severe [110]. Numer-
ical simulations [74,77], based on simple models ignoring
800 spatial gradients and for the conditions (sample size and
heating rate) typical of thermal analysis, show the existence
of a thermal lag between the sample and the external
(heating) temperature. It is a consequence of the endother-
micity of biomass decomposition and has been related by
Narayan and Antal [74] to compensation effects. If the
thermal lag is non-negligible, estimated values of the
apparent activation energy and pre-exponential factor will
be less that their true (intrinsic) values. Conesa et al. [59], in
their literature review, also agree with this explanation.
Hence, in order to determine the intrinsic reaction kinetics,
such effects should be avoided. It is suggested that [59] ‘‘the
fitting of various runs performed in different conditions
(different heating rates, or different temperature program
in general) at the same time, using the same kinetic model
and parameters, could be a method valid for distinguishing
an actual model and for solving the compensation effect. A
model involving a change in kinetic constants with the
heating rate and/or the extension of the reaction can only
be considered a correlation model very far from the actual
kinetics’’. The inclusion of several heating rates, especially
the higher values, in kinetic analysis of wood/biomass
devolatilization is also important from the practical side.
Indeed, the fuel particles in industrial systems usually
experience widely variable heating rates, which often are
higher than those typical of thermal analysis.
In some cases, thermogravimetric curves of biomass
decomposition are measured at several heating rates but
the kinetic analysis is incomplete as no effort is made to
produce a general kinetic model applicable for the different
thermal conditions (for instance, see [66] for rice husks).
The separate analysis of each curve, based on analytical
solutions, usually produce sets of kinetic parameters highly
variable with the heating rate. This result can be partly
attributed to non-negligible effects of transport phenom-
ena, especially at the higher heating rates, and partly to the
simplified method for extracting kinetic parameters from
the measured curves. In any case, such kinetics should not
be incorporated in transport models for the description of
practical conversion systems.
The simultaneous evaluation of multiple thermogravi-
metric curves for different heating rates is examined in
several studies, which include 2–25 K/min for olive stones
and almond shells [102], 3–100 K/min for untreated and
 ARTICLE IN PRESS
56 C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
water washed rice husks [103], 0.5–108 K/min for water-
washed beech wood [106] and 5–20 K/min for waste wood
and other residues [108]. Apart from the different fuels and
pre-treatments examined, the comparison between the
results is difficult owing to power-law dependence on the
mass fraction [102,106,108], the use of integral data
[103,106] and the selection of widely different values of
the component fractions. The overall trend is that the
kinetic evaluation of cellulose devolatilization remains
roughly unchanged (activation energies of 192–250 kJ/
mol, which compare well with single-curve results), but
higher activation energies of hemicellulose degradation are
reported (154–200 kJ/mol). As for the reaction of the third
pseudo-component, activation energies of 36 kJ/mol [103],
associated with a strong dependence of the corresponding
pre-exponential factor on the heating rate, 188–219 kJ/mol
[102,106], and 54–61 kJ/mol [108] are given (in [106], the
devolatilization of this component takes place along the
low-temperature region typical of hemicellulose).
The recent study by Branca et al. [109] tries to explain
the differences in the kinetic constants when the three-
component mechanism, with rates linearly dependent on
the volatile content, is applied for the interpretation of
thermogravimetric curves obtained at several heating rates
(range 3–100 K/min). It is found that the set of activation
energies estimated in [107] (100, 236 and 46 kJ/mol,
respectively) and representative of values obtained when
only one differential thermogravimetric curve is processed,
gives rise to very high deviations between predicted and
measured rate curves. The agreement is highly improved by
a new set of data consisting of activation energies of 147,
193 and 181 kJ/mol, respectively, for the pseudo-compo-
nents hemicellulose, cellulose and lignin. An example of the
predicted dynamics is shown in Fig. 7 for beech wood and
a heating rate of 5 K/min. A comparison with the kinetics
determined with the use of one heating rate only (Fig. 6)
shows that the overlap is reduced between the devolatiliza-
tion rates of the three pseudo-components whose chemical
composition is also modified. The amount of volatiles
released in the second (cellulose) stage is increased
(46–49% versus 38–44%) at the expenses of that associated
with the first (hemicellulose) stage (about 18–24% versus
23–30%). Furthermore, instead of a slow decomposition
rate over a broad range of temperatures, the activity of the
third reaction (lignin devolatilization) is mainly explicated
along the high-temperature (tail) region of the weight loss
curves.
Sometimes the three-component mechanism is modified
to include additional steps for improving the accuracy of
the predictions, as in [112] for isothermal data, and
[107,113,114] for dynamic data. In [112] wood (pine,
chestnut and pine bark), devolatilization is modeled by
means of six parallel reactions corresponding to different
volatile fractions. The first two, quantitatively more
important, are associated with hemicellulose and cellulose,
respectively (the corresponding activation energies of 83
and 146 kJ/mol are in good agreement with the values
1.0
0.8
-dY/dt x 103 [s-1]
0.6
cellulose
hemicellulose
0.4
0.2 lignin
0.0
400 500 600 700 800
T [K]
Fig. 7. Comparison between the observed (symbols) and simulated
differential curves (solid line) for beech wood heated at 5 K/min, by
means of a three-component devolatilization model (parameters estimated
for heating rates between 5 and 104 K/min [109]). Lines with various styles
denote the predicted volatile evolution from the different pseudo-
components.
reported for single dynamic curves of the weight loss rate).
The other components are assumed to correspond mainly
to parts of the lignin macromolecule (activation energies
between 60 and 130 kJ/mol).
Two additional reactions, in the low-temperature region
(below 553 K) associated with extractive decomposition,
are considered in [107] for both hardwood and softwood
species. In [113], thermogravimetric curves of wood
(hornbeam, walnut, pine) are interpreted using five parallel
reactions, with a power-law dependence on the volatile
mass fraction, with parameters dependent on the wood
species. Two fractions are considered for both the
hemicellulose (activation energies in the ranges 101–175
and 257–272 kJ/mol, respectively) and cellulose (activation
energies 93–99 and 181–183 kJ/mol, respectively) pseudo-
components and one for lignin (activation energies of
93–105 kJ/mol), though it is pointed out that the evalua-
tions for the small fraction of cellulose, characterized by a
low activation energy, are uncertain. Reaction orders are
comprised between 0.8 and 1.8. It can be noted that this
study again confirms high activation energies for the
decomposition of the cellulose component.
It is also found [114] that, to obtain accurate predictions
of the devolatilization rates of wood (poplar, black locust
and willow) at different heating programs (heating rates
between 20 and 40 K/min), it is necessary to use at least six
or four reactions depending on the assumption of a linear
or a power-law dependence on the volatile fraction. This is
an indirect confirmation of the large inaccuracies intro-
duced in multiple-curve predictions by the set of kinetic
parameters of the three-component mechanism as esti-
mated for single curves. The use of additional reactions or
parameters, compared with previous slow heating rates
analysis, is justified [114] with the consideration that a
‘‘wider range of experimental conditions reveals more of
 ARTICLE IN PRESS
C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
the chemical inhomogeneities of the biomass components’’.
The pseudo-component cellulose is still characterized by a
quite high value of the activation energy (188 kJ/mol),
whereas a wide range of activation energies is proposed for
the remaining reactions (84–241 kJ/mol).
Although the differences in the kinetics of wood/biomass
devolatilization may be a consequence of model features
and procedure of parameter estimation (in addition to the
chemical properties of the samples), a round robin with
eight participants [115], carried out to evaluate the
chemical kinetics of Avicel PH 105 microcrystalline
cellulose, clearly puts into evidence the existence of some
flaws in the temperature measurements even for standard
thermogravimetric systems. It shows that, for low heating
rates (5 K/min), the agreement is acceptable (scatter in the
temperature measurements of about 17 K and char yields
between 4% and 10.9%) and, in terms of kinetic
parameters, the differences can be accounted for by some
uncertainty on the pre-exponential factor of the one-step
first-order reaction (devolatilization). At higher heating
rates (40 K/min), the impact of thermal lag is larger and
appears as reduced values of activation energies and pre-
exponential factors. The authors also point out that the
scatter in the experimental data and the instrumental errors
well represent the performances of the state-of-the-art
instruments, so that they ‘‘are inclined to acknowledge the
fact that biomass pyrolysis kinetics are inherently difficult
to study by any technique, and these difficulties contribute
significant uncertainties’’ in the ‘‘understanding of the
phenomena’’.
2.4. Multi-component mechanisms of primary pyrolysis
A very few multi-component (or multi-stage) mechan-
isms of wood/biomass pyrolysis are available, that is,
mechanisms for predicting the formation rates and the
yields of reaction products or solid- and gas-phase
intermediates. Examples based on series reactions, which
try to take into account the presence of several zones in the
isothermal weight loss curves, are given in [116,117] for
straw and beech wood, respectively. The mechanism of
wood pyrolysis, proposed by Miller and Bellan [118], also
belongs to this category, which incorporates multi-step
mechanisms for the main components and uses the
superposition of the different contributions, taking into
account chemical composition. It can be considered a re-
examination of the mechanisms originally proposed in
[64,65].
A three-stage series mechanism (Fig. 8) is proposed in
[116,117], which takes into account the competitive
formation of classes of compounds belonging to either
the gas (vapor) or the solid phase. However, kinetic
parameters are estimated only for each global reaction
(simultaneous charring and devolatilization processes) of
the three stages. In the case of beech wood, estimations are
carried out in the temperature range 528–593 K (k1),
528–708 K (k2) and 603–708 K (k3), for three zones clearly
57
Fig. 8. The multi-component pyrolysis mechanism proposed in [117] (A is
the fuel, B and D are reaction intermediates).
visible in the isothermal weight loss curves and correspond-
ing to the main pseudo-components introduced in Fig. 8.
The inclusion of low-temperature (528–573 K) data in the
Arrhenius plot does not result in significant changes in the
kinetic parameters for the central part of the reaction zone
(an activation energy of 143 kJ/mol against 141 kJ/mol
previously estimated [99] for temperatures above 573 K),
which are also close to those of other isothermal analyses
[64,97,98,112]. These values are, however, lower than those
estimated for the devolatilization mechanisms based on
dynamic measurements. As for the hemicellulose stage, the
activation energy (76 kJ/mol) reported in [117] is in the
range of those obtained from the evaluation of single
dynamic curves and the isothermal analysis in [112]. The
low activation energy for the third (lignin) stage also agrees
with the results obtained from evaluation of single dynamic
curves.
In the light of the criticism raised by the recent analysis
by Branca et al. [109] about the kinetic constants of the
three-component devolatilization mechanism estimated by
the use of single curves (also taking into account possible
flaws in the thermogravimetric measurements [115]), it can
be argued that the kinetic constants estimated by means of
isothermal curves also produce poorly accurate predic-
tions. Moreover, the consecutive reactions of Fig. 8 suffer
from a higher overlap between the degradation rates of the
main components compared with slow heating rate
dynamic analyses. On the other hand, if the formation
rate of the product classes for each stage should be
determined, the corresponding final yields should be
measured. However, this is not possible because, as already
pointed out, only integral data concerning complete
conversion can be measured from chemical reactors.
A multi-component mechanism, taking into account the
decomposition rate of hemicellulose, cellulose and lignin, is
proposed in [118], as already in [64–65]. The model in not
based on a specific set of experiments but relies upon a re-
examination of literature data. It is assumed that the
mechanism of cellulose pyrolysis by Bradbury et al. [91]
is also applicable for the other two main components
(Table 2). The reaction rates present the usual Arrhenius
dependence on temperature and are first order in the
reactant mass fraction. The depolymerization step does not
introduce any change in the chemical composition but it is
suggested to modify the physical properties, for instance,
porosity. The kinetic constants estimated by Bradbury et
al. [91] are used for cellulose. The corresponding initial
estimates for the activation step of the hemicellulose and
lignin components are derived from [64]. The cellulose
parameters reported in [64] are also assigned for the other
 ARTICLE IN PRESS
58 C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
Table 2
Multi-component mechanism and kinetic constants for wood pyrolysis based on the contribution of the three main components [118]
TAR
k2
k1
C A
k3
νC CHAR+(1- νC)GAS
C Kinetic constants: A (s1), E (kJ/mol)
Cellulose
19
k1 2.80  10 exp(242.4/RT)
k2 3.28  1014 exp(196.5/RT)
k3 1.30  1010 exp(150.5/RT)
nc 0.35
steps of the hemicellulose mechanism whereas those for the
lignin component are derived from [65] disregarding the
power-law dependence for the solid mass fraction. The
final parameter values are estimated so as to get the best fit
with the char yields obtained in [65,119] for beech wood
(TGA tests executed with heating rates of 5–80 K/min) and
lignin (isothermal tests for temperatures in the range
673–1073 K for small-sized particles) and in [21] for
small-sized maple wood particles (isothermal tests in a
fluidized-bed reactor with temperatures in the range
673–1073 K). Extractive and ash contents are incorporated
in the hemicellulose component. The resulting set of kinetic
parameters is reported in Table 2. Comparison with other
experiments is made a posteriori without any readjustment
of the parameters. Good qualitative agreement is attained
with the expected behavior of the three components for the
range of pyrolysis temperatures and both location and
magnitude of the peak rates. The predicted char yields
decrease as the temperature is increased for all the
components: the largest values are obtained for lignin,
the minimum for cellulose and hemicellulose yields are
bounded by the former two. A slight delay in the beginning
of the devolatilization process occurs but it is related to a
region of small weight loss. Although not extensively
tested, this remains one of the few attempts to produce a
general mechanism of biomass pyrolysis.
2.5. Secondary reactions
At high temperatures and given sufficiently long
residence times, secondary reactions of primary tar vapors
also become active [30,120,121]. These alter both the yields
and composition of the wood/biomass pyrolysis products.
They may occur in the pores of the particles, while
undergoing primary degradation, homogeneously in the
Hemicellulose Lignin
16
2.10  10 exp(186.7/RT) 9.60  108 exp(107.6/RT)
8.75  1015 exp(202.4/RT) 1.50  109 exp(143.8/RT)
2.60  1011 exp(145.7/RT) 7.70  106 exp(111.4/RT)
0.60 0.75
Fig. 9. A global mechanism for the secondary reactions of vapor-phase
tarry species as proposed by Antal [120,121].
vapor phase and heterogeneously over the char surfaces
and the extra-particle surfaces. The latter aspect is not
considered here, but extensive research on biomass
gasification confirm the catalytic effects exerted by
different materials on the cracking of tarry components
(see, for instance, the reviews [122,123]).
Secondary reactions of tar vapors are classified as
homogeneous and heterogeneous and include processes
such as cracking, partial oxidation, re-polymerization and
condensation [36]. The complex chemical composition of
tarry products would require a huge number of chemical
reactions to describe the details of the transformations.
However, despite the quantitative understanding about the
chemical composition of this class of products, the most
cited mechanism simply consists of two competing reac-
tions [120,121] as reported in Fig. 9. The reactive volatile
matter is assumed to be consumed by two competitive
reactions leading to the formation of permanent gases and
a refractory condensable material. The existence of the
second reaction is inferred from the gas yield data, which
display an asymptotic behavior (after residence times of
about 5 s) that is strongly dependent on temperature.
Higher temperatures result in dramatic increases in the
asymptotic yields of all the light permanent gases
produced. The temperature-dependent asymptotes require
the existence of the second reaction in order to explain the
disappearance of carbon atoms in the gas phase when the
gas phase temperature is reduced. However, the kinetic
 ARTICLE IN PRESS
C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
models usually neglect this competition because either the
temperatures are sufficiently high so that the amount of
refractory tar formed is small or a ‘‘devolatilization’’
process is considered (similar to devolatilization versus
pyrolysis for the mechanisms of primary reactions). In the
former case, the rate of tar cracking is generally described
by a global reaction, with a rate linearly dependent on the
mass concentration of the vapor-phase tar (rV) and the
usual Arrhenius dependence on temperature. In alterna-
tive, the cracking rate is linearly dependent only on the
reactive fraction of the primary tar (rVT). In a few cases,
the existence of tar fractions with different reactivities is
explicitly acknowledged.
The competition between the chemical paths of gas and
refractory tar formation (Fig. 9) has important implica-
tions from the point of view of process development. The
thermal stability of tars for temperatures below 773 K
[18–22,27,28,30] is a key issue in the fast pyrolysis processes
aimed at bio-oil production, as extensively discussed in
several technology reviews [39–43]. The kinetics of
secondary tar reactions is also of paramount importance
in biomass gasification. The amount of tar produced and
its composition depend on the type of gasifier and the
process conditions. In principle, producer gas with a low
tar content can be obtained if a high-temperature zone can
be created where the volatile products of pyrolysis are
forced to reside sufficiently long to undergo secondary
gasification. However, the discover of a refractory tar
product [120,121] of secondary reactions has motivated
extensive research activities on catalytic pyrolysis for the
vapor phase products which, as anticipated, have been
reviewed.
Compared with primary reactions, secondary reactions
are less investigated and evaluations of the kinetic
constants are essentially available only for the cracking
process. This information, together with the range of
experimental conditions, is summarized in Table 3. Fig. 10
provides the corresponding Arrhenius plot. It can be seen
that the estimated activation energies vary between 66 and
123 kJ/mol though, for the majority of the studies, the
range is narrower and roughly corresponds to 80–100 kJ/
mol, with the exception of cellulose tars [120]. It is plausible
that the comparable values of the cracking rates, reported
in all cases, are the result of the high simplification
represented by the global one-step reaction applied to
model the cracking process and the assumption of ideal
plug-flow behavior for the gas/vapor phase. Indeed,
experimental conditions (thermal and fluid-dynamic con-
ditions of primary and secondary degradation), sample
characteristics (biomass/wood, size, shape, ash and moist-
ure content), and mathematical treatments of the data are
highly different among authors.
Experiments consider either one reactor [124,127,
129,133] for both primary and secondary reactions, or
two reactors (or zones) in series [36,120,121,125,
128,132,135]. The variety of experimental conditions
established during primary pyrolysis (nominal heating
59
rates from a few to thousands K/min with final tempera-
tures between 723–1327 K) results in different composition
(and reactivity) of tarry species. In other words, the activity
of secondary reactions is also explicated, at different
extent, during the process of primary decomposition of
the starting material. Moreover, apart from the cases where
continuous systems are used [36,127], the composition of
the vapor stream undergoing secondary reactions is also
highly variable with time and may be affected by the
location and type (total gas or single gaseous species, liquid
yields, etc.) of measurements [135]. In addition to the
differences in the temperature and residence times of the
vapor phase, the presence of reactive species, such as steam
(also from primary decomposition), and char may have an
important impact on the tar decomposition rates. For
instance, char freshly formed is reported [136] to cause the
heterogeneous conversion of about 14% of the primary tar
product. The catalytic role exerted by charcoal on tar
conversion is also recognized in biomass gasification. To
exploit this feature, peculiar reactor design schemes have
been proposed, such as for the downdraft gasifier, modified
to include internal recycle of vapor-phase tars over the
glowing char and combustion of pyrolysis gases [137], and
two-stage fixed-bed gasifiers [138]. Also, the catalytic
action exerted by charcoal on tar conversion is confirmed
for supercritical water gasification of biomass [139].
Given that the presence of specific compounds in the
pyrolysis liquids is directly related to the decomposition of
the main constituents of wood/biomass and also affected
by the chemistry of the ligninic fraction [37], it can be
understood that differences in the reactivity are also caused
by the type of feedstock. Different woods [36,120,121,125,
127,128,133,135] are examined together with cellulose
[120,121], biomass [129,134], municipal solid waste
(MSW) [124], refuse-derived fuel (RDF) [131] and lignin
[132].
Differences in the rate expressions also produce varia-
tions in the estimated values of the kinetic parameters. As
anticipated, the global cracking rate is assumed to be
linearly dependent on the mass concentration of the vapor-
phase tar (rV). Exceptions are represented by the studies of
Refs. [36,125,128]. Boroson et al. [128] assume that it is
linearly dependent only on the reactive fraction of the
primary tar (rVT) which, for the experimental conditions
investigated and sweet gum hardwood, corresponds to
about 94%. The same kinetic equation and activation
energy reported in [128] are also used in [140] for predicting
the decomposition of beech wood tar in a thermogravi-
metric system and a muffle furnace. The reactive fraction of
tar is, however, lowered to 78% and the pre-exponential
factor is modified to become A ¼ 105.14 s1.
Tar vapors are also assumed to consist of two [124] or
three [125] fractions with different reactivities. Garcia et al.
[124] use either one or two parallel reactions with rates
linear in the total tar concentration. It is found that the
latter mechanism is associated with significantly higher
values of the activation energies (150–290 kJ/mol). More-

Table 3
Kinetic constants for the global reaction of tar cracking, where rV and rVT are the total and reactive mass concentration of vapor-phase tar, respectively (same data as in Fig. 10)
Author (Ref.)
Antal [120,121]
Diebold [126]
Liden et al. (1988) [127]
Boroson et al. [128]
Font et al. [129]
Graham et al. [130]
Cozzani et al. [131]
Garcia et al. [124]
Caballero et al. [132]
Lede [133]
Fagbemi et al. [134]
Rath and Staudinger [125]
Morf et al. [36]
Baumlin et al. [135]
Reactor; atmosphere
Tubular, two zone, batch reactor; steam
Continuous vortex reactor+tubular
reactor; steam
Continuous, bubbling fluidized-bed
reactor; nitrogen
Series-connected, tubular reactors;
helium
Batch, fluidized-bed reactor; nitrogen
Continuous ultrapyrolysis reactor;
nitrogen
Two-zone tubular reactor; helium
Batch, fluidized bed reactor; nitrogen
Pyroprobe 1000+tubular reactor
packed with quartz particles; helium
Cyclone reactor; mixture of helium/
argon and steam
Tubular reactor+packed-bed (metallic
rings) reactor; helium
TGA+tubular quartz reactor; nitrogen
Continuous fixed-bed reactor+tubular
reactor; nitrogen
Tubular reactor+perfectly stirred
reactor; argon
Primary pyrolysis: material; heating
conditions
100–300 mg of cellulose, cherry wood,
yellow pine powder; 773 K
Softwood sawdust; 898 K
0.6–1.1 mm thick poplar; 723–823 K
20 mm deep bed of sweetgum hardwood
powder; 0.2 K/s up to 723 K
3–4 g of almond shells,
0.3–0.5 mm thick;
978–1123 K
Cellulose powder; 923–1173 K
15 g of milled RDF; 773–1173 K
0.8–5 g of MSW;
973–1123 K
1 mg of Kraft lignin (Ecalyptus wood)
powder; 300 K/s up to 973 K
0.2–1 mm thick beech wood particles;
793–1327 K
20–30 g of wood, straw, coconut shells
powder; 673–1173 K
500 mg of spruce wood (0.5–1 mm thick
particles); 5 K/min up to 1323 K
10–40 mm thick spruce and fir particles;
653 K
1 g of beech wood sawdust; 820 K
60
Secondary pyrolysis: temperature; Kinetic law A (s1); E (kJ/mol)
vapor residence time
773–1023 K; 0.5–12 s r ¼ 3.57  1011 exp(204/RT)rT;
C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
(cellulose); E (cherry wood) ¼ 98.6;
E (yellow pine) ¼ 101
923–1098 K; o1 s r ¼ 1.55  105 exp(87.6/RT)rT
723–823 K; 0.5–0.7 s r ¼ 4.28  106 exp(107.5/RT)rT
773–1073 K; 0.9–2.2 s R ¼ 104.8 exp(93.3/RT)rTV;
ARTICLE IN PRESS
yNR ¼ 6%
978–1123 K r ¼ 4.5  106exp(110.1/RT)rT
923–1173 K; 0.05–0.9 s r ¼ 1.1  106 exp(100.8/RT)rTV
773–1173 K; 6–22 s r ¼ 4.1  104 exp(102.3/RT)rTV
973–1073 K; r ¼ 1.9  106 exp(99.5/RT)rT
o5 s
673–1033 K; r ¼ 4.138  103 exp(84.7/RT)rT
793–1327 K; 0.04–0.15 s r ¼ 5.9  107 exp(123.5/RT)rT
673–1173 K; 0.3–0.4 s r ¼ 4.34 exp(23.4/RT)rT
873–1073 K; 0.5–2 s rI ¼ 3.076  103 exp(66.3/
RT)rT(I); rII ¼ 1.13  103 exp(109/
RT)rT(II); yNR ¼ 22%
773–1273 K; o0.2 s r ¼ 4.0  104 exp(76.6/RT)rT
836–1303 K; 0.3–0.5 s r ¼ 1.9  103 exp(59/RT)rT

C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
8 Table 4
[133]
6 cosan and hydroxyacetaldehyde proposed in [141]
[126]
[130]
4 [36] [129] [125 ]
[135]
2 E1 (kJ/mol)
lnk
[124]
[125]
0
[134]
-2
[128]
-4
[131]
-6
0.7 0.8 0.9 1.0 1.1 1.2
-1
1000/T [K ]
Fig. 10. Arrhenius plot for the global reaction of vapor-phase tar cracking
(see Table 3 for the values of the kinetic parameters).
over, for the specific experimental conditions, around
70–80% of primary tar generates permanent gases, whereas
the remaining fraction is a refractory matter or char, a
confirmation of varying reactivities among the tar frac-
tions. From the mathematical point of view, when a multi-
step process is fitted by a single step reaction model, the
estimated activation energy is lower than the intrinsic
(actual) values of the different steps. However, although in
[125] primary tar is assumed to consist of two reactive and
one unreactive fraction, kinetic evaluation for the two
parallel reactions still produces low values of the activation
energies (Table 3). A competition between the reactions
leading to the formation of permanent gases and a
refractory tar is explicitly postulated in [120,121] where
an evaluation is also provided of the kinetic parameters for
the polymerization process.
Little work has been made on the kinetics of the
reactions undergone by primary products of wood/biomass
pyrolysis. Levoglucosan has often been considered
[79–81,141] as a model compound for tar. The results of
a comprehensive study on the influences of the gas flow at
various pressures on the yields of char generated from
cellulose are summarized [80] by a conceptual mechanism,
which includes both primary and secondary decomposi-
tion. Low-temperature paths are evidenced (formation of
anhydrocellulose and char), which are not of great
importance because associated with slow heating rates,
that are uneconomical for practical applications [38]. The
most important results concern the pathway associated
with the formation of levoglucosan, favored by fast
heating, and its evolution. At high flow rates and pressures
below 1 MPa, an endothermic zone is observed and
associated with levoglucosan evaporation. However, at
low flow rate, the endothermic zone is replaced by a
strong exothermic zone, attributed to decomposition
reactions with formation of gas and carbonized levogluco-
san. The decomposition of this compound occurs via two
ARTICLE IN PRESS
61
Mechanism and kinetic constants for 5-hydroxymethylfurfural, levoglu-
k1 k2
Primary ! Secondary ! Tertiary
E2 (kJ/mol) A1 (s1) A2 (s1)
[127]
5-Hydroxymethyl 76 117 3.3  104 1.7  107
furfural
Levoglucosan 185 228 3.5  1010 7.0  1012
Hydroxyacetaldehyde 218 — 1.2  1012 —
[120]
[132]
competing reactions affected by the heating rate (high
values of these favor gas formation). Kinetic constants for
1.3 1.4
the different reaction paths are not available, so this
mechanism has never been incorporated in transport
models.
Information is also available [141] on the global kinetics
for the formation of primary, secondary and tertiary
products from the decomposition 5-hydroxymethylfurfural
(5-HMF), levoglucosan and hydroxyacetaldehyde. Mea-
surements are carried out by means of a tubular gas phase
pyrolysis reactor coupled to a molecular-beam mass
spectrometer (MBMS). Multi-variate data analysis is used
for the estimation of kinetic constants for the reaction
mechanism formulated by analysis of the temporal profiles
of the pyrolysis products. For 5-HMF and levoglucosan,
two sequential reactions are proposed (Table 4) for
describing primary, secondary and tertiary products
(primary components are the evaporated reactants and
their fragment ions). Products from hydroxyacetaldehyde
(Table 4) only require a one step reaction.
Recent investigations [142–145] on the low-temperature
devolatilization (evaporation and cracking) of pyrolysis
liquids produced from different fuels and variable heating
conditions confirm the importance of polymerization
versus cracking reactions. For fast pyrolysis liquids and a
devolatilization process carried out under the conditions of
thermal analysis, secondary char retains about the half of
the initial carbon content of the liquid. Moreover, high
yields are obtained especially for liquids produced from
cellulose, indicating the important role played by sugars
and not only by the products of lignin decomposition.
However, while the global devolatilization kinetics is
provided [144,145], further experimentation is still need
for an evaluation of the secondary char formation rate.
2.6. Outline of multi-step mechanisms of cellulose pyrolysis
Given its large share in wood and biomass composition,
cellulose pyrolysis is the subject of a significant number of
studies. Reviews [53–56] are also proposed. The most
recent modifications are discussed here of the mechanism
proposed by Bradbury et al. [91] extended to include the
reaction of tar cracking (Fig. 11), which is often coupled
with transport equations. The first step, not detected by
thermogravimetric systems and associated with the forma-
 ARTICLE IN PRESS
62 C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
tion of a molten-phase intermediate (active cellulose), is the
subject of research studies [146]. Recent experiments [147]
carried out for very short residence times (35–75 ms) show
that it is possible to selectively depolymerize pure cellulose
powder, which passes through a molten phase, to give
significant yields of anhydro-oligosaccarides in the range
C2–C7. The active cellulose decomposes via two competi-
tive reactions associated with weight loss. The first is a
depolymerization process, favored at high temperatures
(high activation energy, Bradbury et al. [91]), and leading
to the formation of volatile species (following the studies
carried out by Shafizadeh et al. [148] and Shafizadeh [149],
mainly levoglucosan), which may also undergo secondary
reactions. The second pathway, favored at low tempera-
tures, foresees the formation of char, carbon dioxide and
steam.
Extensive analyses on the products of cellulose pyrolysis
and their dependence on temperature [150–155] support the
speculation that hydroxyacetaldehyde is a product of
primary decomposition, specifically through a process of
ring scission which becomes progressively more important
at high temperatures. Furthermore, it is noted that when
large amounts of hydroxyacetaldehyde are formed, the
formation of char (favored at low temperatures and/or by
the presence of ionic substances) is reduced. As a result of
these studies, Piskorz et al. [151] propose a modified
version (Fig. 12) of the mechanism by Bradbury et al. [91].
The initial stage takes into account the competitive
formation of char (with carbon dioxide and steam), which
is again favored by low temperatures, and a rapid
Fig. 11. The mechanism of cellulose pyrolysis proposed by Bradbury et al.
[91].
Fig. 12. The mechanism of cellulose pyrolysis proposed by Piskorz et al. [151].
reduction in the degree of polymerization associated with
the formation of active cellulose. Successively, a further
competition is established between two pathways. The first
is ring fragmentation (decarbonylation, dehydration) with
the formation of hydroxyacetaldehyde (and other products
including formic acid, acetic acid, glyoxal, methylglyoxal,
etc.), which is favored by high temperatures and catalyzed
by metallic compounds. The low-temperature process,
favored by the absence of impurities in the substrate, is
depolymerization by transglycosylation with the formation
of levoglucosan, cellobiosan (and other sugars, such as
glucose, fructose) in high yields. Possible decomposition of
cellobiosan is indicated as the major route for formalde-
hyde production.
More recent studies [156–158] largely confirm the
findings summarized by the conceptual mechanism by
Piskorz et al. [151] and contribute in the determination of
the kinetic constants for the formation of some com-
pounds. Baniasz et al. [156,157] measure the release curves
of formaldehyde, hydroxyacetaldehyde, carbon monoxide
and carbon dioxide during the rapid pyrolysis of cellulose
in the temperature range 673–1073 K. The yields of
formaldehyde, hydroxyacetaldehyde and carbon monoxide
are observed to increase as the reaction conditions are
made more severe, whereas the yields of carbon dioxide
decrease. Independent mechanisms are proposed for the
interpretation of the different dynamics, but the estimation
of the kinetic constants points out that inter-relations exist
between the examined products. The proposed mechanism
is reported in Fig. 13 together with the kinetic constants.
The pathway leading to intermediates is the limiting step
for the formation of formaldehyde and carbon monoxide,
which are indicated as products of secondary reactions.
Levoglucosan is considered the major contributor (with
carbon dioxide) among the competing species for the
formation of hydroxyacetaldehyde. The difference, with
respect to the mechanism proposed by Piskorz et al. [151],
 ARTICLE IN PRESS
C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
Fig. 13. The mechanism of cellulose pyrolysis proposed by Banyasz et al. [156,157] (activation energies are expressed as cal/mol).
is that the formation of hydroxyacetaldehyde occurs
through the formation of reaction intermediates.
2.7. Distributed activation energy (DAE) models
The chemical complexity of both the biomass and the
related pyrolysis products motivate the introduction of
kinetic models based on kinetic laws different from those
presented above. A few cases, not considered in [58] and
specifically formulated for biomass fuels, are examined
here [128,159–162]. A DAE model is always proposed
starting from treatments already used for coal. This
approach avoids the low values of the activation energies
which result when a single-step reaction is applied to fit a
temperature dependence that arises from the occurrence of
different reactions in different temperature intervals [128].
Chen et al. [159] combine a functional group (FG) model
for gas evolution and a statistical depolymerization,
vaporization and crosslinking (DVC) model for tar and
char formation. The evolution of each FG is described by a
first-order Arrhenius reaction with a DAE of width s.
Measurements are made using thermogravimetric analysis
coupled with Fourier transform infrared spectroscopy
(TG-FTIR) for cellulose, wood and some biomasses.
Compared with coal, the number of FGs is lower and,
apart from methane, each gaseous species (tar, CO, CO2,
H2O) evolves in the form of a single peak. The estimated
values of the average activation energies are of the order of
167–250 kJ/mol (in the case of cellulose up to 318 kJ/mol).
The agreement is good between measurements and predic-
tions for moderate heating rates, whereas it becomes poor
when the screen heater measurements by Nunn et al. [94]
are considered. The same modeling approach and compar-
able values of the activation energies are reported in [160]
for wood and Miscanthus pyrolysis, but the analysis is
extended to 15 species, including problematic compounds
such as HCN and HNCO (the release rate of nitrogen
compounds, in biomass combustor models, is usually
assumed to be directly proportional to the rate of solid
devolatilization, although thermogravimetric measure-
ments indicate a temporal lag between the two processes
[48]), and makes use of one to three FGs for each species.
Difficulties are again found for the correct predictions of
63
the gaseous species release curves for different heating
rates, probably in consequence of a lack of competition
between tar and gas formation in the proposed model
(comparable values of the kinetic parameters). Rostami et
al. [161] modify the DAE model to facilitate its coupling
with mathematical descriptions of transport phenomena.
Although special care [160] may be taken in reducing the
activity of secondary reactions, the results of the kinetic
analyses discussed above combine the activity of both
primary and secondary reactions in the estimated para-
meters. Specific for the secondary reactions is the DAE
model proposed by Boroson et al. [128], to take into
account the complex chemistry of tarry products and to
extend the range of applicability of the proposed kinetics.
This treatment assumes that each species is the result of a
large number of independent parallel first-order reactions
with invariant pre-exponential factor and activation
energies described by a continuous distribution function.
The estimation procedure assumes a constant pre-expo-
nential factor (1013 s1) and produces an activation energy
of 234 kJ/mol (standard deviation 21 kJ/mol and unreactive
tar fraction 4.77%), which is about 2.5 higher than that of
the single reaction previously considered. A DAE model is
also used in [162] to evaluate the kinetics of tar cracking,
based on measurements carried out with a fluidized-bed
reactor with variable freeboard height (approximated by a
plug-flow reactor) for cellulose, MSW and birch wood
pyrolysis (particles of 0.08–0.15 mm, temperatures in the
range 673–973 K and vapor residence times of 0.25–3 s).
However, the average activation energies (81 (cellulose), 73
(birch wood) and 89 (MSW) kJ/mol) are much lower that
than those reported by Boroson et al. [128].
2.8. Conclusions and further developments
One-component or multi-component mechanisms of
primary pyrolysis have been proposed based on the
analysis of experimental data on wood/biomass pyrolysis,
obtained for isothermal conditions or fast heating rates.
One-component mechanisms generally consist of three
parallel reactions, as proposed by Shafizadeh and Chin
[88], for the formation of the three classes of pyrolysis
products: char, gas and tars (or liquids). The activation
 ARTICLE IN PRESS
64 C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
energies of the global pyrolysis rate lie within two separate
ranges: 60–90 and 124–174 kJ/mol, respectively. It appears
that the former range of low values results from either
severe heat and mass transfer limitations in the experi-
ments, owing to high temperatures/heating rates, or
simplifications in the reaction mechanism, that is, the use
of a single global reaction for the description of the entire
curves of weight loss. The second set of high activation
energies is produced from measurements carried out under
moderate thermal conditions and the description of the
central part of the weight loss curves only, where the
contribution of the cellulosic component is predominant.
In this case a fast increase of the decomposition rate with
temperature, as observed from the measurements, is
predicted and therefore this set of data appears to be more
appropriate for inclusion in transport models for the
simulation of particle and/or reactor dynamics.
The kinetic parameters for the formation rates of the
three products classes from wood/biomass pyrolysis (one-
component mechanisms) have also been estimated. In some
cases even the qualitative trends, on dependence of
temperature, are not predicted and the final char yields
remain high, presumably again as a consequence of
transport phenomena control or too low reaction tempera-
tures. Only in two cases [97,99], a strong dependence of the
yields of products on temperature is predicted and thus
these kinetic parameters appear to be suitable, in principle,
also for modeling fast pyrolysis processes. Another critical
point of high-temperature experiments is that the yields of
products, needed in combination with weight loss measure-
ments for parameter estimation, may result from the
activity of both primary and secondary degradation.
The advantage of one-component pyrolysis mechanisms
is that, when coupled with transport equations, both the
yields of products and the decomposition rate (conversion
time) can be predicted. However, the assumption of one-
component behavior for composite fuels, such as wood and
biomass, unavoidably produces inaccuracies in the details
of the decomposition rates (and conversion time). The few
multi-component mechanisms of biomass/wood pyrolysis,
based on the description of different zones in the
isothermal weight loss curves (for instance, [117]) or on
the combination of multi-step mechanisms for the decom-
position of the pseudo-components hemicellulose, cellulose
and lignin (treatment proposed in [118]), have been
formulated with the scope of improving these aspects.
However, in the first approach, the product formation rates
cannot be predicted for the different stages given that
product yields can be measured only on an integral basis.
In the second case, although the combination of multi-step
kinetics for components is capable of predicting both
conversion times and yields of products, the general
validity of this approach is not supported by reliable and
extensive experimentation and, on the other hand, the
difficulties and inaccuracies associated with the use of
component degradation rates are well known to the
researches of this field.
Multi-component mechanisms, for the large majority,
simply describe the devolatilization process (the global
devolatilization rate on dependence of time). That is, the
final char yields should be known or assigned a priori and
product distribution cannot be predicted. Usually, three
parallel, first-order reactions in the amount of volatiles
released from the pseudo-components hemicellulose, cellu-
lose and lignin are considered. The analysis of single
dynamic thermogravimetric curves assumes that hemicel-
lulose and cellulose are associated with the shoulder and
the peak of the rate curves, respectively, whereas lignin
decomposes slowly over a very broad range of tempera-
tures. The activation energies vary between 80 and 116 kJ/
mol for hemicellulose, 195–286 kJ/mol for cellulose, and
18–65 kJ/mol for lignin. Analyses based on the simulta-
neous evaluation of thermogravimetric curves, obtained for
several heating rates, needed to avoid compensation effects
in parameter estimation, confirm only the kinetics for the
cellulosic components. Although the comparison between
different results is difficult owing to variations in the
experimental conditions, mathematical treatment of
the data, nature of the fuel and possible flaws in the
measurements, it appears that the heating rate effects,
when assuming first-order reactions, result in higher
activation energies for the devolatilization of the pseudo-
components hemicellulose (147 kJ/mol) and lignin (181 kJ/
mol) [109]. Furthermore, the activity of the lignin
devolatilization reaction is mainly explicated along the
high-temperature (tail) region of the weight loss curves.
Devolatilization mechanisms are also available where
additional reactions are introduced, to describe volatile
formation from minor components, such as extractives, or
to take into account different steps in the volatile release
from the chief biomass components, or power-law depen-
dence on the mass fractions are assumed. It can be
understood that the accuracy in the predictions of the
weight loss characteristics is improved as the number of
model parameters is increased. However, simplicity is
always desired for the global reaction mechanisms espe-
cially in the view of inclusion in transport models.
Secondary degradation of tar products has been
observed [120,121] to take place according to two
competitive reactions for the formation of permanent gases
(cracking) and refractory condensable materials which,
depending on pressure, temperature and flow rate condi-
tions, may also lead, in addition to further gas, to
(secondary) char formation. The large majority of kinetic
studies disregards this competition and simply assumes a
global cracking rate, proposing a convergence toward
activation energies roughly comprised between 80 and
100 kJ/mol. In a few cases, the recognition of different tar
fractions with variable reactivity and the use of two or
three reactions to describe the cracking process give rise to
higher activation energies. Levoglucosan has often been
used as a model compound (more recently also 5-HMF and
hydroxyacetaldehyde) of tar to investigate secondary
reaction chemistry. However, the understanding of the
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reaction paths of refractory tar and secondary char
formation is still only qualitative.
The chemical characterization of the gas and vapor
phase products generated from pyrolysis of cellulose has
also been used to formulate conceptual mechanisms for the
formation of single products (levoglucosan, hydroxyace-
taldehyde, hydroxy-2-propanone), starting from the pro-
posal by Bradbury et al. [91]. The main findings,
summarized by Piskorz et al. [151], are supported by more
recent experiments and preliminary evaluations of the rate
constants [156–158]. However, no quantitative information
is available for wood or biomass, even with reference to the
main components of the pyrolysis liquid, for instance
water, which is an important parameter for the quality of
this product. Moreover, only a few attempts have also been
made to develop DAE models.
Although the performances of the mechanisms for
primary and secondary pyrolysis can be fully evaluated
after combination with the transport equations to describe
applications at a laboratory or industrial scale, it can be
concluded that, even for a kinetic control, only in a very
few cases the correct trends are predicted. The under-
standing of the pyrolysis kinetics is essentially qualitative
(for instance, in relation to the influences of some variables,
such as, ash content/composition, pressure, gaseous
environment and gas flow rate). The large scatter in the
predictions is caused by the fuel type, the mathematical
treatment of the data and possible errors in the measure-
ments. Hence, extrapolations to conditions different from
those of the experiments is highly questionable.
Following these conclusive remarks on the biomass
pyrolysis kinetics, aspects which deserve further investiga-
tion and/or consideration are related to the formulation of
both (a) lumped-reaction mechanisms and (b) detailed
reaction mechanisms taking into into account the dynamics
of single-product species, valid for widely variable thermal
conditions and biomass/wood varieties. While lumped
kinetics, referred to product classes (either char, gas and
liquid or, simply, volatiles and char), can be very useful for
the design of different reactor types capable of achieving,
for instance, fast pyrolysis or flash carbonization, detailed
kinetics are needed for selecting optimal operating condi-
tions apt to maximize the yields of specific compounds.
Further efforts in both directions are highly desirable. To
improve kinetic models, experimental data should be
produced on the quantitative aspects of pyrolysis product
yields and composition and their dependence on sample
properties and conversion conditions.
As for the lumped-reaction mechanisms, although the
degree of detail may be determined by the final application,
the validity of one-component versus multi-component
mechanisms for the quantitative prediction of both the
conversion time and decomposition rates should be
assessed. Another aspect of great importance concerns
the extension of multi-component mechanisms to predict
product distribution. As for detailed mechanisms, signifi-
cant experimental effort is needed to produce quantitative
65
data on the chief tar components and their dependence on
the reaction conditions and the wood/biomass species. This
could provide the basis for the successive formulation of
kinetics for tar component formation, for improving the
quality of fast pyrolysis oils, and destruction, for the
optimization of the gasification processes.
The influences of the heating rate on the kinetic
constants of the multi-component mechanisms or, in other
words, the verification of the absence of compensation
effects in the kinetic constants currently available are only
partially addressed. Moreover, it is often pointed out that
kinetic analysis does not use thermal conditions compar-
able with those of practical applications. This is a very
critical issue. Indeed, to produce experimental data
representative of the intrinsic kinetics of primary reactions
at high temperatures, adequate consideration should be
given to the separation between chemistry and transport
effects, on one side, and between primary and secondary
reaction processes, on the other. In reality, for correct
measurement of high-temperature data, there could be a
need to introduce innovative concepts in experiment
design. Another aspect, often overlooked despite of the
clear evidence shown by accurate investigations in this
sector, is the presence of errors in the measurements even
when carried out with commercial thermogravimetry.
Kinetic analysis of pyrolysis/devolatilization processes
has been mainly focused on wood species and, in a few
cases, on agricultural residues. Thus, the search of general
reaction schemes applicable for the different varieties of
biomass fuels has not yet been extensively pursued. Given
the wide variability among the chemistry of the different
species and the influences of sample origin, this issue is of
particular practical importance.
The application of mathematical modeling of conversion
systems also requires sub-models for the release of volatile
nitrogen species and other minor compounds, such as
chlorine, during pyrolysis. Simplified treatments, in trans-
port models of biomass combustors, usually assume that
these compounds are released together with gases and tar
vapors. Further effort is needed on these aspects as results
of experimental investigations have not yet been inter-
preted by kinetic models.
3. Transport models of biomass particle pyrolysis
In practical conversion systems, wood or biomass
conversion takes place as a result of a strong interaction
between chemistry and transport phenomena at the level of
both the single particles and the reaction environment.
When exposed in a high-temperature environment, the
particle is initially interested by transient heat conduction.
Then the process of moisture evaporation occurs, which is
highly endothermic. Depending on the initial moisture
content, capillary flow of free water through the voids,
bound water diffusion and convective and diffusive
transport of water vapor are controlling. Successively, the
already dried portion of the particle, in the neighborhood
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66 C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
of the heated surface, undergoes thermal degradation.
When all the volatile species are removed from the solid, a
char layer is formed. Therefore, the following spatial zones
appear during the process transients: an inert char layer, a
pyrolysis region, a drying region and the virgin moist solid.
Water vapor and volatile pyrolysis products, partly leave
the particle flowing across the heat-exposed surface. A
fraction may also migrate toward low-temperature regions,
where re-condensation may occur. The flow of products,
owing to larger permeabilities, mainly occurs toward the
heated surfaces and, because of the high temperature,
secondary reactions of tar degradation may occur. In
addition to heat, momentum and mass transfer, changes in
the physical structure of the reacting solid are observed
with the development of a network of cracks in the already
pyrolyzed region, surface regression, internal shrinkage
and/or swelling and, in some cases, (primary) fragmenta-
tion. The reaction environment affects the particle pyr-
olysis, essentially through the rate of external heating, and
also the final yields of products. Indeed, secondary
reactions of primary tar vapors also take place outside
the wood/biomass particle given temperature and residence
times sufficiently high.
The most important achievements in transport models of
wood/biomass pyrolysis, which couple the chemical ki-
netics with mathematical descriptions of physical processes
are reviewed in [16,17] and, with special emphasis on
material flammability characteristics, in [163]. Papers
published afterwards, which include innovative features
in relation to model development or present significant
improvements in the understanding of wood pyrolysis
processes, are reviewed here.
Transport models for single wood particles/logs assume
that the porosity is fine and uniformly distributed so that
the material is a homogeneous medium, where gas and
solid are in good thermal contact. The detailed models
couple kinetics of primary and secondary reactions for the
three classes of lumped products with the description of the
relevant physical processes. Transport models are also
available consisting of more simplified kinetics with
descriptions of transport phenomena using different
degrees of approximation. In contrast with the assumption
of volumetric decomposition rates, a further category of
simplified models uses the unreacted-core-shrinking treat-
ment, where decomposition takes place at an infinitely thin
surface with either infinite- or finite-rate kinetics. Finally,
the empirical formulae for the conversion time and the
parameters of apparent global kinetics, useful for the
design of conversion units, are briefly examined.
The numerical simulation of biomass pyrolysis, often
controlled by intra-particle heat conduction, usually does
not present specific computational problems. Standard
numerical methods, for instance finite-difference schemes
which, in addition to the properties of convergence,
consistence and accuracy, guarantee the absence of phase
and amplitude errors (causing unphysical oscillations or
instabilities), also preserve conservation of mass, momen-
tum and energy of the discretized version of the conserva-
tion equations. Critical conditions, which require a careful
selection of time and space steps, may be shown by fast
pyrolysis, where gradients of temperature, chemical species
and flow velocity become very high.
3.1. Transport models with volumetric decomposition rates
Detailed models couple mechanisms of primary and
secondary reactions for the three main product classes
(liquids, gas and char) with the conservation equations of
mass, momentum and energy. This model category
includes the work presented in [77,118,164–181]. The one-
component mechanism of primary wood degradation,
based on three parallel reactions for the formation of
primary pyrolysis products, as proposed by Shafizadeh and
Chin [88], is generally used in the transport models where
predictions of product yields are of interest. The kinetic
constants estimated by Thurner and Mann [92] are used in
[166,178,179,181], those by Chan et al. [14] in [16,170,
172,176], those by Di Blasi and Branca [99] in [180], those
by Wagenaar et al. [97] in [177]. A comparison is provided
in [166] between the kinetic constants estimated in
[14,92,95], whereas different description of chemical
kinetics are also considered in [173]. A three-component
mechanism, accounting for the competitive formation of
tar and linked gas and char, is used in [167]. Given its
important contribution in wood composition, cellulose is
considered as the starting material in several cases
[77,165,167,168,171], where the chemical kinetics are
described as in Bradbury et al. [91]. Secondary reactions
of tar cracking are generally described according to the
kinetics by Liden et al. [127], but several rate constants are
compared in [180]. Tar polymerization is modeled in
[167,178,179,181] with kinetic constants as in [182].
Associated with primary and secondary degradation,
enthalpy variation takes place. Janse et al. [177] assume
that the formations of the primary products from wood
pyrolysis are endothermic processes, whereas in
[118,167,174,180] primary char formation is an exothermic
process and tar formation/vaporization is an endothermic
process. Secondary tar cracking is always modeled as a
weakly exothermic process. In the Bradbury et al. [91]
mechanism, the formation of the active intermediate, which
is however not rate-limiting, is described as an isothermal
process [77,165,168].
Some transport models make use of simplified kinetics of
devolatilization or decomposition without secondary reac-
tions. These include the works of Refs. [85,183–193]. A
one-step pyrolysis reaction is used with assigned yields of
volatile and solid products and guessed values of the
kinetic parameters in [183,184,186,188,190] or with differ-
ent sets of kinetic constants referred to the cellulosic
component in [192]. Two parallel reactions for the
formation of volatile species and char are proposed in
[191], with parameters previously determined [194] and
representative of apparent kinetics. Bilbao et al. [85,189]
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use kinetic constants for the devolatilization process
extracted from thermogravimetric analysis [195,196]. These
foresee a low- and a high-temperature step, with a
demarcation temperature of 563 K. The first endothermic
step, associated mainly with cellulose devolatilization,
presents a kinetic constant independent of temperature
but affected by the heating rate. The second exothermic
step is related to lignin decomposition and presents the
usual Arrhenius dependence on temperature. Saastamoi-
nen and Richard [187] use a global decomposition reaction,
where the yield of char is assigned by means of an empirical
correlation to account for the temperature effects. Mod-
ifications in the kinetic law would require, as pointed out
by the authors, a congruent evaluation of the kinetic
parameters. However, the estimations provided by Nunn et
al. [94] are used. Boutin et al. [193] disregard char
formation in the mechanism by Bradbury et al. [91] of
cellulose pyrolysis, to describe pellets behavior under fast
external heat transfer rates.
3.2. Intra-particle transport phenomena
In the description of intra-particle transport phenomena,
the majority of the models [77,164–170,172–174,
176–181,184,185,187,189,190–193] uses a one-dimensional
system with the following assumptions: local thermal
equilibrium, perfect gases, negligible kinetic and potential
energy and replacement of internal energy with enthalpy,
negligible enthalpy flux due to species diffusion and body
forces. Sometimes diffusive transport of species within the
pores and accumulation of energy in the gas phase
[178,179,181,185,190] and pressure variations [185,187,189,
190] are neglected. The most advanced models take into
account the following physical processes [77,118,165–181,
183,184,188]: heat transfer by convection, conduction and
radiation, convective transport of volatile species, gas
pressure and velocity variations. The latter variables are
described by means of the Darcy law, except in [118,167],
where the conservation equations for the gas phase
momentum are written assuming that the gaseous mixture
flows through individual channels (pores) within the
particle. Convective transport of enthalpy is simplified in
[189] by means of a global term at the particle surface using
a finite-difference balance, to express the boundary
condition. The assumption of one-dimensional system is
removed in a few cases [85,171,175,183,184,186,188,191].
These are simplified models with the exception of the model
presented in [171] which couples the kinetics of primary
and secondary reactions with the description of the chief
heat, mass and momentum transfer processes. Thermal
conductivity and permeability along the two directions are
assigned so as to reproduce those parallel and perpendi-
cular to wood fibers, respectively. The same features in the
description of physical processes are presented by the
models developed in [183,184,188]. Bilbao et al. [85]
consider a two-dimensional unsteady equation for enthalpy
convection and conduction, formulated for constant-
67
volume (spherical) particle at a constant pressure. In other
cases, a simple unsteady two-dimensional heat conduction
equation is introduced [186,191]. To take into account the
effects of wood anisotropy on heat transfer, a simplified
description of convective transport along the wood fibers is
also proposed in [175] in conjunction with a comprehensive
description of the processes for the perpendicular direction.
Volume variation is modeled in relation to the shrinkage
of the particle [166,172,173,175,178–181,191]. A general
model is proposed in [166] and used in [172,173,175,180].
Equations describing the time evolution for the volume
occupied by the solid and the gas are written. It is assumed
that the volume occupied by the solid decreases linearly
with the wood mass and increases with the char mass, by a
chosen shrinkage factor, a, as devolatilization takes place.
Hence, the volume occupied by the gas is made by two
contributions, the first due to the initial volume occupied
by volatile species and the second by the fraction, b, of
volume left by the solid as a consequence of the
devolatilization process. In order to account for possible
structural changes during devolatilization, the initial
volume of volatiles may also vary linearly with the
composition of the degrading medium, from an initial
value, determined by the initial solid porosity, to a final
value taken as a fraction, g, of the initial one. The
parameters a, b, g, which vary from 0 (total disintegration
of the particle) to 1 (no shrinkage), should be assigned.
In [178,181], shrinkage is defined as the ratio between the
current and the original size of the computational cell of
the one-dimensional integration domain. It is assumed to
vary linearly with the composition of the solid and the final
size of the sample should be assigned. In the two-
dimensional cylindrical domain modeled in [191], particle
shrinkage is made to occur simply by varying the size of the
elementary control volumes of the discretized integration
domain in proportion to the averaged conversion, without
modifications in the formulation of the conservation
equations. Three models are proposed corresponding to
uniform shrinkage, shrinking shell and shrinking cylinder,
which produce the shrinkage factors along the radial and
axial directions. The models differ in the way they average
the conversion. The final shrinkage is always calculated by
means of an empirical formula obtained considering data
for cylindrical particles (60–650 mg) exposed to furnace
temperatures of 586–673 K. Bharadwaj et al. [192] examine
the effects of particle shrinkage according to two limit
approximations corresponding to constant volume (no
shrinkage) and constant density (shrinkage proportional to
the mass of volatile products). The model equations do not
include any term related to volume variations and thus it is
likely that variations in the grid size are used to describe
this process.
Volume variation should also be accounted for in the
case of ablative pyrolysis. Di Blasi [168] describes char
ablation and the chief transport phenomena through the
porous solid and the molten layer (adjacent to the hot
plate) whose properties and size vary during the thermal
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68 C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
degradation. The early stages of cellulose pellet pyrolysis
subjected to image furnace heating (high, controlled heat
flux intensities delivered for assigned period of time) are
modeled in [193] by describing heat conduction through the
solid and the liquid phase and neglecting char formation.
Models of high-temperature evaporation of moisture in
wood are available. In some cases, a detailed description of
these processes is made [197], also coupled [16,170,172,
173,175] with the description of the main processes of wood
pyrolysis. The mathematical formulation is based on the
conservation equations for enthalpy, mass and momentum
for the solid, the liquid and the gas phase. Phenomena of
moisture transport include water vapor convection and
diffusion and capillary water convection in the pores of the
particle, and bound water diffusion in the solid wood.
Momentum transfer, for the liquid and the gas phase, is
described according to the multi-phase Darcy law. Local
thermodynamic equilibrium is assumed, with a sorption
isotherm that couples the moisture contents in the solid
and the gas phase.
In simplified models of moisture evaporation, the
transport phenomena of liquid-phase water and vapor
diffusion are assumed to be negligible [85,179,183–187,
189]. In [183,184] the moisture evaporation rate is derived
from the saturation vapor pressure, whereas Bilbao et al.
[189] adopt the treatment originally proposed in [198]. The
drying rate is controlled by heat supply and takes place at
the normal boiling point of water or, for low moisture
contents, at a temperature as empirically determined. In
this way, the vapor pressure depression is treated as a rise
in the moisture boiling point, defined as the temperature at
which moisture is in equilibrium with water vapor at
atmospheric pressure.
An Arrhenius law temperature dependence of the
moisture evaporation rate is proposed in several cases
[179,186,199]. In [179], moisture evaporation begins only
for temperature above 368K and the corresponding rate is
approximated by a first-order Arrhenius law. The activa-
tion energy is the same as proposed in [14] whereas the
corresponding pre-exponential factor is increased by a
factor of 104 to provide a plateau between 373 and 393 K in
the case of thick wood. Re-condensation of water vapor is
modeled assuming supersaturated state conditions with a
condensation rate proportional, through an empirical
parameter, to the flow rate. In [199], the pre-exponential
factor of Ref. [14] is again modified but re-condensation is
not taken into account. This approach allows for a finite
thickness of the evaporating region and also eliminates the
complications in the numerical solution [197], due to the
presence of the unknown moisture evaporation rate with
an empirical expression for the vapor pressure, instead of
an evolution equation or a simple production term. The
main qualitative features of the process are also retained,
that is, the temperatures rises continuously into and out of
a drying plateau [179].
Moisture evaporation takes place at an infinitely thin
front at constant temperature in the transport models of
wood pyrolysis proposed in [85,187,192]. The process is
controlled by heat transfer, that is, the heat transferred at
the front is entirely used for moisture evaporation. The
evaporation temperature is assumed to coincide with the
normal boiling point of water or with a close value. In
particular, in [192], when locally (at a certain control
volume of the computation grid) attained, this temperature
is assumed to remain constant as long as the moisture
content is different from zero. The steady-state formulation
of the enthalpy conservation equation is used to evaluate
the evaporation rate. This treatment avoids the numerical
complications due to the assumption of an infinitely thin
front of moisture evaporation at constant temperature. On
the other hand, it does not introduce any special
complication in unreacted-core-shrinking models of wood
pyrolysis, as discussed in the following.
An important aspect of transport models is represented
by the description of physical properties and their
variations during the conversion process. A comprehensive
review is given by Gronli [16] of correlations and values of
the thermal conductivities, gas permeability, specific heats
and other properties of several wood species and char. In
the majority of transport models, thermal conductivity,
mass diffusivity and permeability are assumed to vary
linearly with conversion between the values for the virgin
solid and the char (for instance, [16,77,164–181]). Effective
values are used for the thermal conductivity, which also
includes a radiative contribution dependent on tempera-
ture. In a few cases, correlations explicitly incorporating a
temperature dependence are used [183,184]. Specific heats
for the virgin solid and the pyrolysis products, and
dynamic viscosity are assumed to vary with the tempera-
ture [170,178–180,183,184] or to remain constant. Model-
ing results of inert char heating [200] show that a better
agreement between predicted and measured temperature
profiles is obtained when a constant value of the thermal
diffusivity is used. A possible compensation is suggested
between the simultaneous increase in the specific heat and
the effective thermal conductivity with temperature. The
void fraction is assumed to vary with the solid density
[178,179,181], the conversion [77,164–166,168–176] or to
remain constant [192].
Primary fragmentation of wood particles is attributed
[201,202] to the pressure build-up, when the rate of
volatiles production internally is faster than their escape
rate through the pores in the charred wood. A mechanical
model for this process is available [202]. The heating rate,
the rate and heat of reactions and the thermophysical
properties are indicated as the factors responsible for the
details of structural behavior. At both low and high
temperatures, the pressure peaks before the center tem-
perature exceeds the external temperature. Then, particle
break-up suddenly occurs and the pressure drops quickly
to the ambient value. It is worth noting that fragmentation
of coal particles, fed to fluidized-bed combustors, is also
concentrated around the end of the devolatilization regime
[203]. It is plausible that, despite the slow devolatilization
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rates established for the inner core of the particles, the
outward flux rates of volatile products are even slower,
owing to the presence of a thick char layer, creating in this
way the conditions for the pressure to increase. On the other
hand, as overpressures attain a maximum at near complete
conversion, it can be postulated that for a large part of the
conversion process the particles are not highly affected by
structural failure. On the contrary, the effects of primary
fragmentation are important for the subsequent oxidation
of char as reported for both coal [203] and wood [204,205].
3.3. External heat transfer coefficients
The boundary conditions, at the particle surface, can be
used to describe the effects of external heating rates
established in different reactor configurations. However,
in several cases, the transport models are applied to
simulate conversion of particles exposed to hot gases
and/or radiative heating, where external conditions are
assigned so as to describe bench-scale systems without
reference to any specific conversion unit. More precisely,
the majority of the models [16,85,165–167,169,170,172,
173,175,176,178,179,181] examines the conventional pyr-
olysis of particles or logs exposed to thermal radiation. To
evaluate the Biot number, a radiative external heat transfer
coefficient is introduced [178,179,181] as hrad ¼ fs
(Ts+TN)(T2s +TN2), where the surface temperature TN is
a function of time. However, evaluations can be made for
steady conditions (char heating) assuming, for simplicity,
that Ts and TN are coincident. This leads to maximum heat
transfer coefficients between 80 and 230 W/m2 for tem-
peratures in the range 700–1000 K. Convective heat
transfer is comparatively much smaller and described by
coefficients of the order of 5 W/m2 or using the Ranz–Mar-
shall correlation [206]. In a few cases [85,173,183,184], the
measured temperatures are used as boundary conditions at
the solid surface.
Several applications deal with the fast pyrolysis of
cellulose or wood, that is ablative pyrolysis of cellulose
pellets subjected to a high-pressure contact against a hot
spinning disk [168] or to concentrated radiation [193], and
conversion in fluidized-bed reactors of cellulose pellets
[174] and wood particles [177,180]. The conditions typically
established in pulverized coal/biomass burners are investi-
gated in [192], where millimeter-sized biomass particles are
exposed to rapid heating and high temperatures. This last
feature introduces a significant difference with fast
pyrolysis systems.
As the external heat transfer coefficient is the most
important parameter for the design of pyrolysis reactors,
especially for fast pyrolysis processes, specific investiga-
tions are available for ablative pyrolysis [207,208], the
Pyrovac process [209], the rotating cone reactor [210], not
to mention the numerous studies for fluidized-bed reactors
(for instance, [206,211]).
For contact (ablative) pyrolysis the global external heat
transfer coefficient is found to be proportional to the
69
applied pressure [207,208], with values in the range
500–1675 W/m2 K as simulated in [168] by the transport
model for cellulose pellets pressed against a hot spinning
disk.
The Pyrovac process is based on a moving and stirred
bed reactor using an eutectic mixture of high-temperature
molten salts as heat carrier and a sophisticated agitation
device to enhance heat transfer between the feedstock and
the heating plate. During pyrolysis, the feedstock is heated
under vacuum to a temperature of about 770 K. The range
of estimated values [209] for the heat transfer coefficient is
100–200 W/m2 K (versus 5–30 W/m2 K of static bed reac-
tors). Agitation speed, properties of the bed and particle
movement are the chief parameters affecting the heat
transfer process. This model has not yet been coupled with
the description of transport phenomena and chemical
reaction of vacuum pyrolysis of biomass.
The external heat transfer coefficient for particles
flowing along the surface of a rotating cone reactor is
evaluated in [210]. For biomass particles (without sand) the
values are in the range 100–1000 W/m2 K and an improve-
ment up to 1500 W/m2 K is reported when sand is also
supplied. The rotating cone frequency (variations in the
contributions of gas-phase convection and wall heat
transfer rate) and size of the particle (variations in the
particle flow pattern over the conical surface) are the key
variables.
Fluidized-bed reactors allow for very high heat transfer
rates between the gas and the solid, as a result of the high
surface area of the particle phase. It is widely recognized
that, for large particles, convective heat transfer between
the two phases may become controlling [212] and that the
low biomass thermal conductivity introduces significant
internal heat transfer limitations even for very small
particle sizes [174,180]. Therefore, isothermal conversion
at the temperature of the surrounding environment and
chemical reaction control are not established in practical
situations. Numerous correlations are proposed for the
heat transfer coefficient between fluidizing gas and beds of
uniform particles [206] and for fixed tubes of diameter
much larger than the bed particles [206,212]. These are of
interest for thermochemical conversion processes, given
that the active particles are larger (and with different
density) than the inert bed particles. Also, correlations for
heat transfer to large mobile particles in fluidized beds are
reported especially in relation to coal conversion (reviews
are reported in [211,212]), based on the assumption that
they reside only in the emulsion phase. In reality, the bed-
to-surface heat transfer is an unsteady process and
instantaneous measurements show sharply varying values,
suggesting that the object surface is being bathed alter-
nately by gas bubbles (low values) and emulsion packets
(high values) [206]. The unsteadiness of the heating process
is enhanced for active particles as they are not fixed. Active
particles show a circulation pattern which causes heat
transfer with the emulsion phase and at a certain extent
with the bubble phase. In addition, the average contact
 ARTICLE IN PRESS
70 C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
time with the emulsion phase (and the heat transfer rate)
during ascent is different in comparison with that during
descent.
The model for the average heat transfer coefficient
developed by Agarwal [211] takes into account all the
features listed above and is used to simulate the fast pyrolysis
of cellulose and wood in a fluidized bed [174,180]. It
expresses the overall heat transfer coefficient, h, as the sum
of three components, hpc, the particle convective component
during ascent (a) and descent (d), the gas convective
component, hgc, and the bubble component hbub, averaged
according to the probabilities of the particle to reside in the
emulsion phase during one circulation or to be rising during
one circulation, p and p0 , respectively. The assumptions and
the resulting equations, based the two-phase flow theory, are
the same as those in the original paper [211]. The model
predictions [211] compare well with experimental data for the
average heat transfer coefficient, although improvements
could be probably obtained by taking into account the
variation of the bubble parameters within the bed and with a
more accurate description of the movement of the particle. In
general, the gas convective component is of importance only
for beds of large group B and group D materials [212], while
for group A and small group B powder the particle
convective contribution dominates.
In addition to the Agarwal model [211], two further
models are considered to describe cellulose or wood
pyrolysis in a fluidized-bed reactor [174,180]: the Ranz–-
Marshall correlation which is representative of the
convective heating of a single particle, and the whole bed
coefficient, corresponding to a bed of particles heated by a
hot gas stream [206]. For the wood particle characteristics
typical of fuidized-bed reactors (particle half thickness
between 0.1 and 5 mm and bed temperature of 800 K), the
following range of values for the global heat transfer
coefficient is evaluated [180]: 650–22 W/m2 K (Ranz–Mar-
shall correlation), 1.5–4.5 W/m2 K (whole-bed correlation),
1880–440 W/m2 K (the Agarwal model). Janse et al. [177]
use a global heat transfer coefficient equal to 500 W/m2 K.
Furthermore, the assumption of an infinitely fast external
heat transfer rate is also examined for comparison
purposes [177,189]. Finally, effects of the efflux of volatiles
generated as a consequence of the degradation process on
the heat transfer to the particle are taken into account
through the introduction of a correction factor.
In Bharadwaj et al. [192], the particle surface exchanges
heat with the external environment through convection and
radiation. A global mass transfer coefficient is also used for
the volatile species equations. Empirical correlations are
applied for such parameters suitable for small-sized
particles and the thermal conditions of commercial coal-
fired boilers.
3.4. Extra-particle processes
Extra-particle processes are not taken into account
except for the simplified treatments proposed for an
updraft gasifier [185], a fluidized-bed reactor [174,180]
and an entrained-flow reactor [192]. Also, Miller and
Bellan [118,167] describe extra-particle processes to simu-
late conversion in an infinite domain.
In the simplified model for the pyrolysis of a moist wood
particle in an updraft gasifier [185], the effects of the
reaction environment are taken into account by means of
the boundary conditions at the particle surface where
heating occurs essentially by convection. The external
temperature is obtained from the energy equation taking
into account the heat transported by the gas flow and the
heat exchanged between the gas and the particle surface.
The temperature of the gas at the inlet section of the
drying/pyrolysis zone of the gasifier should be assigned.
The effects of particle shrinkage are incorporated only in
the calculation of the height of the reaction zone.
Extra-particle processes for fluidized bed reactors
[174,180] are described according to the following assump-
tions: (1) all the particles experience the same thermal (and
conversion) history, (2) the organic fraction of liquids
produced undergo extra-particle cracking according to an
apparent residence time as defined by Scott and Piskorz
[18,19] and Scott et al. [20,21], or to a residence time
evaluated with reference to the expanded bed height and
the bubble velocity, (3) secondary reactions occur at the
bed temperature.
The model of Ref. [192], for conversion in an entrained
flow, considers a particle traveling through a one-dimen-
sional plug flow reactor, where the assigned temperature
and the velocity profiles are used to evaluate the external
heat and mass transfer coefficients.
For the spherical geometry considered in [118,167], a
fictitious sphere is introduced whose radius is from 5 to 10
times larger than that of the particle. These are a measure
of the distance from the sample at which the computational
boundary must be placed in order to correctly simulate
particle pyrolysis in an infinite domain. The conservation
equations are valid for the entire integration domain which
takes into account the spatial variation in the medium
properties. However, the schematization of a particle
undergoing pyrolysis in an infinite domain does not
reproduce the experimental conditions established either
at laboratory scale or in practical chemical reactors.
3.5. Unreacted-core-shrinking models
Another approach used in wood pyrolysis modeling is
based on the use of the unreacted-core shrinking approx-
imation usually associated with the assumptions of no
moisture content and one-dimensional system [213–220].
Degradation is described by a one-step reaction, where the
ratio between the yields of char and volatiles (composition
resulting from the activity of both primary and secondary
reactions) is constant. The reaction takes place at an
infinitely thin surface which propagates from the surface of
the particle toward the center. It is the moving boundary
between the completely charred and the virgin solid
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C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
(unreacted-core-shrinking approximation), where the solid
properties (density, porosity, thermal conductivity, etc.)
vary from the initial virgin wood values to the final char
values. Both infinite-rate kinetics [214–217], that is, a
constant pyrolysis temperature, and finite-rate kinetics
[213,218–220], based on the usual Arrhenius law and a
linear dependence on the solid density and the surface area,
are considered.
The thickness of the reaction zone is proportional to
l DTqc [213] (l is the thermal conductivity, DT a
characteristic temperature difference across the reaction
front and qc the heat flux reaching the reaction front). As l
and DT are determined by the nature of the fuel (l is a fuel
property and DT is of the order of 200 K, given wood
pyrolysis temperatures between 550 and 750 K [99]), high
applied external heat fluxes appear to be a condition
necessary for the validity of this treatment.
In the dynamic evolution of the process, different stages
exist, which should be properly modeled. The sample,
initially at ambient conditions, is exposed to radiative/
convective heating. Hence, a pre-heating stage occurs, with
negligible activity of the degradation reactions and an
extension of the unreacted core (and integration domain)
coincident with the sample thickness. This is followed by
the reacting stage, where the unreacted shrinking core is
surrounded by a char layer. The passage from the pre-
heating to the reacting stage is assumed to occur, for
instance [218] when the thickness of the char layer equals a
small assigned value. From here on, the integration domain
is divided into two zones, the char layer and the unreacted
core.
The special techniques needed to track infinitely thin
fronts [221] may become computationally complicated and
expensive. On the contrary, a uniform temperature profile
for the unreacted core associated with a quasi-steady char
zone [213] or the use of integral solution methods for the
heat conduction problem [214–220] are particularly attrac-
tive because they simplify the mathematical model from
partial to ordinary differential equations. In the integral
method, the temperature profile is assumed to be a known
function of the spatial coordinate, chosen so as to satisfy
the boundary conditions. It is then substituted into the
enthalpy equation which, upon integration with respect to
the space variable, reduces to an ordinary differential
equation. Different treatments, including polynomial and
exponential profiles, are reported in the literature. How-
ever, a quadratic profile is observed to describe well not
only several moving boundary problems but also experi-
mental data obtained for standard fire resistance test
conditions and wood particle conversion [218]. In this case,
a parabolic profile is used for the one-dimensional
unsteady enthalpy equation written for either the char
layer or the unreacted core.
Some of the unreacted-shrinking-core models are pro-
posed for fire safety engineering, thus there are several
specific features and limitations which do not allow their
straightforward application in the biomass thermochemical
71
conversion sector. These include: the geometry of the solid
(a slab [215], generally with infinite thickness [214,
216,217]), the completely absent [213,214] or very limited
[215] experimental verification, the lack of sensitivity
analysis on model assumptions and parameters. In
contrast, the model presented in [218,220] is specifically
developed for biomass thermochemical conversion and
thus takes into account the effects of finite sample size.
Aside from a more accurate description of pyrolysis
processes (convective, conductive and radiative heat
transfer, finite-rate kinetics), it uses realistic input data
and is experimentally validated in relation to mass loss
characteristics and conversion times.
The unreacted-shrinking-core model, originally devel-
oped for dry wood [218,220] is also modified to include the
effects of moisture evaporation [219]. This process is
described assuming that (1) evaporation takes place at an
infinitely thin, constant-temperature front, which separates
the moist from the dry region; (2) the evaporation
temperature at the drying front coincides with the normal
boiling point of water; (3) the moist core of the particle is at
ambient (initial) temperature; (4) the heat flux at the drying
front is applied exclusively for raising the surface
temperature, from the initial to the evaporation value,
and sustaining the endothermic evaporation process.
3.6. Simulation results
Detailed particle models are extensively applied to
simulate the effects of sample properties and heating
conditions on the pyrolysis characteristics. More specifi-
cally, parametric analysis is focused on the role of model
assumptions [77,85,165,175,192], physical properties, such
as particle size, initial moisture content, shrinkage, trans-
port parameters, and operating conditions [164,166–181].
Simplified models, based on either volumetric reaction
rates or a reaction located at an infinitely thin surface, are
also extensively used for numerical simulation. In the latter
case, attention is mainly focused [218,219] on mass loss
characteristics, as these are the key variables of interest
when considering the coupling of particle and reactor
models. On the other hand, it cannot be expected that this
simplification can provide quantitatively accurate tempera-
ture and concentration profiles. The main results are
discussed below for both conventional and fast pyrolysis.
The dynamics of wood particle/log conversion are
examined by all the transport models cited above. The
qualitative features for one-dimensional systems remain the
same as already discussed in a previous review [17].
Numerical simulation of two-dimensional particle dy-
namics [171,183,184] shows that the propagation of
pressure and reaction fronts from the heat-exposed surface
toward the inner core of the particle is highly affected by
the anisotropic structure of wood. These features clearly
appear from the example of process dynamics shown in
Figs. 14A–D (temperature color maps), Fig. 15A–D
(pressure color maps) and Fig. 16A–D (vector velocity
 ARTICLE IN PRESS
72 C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
Fig. 14. Color maps of temperature for a particle (half thickness equal to 5 mm) exposed to an external temperature of 900 K as simulated in [171] for
times of 31 s (A), 63 s (B), 93 s (C) and 125 s (D).
field) as simulated in [171] for the cross section of a particle
exposed to a high-temperature environment. In this case, a
comparison is also made [171] between the total heat
transferred to the virgin solid (conduction minus convec-
tion) along and across the grain. Despite the lower thermal
conductivities, owing the concomitant slower convective
transport (lower gas permeabilities), the largest contribu-
tion is that across the solid grain. The role played by
convective heat transport becomes successively less im-
portant as the particle size is increased. A comparison
between the two-dimensional and the one-dimensional
simulations shows that the multi-dimensional structure of
the reaction zone affects not only the details of sample
conversion dynamics, but also global parameters, such as
conversion time and product distribution. On the average,
the process is faster and the volatiles yields larger for the
two-dimensional configuration. Further results of the
comparison between the two-dimensional model [171]
and a one-dimensional pure heat conduction model are
presented in [222,223].
Conversion regimes are defined for particles exposed to
radiative heating, based on either limit values for the total
solid residue [77] or the Biot number [181]: the pure kinetic
regime (chemical time much longer than heat transfer
times), the thermally thin regime (internal heat transfer
rates much faster than external heat transfer rates), the
thermally thick regime (comparable values for the internal
and external rates of heat transfer) and thermal wave
regime (internal heat transfer rates much slower than
external heat transfer rates). In the presence of moisture
[181], drying and pyrolysis occur in series (thermally thin
regime), slightly overlap (thermally thick regime) or occur
simultaneously through a large part of the conversion
process (thermal wave regime). In general, the overlap
between the two processes is enhanced as successively
higher initial moisture contents are considered [181,187].
Given that the separation between char and virgin solid, on
one side, and between drying and pyrolysis, on the other, is
absent or scarce, the initial moisture content and shrinkage
essentially affect only the conversion time for the first two
regimes. The effects are comparatively much higher for the
thermal wave regime, where the impact on the product
yields is also important.
These results are also confirmed by the simulations
obtained with an unreacted-shrinking-core model [219], as
shown by Fig. 17A, where the thickness of the dry wood
layer is plotted as a function of time for several particle
sizes and two initial moisture contents. In all cases, it
initially increases to attain a maximum, as consequence of
the faster propagation speed of the evaporation front with
respect to the decomposition front. Then, as moisture
evaporation terminates and the decomposition front moves
 ARTICLE IN PRESS
C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
Fig. 15. Color maps of gas pressure (atm) for a particle pyrolysis as simulated in [171] for the same conditions and times of Fig. 14.
toward the particle center, it rapidly goes to zero. The dry
wood layer also becomes successively thinner as the particle
size or the initial moisture content are increased, that is,
moisture evaporation becomes more strongly coupled with
wood decomposition. For the strongest coupling (initial
moisture contents of 50% and particle radius of 100 mm),
the dry wood layer only varies between about 5 and 20% of
the initial particle radius (R0). This finding supports the
assumption of a single infinitely thin front where both
moisture evaporation and wood decomposition take place.
This simplification is clearly not applicable for thin
particles (for instance, the case of R0 ¼ 20 mm), where
the maximum thickness of the dry wood layer may attain
values of about 50% of the initial particle radius. For thick
particles (R0 ¼ 100 mm), the assumption of a single
evaporation/decomposition front becomes progressively
less accurate as the heating conditions are made less severe,
as shown in Fig. 17B (the dry wood layer as a function of
time for several heat fluxes and two moisture levels).
Model results can also be used to construct maps
[77,181], where the main features (regime) of the pyrolysis
process can be read, for instance, on dependence of sample
size and final temperature. However, it should be noted
that they are valid only for the specific material properties,
mode of external heating and reaction kinetics used in the
numerical simulations.
73
Extensive simulations are also used to evaluate the
effects of the initial moisture contents on the conventional
pyrolysis of wood based on descriptions of the evaporation
process more accurate [16,167,176,183,184,197] than the
first-order Arrhenius law or the infinitely thin evaporation
front at constant temperature examined above. In all cases
it is found that moisture evaporation occurs at tempera-
tures near to the normal boiling point of water. Water
vapor is driven toward the cooler zones and condenses.
This is a local process which takes place over a distance of
a few millimiters in the zones with temperatures around
373 K. For the conditions of interest in thermochemical
conversion (external temperatures well above the boiling
point of water) it is found [197] that liquid phase processes
are not controlling. Moreover, the thickness of the
evaporation zone is relatively thin, gas overpressures in
the wet region are significant and gas phase convective
transport is important. These results and the consideration
that the parameters for the drying process are determined
for conditions quite different from those of interest in
practical systems [178] support the application of simplified
models of moisture evaporation during wood pyrolysis.
The role of some model assumptions is discussed for
conditions of internal heat transfer control using detailed
transport models. It is shown that, for permeability values
typical of cellulosic materials, the assumption of constant
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74 C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90

Fig. 16. Constant contour levels of the decomposition rate (kg/m3s) from 1 and then with step 1 and vector velocity field for a particle pyrolysis as
simulated in [171] for the same conditions and times of Fig. 14. Maximum velocity (m/s): 0.126 (A), 0.095 (B), 0.08 (C) and 0.09 (D).

pressure does not affect significantly process predictions
[165]. This finding is also confirmed by the negligible
sensitivity of model outputs to variations in the biomass
and char permeabilities [169,176]. The assumption of
constant properties does not modify the qualitative trends
of the conversion process but quantitative variations may
be high, especially for density and thermal conductivity
[165,169]. The important role played by the last parameter
is also confirmed by the analysis reported in [16,176] where
different correlations are compared. The quasi-steady
assumption is not applicable [165] for the gas-phase species
owing to secondary reaction activity, whereas it can be
made for the energy conservation equation.
Analyses carried out by different authors indicate that an
important role on the conversion time is played by
convective transport [85,174,177,180,189], although struc-
tural failure and cracks may reduce the cooling effects as a
result of a lack of local thermal equilibrium between the
solid and the vapor phase. The role played by different
model assumptions is also examined for the unreacted-
core-shrinking models. The model presented in [218]
provides a careful analysis about the influences on the
predicted process characteristics of three assumptions often
made in this class of simplified models of wood pyrolysis:
(1) steady formulation of the enthalpy equation for the
char layer, (2) no convective heat transport across the char
layer, (3) uniform temperature of the unreacted core. The
removal of assumption (1) does not result in any significant
variation in the output variables but the computational
time may increase up to factors of three. The computa-
tional time is practically unaffected by the assumption (2)
when the quasi-steady formulation of the equations is
adopted, though the process is made faster up to maximum
factors of about 20–40%. The assumption (3), while
weakly affecting the computational time and the qualita-
tive trends of the solution, introduces highly quantitative
differences which hinder its application for the prediction
of real conversion systems. A comparison is also made
between finite- and infinite-rate kinetics of the pyrolysis
reaction [220]. Both models predict particle dynamics
qualitatively similar. Extensive simulations, carried out
by varying the parameters of the kinetic models, the
external heating conditions and the particle size, indicate
that the unknown parameter Tp (pyrolysis temperature),
though comprised in the range of experimental values,
should not be chosen coincident with the pyrolysis
temperatures predicted by the finite-rate model. However,
a range of Tp values can be determined which produces
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C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90 75

char yields, are computed for the solid density. Therefore,

0.5 for primary degradation, this is the most important
R0=20mm Qf=49 kW/m2 variable. Large variations in the conversion time are also
0.4 U=25% associated with the char thermal conductivity with
40
U=50% significant changes in the yields of gas and tar, that is, on
60 the activity of secondary reactions.
80
(Rp-Ru)/R0

0.3 100
An extensive sensitivity analysis is also presented for the
unreacted-shrinking core models (kinetic constants, physi-
0.2 cal property values and model parameters) for dry wood
[218]. The most important variables are the activation
0.1 energy of the pyrolysis reaction, the thermal conductivities
of wood and char and the thermal capacity of wood. These
findings are also confirmed in the presence of moisture
0.0
[219]. As for the parameters specific to moist wood, the
0 5000 10000 15000 20000 25000 30000
strongest effects are caused by the initial moisture content
t [s]
and the enthalpy of water evaporation on all the output
variables, except for the temperature at the pyrolysis front,
0.4
R0=100mm whose variations are comparatively smaller. The high
sensitivity of the simulated process to the endothermicity
of moisture evaporation also suggests that, in some cases,
0.3
Qf=40 kW/m2 the energetics of the pyrolysis reactions may become
important. In reality, they have not been described
(Rp-Ru)/R0

0.2
49
69
0.1
U=25%
80
U=50%
0.0
0 5000 10000 15000 20000 25000 30000
t [s]
Fig. 17. A–B predictions [219] of the dry wood layer, expressed as a
fraction of the initial radius, R0, of cylindrical particles (Rp and Ru are the
positions of the pyrolysis and drying fronts, respectively), as a function of
time for different radii (A, external heat flux, Qf, equal to 49 kW/m2) and
different external heat fluxes (B, particle radius, 100 mm) for two initial
moisture contents (dry wood basis), U.
chief process characteristics, such as maximum devolatili-
zation rate and conversion time, very close to those of the
finite-rate model. In this way, acceptable agreement is also
obtained between predicted and measured integral and
differential mass loss curves of thick wood exposed to
radiative heating.
Physical properties influence both the dynamics and the
global characteristics of the thermal degradation [165,169],
especially when internal heat transfer rates are controlling.
The conversion time becomes successively longer as the
density increases and/or the thermal conductivities de-
crease, but primary products change only slightly. On the
contrary, the activity of secondary reactions is highly
affected by physical properties, through variations in the
volatile residence times, resulting from variations in the
velocity profiles. As expected, for thin samples the influence
of physical properties is completely negligible on the final
product yields, though the conversion time is still affected.
The highest sensitivities, in relation to conversion time and
accurately, most likely as a consequence of the widely
variable reaction enthalpies reported in literature and the
difficulty in separating the thermal effects of primary and
secondary decomposition. For instance, the high exother-
micity associated with char formation at high pressures
[80], has not yet been described by a transport model.
Numerical simulations of the ablative pyrolysis of
cellulose pellets [168] investigate the process on dependence
of two key parameters, the plate temperature and the
external heat transfer coefficient. The experimentally
observed behavior is well predicted, that is, rather sharp,
thin, thermal and reactive waves propagate through the
cold, unreacted solid at comparable rates. The simulation
of the detailed reaction zone shows the existence of two
reaction fronts, the first associated with the melting of
cellulose and the second with the vaporization of the
molten intermediate. Thus, from a rigorous point of view,
solid conversion in the ablation regime cannot be
assimilated to a fusion-like process, though at the high
external heat transfer rates, a tendency of the two fronts to
coincide is found. Furthermore, other important experi-
mental findings are confirmed such as those related to the
low char yields, the linear dependence of the ablation rate
on the plate temperature and the constant value of the
product between the thickness of the molten layer and the
ablation rate.
The main result of the experimental and modeling study
by Boutin et al. [193] is a confirmation of the existence of a
liquid-phase intermediate product in the fast pyrolysis of
cellulose. Given the difficulties in carrying out measure-
ments, the model is used only to evaluate the characteristic
temperatures of the process. These correspond to the
ablation and the phase change (solid-phase cellulose and
liquid-phase intermediate product) fronts and are in the
range 810–1100 K and 705–739 K, respectively. The time

76 C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
needed to achieve quasi-steady conditions, that is ablation
with a constant rate, is also predicted but quantitative
comparison with the experiments is not discussed. In fact,
given the absence of char ablation, steady conditions could
not be experimentally investigated.
Simulation results reported by Janse et al. [177] for the
experimental conditions typical of fluidized-bed reactors
indicate that intra-particle transport phenomena do not
influence product yields from fast pyrolysis of wood.
However, conversion times are significantly affected by
particle size and convective cooling due to the outflow of
volatile products. These results are also confirmed by other
studies [174,180,192]. It is also observed [192] that, when
volatiles and water vapor are assumed to leave instanta-
neously the particle, the qualitative features of the
predictions are preserved but the quantitative agreement
with the measured conversion time and shape of the weight
loss curve is lost. However, because of uncertainty about
the applicability of the global devolatilization kinetics
(representative of cellulose chemistry) to wood/biomass
and the rough estimates of the physical properties used in
this model, this is not a conclusive remark.
In [174,180], an analysis is carried out of the actual
particle heating rate and conversion temperatures during
fluidized-bed pyrolysis, as several model and process
parameters are varied. As expected, the heating rate
becomes successively slower as the particle size is increased,
and/or successively higher conversion levels are considered
because of enhanced internal heat transfer resistance and
convective cooling caused by volatile release. For condi-
tions of interest in fast pyrolysis, actual heating rates
experienced by wood particles are roughly comprised
between 450 and 5 K/s and are significantly lower than
usually assumed. The actual reaction temperatures are
between 770 and 640 K and again lower than the bed
temperature. Examples of the simulated values are reported
in Figs. 18 and 19.
775
Tc
725
Tc [K]
675
0.25
hr
625
0.5 0.5
0.25
0.8 Y=0.8
575
0.0 1.5 3.0 4.5
τ[mm]
Fig. 18. Predicted temperature, Tc, and heating rate, hr, at the wood
particle center when the total mass fraction is equal to 0.8 (solid lines), 0.5
(dashed lines) and 0.25 (dashed-dotted lines) as functions of the half-
thickness of the particle, t, for a reactor temperature of 800 K [180].
ARTICLE IN PRESS
750 180
0.25
725 150
120
700 0.5
hr [K/s]
Tc [K]
Tc 90
675 Y=0.8
0.25 60
650 hr 30
625 0
700 800 900 1000 1100
Tr [K]
Fig. 19. Predicted temperature, Tc, and heating rate, hr, at the particle
center when the total mass fraction is equal to 0.8 (solid lines), 0.5 (dashed
lines) and 0.25 (dashed-dotted lines) as functions of the reactor
temperature, Tr, for a particle half thickness of 1 mm [180].
The role played by the external heat transfer coefficient
on the predictions of the pyrolysis characteristics is
examined [180] for: (a) infinitely fast external heat transfer
rates, (b) the model by Agarwal [211], (c) the Ranz–
Marshall correlation [206] and (d) the whole bed correla-
tion [206] (actual coefficient values for cases (b)–(d) are
listed in Section 3.3). From the physical point of view, aside
from different conversion units, the actual external heat
transfer rates experienced by the wood particle may be
different, owing to the flow conditions, the mixing degree,
the particle properties (highly variable in the course of the
reaction process). For instance, segregation may cause that
particle conversion takes place above the sand bed, so that
external heating rates can be more adequately described by
the Ranz–Marshall correlation (convective heating of a
single particle), or by a whole bed coefficient (a bed of
particles heated by a hot gas stream), instead of the more
accurate Agarwal [211] model. As expected, qualitative
trends are the same in all cases, as shown in Fig. 20 for the
final char yields and the conversion time. Predictions of
case (a) are very close to those obtained for the case (b).
650 Predictions for the models (b), (c) and (d) are highly
different. Assuming sizes of 1–2 mm as representative of
520 fast pyrolysis conditions, the Agarwal model [211], which is
a realistic approximation of the actual external heat
390 transfer rate between a particle and a fluid bed under
hr [K/s]
conditions of good mixing, provides conversion times of
260 10–22 s and char yields of 11–13%. Departures from these
optimal operating conditions may result in conversion
130 times of 18–42 s and char yields of 13–16% (Ranz–Mar-
shall correlation) or even of 34–62 s and char yields of
0 15–17%. Hence, variations in the external heat transfer
6.0 rates, caused by poor solid mixing and/or segregation, are
quantitatively important and affect both conversion times
and product yields. Miller and Bellan [167] also show that
simplified descriptions of extra-particle processes introduce
approximations in the predictions of both pyrolysis rate
and yields of liquid products.

C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
30
d
c
25
YC [wt %]
20 YC b 960
d
15 a c
10
b loss curves in [166], using the experiments [224] for parallel
tc a
5 0
0.0 1.5 3.0 4.5 6.0
τ[mm]
Fig. 20. Char yields and conversion times as functions of the half-
thickness of the particle, t, as predicted [180] for a reactor temperature of
800 K and different external heat transfer models: (a) infinitely fast
external heat transfer rate; (b) model by Agarwal [211]; (c) Ranz–Marshall
correlation [206]; (d) whole-bed correlation [206].
It is also found [180] that the effects of particle shrinkage
and shape are scarcely important for small sized particles
and mainly appear as variations in the conversion times.
On the other hand, it is observed [185] that mass loss curves
of particles of different shapes undergoing pyrolysis fall
close to each other if each test is made for the same particle
volume to surface area ratio. It is worth noting that
shrinkage is very important for the dynamics of thick
particles [166].
3.7. Experimental validation
Extensive experimental validation of both detailed and
simplified models is carried out only in a few cases. For
conventional pyrolysis, the comparison between model
predictions and experimental measurements concerns the
conversion time, weight loss characteristics and the thermal
profiles as, given external temperatures sufficiently high,
the yields of products are only weakly affected by the
conversion conditions. On the contrary, the focus is on
product yields for fast pyrolysis processes.
Experiments carried out under well-controlled condi-
tions (temperature profiles and yields of products) are used
to validate the model proposed in [16,176] for thick wood
particles. Measured and predicted temperature and con-
version profiles are compared of spherical pine wood
particles (diameters between 2 and 5.6 cm) in a furnace
heated at 2 and 12 K/min in [85] and 19-mm-thick slabs
exposed to thermal radiation in [189]. Acceptable agree-
ment is obtained for both cases and it is suggested that
structural failure, possible mass transfer resistance and
activity of secondary reactions, not taken into account in
the mathematical descriptions, are among the causes of the
disagreement for thick spheres or high heating rates.
A detailed comparison between the measured and
predicted profiles of temperature, pressure and density is
given in [183,184], limited to a single experimental test (a
wood block exposed on one side to an assigned radiative
ARTICLE IN PRESS
77
1600 heat flux). Quantitative agreement is good except for the
pressure profiles, which are only qualitative, presumably as
1280 a consequence of structural changes not accounted for by
the model. In reality the one-dimensional version of the
model is used for an extensive analysis to evaluate the fire
tc [s]
resistance defined as the time when the unexposed surface
640 temperatures exceed 413 K. Comparison with experiments
is then limited to this parameter.
320 The validation considers temperature profiles and mass
and perpendicular grain heating of wood logs exposed to
high radiative heat fluxes. In particular, it is observed that
heat transfer and related properties play a controlling role
and, to get quantitative agreement, shrinkage should be
taken into account. In [178,179,181], only the average
charring rate is considered, providing a comparison
between the model predictions and the measurements
[225] made in a heat release rate calorimeter for external
heat fluxes between 15 and 55 kW/m2.
Experimental validation of the model presented in [118]
makes use of the measured char yields for beech and poplar
wood and olive husks [119]. It is interesting to observe that,
in qualitative agreement with experimental observation, the
use of a three-component mechanism allows the tempera-
ture overshoot to be predicted resulting from a large
production of char. The weight loss characteristics
measured in [62,85] are also considered. However, though
the predictions are qualitatively correct, quantitative
agreement is barely acceptable.
In some cases, when simplified models are proposed, the
main objective of the simulation results is not to improve
the understanding of the conversion process. On the
contrary, the models are considered essentially as tools
for engineering applications and the focus is on the
experimental validation, which is, however, limited to a
restrict range of experimental conditions [185–188]. More-
over, the simplification introduced in the description of
both chemical and physical processes and the use of
uncertain kinetics and approximate values of the physical
properties do not lead to a final conclusion about the
general validity of such models.
Extensive experimental validation is carried out for the
unreacted-core-shrinking models developed in [218–220] in
relation to integral and differential data of weight loss from
thick cylinders of beech wood exposed to thermal radiation
[27,28]. The models predict correctly both the qualitative
and the quantitative trends observed in the experiments.
For dry particles (Figs. 21 and 22) [218], the agreement is
good for the integral data and, for the higher heat fluxes,
also for the differential data. The fair agreement at low
heat fluxes obtained in the latter case can be probably
attributed to the wide extension of the reaction zone, which
is poorly described by the unreacted-core-shrinking
approximation. For moist particles [219] (Figs. 23 and
24), the model is again capable of predicting the main
qualitative and quantitative features of the weight loss
curves.
 ARTICLE IN PRESS
78 C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90

1.0 1.0

0.8 0.8
Qf=49 kW/m2
0.6 0.6
Y

Y
0.4 0.4

0.2 Qf=80 kW/m2 49 40 0.2 U=0%

69 11 27 35 47

0.0 0.0
0 200 400 600 800 1000 0 300 600 900 1200 1500 1800
t [s] t [s]

Fig. 21. Solid mass fractions, Y, (solid lines) as functions of time as
predicted by the unreacted-core-shrinking model [218] for several external
heat fluxes, Qf. Experimental measurements (symbols) derived from [28]
are also reported.
Fig. 23. Solid mass fractions, Y, (solid lines) as functions of time as
predicted by the unreacted-core-shrinking model [219] for several initial
moisture contents (dry wood basis), U, and an external heat flux, Qf, of
49 kW/m2. Experimental measurements (symbols) derived from [27] are
also reported.

4
2.0
Qf=80 kW/m2
Qf=49 kW/m2
3
U=0%
-dY/dt x 103 [s-1]

69 1.5
-dY/dt x 103 [s-1]

2
1.0 27
49

1 47
0.5
40
0
0 200 400 600 800 1000 0.0
0 300 600 900 1200 1500 1800
t [s]
t [s]
Fig. 22. Devolatilization rates, dY/dt, (solid lines) as functions of time
as predicted by the unreacted-core-shrinking model [218] for several Fig. 24. Devolatilization rates, dY/dt, (solid lines) as functions of time
external heat fluxes, Qf. Experimental measurements (symbols) derived as predicted by the unreacted-core-shrinking model [219] for several initial
from [28] are also reported. moisture contents (dry wood basis), U, and an external heat flux, Qf, of
49 kW/m2. Experimental measurements (symbols) derived from [27] are
also reported.

For fast pyrolysis, extensive validation is made in

relation to the product yields for both cellulose [77,174]
and wood [180]. The models of particles conversion in a
fluidized bed, incorporating the kinetics of primary (Brad-
bury et al. [91] for cellulose and by Di Blasi and Branca [99]
for wood) and secondary (essentially Liden et al. [127])
reactions, predict with acceptable accuracy the product
yields on dependence of the bed temperature and gas flow
rate, with reference to experimental data obtained for
cellulose and hardwood species [18,19,21,26]. Examples are
shown for wood in Figs. 25–28. For reactor temperatures
below 800K and apparent residence times of volatiles
typically achieved in fast pyrolysis devices (0.5 s), product
yields are determined by single-particle behavior. Hence,
given the small sizes, intra-particle degradation of tarry
species is negligible. A critical parameter is the conversion
time which should be at least equal to the residence time of
particles within the hot reactor environment. Indeed,
before all the pyrolysis products are swept from the
reactors to cyclones, where a large part of char is separated
from gas and vapors, it is highly desirable to attain the
highest conversion of wood to volatiles. It is understood
that this may be problematic at very low temperatures
(below 700 K) which, however, are not of interest in
practical applications. For reactor temperatures above
800 K and the small-sized particles of fast pyrolysis
technologies, the product yields are essentially determined
by the extra-particle activity of tar degradation reactions
even for the short residence times of fast pyrolysis units.
Estimations of chemical kinetics derived from literature
correctly predict the magnitude of the reaction rates to be
 ARTICLE IN PRESS
C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90 79

100 90
Ref. Ref.
[128] [126]
75 d
80 [127] [120]
YC, YG, YL [wt%]

60
60 YL

YL [wt%]
45
40 Ref.
YG c
30 [18] b
a
[19]
20 [21]
15
YC [26]
0 0
0 100 200 300 400 600 700 800 900 1000 1100
tr [ms] Tr [K]

Fig. 25. Gas, liquid and char yields (lines) as functions of the (extra-
particle) residence time of volatiles as predicted [180] for a particle half
thickness of 0.1 mm and a bed temperature of 973 K (kinetics of tar
cracking from [120,126–128]). Experimental data (symbols) from [21]
(maple wood, entrained-bed reactor) are also included for comparison
purposes.
Fig. 27. Liquid yields (lines), as predicted [180] for wood pyrolysis (6 mm
thick particles) in a fluidized bed reactor, as functions of the reactor
temperature, for different volatile residence times, tr, and tar cracking
kinetics: (a) tr ¼ 0.44 s and [127], (b) tr ¼ 0.154 s and [127], (c) tr ¼ 0.44 s
and [128], (d) tr ¼ 0 and [127]. Experimental data (symbols) are also
included for comparison purposes.

50 those proposed for coal pyrolysis [203,229,230]: tv ¼ Acdn,

Ref. where Ac and n are empirical parameters and d a
[18] characteristic particle size (the diameter for spherical
40
[19] shapes). The values of n are comprised in the range 1–2
[21] with variations caused by the different fuel, technique of
30 measurement and definition of devolatilization time. It is
YC, [wt%]

20
10
0 usually incorporated in the parameter Ac. In particular, a
600 700 800 900
Tr [K]
Fig. 26. Char yields, as predicted [180] for wood pyrolysis in a fluidized
bed reactor, as functions of the reactor temperature, for complete
conversion (solid line) and a particle residence time of 60 s (dotted line).
Experimental data (symbols) are also included for comparison purposes.
used for optimization and scaling purposes. However, as
discussed in [222,223], none of the mechanisms of biomass
pyrolysis currently available can predict the quality of the
liquid products. Moreover, poor predictions are also
shown of the yields of products for a laboratory-scale
fluidized bed reactor batch-fed with different biomass fuels,
which put into evidence the problematic aspects of the
kinetic mechanisms already illustrated in Section 2.2.
3.8. Empirical correlations and apparent kinetics
The most simplified formulation of wood pyrolysis
(devolatilization) models consists of empirical correlations
for the conversion time [190,204,205,226–228], similar to
[26]
known that the use of simple thermal theories [231] applied
to combustible spheres exposed in a hot gas environment,
leads to devolatilization times proportional to either d or
d2, depending on external or internal heat transfer control.
The dependence of tv on other parameters, such as bed
temperature, coal rank, oxygen concentration, etc., is
1000 1100 treatment of the devolatilization times by regression
analysis, assuming a power-law function of the operating
variables, results in an exponent for the bed temperature
varying from 1.8 to 3 for different coal varieties
[203,229,230]. Also, an Arrhenius temperature dependence
is postulated, as it fits equally well the experimental data
with activation temperatures varying in the range
1122–3396 K: tv ¼ aeb=T r d n .
The thermal history undergone by pre-dried cylindrical
beech wood particles, injected in a sand bed fluidized by
nitrogen, for conditions typical of fast pyrolysis (particle
diameter d ¼ 2–10 mm and bed temperature Tr ¼ 712–
1107 K) is reported in [228]. The analysis allows the particle
heating rates, reaction temperatures and conversion times
to be evaluated. In qualitative agreement with coal particle
analyses, the latter is well predicted by an empirical power-
law relation: tv ¼ 0.8e1525/Trd1.2s, over the entire range of
experimental conditions examined, as shown in Fig. 29.
The analysis of char particles also reveals significant
shrinkage and structural failure.
A power-law correlation between devolatilization time
and particle size is also proposed by de Diego et al.
 ARTICLE IN PRESS
80 C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90

90 extended to include the effects of particle shape, by

Ref. replacing the particle diameter with the equivalent particle
75 [18] diameter multiplied by the shape factor, and moisture
[19] evaporation: tv ¼ a(deqF)n, where deq is the diameter of a
60 [21] sphere having the same volume as the particle and F the
[26] ratio between the surface area of the equivalent sphere and
YG [wt%]

45 b c the initial surface area of the particle. The parameters a and

a n are reported to be functions of temperature (n comprised
30 between 1.5 and 1.7 for deq between 7–39 mm and F
between 0.4 and 0.75). In this way, non-spherical wood
15 d particles can be modeled as spherical particles by means of
the equivalent diameter and the shape-factor, which
0 extends the applicability of models developed for spherical
600 700 800 900 1000 1100 particles. A further correlation is also developed describing
Tr [K] a linear dependence of the particle devolatilization time on
the initial moisture content.
Fig. 28. Gas yields (lines) as functions of the reactor temperature as In some cases, highly simplified descriptions of the
predicted [180] for wood pyrolysis (6 mm thick particles) in a fluidized bed
reactor, as functions of the reactor temperature, for different volatile
transport phenomena are coupled with a one-step reaction,
residence times, tr, and tar cracking kinetics: (a) tr ¼ 0.44 s and [127], (b) with the aim of evaluating the kinetic parameters by curve
tr ¼ 0.154 s and [127], (c) tr ¼ 0.44 s and [128], (d) tr ¼ 0 and [127]. fitting of selected variables for a set of experimental
Experimental data (symbols) are also included for comparison purposes. conditions, such as in [194,205,226]. As pointed in [226],
the important role played by physical processes (intra-
particle processes, external heat transfer rate, etc.) and
Tr [K] their highly simplified description produce parameter
625 725 825 925 1025 1125 values representative of apparent kinetics, whose applic-
100 ability is limited to empirical design rules.
Mass loss curves of different amounts (1–800 mg) of
80 807 birch or pine wood particles obtained for reactor tempera-
d=8mm tures in the range 588–1029 K are presented in [194]. They
are interpreted by a simple one-step devolatilization
60 reaction assuming isothermal conditions, although the
tv [s]

authors note that the actual reaction temperatures may

40 4 be significantly different from the external (reactor)
20
Tr=1107K
0 described by A ¼ 3 s1 and E ¼ 31 kJ/mol, a clear indica-
1 3 5 7 9 11
d [mm]
Fig. 29. Devolatilization times, tv, as functions of the particle diameter
(reactor temperatures of 807 and 1107 K) and the bed temperature
(particle diameters of 4 and 8 mm) as measured (symbols) and predicted
(solid lines) by an empirical correlation for beech wood particles injected
in a hot fluidized bed [228].
[204,226,227] for higher temperatures (923–1223 K), in the
view of applications in gasification and combustion
processes. Experiments are carried out for pine wood
particles of different shapes and initial moisture contents
up to 50%. Particle characteristics, in a fluidized bed
reactor, are evaluated using continuous measurements of
CO2 and O2 concentrations, obtained after the complete
combustion of volatiles (the presence of oxygen is not
influent on the devolatilization times) and visual observa-
tion of volatile species burning. The correlations are
temperatures. The Arrhenius plot evidences two different
reaction zones separated by a temperature of 643 K. The
first (low temperature) zone corresponds to A ¼ 1.19 
1012 s1 and E ¼ 177 kJ/mol, whereas the second zone is
tion of internal/external heat transfer control.
De Diego et al. [226] propose an unsteady and one-
dimensional equation of heat conduction coupled with a
DAE model to describe the devolatilization of wood
particles in a fluidized-bed reactor (temperatures of
923–1223 K and particle of different shapes with maximum
sizes of about 15–20 mm). Moisture evaporation is
assumed to occur at an infinitely thin front at a constant
temperature. Also, the particle volume is assumed to be
proportional to the amount of volatiles released. The
external heat transfer coefficient takes into account both
convective and radiative heat transfer according to
correlations specifically developed for fluidized-bed reac-
tors. Possible numerical complications associated with the
treatment of an evaporation front are not discussed. The
parameters of the kinetic equation are obtained by curve
fitting of the release rate curves of combustible species
(A ¼ 1013 s1 and E ¼ 20076 kJ/mol and s ¼ 2573 kJ).
The authors do not exclude possible compensation effects
 ARTICLE IN PRESS
C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
and point out that the set of values determined are typical
of fluidized bed combustion.
Apparent kinetics for a global reaction are also
determined in [205] for the pyrolysis of beech wood spheres
(diameters between 5 and 20 mm) in a fluidized-bed
reactors (temperatures in the range 833–913 K). Yields of
char and gaseous species are determined and the on-line
analysis of gaseous species is used to evaluate the
devolatilization time. The model consists of a one-
dimensional and unsteady heat conduction equation with
boundary conditions accounting for convective and radia-
tive heating. An additional term describes convective
cooling assuming that volatiles have to be heated from
the average particle temperature to the bed temperature.
Physical properties are assumed to remain constant. Solid
conversion obeys a first-order law where the kinetic
constant is obtained by volume averaging local values
along the particle radius and incorporating the usual
Arrhenius law dependence on temperature (negligible
reaction energetics). The pre-exponential factor is assumed
to present a power-law dependence on the initial particle
diameter. Moreover, the particle shrinks linearly with
conversion (up to 50% of the initial volume). The model
parameters are estimated using a two-step procedure.
Experimental measurements for thin particles give the
parameters A and E, whereas results obtained for thick
particles give the exponent. The validity of the estimated
set of values (A ¼ 1.5 s1, E ¼ 20.576 kJ/mol and n ¼ 0.7)
is then checked against measurements carried out for
intermediate particle sizes. The very low activation energy
confirms that apparent kinetics are determined.
3.9. Conclusions and further developments
Comprehensive models of single-particle dynamics are
available where the description of physical processes is
coupled with primary and secondary reaction kinetics.
Heat, mass and momentum transport are taken into
account across a medium where volume and other physical
properties vary with the conversion degree and/or tem-
perature. In a few cases, multi-dimensional equations are
considered to model anisotropy effects. External heat
transfer is approximated in terms of global coefficients,
specifically determined for different reactor configurations.
Extra-particle processes are either disregarded or subjected
to high simplifications. Numerical simulations are used to
understand the role played by model assumptions, sample
properties and operating conditions on the pyrolysis
characteristics and to clarify the interactions between
physical and chemical processes. In particular, the actual
temperatures and heating rates experienced by particles are
evaluated, when exposed to conditions typical of practical
conversion systems. Among the physical properties, density
and thermal conductivity cause the highest sensitivity of
the model predictions. The effects of particle shrinkage and
shape become successively more important as the particle
size become larger and mainly appear as variations in the
81
conversion times. For fluidized-bed conditions, variations
in the external heat transfer rates, caused by poor solid
mixing and/or segregation, may become quantitatively
high and affect both conversion times and product yields.
Structural failure and primary fragmentation have not yet
been described in detail. In general, the limits of detailed
models lie in the use of questionable kinetics or arbitrary
values of physical properties and, in numerous cases, in the
scarce experimental validation. In other words, only a
better knowledge about decomposition kinetics and phy-
sical properties of the biomass fuels can improve the
predictive capabilities of transport models.
Numerical simulations of particle dynamics confirm that
only a few of the one-stage mechanisms can predict the
correct trends of the yields of char, liquid and gas on the
operating conditions. For conditions of interest in flui-
dized-bed reactors, experimental verification of the models
is focused only on product distribution on dependence of
the reaction conditions, whereas scarce attention is given to
conversion times and global decomposition rate. This may
be due to the lack of measurements on single-particle
characteristics. Systematic measurements of conversion
times of single wood and biomass particles in fluidized-
bed reactors could be useful for improving the operating
conditions of industrial plants and the validation of
transport models currently available. Conversely, for the
conditions of interest in wood log boilers, essentially the
conversion times and the global mass loss characteristics
are considered in a few cases. Hence, extensive model
validation in relation to both product yields and conver-
sion times is required.
Detailed modeling of single-particle dynamics can still
contribute to improve the understanding of pyrolysis
fundamentals, by developing additional submodels in rela-
tion to (1) absence of thermal equilibrium between the
degrading solid and the volatile products, (2) medium
anisotropy, (3) structural changes, (4) dependence of physical
properties on conversion conditions and biomass species, (5)
reaction energetics, (6) more accurate kinetics for the global
characteristics (conversion time and yields of products) of
biomass pyrolysis, (7) detailed mechanisms of primary and
secondary degradation. Furthermore, although several
treatments are available for moisture evaporation in wood,
they are scarcely used. In reality, even small moisture
contents exert a significant impact on pyrolysis. Simplified
models can be applied as for the high temperatures of interest
in thermochemical conversion of biomass, transport phe-
nomena of the liquid phase do not play a controlling role.
It should be pointed out that significant effort, in both
theoretical and experimental research activities, is still
required to formulate and validate truly comprehensive
models. Indeed, not only additional processes should be
mathematically described but new experimental systems
and extensive measurements are needed to provide the
basis for process understanding and model formulation
and to produce data to be used as inputs for numerical
simulation and comparison terms for model validation. It
 ARTICLE IN PRESS
82 C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
is likely that such an objective cannot be accomplished over
a short time. Therefore, simplified models are still
appealing and worth additional efforts for improvement.
Furthermore, though the current detailed models of
biomass particle dynamics have greatly contributed to
process understanding, due to the significant computa-
tional requirements, they are unsuitable for describing
single-particle effects in reactor modeling. Indeed, to
reduce the mathematical complexity of the problem, solid
devolatilization is usually described assuming infinitely fast
reaction rates or external heat transfer control, which
introduce severe inaccuracies in the predictions of im-
portant design parameters. Hence, simplified descriptions
of single-particle pyrolysis accounting for spatial gradients
of temperature, once incorporated in reactor models, could
produce a significant advancement with respect to the
current state of the art.
For this purpose, unreacted-core-shrinking models are
available, where the char region is separated from the virgin
wood by an infinitely thin (surface) front, where pyrolysis
takes place. It is shown that a quasi-steady char zone
combined with the use of integral solution methods for the
heat conduction problem across the unreacted core are
particularly attractive because they transform from partial to
ordinary the differential equations of the model. Such
formulations include one-step finite-rate kinetics of wood
pyrolysis, heat convection and conduction, different proper-
ties for the unreacted solid and the char, moisture evapora-
tion and the use of realistic input data. However, extensive
experimental verification is made only for the conditions
typical of conventional pyrolysis, assuming that the yields of
the three classes of pyrolysis products are assigned. Thus,
before application for fast pyrolysis, the unreacted shrinking
core models should be extended to include competitive
reaction rates for primary product formation and secondary
reactions of tar vapors. The applicability should also be
checked of other simplified models, which still retain the
assumption of volumetric reaction rates for the decomposi-
tion process. Indeed, the few examples currently available are
used only in the view of determining the apparent kinetics of
a global reaction, which are of small scientific relevance and
limited practical applicability.
Empirical correlations, which give the conversion time as a
function of the external temperature and the properties (size,
moisture content, shape) of the biomass particle, can also be
considered as simplified models. The work currently done
concerns different types of woods. Further developments
should consider the enlargement of the range of experimental
conditions investigated, the type of measurements carried out
(temperature profiles, rate of mass loss, product yields and
composition) and the influence of the biomass type.
4. Models of pyrolysis reactors
Modeling chemical reactors, applied for biomass pyr-
olysis, is the subject of only a very few papers. A rough
classification of the models currently available can be made
based on conventional or fast pyrolysis processes.
4.1. Fixed-bed reactors
The particle heating rates established in fixed-bed reactors
are usually slow, because of indirect heating. Therefore, this
configuration is suitable to carry out conventional pyrolysis of
biomass. Models are proposed in [232–236]. In [234], a
packed-bed of wood particles undergoing drying and pyrolysis
is modeled as an ensemble of finite number of particles with
specific properties, but the assumption that the bed is a
continuum porous solid is generally made. In [232], an
unsteady one-dimensional (along the radial co-ordinate)
model is presented for a cylindrical fixed-bed, batch pyrolyzer,
where convective transport is neglected. Decomposition of
coconut shells is described by a deactivation model for the
separate formation of char and volatiles. The one-dimensional
and steady model of maize pyrolysis in a bench-scale rotatory
kiln in semi-continuous operation, proposed in [233], takes
into account the difference between the temperatures of the
two phases. Kinetics are described by a five-step reaction
scheme, where the formal parameters are determined by the
analytical solution of the mass balance equations for
experiments carried out with both the rotatory kiln and a
thermogravimetric balance. The pyrolysis of sawdust in a
packed bed of annular shape is modeled in [235] with a pure
heat conduction equation (unsteady state and radial and axial
coordinates) combined with a first order global reaction and
an empirical formula for the effective thermal conductivity.
The use of empirical parameters in these models [232–236]
highly limit their general validity. Thus, they are in reality
empirical models capable of simulating only the specific
measurements upon which they are based. The assumptions
made highly simplify the solution procedure, but a realistic
description of heat and mass transfer effects is not retained for
reliable process design and development.
The unsteady, two-dimensional model of a continuous
fixed-bed reactor (a horizontal cylindrical reactor continu-
ously fed from the end by straw, while hot gas enters
through holes distributed along the lateral surface),
developed in [236], represents a significant advancement
in the field of fixed-bed pyrolyzer modeling. The model
includes the unsteady, two-dimensional conservation equa-
tions of heat and mass transfer for the solid and the gas
phase, the generalized Darcy law and a multi-component
mechanism for straw pyrolysis, previously determined
[116]. The influences of gas temperature and gas to straw
ratio are investigated. It is found that the key parameter for
high conversion of straw to volatile products and char is
the solid residence time. Predicted and measured conver-
sion efficiencies, at a pilot scale, compare well.
4.2. Fast pyrolysis reactors
Among the fast pyrolysis technologies applied for
wood/biomass conversion into liquid fuels, the bubbling
 ARTICLE IN PRESS
C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
fluidized-bed reactor is extensively applied at both labora-
tory and industrial scale. A major effort in modeling
fluidized bed reactors arises from the description of the
hydrodynamic behavior of the bubbling bed. Though, in
principle, the motion of the fluid can be described by the
Navier–Stokes equations and the motion of particle by the
Newtonian equations, the huge number of particles does
not make this approach computationally feasible. The
introduction of a continuum mathematical description of
the fluid-solid flow processes, based on spatial averaging
techniques, highly reduces the number of partial differ-
ential equations. That is, the point variables, referred to the
particle size scale, are replaced by averaged variables
representative of processes on a scale large than the particle
size but small compared to the reactor size. Usually, the
mathematical models are based on the conservation
equations of mass, momentum and energy for the solid
and the gas fluid which may foresee several components.
Conservation equations are completed by appropriate
interaction terms representing the coupling between the
two fluids. This approach provides detailed simulations of
the fluid dynamics of the fluidized bed through the time
and space distribution of process variables. Hence, it is
especially suitable for the description of the influences of
the reactor geometry (design) on the hydrodynamic
behavior. Applications in the field of biomass pyrolysis
are reported in [237–240].
In [237], a single-particle model [118] is coupled with a
detailed hydrodynamic model for the gas/particle mixture
in a fluidized bed reactor. The latter model is based on a
three-fluid description (sand, biomass, gas) where macro-
scopic transport equations are derived from the kinetic
theory of granular flows using inelastic sphere models, in
this way accounting for collisional transfer in high-density
regions. Separate transport equations are formulated for
different particle classes, allowing for the independent
acceleration of particles in each class and the interaction
between the size classes and the processes following
momentum and energy exchange between the particle
phases and the gas. The reactor model is used only for a
parametric analysis about process variables in relation to
efficiency in bio-oil production and potential for scale-up.
The platform provided by the software CFX is used at
Aston University [238–240] to model the hydro-dynamic
behavior of fluidized bed pyrolysis reactors. The bulk of
the particles in the fluidized bed is modeled using the
standard Eulerian-Eulerian two-phase model. According to
this approach the particles are not single entities but a
locally averaged second phase. With reference to biomass
pyrolysis, fuel, char and any solid phase reaction inter-
mediate, such as active cellulose, are implemented as
scalars within the solid phase. Heat transfer and particle
entrainment are also taken into account. The analysis is
focused on the validation of the bed hydrodynamics for
several geometric configurations using cold flow experi-
ments with reactor diameters up to 0.5 m. Interactions
between bed hydrodynamics and chemical reactions are
83
significant. In particular, the location of vapor release and
the flow field highly affect the vapor residence time and, in
this way, the bio-oil yield.
Miller and Bellan [241] propose a model for the vortex
pyrolysis reactor developed at NREL (Colorado), which
uses the concept of ablative (contact) pyrolysis between
particle and hot reactor walls. The mathematical descrip-
tion is based on submodels for the single-particle pyrolysis,
a turbulent reactor flow and the test particles trajectories.
The intra-particle processes are described using a model
previously developed [118] and modified to take into
account fragmentation (mechanical break-up of the char
layer formed during ablative pyrolysis and absence of a
molten phase intermediate product class). The individual
particle trajectories are modeled assuming a prolate
spheroid particle drag coefficient and contact friction with
the reactor wall. Numerical simulations indicate that
single-particle dynamics are de-coupled from the temporal
disturbances of the temperature and pressure of the
external flow. Thus, time-averaged values of the flow
properties are used for the particle boundary conditions.
The reactor flow is described by a compressible form of the
full Reynolds stress transport model for swirling axisym-
metric flow. Despite the detailed modeling and the quite
high number of simulations presented, the results are still
only qualitative because, owing to the lack of experimental
data, the model is not experimentally validated.
Engineering models, based on highly simplified descrip-
tion of the fluid dynamics, are also proposed for some fast
pyrolysis units, such as rotating cone reactor [242] and
circulating fluidized-bed reactor [243,244]. It should be
noted that, although the specific applications of engineer-
ing models for fluidized-bed reactors for biomass pyrolysis
are practically inexistent, a huge literature on such a topic
is available, starting from a classical textbook [206] and
numerous references for gasification and combustion of
coal (for instance, among the most recent publications, see
[245,246]).
The rotating cone reactor model [242] includes the
description of the particle flow behavior, the particle
conversion and the gas-phase cracking of tar vapors. The
particle flow model, based on the Newton second law of
motion takes into account bouncing flow (similar to a
series of particles-on-wall collisions and free flights of the
particle through the gas phase), sliding flow (particles slide
over the cone wall) and sticking particles (particles sticking
to the cone walls). The particle model disregards the
presence of spatial gradients and secondary reaction
activity. Primary decomposition is described by the
Shafizadeh and Chin mechanism [88] with the kinetic
constants estimated in [97] and an assigned yield of char
always corresponding to 10% of the initial wood dry mass.
The external heat transfer rate is expressed by correlations
depending on the type of particle flow. The reactor volume
and the dead volume of the surrounding oven, which serves
as a collection chamber for ash, char and unconverted
wood, are the sites for the secondary reactions. They are
 ARTICLE IN PRESS
84 C. Di Blasi / Progress in Energy and Combustion Science 34 (2008) 47–90
modeled as continuous stirred tank reactors under steady
state conditions, where the inlet volumetric flow rate is
produced from primary decomposition. Simulations, made
upon selection of the particle flow type and using small
sized particles, indicate that the gas-phase kinetics and the
residence time of volatile pyrolysis products (the latter is
determined by the reactor volume and the wood fed rate)
are the key parameters of the process.
A single-particle model, previously developed [244], is
modified to express variable boundary conditions repre-
sentative of a circulating fluidized bed and is combined
with additional equations for the particle motion and the
gas flow in the model proposed in [243]. Simple steady and
one-dimensional (along the reactor axis) mass balances use
empirical correlations for the drag coefficient, the apparent
particle density and the bed voidage. Variables of relevant
importance (profiles of conversion, solid and gas velocity,
etc.) are predicted, but experimental validation is again
lacking.
4.3. Conclusions and further developments
Contrary to single-particle processes, models of pyrolysis
reactors are only a few but both fixed-bed reactors, applied
for conventional pyrolysis, and fast pyrolysis units
(fluidized-bed and rotating cone reactors) have been
considered. The fixed-bed models are usually based on
the assumption that the bed is a continuum porous solid,
where the flow velocity is constant or, in the most advanced
formulation, obtained from the generalized Darcy law.
With the exception of [236], where a novel reactor for the
conversion of straw and herbaceous biomass is modeled,
these are highly simplified models presumably not valid
outside the narrow range of experimental conditions used
for the determination of the input and validation data.
Therefore, design and operation of fixed-bed reactors are
still, for a large part, empirical. Only the development and
validation of more advanced models can provide a reliable
basis for technology optimization and scale-up. More
accurate models should be developed for the particle flow
and gas, which are affected by the non-isotropic and
continuously changing properties of the bed. Indeed,
correlations/models are also needed for the properties of
the bed, such as porosity, density, effective thermal
conductivity, solid-gas heat transfer coefficients, etc., and
their dependence on the operating conditions and/or
conversion degree. As already observed for particle
processes, detailed experimental data should be produced
or made public for the experimental validation of models
for the different reactor categories. In particular, informa-
tion should be produced not simply on the yields of the
three classes of pyrolysis products but also on conversion
time, temperatures of solid and volatile species, composi-
tion of the gas and tar vapors and pressure, and reactor
characteristics and operating conditions.
Models for entrained- and fluidized-bed reactors have
been proposed using the conservation equations of mass,
momentum and energy for the solid and the gas fluid,
based on either proprietary or commercial CFD codes. As
this approach is especially suitable for the description of
the influences of the geometry (design) on the reactor
hydrodynamics, the validation of the bed hydrodynamics
for several geometric configurations using cold flow
experiments has been made. However, simulation results
of biomass pyrolysis produced until now are again only
qualitative. Indeed, further improvements should be made
in the mathematical formulation of the problem to couple
the detailed description of the flow field with the chemistry
and transport phenomena of the solid phase, also using
simplified models of single-particle processes. These
improvements are not likely to be achieved shortly and,
in any case, adequate experimental validation will be
required before applications for process scaling and
optimization. For this reason, the development of engi-
neering models is still of great importance. However, these
models, usually based on simplified description of the fluid
dynamics, have been given scarce consideration.
In particular, consideration should be given to the two-
phase theory of fluidization for fluidized-bed reactors. This
treatment, widely used in chemical reaction engineering,
assumes that the fluidized bed consists of a solid-free
bubble phase and a solids-laden emulsion (dense) phase.
Different treatments for the bubble (well mixed, in plug
flow or in dispersed plug flow) and the emulsion (well
mixed or with a dispersion term in the mass balance) phase
and also more complex three-phase or bubble-assemblage
models are available, where the fluid-dynamic processes are
approximated by means of empirical correlations. This
simplification permit accurate descriptions of particle
processes and their interaction with the bed, as shown by
the numerous publications dealing with coal conversion,
and can be used as an intermediate research stage between
single particle and CFD reactor models.
Acknowledgments
This review is part of the activities carried out in the
framework of the European network PyNe (Pyrolysis
Network), the partial support of which is gratefully
acknowledged. CDB also thanks all the PyNe members,
for the numerous and fruitful discussions on biomass
pyrolysis, and M.J. Antal and two other anonymous
reviewers for their constructive comments on this work.
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