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Corresponding author. Present address: USDA, ARS, Pacic Basin Agricultural Research Center, 64 Nowelo St., Hilo, HI 96720, USA. Tel.: +1 808 932 2177;
fax: +1 808 959 5470.
E-mail address: John.White2@ars.usda.gov (J.E. White).
1
Deceased.
0165-2370/$ see front matter. 2011 Published by Elsevier B.V.
doi:10.1016/j.jaap.2011.01.004
2 J.E. White et al. / Journal of Analytical and Applied Pyrolysis 91 (2011) 133
6.3. Signicance of surrounding atmosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
6.4. Catalytic effect of inorganic material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
7. Variations in kinetic data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
7.1. Systematic errors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
7.2. Temperature gradients. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
7.3. Temperature lag. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
7.4. Kinetic compensation effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
8. Sugarcane bagasse case study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
8.1. Sugarcane bagasse background and properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
8.2. Review of sugarcane bagasse pyrolysis studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
8.3. Analysis of published kinetic data for sugarcane bagasse pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
8.4. Suggestions for mitigating inconsistencies in kinetic triplet data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
8.5. Evaluation of kinetic compensation effect for sugarcane bagasse data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
9. Recommendations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
10. Conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
1. Introduction
Increased volatility in traditional fossil fuel markets has revived
interest intheproductionof alternativefuels frombiomass. Renew-
able energy derived from biomass reduces reliance on fossil fuels
and it does not add new carbon dioxide to the atmosphere [1].
Pyrolysis is a fundamental thermochemical conversionprocess that
can be used to transform biomass directly into gaseous and liquid
fuels. Pyrolysis is alsoanimportant stepincombustionandgasica-
tionprocesses. Inthis regard, athoroughunderstandingof pyrolysis
kinetics is vital to the assessment of items including the feasibility,
design, and scaling of industrial biomass conversion applications
[2,3]. An awareness of pyrolysis kinetics can also be useful in mod-
eling the propagation of wildres [4], which ravage 550 million ha
worldwide annually [5].
Vegetative biomass, also known as phytomass, is comprised
primarily of cellulose, hemicellulose, and lignin along with lesser
amounts of extractives (e.g., terpenes, tannins, fatty acids, oils, and
resins), moisture, and mineral matter [6]. Cellulose is the most
abundant organic compound in nature, comprising up to 50wt%
of dry biomass [7,8]. It is a linear polysaccharide formed from
repetitive -(1,4)-glycosidic linkage of d-glucopyranose units. Cel-
lulose fromdifferent biomass types is chemically indistinguishable
except for its degree of polymerization (DP), which can range
from 500 to 10,000 depending on the type of biomass [9]. Strong
hydrogen bonding between the straight chains imparts a crys-
talline structure to the cellulose, making it highly impervious
to dissolution and hydrolysis using common chemical reagents
[9,10]. Unlike cellulose, the composition of hemicelluloses and
lignin is heterogeneous and can vary greatly even within a given
biomass species. Hemicelluloses have an amorphous structure
and display branching in their polymer chains. Several sugar
monomers are contained in hemicellulose, including xylose, man-
nose, galactose, and arabinose. Lignin accounts for almost 30%
of terrestrial organic carbon and provides the rigidity and struc-
tural framework for plants [11]. The lignin biopolymer consists
of a complex network of cross-linked aromatic molecules, which
serves to inhibit the absorption of water through cell walls. The
structure and chemical composition of lignin are determined by
the type and age of the plant from which the lignin is isolated
[12]. Studies addressing the transformation kinetics of biomass
must account for the intrinsically heterogeneous nature of the sub-
strate. In this regard, the frequent practice of typifying the overall
kinetic behavior of a particular biomass substrate based on the
kinetic results from just a single benchmark component is trou-
blesome.
Pyrolysis of solid state materials, such as biomass, can be classi-
ed as a heterogeneous chemical reaction. The reaction dynamics
and chemical kinetics of heterogeneous processes can be affected
by three key elements [13], i.e., the breakage and redistribution of
chemical bonds, changing reaction geometry, and the interfacial
diffusion of reactants and products. Unlike homogeneous reac-
tions, concentration is an inconsequential parameter that cannot
be used to monitor the progress of heterogeneous reaction kinet-
ics because it can vary spatially [1316]. Heterogeneous reactions
usually involve a superposition of several elementary processes
such as nucleation, adsorption, desorption, interfacial reaction, and
surface/bulk diffusion, each of which may become rate-limiting
depending on the experimental conditions. The initiation step in
solid state decomposition reactions frequently involves a random
walk of defects andvacancies withinthe crystal lattice whichgives
rise to nucleation growth [17]. Equally signicant is the concept
of a reaction interface, which is dened as the boundary sur-
face between the reactant and the product. This representation has
been used extensively to model the kinetics of solid state reactions
[18].
The only extant review of sugarcane pyrolysis was published
more than thirty years ago [19]. Solid state kinetic theory was in
a state of considerable disarray during this era and decomposition
mechanisms for cellulose pyrolysis were in their formative stages.
Understanding of the reaction dynamics involved in pyrolytic pro-
cesses has evolved substantially since then, and the corresponding
kinetic schemes have been rened to encompass the entire ligno-
cellulosic substrate. In light of this, the original intent of this paper
was to provide a succinct overview of modern biomass pyrolysis
kinetics supported by an analytical survey of rate data obtained
from a particular biomass species (i.e., sugarcane bagasse). How-
ever, considering the uncertainty and ux that continue to envelop
the eld of thermal analysis, it was decided that an experimental
case study isolated froma contextual discourse on the current state
of affairs in heterogeneous kinetics might only add to the existing
turmoil. Therefore, the objective of this critical reviewis to not only
expose the nature andoriginof the rampant inconsistencies inpub-
lished biomass kinetic data but also emphasize the urgent need to
dispense with the . . .hundreds of cute and clever mathematical
manipulations [that] were performed on variations of three (highly
stylized) equations [i.e., the degree of conversion rate equation
(Eq. (2)), the Arrhenius expression (Eq. (1)), and the temperature
integral (Eq. (11))], and instead focus on the reexamination of fun-
damental solid state reaction kinetic theory as it applies to biomass
pyrolysis. After a prcis of experimental kinetic techniques andfun-
damental rate equations, various biomass degradation models and
process parameters that impact rates of biomass degradation are
examined. This treatment is then followed by an analytical evalu-
ation of experimental studies on the kinetics of sugarcane bagasse
pyrolysis.
J.E. White et al. / Journal of Analytical and Applied Pyrolysis 91 (2011) 133 3
Nomenclature
A frequency factor (s
1
)
a,b correlation parameters in the linear compensation
effect relation
C constant of integration
E
a
apparent activation energy (kJ mol
1
)
f() reaction model (function expressing the depen-
dence of the reaction rate on the conversion)
g() integrated reaction model
I(E
a
,T
Cs
1
)
minimization function
deactivation rate constant
Superscripts
c, d, e adjustable reaction exponents in the SB equation
n reaction order
q number of experiments
s adjustable nucleation parameter used in the modi-
ed ProutTompkins model
Subscripts
0 initial
a apparent
f nal
iso isokinetic
i volatile fraction
j ordinal number of experiment
k ordinal number of experiment
m maximum
2. Fundamentals of thermal analysis
2.1. Concise history of thermal analysis
The storied eld of thermal analysis is no stranger to disagree-
ment and uncertainty. Thus it should come as no surprise that
even the origins of modern thermal analysis remain blurred in
controversy. Although Le Chatelier is frequently credited with hav-
ing initiated thermal analysis in 1887 [2023], Jakob Rudberg had
alreadyemployedacrudeformof thermal analysis in1829toobtain
rate data for various metals and their alloys [22], and as early as
1780, Bryan Higgins had observed the effect of heating chalk and
limestone at various temperatures [24]. Likewise, dissent has pre-
ventedthe adoptionof a mutually acceptable denitionfor thermal
analysis methods. Thermal analysis has been formally dened by
theInternational Confederationfor Thermal Analysis andCalorime-
try (ICTAC) as a group of techniques in which a property of the
sample is monitored against time or temperature while the tem-
perature of the sample, in a specied atmosphere, is programmed
[25]. The ICTAC denition has been criticized [26] for being too
constrictive (i.e., monitoring does not adequately reect the ele-
ments of evaluation and experimental investigation that comprise
thermal analysis) or immaterial (i.e., a specied atmosphere is
a unique, local operational factor that is inappropriate for a global
denition). It has been proposed that the essence of thermal analy-
sis canbe summarizedas the measurement of a change ina sample
property, which is the result of an imposed temperature alteration
[26].
2.2. Experimental kinetic analysis techniques
Kinetic data from solid state pyrolysis reactions has tradi-
tionally been obtained using discrete isothermal methods of
analysis. Isothermal kinetic data usually is acquired by perform-
ing several experiments under isothermal conditions at different
temperatures. Additionally, isothermal experiments still possess an
element of non-isothermal behavior duringthe initial heatingramp
to the desired temperature. Interest in isothermal methods, how-
ever, has gradually waned because they are considered toilsome
[27]. Conversely, dynamic methods, which are performed under
non-isothermal conditions, have attracted much appeal given their
ability to investigate a range of temperatures expeditiously [27,28].
Non-isothermal analytical techniques use modern thermobalances
that subject samples to a programmed continuous temperature
rise, which ensures that no temperature regions are omitted, as
can occur during a sequence of discrete isothermal measurements.
Despite their touted convenience [29,30], non-isothermal tech-
niques have received pointed criticism [3135] and, sometimes,
outright rejection [36] because of their perceived inability to reli-
ably assess kinetic parameters, besides their increased sensitivity
to experimental noise as compared to isothermal methods [37,38].
Benoit et al. [39] advised against the use of non-isothermal tech-
niques for solid state decomposition processes where there is a
change in the reaction kinetics over the temperature range or
degree of conversion. Studies have shown that there are wide dis-
parities among values obtained from dynamic techniques that use
only a single heating rate. A consensus emerged that the accuracy
of these methods could be improved using multiple sets of ther-
mal data collected by performing experiments at multiple heating
rates [33,40]; it is a perspective shared by participants in a recent
kinetics project commissionedby ICTAC[4145]. Paradoxically, the
inherent efciency with which dynamic methods collect kinetic
data is partially negated in that reasonably resolved data typically
is obtained using low heating rates [46].
Thermogravimetric analysis (TGA) is the most commonly
applied thermoanalytical technique in solid-phase thermal degra-
dation studies [47], and it has gained widespread currency in
thermal studies of biomass pyrolysis [4854]. TGA measures the
decrease in substrate mass caused by the release of volatiles, or
devolatilization, during thermal decomposition [55]. In TGA, the
mass of a substrate being heated or cooled at a specic rate is
monitored as a function of temperature or time. Taking the rst
derivative of such thermogravimetric curves (i.e., dm/dt) curves,
known as derivative thermogravimetry (DTG), provides the maxi-
mumreactionrate [56]. The development of a systemin1899 by Sir
William Roberts-Austen [57] that uses thermocouples to measure
the temperature difference betweena sample and anadjacent inert
reference material subjected to an identical temperature alteration
was the naissance of differential thermal analysis (DTA) [58]. By
4 J.E. White et al. / Journal of Analytical and Applied Pyrolysis 91 (2011) 133
Table 1
Classication scheme of thermoanalytical techniques.
Property Technique Parameter measured Abbreviation
Mass Thermogravimetric analysis Sample mass TGA
Derivative thermogravimetry First derivative of mass DTG
Temperature Differential thermal analysis Temperature difference between sample and inert reference material DTA
Derivative differential thermal analysis First derivative of DTA curve
Heat Differential scanning calorimetry Heat supplied to sample or reference DSC
Pressure Thermomanometry Pressure
Dimensions Thermodilatometry Coefcient of linear or volumetric expansion
Mechanical properties Thermomechanical analysis TMA
Electrical properties Thermoelectrical analysis Electrical resistance TEA
Magnetic properties Thermomagnetic analysis
Acoustic properties Thermoacoustic analysis Acoustic waves TAA
Optical properties Thermoptical analysis TOA
plotting the time (t) versus temperature difference (T) a DTA
curve can be generated from which the reaction rate can be cal-
culated in terms of the slope (dT/dt) and height (T) of the curve
at any temperature [59]. Another commonmethodof thermal anal-
ysis is differential scanning calorimetry (DSC). In DSC, heat ux into
or out of a sample is compared against an inert reference material,
usually alumina, as the two specimens are simultaneously heated
or cooled at a constant rate. The integral (or area) of the DSC peak is
directly proportional to the heat of transition for a particular reac-
tion and the change in heat capacity can readily be correlated to
the enthalpy change of the reaction. DTA is similar to DSC, except
that the conditions in DTA are adiabatic causing a temperature dif-
ference between the sample and the reference material. Table 1
provides a listing of thermoanalytical techniques classied accord-
ing to the physical properties that are measured.
Thermal analysis provides an excellent tool that may provide
insight regarding the kinetic workings of heterogeneous reactions.
However, it cannot be overstressed that the kinetic data obtained
from a single thermoanalytical technique, in and of itself, does not
provide the necessary and sufcient evidence to draw mechanistic
conclusions about a solid state decomposition process [60]. The
kinetic behavior of a given heterogeneous reaction system may
change during the process and so it is possible that the complete
reactionmechanismcannot be representedsuitablybya single spe-
cic kinetic model [61]. Various other analytical techniques (e.g.,
electrical, nuclear, optical, and X-ray) must be employed to detect
and analyze changes that occur in the chemical composition and/or
structure of the sample. One such specialized method, evolved gas
analysis (EGA), involves a qualitative and quantitative assessment
of the gases that are evolved during thermal analysis. EGA can
be performed using a variety of analytical tools, including Fourier
transform infrared spectroscopy (FTIR), gas chromatography (GC),
high performance liquid chromatography (HPLC), mass spectrom-
etry (MS), and GCMS. The use of these species-specic techniques
in consort with thermal analysis can help facilitate the elucidation
of anappropriate kinetic scheme and, hopefully, bring investigators
one step closer to understanding the actual reaction mechanism.
2.3. Arrhenius rate expression and the signicance of the kinetic
parameters
Virtually every kinetic model proposed employs a rate law that
obeys the fundamental Arrhenius rate expression:
k(T) = Aexp
_
E
a
RT
_
(1)
where T is the absolute temperature in K, R is the universal gas
constant, k(T) is the temperature-dependent reaction rate con-
stant, A is the frequency factor, or pre-exponential, and E
a
is the
activation energy of the reaction. The main temperature depen-
dence in the Arrhenius equation arises from the exponential term,
although the frequency factor, A, does exhibit a slight temperature
dependency [17,62]. For homogeneous reactions involving gases,
the physical signicance of the Arrhenius parameters (i.e., E
a
and
A) can be interpreted in terms of molecular collision theory. The
activation energy, E
a
, can be regarded as the energy threshold that
must be overcome before molecules can get close enough to react
and form products. Only those molecules with adequate kinetic
energy to surmount this energy barrier will react. Alternatively,
transition state theory describes the activation energy as the differ-
ence betweenthe average energy of molecules undergoing reaction
and average energy of all reactant molecules [63]. The frequency
factor provides a measure of the frequency at which all molecular
collisions occur regardless of their energy level [64]. The exponen-
tial term in Eq. (1) can be thought of as the fraction of collisions
having sufcient kinetic energy to induce a reaction [65]. Thus,
the rate constant, k(T), being the product of A and the exponen-
tial term, exp
Ea/RT
, yields the frequency of successful collisions
[65].
Vociferous debate continues to swirl about the relevancy of
kinetic parameters obtained from solid state reactions. The crux
of the controversy stems from the indiscriminate adoption of
homogeneous reaction kinetic theory to describe heterogeneous
processes [6668]. Indeed, it is plausible that much of the incon-
sistency arising in biomass kinetic data is ascribable to the use of
kinetic expressions that are merely adaptations of those used in
homogeneous reactions and that do not incorporate terms that
depend upon the solid state nature of biomass. Over thirty years
ago, Garn [69] contended that the discrepancies observed in cal-
culated activation energies for solid phase decomposition are a
reminder that the concept of a symmetric distribution of energy
states as impliedby the Arrhenius equationdoes not apply tosolids.
The fact that the most commonly occurring and minimum pos-
sible energy state in solids is that of the perfect crystal obviates
the use of a statistical treatment for solids [70]. Garn advised [69]
that if the calculated activation energy varies with experimental
conditions then it is necessarily true that: (1) there is no uniquely
describable activated state and consequently the Arrhenius equa-
tion has no application to solid reactions; or (2) the assumption
that the rate is a function only of temperature and the [mass] frac-
tionremaining is incorrect; or (3) both. Consequently, the physical
connotationof the Arrhenius parameters inheterogeneous kinetics
is opaque and . . .they do not characterize the chemical reaction
itself, but only the whole complexity of processes occurring dur-
ing the pyrolysis under the given experimental conditions [71].
Hence, experimentally determined kinetic parameters from ther-
mally activated, solid state transformations can only be expected
to provide a rough approximation for the overall rate of a com-
plex process that typically entails numerous steps, each having
distinct activation energies [40,72]. Garn [66] also raised salient
concerns about other weaknesses associated with the transfer of
homogeneous kinetic principles to heterogeneous processes.
J.E. White et al. / Journal of Analytical and Applied Pyrolysis 91 (2011) 133 5
Table 2
Unconventional phenomena represented by the Arrhenius rate law.
Temperature-dependent phenomenon
(applicable temperature range)
Ea (kJ mol
1
)
Rate of counting 100.4
Rate of forgetfulness 100.4
Frequency of the heart beat of a terrapin
(1834
C)
76.6
Creeping velocity of the millipede (Parajulus
pennsylvanicus) (630
C)
51.2
Creeping velocity of the ant (Liometopum
apiculatum) (1638.5
C)
51.0
Frequency of ashing of reies 51.0
Rate of chirping of common tree crickets
(Oecanthus)
51.0
Velocity of amoeboid progression in human
neutrophilic leucocytes (2740
C)
45.2
Creeping velocity of the spotted leopard slug
(Limax maximus) (1128
C)
44.8
Rate of lament movements in the blue-green
algae (Oscillatoria) (636
C)
38.7
Human alpha brain-wave rhythm 29.3
Although alternative expressions (e.g., linear relationships
betweenlnkandT, andbetweenlnkandlnT) doexist for describing
the inuence of temperature onthe rates of chemical reactions, Lai-
dler [73] emphasized that none of these other relationships enjoys
the universal acceptance bestowed upon the Arrhenius equation
because of their theoretical sterility. The additional parameters
that are included in these surrogate rate expressions presum-
ably would permit better tting of experimental data, but there
is no theoretical rationale for their existence, thereby, depriving
them of any physico-chemical signicance [62]. Were the ther-
mal analysis community to approve an alternative expression for
the temperature dependence of reaction rates, it would neces-
sitate the recalculation of all previous E
a
and A values so that
kinetic parameters dating back to 1899 could be compared against
those generated by the new rate law [62]. An undertaking of this
magnitude would be incredibly laborious and seems improbable.
Moreover, rejection of the Arrhenius expression would, as
Sestk
[74] said, certainly deny the fty [i.e., now eighty] years work
of famous scientists in the eld of heterogeneous kinetics. For all
the barbed accusations that have been hurled against the Arrhe-
nius rate law, it remains the only such kinetic expression that can
satisfactorily account for the temperature-dependent behavior of
even the most unconventional processes, as shown in Table 2 and
notedoriginallyinaseries of reviewpapers byCrozier et al. [7577],
and subsequently expanded by Laidler [78] and then tabulated by
Brown [68]. Laidlers purpose for revisiting these intriguing pro-
cesses was to underscore that relatively complex reaction systems
can be represented by the Arrhenius law and also that above a cer-
tain energy threshold (i.e., about 21kJ mol
1
) many phenomena
are likely to proceed via chemical reactions rather than by phys-
ical processes. The prominent role of the Arrhenius expression in
heterogeneous reaction systems is undeniable and was acknowl-
edged by Agrawal [28], who stated, . . .it is perhaps the most
widely used equation and is satisfactory in explaining the temper-
ature dependence of the rate constant in solid-state decomposition
kinetics.
3. Biomass pyrolysis kinetics
3.1. Kinetic expressions for biomass thermal decomposition
The kinetics of biomass decomposition are routinely predicated
on a single reaction [79,80] and can be expressed under isothermal
conditions by the following canonical equation:
d
dt
= k(T)f () = Aexp
_
E
a
RT
_
f () (2)
where t denotes time, signies the degree of conversion, or extent
of reaction, d/dt is the rate of the isothermal process, and f() is
a conversion function that represents the reaction model used and
depends on the controlling mechanism. The extent of reaction, ,
can be dened either as the mass fraction of biomass substrate that
has decomposed or as the mass fraction of volatiles evolved and
can be expressed as shown below:
=
w
0
w
w
0
w
f
=
v
v
f
(3)
where w is the mass of substrate present at any time t, w
0
is the
initial substrate mass, w
f
is the nal mass of solids (i.e., residue and
unreacted substrate) remaining after the reaction, v is the mass of
volatiles present at any time t, and v
f
is the total mass of volatiles
evolved during the reaction. The combination of A, E
a
, and f() is
often designated as the kinetic triplet, which is used to characterize
biomass pyrolysis reactions [81,82]. Non-isothermal rate expres-
sions, which represent reaction rates as a function of temperature
at a linear heating rate, , can be expressed through an ostensibly
supercial transformation [81,83] of Eq. (2):
d
dT
=
d
dt
dt
dT
(4)
where dt/dT describes the inverse of the heating rate, 1/, d/dt
represents theisothermal reactionrate, andd/dTdenotes thenon-
isothermal reaction rate. An expression of the rate law for non-
isothermal conditions can be obtained by substituting Eq. (2) into
Eq. (4):
d
dT
=
k(T)
f () =
A
exp
_
E
a
RT
_
f () (5)
The use of reaction-order models is ubiquitous in the thermal
analysis of biomass because of their simplicity and propinquity to
relations used in homogeneous kinetics [28,83]. In these order-
based models, the reaction rate is proportional to the fraction of
unreacted substrate raised to a specic exponent, known as the
reaction order:
d
dT
= k(T)(1 )
n
(6)
where (1) is the remaining fraction of volatile material in the
sample and n represents the reaction order. The devolatilization
dynamics of biomass pyrolysis are frequently expressed as a rst
order decomposition process that results in the formation of dis-
crete volatile fractions [49,8491]:
dV
i
dt
= k
i
(T)(V
i
V
i
) (7)
where k
i
(T) is the rate constant for an evolved volatile fraction
i, V
i
is the cumulative mass of released volatiles correspond-
ing to fraction i through time t, and V
i
* is the effective volatile
content for fraction i. In most devolatilization schemes, the
separate volatilized fractions are classied in terms of three prin-
cipal biomass pseudo-components (i.e., hemicellulose, cellulose,
and lignin) and, sometimes, moisture [49,88,89,92,93]. The total
devolatilization rate for a particular system is given by linear sum-
mationof the individual volatilizationrates for eachfraction, which
are weighted according to the percentage of respective pseudo-
component initially present in the unreacted solid substrate. The
release of biomass volatiles has also been hypothesized to involve
several independent concurrent reactions that produce a set of
lumped volatile products [94,95]. This alternative kinetic represen-
tation uses Eq. (7) as a template but the rate of devolatilization is
6 J.E. White et al. / Journal of Analytical and Applied Pyrolysis 91 (2011) 133
Table 3
Expressions for the most common reaction mechanisms in solid state reactions.
Reaction model f() =(1/k)(d/dt) g() =kt
Reaction order
Zero order (1)
n
_
d
dT
__
= ln[Af ()]
E
a
RT
(9)
It is assumed that the conversion function f() remains constant,
which implies that biomass degradation is independent of temper-
ature and depends only on the rate of mass loss. A plot of ln[d/dt]
versus 1/T yields a straight line, the slope of which corresponds to
E
a
/R.
The FlynnWallOzawa (FWO) method [62,145150] is an
integral isoconversional technique that assumes the apparent acti-
8 J.E. White et al. / Journal of Analytical and Applied Pyrolysis 91 (2011) 133
vation energy remains constant throughout the duration of the
reaction (i.e., from t =0 to t
, where t
_
T
0
exp
_
E
a
RT
_
dT (10)
where T
exp
x
x
2
=
AE
a
R
p(x) (11)
where p(x) representing the rightmost integrand in Eq. (10) is
known as the temperature integral. The temperature integral does
not have an exact analytical solution in closed form[29] but can be
approximated via an empirical interpolation formula proposed by
Doyle [62,149,151,152]:
logp(x)
=
exp
x
x
2
, for 20 x 50 (14)
Substitution of Eq. (14) into Eq. (11) and taking the ln of both
sides leads to the expression for the KAS integral isoconversional
method:
ln
_
T
2
m
_
=
E
a
R
_
1
T
m
_
ln
_
_
E
a
AR
_
_
0
d
f ()
_
(15)
where T
m
is the temperature at the maximumreactionrate. Assum-
ing has a xed value, E
a
can be determined from the slope of the
straight line obtained by plotting ln(/T
m
2
) versus 1/T
m
.
The integral method based on the Coats and Redfern (CR) equa-
tion [155,156] is a popular non-isothermal model-tting method
that requires an assumption be made regarding the value of the
reaction order for g(). The method approximates p(x) in Eq. (11)
using a Taylor series expansion to yield the following expression:
ln
_
ln(1 )
T
2
_
= ln
_
AR
E
a
_
1
2RT
E
a
__
E
a
RT
(16)
Eq. (16) can be simplied by recognizing that for customary values
of E
a
(e.g., 80260kJ mol
1
), the term 2RT/E
a
1:
ln
_
g()
T
2
_
= ln
_
AR
E
a
_
E
a
RT
(17)
A straight line can be obtained from single heating rate data by
plotting ln[g()/T
2
] versus T
1
. From the slope of the line, E
a
/R,
and its intercept ln(AR/E
a
), E
a
and A can be derived. The attrac-
tiveness of the CR method resides in its ability to directly furnish
A and E
a
for single heating rate. The criticism of the CR approach
follows the same general arguments presented against all of the
model-tting methods, namely, that the kinetic triplet resulting
fromevaluation of a single DTGcurve may be non-unique, or indis-
tinguishable, because of the high degree of correlation between
andd/dt (or dT/d) [28,157160]. Amulti-heatingrateapplication
of the original Coats and Redfern equation, known as the modied
CoatsRedfern (CR*) method [41,161], has been advanced that pro-
vides an integral isoconversional technique equivalent to those of
FWOandKAS. The CR* methodrearranges terms inEq. (16) toyield:
ln
_
T
2
(1 2RT/E
a
)
_
=
E
a
RT
+ln
_
AR
g()E
a
_
(18)
Given a xed degree of conversion, the left-hand term is plotted
versus T
1
for each heating rate, generating a set of straight lines,
each having slope E
a
/R. The frequency factor, A, is calculated by
inserting E
a
/R into the intercept. Because the left-hand side of Eq.
(18) is weakly dependent on E
a
, an iterative process must be used
by assuming an initial value for E
a
and then re-evaluating the left-
hand side until the desired level of convergence [161]. It should be
noted as a point of clarity that there are other so-called modied
CoatsRedfern methods in the literature, but they cannot be con-
sidered isoconversional because they still require the selection of
a reaction order. These alternative modied CoatsRedfern for-
mulations often involve a regression analysis of one or more of the
kinetic triplet parameters [162,163]. One such modied method
[163] reported errors for E
a
estimates that are an order of magni-
tude lower than those obtained from isoconversional techniques.
3.5. Comparative evaluation of integral and differential
isoconversional techniques
The advantages of the integral isoconversional methods are
tempered by several weaknesses not present in the differential
methods [164], viz.,
(1) Picard iteration [165] of the temperature integral is needed.
(2) Integral methods are prone to error accretion during such suc-
cessive approximations.
(3) The temperature integral requires boundary conditions which
are frequently ill-dened.
Flynn [62] remarked that use of . . .the mathematically
intractable temperature integral has often become a necessary evil
in the analysis of thermal analysis kinetics. To circumvent the
hazards posed by these oversimplied approximations, Vyazovkin
and Dollimore [166] introduced a non-linear isoconversional tech-
nique, known as the Vyazovkin (V) method, which uses a revised
expression for the temperature integral, p(x):
I(E
a
, T
) =
_
T
0
exp
_
E
a
RT
_
dT = p(x) (19)
The V method evaluates E
a
for a set of q experiments conducted
at different heating rates,
j
and
k
, where the subscripts j and k
denote the ordinal number of the experiment:
q
j=1
q
k / = j
k
I(E
a
, T
,j
)
j
I(E
a
, T
,k
)
= (E
a
) (20)
where I(E
a
,T
,j
) and I(E
a
,T
,k
) represent the temperature integral
p(x) corresponding to the heating rates
j
and
k
, respectively.
The apparent activation energy is given by the value that mini-
mizes . Values of I(E
a
,T
E
i
RT
__
(23)
where z is the activity of the solid substrate expressed as a func-
tion of a deactivation rate constant, , and k
app
is the apparent rate
constant.
Reynolds et al. [161,184,185] developed a generalized
nucleation-growth model, which is essentially a modication
of the ProutTompkins rate equation [186], rst used to describe
10 J.E. White et al. / Journal of Analytical and Applied Pyrolysis 91 (2011) 133
the thermal decomposition kinetics of potassium permanganate
[187]:
d
dt
= ky
n
(1 ry)
s
(24)
where y designates the remaining fraction of substrate, n is still the
reaction order, r is an initiation parameter frequently set to 0.99, s
is used as an adjustable nucleation parameter that can reduce Eq.
(24) toarst order reaction, andthequantityinparentheses (1ry)
replaces (1y) toprevent theinitial ratefrombeingzero[188]. This
model demonstrated a better t with experimental data than con-
ventional rst order models, yielding a much tighter degradation
curve [184].
The distributed activation energy model (DAEM) has been
successfully applied to both plant [91,117,189196] and fossil
[95,190,197202] biomass pyrolysis. The DAEM assumes that sev-
eral irreversible rst order parallel reactions having unique kinetic
parameters take place concurrently [202]. A continuous distribu-
tion function, f(E
a
), is used to represent the activation energies
from the various reactions. The distribution function is approx-
imated by a Gaussian distribution that yields a mean value and
standarddeviationof E
a
. Vrhegyi et al. [189] have assertedthat the
DAEMis thebest methodavailablefor mathematicallyrepresenting
the physical and chemical heterogeneity of substances. Miura and
Maki [203] proposed a revised distributed activation energy model
(DAEM) that provides a method for estimating the frequency factor
and f(E
a
) without requiring a priori assumptions of either kinetic
parameter. This method was used to successfully predict weight
loss curves from the pyrolysis of coal at different heating rates. Cai
and Liu [204] advocated the use of a Weibull distribution model
to t non-isothermal kinetic data. Under this approach, the kinetic
degradation for each biomass component is represented by one or
more Weibull distribution functions. This procedure allows over-
lapping processes in the TGA curve to be deconvoluted. The use of
this model requires estimation of the scale and shape parameters
that are unique to the Weibull distribution function.
The cacophonous debate over the relative merits of isothermal,
non-isothermal, andisoconversional methods cansometimes over-
arch the common thread among all these methods: the use of a
kinetic model that has been preordained by the scientic commu-
nity. A signicant liability can be incurred by simply consulting the
Table for the best model and expecting that it indeed is the
correct model. Galwey and Brown [13] commented that the for-
mal models in the accepted set [i.e., the Table] are far too simple
to account for all the features of real processes. Using a gener-
alized description of the kinetics involved in solid state reaction
systems offers thefreedomandexibilitytochoosethemost appro-
priate elements from the set of existing formal models in order to
best characterize the various aspects of the true process [13]. The
3
3
1
1
Table 4
Kinetic parameters for thermal decomposition of various nutshell types.
Nutshell type Heating prole, rate (
Cmin
1
) Temp. range (
3
3
Table 4 (Continued)
Nutshell type Heating prole, rate (
Cmin
1
) Temp. range (
Cmin
1
to 110
C for 10min.
J.E. White et al. / Journal of Analytical and Applied Pyrolysis 91 (2011) 133 13
Fig. 1. Comparison of apparent activation energies for nutshells evaluated using various 1st order, single-step kinetic models, including the biomass deactivation model
(DM), the standard kinetic model (SM), and the Friedman model.
may be attributable to dissimilarities in the thermal characteris-
tics of the experiments themselves (i.e., static versus dynamic), it
would appear from the preceding analysis that the nature of the
kinetic approach used to model the reactions also has a substantive
impact on the activation energy and should, therefore, not be dis-
counted. This latter observationis further borne out if the results for
cashewnut shells in Table 4 are evaluated [110,207]. In both cases,
the experiments were conducted under non-isothermal conditions
andmodeledusing rst order CRkinetics. The onlymajor difference
is that one labgroupuseda parallel reactionscheme [110], whereas
the other scientic team used a single-step format [207]. Accord-
ingly, the minimumE
a
value obtainedusing the single-stepmethod
is 56% lower than the E
a
value realized using the parallel reaction
scheme.
The effect of heating rate on E
a
for non-isothermal almond
shell pyrolysis [214,216] modeledusingtwoconcurrent reactions is
depictedinFig. 2. ThemaximumE
a
valuefor therst order reactions
declines 16% when the heating rate is increased from5
Cmin
1
to
40
Cmin
1
, while the minimum E
a
value for rst order reactions
decreases 10% over the same heating rate increase. Interestingly,
the minimum E
a
value for nth order reactions rises 21% when the
heating rate is increased from 2
Cmin
1
to 25
Cmin
1
. A his-
togram illustrating the effects of particle size on E
a
is presented
in Fig. 3. A reduction in the particle size range of pistachio shells
[8] from 0.2500.600mm to 0.0710.125mm decreases the aver-
Fig. 2. Comparison of apparent activation energies for almond shells at different
heating rates using parallel reaction models of either 1st order or nth order.
Fig. 3. Comparisonof apparent activationenergyvalues obtainedfor pistachioshells
for various particle sizes using two-step sequential CR and FWO models.
age value of E
a
by 10% and 20% for the CR and the FWO models,
respectively. This result serves to reafrm the theory that larger
particles require a higher level of energy to react because they are
more prone to transport limitations. Fig. 3 also depicts that the CR
model consistently returns higher E
a
values than the FWO model.
Taken collectively, the data from Figs. 13 indicate that there is
a strong correlation between the kinetic model that is chosen to
evaluate E
a
and the resulting value. Another probable source of
variance in the presented nutshell data might be a result of changes
in major reaction mechanisms occurring at different temperatures.
The differences in lignocellulosic composition of the various nut-
shell types, as shown in Table 5, are also a possible factor behind
the inconsistent E
a
values. In the case of heterogeneous thermal
reactions, the measured kinetic data are . . .primarily inuenced
by the experimental conditions and not the reaction itself. There-
fore, a change in experimental factors makes the interpretation of
the estimated parameters impossible [221]. In light of this, the
unpredictability of the results provided in Table 4 illustrates the
frustrating inability to use kinetic parameters for anything other
than providing local comparisons of the thermal stability of iden-
tical processes.
5. Biomass thermal decomposition mechanisms
In addition to the large assortment of kinetic models available
for biomass pyrolysis, the literature contains a diverse set of possi-
ble decomposition pathways. It is generally accepted that biomass
14 J.E. White et al. / Journal of Analytical and Applied Pyrolysis 91 (2011) 133
Table 5
Lignocellulosic composition of various nutshell types (dry wt% basis).
Nutshell type Cellulose Hemicelluloses Lignin
Almond shell
a
[214] 31.1 38.0 27.7
Almond shell
a
[222] 37.4 31.2 27.5
Almond shell
a
[223] 50.7 28.9 20.4
Almond shell
b
[224] 24.7 27.0 27.2
Brazil nut shell
a
[217] 48.5
c
59.4
Coconut shell [225] 35.0 29.0 28.0
Coconut shell
b
[224] 24.2 24.7 34.9
Hazelnut shell
a
[209] 25.9 28.7 44.4
Hazelnut shell
a
[223] 26.8 30.4 42.9
Macadamia nut shell
b
[224] 26.9 17.8 40.1
Peanut shell [226] 36.6 19.4 33.4
Peanut shell [52] 35.7 18.7 30.2
Pecan shell
b
[224] 5.6 3.8 70.0
Pistachio shell [227] 60.6 NA 20.8
Walnut shell
a
[223] 25.6 22.1 52.3
Walnut shell
b
[224] 21.0 18.8 32.7
a
Dry ash free basis.
b
Calculated using the following formulas: % cellulose =0.9 (% glucose) and % hemicellulose =0.9 (% galactose +% mannose) +0.88 (% xylose +% arabinose).
c
Value reported is for holocellulose which is the term used to indicate the total fraction of plant material left after removal of lignin.
pyrolysis proceeds via the following primary transformations: ini-
tiallyfree moisture inthe solidevaporates, followedbydegradation
of the more unstable polymers, and, nally, with increasing tem-
perature the more refractory components begin to decompose and
volatiles are released from the substrate matrix [228,229]. Solid
char residue that is formed during the primary decomposition
phase, i.e., 200400
C) cellu-
lose degradation follows a different pathway. In this temperature
region, depolymerization reactions associated with the cleavage
of glycosidic bonds prevail and yield a tarry pyrolyzate contain-
ing levoglucosan, other anhydrosugars, oligosaccharides, and some
glucose decomposition products [9,233]. A possible third route
employing ash pyrolysis at even higher temperatures (>500
C)
could involve the direct conversion of cellulose to low molecular
weight gases and volatiles via ssion, disproportionation, dehydra-
tion, and decarboxylation reactions [9]. The DP, crystallinity, and
crystallite orientationof cellulose bers inlignocellulosic materials
have been proposed as fundamental factors that regulate thermal
decomposition behavior [234,235].
The seminal predictive mechanismfor cellulose pyrolysis kinet-
ics, which was developed during the mid 1960s to mid 1970s by
Broido and his colleagues [231,236238], involved a competitive,
multi-step reaction sequence, as shown in Scheme 1. In Scheme 1,
a stable form of cellulose is converted to a more reactive cellulose
Cellulose Active Cellulose
C
A
+vols. C
B
+vols. C
C
+vols.
Volatile tars
k
i
k
v
k
cA
k
cB
k
cC
Scheme 1. Broido mechanism, where C
A
, CB, and C
C
denote successive fractions of
chars A, B, and C, respectively, that are produced along with accompanying volatiles
formation.
(i.e., labeled active cellulose) at elevated temperatures, with rate
constant k
i
. The active cellulose can then degrade thermally by
two parallel routes, forming either volatiles with no char, or pro-
ceeding via a sequence of serial reactions to form chars C
A
, C
B
, and
C
C
and accompanying volatiles.
In 1979, Shazadeh [239] modied the Broido model slightly by
neglecting the secondary reactions inthe char andgas product. This
proposed model, nowknown as the BroidoShazadeh (BS) model
(Scheme 2), has become widely cited in biomass pyrolysis and gasi-
cation literature [92,134,174,240246]. Although the validity of
this model has also been frequently assailed [6,92,241,247249],
there appears to be consensus that the main features of the BS
model are serviceable. Specically, it is widely acknowledged that
pyrolysis consists of primaryinitiationandfragmentationreactions
followed by secondary cracking reactions of volatiles [250]. Con-
versely, the chief criticism regards the inclusion of the zero-order
initiation step at low temperatures (<300
C) to convert cellulose
from an inactive to an active stage. Once cellulose is converted
from an inactive to an active state, pyrolysis is then able to
proceed at higher temperatures. It is likely that this initiation step
was included because several cellulose pyrolysis studies produced
results suggesting the initial stage of pyrolysis did not followa rst
order reaction law. The initiation step is sometimes described as
a depolymerization process because the DP of the starting, native
cellulose typically has a value of around 2500, whereas the DP for
active cellulose is generally below 200 [251,252]. According to
the BS model the initiation step requires a high apparent activa-
tion energy (242.7kJ mol
1
), yet only a 36% mass loss is observed
during this period [251,252]. It has been shown that the rate of cel-
Scheme 2. BroidoShazadeh mechanism.
J.E. White et al. / Journal of Analytical and Applied Pyrolysis 91 (2011) 133 15
lulose pyrolysis can be inuenced by several structural elements,
including the DP, crystallinity, orientation, and accessibility of the
sample [234,251,253].
The thermal decomposition behavior of plant biomass fre-
quently is assumed to be approximated by the sum of the
contributions of the respective components [2,6,92,119,254258].
Thermogravimetric (TG) curves for biomass pyrolysis data conrm
that the pyrolysis rate is related to the biomass composition. The
pyrolysis curves of biomass species closely trace the decomposi-
tion curves of their dominant lignocellulosic constituents; hence,
the curves of primarily cellulosic biomass share resemble those
of pure cellulose, while degradation curves for biomass with high
lignin contents are similar to those of lignin standards [118]. The
order of decomposition of the biomass components is a function
of their intrinsic reactivity [259]; hence, the typical sequence in
which biomass degrades is given here: extractives, hemicellulose,
cellulose, and nally, ash. Notably, lignin was excluded from the
preceding sequence because lignin begins to decompose beginning
at temperatures that are equivalent to those seen for hemicellulose
degradation and continues to degrade slowly over a very broad
temperature range [260]. Typically, the rate of biomass pyrolysis
is controlled by the rate of cellulose degradation which is subject
to autocatalytic effects [19].
The composition of lignin varies intrinsically according to its
source and the manner in which it is extracted [261]. The complex
hydrogen-bonding network present within lignin [262] serves as
a rigid structural lattice that is resistant to thermal decomposition
(i.e., tends to char more than less stable cellulose or hemicellu-
lose) [263265]. Although there typically is no discernible peak
assignable to lignin degradation because of its slow decomposi-
tion over a broad temperature span [241,257], the wide, oblique
tailing that follows the cellulose peak in DTG diagrams is sugges-
tive of lignindegradation[49,266]. It has beennoted that this broad
tailing baseline appears to be a prolongation of the rst peak corre-
sponding to hemicellulose degradation [214], suggesting that the
thermal decomposition of lignin may occur simultaneously with
that of hemicellulose. Some researchers have been able to over-
come the challenges of delineating the boundaries of this poorly
dened lignin degradation zone, or fourth lump, by deconvolut-
ing the TG curve through second-order differentiation techniques.
Using real-time molecular-beam, mass spectrometry (MS) Evans
and Milne [267] were able to monitor the chronological evolution
of primary pyrolysis oils from different biomass substrates under
both slow and rapid heating settings. Primary pyrolysis oils are
those that have not been subjected to temperatures (>600
C) and
residence times (>1s) that would promote secondary gas-phase
cracking reactions. Mass spectra revealed that primary pyrolysis
oil composition was not signicantly affected by changes in the
heating rate of the wood substrate. The mass spectra from sweet
gumrevealedthat products containing hardwoodligninmonomers
were generated early and in high abundance. The earliest pyrolysis
product toformwas coniferyl alcohol at a mass tocharge (m/z) peak
of 180amu. This was followed by a derivative of hemicellulose (3-
hydroxy-2-penteno-1,5-lactone) at m/z 114amu. Aspecies derived
from cellulose (CH
3
O
+
) evolved next at m/z 43amu and a lignin-
derived product (methylguaiacol) at m/z 138amu eluted last [266].
Lignin peaks were observed to evolve sequentially over the dura-
tionof the pyrolysis suggesting that lignindecompositioncoincides
not only with the degradation of hemicellulose, but also cellulose.
A separate study [268] has found substantial interactions between
cellulose and lignin during pyrolysis at high temperatures (800
C).
The presence of cellulose promoted the formation of guaiacol, 4-
methylguaiacol, and 4-vinylguaiacol but curtailed char production
fromsecondary cracking reactions. The presence of ligninwas asso-
ciated with increased production of levoglucosan, glycoaldehyde,
and hydroxyacetone from cellulose and reduced char formation.
These ndings would appear to contradict the earlier postulate
[2,6,92,119,254258] that suggests the pyrolysis of lignocellulosic
materials consists of three independent decomposition reactions,
each involving a major pseudo-component: cellulose, hemicellu-
lose, and lignin.
The temperature regime giving the most rapid decomposition
rates is aptly designated the active pyrolysis zone, or sometimes,
primary pyrolysis region [269]. The active pyrolysis zone can vary
depending upon the heating rate applied in the thermal analy-
sis and the type of biomass being investigated. Though there is
disagreement on the exact temperature boundaries of the active
pyrolysis zone, it is generally accepted to be in the range of
200400
C, with
minor mass losses associated with the removal of moisture and the
hydrolysis of some extractives [54]. TGA data has revealed that the
degradation of the principal lignocellulosic components can be cat-
egorized into discrete temperature ranges [191,254]. This indicates
that a key step in the reaction mechanism of the primary biomass
components occurs at some critical transition temperature, T
c
, dur-
ing thermal decomposition.
6. Inuence of experimental conditions on biomass
reaction kinetics
Seemingly slight differences in certain process variables along
with heat and mass transport limitations can have signicant
impacts on the nature and rates of lignocellulosic decomposi-
tion reactions [259]. Experimentally derived kinetic parameters
are affected by reaction conditions, including temperature, heat-
ing rate, residence time (i.e., for solids and volatiles), particle
size, pressure, gaseous atmosphere, and the presence of inorganic
mineral content within the biomass material [85,229]. From the
observation that the amount of char produced in cellulose pyroly-
sis varies proportionally with sample size and reaction pressure,
it was inferred that the residence time of the volatiles in the
biomass matrix during pyrolysis is instrumental in determining
the extent of char formation [239,270]. Extended residence times
for the volatile components can promote secondary reactions (e.g.,
cracking, cross-linking, and repolymerization) that lead to more
char formation. Conversely, the yield of volatiles can be adversely
impacted if the residence time of various autocatalytic volatile
species in the biomass substrate is too brief. Lewellen et al. [270]
demonstrated that char formation can be nearly eliminated at very
short residence times (i.e., 0.230s) given appropriate selection of
the operational temperature and heating rate. Cognizance of the
prominent role played by the residence time of volatiles within the
pyrolyzing biomass matrix foreshadowed the importance of dif-
fusional constraints upon biomass kinetics because the residence
time of volatile vapors inthe biomass matrix depends onthe nature
of heat and mass transfer through the substrate.
6.1. Heat and mass transport models
Internal and external heat and mass transport limitations often
play a pivotal role in inuencing biomass pyrolysis kinetics and
yields. Bamford et al. [271] developed the rst kinetic model to
account for heat conduction and generation in pyrolytic reactions.
Kung [272] explored the dependence of weight loss rates on the
thermal conductivity of char. Through the use of dimensionless
groups, Pyle and Zaror [273] were able to validate whether pyroly-
sis reactions arecontrolledbykinetic processes or heat transfer (i.e.,
either external or internal). Chanet al. [130] extendedthe function-
ality of heat and mass transport models by considering a lumped
16 J.E. White et al. / Journal of Analytical and Applied Pyrolysis 91 (2011) 133
scheme and also by avoiding the necessity of having to assume nal
char values. Alves and Figueiredo [274] provided a useful mathe-
matical model for the pyrolysis of wet wood. These earlier models
provided satisfactory assessments of the heat and mass transfer
limitations in pyrolytic reactions and the hallmark common to all
was their pragmatic approach, which lends itself well for possible
implementation in an industrial environment. Since then, many
studies [275289] have developed sophisticated kinetic models for
biomass pyrolysis that incorporate various elements of transport
phenomena. Generally these increasingly complex kinetics mod-
els are used to describe the pyrolysis of a single biomass particle
and are contingent upon several assumptions. Although some of
these transport models have been validated using simulated or
empirical data, it is unlikely that such complicated models will be
of practical use in industrial applications [290]. The environment in
actual pyrolytic systems is far from any normative standard used
in such models and the conditions experienced by one particle
may be wildly different than those experienced by an adjacent
particle, let alone the substrate bulk. Furthermore, in real ther-
mal decomposition processes there are numerous factors that may
inuence the rate of reactionthat are oftenomittedfromsuchmod-
els (i.e., lattice defects, impurities, melting, sintering, weak bonds,
mechanical strain, catalytic effects from metal reaction vessels,
and ambient or evolved gases that may interact with the reactant
or product) [13,291]. The validity of these models can also suf-
fer from the erroneous assumption that the particles in the bulk
are entirely uniform and thus neglect the inuence of particle-size
effects [13]. This is impracticable when dealing with lignocellu-
losic matter, whose constituent particles can have not only a range
of sizes and shapes but also different chemical compositions and
reactivities. Aconclusion drawn by Garn [70] is apropos here, Lim-
itingthediffusionmodels tocollections withuniformgeometryand
size is not productive: it divorces the computation from reality.
Simple or uniform geometries are seldom encountered in prac-
tice, and should not be accepted even as approximations without
experimental evidence.
6.2. Heating rate and particle size effects
The dependence of biomass pyrolysis kinetics on heating rate is
still unresolved, withsome evidence supporting the notionthat the
use of different heating rates during biomass pyrolysis has minimal
impact onthe frequency factor [191], and other data indicating that
biomass conversion reactions are kinetically slower at higher heat-
ingrates [134,241,292]. Suuberget al. [293] hypothesizedthat mass
transport limitations become increasingly inuential as the heat-
ing rate increases during rapid cellulose pyrolysis. The evaporative
escape of tars from the substrate matrix via diffusive processes or
convective ow was proposed as the primary weight loss route.
This result has been corroborated by recent research at Philip
Morris that employed EGA-FTIR [233,294]. Milosavljevic and Suu-
berg [292] observed that a shift in the mechanism of cellulose
pyrolysis occurs at 327
Cmin
1
are used, such that a relatively low apparent activation energies
(140155kJ mol
1
) are obtained above this temperature. Below
this temperature threshold at lower heating rates, Milosavljevic
et al. reported that the pyrolytic weight loss of cellulose was char-
acterized by a high apparent activation energy (218kJ mol
1
).
It has been established that high heating rates signicantly
lower char yields when compared with slower heating rates
[108,295]. A study involving rapeseed revealed that the total quan-
tity of substrate that was decomposed decreased when the heating
rate was increased, but the loss was more pronounced when the
heating rate was changed from 25 to 50
Cmin
1
(4.8wt%) than it
was changed from 50 to 100
Cmin
1
(1.9wt%). It was speculated
that the increased heating rate allowed ample time for the comple-
tion of thermal degradation reactions. Grnli et al. [296] observed
that the apparent activation energy of cellulose (242kJ mol
1
at
5
Cmin
1
) decreased with increased heating rate (222kJ mol
1
at
40
Cmin
1
). It has beensuggestedthat inter-particlediffusionlim-
itations are accentuated at increased heating rates, thereby leading
to reduced kinetic rates [293]. Studies of cellulose pyrolyzed at
15
Cmin
1
and 60
Cmin
1
yielded an apparent activation energy
of 140kJ mol
1
, a value which is similar to the latent heat of
vaporization of fresh cellulose tar (141kJ mol
1
) [293]. Pyrolysis of
mustard straw and stalk under a nitrogen atmosphere at different
heating rates gave further evidence that the heating rate can inu-
ence reaction kinetics [297]. The reaction order was observed to
be higher at lower heating rates, which may imply the occurrence
of complex, concurrent reactions. Nassar [298] noticed the exis-
tence of a transition temperature corresponding to 360
C, based
on changes measured in the apparent activation energy of sugar-
cane bagasse pyrolyzed in air. Bagasse in the slow decomposition
regime below this temperature had an E
a
value of 139.7kJ mol
1
,
while in the exothermic zone above this temperature bagasse had
an E
a
value of 76.6kJ mol
1
.
In general, the solid-state kinetic theory involves the assump-
tion that solid materials are at uniform temperatures during
pyrolytic decomposition. However, the poor thermal conductiv-
ity exhibited by lignocellulosic substances impedes heat transfer
within biomass particles and can result in a particle tempera-
ture gradient. As heating rates increase, the temperature gradient
within the biomass particle increases, elevating the minimumtem-
perature by which the pyrolysis process may progress [52]. The
kinetic rate of biomass decomposition eventually surpasses the
associated heat transfer rate as the reaction temperature rises.
At some point the biomass degradation kinetics will be restricted
by heat transfer limitations and kinetic analysis then requires a
transport model for the system [299]. The regime in which this
crossover occurs (i.e., between kinetically driven rates and heat
transfer regulated rates) is dependent upon the biomass particle
dimension, making the use of relatively small particles absolutely
imperative for the validity of the aforesaid uniform biomass tem-
perature assumption. It has been reported [299] that the thermal
decomposition of biomass materials with particle thicknesses up
to 0.2mm may be kinetically evaluated up to about 450500
C
without accounting for internal heat transport restrictions. Lower
temperature thresholds, however, apply if the rate of external heat
transfer to the particle surface is sufciently slow. Coincidentally,
most of the biomass pyrolysis conversion is completed in this
temperature range, which implies that conclusions derived from
previous kinetic studies conducted at or below this temperature
zone are not affected by transport limitation inaccuracies. Detailed
mathematical kinetic models have been developed to describe
larger biomass particles up to 2cm in dimension [279,300,301].
6.3. Signicance of surrounding atmosphere
The ambient gas atmosphere in the reaction system can have
a substantial impact on the behavior of biomass thermal decom-
position. It has long been known that the thermal degradation of
wood is greater in the presence of air than in a vacuum [302].
Thermal degradation in air has been shown to lower the active
pyrolysis temperature and boost the combustion of chars at higher
temperatures [4]. Roque-Diaz et al. [303] noticed that the ther-
mal decomposition of sugarcane bagasse was more active in an
oxidative environment than in an inert atmosphere. In this study,
the activation energy of bagasse in air between 170 and 250
C
was 1429% higher than it was in helium for the corresponding
temperature region (see Tables 8 and 9). The greater produc-
tion of char in the presence of air supports the observation of
Mamleev et al. [244] that oxygen interacts vigorously with the
J.E. White et al. / Journal of Analytical and Applied Pyrolysis 91 (2011) 133 17
products derived from the thermal depolymerization of cellulose.
Reduced tar production from biomass pyrolyzed in air can be
explained by returning to the reaction interface of the biomass
substrate. It is conceivable that the cellulose structure, which is
chemically resilient to the penetration of even the most aggressive
chemical agents (e.g., H
2
SO
4
), is equally inaccessible for oxygen
diffusion; hence, only the surface of the cellulose is available for
oxidation.
6.4. Catalytic effect of inorganic material
The inorganic mineral matter present in biomass has previously
been found to catalytically promote char-forming secondary tar-
cracking reactions while concomitantly suppressing additional tar
formation [304]. Mller-Hagedorn et al. [305] found that alkaline
metal chlorides can substantially lower the pyrolysis temperature
of biomass. Anion type was also observed to affect the pyroly-
sis temperature, as given in order of decreasing inuence by the
following list: chlorides >sulfates >bicarbonates. The presence of
even trace levels (e.g., 0.1wt% NaCl) of mineral matter in biomass
can alter pyrolysis behavior appreciably [92,306]. The pyrolysis
rate, tar yield, and initial degradation temperature are all observed
to increase with decreasing mineral content [306]. For instance,
wood (e.g., 1wt% [average] ash) undergoes more rapid thermal
degradation than bagasse (e.g., 4wt% ash) because of the lower
mineral content in wood [307]. Broido [308] discovered that cel-
lulose pyrolysis was affected by the addition of as little as 0.15wt%
potassium carbonate. Tang [309] detected that the reaction rate
for wood pyrolysis jumped by two orders of magnitude when
2wt% monobasic ammonium phosphate was added. Exceptions
to this rule include species that have high lignin contents cou-
pled with high potassium levels (e.g., rice husks, ground nutshells,
and coir pith). Lignin is known to be intractable in pyrolytic
processes [309,310] and potassium strongly promotes char gasi-
cation [306]. Nassar [298] concluded that the presence of alkaline
salts in biomass (i.e., rice straw and bagasse), whether added
or innate, acts to lower the apparent activation energy of ther-
mal reactions and promote the formation of char. Vrhegyi et al.
[311] treated sugarcane bagasse samples with dilute inorganic
salt solutions (i.e., MgCl
2
, NaCl, FeSO
4
, and ZnCl
2
). Treated and
untreated samples were then thermally decomposed and the evo-
lution of low molecular weight products was evaluated using MS.
The treated samples had higher char yields than the untreated
samples, except in the case of MgCl
2
for which there was no sig-
nicant difference. The increased char production was attributed
to the alteration of reaction pathways by the salts. The MS inten-
sities of all the catalytically treated samples were lower than
those of the untreated samples, suggesting that the presence of
inorganic additives suppresses the secondary cracking of high
molecular weight primary products. It was speculated that inor-
ganic salts cause the brous structure of the bagasse to expand,
thereby assisting the release of vapors fromthe solidmatrix. Wash-
ing experimental samples with water before has been shown to
eliminate much of the mineral salt content present in the native
biomass [305]. Removal of the catalytically active mineral mat-
ter via washing has been linked with a corresponding increase in
the apparent activation energy of biomass. Teng and Wei [312]
compared the kinetic data from pyrolysis experiments that uti-
lized both water-washed rice hulls (i.e., 80
C are unavoidable, 10
C) after it is
combusted and the products cool back to 20
C; the
largest peak observed was at 370
C. An endothermic peak
attributed to the vaporization of volatile products interposed itself
intheexothermic peakat about 420
Cligninandhemi-
cellulose degradation control the rate of bagasse decomposition
[307,385].
Similar to most other biomass types, pyrolysis of sugarcane
bagasse under an oxidative environment inuences the reaction
dynamics by lowering the pyrolytic reaction temperature and sub-
stantially increasing the rate of bagasse volatilization[307,385]. For
instance, it was foundthat 5wt%of bagasse is vaporizedat 262
Cin
N
2
, 240
Cindryair, and228
CinO
2
[307]. Arecent investigationof
bagasse pyrolysis by Munir et al. [387] foundthat peak devolatiliza-
tion under an oxidative (air) environment occurred between 304
and 312
Cmin
1
and with a residence time of 30s. The choice of kinetic model sur-
faced as a parameter that had a crucial impact on the evaluated
apparent activation energy. An average total E
a
value was calcu-
lated for every pyrolytic process in Table 8 that incorporated a
sequential reaction model (N.B., all of the experiments employing
a sequential model used unwashed bagasse). The mean value of
E
a
for the ve sets of sequential processes is 72.3kJ mol
1
, with a
standard deviation of 13.1kJ mol
1
.
In Table 8, fourteen sets of kinetic data evaluated using a par-
allel reaction model are presented, of which three utilized washed
bagasse and the remainder used unwashed bagasse. It should be
noted that the four sets of data for the unwashed bagasse that
were obtained by Garcia-Perez et al. [382] at various heating rates
all have identical E
a
values resulting from the use of a compen-
satory shift in the logA values and can, thus, be considered as a
single set of unique E
a
values. The apparent activation energies
for each of the resulting eight unique sets of data for unwashed
bagasse pyrolysis were separated into three fractions according
to the respective contributions from each lignocellulosic compo-
nent. An overall average E
a
value was obtained by normalizing the
pseudo-component fractions according to a nominal average ligno-
cellulosic composition of sugarcane bagasse [361] taken on a dry
ash- and extractive-free basis (i.e., 24% lignin, 32% hemicellulose,
and 44% cellulose). The mean value of E
a
obtained for the eight
parallel processes was determinedtobe159.6kJ mol
1
, withastan-
darddeviationof 40.5kJ mol
1
. The121%averageincreaseinE
a
that
occurs when the kinetic model is amended from a consecutive to
a concurrent reaction scheme is a stark reminder that inappropri-
ate model selection can have dire implications on the validity of
the generated kinetic parameters. The four isoconversional tech-
niques (Friedman, CR, FWO, and KAS) used by Yao et al. [245] to
analyze bagasse pyrolyzed under inert conditions (N
2
) had a mean
E
a
value of 167.0kJ mol
1
, which is only 5% higher than the mean
value for the concurrent model but also 131% higher than the mean
value for the consecutive model. Miranda et al. [370] evaluated
kinetic data from bagasse pyrolyzed under a nitrogen atmosphere
using the Friedmandifferential isoconversional method, along with
serial and parallel methods, and obtained an overall E
a
value of
154.4kJ mol
1
, which was calculated based on their reported com-
positionof bagasse(i.e., 40wt%cellulose, 32wt%hemicellulose, and
20wt% lignin). This value compares reasonably well with the E
a
value of 168.5kJ mol
1
reported by Yao et al. using the Friedman
isoconversional method.
The impact of an oxidative environment versus that of an inert
atmosphere upon bagasse pyrolysis was investigated by several
research groups [303,387,392,393]. In each case, there was an
increase in apparent activation energy when the inert (N
2
) atmo-
sphere was replaced with an oxidative environment. Excluding
the extraordinary 1429% increase in E given by Roque-Diaz et al.
[303], the average increase in E
a
on the basis of ve studies by
these four groups was 47% with a standard deviation of 17%. Nassar
[298,385,392] conducted his bagasse pyrolysis experiments under
two different types of inert atmosphere (N
2
and He). The E
a
val-
ues recorded for pyrolysis under nitrogen were 87.9kJ mol
1
and
46.7kJ mol
1
for the low and high temperature regions, respec-
tively, while the corresponding E
a
values obtained for pyrolysis
under helium were 118.1kJ mol
1
and 69.1kJ mol
1
, respectively.
These results suggest that the type of inert atmosphere also has
an impact on the apparent activation energy of sugarcane bagasse.
This is consistent withndings inliterature that report a shift inthe
DTA and DTG peaks toward higher temperatures as the molecular
weight of the inert gas increases [138,398].
The last set of kinetic data given for oxidative pyrolysis in
Table 9 was obtained from non-isothermal thermogravimetric
experiments run at different heating rates using unwashed bagasse
and then estimated as a function of temperature using the V iso-
conversional technique [135]. The rst E
a
value (76.1kJ mol
1
)
reported occurs in the region of 25% bagasse conversion (i.e.,
T <200
CT 350
C),
where there is 1560% bagasse conversion. The nal step involves
the secondary combustion of the initial pyrolysis products (i.e.,
400
CT 600
Cmin
1
(E
a
=59.5kJ mol
1
, A=1.1010
4
s
1
) [391]
and for a slow pyrolysis (Table 8) at 10
Cmin
1
(E
a
=215kJ mol
1
,
A=2.5110
15
s
1
) [125] returns values of 1.4s
1
and 23s
1
,
respectively, which is a factor of almost 16. Although it could
ordinarily be surmised from the above result that rapid pyroly-
sis processes have much lower rate constants than slow pyrolysis
reactions, the capriciousness of the data indicates otherwise. The
above conjecture is proven to be incorrect when the theoretical
rate constant at 800K calculated for ultrafast bagasse pyroly-
sis (Table 10) at heating rates between 60,000 and 600,000
C
min
1
(E
a
=54.0kJ mol
1
, A=3.3110
3
s
1
) [391] and that for a
moderately slow pyrolysis (Table 8) conducted at 50
Cmin
1
(E
a
=52kJ mol
1
, A=5.5010
2
s
1
) [386] are compared, providing
2
2
J
.
E
.
W
h
i
t
e
e
t
a
l
.
/
J
o
u
r
n
a
l
o
f
A
n
a
l
y
t
i
c
a
l
a
n
d
A
p
p
l
i
e
d
P
y
r
o
l
y
s
i
s
9
1
(
2
0
1
1
)
1
3
3
Table 8
Kinetic parameters for slow pyrolysis of sugarcane bagasse under an inert atmosphere.
Cmin
1
)
Sample mass
(mg)
Particle size
(mm)
Temp. range
(
C)
Reaction
model
n Ea
(kJ mol
1
)
logA
(s
1
)
Apparatus Region Refs.
Nitrogen atmosphere
5 18 0.8411.00 RT800 Sequential
(dual-step)
1 87.9 (225350)
a
46.7 (380560)
b
4.60
a,c
0.22
b,c
CST Stona Premco
Model 202 DTA
Model 1050 TGA
Egypt [392]
5 10 0.251.2 RT900 Parallel
(3 reactions)
1
1
3
194.0 hemicellulose
243.3 cellulose
53.6 lignin
15.7
18.0
1.9
Cahn TG-151
Tucumn,
Argentina [97]
5
d
10 0.251.2 RT900 Parallel
(3 reactions)
1
1
3
200.0 hemicellulose
249.6 cellulose
58.2 lignin
15.7
18.0
2.3
Cahn TG-151
Tucumn,
Argentina [97]
10 RT1500 Single-step 1 460.6 2.58 Netzsch STA 409
PC Luxx
Tanzania [207]
10
e
2 <0.2 RT500 Initial rate
(single-step)
1 63 (220260) 2.70
c
Mettler-Toledo
TGA/SDTA 851e
Hawaii [393]
10/20
f
57 <0.3 RT105950 Sequential
(triple-step)
0.5 58 (216445) Shimadzu TGA-50 C Punjab,
Pakistan
[387]
10/20
f
57 <0.3 RT105950 Sequential
(triple-step)
0.5 71 (214424) Shimadzu TGA-50 S Punjab,
Pakistan
[387]
20 10 0.251.0 RT900 Parallel
(3 reactions)
1
1
3
198.0 hemicellulose
246.5 cellulose
57.3 lignin
15.67
18.00
2.58
Cahn TG-151 Tucumn,
Argentina
[394]
20
d
10 0.251.0 RT900 Parallel
(3 reactions)
1
1
3
202.4 hemicellulose
253.5 cellulose
52.3 lignin
15.43
18.09
2.28
Cahn TG-151
Tucumn,
Argentina
[394]
50 10 0.0370.044 25450 Single-step 1 49
g
2.75 Netzsch STA 409 Tucuman,
Argentina
[395]
50 10 0.0370.044 25900 Singlestep 1 52
h
2.74 Netzsch STA 409 Tucuman,
Argentina
[395]
215
i
810 0.5950.841 25800 Model-free
j
168.5 Friedman
169.5 FWO
168.7 CR*
161.1 KAS
TA Instrument
TGA Q50
Louisiana [245]
140
k
10 0.450 201000 Differential
l
Parallel/Serial
(3 reactions)
1 250 hemicellulose
125 cellulose
60 lignin
TA Instrument
TG/DTG Q500
Tamaulipas,
Mexico
[370]
550
m
4.37.5 0.0640.076 RT800 Single-step 1 93.2 (195395) 5.64 DuPont 951 TGA/
Dupont Series 99
Thermal Analyzer
Queensland,
Australia
[390]
10 4 0.4501.00 RT600 Parallel
(3 reactions)
1 235 hemicellulose
105 cellulose
26 lignin
17.71
7.43
0.78
Seiko SSC/5200
TG/DTA 220
Clewiston,
Florida
[382]
20 4 0.4501.00 RT600 Parallel
(3 reactions)
1 235 hemicellulose
105 cellulose
26 lignin
17.62
7.52
0.42
Seiko SSC/5200
TG/DTA 220
Clewiston,
Florida
[382]
40 4 0.4501.00 RT600 Parallel
(3 reactions)
1 235 hemicellulose
105 cellulose
26 lignin
17.48
7.58
0.18
Seiko SSC/5200
TG/DTA 220
Clewiston,
Florida
[382]
60 4 0.4501.00 RT600 Parallel
(3 reactions)
1 235 hemicellulose
105 cellulose
26 lignin
17.50
7.67
0.08
Seiko SSC/5200
TG/DTA 220
Clewiston,
Florida
[382]
Helium atmosphere
5 18 0.8411.00 RT800 Sequential
(dual-step)
1 118.0 (RT350)
69.0 (350800)
CST Stona Premco
Model 202 DTA
Model 1050 TGA
Egypt [298]
10 RT800 Sequential
(multi-step)
0.1
1
0.4
1
21.0 (110170)
14.0 (170250)
64.0 (250310)
188.0 (310380)
DuPont 1090
Thermal Analyzer/
MOM OD-130
Cuba
[303]
[396]
Argon atmosphere
10 12 RT450
n
Parallel
(3 reactions)
(1)
o
215
p
15.4 Perkin Elmer TGS-2 Hawaii [241]
J.E. White et al. / Journal of Analytical and Applied Pyrolysis 91 (2011) 133 23
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values of 0.99s
1
and 0.22s
1
, respectively. Not only are the rate
constants much closer but this comparison would lead to the spu-
rious conclusion that rate constants obtained from fast pyrolysis
are larger than those from slow pyrolysis; exactly contrary to the
earlier hypothesis.
8.4. Suggestions for mitigating inconsistencies in kinetic triplet
data
Irrespective of the multiple causes, the incongruence among the
kinetic parameters clearly reects the need for a more uniform
approach toward the kinetic analysis of biomass pyrolysis, espe-
cially one that minimizes the substantial impact that experimental
conditions can have upon the process chemistry, physical proper-
ties of the biomass substrate, and systematic experimental errors.
Vrhegyi [80] has recently proffered a list of suggestions to cir-
cumvent the evaluative quandary posed by changing experimental
conditions, viz.,
(1) The experiments can be evaluated simultaneously by the
method of least squares and using exactly the same kinetic
parameters [49,87,189,214,257].
(2) Additional terms can be included in the kinetic model (i.e., sim-
ilar to the general description approach used in the SB model)
to describe the systematic experimental errors [51]. Again, the
inclusion of too many terms may lead to strong interdepen-
dencies among the kinetic parameters that can obscure their
physical signicance and also complicate the numerical solu-
tion of the model.
(3) A few parameters can be allowed to oat, while the remain-
ing parameter(s) is/are held constant [249,312]. This technique
can help assess model validity over a specied range of exper-
imental conditions.
(4) Each experiment can be evaluated individually so that com-
parisons can be made among the resulting kinetic parameters
[214,248,249,399]. This procedure requires a comprehensive
experimental design that will permit collection of sufcient
data to determine the unknown parameters.
Aiman and Stubington [390] emphasized that the derived
kinetic parameters arehighlysensitivetothevalueof w
f
that is used
calculate the degree of conversion. Drummond and Drummond
[383] concludedthat the use of different heating rates canaffect the
kinetic parameters obtained for the pyrolysis of sugarcane bagasse.
These conclusions might now be amended to accurately reect
the kinetic triplets dependence on differences in the chemical and
physical properties of thepyrolyzedbagasse(e.g., moisture, particle
size, sugarcane variety, and lignocellulosic composition), different
operating conditions (e.g., heating rate, temperature range, process
atmosphere, sample size, and isothermal or non-isothermal oper-
ational mode), experimental systematic errors (e.g., thermocouple
and reaction thermal lag), the kinetic model selected, the mathe-
matical approximations employed in these models, and the criteria
used to evaluate the endpoint (i.e., w
f
) of pyrolytic reactions.
8.5. Evaluation of kinetic compensation effect for sugarcane
bagasse data
Acomprehensive survey of the published kinetic data for sugar-
cane bagasse pyrolysis would be incomplete without ascertaining
the existence of a KCE between the variables lnA and E. The
data used to construct the KCE plot in Fig. 4 was obtained from
Tables 810 using only those investigations whose activation ener-
gies and frequency factors were evaluated using rst order models.
A few important caveats are specied forthwith regarding the
2
4
J
.
E
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W
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1
(
2
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1
1
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1
3
3
Table 9
Kinetic parameters for slow pyrolysis of sugarcane bagasse under an oxidative atmosphere.
Cmin
1
)
Sample mass
(mg)
Particle size
(mm)
Temp. range
(
C)
Reaction
model
n Ea
(kJ mol
1
)
logA
(s
1
)
Apparatus Region Refs.
Air atmosphere
5 18 0.8411.00 RT800 Sequential
(dual-step)
1 139.7 (RT360)
76.6 (360800)
CST Stona Premco
Model 202 DTA
Model 1050 TGA
Egypt [298]
5
a
0.2500.420 RT480
b
Sequential
(multi-step)
1 53.6 (212380) 2.90 Netzch 348472c Egypt [397]
5
c
0.2500.420 RT480
b
Sequential
(multi-step)
1 38.5 (220430) 1.54 Netzch 348472c Egypt [397]
10 RT800 Sequential
(multi-step)
0.84
0.36
0.90
1.00
0.62
34.0 (20110)
46.5 (110170)
214.0 (170245)
74.8 (245380)
33.2 (380600)
DuPont 1090
Thermal Analyzer/
MOM OD-130
Cuba [303]
[396]
10/20
d
57 < 0.3 RT105950 Sequential
(triple-step)
0.5 75 (226350) Shimadzu TGA-50 C Punjab,
Pakistan
[387]
10/20
d
57 < 0.3 RT105950 Sequential
(triple-step)
0.5 116 (247357) Shimadzu TGA-50 S Punjab,
Pakistan
[387]
Oxygen atmosphere
10
e
2 <0.200 RT500 Initial rate
(single-step)
1 78 (220260) 2.95
f
Mettler-Toledo
TGA/SDTA 851e
Hawaii [393]
520 12 251000 Model-free
g
76.1 (25100)
333.3 (200350)
220.1 (400600)
Mettler-Toledo
TGA/SDTA 851e
DSC 822e
Olimpia,
SP, Brazil
[135]
a
Values reported are for bagasse holocellulose.
b
Estimated from DTG curve plots.
c
Values reported are for bagasse hemicellulose.
d
10
Cmin
1
ramp from RT to 105
Cmin
1
ramp from 105
C to 950
C
m
i
n
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s
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(
C
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E
a
(
k
J
m
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A
(
s
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A
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.
Fig. 4. Compensation plot for Arrhenius parameters obtained from sugarcane
bagasse pyrolysis data listed in Tables 79.
treatment of the data. A single set of averaged lnA values was
used for the data supplied by Garcia-Perez et al. [382]; the datum
point from Wilson et al. [207] was rejected from the analysis
because of its anomalously high E
a
value (460.6kJ mol
1
) at a
relatively low lnA value (5.94s
1
). The remarkably linear relation-
ship between lnA and E in Fig. 4 (i.e., coefcient of determination
equal to 0.972) would seem to imply the existence of a KCE. How-
ever, the plot in Fig. 4 contains several important assumptions
regarding the data used therein. Namely, it is assumed that a
valid kinetic conversion function was chosen and that the data
is free of computational, experimental, and instrumental errors.
If none of these assumptions is violated, then the only possi-
ble conclusion that can be drawn from Fig. 4 is that there is an
apparent KCE.
However, an Arrrhenius plot, as shown in Fig. 5, is required to
establish whether the necessary criterion met by the data in Fig. 4
is indeed sufcient to conrm an actual KCE in the pyrolysis of
sugarcane bagasse. The Arrhenius plot in Fig. 5 consists of a sub-
set of data from Fig. 4 because valid temperature ranges were not
available for all of the calculated activation energies. The lack of a
common isokinetic point in the Arrhenius plot indicates that the
linear relation between lnA and E
a
in Fig. 4 is spurious and repre-
sentative of a pseudoKCE. This reviewer does not ndthe preceding
result entirely unexpected given the tremendously diverse testing
conditions employed in the sugarcane pyrolysis reactions surveyed
in this paper.
9. Recommendations
The gross disparities evidenced in the kinetic data fromthe nut-
shells and sugarcane bagasse are representative of the ambiguous
kinetic results that have paralyzed the broader biomass pyrolysis
community. In the rush to identify the culprits behind this shifty
data, another skulking variable is frequently forgotten: the het-
erogeneity of the biomass itself. Such inconsistencies demonstrate
the need to reassess the fundamental principles and phenomena
underlying biomass thermal degradation. In particular, the identi-
cation and improved control of all possible experimental factors
(seen and unseen) that may regulate the behavior of solid state
reactions is imperative. Moreover, elucidation of reaction mecha-
nisms for solidstate thermal processes cannot occur unless thermal
analysis is used in tandem with an ancillary analytical tool that
can evaluate the chemical composition and structure of evolved
products, suchas FTIR[12,233,400,401], GC[84,108,402,403], HPLC
26 J.E. White et al. / Journal of Analytical and Applied Pyrolysis 91 (2011) 133
Fig. 5. Arrhenius plot for a subset of data shown in Fig. 4 illustrating the absence of a true compensation effect for sugarcane bagasse pyrolysis. The labels for the individual
lines refer to the references cited in Tables 79. Lines from reference sources containing more than one data pair are labeled in order of appearance from Tables 79 (e.g.,
[399-2] refers to the second set of data from Ref. [399]). Lines from reference sources containing Arrhenius parameters for multiple reactions or lignocellulosic components
are also listed in order of appearance of the respective reactions or components (e.g., [366-2c] refers to the third component from the second set of data for Ref. [366]).
[12], MS [311,401,404,405], GCMS [305], and scanning electron
microscopy (SEM) [53,211].
Extravagant mathematical manipulations of kinetic data will
do nothing to further the understanding of the fundamental
physicochemical mechanisms that govern the thermal decompo-
sition of biomass. Elaborate models that integrate reaction kinetics
with transport phenomena are often developed in a theoreti-
cal vacuum that fails to properly account for the myriad factors
involved in actual pyrolysis reactions. Application of these intrin-
sically incomplete models to industrial processes is constrained
by idealized assumptions that are not valid under a bona de
pyrolytic environment. Furthermore, the use of numerous input
variables that cannot be measured accurately presents an engi-
neering nightmare. Antal and Vrhegyi [241] commented that
the best approach to modeling the kinetic behavior of single,
macroscopic biomass particles may involve statistical methods
developedbyKrieger-Brocketts laboratory[406,407] that correlate
kinetic data fromjudiciouslydesignedexperiments using empirical
methods.
It has been suggested that the existing body of heterogeneous
kinetic data is so hopelessly awed that much of it should simply
be relegated to a circular le [182]. The current authors strenu-
ously oppose the notion that previously collected data should be
dismissed as rubbish. Although it is possible that the analytical
treatment of such data was unsound, the data itself should be pre-
served. Discarding old empirical data to make roomin the kinetics
cupboard is not a viable solution, and it disregards the possibil-
ity of future advances in heterogeneous kinetics theory that may
afford the opportunity to accurately interpret the kinetic behavior
of re-examined data. Nevertheless, the current authors can appre-
ciate the paucity of reliable kinetic data in the current literature;
it is true that kinetic parameters drawn from the raw data may
indeed be unsalvageable. Still, it would be premature to discard
these awed kinetic triplets before agreement can be achieved
regarding which mathematical methods are truly inappropriate
and, ergo, which kinetic results are also incorrect.
Although integral isoconversional techniques (i.e., CR*, FWO,
KAS, and V) appear to provide reasonably consistent results for the
kinetic triplet in certain controlled situations, it remains unclear
whether these isoconversional methods can be used reliably to
compare kinetic data obtained from identical biomass species
tested under similar, yet not identical, conditions. Regrettably,
there appears to be a perception that the current concepts used
to describe biomass pyrolysis kinetics are satisfactory. Perhaps the
eld of solid state kinetics has become somewhat jaded after all the
years of acrimonious and incisive debate regarding the competi-
tion between isothermal and non-isothermal kinetic techniques.
Nevertheless, there is also a growing undercurrent of exasperation
in the biofuels community regarding the failure of modern kinetic
theory to accurately predict the pyrolytic behavior of biomass.
A literature survey [38] of the apparent activation energies for
wood and cellulose pyrolysis reactions reveals an E
a
range of
15217kJ mol
1
for woodand109251kJ mol
1
for cellulose; a sit-
uation which is described as very unsatisfactory and that needs
to be claried. This annoyance is further compounded by the
inability to use the resulting kinetic data for comparative evalu-
ations between different biomass feedstocks under similar process
conditions or identical biomass species under different operating
conditions. Maciejewski and Reller [106] recognized that interest
in the course of solid state thermal decomposition processes is
spurred in part by the desire to obtain . . .kinetic and mechanistic
data [that] could be of great help in accurate process control. . . A
subsequent paper by Maciejewski [138], however, concludes that
if . . .for whatever reason, the quantitative characterization of the
process is required, it is necessary to treat the kinetic parame-
ters as mathematical numbers only, which describe the course of
the reaction under particular conditions, but which do not have
particular signicance and are not intrinsic to the investigated
compound. Obviously, this paradoxical disconnect between the
needs of industry and the exclusivity of the kinetic data obtained
fromsolid state reactions is problematic. Thermochemical biomass
conversion facilities often operate using variable feedstocks under
different operatingconditions. It is naivetoassumethat suchindus-
trial systems can be optimized without the use of generalized
correlations to predict the kinetic behavior of different biomass
materials under various processing environments. Font et al. [408]
recognized the industrial importance of being able to compare
kinetic rate constants and devised a convenient, yet seldom used
J.E. White et al. / Journal of Analytical and Applied Pyrolysis 91 (2011) 133 27
[409], comparison factor to relate rate constants having similar
activation energy and reaction order.
Underlying principles in solid state reaction theory need to be
thoroughly re-evaluated and those that are unsound should be dis-
carded. The venerability and prior adequacy of certain constructs,
including the Arrhenius rate law, should not be used as justica-
tionfor their continuedpresenceinkinetic expressions. At thesame
time, it may be appropriate to revisit generalized kinetic equations
that permit additional process factors to be introducedinto the the-
oretical model. In addition, the use of novel kinetic approaches that
t data according to semi-empirical and logistic models may help
identify phenomenological regularities and patterns present in the
measurements [173,400,410].
10. Conclusion
The chaos insolidstate reactionkinetics has spilledover intothe
biomass pyrolysis community and continuation of the status quo
is utterly unacceptable. Ultimately, the thermal analysis commu-
nity may have to further probe troublesome reaction systems on
an individual basis to develop rate equations specic to each one
[102]. It was the long-suffering work of Bodenstein on the gaseous
reaction between bromine and hydrogen that led to his discovery
of the unique rate equation for hydrogen bromide formation [411].
In conclusion, a few memorable quotations found in Churchills
engrossing book, The Interpretation and Use of Rate Data: The Rate
Concept [412] are betting of the quandaries confronting the eldof
solid state reaction kinetics: It is a condition that confronts us not
a theory President Grover Cleveland; No satisfactory justication
has ever been given for connecting in any way the consequences of
mathematical reasoning with the physical world Bell; Life is the
art of drawing sufcient conclusions from insufcient premises
Samuel Butler; Close to the western summit there is the dried and
frozen carcass of a leopard. No one has explained what the leop-
ard was seeking at that altitude Ernest Hemingway in The Snows of
Kilimanjaro.
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