Fuel 80 (2001) 1245±1258

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Co-pyrolysis of sugarcane bagasse with petroleum residue.

Part I: thermogravimetric analysis
M. GarcõÁa-PeÁrez a, A. Chaala a, J. Yang a, C. Roy a,b,*
a
DeÂpartement de geÂnie chimique, Universite Laval, Ste-Foy, P. Que., Canada G1K 7P4
b
Institut Pyrovac Inc., 333 rue Franquet, Ste-Foy, P. Que., Canada G1P 4C7
Received 1 July 2000; revised 6 December 2000; accepted 6 December 2000

Abstract
Thermal decomposition under nitrogen of sugarcane bagasse, petroleum residue and their blends was studied by thermogravimetry (TG) at
different heating rates (10, 20, 40 and 608C/min). Thermal decomposition kinetic parameters were determined. Sugarcane bagasse pyrolysis
was described as the sum of cellulose, hemicellulose, and lignin individual contributions. First order equations were used to determine the
bagasse component thermal decomposition kinetics. Activation energies calculated were 235, 105, and 26 kJ/mol for cellulose, hemicellu-
lose and lignin, respectively. Thermal decomposition of petroleum residue can be explained by the additive effect of its three major fractions,
following kinetic equation orders of 2.5, 2.3 and 1.5 with activation energies of 100, 180, and 220 kJ/mol, respectively. It has been found that
during thermal decomposition of bagasse/petroleum residue mixtures, no signi®cant interaction occurred in the solid phase between the
components under the experimental conditions investigated. The kinetic parameters associated with the bagasse/petroleum residue mixture
involved the sum of bagasse and petroleum residue individual component kinetic parameters. The information obtained can be used to
develop a correlation between the thermogravimetric data and the feedstock composition. q 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Co-pyrolysis; Bagasse; Petroleum residue; Bitumen

1. Introduction ogy for the conversion of sugarcane bagasse to charcoal and

Biomass ranks fourth as an energy resource on a global
basis, providing approximately 14% of the world energy
needs. In developing countries, biomass often accounts for
approximately 35% of the energy consumed [1]. The esti-
mates vary considerably, from as little as 5% of the total
energy in Argentina to over 95% in several African
countries. Overall in Africa about 2/3rds of the energy
consumed is from biomass, about 1/3rd in Asia, and 1/4th
in Latin America [2]. In rural areas of these countries,
biomass is often the only accessible and affordable source
of energy. Sugarcane is the world's largest agricultural crop.
Located in tropical and subtropical areas of the world, over
1200 sugarcane factories in 80 countries grind and process
nearly 800 Mt of sugarcane [3,4]. Crushing 1000 kg of
sugarcane produces approximately 255 kg of moist bagasse
(50 wt% moisture content).
A new generation of advanced thermal processes favour-
ing the chemical and energy upgrading of biomass have
been developed. Pyrolysis seems to be a promising technol-
* Corresponding author. Tel.: 11-418-656-7406; fax: 11-418-656-2091.
E-mail address: croy@gch.ulaval.ca (C. Roy).
0016-2361/00/$ - see front matter q 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0016-236 1(00)00215-5
oil [5±9]. The industrial development of thermochemical
installations for biomass conversion will require, however,
a better knowledge of the governing pyrolysis parameters
and their effects on the process kinetics.
The co-pyrolysis of biomass with petroleum residues
could potentially be a good solution to improve the bio-oil
quality. The high sulphur content of petroleum residues, the
undesirable ash content and low pH of pyrolytic bio-oils
might all be mitigated if biomass and petroleum residues
are mixed together before being subjected to pyrolysis. On
the other hand the presence of petroleum residue in a
biomass feedstock could improve the reactor feeding
process, leading to an increased reactor throughput capacity.
The purpose of this study is to investigate the presence of
possible synergetic phenomena that may occur during the
co-pyrolysis of sugarcane bagasse with petroleum residue,
while Part II focuses on fuel properties of the composite oils
and charcoals obtained.
Dif®culties arising from the complex composition of
lignocellulosic and petroleum residue materials, as well as
from the large number of complex reactions involved in the
pyrolysis process, make it dif®cult to achieve a precise
model describing pyrolysis mechanisms. To obtain some
1246 M. GarcõÁa-PeÁrez et al. / Fuel 80 (2001) 1245±1258
kinetic parameters, thermogravimetric analysis (TG) has
been used extensively. The kinetic parameter calculations
are based on simpli®ed assumptions which do not neces-
sarily relate to the real complex chemical reactions.
However, the data provide a useful comparison of reaction
parameters such as temperature and heating rate [10±12].
1.1. Biomass thermal decomposition
A broad outline of the kind of transformations occurring
during biomass pyrolysis can be obtained from mechanisms
proposed by Sha®zadeh, Broido and Koufopanos [13,14].
Some of these physical and chemical models were devel-
oped as theoretical tools to describe the product yields
during the pyrolysis process. These models provide a unique
theoretical tool for mathematical model developers and
are useful for reactor designers. No accurate physical or
chemical models are available to explain the effect of the
pyrolysis operating conditions on the pyrolytic oil chemical
composition.
The large majority of the kinetic studies that are available
for biomass and petroleum residues point to a poor ®t of
single reaction models with a constant activation energy
over the whole conversion range. Assumptions are
frequently included in the calculations in order to obtain
an acceptable ®t to the experimental results [15,16]. An
alternative solution consists of using a single reaction
model with the activation energy as a conversion function
[16±19]. The most recent and realistic approaches use a
model with parallel independent reactions to describe the
biomass kinetics behaviour [13,20±22]. Pine wood, bark,
eucalyptus wood, hazelnut, rice husk, rice straw and sugar-
cane bagasse are among the most common biomasses inves-
tigated [17,20±23].
Several kinetic studies have pointed out the existence of
slight interactions between cellulose, hemicellulose, extrac-
tives and lignin during biomass thermal decomposition,
indicating that the biomass pyrolysis behaviour is not a
simple additive function of each contributing fraction
[12,24,25]. In TG±DTG analysis of lignocellulosic materi-
als two or three peaks appear. These peaks can be assigned
to cellulose, hemicellulose and lignin indicating that
although there are interactions between fractions, their
basic identity is maintained [12,24]. Several studies have
been performed in order to determine the kinetics of the
individual fractions composing biomass [13,22,26±29].
Several studies using lignin model compounds [30±34]
have been carried out to investigate the splitting mechanism
of various chemical bonds. The most frequently studied
reaction is the thermal scission of the a and b alkyl aryl
ether bonds due to their prominent role in lignin chemistry.
Yet the predominant chemical mechanism governing forma-
tion of the major volatile products from cellulose and hemi-
cellulose pyrolysis cannot be stated with con®dence [35,36].
Generally the thermolysis reactions of polysaccharides can
be divided into cleavage of glycosidic, C±H, C±O, and
C±C bonds, dehydration, decarboxylation, decarbonylation
reactions, formation C±C, CyC, C±O bonds as well as
carbonyl and carboxyl groups.
Bilba and Ouensanga [37] studied the thermal degrada-
tion of sugarcane bagasse using the data provided for solid
FTIR analysis. The data suggested that structure modi®ca-
tions appeared at 2008C and intensi®ed between 300 and
4008C. These changes were characterised by the decrease
of O±H, C±O, CyC peak intensities and the formation of
alkyl bonds. Between 300 and 4008C, the dehydration reac-
tions of the sugarcane bagasse components is predominant.
It has been found that at intermediate temperatures (300±
3208C) the dehydration of carbohydrates is favoured, while
higher temperatures (340±3808C) facilitate the dehydration
of lignin [37]. Further heat treatment leads to saturation of
aromatic rings, rupture of the C±C linkages present in
lignin, water, CO and CO2 release and rearrangement of
carbohydrates and lignin structures. A high heating rate
seems to be favourable for the release of hydrogen and
hydrocarbon molecules.
1.2. Petroleum residue thermal decomposition
Kinetics studies of petroleum residue and its components
such as maltenes and asphaltenes are detailed in the litera-
ture [16,38,39]. Pyrolysis of hydrocarbons usually starts
with the cracking of high molecular weight non-aromatic
hydrocarbons. During thermal decomposition of petroleum
residue, cracking and polycondensation reactions occur
together. The cracking reactions are responsible for volatile
material generation, while polycondensation reactions
favour the formation of carbonaceous materials (coke).
Thermal stability of the aliphatic hydrocarbons decreases
when the chain length increases. The stability of aromatics
increases with the increase in ring number. It has been
shown that the C±H bond is more stable than the C±C
bond. The acetylene bond (CxC) exhibits a bonding energy
higher than that of ethylene bond (CyC). This explains the
dehydrogenation tendency of aliphatic hydrocarbon towards
ole®ns and acetylene at high temperature. Thus, the yield of
volatile matters will increase as long as aliphatic hydro-
carbons are present in the petroleum residue. Polycondensa-
tion reactions lead to the formation of mesophase structures
with a progressive increase of the structural order until coke
is obtained. This may be due to the increase of the resonance
energy which is considered to be the driving force for the
polycondensation reactions.
It has been reported that the average activation energy
related to cracking reactions was approximately 231 kJ/
mol [40]. The same author suggested an activation value
of approximately 197 kJ/mol for the condensation reactions.
Jimenez-Mateos et al. [39] separated the oil into two
primary fractions: asphaltenes, and maltenes. The maltene
fraction was further separated by chromatographic methods
into saturated compounds, aromatics and resins. Stability
generally increases in the order: saturates, aromatics, resins,
 M. GarcõÁa-PeÁrez et al. / Fuel 80 (2001) 1245±1258 1247

Table 1
Elemental composition (wt% on organic basis) and proximate analysis
(wt% anhydrous basis) of the bagasse feedstock
C H N Oa Volatile matter Fixed carbon
49.6 6.0 0.5 43.9 82.1 16.3
a
By difference.
asphaltenes. It has been reported that during liquid phase
pyrolysis under atmospheric pressure, only aromatics
containing more than 14 carbon atoms can undergo crack-
ing. Aromatic hydrocarbons containing more than 30 carbon
atoms decompose prior to evaporation [41].
No previous work relating to the kinetics of sugarcane
bagasse/petroleum residue co-pyrolysis has been reported to
our knowledge in the literature. The present work has been
carried out in order to understand and predict the yield and
quality of the products generated by bagasse and petroleum
residue co-pyrolysis. To achieve this goal, a TG analysis of
bagasse, petroleum residue and their mixtures has ®rst been
performed. Whether a correlation exists between the experi-
mental data and the simulated results will be investigated to
detect any possible synergetic phenomena.
shown in Table 1. The sieved bagasse was milled into ®ne
powder (diameter less than 1 mm) in order to perform the
TG analysis.
Ash
2.1.2. Petroleum residue
1.6
The petroleum residue tested in this study was graciously
supplied by Shell Canada, MontreÂal. The petroleum residue
was a 150/200 penetration grade bitumen. It contained
76.9 wt% maltenes, 23.0 wt% asphaltenes and 0.1 wt%
toluene insoluble. Its main characteristics are presented in
Table 2. The bitumen material was assumed to be equivalent
to a heavy crude oil.
2.2. Sample preparation
As the density of bagasse is very low compared to that of
petroleum residue, direct blending of the two materials in
order to obtain a homogeneous mixture is dif®cult. To avoid
this problem, the petroleum residue was ®rst dissolved in
toluene and then mixed with sugarcane bagasse. The
mixture was carefully stirred. The toluene was partially
removed from the mixture after 12 h under ambient condi-
tions. The remaining solvent was eliminated by heating at
1068C for 10 h.

2.3. Thermogravimetric analysis

2. Experimental
A SSC/5200 TG/DTG (220) microbalance from Seiko
2.1. Materials was used for the thermogravimetric tests. The apparatus
uses a horizontal differential balance mechanism. The
2.1.1. Sugarcane bagasse samples were heated from room temperature to 6008C,
The sugarcane bagasse was graciously provided by the under a nitrogen ¯ow of 150 ml/min at constant heating
United States Sugar Corporation, Clewiston, Florida. The rate. Samples of approximately 4 mg were used in order
moisture content of the as-received sample was approxi- to ensure a decomposition process controlled by the chemi-
mately 46 wt%. The sample was air-dried to 6.1 wt% for cal kinetics.
the pyrolysis tests. The bagasse was sieved and the particles
with a size smaller than 0.450 mm, representing 7 wt% of
total bagasse, were removed due to their high ash content. 3. Results and discussion
This eliminated approximately 35 by wt% of the total ash
present in the feedstock. Elemental and proximate analyses 3.1. Thermogravimetric analysis of sugarcane bagasse
of the bagasse remaining fraction used in this study are
The DTG and TG curves of sugarcane bagasse with
Table 2 particle size larger than 0.450 mm performed at different
Petroleum residue properties heating rates are presented in Figs. 1 and 2. It is shown
that bagasse thermal decomposition seems to be a gradual
Penetration at 258C (1/10 mm) 163
Kinematic viscosity at 1358C 185 process with no clear steps in the TG curves. However, two
(cSt) overlapping peaks can be clearly observed on the DTG
curves. The ®rst peak corresponds to hemicellulose
Elemental composition (wt%)
C 82.83 (2998C) and the second one corresponds to cellulose
H 10.02 (3518C). The peak corresponding to lignin is completely
N 0.74 overlapped by the other two peaks. The TG curve shows
S 6.00 that at 108C/min, the bagasse thermal degradation started at
O (by difference) 0.41
2008C. The cellulose thermal degradation was almost
Generic composition (wt%) complete at approximately 3738C. At higher temperatures,
Asphaltenes 23.0 slight weight losses caused by the lignin decomposition
Maltenes 76.9
reactions were observed. At higher heating rate the maxi-
Toluene insolubles 0.1
mum degradation rate shifted from 3518C at 108C/min to
1248 M. GarcõÁa-PeÁrez et al. / Fuel 80 (2001) 1245±1258

Fig. 1. Sugarcane bagasse …d . 0:450 mm† DTG curves at different heating rates.

3858C at 608C/min. The TG curves obtained at different The overall activation energy does not change drastically
heating rates approached a common value, approximately (150±200 kJ/mol) over a wide range of conversions (Fig. 4).
16 wt%, for the charcoal generated except at 608C/min These results indicate that the pyrolysis occurs through the
where the charcoal yield was approximately 20 wt% cleavage of linkages with similar energy bonds.
(Table 3). Similar results were reported by Teng and Wei The pyrolysis rate of bagasse was assumed to be the sum
[42] and Caballero et al. [12] for rice hulls and olive stones, of its component pyrolysis rates (Fig. 5). According to this
respectively. formulation each component (cellulose, hemicellulose, and
A TG study consists of performing a kinetic analysis lignin) proportionally contributes to the global process. The
which includes weight loss curves obtained at different heat- equations generally used to describe the thermal decompo-
ing rates in order to deduce the dependence of the kinetic sition of the individual fractions are:
parameters with the conversion. Friedman method is the
most common one used in this kind of kinetic studies. The da XN
d aj
ˆ zj0 …1†
Friedman plots are shown in Fig. 3. The downward in the dt jˆ1
dt
Friedman signature at higher heating rate can be attributed
to heat transfer problems. In the calculation of the overall
 
activation energy only the data corresponding to 10, 20 and d aj Ej
ˆ Aj exp 2 …1 2 aj †n …2†
408C/min were used. dt R£T

Fig. 2. Sugarcane bagasse …d . 0:450 mm† thermogravimetric analysis at different heating rates.
 M. GarcõÁa-PeÁrez et al. / Fuel 80 (2001) 1245±1258 1249

Table 3 The thermal decomposition kinetic parameters of bagasse

TG results for sugarcane bagasse at different heating rates (T0 is the components were determined using Eqs. (1)±(5). The
temperature corresponding to 1 wt% of dry material weight loss, Tf the
®nal temperature of cellulose degradation, TP the peak temperature corre-
values obtained at different heating rates are summarised
sponding to a maximum weight loss for hemicellulose and cellulose, in Table 4. Small changes are observed in the pre-exponen-
respectively, and Rs the ®nal residue) tial factor and the volatile fraction corresponding to each
individual macro-component. These changes may be due to
Temperature (8C) 108C/min 208C/min 408C/min 608C/min
the thermal lag in¯uence. Similar results have been reported
T0 199 207 215 215 [12,28,44]. Disagreements reported in the literature
Tf 373 385 407 414 [10,11,20±22,28,29,42,45±51] concerning the rate of cellu-
TP1 299 310 324 329 lose, hemicellulose and lignin thermal decomposition
TP2 351 364 378 385
kinetics parameters can be analysed in Fig. 6. Some repre-
%Rs 16.2 15.7 15.6 20.4
sentative values are equally presented in Table 5. It is inter-
esting to note that the values of E and ln A changes in such a
X
N way that their ratio remains constant (Eq. (5)). Chornet and
zj0 ˆ 1 …3† Roy [51] called attention to this phenomenon, known as the
iˆ1 `compensation effect'.

…Wj0 2 Wj1 † ln A ˆ m £ E 1 ln k0 …5†

zj0 ˆ …4†
…W0 2 W1† where the parameters m and k0 become characteristics of the
group of reactions for which the compensation effect
where:
applies. The constant m, in Eq. (5), is related to the isoki-
da=dt instantaneous reaction rate netic temperature Ti (K) Ð the temperature at which all the
daj =dt instantaneous reaction rate for component j pyrolytic reactions within a given group proceed at the same
aj parameter de®ned as: aj ˆ …Wj0 2 Wj †=…Wj0 2 rate k0 Ð through the following expression:
Wj1 †
zj0 mass fraction of volatile materials from component Ti ˆ R21 £ m21 …6†
j
where R is the gas constant.
Aj pre-exponential factor corresponding to compo-
The calculated values of the isokinetic temperature for
nent j thermal degradation
hemicellulose, cellulose, and lignin are 273, 352 and
Ej activation energy corresponding to component j
3008C, respectively. To explain the compensation effect,
thermal degradation
Antal et al. [28] pointed out the thermal lag effect (differ-
W mass of solid residue
ences between the true value sample temperature and the
The procedure used to adjust the kinetic parameters (Ej, thermocouple temperature) on E and log A determinations.
Aj, z0j) has been reported by Yang et al. [43] and Miranda This thermal lag increased drastically with the heating rate
et al. [44]. [28].

Fig. 3. Friedman plots for bagasse thermal decomposition under nitrogen atmosphere.
1250 M. GarcõÁa-PeÁrez et al. / Fuel 80 (2001) 1245±1258

Fig. 4. Sugarcane bagasse and petroleum residue overall activation energy versus conversion (X).

Table 4 summarises the experimental values obtained for …Rs ˆ 1 2 X1 † can be determined experimentally (Table
the mass of volatiles corresponding to each of the bagasse 3) or by using Eq. (8):
fractions (zj0). In order to determine the initial biomass
X
N
composition (yj0), it is necessary to use Eq. (7). Therefore, X1 ˆ …yj0 £ Xj1 † …8†
the maximum volatile yields that can be obtained for each jˆ0
isolated fraction must be known.
zj0 £ X1 The cellulose volatile yield has been established in
yj0 ˆ …7† several papers, namely Varhegyi et al. [21] and Antal et
Xj1
al. [28]. In these studies, its value varied between 92 and
where: 97 wt% when the heating rate varied from 2 to 508C/min.
The volatile yield for the hemicellulose has been investi-
yj0 initial mass fraction of component j
gated by Varhegyi et al. [21], Orfao et al. [22] and Di Blasi
zj0 mass fraction of volatile material for component j
and Lanzetta [52]. They obtained values between 75 and
Xj1 maximum volatile yield corresponding to compo-
79 wt% over the same range of heating rates. According
nent j
to Jakab et al. [34], the lignin volatile yield varies between
X1 maximum volatile fraction, W0 2 W1=W0
61 and 74 wt% depending on the nature of the lignin
The biomass ®nal conversion X1 and the ®nal residue studied. It was established that lignins of low methoxy

Fig. 5. Sugarcane bagasse DTG curve at 108C/min.

 M. GarcõÁa-PeÁrez et al. / Fuel 80 (2001) 1245±1258 1251

Table 4
Parameters used in sugarcane bagasse DTG curves simulation

Component E (kJ/mol) log A (min 21) n Heating rate (8C/min) Weight

fraction of
released gases
(zj0) (%)

Cellulose 235 19.489 1.0 10 48

Hemicellulose 105 9.204 1.0 10 33.5
Lignin 26 1 1.0 10 18.5
Cellulose 235 19.398 1.0 20 48
Hemicellulose 105 9.301 1.0 20 33.5
Lignin 26 1.361 1.0 20 18.5
Cellulose 235 19.255 1.0 40 45
Hemicellulose 105 9.362 1.0 40 35.5
Lignin 26 1.602 1.0 40 19.5
Cellulose 235 19.279 1.0 60 44.5
Hemicellulose 105 9.447 1.0 60 36
Lignin 26 1.699 1.0 60 20

group content (guaiacyl lignins) produced the highest char
yield, whereas hardwood lignins with high methoxyl group
content yielded the lowest amounts of char. In the present
work the data provided by Orfao et al. [22], Antal et al. [28]
and Cozzani et al. [50] were used. They found maximum
volatile yields of 94, 79 and 74 wt% for cellulose, hemicel-
lulose and lignin, respectively, for a heating rate of 108C/
min under nitrogen.
According to the calculations performed using Eq. (8)
and the experimental values of zj0 and X1 obtained at
108C/min (Table 4), the bagasse composition (yj0) is
35.2 wt% of hemicellulose and extractives, 42.4 wt%
cellulose and 20.8 wt% lignin. These results were obtained
assuming an ash content in the biomass of 1.6 wt%. The
biomass ®nal conversion (83.1 wt%) calculated with Eq.
(9) was slightly lower than that obtained experimentally
(83.8 wt%). The difference may be due to experimental
errors, wrong assumptions, slight interactions or it could
be due to the ash catalytic effect as reported by Teng and
Wei [42]. The composition determined by this method is in
accordance with the typical values reported in the literature:
20±30 wt% hemicellulose, 35±50 wt% cellulose, 20±
27 wt% lignin, 8±12 wt% extractives (ether and alcohol
extractives, etc.) and 1±3 wt% ash [6,7,53,54]. These results
seem to con®rm that the method used is suitable for the
determination of bagasse composition.
3.2. Thermogravimetric analysis of petroleum residue
Thermal degradation of maltene and asphaltene fractions
have been performed. Their TG and DTG plots are
presented in Fig. 7. The kinetic parameters used to describe
the maltene and asphaltene behaviour are shown in Table 6.
The activation energy obtained for asphaltenes is in the
range reported by Calemma and Rausa [16], 230±270 kJ/
mol. The yield of coke obtained from the maltene fraction

Fig. 6. Cellulose, hemicellulose and lignin thermal degradation kinetic parameters reported in the literature. Compensation effect.
1252 M. GarcõÁa-PeÁrez et al. / Fuel 80 (2001) 1245±1258

Table 5
Literature review of some kinetic parameters for thermal degradation of biomass components under nitrogen

Biomass component E (kJ/mol) log A (min 21) Reference Biomass component E (kJ/mol) log A (min 21) Reference

Cellulose Hemicellulose
a-Cellulose 48.1 4.0 [51] Commercial xylan 42.63 2.77 [52]
a-Cellulose 55.6 4.0 [51] From pine bark 48.5 3.4 [22]
a-Cellulose 79.4 6.0 [51] Birch xylan 62.7 ± [29]
Cellulose triacetate 121±195 10.0±15.2 [49] Commercial xylan 71.89 6.08 [52]
Filter cotton (FC) 121±160 9.6±12.6 [49] From pine wood 72.8 4.2 [50]
Cellulose 125.4 9.6 [51] From eucalyptus 79.4 6.7 [22]
Cellulose diacetate 125±159 9.6±12.6 [49] From poplar wood 80.7 6.8 [50]
Cellulose 139.6 11.6 [51] Commercial xylan 86.11 7.66 [52]
a-Cellulose 146.3 11.6 [51] From pine wood 88.4 7.5 [22]
Cellulose R 150 ± [29] From almond shells 100±112 ± [46]
FC 151 11.73 [49] From beech 103.2 8.8 [50]
Cellulose 166.4 13.4 [51] From sugarcane bagasse 105±111 ± [21]
CDA 183 14.35 [49] A sample prepared 108.68 ± [29]
extracted with NaOH
Cellulose 185±240 ± [22] Hemicellulose 119.1 10.5 [51]
Cellulose ICR-1 A 192 ± [29] Hemicellulose 123.7 10.9 [51]
Cellulose from sugarcane 195±213 ± [21] From wood 123.73 10.94 [52]
bagasse
Cellulose ICR-3 A 196 ± [29] Potassium xylan 125.4 11.12 [52]
From rice hulls 199 16.6 [44] From rice hull 154 13.9 [44]
Cellulose 200±240 ± [46] Commercial xylan 193.53 17.24 [52]
Avicel PH-101 201 ^ 7 16.8 [22] Commercial xylan 256.65 24.20 [52]
Cellulose 218 18 [48] Commercial xylan 258.32 24.05 [52]
Cellulose 226.9 18.2 [51] Lignin
Avicel 228 19.18 [28] From pine wood 18.1 20.027 [22]
CF-11 228 18.38 [28] From eucalyptus 20.2 0.16 [22]
Cellulose 230 ^ 8 ± [45] From pine bark 20.4 20.13 [22]
a-Cellulose 234 19.4 [51] From rice hull 34 1.7 [44]
Cellulose 234.1 19.4 [51] From milled wood 34±65 2.1±4.8 [21]
Avicel PH-105 235 19.6 [28] Lignin 37.6 1.7 [51]
Avicel PH-105 238 ^ 10 19.8 [21] Spruce periodate lignin 54.34 ± [29]
Cellulose from almond shell 240 20.3 [21] Lignin 67 6.51 [20]
Avicell 244 20.68 [28] Lignin 70.7 7.1 [20]
Cellulose 245 20.78 [28] Douglas ®r Klason Lignin 79.4 ± [29]
CF-11 249 20.28 [28] Lignin 87.8 6.0 [51]
Avicel P2 250 ± [29] Lignin 141.3 9.9 [51]
Cellulose 282 24.9 [20] Lignin 145.5 12.6 [51]

Fig. 7. Asphaltene and Maltene TG and DTG curves at 108C/min.

 M. GarcõÁa-PeÁrez et al. / Fuel 80 (2001) 1245±1258 1253

Table 6
Parameters used in the maltene, asphaltene and petroleum residue thermogravimetric modelling

Component E (kJ/mol) log A (min 21) n Weight fraction (%) Weight fraction (%) (expected from
(experimental) (zj0) maltene and asphaltene behaviour)

Petroleum residue
Fraction 1 100 8.477 2.5 32 22.8
Fraction 2 180 14.204 2.3 15 19.2
Fraction 3 220 15.778 1.5 52 56.0
Maltenes
Fraction 1 100 8.477 2.5 26 ±
Fraction 2 180 14.204 2.3 22 ±
Fraction 3 220 15.778 1.5 50 ±
Asphaltenes
Fraction 1 100 8.477 2.5 5 ±
Fraction 2 180 14.204 2.3 4 ±
Fraction 3 220 15.778 1.5 90 ±

(4.1 wt%) is much lower than that obtained for the
asphaltene fraction (42.4 wt%). The coke yield expected
from the petroleum residue decomposition, without taking
into account the interactions which may occur between
maltene and asphaltene, was 13 wt%. However, the yield
obtained experimentally was 16.3 wt%.
Figs. 8 and 9 depict the DTG and TG curves of the petro-
leum residue at different heating rates. No clear decomposi-
tion steps can be established from the DTG curves. The
thermal degradation is gradual. As shown in Fig. 12, when
the sample is heated at 108C/min, the petroleum residue
weight loss starts to be intensive at 2278C. The process is
almost ®nished at 5008C. The maximum degradation rate
was reached at approximately 4428C. When the sample is
heated at 608C/min the maximum appeared at 4758C. The
coke yield does not seem to be affected by the heating rate.
Some important TG curve parameters are shown in
Table 6. The Friedman plots are shown in Fig. 10. The
petroleum residue behaviour was explained using the
same pseudo-component kinetic parameters determined
previously for the maltene and asphaltene. The kinetics
of petroleum residue thermal decomposition cannot be
explained satisfactorily through a simple addition of the
independent decomposition behaviour of maltenes and
asphaltenes (Table 5). These results con®rm that the
asphaltenes are coke precursor [36]. The relation between
the three fractions (peaks) used to describe the petroleum
residue thermal decomposition (Fig. 11) and the concen-
tration of saturates, aromatics, resins and asphaltenes must
be subjected to further studies.
The large number of reactions which may simultaneously
occur and the complex nature of petroleum residues can
explain the progressive increase in the activation energy
from 120 to approximately 300 kJ/mol (Fig. 4). The increasing
activation energy indicates that the pyrolysis occurs
progressively through the cleavage of stronger bonds.

Fig. 8. Petroleum residue DTG curves at different heating rates.

1254 M. GarcõÁa-PeÁrez et al. / Fuel 80 (2001) 1245±1258

Fig. 9. Petroleum residue TG curves at different heating rates.

Fig. 10. Friedman plots for petroleum residue under nitrogen.

Fig. 11. Petroleum residue DTG curve at 108C/min.

 M. GarcõÁa-PeÁrez et al. / Fuel 80 (2001) 1245±1258 1255

Fig. 12. TG and DTG curves of sugarcane bagasse/petroleum residue mixtures. (a) TG, (b) DTG at 108C/min, (c) TG, (d) DTG at 208C/min.

3.3. Thermogravimetric analysis of sugarcane bagasse/ through the following equations:

petroleum residue mixtures
ybag0 £ Xbag1
zbag0 ˆ …9†
Samples of bagasse with 15, 30 and 50 wt% of petroleum ybag0 £ Xbag1 1 ybit0 £ Xbit1
residue were prepared and thermogravimetrically tested at
heating rates of 10, 20, 40, and 608C/min. The experimental ybit0 £ Xbit1
TG and DTG data obtained at 10 and 208C/min are illu- zbit0 ˆ …10†
ybag0 £ Xbag1 1 ybit0 £ Xbit1
strated in Fig. 12. The main peaks observed in the bagasse
and petroleum residue mixture remained at the same The volatile fraction (zj0) that corresponds to each compon-
temperature position as if they were in isolated systems. ent previously identi®ed can be obtained by multiplying the
The charcoal yield was not signi®cantly affected by the bagasse and bitumen volatile fraction (zbag0, zbit0), by their
presence of petroleum residue. In order to simulate the respective volatile fractions (Tables 4 and 6). The kinetics
mixture thermal behaviour, bagasse and petroleum residue of the bagasse/petroleum mixtures were simulated using the
volatile fractions were determined using the individual data volatile fraction mentioned above and the kinetic para-
previously obtained for the bagasse and petroleum residue meters obtained for the isolated systems. The simulation
1256 M. GarcõÁa-PeÁrez et al. / Fuel 80 (2001) 1245±1258

Fig. 12. (continued)

Fig. 13. Experimental vs. calculated DTG values.

 M. GarcõÁa-PeÁrez et al. / Fuel 80 (2001) 1245±1258
Table 7
TG results for petroleum residue at different heating rates (T0 is the
temperature corresponding to 1 wt% of dry material weight loss, Tf the
®nal temperature, TP the peak temperature corresponding to a maximum
weight loss and Rs the ®nal residue)
Temperature (8C) 108C/min 208C/min 408C/min 608C/min
T0 227 230 233 240
Tf 500 522 526 535
TP 442 454 467 476
%Rs 16.3 16.2 15.8 15.2
was done using the method reported by Yang et al. [43] and
Miranda et al. [44].
The present work was carried out in order to show
whether important interactions exist between the bagasse
and petroleum components in the solid phase during the
pyrolysis process. The DTG curves calculated by supposing
that no interaction occurred and the experimental curves
obtained for some mixtures are shown in Fig. 13. The cal-
culated ®t is also presented in Fig. 13. The values obtained
are low in all cases indicating a good ®t. There is some
tendency of increasing the ®t coef®cient as the heating rate
increases, perhaps due to heat transfer limitations. The method
to calculate the ®tting coef®cient is reported elsewhere [55].
There are small differences between experimental and pre-
dicted thermal degradation rates. Between 300 and 3508C,
the thermal degradation rates obtained were slightly higher
than expected. This difference can be explained by the
transfer of some extractive compounds by the toluene during
the mix preparation. When the toluene was evaporated, these
extractives remained on the bagasse particles surface and
started to evaporate or subsequently cracked during the heat-
ing process.
Another plausible explanation could be the formation of a
very thin ®lm of petroleum residue on the bagasse particles
surface during the mix preparation, after the toluene
evaporation. This ®lm might rapidly reach the imposed
heating temperature during the heating test. Consequently,
an earlier evaporation or fast cracking may occur.
When the temperature is between 450 and 5508C, small
differences between the expected and the calculated thermal
degradation rates were also observed. These differences
might be due to the presence of some condensation reactions
of the petroleum residue components enhanced by its
contact with bagasse char. Differences observed in the
temperature range between 300 and 3508C seem to cancel
each other. In the end, the charcoal yield remains basically
unchanged.
According to the results obtained one can conclude that
the primary reactions of the thermal decomposition of
biomass are not signi®cantly affected by the presence of
petroleum residue (Table 7). However, small modi®cations
in the pyrolysis secondary reactions cannot be excluded.
Possible interactions between the vapour produced and the
hot solid surface may also take place.
1257
4. Conclusions
The kinetics of sugarcane bagasse thermal decomposition
can be successfully modelled by a scheme consisting of
three independent ®rst order decomposition reactions of
three constituting components. The ®rst and second com-
ponent corresponding to the hemicellulose and cellulose
fractions, react at relatively low temperature (200±4008C).
The third component (lignin) thermal degradation reaction
occurs over a relatively wide range of temperatures
(between 200 and 6008C). The cellulose, hemicellulose
and lignin contents of the bagasse which are determined
by thermogravimetry correspond very well to the values
reported in the literature.
The kinetics of the petroleum residue thermal degradation
can be modelled by a scheme consisting of three indepen-
dent reactions which are related to the thermal decomposi-
tion of three pseudo-macro-components. Each of these
pseudo-macro-components behaves like a group of com-
pounds with similar bond energy and thus similar thermal
degradation behaviour. Interactions between asphaltenes
and maltenes were observed.
Co-pyrolysis of sugarcane bagasse/petroleum residue
apparently occurs without major interaction reactions in
the solid phase between the petroleum residue fractions
and the sugarcane bagasse components. However, possible
gas±solid interactions or reactions in the gaseous phase and
minor modi®cations during the pyrolysis secondary reac-
tions might occur during co-pyrolysis.
Acknowledgements
The authors are thankful to the United States Sugar
Corporation (Clewiston, Florida) and Shell Canada
(MontreÂal, Canada) for providing free of charge the sugar
bagasse and petroleum residue, respectively. The authors
are also grateful to Dr Annette Schwerdtfeger for the tech-
nical review of the paper. Thanks are due to Mrs M. Gingras
and Mrs J. Lagace for performing the laboratory analyses.
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