b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 2 1 0 6 e2 1 1 6

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http://www.elsevier.com/locate/biombioe

Waste biomass to liquids: Low temperature conversion

of sugarcane bagasse to bio-oil. The effect of combined
hydrolysis treatments
Josilaine A. Cunha a, Marcelo M. Pereira a, Ligia M.M. Valente a,
Pilar Ramrez de la Piscina b, Narcs Homs b,c,*, Margareth Rose L. Santos a,**
a

Universidade Federal do Rio de Janeiro, Centro de Tecnologia, Instituto de Qumica, Departamento de Qumica Inorganica, Cidade
Universitaria, Rio de Janeiro, 21949-900 RJ, Brazil
b
Departament de Qumica Inorga`nica and Institut de Nanocie`ncia i Nanotecnologia, Universitat de Barcelona, C/Mart i Franques 1-11,
08028 Barcelona, Spain
c
Catalonia Institute for Energy Research (IREC), C/Jardins de les Dones de Negre 1, 08930 Barcelona, Spain

article info

abstract

Article history:

This article describes the influence of different sugarcane bagasse hydrolysis pretreatments

Received 10 March 2010

on modifications to biomass feedstock and the characteristics of the resultant pyrolysis

Received in revised form

products. Sugarcane bagasse was pretreated with acid, alkaline or sequential acid/alkaline

9 February 2011

solutions and pretreated samples were then subjected to a low temperature conversion (LTC)

Accepted 10 February 2011

process under He or O2/He atmospheres at 350e450

C. Both pretreated samples and

sugarcane bagasse in natura were analyzed by determination of their chemical composition

and by thermogravimetric, FTIR and SEM analyses. The gases yielded during LTC were
Keywords:

monitored on-line by quadrupole mass spectrometry, and the liquid fractions obtained were

Biomass

characterized by FTIR and 1H and

Sugarcane bagasse

ment applied, the main bio-oil component obtained was levoglucosan. However, the LTC

Pyrolysis

yield of bio-oil depended on the hydrolysis treatment of the biomass and decreased in the

Bio-oil

presence of O2. The acid hydrolysis pretreatment increased the LTC bio-oil yield notably.

LTC-pyrolysis

13

C NMR. Irrespective of the sugarcane bagasse pretreat-

2011 Elsevier Ltd. All rights reserved.

Biofuels

1.

Introduction

The demand for energy is growing at a rapid rate due to an

increase in both world population and industrialization. There
is a recognized need, therefore, to move toward sustainable
energy production in order to reduce greenhouse gas emissions and fossil fuel dependence [1e3].
In this context, biomass has been shown to be a potential
source of renewable energy. Thus, both developing and

industrialized countries are now seeking new technologies

which can efficiently transform biomass resources into
alternative fuels [4]. The use of agricultural waste or agricultural residues for these purposes, in principle, does not
add carbon dioxide to the atmosphere, in contrast to the use
of fossil fuels [5e7]. Moreover, second-generation biofuels
will not compete with food crops, since the raw material
they use is the crop wastes that would otherwise be discarded [8e10].

* Corresponding author. Departament de Qumica Inorga`nica and Institut de Nanocie`ncia i Nanotecnologia, Universitat de Barcelona,
C/Mart i Franques 1-11, 08028 Barcelona, Spain.
** Corresponding author.
E-mail addresses: narcis.homs@qi.ub.es (N. Homs), megrose@iq.ufrj.br (M.R.L. Santos).
0961-9534/$ e see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biombioe.2011.02.019

b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 2 1 0 6 e2 1 1 6

Biomass can be transformed using biochemical methods

(such as alcoholic fermentation) and thermochemical
methods (such as direct combustion, pyrolysis or gasification)
[11,12]. Pyrolysis of biomass has been employed to produce
organic intermediates (methane and acetic acid), charcoal and
fuel gas [13]. Many studies devoted to the thermal decomposition of lignocellulosic materials have been reported in the
last two decades, due to the production of activated carbons
from solid char derived from agricultural waste pyrolysis
[14,15]. Nowadays, pyrolytic processes can be refined to obtain
char, oil and/or gas, depending on the temperature and reaction time [16e18]. In this context, the Low Temperature
Conversion (LTC) process, initially developed by Bayer et al.
[19], involves pyrolysis at around 400
C. The aim of this
process is to maximize the yield of liquid products having
high-heating power (bio-oil) [20]. The pyrolysis treatment at
temperature higher than 400
C can modify the bio-oil
composition leading to undesirable products as polycyclic
aromatic hydrocarbons [21].
On the other hand, the distribution of pyrolysis products
can be modified by the presence of catalysts and/or by the
chemical pretreatment of the biomass [21,22]. It is now well
recognized that the chemical pretreatment of lignocellulosic
materials can remove extractives, hemicellulose, and lignin,
reduce the crystallinity of cellulose, and increase the porosity
of material [23,24]. Thus, the yield and composition of ulterior
bio-oil obtained by pyrolysis could be modified [25].
Sugarcane has historically played an important role in the
Brazilian economy [26,27]. In recent years, special Brazilian
governmental programs have led to a significant increase in
the crop areas devoted to sugarcane and to an improvement in
the sugarcane yield per hectare in order to meet the demand
for ethanol as fuel. According to the Brazilian Institute of
Geography and Statistic, this rise in sugarcane production
generated about 160 million tons of bagasse in 2008 [28]. In this
respect, sugarcane bagasse constitutes a typical example of an
agricultural byproduct that is abundantly available worldwide
[29e31]. Sugarcane bagasse typically has a cellulose:hemicellulose:lignin ratio of around 40:35:15. This lignocellulosic
content can be hydrolyzed to liberate the lignin and depolymerize the polysaccharides [32,33]. Polysaccharides and lignin
are bound through reactive ether and ester links [34,35] which
may be hydrolyzed at mild temperatures in the presence of
acids or bases. All these processes involve complex carbohydrate and lignin reactions [36].
We report here the influence of the acidic or alkaline
nature of the sugarcane bagasse hydrolysis pretreatment on
solid residue composition and on that of the bio-oil yielded
after the LTC-pyrolysis process carried out at 350e450
C. We
focused on the characteristics of the bio-oil liquid fraction due
to its potential future interest for second-generation bio-fuel
production.

2.

Materials and experimental procedures

Sugarcane bagasse in natura was sundried, ground and sieved.

Only particles in the 20e80 mesh range were retained for
analysis and experiments; the corresponding samples of
bagasse in natura used were labeled BC. For comparative

2107

purposes, a sample of BC was washed with water at room

temperature and then dried at 105
C until constant weight;
the resulting sample was labeled BCW.
Chemical composition of samples (C, H, N, %wt/wt) was
determined using a Perkin Elmer 2400 CHN model and the
oxygen content (%wt/wt) was then calculated by subtraction.
Thermogravimetric and derivative thermogravimetric
analysis (TG/DTG) data were recorded using a Universal TA
2060 apparatus. A heating rate of 20
C min1 and a N2 flow of
100 mL min1 were used.
The infrared spectra were obtained with a Nicolet Magna
760 spectrometer at 4 cm1 of resolution.
A Hitachi H-2300BSE microscope was used for the scanning
electron microscopy study of the materials.
1
H NMR and 13C NMR were recorded using a Bruker 300
spectrometer (300 MHz for 1H and 75 MHz for 13C) and a Bruker
200 (200 MHz for 1H). Spectra were recorded at 25
C using
acetone-d6, dH 2.04 ppm and dC 206.58 ppm as solvent
signals references.

2.1.

The hydrolysis experiments

BC hydrolysis was carried out under acidic, basic or sequential

acid/base treatments at 25
C or 122
C at ambient pressure for
1 h.
For the hydrolysis treatments, BC samples (2.0 g) were
treated with 2 M HCl (25 mL) or 0.5 M NaOH (25 mL) solutions at
25
C (samples BCA1 and BCB1 respectively), 122
C (BCA2 and
BCB2 samples respectively) or under ultrasonic irradiation
(BCA3 and BCB3 samples). In the sequential acid/base treatment, BC samples were first hydrolyzed under acidic conditions and then treated with the alkaline solution; the
corresponding samples treated at 25
C, 122
C or under
ultrasonic irradiation at 25
C were BCS1, BCS2, and BCS3,
respectively.
In all cases, the resulting samples were filtered off and
washed with distilled water until the wash-water remained
neutral. The samples were oven dried at 105
C until constant
weight, their chemical composition was then determined and
finally, they were analyzed by FTIR, TG/DTG and SEM.

2.2.

The pyrolysis experiments

The LTC-pyrolysis experiments were performed in an apparatus designed for this purpose using about 0.1 g of BC or
hydrolyzed samples. The main element of this device was
a tubular reactor inserted vertically into an electrically heated
tubular furnace; the temperature was controlled inside the
sample bed by a NieCr thermocouple. In all cases, gaseous,
liquid and solid fractions were formed. The gases produced
were analyzed on-line by a mass spectrometer (MS) with
a quadrupole analyzer MKS model e-vision. The liquid fraction was condensed at the reactor outlet, extracted with
acetone and then the solvent was removed at low pressure
and the residue analyzed by FTIR, 1H and 13C NMR.
The LTC-pyrolysis experiments were carried out in three
series; in all cases the samples were heated at a rate of
10
C min1 and the final pyrolysis temperature was maintained for 15 min. All experiments were performed in duplicate. The first series of experiments was carried out to

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determine the effect of the final pyrolysis temperature on the

yield of gas, liquid and solid fractions. In this series, LTCpyrolysis of BC samples was carried out under an inert
atmosphere (He, 150 mL min1) with pyrolysis temperatures
of 350, 400 or 450
C.
The second group of experiments was performed to
establish the effect of the bagasse hydrolysis pretreatment on
LTC-pyrolysis yields, and this series of experiments was
carried out under inert atmosphere (He, 150 mL min1) at
350
C.
The last group of experiments was performed to establish
the effect of the use of an oxidant atmosphere (5% O2/He,
150 mL min1) on LTC-pyrolysis yields; a final temperature of
350
C was used.

3.

Fig. 1 e FTIR spectra of a) sugarcane bagasse in natura (BC)

and b) water washed sugarcane bagasse (BCW).

Results and discussion

3.1.
Effect of different treatments on sugarcane bagasse
characteristics
As stated above, BC samples were hydrolyzed with acidic,
alkaline or sequential acidic/alkaline treatments at 25
C,
122
C or under ultrasonic irradiation. All treated samples
were studied by chemical analysis, FTIR, DT/DTG and SEM. For
each treatment, acidic, alkaline or sequential acidic/alkaline,
the sample treated at 122
C showed the highest degree of
modification when compared with the original bagasse in
natura; consequently, throughout the rest of the paper, the
results of characterization of pretreated samples will refer
exclusively to those samples treated at 122
C. The subsequent
LTC experiments were carried out using BCA2, BCB2 and BCS2
samples.
Table 1 shows the chemical composition of the BC and the
modified sugarcane bagasse following the different hydrolysis
treatments at 122
C. Although no significant differences in
the chemical composition were observed after the hydrolysis
treatments, a slight reduction in oxygen content was noted
following acidic treatment, which could be related to the
removal of oxygen-rich compounds by the acid treatment.
As stated in the experimental section, for comparative
purposes we prepared a blank sample (BCW) by washing in
water and subsequently drying (105
C) a BC sample. Fig. 1
shows FTIR spectra of both BC and BCW samples. No significant differences can be distinguished related to the simple
removal of extractives when BC was treated with water to give

Table 1 e Chemical composition of the sugarcane bagasse

in natura and that of the samples obtained after
hydrolysis treatments at 122
C.
(%wt/wt)
C
H
N
Oa

BC

BCA2

BCB2

BCS2

43.89
7.05
0.32
48.74

48.62
6.90
0.08
44.40

42.48
7.37
0.15
50.00

44.69
7.43
0.16
47.72

a Calculated by subtraction.

BCW. The spectra are complex but the presence of different

functional groups corresponding to the expected composition
based on cellulose, hemicellulose and lignin structures can be
deduced [37]. A broad band above 3000 cm1 was observed,
corresponding to the y(OeH) of hydroxyl groups, such as those
of alcoholic and phenolic components. y(CeH) absorptions in
the 2800e3000 cm1 region were also clearly observed. Below
1800 cm1, the spectra fingerprint enabled the presence of C]O,
CeOeC and C]C linkages, among others, to be determined.
In the following paragraphs, we will analyze the more
relevant features observed in the infrared spectra of the BCW
and those of the different pretreated samples at 122
C (Fig. 2).
The bands in the region 1700e1760 cm1 are characteristic
of y(C]O) (Fig. 2A). The spectrum corresponding to the BCW
sample showed a broad band with maximum at 1732 cm1.
Absorptions at ca. 1735e1740 cm1 are associated with y(C]O)
of carbohydrate structures; and a band at 1740 cm1 has been
assigned to the acetyl, uronic, and feluric ester groups of
hemicellulose [38]. On the other hand, a component of the
carbonyl band appearing at a lower wavenumber is related to
the conjunction of a carbonyl group with an aromatic ring, as
occurs with carbohydrate linked with lignin components [39].
Following acidic hydrolysis, it was mainly the component at
ca. 1702 cm1 which remained, although a shoulder at ca.
1735 cm1 was still present. No bands in the 1700e1735 cm1
region were observed for the samples BCB2 and BCS2. y(C]O)
bands usually disappear with high-temperature treatments of
cellulose, hemicellulose and lignin structures due to formation of CeOeC bonds between rings [40]. However, in our
study, the intensity of the bands at ca. 1250 cm1 and
1050 cm1 characteristic of CeOeC and CeO bonds respectively, diminished following acid or basic treatment.
On the other hand, when the FTIR spectra of BCB2 and
BCS2 samples were compared with those of BCW and BCA2
(Fig. 2A), a high reduction in the intensity of the bands located
ca. 1515 cm1, 1605 cm1 and 834 cm1 in the spectra of the
samples BCB2 and BCS2 with respect to those of BCW and
BCA2 was clearly noted. These bands are associated with the
presence of lignin; 1515 cm1 and 1605 cm1 (aromatic ring
vibrations) and 834 cm1 (CeH in plane bending) [38,41].

b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 2 1 0 6 e2 1 1 6

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Fig. 2 e FTIR spectra, A) 1800-600 cmL1 region and B) 4000-2500 cmL1 region, of several treated sugarcane bagasse samples;
a) BCW, b) BCA2, c) BCB2 and d) BCS2.

Besides the reduction in the y(C]O) absorption intensity,

the extraction of carbohydrates would produce a higher
reduction in y(OeH) absorption intensity (band centered at
3400e3450 cm1) with respect to that of y(CeH) (band centered
at ca. 2900 cm1); this can be observed clearly in Fig. 2B, if the
spectra of BCA2, BCB2 or BCS2 are compared with that of BCW.
The spectral changes of the BCB2 and BCS2 with respect
BCW agree with the extraction of hemicellulose and the
partial release or degradation of lignin; the partial release of
both hemicellulose and lignin has already been reported as
taking place at 55
C under alkaline conditions [38].
The thermogravimetric behavior of samples was analyzed
and TG (%wt/wt) and DTG (%wt/wt/
C) curves were obtained
up to 1000
C. Fig. 3 shows the curves corresponding to
the bagasse in natura (BC) and those corresponding to the
sample washed with water (BCW) (Fig. 3A and B respectively).
Fig. 4 displays the thermogravimetric curves of pretreated
samples. The DTG curve of BC shows three well-defined peaks
with maximum at 225
C, 320
C and 370
C (Fig. 3A), whilst that
of BCW shows peaks at 320
C and 370
C. The peak at 225
C in
the DTG curve of BC (Fig. 3A) was related to the extractive
residues present in this sample, which were removed after
washing with water (see the DTG curve of BCW in Fig. 3B).
The two peaks in the DTG curve of BC and BCW, with
maxima at 320
C and 370
C, can be assigned primarily to the
decomposition of hemicellulose and cellulose respectively
[42,43]. Hemicellulose is formed of short branched polymer
chains of several C6 (mainly glucose, mannose and galactose)
and C5 (xylose and arabinose) sugars. The side chains and the
axial hydroxyl groups of the sugars prevent hemicellulose
from forming semi crystalline domains; around 200 sugar
units comprise the hemicellulose chain. Cellulose is a polymer
of glucose units (ca. 10000) without any branches. The
hydroxyl groups in equatorial position permit strong hydrogen
bonds, giving semi crystalline polymer chains of glucose.
Hemicellulose presents an easier hydrolysis and thermal
decomposition than cellulose, due to its amorphous structure.
Although the highest weight loss took place up to ca.
400
C, in all cases a continuous loss of weight above this
temperature, and up to the final temperature of the experiment, was observed; this loss did not produce significant

peaks in the DTG curves. The degradation of lignin has been

reported to occur preferably above 300
C, with a very low
mass loss rate. Lignin is a tri-dimensional polymer which
comprises phenyl-propane units highly cross-linked and
consequently it is difficult to decompose [44e46].
Fig. 4 shows the thermogravimetric analysis of sugarcane
bagasse after acid (Fig. 4A), alkaline (Fig. 4B) and sequential
acid/alkaline treatments (Fig. 4C) at 122
C. Several differences
can be observed if the DTG profiles of pretreated samples are
compared with that of BCW (Fig. 3B). Samples pretreated with
alkaline (BCB2) or sequential acid/alkaline (BCS2) solutions
showed only one wide DTG peak, which started at 250
C and
reached maximum at ca. 350
C (Fig. 4B and C); this is mainly
attributed to the superimposed thermal decomposition of
cellulose and lignin. Although the peak is asymmetric, the
disappearance of the maximum at 320
C indicates degradation of hemicellulose produced by the alkaline hydrolysis, in
agreement with FTIR analysis of these samples. On the other
hand, the main DTG peak for BCB2 and BCS2 appeared at
a lower temperature (350
C) than that of BCW, and this could
be related to a partial modification of the cellulose and/or
lignin structure, agreeing with FTIR results, which indicated
that the basic treatment produced partial degradation of
lignin structures.
On the other hand, a wide peak at 300e400
C with two
maxima at 320
C and 370
C was still noted in the DTG profile
of the sample pretreated with acid (sample BCA2 Fig. 4A); in
this case, the intensity of the first maximum was slightly
lower than that of BCW (compare Figs. 4A and 3B), which
would agree with the partial removal of hemicellulose by an
acid treatment as was shown by FTIR. The easy hydrolysis of
hemicellulose can once again be related to its amorphous
random branched structure, whereas the crystalline structure
of cellulose and the cross-linked phenolic units present in
lignin structure are more resistant to hydrolysis. The thermogravimetric results indicate that hydrolysis treatment
affects the composition of sugarcane bagasse, and are in good
agreement with the observed infrared features of the pretreated samples previously discussed. Both TG/DTG and FTIR
results enable us to conclude that a basic hydrolysis treatment
produces a more effective extraction of hemicellulose.

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b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 2 1 0 6 e2 1 1 6

Fig. 3 e TG and DTG curves of A) BC and B) BCW samples.

Fig. 5 comprises micrographs corresponding to the sugarcane bagasse in natura (BC) and those corresponding to the
samples treated at 122
C with acidic, alkaline or sequential
acidic/alkaline treatments, BCA2, BCB2 and BCS2 respectively.
Several differences can be observed when comparing the
micrographs of the samples treated at 122
C with different
hydrolysis media.
The BC micrographs show the presence of sugar crystallites on the surface of the material, which correspond to the
residual extractives in this sample. The micrographs of the
pretreated samples do not show the sugar crystallites, due to
the easy removal of extractives. In the BCA2 sample,
substantial disorganization can be observed in the fibers,
compared to the BC sample. As stated above, it was deduced
that acid treatment led to partial removal of hemicellulose.
Basic or sequential acid/basic hydrolysis treatments resulted
in materials consisting of skeletal structures without apparent

amorphous surface morphology. This effect was more notable

in the BCS2 sample. These results indicate that extraction of
hemicellulose by an alkali or sequential treatment is more
efficient than that achieved by acidic hydrolysis, and are in
good agreement with FTIR and thermogravimetric analyses.

3.2.

LTC-pyrolysis results

The effect of the pyrolysis process temperature (350
C, 400
C,

450
C) was firstly investigated in sugarcane bagasse in natura.
Table 2 shows the liquid (bio-oil) and solid fraction yield
obtained as a function of the temperature used in the pyrolysis experiments under inert atmosphere. An increase in biooil yield was obtained when the pyrolysis temperature
decreased from 450
C to 350
C, with a bio-oil fraction of 18 (%
wt/wt) at 350
C. Since the highest bio-oil yield was observed
at the lowest LTC temperature (350
C), this was the

b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 2 1 0 6 e2 1 1 6

Fig. 4 e TG and DTG curves of several treated sugarcane bagasse samples; A) BCA2, B) BCB2 and C) BCS2.

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Fig. 5 e Scanning electron microscopy of BC and several treated sugarcane bagasse samples.

temperature selected for the subsequent pyrolysis experiments of modified sugarcane bagasse.
As stated above, LTC-pyrolysis of BC, BCA2, BCB2 and BCS2
samples was carried out and the effect of inert (He) and
oxidant (5% v/v O2/He) atmospheres was explored. As
described in the experimental section, the formed gases were
analyzed by MS; in all cases, CO2, CO, C2H6, CH4 and H2O, were
detected. Fig. 6 shows the amount of liquid and solid fractions
(%wt/wt) obtained from LTC experiments of BC and pretreated

Table 2 e Distribution of products obtained after LTC

under inert atmosphere of sugarcane bagasse in natura at
different temperatures.
T (
C)
350
400
450

Oil (%wt/wt)

Solid (%wt/wt)

18.0
16.0
12.5

11.0
16.5
15.0

b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 2 1 0 6 e2 1 1 6

Fig. 6 e Yield of liquid (>, A) and solid (,, -) fractions

(% wt/wt) obtained after the LTC process of BC and several
treated sugarcane bagasse samples. LTC process was
carried out at 350
C under He (filled symbols) or 5% O2/He
(empty symbols) atmosphere.

samples. The yields of liquid and solid fractions depended on

both the hydrolysis pretreatment and the LTC atmosphere
used. In all cases, an LTC oxidant atmosphere led to the
formation of a higher amount of solid fraction, whereas the

2113

liquid fraction was lower. However, the LTC atmosphere had

less influence on the liquid yield than on the solid yield. On
the other hand, when results of LTC of the pretreated samples
were compared to those of sugarcane bagasse in natura,
several differences in the amount of liquid and solid fractions
obtained could be appreciated. The amount of solid fraction
obtained was always higher for pretreated samples, being in
the order BC < BCA2 < BCB2 < BCS2. The LTC of BCB2 and BCS2
led to a lower amount of bio-oil than that of the original BC
sample. However, when the LTC products of BCA2 and BC
were compared, a higher amount of bio-oil in the case of BCA2
was observed. Under inert atmosphere, the LTC of BCA2
sample gave a bio-oil yield (31 %wt/wt) 72% higher than that
obtained from the BC sample (18 %wt/wt). These results
indicate that LTC of extractives does not significantly
contribute to bio-oil formation. Moreover, as stated above, the
acid treatment produced structural modification, fiber disorganization and the partial extraction of hemicellulose. Thus,
the relative amount of cellulose in the acid-treated sample
increased when it was compared with BC sample, and this
may be related with the higher bio-oil yield produced by the
LTC process of the former. On the other hand, alkaline or
sequential treatments, besides a more effective extraction of

Fig. 7 e 1H NMR spectra, corresponding to the bio-oil obtained by LTC of BC sample at 350
C under different atmospheres;
A) under He (spectrum registered at 200 MHz), B) under 5% O2/He (spectrum registered at 300 MHz).

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hemicellulose than acid treatment produced the partial

degradation of lignin. Under LTC conditions unprotected
cellulose may suffer dehydration and oxidation reactions
producing the diminution of bio-oil yield [25].
The obtained bio-oil was analyzed by NMR and FTIR
spectroscopy. Fig. 7 shows the 1H NMR spectra of the bio-oil
obtained by LTC of sugarcane bagasse in natura in inert (He)
(Fig. 7A) and in oxidant atmosphere (5% O2/He) (Fig. 7B). Both
1
H NMR spectra showed prominent signals at d 9.54, s; 7.32, d,
J 3.3 Hz; 6.53, d, J 3.3 Hz and 4.60, s characteristic of
5-hydroxymethylfurfural. The singlet at d w5.2 is related to
levoglucosan [47]; signals at d 3.30e4.50 are ascribed to
carbohydrate moiety (carbinolic protons). The signal at ca.
1.2 ppm is due to water impurity.
Interestingly, the NMR characterization of the bio-oil
produced by LTC of modified sugarcane (BCA2, BCB2, BCS2)
indicated in all cases that levoglucosan was the main
component. As an example, Fig. 8 shows 1H (Fig. 8A) and 13C
NMR (Fig. 8B) spectra corresponding to the bio-oil produced

after the LTC under He atmosphere of BCA2. Characteristic

signals of levoglucosan can be distinguished; 1H NMR signals
at d 5.24, s (H-1); 4.43, m (H-5); 4.09, bd, J 7.0 Hz (H-6a); 3.58,
dd, J 5.9 and 7.0 Hz (H-6b); 3.51 bs (H-4) and 3.37, bs (H-2) and
those from the 13C NMR spectrum at d 103.22, 77.57, 74.53,
72.54, 72.25 and 65.83.
FTIR spectra of the bio-oil produced by LTC of different
samples are presented in Fig. 9. The broad absorbance bands of y
(OeH) stretching vibration between 3200 and 3600 cm1 indicated the presence of highly polymeric hydroxyl groups and
water impurities in the oil. The absorptions at 2800e3000 cm1
region and those around 1460 cm1 are characteristic of y(CeH)
and d(CeH) vibrations of eCH3 and/or eCH2-groups. Other
absorptions between 1630 and 1760 cm1 were also observed. As
stated above, this is a characteristic spectral region of y(C]O)
and could indicate the presence of ketones, aldehydes and acids
or esters. Specifically, 5-hydroxymethylfurfural shows a characteristic and intense absorption at 1666 cm1. The FTIR spectrum of the bio-oil obtained from sugarcane bagasse in natura

Fig. 8 e NMR spectra of the bio-oil obtained from the BCA2 sample after LTC at 350
C under He atmosphere. A) 1H NMR (300
MHz); B) 13C NMR (75 MHz).

b i o m a s s a n d b i o e n e r g y 3 5 ( 2 0 1 1 ) 2 1 0 6 e2 1 1 6

2115

The degradation of lignin after the basic and sequential

treatments may leave cellulose unprotected and favor dehydration and oxidation reactions under LTC conditions, thus
leading to a decrease in bio-oil yield.

Acknowledgments
The authors are grateful to ANP/CENPES-Brazil, and the
Spanish and Catalan governments (Consolider Ingenio 2010,
Multicat CSD2009-00050, MAT2008-02561 and 2009SGR-0674
projects) for the financial support and to CAPES-Brazil, for
a scholarship.

Fig. 9 e FTIR spectra of the bio-oil obtained after LTCpyrolysis at 350
C under He atmosphere of several
samples; a) BC, b) BCA2, c) BCB2, d) BCS2.

(BC) (Fig. 9, spectrum a) shows a band at 1668 cm1 which could

be assigned to the presence of 5-hydroxymethylfurfural, in
agreement with NMR results. The intensity of this band
decreased strongly in the spectrum corresponding to bio-oil of
BCA2 (Fig. 9 spectrum b), and it was no longer present in the
spectra of the bio-oil obtained from BCB2 and BCS2 samples
(Fig. 9, spectra c and d). The residual extractives of BC sample
may produce 5-hydroxymethylfurfural under the LTC conditions applied in this study.

4.

Conclusions

Sugarcane bagasse was modified by acid, alkaline and

sequential acid/alkaline hydrolysis. SEM, TG-DTG and FTIR
analysis showed that the hydrolysis treatments determined
the composition and fiber organization of the sugarcane
bagasse. Acid treatment removed extractives and hemicellulose and led to amorphous, highly disordered fibers.
Alkaline hydrolysis removed more effectively hemicellulose,
degraded lignin and left highly ordered residual fibers.
With the goal of producing bio-oil, low temperature
pyrolysis of modified biomass was carried out under inert or
oxidant atmospheres. Bio-oil yielded by LTC of modified
samples did not differ qualitatively in composition, and levoglucosan comprised its main component. The acid
pretreatment increased the bio-oil yield of the LTC process,
whereas the basic treatment produced the opposite effect
when compared to that of the in natura sugarcane bagasse.
The yield of bio-oil increased by 72% when the LTC process of
BCA2 was carried out under He, and by 53% when it was
carried out under oxidant atmosphere. The LTC bio-oil yield
correlated with the fiber organization and composition of
pretreated samples. The higher bio-oil production in LTC
process from BCA2 sample with respect to BC sample is
related to the relative amount of cellulose, which is higher in
the acid-treated material because this treatment mainly
removes extractives and hemicellulose.

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