Optimization of acid hydrolysis from the hemicellulosic fraction of

Eucalyptus grandis residue using response surface methodology

Eliana Vieira Canettieri
a,b
, George Jackson de Moraes Rocha
c
,
Joao Andrade de Carvalho Jr.
a,
*
, Joao Batista de Almeida e Silva
c
a
Department of Energy, Engineering Faculty of Guaratingueta FEG/UNESP, Av. Ariberto Pereira da Cunha, 333, Pedregulho,
Guaratingueta 12516-410, SP, Brazil
b
Laborato rio Associado de Combustao e PropulsaoLCP, Instituto Nacional de Pesquisas EspaciaisINPE, Rodovia Presidente Dutra,
km 40, Cachoeira Paulista 12630-000, SP, Brazil
c
Department of Biotechnology, Chemical Engineering Faculty of LorenaFAENQUIL, Rodovia Itajuba -Lorena km 74.5,
Campinho, Lorena 12600-970, SP, Brazil
Received 13 June 2005; received in revised form 3 December 2005; accepted 4 December 2005
Available online 10 February 2006
Abstract
Biotechnological conversion of biomass into fuels and chemicals requires hydrolysis of the polysaccharide fraction into monomeric
sugars. Hydrolysis can be performed enzymatically and with dilute or concentrate mineral acids. The present study used dilute sulfuric
acid as a catalyst for hydrolysis of Eucalyptus grandis residue. The purpose of this paper was to optimize the hydrolysis process in a 1.4 l
pilot-scale reactor and investigate the eects of the acid concentration, temperature and residue/acid solution ratio on the hemicellulose
removal and consequently on the production of sugars (xylose, glucose and arabinose) as well as on the formation of by-products (fur-
fural, 5-hydroxymethylfurfural and acetic acid). This study was based on a model composition corresponding to a 2
3
orthogonal factorial
design and employed the response surface methodology (RSM) to optimize the hydrolysis conditions, aiming to attain maximum xylose
extraction from hemicellulose of residue. The considered optimum conditions were: H
2
SO
4
concentration of 0.65%, temperature of
157 C and residue/acid solution ratio of 1/8.6 with a reaction time of 20 min. Under these conditions, 79.6% of the total xylose was
removed and the hydrolysate contained 1.65 g/l glucose, 13.65 g/l xylose, 1.55 g/l arabinose, 3.10 g/l acetic acid, 1.23 g/l furfural and
0.20 g/l 5-hydroxymethylfurfural.
2006 Published by Elsevier Ltd.
Keywords: Biomass; Dilute-acid hydrolysis; Hemicellulose; Xylose; Response surface methodology
1. Introduction
With the Kyoto agreement being in force since 16 Feb-
ruary 2005with the aim of obliging the industrialized
countries to diminish, between 2008 and 2012, the emission
of greenhouse gases resulting from the burning of fossil
fuels to an average level 5.2% lower than the values of
1990, governments are investing worldwide in the search
for alternative and renewable sources of fuel and feedstock
chemicals. Biomass resources include wood and wood
wastes, agricultural crops and their waste by-products,
municipal solid wastes, animal wastes, wastes from food
processing and aquatic plants and algae (Nogueira and
Lora, 2003). Biomass can be used to meet a variety of
energy needs, including generating electricity, heating
homes, fueling vehicles and providing process heat for
industrial facilities. In addition, biomass residues originat-
ing from agricultural and forest processing constitute a
potential source for production of value-added chemicals
such as reducing sugars, furfural, and ethanol, by enzyme
or acid catalyzed hydrolysis. One such alternative receiv-
ing attention involves the separation of wood into its
0960-8524/$ - see front matter 2006 Published by Elsevier Ltd.
doi:10.1016/j.biortech.2005.12.012
*
Corresponding author. Tel.: +55 12 31232838.
E-mail address: joao@feg.unesp.br (J.A. de Carvalho Jr.).
Bioresource Technology 98 (2007) 422428
components, namely cellulose, hemicellulose and lignin,
followed by conversion to chemical feedstock. Dierent
aspects of acid hydrolysis of hemicellullosic materials have
been studied by others (Montane et al., 2002; Lavarack
et al., 2002; Kim et al., 2000).
The indiscriminate use of wood coming from native for-
ests caused its scarcity and aroused interest in the search of
alternative materials to supply the wood market. In this
way, the discovery of eucalyptus wood represented a great
advance for the forest sector. As the planting of eucalyptus
is renewed every seven years, the yield obtained from one
hectare is equivalent to the yield obtained from ten hectares
of a native forest (Meadows, 1994). In the production of
wood for building or for making paper paste, only part
of a tree is utilized. The branches and the top represent
about 3040% of the weight of the conifers and over 50%
of the weight of trees with massive foliage (Antunes and
Almeida, 2003). According to Granthan and Howard
(1980), half the total weight of the trees felled in the forests
remains in the elds as residue. The upper parts of the trees
with diameters smaller than 57 cm are not utilized by the
cellulose and paper industry (Gomide, 1986). According to
Antunes and Almeida (2003), a large amount of residue of
pine trees and oaks felled by the industry (about 54.8% and
56.2%, respectively) is not utilized at all. However, this res-
idue could be used as an energy source. Brazil possesses
about 3,600,000 hectares of land reforested only with euca-
lyptus (SBS, 1990; ANFPC, 1993; Prado, 1995). Currently,
Brazil ranks seventh in the world as a cellulose producer
and twelfth as a paper manufacturer. The Brazilian sector
of paper and cellulose contributes in a relevant way to the
development of the country, generating jobs and increasing
income (Bracelpa, 2000). Among more than 100 eucalyptus
species introduced into Brazil, the most common is Euca-
lyptus grandis (occupying 55% of the total planted area),
followed by Eucalyptus saligna (17%) and Eucalyptus uro-
phyla (9%). The bark volume in eucalyptus plantings usu-
ally corresponds to 1020% of the commercial volume of
the tree (Husch et al., 1973). The wood bark can be consid-
ered a problem to some forest companies, because there are
few economical alternatives for its use, and the companies
need to have a destination for this material. Eucalyptus res-
idue contains carbohydrates in the form of hemicellulose
and cellulose. Hemicellulose is primarily a polymer of pen-
toses and hexoses. Cellulose is a polymer of hexoses. These
polymers can be reduced to monomeric sugars, primarily
xylose and glucose, by hydrolysis with mineral acids. This
paper focuses on the use of dilute acid hydrolysis as a pro-
cess to separating the biomass components. The biomass
employed in this study was eucalyptus residue (branches,
foliage and bark) left in the eld after removal of the wood
utilized by the paper and cellulose industry. The objective
of this work was determine the eects of the variables tem-
perature (T), acid concentration (CA), and residue/acid
solution ratio (R/A) on xylose extraction from the hemicel-
lulosic fraction of E. grandis residue using the response sur-
face methodology (RSM). This methodology is a group of
mathematical and statistical techniques extremely useful
for analyzing the eects of several independent variables
on dierent chemical processes.
2. Methods
2.1. Preparation and chemical analysis of
Eucalyptus grandis residue
E. grandis residue (branches, foliage and bark), collected
in a farm in Sao Luiz do Paraitinga (State of Sao Paulo,
Brazil) owned by Suzano Paper and Cellulose Company,
was used as the raw material. The residue was air-dried,
milled, homogenized in a single lot and stored under dry
conditions before use. The residues were milled in a Mane-
sco and Ranieri knife mill to pass through a 0.5 mm screen.
Their moisture content (14.7%) was determined using an
OHAUS-MB 200 dry weight scale (105 C, 20 min).
Approximately 3 g of milled sample was extracted with
95% ethanol for 6 h in a Soxhlet apparatus. Two extracted
subsamples were taken for wet chemical analysis. The
extracted eucalyptus residue was hydrolyzed with 72% sul-
furic acid at 30 C for 1 h (300 mg of sample and 3 ml of
sulfuric acid). The acid was diluted to a nal concentration
of 3% (addition of 79 ml of water) and the mixture heated
at 125 C/1 atm for 1 h. The residual material was cooled
and ltered through a porous glass lter number 3. The sol-
ids were dried to constant weight at 105 C and determined
as insoluble lignin. The soluble lignin concentration in the
ltrate was determined by measurement of the absorbance
at 205 nm and using the value of 110 l g
1
cm
1
as the
absorptivity of soluble lignin (Dence, 1992; Goldschmid,
1971). The concentrations of monomeric sugars in the sol-
uble fraction were determined by an HPLC/RI detector.
The monosaccharides present in hydrolyzates were con-
verted to percent polysaccharides: D-glucose to glucan,
D-xylose to xylan and D-mannose to mannan. The mono-
saccharide peak areas were converted using standard
equations ascertained with the appropriate internal stan-
dards (curves standards of D-glucose, D-xylose, D-mannose,
L-arabinose and acetic acid). The monosaccharide weights
were converted to polysaccharide percentage by consider-
ing hydrolyzate sample dilution, water of hydrolysis factors
and the original sample dry weight. The factors used to
convert sugar monomers to anhydromonomers were 0.90
for glucose and 0.88 for xylose and arabinose. The acetyl
content was calculated as the acetic acid content multiplied
by 0.7. These factors were calculated based on water addi-
tion to polysaccharides during acid hydrolysis (Laver and
Wilson, 1993; Rocha, 2000).
2.2. Hydrolysis experiments
The hydrolysis experiments were carried out in a system
consisting of four 1.4 l cylindrical containers, each of them
being 55 cm in length and 6.8 cm in diameter, immersed in
water in a 40 l stainless steel reactor. An insulated electrical
E.V. Canettieri et al. / Bioresource Technology 98 (2007) 422428 423
coil arranged around the reactor provided heating. A
manometer was used to read pressure. Reaction time was
xed at 20 min. A orthogonal 2
3
design with dierent sulfu-
ric acid concentrations as well as dierent residue/acid
solution ratios and temperatures was applied according
to the experimental design shown in Table 1. The reactor
rotates around its own axis for agitation. After the resi-
dence time, the reactor was turned o and cooled for
approximately 18 h. The liquid fraction (hemicellulosic
fraction) was then removed and analyzed for solubilized
sugars (glucose, xylose and arabinose).
Xylose yield (Y) and % of xylose extraction (g) from the
hemicellulosic fraction of the eucalyptus residue were cal-
culated according to Eqs. (1) and (2), respectively.
Y 100
c V
M
; 1
where Y is the xylose yield (g xylose/g dry matter), c is the
component concentration (xylose) in the liquid phase ob-
tained by HPLC (g l
1
), V is the volume used for hydrolysis
(= V
water
+ V
acid
) (l), and M is the amount of residue uti-
lized for hydrolysis, discounting moisture (dry matter used
for hydrolysis) (g).
g
Y 100
m
; 2
where Y is the sugar yield (xylose), and m is the amount of
xylose contained in the residue (g).
In this case, 14.64 g of xylose were found in the eucalyp-
tus residue (value determined by analysis of the chemical
composition of the eucalyptus residue, as shown in Section
3). Eq. (2) can be then rewritten in the form of Eq. (3):
g
Y 100
14:64
. 3
Neureiter et al. (2002) also adopted this method of cal-
culation to homogenize and treat their results for sugar
cane acid hydrolysis. According to these authors, this value
is more useful for comparing dierent experiments than the
sugar concentrations, because experiments with higher val-
ues of dry mass in general yield hydrolysates with higher
sugar concentrations, although the eective yields can be
lower.
2.3. Experimental design and optimization by response
surface methodology (RSM)
The initial assays were based in a 2
3
factorial design with
three dierent sulfuric acid concentrations (0.10%, 0.50%,
0.30%), as well as three dierent residue/acid solution
ratios (1/3, 1/4.5 and 1/6) and temperatures (120, 140
and 160 C). The composition of the model was established
from these preliminary assays. The model composition cor-
responded to an orthogonal 2
3
design, following the meth-
odology of Box et al. (1978) and Barros Neto et al. (2001).
For statistical calculation, the variables were coded accord-
ing to Eq. (4):
V
0
c

V
R

P
V sV
i

2

DV sV
i

2
; 4
where V
0
c
is the coded value of the independent variable; V
R
is the real value corresponding to the coded value of the
independent variable V
0
c
;
P
V
s
V
i
is the sum of the high-
er and the lower real values of the independent variable and
D(V
s
V
i
) is the dierence between the two values.
The statistical model was based on the RSMwhose equa-
tion was determined by analysis of linear multiple regression
using the software Design-expert (version 5.0, Stat-Ease
Inc., Minneapolis, USA) and STATISTICA 6.0 (Statsoft,
USA). The xylose extraction from hemicellulosic fraction
of eucalyptus residue was taken as the dependent variable
or response of the design experiments. The statistical signi-
cance of the regression coecients was determined by the
Students t test. The variables were correlated by empirical
models. The following generalized equation was used:
Y
i
b
0

X
b
i
X
j

X
b
ij
X
i
X
j

X
b
ii
X
2
i
e
i
; 5
where Y
i
is the dependent variable or response variable, b is
the regression coecient, X
i
and X
j
are the experimental
factors with coded units (variables studied), and e
i
is the
random error.
2.4. Analytical methods
The concentrations of D-xylose, D-glucose, L-arabinose
and acetic acid were measured by a Shimadzu Corporation
Table 1
Scheme of a orthogonal 2
3
design with ve centerpoints, considering the
units of the natural and coded factors and the results of xylose extraction
from the hemicellulosic fraction of eucalyptus residue after acid hydrolysis
Coded unit Natural unit
X
1
:T X
2
:CA X
3
:R/A T (C) CA (%) R/A Xylose
extraction (%)
1 1 1 150 0.25 1/4 2.89
+1 1 1 170 0.25 1/4 16.90
1 +1 1 150 0.75 1/4 48.28
+1 +1 1 170 0.75 1/4 30.30
1 1 +1 150 0.25 1/8 12.40
+1 1 +1 170 0.25 1/8 56.94
1 +1 +1 150 0.75 1/8 82.95
+1 +1 +1 170 0.75 1/8 35.30
0 0 0 160 0.50 1/6 78.96
0 0 0 160 0.50 1/6 71.52
0 0 0 160 0.50 1/6 70.90
0 0 0 160 0.50 1/6 68.69
0 0 0 160 0.50 1/6 74.63
1.29 0 0 147 0.18 1/6 22.63
+1.29 0 0 173 0.82 1/6 58.26
0 1.29 0 160 0.50 1/6 14.30
0 +1.29 0 160 0.50 1/6 66.00
0 0 1.29 160 0.50 1/3.4 35.41
0 0 +1.29 160 0.50 1/8.6 83.42
T = temperature, CA = acid concentration and R/A = residue/acid solu-
tion ratio.
424 E.V. Canettieri et al. / Bioresource Technology 98 (2007) 422428
(Kyoto, Japan) high-performance liquid chromatography
(HPLC) with a refractive index (RI) detector and BioRad
(Hercules, CA, USA) Aminex HPX-87H column
(300 7.8 mm) at 45 C. The eluent was 0.005 M H
2
SO
4
,
at a ow rate of 0.6 ml/min and a sample volume of
20 ll. The eluent was previously vacuum-ltered through
an HAWP 0.45 lm membrane (Millipore) and degassed
in an ultrasound bath (Microsonic SX-50) for 15 min.
After diluted, the samples were ltered through a Sep
Pak C18 lter (Millipore). Furfural and 5-hydroxymethyl-
furfural concentrations were also determined by HPLC
using a Hewlett-Packard RP 18 column (200 mm) with a
SPD-10A UVVIS ultraviolet detector. In this case, the
eluent was acetonitrile/water (1:8) with 1% acetic acid, at
a ow rate of 0.8 ml/min, with temperature of 25 C and
an injected sample volume of 20 ll. This eluent was also
previously vacuum-ltered through the same procedure of
the previous one. After diluted, the samples were ltered
through a Minisart 0.22 lm membrane (Sartorius).
3. Results and discussion
3.1. Composition of eucalyptus residue
A comparison with data from other authors is presented
in Fig. 1, which shows the results of average chemical com-
position of eucalyptus residues (current study) compared
with other biomass sources. These results show that the cel-
lulose content found in the eucalyptus residue (current
study) was lower than eucalyptus chips and sugarcane
bagasse (Mendonca, 1997; Almeida e Silva, 1996; Rocha,
2000). This is attributed to the greater amount of branches,
leaves and peels contained in the residues, and this resulted
in lower cellulose concentration and higher hemicellulose
concentration. A similar behavior was obtained by Marti-
nez et al. (1995). The amounts of hemicellulose and soluble
lignin were larger, which agrees with the hypothesis that
the sample contains larger amount of tannins when com-
pared with the other samples of chips. The residue pre-
sented larger concentration of ashes, a fact that can also
be attributed to the presence of peels, leaves and branches.
In addition, it was collected on the ground, containing
large amounts of sand, which could increase the content
of ashes. The average chemical composition of the eucalyp-
tus residues was very similar to the materials already used
in the acid hydrolysis for obtaining of hemicellulosic
hydrolysate (Herrera et al., 2003; Aguilar et al., 2002;
Roberto et al., 2003; Pessoa Jr. et al., 1997).
3.2. Optimization of acid hydrolysis and validation of
statistical model
The inuence of temperature (T), acid concentration
(CA) and residue/acid solution ratio (R/A) on the hemicel-
lulose removal of eucalyptus residue without the degrada-
tion of other fractions as the cellulose and lignin was
evaluated on a model composition corresponding to a 2
3
orthogonal factorial design (Table 1) through dilute acid
hydrolysis. The results on estimated eects, standard errors
(SE), Students t test and signicance level for the model
representing xylose extraction from the hemicellulosic frac-
tion of eucalyptus residue are presented in Table 2. An
analysis of this table shows that p values are lower than
0.01, which indicates that there is a statistically signicant
relationship between the variables within a 99% condence
interval. Analysis of variance of the regression was
Fig. 1. Comparison of the average chemical composition (% dry basis) with data published in the literature and the current study.
E.V. Canettieri et al. / Bioresource Technology 98 (2007) 422428 425
obtained for the model representing xylose extraction from
the hemicellulosic fraction of eucalyptus residue within the
studied region. The obtained model was signicant, pre-
senting a determination coecient of R
2
= 0.87, which
means it explains 87% of the variability in the responses
for the region studied, the remaining 13% being explained
by the residue. The estimated eects from Table 2 were
the values that established the equation of the model. For
the conditions utilized in this study, the model with coded
variables expressed in Eq. (6) represents the maximum
xylose extraction (Y) from the hemicellulosic fraction of
E. grandis residue, as a function of acid concentration
(X
1
) and temperature (X
2
):
Y 69:00 15:39X
1
16:70X
2
2
15:52X
1
X
2
16:88X
2
1
.
6
Response surface and the contour lines are presented in
Fig. 2 and they were used to estimate the xylose extraction
over the independent variables acid concentration (X
1
) and
temperature (X
2
). This region contains a maximum point
corresponding to approximately 80% of xylose extraction
from the hemicellulosic fraction of eucalyptus residue. To
determine the values for acid concentration (CA), resi-
due/acid solution ratio (R/A) and temperature (T) that
supplies a maximum xylose extraction it was necessary to
maximize the equation of model. The estimation of con-
tour lines for model (Y) shown in Eq. (6) presented the
maximum value of xylose extraction for the coded values
of sulfuric acid concentration (+0.58), residue/acid solu-
tion ratio (+1.29) and temperature (0.27), which are
equivalent to 0.65%, 1/8.6 and 157 C, respectively. The
behavior of Fig. 2 indicates that according to the model
an increase of temperature in the process provided a higher
xylose extraction; however, it became clear that tempera-
tures above 160 C (170 C for example) initiated forma-
tion of sugar degradation products including furfural and
5-hydroxymethylfurfural, exhibited a displacement in the
hydrolysis reaction in the direction of the conversion of xy-
lose to furfural, which, in this case, was not desired. The
furfural is formed from the degradation of pentoses and
5-hydroxymethylfurfural is formed from the degradation
of hexoses. The temperature became a limiting factor of
acid hydrolysis for the maximum xylose removal. The main
conclusion is that a higher reaction temperature promoted
the formation of furfural and decreased the maximum xy-
lose extraction attainable in the process. The factors that
determine the acid hydrolysis process were mainly temper-
ature, acid concentration and residue/acid solution ratio.
These three factors exert a synergic eect in the hydrolysis
process.
To conrm the validity of the model, four assays were
performed under the optimal conditions established by the
model, resulting in 79.6% xylose extraction (Table 3). The
value of xylose extraction estimated by the model was
90.68 4.25% and the experimental value encountered
was 79.56 1.52%. This xylose extraction agrees with the
value predicted by the model in a 95% condence interval.
This behavior shows that the model adapts to the experi-
mental results. These conditions provided a hemicellulosic
hydrolysate containing 1.65 g l
1
glucose, 13.65 g l
1
xylose, 1.55 g l
1
arabinose, 3.10 g l
1
acetic acid,
1.23 g l
1
furfural and 0.20 g l
1
5-hydroxymethylfurfural.
This composition of hemicellulosic hydrolyzate contained
low concentration of other components as glucose,
Table 2
Estimated eects, standard errors (SE), Students t test and signicance
level for the model representing xylose extraction from the hemicellulosic
fraction of eucalyptus residue
Factors Estimated eects SE t p
Constant 69.0021 4.25399 16.2206 0.0000
X
1
15.3946 3.36395 4.57634 0.0005
X
2 *
X
2
16.6965 4.42207 3.77641 0.0023
X
1 *
X
2
15.5225 4.00299 3.87772 0.0019
X
1 *
X
1
16.8768 4.42207 3.81649 0.0021
X
1
= acid concentration (%) and X
2
= temperature (C).
Fig. 2. Response surface and contour lines described by the model
equation (6) representing xylose extraction from the hemicellulosic
fraction of E. grandis residue.
Table 3
Test of validity of model Y for acid hydrolysis of the hemicellulosic
fraction of eucalyptus residue in the optimal conditions proposed in this
study
Response: xylose extraction (%)
Estimable values by statistical model
Estimate based on model 90.68 4.25
Lower limit, 95% condence 77.81
Higher limit, 95% condence 103.55
Experimental values
(1) 80.92
(2) 79.39
(3) 78.69
(4) 79.23
Average 79.56 1.52
95% IC (condence interval) 78.04 81.08
426 E.V. Canettieri et al. / Bioresource Technology 98 (2007) 422428
arabinose, acetic acid, furfural and 5-hydroxymethylfurf-
ural, which shows an ecient hydrolysis, demonstrating
that the reaction occurred in the direction of the maximum
degradation of hemicellulose in monomers of xylose.
Chambers (1979) produced hemicellulosic hydrolysate
from oak hardwood utilizing 0.2% sulfuric acid, 150 C
and 90 min, and attained 83% xylose yield. Roberto et al.
(2003) obtained similar results working with sulfuric acid
hydrolysis of rice straw. These authors achieved 77% xylose
extraction with 1% H
2
SO
4
, 121 C and 27 min of reaction
time. Pessoa Jr. et al. (1997) conducted sulfuric acid hydro-
lysis of sugarcane bagasse at 140 C, for 20 min, using
100 mg
acid
/g
dm(weight of dry matter ingram)
, and obtained 83.3%
xylose extraction. In this case, the hemicellulosic hydroly-
sate contained 0.08 g l
1
5-hydroxymethylfurfural,
2.0 g l
1
furfural and 3.7 g l
1
acetic acid. Sanchez et al.
(2004) studied the hemicellulose hydrolysis of Paja Brava
for an H
2
SO
4
of 0.5%. The optimum temperature was
190 C for a residence time of 5 min and they reported a
maximum yield of recovered xylose of about 80%, which
is very similar to the result of the present study. Previous
reports of yields of recovered xylose from hemicellulose
hydrolysis of similar biomass closely agree with those
found in the present study. However, the optimum condi-
tions of operation (acid concentration, temperature and
time reaction) found for dilute acid hemicellulose hydroly-
sis of other materials were dierent. The reason for the dif-
ference in the optimum conditions of hydrolysis can be
attributed to the type of equipment used for hydrolysis
and the variation in the chemical composition of the bio-
mass. Both inuence the degree of hemicellulose degrada-
tion. In reality, when the temperature is increased, the
speed of the reaction is also increased and, therefore, the
reaction time decreases. After an extensive study concern-
ing acid hydrolysis of hemicellulose, Lee et al. (1999)
reported that the maximum yield possible in a batch reac-
tor (with a certain solids to liquid ratio) will be decided by
the ratio between the rate constants, which in turn will
depend on temperature and acid concentration.
4. Conclusion
The chemical characterization of eucalyptus residue and
its hydrolysis catalyzed by sulfuric acid allowed the maxi-
mum removal of hemicellulose. The highest yield of xylose
was at 79.6%, at a temperature of 157 C, an acid concen-
tration of 0.65% and a reaction time of 20 min. This result
can conrm the higher facility of degradation of hemicellu-
lose when compared to cellulose and lignin. During hemi-
cellulose hydrolysis there is a signicant parallel reaction,
which is the xylose conversion to furfural. The control of
this reaction is directly on the temperature, acid concentra-
tion, and the reaction time. This ecient hydrolysis of
hemicellulose is an alternative promising process to trans-
form the eucalyptus residue, a source of fermentable carbo-
hydrate, into chemicals of high aggregate value, such as
furfural, 2,3-butanediol, xylitol, among others.
Acknowledgements
The authors are grateful to Fundacao de Amparo a` Pes-
quisa do Estado de Sao PauloFAPESP for the nancial
support through project number 00/09099-0 and to Suzano
Paper and Cellulose Company for the Eucalyptus grandis
residue.
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