Industrial Crops and Products 71 (2015) 163–172

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Industrial Crops and Products

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Oxalic acid as a catalyst for the hydrolysis of sisal pulp

Talita M. Lacerda, Márcia D. Zambon, Elisabete Frollini ∗
Macromolecular Materials and Lignocellulosic Fibers Group, Center for Science and Technology of BioResources, Institute of Chemistry of São Carlos,
University of São Paulo, CP 780, 13560-970 São Carlos, São Paulo, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: The possible shortage of crude oil has led to the search for alternative sources of chemicals and energy
Received 8 May 2014 producers from biomass.The current results are related to the analysis of the unreacted cellulosic material
Received in revised form 18 February 2015 and the liquor, from the acid hydrolysis of an industrial Kraft sisal pulp. An important characteristic
Accepted 22 March 2015
involving the acid hydrolysis of biomass is the possibility to utilize different acids because the only
requirement for the reaction to occur is the presence of a proton source in the media. In this context,
Keywords:
a series of acid hydrolysis reactions of a prior mercerized sisal pulp was performed with 4.6 mol L−1
Sisal pulp
oxalic acid at varying temperatures (from 80 to 100 ◦ C), and aliquots were withdrawn from the reaction
Acid hydrolysis
Oxalic acid
media.The liquor composition was analyzed by HPLC and the unreacted pulps (e.g., the material that
was not decomposed to sugars) were characterized by SEM, average molar mass, crystallinity index, and
their size distribution was determined using a fiber analyzer. The kinetic model developed by Saeman
was applied to calculate the activation energy for the acid hydrolysis of sisal pulp. A higher glucose
concentration (approximately, 8 g L−1 ) was detected at 100 ◦ C, after 16 h. The percentage of hydrolyzed
cellulose under these conditions was 50.4%, and the amount of glucose recovered as a percentage of
the amount in the raw sisal pulp was 22.3%. Unreacted cellulose was isolated at a low average molar
mass (approximately 6000 g mol−1 ) and high crystallinity (approximately 88%), at 100 ◦ C. Oxalic acid is
a promising catalyst for the hydrolysis of cellulose for the production of sugars and for pretreatment of
the fibers prior to other processes (e.g., enzymatic hydrolyses).
© 2015 Elsevier B.V. All rights reserved.

1. Introduction the following processes are required in this order: concentration,

The current trend toward environmentally friendly energy has
promoted a worldwide effort in recent decades to develop the use
of biomass for the productionof biofuels so that it is economi-
cally feasible (Lu and Mosier, 2008; Tomme et al., 1995; Xiang
et al., 2004; Xu et al., 2011). Therefore, ethanol has become the
most promising short-term alternative fuel due to its compatibil-
ity with current car engines and the gasoline supply chain (Cole,
2011). In this context, the search for non-fossil fuels has led to the
development of so-called second-generation ethanol (e.g., ethanol
derived from biomass) through the acid or enzymatic saccharifica-
tion.
The possibility of converting cellulose into glucose is especially
useful because these sugars can be easily converted to ethanol,
which justifies the growing interest in research into the use of
lignocellulosic material, which is typically agricultural waste, for
the production of bioethanol. The hydrolysates obtained from the
hydrolysis are processed for use as fermentation media. In general,
∗ Corresponding author. Tel.: +55 16 3373 9951; fax: +55 16 3373 9952.
E-mail address: elisabete@iqsc.usp.br (E. Frollini).
detoxification, neutralization and supplementation with nutrients
(Lenihan et al., 2010).
Biomass obtained from different raw materials, including corn-
cob (Sun et al., 2013), rice hulls (Dagnino et al., 2013), palm leaves
(Werle et al., 2013), sugarcane bagasse (Rocha et al., 2012), and
softwood pulps (Hoeger et al., 2013), have been investigated as a
source of sugar for further conversion to ethanol. When a lignocel-
lulosic feedstock is used as a source of sugar in ethanol production,
the polysaccharides content, especially the cellulose content, of the
respective feedstock is highly relevant. In the present study, sisal
was chosen as the lignocellulosic raw material due to the high cel-
lulose content of its fibers (approximately 65% cellulose (Da Silva
et al., 2012; Frollini et al., 2013) and other reasons, as its abundance
in Brazil (de Paula et al., 2012).
The production of bioethanol from lignocellulosic biomass
typically requires some sort of pretreatment to disrupt the
cellulose–hemicelluloses–lignin complex to make the cellulose and
hemicellulose more accessible for conversion into sugars. Diverse
pretreatments have been reported in the literature, such as steam
explosion (Rocha et al., 2012; Liu et al., 2013; Martin-Sampedro
et al., 2014; Rocha et al., 2014), microwave treatment (Xu et al.,
2011), mechanical fibrillation (Hoeger et al., 2013), organosolv (Koo

http://dx.doi.org/10.1016/j.indcrop.2015.03.072
0926-6690/© 2015 Elsevier B.V. All rights reserved.
164 T.M. Lacerda et al. / Industrial Crops and Products 71 (2015) 163–172
et al., 2012), and treatments with concentrated phosphoric acid and
ionic liquids (Sathitsuksanoh et al., 2012). The cellulosic pulp or cel-
lulose obtained from the pretreatment of lignocellulosic biomass is
often further subjected to treatments that disrupt the structure of
cellulose in order to increase the accessibility of the hydrolyzing
agents (Abushammala and Hashaikeh, 2011). The pretreatments
may have two functions, i.e., to release the cellulose from the resid-
ual recalcitrant lignin and disrupt its crystalline structure, as is the
case when alkali pretreatment is utilized (Rawat et al., 2013). In the
present study, the sisal lignocellulosic fiber was delignified on an
industrial scale through a Kraft process, as described in Section 2.1,
and the cellulosic pulp received from the industrial process was
treated with an aqueous NaOH solution via mercerization (Lacerda
et al., 2012; Okano and Sarko, 1985).
The mercerization process was used for pretreatment of the sisal
pulp, which was determined to be efficient in a previous study
(Lacerda et al., 2012). This treatment alters the fine structure and
morphology of the fiber as well as the conformation of the cellulose
chains (transforming it from cellulose I to II). During this process,
the material swells, the polysaccharide chains are rearranged, and
usually the crystalline portion decreases. These changes result in
higher adsorption because mercerization increases the specific sur-
face area of the fiber, thus making the chains more accessible to
reagents (Ass et al., 2006; Dinand et al., 2002; Okano and Sarko,
1985). In general, the crystallinity index of cellulose fibers has a
direct relationship to reagent accessibility (Ciolacu et al., 2012),
and an increase in the crystallinity index decreases the hydroly-
sis ratio and sugar production (Wang et al., 2012). Therefore, prior
to their hydrolysis, the lignocellulosic sisal fibers were subjected
first to Kraft process and then to mercerization. The combination
of two pretreatments (as two different steps or as a coupled step)
prior to the hydrolysis of the cellulosic biomass has been consid-
ered in several studies, as for instance pretreatment with alkaline
peroxides followed by steam explosion (Balcu et al., 2011; Chen
and Qiu, 2010), ionic liquid treatment coupled with steam explo-
sion (Chen and Qiu, 2010), alkali combined extrusion pretreatment
(Zhang et al., 2012), among others.
Over the years, a number of methods for the conversion of
cellulose to glucose involving the depolymerization of cellulose
via hydrolysis have been developed (Arantes and Saddler, 2010;
Bustos et al., 2003; Cho et al., 2011; Martín and Grossmann 2012;
Rodrigues and Guirardello, 2008; Shields and Boopathy, 2011;
Tásic et al., 2009). Among these methods, the two most commonly
used involve cellulolytic enzymes (Arantes and Saddler, 2010;
Dagnino et al., 2013; Hoeger et al., 2013) or acids, including various
strengths of sulfuric acid (de Paula et al., 2012; Lacerda et al.,
2012). Solid acid catalysts have also been employed (Ma et al.,
2012; Zhang et al., 2013).
Enzymes are still relatively expensive for application to the
large-scale production of fuel ethanol from biomass. Therefore, acid
catalysis is more attractive even though acids tend to degrade glu-
cose. This degradation lowers the yield of fermentable sugars from
the biomass and results in degradation products, such as hydrox-
ymethyl furfural, levulinic acid, and formic acid, which inhibit yeast
fermentation (Mosier et al., 2001).
An interesting feature that involves the acid hydrolysis of
biomass is the possibility of using different acids as catalysts
because in principle, the process only requires a source of protons
in the aqueous medium for the reaction to occur. Several studies
have been conducted involving various types of acids (Sivers and
Zacchi, 1995; Taherzadeh and Karimi, 2007), including H2 SO4 (de
Paula et al., 2012; Lacerda et al., 2012; Lacerda et al., 2013), HCl
(Hernández-Salas et al., 2009), H3 PO4 (Gámez et al., 2004; Lenihan
et al., 2010), heteropoly acids (Tian et al., 2010), and formic acid
(Sun et al., 2008). Marzialetti et al. (2011) described a process
involving dilute hydrolysis of switch grass using formic acid as the
catalyst. This process exhibited good performance with a low yield
of decomposition products.
Although a wide range of acids may be used as a source of pro-
tons for cellulose hydrolysis, the most commonly used is sulfuric
acid, which is the only common polyprotic acid that exhibits com-
plete first deprotonation. The second deprotonation only slightly
increases the molarity of H3 O+ (i.e., pKa1 = −3 and pKa2 = 1.92 at
25 ◦ C) (Budavari, 1996). Oxalic acid, which is a dicarboxylic acid
(HOOC-COOH), shows a lower degree of ionization than sulfuric
acid (pKa1 = 1.27 and pKa2 = 4.28 at 25 ◦ C (Budavari, 1996) and may
require more severe conditions for its use in cellulose hydrolysis.
However, this acid has the advantage that it can be obtained from
natural sources, such as biomass. Fermentation and nitric acid oxi-
dation of carbohydrates can be used for the production of oxalic acid
(Gürü et al., 2001; Sullivan et al., 1983). Oxalic acid, which is present
in many plants and vegetables especially in the Rumex and Oxalis
families, is also a metabolic product in many fungi. Some species of
Penicillium and Aspergillus convert sugar into calcium oxalate with
yields up to 90% (Budavari, 1996).
In recent years, oxalic acid has been used for the pretreatment
of lignocellulosic biomass (Hong et al., 2013), especially prior to
enzymatic hydrolysis. In this application, oxalic acid shows advan-
tages over sulfuric acid because it is less toxic to yeasts and other
microbes and does not produce prejudicial smells (Bo et al., 2013;
Lee et al., 2011). In addition, oxalic acid can be recovered more
easily than sulfuric acid via techniques conventionally used for
organic acids, such as ion-exchange and adsorption, or via less con-
ventional techniques, such as electrodialysis, which can offset the
higher cost of oxalic acid on a weight basis compared to sulfuric
acid (Lee and Jeffries, 2013). Additionally, vom Stein et al. (2011)
have shown that after using oxalic acid to hydrolyze hemicelluloses
and release lignin from a lignocellulosic source, when the aque-
ous phase was concentrated oxalic acid precipitated as a pure solid
(approximately 85 wt%) and could be recovered by simple filtra-
tion. The purity of the recovered oxalic acid allowed its direct reuse
as a catalyst. This set of positive aspects, among others, made the
use of this acid in sustainable biorefineries particularly attractive
(Hongsiri et al., 2015)
In this study, which is a continuation of a previous study that
utilized sulfuric acid (de Paula et al., 2012; Lacerda et al., 2012;
Lacerda et al., 2013), industrial cellulosic sisal pulp was used as the
starting material. Thus, the focus of the present work was not to use
oxalic acid as a pretreatment to remove lignin and hemicellulose,
namely to produce a pulp prior to saccharification (Lee et al., 2011).
The main goal was to explore the performance of this acid as a
catalyst for the saccharification of cellulosic pulp.
The hydrolysis reactions were conducted with mercerized sisal
pulp and monitored over time by evaluating the liquor (sugars and
their decomposition products), which is an important stage in the
production of bioethanol. The physicochemical and morphological
characteristics of the solid non-hydrolyzed material were deter-
mined to provide important information on the overall process. In
addition, these results are relevant for applications in the materials
area, such as for the preparation of crystalline cellulosic materials.
To complement the investigation on the performance of oxalic
acid as a catalyst, the kinetic model developed by Saeman et al.
(1945), which is based on the acid hydrolysis reactions of wood
at low acid concentrations and high temperatures, was applied to
calculate the activation energy for the acid hydrolysis of sisal pulp.
2. Materials and methods
2.1. Materials
The sisal pulp used was obtained from the leaves of plants
cultivated in the state of Bahia, a semi-arid region of North-
 T.M. Lacerda et al. / Industrial Crops and Products 71 (2015) 163–172
east Brazil (daily average temperature: exceeds 24 ◦ C, highest
altitude: 600 m, average annual rainfall: from 650 to 1250 mm,
average annual relative air humidity: from 66 to 79%, winds: 3 ms−1
(http://sistemasdeproducao.cnptia.embrapa.br/FontesHTML/Sisal/).
The sisal pulp used in all stages of this study was kindly provided
by Lwarcell (Lençóis Paulista, São Paulo, Brazil), where the ligno-
cellulosic fiber was delignified via the Kraft process and bleached
with Elementary Chlorine Free (ECF) sequences to produce fibers
that averaged 2.9 mm in length and 18.4 ␮m in thickness with an
86% ISO brightness, as reported by the supplier. Klason lignin was
analyzed according to TAPPI T222-om02, and no insoluble lignin
was detected. All of the pulp samples were previously mercerized
(as described in Section 2.2.1), milled in a MARCONI MA048 miller
(30 mesh stainless steel) and dried in a vacuum oven at 60 ◦ C for
4 h.
The pulp was mercerized in a sodium hydroxide solution
(NaOH in pellets, Qhemis) (ASTM1695-07). For the hydrolysis reac-
tions, oxalic acid (Cromato) was used. A 2% cupri-ethylenediamine
(CED) solution (Qeel) was used in the viscometric analysis. Glu-
cose, xylose, arabinose, formic acid, acetic acid, furfural and
hydroxymethylfurfural (Sigma–Aldrich) were used as standards for
high-performance liquid chromatography (HPLC).
2.2. Methods
2.2.1. Mercerization
The process was performed with 20 g of pulp suspended in 1 L
of a 20 wt% NaOH solution for 3 h at 50 ◦ C with stirring. The pulp
was filtered, washed until the washing water reached its initial pH
(approximately 6.5), and dried at room temperature and then in a
vacuum oven at 60 ◦ C for 4 h. These conditions were chosen based
on the results obtained in a prior study (Lacerda et al., 2012).
2.2.2. Acid hydrolysis
The reactions were performed under mechanical stirring, in a
jacketed reactor connected to a thermostatic bath, and provided
with a condenser and a connection to withdraw aliquots. For the
hydrolysis reactions, 900 mL of a 4.6 mol L−1 oxalic acid solution
were heated (80, 85, 90, 95 and 100 ◦ C), and 30 g of dried, milled
and mercerized pulp was added. All of the reactions were per-
formed over a period of 16 h.The conditions were chosen such that
the results obtained in this study could be compared to those of
previous studies (de Paula et al., 2012; Lacerda et al., 2012; Lacerda
et al., 2013). The initial results for the glucose yield indicated that
the length of time should be longer than that used in previous stud-
ies (i.e., 6 h) to obtain similar yields. Therefore, a time interval of
16 h was used in the current study.
During the reaction course, aliquots of the suspension were
withdrawn (t = 1, 2, 3, 4, 5, 6, 8, 10, 12, 14 and 16 h), and the solid (the
unreacted, non-hydrolyzed pulp) was separated from the liquor by
simple filtration. The liquor was stored at approximately 5 ◦ C for
further analysis. The sugars and related decomposition products
were analyzed by high-performance liquid chromatography (HPLC)
using a Shimadzu instrument. Glucose, xylose, arabinose, formic
acid and acetic acid were analyzed using a refractive index detec-
tor (RID-6A; Aminex HPX 87H column (300 × 7.8 mm BIO-RAD);
eluent: 0.005H2 SO4 mol L−1 ; flow: 0.6 mL min−1 ; 45 ◦ C). Furfural
and hydroxymethyl furfural were analyzed using a UV detector at
274 nm (SPD-10AV); BondapakTM C18 column (Waters); eluent:
acetonitrile/water 1:8 (v/v) acetic acid 1% (v/v); flow: 0.8 mL min−1 ;
25 ◦ C). All HPLC analyses were performed in duplicate.
The non-hydrolyzed pulp was thoroughly washed, stored in
Eppendorf tubes and dried in a vacuum oven at 60 ◦ C for 4 h prior
to determination of the viscometric average molar mass (MMvis),
165
crystallinity index (CI), scanning electron microscopy (SEM), and
the average thickness and length of the fibers, as described below
2.2.3. Pulp characterization
Initial and non-hydrolyzed pulps, which were withdrawn dur-
ing the reactions, were characterized as described in the following
sections.
2.2.3.1. Hemicellulose and ˛-cellulose content. The procedure con-
sists of adding an amount of pulp to a 17.5% NaOH solution (liquor
ratio = 1:20, w/v), at room temperature (Sun et al., 1995). The ␣-
cellulose content was determined from the dry masses (dried in an
air-circulating stove at 105 ◦ C, up to constant weight) of pulp before
and after the treatment with the NaOH solution. The difference
between the initial mass and the calculated mass of ␣-cellulose
corresponds mainly to the hemicellulose content (Browning, 1967).
2.2.3.2. Scanning electron microscopy (SEM). For the SEM measure-
ments, a Zeiss LEO-440 instrument was used with a tungsten
filament to generate electrons, as previously described (Ramires
et al., 2010). The samples were dried in a vacuum for 4 h and covered
with gold.
2.2.3.3. Average molar mass (MMvis) by viscometry. Viscometry was
used to determine the average molar mass of the starting and non-
hydrolyzed cellulose using aliquots withdrawn from the reaction
medium at different time intervals during the reactions. Cellulose
was dissolved in a copper(II)-ethylenediamine/water solution (1:1,
v/v), and the flow time in a glass capillary viscometer (Ubbelohde,
f = 0.63 mm, AVS-350 Schott-Geräte) was measured. The average
molar mass of the samples was determined according to TAPPI T230
om-2008, as previously described (Morgado et al., 2011). All of the
measurements were performed in triplicate.
2.2.3.4. Crystallinity index (CI) by X Ray diffraction. Initial and non-
hydrolyzed cellulose (obtained from five pulp samples, t = 1, 4, 8,
12 and 16 h of reaction), previously dried in a vacuum oven (60 ◦ C,
4 h), were analyzed by X-ray diffraction to determine the CI using
a universal X-ray diffractometer (URD-6 model, CARL ZEISS JENA,
40 kV/20 mA,  (Cuk␣) = 1.5406 Å). The CI was calculated according
to the following equation:
I1
CI = 1 − (1)
I2
where I1 is the minimum intensity, which is proportional to the
non-crystalline fraction of the cellulose (18◦ ≤ 2 ≤ 19◦ for cellu-
lose I and 13◦ ≤ 2 ≤ 15◦ for cellulose II), and I2 is the maximum
intensity, which corresponds to the signal of the crystalline frac-
tion (22◦ ≤ 2 ≤ 23◦ for cellulose I and 18◦ ≤ 2 ≤ 22 ◦ for cellulose
II) (Buschle-Diller and Zeronian, 1992).
Because the diffractogram is the intensity as a function of the
diffraction angle (2), it is possible to obtain the half-height [(2)]
for the maximum diffraction intensity. Using the Scherrer equation
(Pouget et al., 1991), the average size of the crystalline domains can
be calculated:
0.9 × 
L= (2)
(2) × cos
where  = 1.5406 Å, which is the wavelength of the X-rays
employed.
2.2.3.5. Average thickness and length of the fibers. The average thick-
ness and length of the fibers were obtained using MorFi Compact
(Techpap) equipment, which measures approximately 5000 fibers
suspended in water. The MorFi automatic fiber-analysis system also
provides the fiber-occurrence density (Millions-per-Gram), which
166 T.M. Lacerda et al. / Industrial Crops and Products 71 (2015) 163–172
Fig. 1. SEM images for the starting pulp (a) and non-hydrolyzed pulps from the reactions performed at 80 ◦ C (b), (e), 90 ◦ C (c, f) and 100 ◦ C (d, g) after 6 h (b–d) and 16 h (e–g).
enables the construction of a density map, i.e., a three-dimensional
graph with the following characteristics: average length values on
the x axis, average thickness values on the y axis, and the fiber-
occurrence density values on the z axis.
3. Results and discussion
3.1. Initial pulp characterization
The values obtained for the average molar mass (MMvis),
␣-cellulose content, hemicellulose content and CI for the pulp
samples were previously presented (Lacerda et al., 2012) and are
119000 ± 700 g mol−1 , 88 ± 4%, 12 ± 3% and 77%, respectively, for
the unmercerized pulp and 99,900 ± 450 g mol−1 , 98 ± 1%, 2 ± 1%
and 69%, respectively, for the mercerized pulp.
As previously discussed (Lacerda et al., 2012), the merceriza-
tion pretreatment is important for the acid hydrolysis of sisal pulp
because it produces a material with a higher ␣-cellulose con-
tent compared to the untreated pulp, thus resulting in fewer side
reactions and undesirable byproducts in the reaction medium. In
addition, the alkaline treatment led to the formation of cellulose
II, as indicated by the characteristic peaks in the diffractograms
with 2 between 18◦ and 22◦ (Lacerda et al., 2012) and reduced the
CI value. Ciolacu et al. (2012) reported that the allomorph with the
most accessible crystal surfaces and amorphous regions is cellulose
II. The increased amount of chains in the non-crystalline regions,
which are more accessible to reagents, and the change of cellu-
lose I to II due to mercerization favor the hydrolysis process. A
comparison between the results reported by Lacerda et al., 2012
(hydrolysis of mercerized sisal pulp) and those found in a previous
study on the hydrolysis reactions catalyzed by sulfuric acid solu-
tions using unmercerized sisal pulp (de Paula et al., 2012) showed
that the changes caused by mercerization significantly improved
the accessibility of the cellulose chains to the reagents. Under the
same reaction conditions (30% sulfuric acid, 100 ◦ C, 6 h), the hydrol-
ysis of mercerized pulp generated yields of up to 50% more glucose,
compared to the unmercerized pulp.
3.2. Characterization of the non-hydrolyzed pulp
3.2.1. SEM
Fig. 1 shows the SEM images of the initial pulp used as raw
material for the hydrolysis reactions (a) and the non-hydrolyzed
cellulose, which was withdrawn at different time intervals (6 and
16 h) and temperatures (80, 90 and 100 ◦ C) (b–g) during the hydrol-
ysis reaction.
At 100 ◦ C, greater fragmentation of the fibers occurred com-
pared to the non-hydrolyzed fibers at 80 ◦ C (Fig. 1d–g and b–e,
respectively). In addition, longer reaction times complement this
effect, which can be observed by comparing images, c and f (6 and
16 h of reaction, respectively, 90 ◦ C) and images d and g (6 and 16 h
of reaction, respectively,100 ◦ C). These images represent the aver-
age of all ofthe other reaction conditions, which resulted in the
same pattern of fiber fragmentation observed by SEM.
 T.M. Lacerda et al. / Industrial Crops and Products 71 (2015) 163–172
Fig. 2. (a) Average molar mass, (b) crystallinity index and (c) crystalline domain
dimensions for the non-hydrolyzed cellulose during the hydrolysis reactions.
3.2.2. The average molar mass (MMvis), crystallinity index (CI)
and crystalline domain dimensions via X-ray diffraction.
Fig. 2 shows the average molar mass (a), crystallinity index (b)
and average size of the 0 0 2 plane (c) as a function of time for the
hydrolysis reactions.
In Fig. 2a, the drastic reduction in MMvis, which was observed
at all of the temperatures, indicates that the oxalic acid acted
as a catalyst for the hydrolysis of sisal pulp. The initial MMvis
value (99,900 g mol−1 ) was reduced after 16 h of reaction to val-
ues ranging from approximately 6000–7000 g mol−1 depending on
the temperature (Fig. 2a).
The preferential hydrolysis of the chains in the non-crystalline
domains led to a significant increase in CI since the early reaction
times (Fig. 2b). The substantial decrease in the average molecular
weight led to significantly shorter chains compared to the starting
pulp used in the hydrolysis, which can favor the organization of the
chains, which can contribute to the increase in CI. A decrease in the
average molar mass, as well as an increase in CI compared to the
beginning of the reaction, were also observed in studies where sul-
furic acid was used as the catalyst for the hydrolysis of sisal pulp (de
Paula et al., 2012; Lacerda et al., 2012). It is important to note that
higher temperatures and longer reaction times increase the hydrol-
ysis of the chains in the crystalline regions, leading to a decrease in
CI (Fig. 2b).
167
For the shorter reaction times, the average size of the crystalline
domains increased at all of the temperatures considered in this
study (Fig. 2c). This result may be due to the joining of smaller
crystalline domains, due to the consumption, during hydrolysis, of
chains present in non-crystalline domains and that were initially
allocated among the smaller crystalline domains. When the tem-
perature is increased to 100 ◦ C, an initial increase in the dimensions
of the crystallites also occurs (Fig. 2c), followed by a reduction after
4 h. This phenomenon is accentuated after 12 h, which is most likely
due to the hydrolysis of chains in the crystalline domain, which also
leads to a decrease in CI (Fig. 2b).
3.2.3. Average thickness and length of fibers (Fiber analyzer –
MorFi).
Fig. 3 shows the density maps obtained from the morphological
analysis using the MorFi Compact equipment for the initial pulp
(mercerized), (Lacerda et al., 2013) and the non-hydrolyzed cellu-
lose withdrawn from the reaction media at 80, 90 and 100 ◦ C after
6 and 16 h of hydrolysis. The reactions at other temperatures (i.e.,
85 and 95 ◦ C, data not shown) exhibited similar behavior.
All of the fibers withdrawn from the reaction media (non-
hydrolyzed pulp) exhibited severe variations in their length and
thickness. From Fig. 3b, which corresponds to 6 h at 80 ◦ C,the
density map exhibits higher quantities of fibers with a length of
129–215 ␮m compared to the initial pulp (Fig. 3a), (Lacerda et al.,
2013) thus indicating that a greater population of fibers have a nar-
rower size distribution of lengths after hydrolysis. The variation in
the fiber thickness after hydrolysis is not as clear as the variation in
the fiber length. However, thinner fibers were formed as the tem-
perature and the exposure time to the acid solution were increased,
which is evident from the increase in the density of the fibers with a
thickness of 11–14 ␮m (Fig. 3b) at higher temperatures and longer
reaction times.
By comparing Fig. 3b and c with Fig. 3f and g, an increase in
the density of the less thick [11–23 ␮m] and shorter [46–129 ␮m]
fibers was observed, and this increase is more significant when
T = 100 ◦ C (Fig. 3f and g) compared to T = 80 ◦ C (Fig. 3b and c). For
the initial pulp (Fig. 3a), (Lacerda et al., 2013) the fraction with a
greater density is located in a broader thickness region [11–39 ␮m]
compared to the maps of the non-hydrolyzed pulps (Fig. 3b–g).
All of these maps exhibit a “valley” dividing two regions of differ-
ent thicknesses, which is due to the consumption of the fractions
between [6 and 8] and [11 and 14] ␮m during the hydrolysis
reactions.When sulfuric acid was used at the same temperature
and concentration (Lacerda et al., 2013), the corresponding den-
sity map for the 6 h reaction at 100 ◦ C exhibited an even higher
fiber density in regions with more narrow [11–14 ␮m] and shorter
[46–77 ␮m] fibers, which indicates that oxalic acid can be uti-
lized for cellulose hydrolysis under milder conditions than with
sulfuric acid.
The density maps shown here represent the average of all of the
other reaction conditions at intermediate time and temperature,
which showed similar patterns for the evolution of the length and
thicknessof the fibers.
3.3. Characterization of the products of the hydrolysis reactions
As described in Section 2.2.2, the sugars and their decomposition
products analyzed in the liquor were glucose, xylose, arabinose,
formic acid, acetic acid, hydroxymethylfurfural (HMF) and furfural.
Glucose (produced primarily by the hydrolysis of cellulose), xylose
(produced by the hydrolysis of hemicellulose), HMF and furfural,
which are the main products from the decomposition of glucose
and xylose, respectively, were observed in all of the reactions. The
presence of glucose under all hydrolysis conditions indicates cleav-
age of the 1,4-␤-glycosidic linkages of the cellulosic chains, and the
168 T.M. Lacerda et al. / Industrial Crops and Products 71 (2015) 163–172

Fig. 3. Fiber-occurrence density (Millions-per-Gram) of the initial pulp (a, (Lacerda et al., 2013)) and non-hydrolyzed cellulose withdrawn from the reaction performed at
80 ◦ C (b and c), 90 ◦ C (d and e) and 100 ◦ C (f and g) after 6 h and 16 h, respectively.
 T.M. Lacerda et al. / Industrial Crops and Products 71 (2015) 163–172
Fig. 4. (a) Xylose (Errors from ±0.01 to ±0.22, and (b) furfural (Errors from ±0.007
to ±0.25) concentrations as function of hydrolysis time.
presence of HMF indicates that all of the reaction conditions led to
the partial decomposition of glucose by dehydration. Formic acid,
which is a decomposition product of HMF (Belgacem and Gandini,
2008), was detected at all of the temperatures studied. Arabinose
and acetic acid, which are both produced from the hydrolysis of
hemicelluloses, were not observed for any of the reactions con-
sidered here. During kraft cooking the acetyl groups are readily
hydrolysed (Sjöström, 1993), which may explain the absence of
acetic acid, since a deacetylated xylan was present in the starting
pulp.
Fig. 4 shows the products observed in the liquor that are directly
obtained from hemicellulose hydrolysis (i.e., xylose) (Fig. 4a) and
its major decomposition product, furfural (Fig. 4b).
For the reactions performed at 80, 85, 90 and 95 ◦ C, the concen-
tration of xylose increased until a reaction time of approximately
12 h (Fig. 4a), and the concentration then remained nearly constant
at longer reaction times. In addition, at 100 ◦ C, the concentration of
xylose increased until a reaction time of approximately 6 h followed
by a decrease in the observed concentration, which indicates that
at this temperature, the decomposition of xylose was significantly
more intense than at the other temperature conditions. All of the
reaction conditions led to the decomposition of xylose, which was
confirmed by the presence of furfural at all of the studied tempera-
tures, as shown in Fig. 4b. However, from 80 ◦ C to 90 ◦ C for reaction
times up to 8 h, the concentration of furfural was zero or quite
low. In addition, at 80 ◦ C and 16 h, approximately 0.6/0.05 g L−1 of
xylose/furfural was observed in the medium, and at 100 ◦ C, approx-
imately 1.5/0.5 g L−1 of xylose/furfural was observed (Fig. 4a and
b).
Fig. 5 shows the products found in the liquor that are primarily
obtained from cellulose hydrolysis (i.e., glucose, Fig. 5a), its major
decomposition product (i.e., HMF, Fig 5b), and formic acid (Fig. 5c).
In sisal pulp, hemicellulose contains only approximately 2.2% glu-
cose (Megiatto et al., 2007). As mentioned above, the content of
␣-cellulose in the mercerized sisal pulp used in the current study is
98% (i.e., the content of hemicellulose is approximately 2%). There-
fore, as an approximation, the glucose content was considered to
originate only from cellulose.
169
Glucose production is directly related to the temperature of the
reaction, and the maximum concentration detected was approxi-
mately 8 g L−1 (after 16 h, 100 ◦ C, Fig. 5a). The amount of glucose in
the raw sisal pulp was 35.9 g L−1 {[glucose] sisal pulp = mass (30 g) × %
cellulose (98%) × q (1.1)/V (0.9L)}, where q is the conversion factor
for anhydrous glucose (162 g mol−1 , in cellulose chain) to glucose
in the liquor (180 g mol−1 , they differ in mass by a water molecule).
Thus, the amount of glucose recovered after 16 h at 100 ◦ C was
22.3% (8/35.9 × 100).
At 80 ◦ C and 85 ◦ C, almost no HMF was formed, and only after
10 h a small fraction was detected at 85 ◦ C. For the reaction per-
formed at 90 ◦ C at reaction times up to 6 h, the production of HMF
is absent or very small, and after 8 h, less HMF was produced com-
pared to that produced at 95 ◦ C. At 80 ◦ C and at reaction time of
16 h, approximately 1.3/0.005 g L−1 of glucose/HMF was observed
in the medium, and at 100 ◦ C, approximately 8.0/0.092 g L−1 of glu-
cose/HMF was observed (Fig. 5a and b).
At 80 ◦ C and 85 ◦ C, the concentration of formic acid was zero
or quite low, and at 90 ◦ C, the production of formic acid followed
the trend observed for HMF. For the reactions performed at 95 to
100 ◦ C, the production of formic acid was observed practically from
the beginning of the reactions(Fig. 5b and c) due to the extremely
low stability of HMF under these conditions, which leads to the
formation of formic and levulinic acids (not analyzed).
The amount of glucose present in the liquor (8 g L−1 , Fig. 5a)
together with the amount of its decomposition products at 100 ◦ C
after 16 h (Fig. 5b and c), was 18.1 g L−1 , which means that the
percentage of hydrolyzed cellulose corresponded to 50.4% (18.1 /
35.9 × 100).
3.3.1. Activation energy for acid hydrolysis.
As previously described (de Paula et al., 2012), to calculate the
reaction constants (i.e., k1 and k2, related to the rates of pulp hydrol-
ysis and decomposition, respectively), the Saeman model (Saeman
et al., 1945) was applied to the experimental glucose concentration
curves using the Origin Pro 8 SRO software version 8.0724 (B724).
With the nonlinear fitting tool software, the data were fitted to the
model. For this purpose, the values of the glucose concentration
([B]) were inserted into the equation that describes the model (Eq.
(4)) for each time (t) starting from the initial cellulose concentra-
tion ([A]0 ), and the values of k1 and k2 were calculated for each
of the studied conditions. The concentration of the initial cellulose
was calculated based on the mass of the pulp added to the reactor
and the ␣-cellulose content (98%) of the starting mercerized pulp.
k1
[B] = (e−k1 t − e−k2 t )[A]0 (4)
k2 − k1
Fig. 6 shows the nonlinear fit of the Saeman model for the glu-
cose concentration as a function of the hydrolysis time (90 ◦ C). The
values of the constants (k1 and k2 ) and the R2 value are shown in
Table 1. The profile of the other reactions (80,85, 95, and 100 ◦ C,
figures not shown) was close to the model proposed by Saeman
(Saeman et al., 1945), as indicated by the values of R2 (Table 1).
Oxalic acid does not catalyze the decomposition of glucose at
temperatures less than 90 ◦ C. At 95 ◦ C and 100 ◦ C, k2 is not zero, but
k1 assumes values that are considerably higher than those at lower
temperatures (Table 1).
In a prior study, the reactions were performed with 4.6 mol L−1
sulfuric acid (Lacerda et al., 2012), which is the same concentra-
tion used here for oxalic acid, and at 100 ◦ C,which is the highest
temperature tested for oxalic acid. It should be noted that when
sulfuric acid was used as the catalyst, aliquots were withdrawn
over a period of 6 h, and for oxalic acid, the first aliquot was
obtained at 1 h and more aliquots were taken until 16 h (see Sec-
tion, 2.2). In addition, although the concentration of both acids
(i.e., sulfuric and oxalic) was the same, the concentration of pro-
170 T.M. Lacerda et al. / Industrial Crops and Products 71 (2015) 163–172

Fig. 5. (a) Glucose (Errors from ±0.01 to ±0.69), (b) HMF (Errors from ±0.01 to ±0.29) and (c) formic acid (Errors from ±0.13 to ±0.66) concentrations as function of the
hydrolysis time.

Table 1
Constants for pulp hydrolysis (k1 ) and glucose decomposition (k2 ) and R2 values for the oxalic acid catalyst.

80 ◦ C (min−1 ) 85 ◦ C (min−1 ) 90 ◦ C (min−1 ) 95 ◦ C (min−1 ) 100 ◦ C (min−1 )

k1 x 103 1.0 4.7 7.4 21.4 33.1

k2 x 103 0.0 0.0 0.0 4.6 6.4
R2 0.996 0.983 0.992 0.986 0.972

tons was considerably higher for sulfuric acid due to the differences
in their respective ionization potentials. The results for k1 and k2
obtained were 5.5 10−3 min−1 and 6.6 10−3 min−1 (reaction time:
6 h), respectively. For oxalic acid, in the current study the values of
these constants were 33.1 10−3 min−1 and 6.4 10−3 min−1 (reaction
time: 16 h) (Table 1). Therefore, despite the differences between the
two reactions, it can be inferred that under oxalic acid catalysis, at a
temperature at which glucose decomposition occurs (100 ◦ C), this
reaction is slower than the reaction under sulfuric acid catalysis at
the same temperature. The relatively weaker ionization potential of
oxalic acid compared to sulfuric acid could decrease the occurrence
of subsequent dehydration reactions (Lee et al., 2011).
The values obtained using sisal pulp and oxalic acid at 100 ◦ C
have the similar magnitudes, more so for k1 , as those presented
by Aguilar et al. (2002), who obtained values for k1 and k2 of 35.7
10−3 min−1 and 0.29 10−3 min−1 , respectively, for the hydrolysis
 T.M. Lacerda et al. / Industrial Crops and Products 71 (2015) 163–172
Fig. 6. Nonlinear adjustment of the Saeman kinetic model for the reaction at 90 ◦ C
with 4.6 mol L−1 oxalic acid.
Fig. 7. Arrhenius plot for the acid hydrolysis of sisal pulp (80–100 ◦ C, 4.6 mol L−1
oxalic acid).
of sugarcane bagasse using low concentrations of H2 SO4 (2%) at
122 ◦ C.
The activation energy was calculated from the general Arrhe-
nius law (Eq. (5)), where w is a pre-exponential factor (same
unit as k1 ), Ea is the activation energy, R is the gas constant
(8.3143 × 10−3 kJ mol−1 K−1 ), and T is the absolute temperature.
−Ea
lnk1 = + lnw (5)
RT
Fig. 7 is generated from the logarithm of k1 as a function of the
inverse of the absolute temperature to obtain Ea .
From Fig. 7, a value of 185.9 kJ mol−1 was obtained for the activa-
tion energy for the hydrolysis of sisal pulp under these conditions.
The calculated value is higher than the one calculated in a
previous study (60.4 kJ mol−1 ) for the hydrolysis of unmercerized
sisal pulp using a sulfuric acid (30%) catalyst at 60–100 ◦ C with
data collected over 6 h (de Paula et al., 2012), and with a higher
concentration of protons in the medium compared to oxalic acid.
Maleic acid, which is a dicarboxylic acid, has a pKa1 and pKa2
(20 ◦ C) of 1.9 and 4.4, respectively, which are relatively close to
those of oxalic acid. The activation energy for the hydrolysis of
cellobiose with maleic acid catalysis was reported to be approxi-
mately 115 kJ mol−1 (Mosier et al., 2002), which is lower than that
determined in this study. However, it should be noted that for
maleic acid, the reaction occurred under homogeneous conditions
because cellobiose is soluble in water. Therefore, issues related
171
to crystallinity, among others, were not present, contrary to what
occurs when pulps are hydrolyzed, as in this study.
4. Conclusions
Under the conditions studied, the results indicated that oxalic
acid can be used as a catalyst for the acid hydrolysis of sisal pulp as
a first step in the production of second generation ethanol because
it allows the formation of glucose even at the lowest temperature
evaluated (80 ◦ C). Higher temperatures facilitate the process, and a
higher glucose concentration (approximately 8 g L−1 ) was detected
when T = 100 ◦ C, which can be considered as the optimal reaction
condition of the present study concerning glucose production.
Unreacted cellulose (e.g., a material that was not totally decom-
posed to simple sugars) was isolated at a low average molar
mass (approximately 6000 g mol−1 , when T = 100 ◦ C) and high crys-
tallinity index (approximately 88%, when T = 100 ◦ C), which are
characteristics of a low DP microcrystalline cellulose. Under mild
conditions (i.e., an acid concentration and a reaction time of
0.9 mol L−1 and 6 h, respectively), oxalic acid can also be used as
a pretreatment agent for sisal pulp because it eliminates approx-
imately 42% of the hemicellulose present in the pulp, which is
responsible for the generation of undesirable byproducts in the
reaction medium. Therefore, oxalic acid is a promising catalyst for
the hydrolysis of cellulose for both the production of sugars and for
pretreatment of the fibers prior to other processes (e.g., enzymatic
hydrolyses).
Acknowledgements
The authors gratefully acknowledge CAPES (Coordination for the
Improvement of Higher Level -or Education- Personnel, Brazil) for
a fellowship for T.M.L. and FAPESP (The State of São Paulo Research
Foundation, Brazil) for financial support. E.F. is grateful to CNPq
(National Research Council, Brazil) for a research productivity fel-
lowship and financial support.
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