Industrial Crops and Products 67 (2015) 1–6

Contents lists available at ScienceDirect

Industrial Crops and Products

journal homepage: www.elsevier.com/locate/indcrop

Kinetic study of the extraction of hemicellulosic carbohydrates from

sugarcane bagasse by hot water treatment
María Evangelina Vallejos a,b,∗ , Fernando Esteban Felissia a , Julia Kruyeniski a ,
María Cristina Area a,b
a
Programa de Celulosa y Papel, Instituto de Materiales de Misiones, Universidad Nacional de Misiones, 1552 Félix de Azara St., C.P.3300, Posadas, Misiones,
Argentina
b
Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), C.P.1033, Capital Federal, Argentina

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

Article history: Sugarcane bagasse is a lignocellulosic agro-industrial waste, which is usually burned in the sugar and
Received 18 September 2014 bio-ethanol mills to produce heat and electricity. This work presents the kinetic study of the carbohy-
Received in revised form drates extracted from the mild hot water pretreatment of sugarcane bagasse, to explain the variation of
16 December 2014
hemicellulosic carbohydrates during the treatment. This could allow the selection of optimum conditions
Accepted 26 December 2014
to obtain the desired products in spent liquors, as high concentration of xylans and low concentrations
Available online 14 January 2015
of fermentation inhibitors. Sugarcane bagasse was hydrothermally treated under isothermal conditions
at 160, 170, and 180 ◦ C, using a liquid to solid ratio of 14:1. Glucans, xylans, arabans, xylose, glucose,
Keywords:
Sugarcane bagasse
arabinose, acetic acid, formic acid, HMF and furfural were first identified in the spent liquor. A kinetic
Hemicelluloses model was applied, considering the direct extraction of xylose and oligomers from the solid, xylose pro-
Hot water treatment duction from the oligomers, and furfural generation from xylose. It was supposed that the reaction rate
Oligomers constants have first-order kinetics. The fractionation by hydrothermal treatment has proven to be effec-
Xylose tive for hemicelluloses removal. Most glucans were retained in the solid, and a partial delignification (at
180 ◦ C, 9.8% and 36.3% of the initial lignin at 20 and 240 min, respectively) was achieved. The maximum
concentration of xylans in spent liquors with the low furfural content (0.5% on oven dry bagasse) was
achieved at 180 ◦ C and 20 min of treatment (17.6% on oven dry bagasse, about 74% of the initial amount).
An activation energy of 128.8 kJ mol−1 has been obtained for the fast hydrolysis of xylans from sugar cane
bagasse. The maximal concentration of xylans + xylose in liquors was obtained with a P-factor of 800.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction Bagasse is usually burned in sugar or bioethanol mills to produce

heat and electricity. It is composed of 32–45% cellulose, 19–24%
Lignocellulosic biomass is an important sustainable resource lignin, 27–32% hemicelluloses (mainly xylans) and minor amounts
of carbohydrates (cellulose and hemicelluloses) due to its renew- of extractives and inorganic compounds (Novo et al., 2011; Area
able nature. Its use allows the production of fuels, cellulosic pulp, et al., 2009; Vallejos et al., 2012). It can, therefore, be an adequate
biomaterials and a variety of chemicals. Lignocellulosic residues source of glucose for the production of second-generation ethanol
generated by agroindustry are available in large quantities at low and xylose for xylitol (Garrote et al., 1999).
cost. The fractionation of this waste in its main components would Conventional pulping processes fractionate biomass to obtain a
allow the production of chemical intermediates for the manufac- pulp rich in cellulose, and energy through burning lignin and other
ture of various products. chemical components. An alternative to further enhance value is
Sugarcane bagasse is an important lignocellulosic waste in to separate all components using sequential processes, and pro-
South America which account about 50% of the world’s sugarcane duce high value products that can be used in different applications
production (about 0.8 billion tonnes in 2012) (FAO, 2014). to improve the profit. This is the conceptual background of the
technologies based on the bio-refinery concept.
The commonly used pretreatments to fractionate lignocellulosic
biomass are essentially hydrolytic either in acidic or basic media,
∗ Corresponding author at: Programa de Celulosa y Papel, Instituto de Materiales
or catalyzed by enzymes.
de Misiones, Universidad Nacional de Misiones, 1552 Félix de Azara St., C.P. 3300,
Posadas, Misiones, Argentina. Tel.: +54 376 442 2198; fax: +54 376 442 2198. Xylans can be depolymerized and extracted from biomass in a
E-mail address: [email protected] (M.E. Vallejos). strong alkali media, but the reaction products are highly degraded,

http://dx.doi.org/10.1016/j.indcrop.2014.12.058
0926-6690/© 2014 Elsevier B.V. All rights reserved.
2 M.E. Vallejos et al. / Industrial Crops and Products 67 (2015) 1–6

completely deacetylated and their solubility in water is limited 2010). However, this pretreatment has some drawbacks, as: (i) its
(Patil, 2012; Li Jansson and Brannvall, 2011). On the contrary, high cost, (ii) its high liquid-solid ratio, making necessary a subse-
autohydrolysis occurs in mild acid medium due to the partial quent concentration of sugars for their recovery, and (iii) the high
breakdown of acetyl groups, and acetic acid release. Moreover, formation of degradation products, inhibitors of the fermentation
the autohydrolysis at mild temperatures produce high molecu- (Cardona et al., 2010).
lar weight xylo-oligosaccharides, without substantially modifying Several kinetic models for autohydrolysis have been proposed
the cellulose and lignin, which allows their recovery for further to describe the hydrolysis reactions of wood and grass species, and
processing (Garrote et al., 1999). Fractionation by hot water is envi- to optimize the production of xylo-oligosaccharides and xylose.
ronmentally friendly since uses pressurized hot water at moderate Nevertheless, no works on kinetic of autohydrolysis reactions of
times and temperatures. It has proven to be effective and selective sugarcane bagasse have been found (Kabel et al., 2002; Nabarlatz
to remove hemicelluloses present in the lignocellulosic material, as et al., 2004; Gullón et al., 2009; Carvalheiro et al., 2004; Garrote
is extensively discussed in the literature (Garrote et al., 1999; Allen et al., 2001; Zhuang et al., 2009).
et al., 1996). This work presents the kinetic study of mild hot water pre-
Water is the best green solvent to be used in biorefinery because treatment of sugarcane bagasse, to explain the variation of
of its environmental benefits, safety and low cost. It has been clas- hemicellulosic carbohydrates released during the treatment. This
sified recently as a recommended solvent by a survey of solvent could allow the selection of optimum conditions to obtain the
selection guides (Prat et al., 2014; Amidon and Liu, 2009). Hot water desired products in spent liquors, as high concentration of xylans
treatment avoids the use of corrosive reagents for the hydrolysis of and low concentrations of fermentation inhibitors.
xylans to reducing sugars. In addition, autohydrolysis at mild condi-
tions (short times and temperatures under 200 ◦ C, without catalyst)
does not modify cellulose and lignin substantially, which can allow 2. Experimental
their recovery for further treatments and utilization (Qing et al.,
2013). 2.1. Raw materials
After the hydrolytic pretreatment, the solid fraction (mainly cel-
lulose) is filtered to separate the liquid fraction (spent liquor), rich Sugar cane bagasse was supplied by a local mill (San Javier Sugar
in xylo-oligomers and sugars derived from hemicelluloses (xylose Mill, Misiones, Argentina). Bagasse pith was removed in two stages.
and arabinose). The chemical and porosity of the solid fraction In the former, bagasse was wet-depithed to break its structure in
(lignocellulosic material) has been modified, allowing for a more a Bauer disc refiner (plate gap of 0.01 in), after which the bagasse
efficient delignification. Treating the material with adequate reac- pith was removed by screening, using a plate with 2 mm wide slits
tives in subsequent biorefinery processing, allow to obtain cellulose (Wenmber). Finally, depithed bagasse was centrifuged and pre-
and lignin fractions of higher added value than the currently avail- served in a refrigerator. The pretreatments were performed in a
able industrial ones (Bujanovic et al., 2012; Bozell and Petersen, MK digester with a capacity of 7 L using 350 g OD of bagasse.
2010).
In the autohydrolysis processes using pressurized hot water, 2.2. Hot water pretreatment
hydronium ions from generated compounds (acetic, uronic, and
phenolic acids) catalyze the hydrolysis of the hemicelluloses The conditions of hydrothermal pretreatments were: water/dry
(Garrote et al., 1999). These processes increase cellulose accessibil- bagasse ratio: 14/1, maximum temperatures: 160, 170 and 180 ◦ C,
ity, and allow pentosans recovery (≥90%), producing hydrolysates maximum time at temperature: 4 h.
almost free of fermentation inhibitors. Hemicelluloses structure As a fraction of the hemicelluloses (mainly xylans) was
and composition vary according to the origin of the lignocellu- hydrolyzed in the pre-heating step (time to reach the maximum
losic material and in different parts within the same material. The temperature), the initial time (0 min) for the isothermal process
hydrolysis reactions generate a random cleavage of the hemicellu- was set after the initial 60 min.
loses, depending of their chemical structure, so the understanding Samples of liquor were obtained at different times of treat-
of differences in the hydrolysis reactions allows maximization of ment, and the content of organic compounds was determined.
biomass use. The remaining xylans in the solid were calculated by subtracting
Modelling of the changes in the composition of the lignocellu- the xylans, xylose and furfural present in the liquor (all species
losic materials during the hydrolysis treatment is applied to design expressed as xylose) to the xylans content (expressed as xylose) in
and optimize the conversion processes. Kinetic models and sever- raw material.
ity parameters are different mathematical methods to describe the
hydrolysis of hemicelluloses. Severity parameters have been used
to compare different pretreatment strategies, whilst kinetic mod- 2.3. Analysis of liquor samples
els have been applied to describe the changes of hemicelluloses by
hydrolysis in function of treatment conditions (Sixta et al., 2006; The samples were characterized by the determination of sugars
Wang et al., 2011). content (glucose, xylose, and arabinose) and degrading products:
The effect of time and temperature on the intensity of the furfural, 5-hydroxymethilfurfural and organic acids (formic and
hot water treatment can be described by the prehydrolysis fac- acetic), according to Technical Report NREL/TP-510-42623 (January
tor (P-factor) based on the Arrehenius equation. P-factor is used 2008) “Determination of Sugars, Byproducts, and Degradation
to compare the hot water treatments performed at different Products in Liquid Fraction Process Samples”, National Renewable
temperatures and to predict the solubilisation of hemicellulosic Energy Laboratory.
components during acid treatments. This factor is similar to the The quantification of sugars, organic acids and degradation
H-factor used in the pulp and paper industry (Sixta et al., 2006). products was carried out by HPLC liquid chromatography (Waters
The kinetics of the hydrolysis reaction for extraction of hemi- HPLC System), using an Aminex-HPX87H column (BIO-RAD) with
celluloses from sugarcane bagasse using diluted sulphuric acid has the following chromatographic conditions: H2 SO4 4 mM as eluent,
been widely studied due its high reaction rates and high extraction 0.6 mL min−1 , 35 ◦ C and refractive index and diode array detec-
yields (Aguilar et al., 2002; Ávila Rodrigues and Guirardello, 2008; tors. The structural carbohydrates in the raw material and in the
Sasikumar and Viruthagiri, 2008; Canilha et al., 2011; Cardona et al., pretreated solid (glucans, xylans, arabans and acetyl groups) were
 M.E. Vallejos et al. / Industrial Crops and Products 67 (2015) 1–6 3

– - The xylose extracted directly from the hydrolysable fraction of

xylans in the raw material (XxylS ), and
– The xylose produced by the hydrolysis of oligomers (XoL ) in the
liquid phase.

Xylose in the liquor (XxL ), in turn, is degraded to furfural (XfL ) in

a greater or lesser extent depending on the conditions of treatment.
Fig. 1. Xylan solubilization during hot water pretreatment proposed for Mittal et al. The hydrolysable fraction of xylans (XxylS ) is obtained by multi-
(2009a). plying the total amount of xylans in the raw material (XxylS RM ) by
the parameter ˛ (“susceptible fraction”).

d[XxylS ]
determined following the Technical Report NREL/TP-510-42618 = −(k1 + k2 )[XxylS ] − (1 − ˛)[XxylS ]RM (1)
dt
(April 2008) National Renewable Energy Laboratory.
d[XoL ]
= k1 [XxylS ] − (1 − ˛)[XxylS ]RM k3 [XoL ] (2)
dt
2.4. Kinetic model and data analysis d[XxL ]
= k2 [XxylS ] − (1 − ˛)[XxylS ]RM + k3 [XoL ] − k4 [XxL ] (3)
dt
The kinetic of the reactions generating products in the liquor,
d[Xf L]
from the xylans in the solid material, was determined by adapting = k4 [XxL ] (4)
the model proposed by Mittal et al. (2009a) for hardwoods. The dt
authors have deduced the parameters of the Arrhenius equation by The kinetic parameters ˛ and ki , were obtained using the inte-
working at different temperatures, assuming a first order kinetics grated version of the Eqs. ((1)–(4)) for 160, 170, and 180 ◦ C for the
and defining four kinetic constants (k1 –k4 ). The model set up the four hours of treatment. The iteration was performed by the SOLVER
formation of xylose in the liquor (XxL ) along two parallel paths, complement of the Excel software. The activation energies (Eai ) for
namely (Fig. 1 and Eqs. ((1)–(4)): the kinetic reactions were calculated from the Arrhenius equations,

Table 1
Composition of liquors extracted at different times of the pre-treatment at 160 ◦ C (% o.d.b.).

Time(min) Glucose Xylose Arabinose Formic acid Acetic acid HMF Furfural Glucans Xylans Arabans

0 0.00 0.04 0.21 0.00 0.14 0.00 0.02 1.22 0.54 0.12
5 0.00 0.00 0.38 0.00 0.19 0.00 0.02 1.51 1.20 0.18
10 0.00 0.09 0.54 0.03 0.27 0.00 0.03 1.86 2.29 0.27
20 0.00 0.16 0.71 0.06 0.41 0.00 0.04 2.30 4.59 0.38
40 0.00 0.42 0.92 0.06 0.97 0.01 0.10 2.98 10.4 0.53
60 0.00 0.88 1.03 0.12 1.38 0.01 0.20 3.17 14.2 0.55
90 0.00 1.86 1.08 0.16 1.79 0.07 0.39 2.93 15.5 0.44
120 0.00 3.24 1.09 0.25 1.80 0.07 0.63 2.88 15.2 0.33
180 0.00 7.21 1.04 0.27 2.60 0.06 1.52 2.95 12.2 0.27
240 0.15 10.9 0.98 0.68 3.31 0.10 2.57 2.86 7.91 0.17

Table 2
Composition of liquors extracted at different times of pre-treatment at 170 ◦ C (% o.d.b.).

Time(min) Glucose Xylose Arabinose Formic acid Acetic acid HMF Furfural Glucans Xylans Arabans

0 0.00 0.10 0.54 0.04 0.28 0.00 0.01 1.84 2.52 0.27
5 0.00 0.16 0.66 0.04 0.40 0.00 0.03 2.25 5.20 0.40
10 0.00 0.28 0.80 0.09 0.57 0.00 0.06 2.72 8.37 0.49
20 0.00 0.63 0.95 0.08 0.91 0.01 0.14 3.03 13.5 0.54
40 0.00 1.90 1.07 0.14 1.50 0.02 0.44 3.19 17.4 0.48
60 0.00 3.59 0.98 0.18 1.85 0.04 0.75 3.22 17.4 0.46
90 0.00 7.98 1.01 0.28 2.82 0.08 1.89 3.18 12.7 0.26
120 0.16 11.3 0.89 0.35 3.64 0.12 3.17 3.03 7.52 0.21
180 0.66 12.0 0.65 0.50 4.36 0.26 5.77 2.43 1.62 0.11
240 1.45 9.50 0.53 0.59 4.43 0.39 7.27 1.39 0.00 0.03

Table 3
Composition of liquors extracted at different times of pre-treatment at 180 ◦ C (% o.d.b.).

Time(min) Glucose Xylose Arabinose Formic acid Acetic acid HMF Furfural Glucans Xylans Arabans

0 0.00 0.19 0.62 0.09 0.49 0.00 0 2.18 5.88 0.37

5 0.00 0.39 0.73 0.14 0.80 0.00 0.09 2.62 11.1 0.48
10 0.00 0.75 0.81 0.18 1.09 0.00 0.20 2.96 15.1 0.50
20 0.00 1.86 0.84 0.28 1.56 0.02 0.50 3.06 17.6 0.44
40 0.00 5.83 0.78 0.43 2.23 0.06 1.75 2.94 13.7 0.26
60 0.00 9.56 0.66 0.73 3.12 0.12 3.54 2.98 7.32 0.19
90 0.50 9.31 0.41 0.82 3.80 0.24 5.86 2.29 1.45 0.20
120 1.31 6.99 0.33 1.06 4.19 0.34 7.55 1.20 0.00 0.12
180 1.72 3.25 0.28 1.49 4.50 0.83 9.13 0.00 0.00 0.00
240 1.59 1.66 0.16 1.62 4.58 1.15 9.30 0.00 0.00 0.03
4 M.E. Vallejos et al. / Industrial Crops and Products 67 (2015) 1–6

Table 4
Constants of the kinetic equations for the studied temperatures.

160 ◦ C 170 ◦ C 180 ◦ C

␣ 0.921 0.925 0.917

k1 0.932 2.274 5.698
k2 0.048 0.075 0.099
k3 0.305 0.597 1.292
k4 0.255 0.367 1.062

using the constants of the regression equations at the three studied

temperatures.
Fig. 2. Xylans solubilisation from bagasse by hot water pretreatment at different
2.5. P-factor temperatures (points: experimental data; dotted line: fitted model).

P-factor or prehydrolysis factor allows the controlling the pre-

hydrolysis step. P-factor is calculated from the relative rate of
prehydrolysis for any desired temperature using activation energy
typical for the cleavage of glycosidic bonds of the carbohydrate
material in the wood and assuming that the rate constant at 100 ◦ C
is 1 (Sixta et al., 2006). P-factor expressing the prehydrolysis time
and temperature relationship is defined as (Eq. (5)):
 t  t  t
kH(T ) EA EA
P= krel dt = dt = Exp( − )dt (5)
t0 t0
k100◦ C t0
373.15 × R T ×R

3. Results and discussion

Fig. 3. Oligomers released in liquors by hot water pretreatment of bagasse at dif-
The chemical composition of the sugar cane bagasse used in ferent temperatures (points: experimental data; dotted line: fitted model).
this work (as a percentage by weight on oven-dry bagasse, %
o.d.b.) involved: 43.1% glucans, 23.8% xylans, 1.7% arabans, 1.7%
acetyl groups, 21.3% lignin, 2.1% extractives in alcohol-benzene,
2.7% extractives in hot water and 1.5% of ashes.
Main compounds in spent liquors were xylans, xylose, acetic
acid, and furfural (generated by the degradation reaction of xylose
and arabinose). The composition of the liquors extracted at differ-
ent times is presented in Tables 1–3.
The hot water pretreatment of bagasse had little effect on cel-
lulose hydrolysis, as it remained almost entirely in the fibrous
material. A small fraction of glucans was hydrolyzed during the
treatment (the maximum release of glucans was 7.5% of their initial
content at 170 ◦ C).
Hemicelluloses were almost fully hydrolyzed to oligomers and
Fig. 4. Xylose released in liquors by hot water pretreatment of bagasse at different
sugars (xylans to xylose and arabans to arabinose) and consecu-
temperatures (points: experimental data; dotted line: fitted model).
tively to furfural, after 240, 90, and 40 min at 160, 170, and 180 ◦ C,
respectively. Xylose and arabinose concentrations decreased after
120 and 60 min at 170 and 180 ◦ C, respectively, because of their perature was already found by other authors working with bagasse
progressive degradation. Maximum concentrations of pentosans (Aguilar et al., 2002).
(xylans + arabans) in spent liquors were 15.9, 17.9 and 18.0% o.d.b. The experimental and theoretical evolutions of xylans extrac-
(oven-dry basis) at 90, 40, and 20 min for 160, 170, and 180 ◦ C, tion and the different products released in liquors are shown in
respectively (Tables 1–3). Figs. 2–6.
These values represent about 62% of the initial amount of pen- The experimental data of xylans removal from the raw material
tosans for 160 ◦ C, whereas it is about 70% for 170 and 180 ◦ C. HMF showed an almost perfect fit to the theoretical ones, at all tem-
and furfural generation were maximal at 180 ◦ C and 240 min (1.15% peratures (Fig. 2), whereas experimental values of oligomers in
and 9.30% o.d.b., respectively). liquors are slightly higher than theoretical ones (about 2–3% o.d.b.
To adjust the models, only data obtained under isothermal con- at the time of maximum extraction), (Fig. 3). The disappearance
ditions were considered. The kinetic parameters ␣ and ki for 160, of the oligomers from the liquors responds to their conversion to
170, and 180 ◦ C are shown in Table 4. xylose -and further to furfural-, and is more pronounced at higher
The value found for the susceptible xylans fraction ˛ (0.92) is temperatures.
high, indicating that almost the total amount of xylans present in Xylose in liquors shows similar behaviour (Fig. 4), but in this
the solid are susceptible to hydrolysis in bagasse. case the shape of the curves is somewhat different, mainly at 160 ◦ C.
This ˛ value is greater than those obtained for the hydrothermal Fig. 5 shows the good fit of the equations corresponding to all the
treatment of corncob (Garrote et al., 2001) (0.850–0.891) and sugar components containing xylose.
maple (Mittal et al., 2009a) (0.780–0.870), being similar to those The activation energies Eai for the kinetic reactions were cal-
obtained for the acid pretreatment of bagasse at 122 ◦ C (Aguilar culated from the Arrhenius equations, using the constants of the
et al., 2002). The lack of correlation between the ˛ value and tem- regression equations at all temperatures (Table 4), as shown in
 M.E. Vallejos et al. / Industrial Crops and Products 67 (2015) 1–6 5

Fig. 5. Oligomers containing xylose plus xylose released in liquors by hot water pre- Fig. 7. Furfural generated from xylans dehydration in liquors by hot water pretreat-
treatment of bagasse at different temperatures (points: experimental data; dotted ment of bagasse at different temperatures (points: experimental data; dotted line:
line: fitted model). fitted model).

Fig.6. Arrhenius plot of ln ki vs. 1/T, to obtain the pre-exponential factors k0i and the
activation energies Eai .

Fig. 8. Xylans + xylose composition in the liquors and xylans remanent in the solid,
Table 5 boht evolutions as function of P-factor (green: 160 ◦ C, blue: 170 ◦ C and brown:
Activation energies of the kinetic reactions calculated from the Arrhenius equation 180 ◦ C). (For interpretation of the references to color in this figure legend, the reader
(ki (T) = k0i exp[−Eai /(RT)]. is referred to the web version of this article.)

Kinetic coefficient ln k0i * Eai (kJ mol−1 ) R2

k1 40.9 148 0.99

In accordance with the above, another reaction representing the
k2 13.5 60 0.99 degradation of furfural, or another byproduct generated by xylose,
k3 31.4 118 0.99 should be incorporated to the model. Other authors used different
k4 30.7 116 0.92 models for another kind of raw material (Gullón et al., 2009), but
they could adapt well to hot water treatment of bagasse. Once iden-
tified, the kinetic equations of decomposition products should be
Fig. 6. The activation energies of the kinetic reactions calculated
included in the model.
from the Arrhenius equation are shown in Table 5.
P-factors were calculated for all conditions (Fig. 8). The activa-
According to the activation energies, the fastest reaction is the
tion energy, EA , for the fast-reacting xylans from sugarcane bagasse
conversion of xylans in the raw material to xylose, and the slowest
was determined in the present study from the slopes of the curves
is their dissolution as oligomers.
in Fig. 2, in the bulk step. In this way, an activation energy of
These results are close to those obtained when chips (Mittal
128.8 kJ mol−1 has been obtained for sugar cane bagasse, and it was
et al., 2009b) and milled wood (Mittal et al., 2009a) are treated,
applied for the calculation of the P-factor as shown in Eq. (6) (Sixta
although they highlight difficulties in the mass transfer for the
and Potthast, 2006).
solubilisation of the polymer in bagasse.
 t  t
The rate of conversion of oligomers to xylose is very similar kH(T ) 15439
to the conversion of this last one to furfural. Furfural generated P= dt = Exp(41.52 − )dt (6)
t0
k100◦ C t0
T
in liquors shows lower experimental values than theoretical ones
from the model at long times of treatment (Fig. 7). P-factor (similar to H-factor) expresses the hydrolysis time and
This behaviour evidences that furfural is degraded to other temperature as a single variable in batch reactors. It is mainly based
components almost simultaneously with its formation, and that on empirical models. The authors consider that it is applicable to
this degradation increases with the treatment temperature. These control the extent of the prehydrolysis process due to its simplicity
degradation products, not considered in the equations, are present and ease of implementation. Hemicelluloses removal from ligno-
in the chromatograms and could even include the degradation of cellulosic material is strongly controlled by temperature and to a
xylose to formic acid and humines (Lau et al., 2014; Zhang et al., lesser extent by acetic acid concentration. It is possible to consider
2013). The furfural can also disappear from the system due to the variation of acid concentration along the prehydrolysis in the P-
resinification and condensation reactions, but these reactions are factor formula. However, the improvements that can be introduced
negligible to the temperatures of this work (Zeitsch, 2000). by the slight change of pH on the autohydrolysis treatment (in this
6 M.E. Vallejos et al. / Industrial Crops and Products 67 (2015) 1–6

work, from pH 4.4 to 3.4) do not justify the use of a more complex S.S., Felipe, M.G.A., Ferraz, A., Milagres, A.M.F., Carvalho, W., 2011. A study on
modified P-factor concept (Sixta and Potthast, 2006). the pretreatment of a sugarcane bagasse sample with dilute sulfuric acid. J. Ind.
Microbiol. Biot. 38, 1467–1475.
An activation energy of 128.8 kJ mol−1 has been calculated in Cardona, C.A., Quintero, J.A., Paz, I.C., 2010. Production of bioethanol from
this work for the fast hydrolysis of xylans from sugar cane bagasse. It sugarcane bagasse: status and perspectives. Bioresour. Technol. 101,
is slightly higher than the value found by Sixta et al. (2006) for euca- 4754–4766.
Carvalheiro, F., Esteves, M.P., Parajó, J.C., Pereira, H., Gírio, F.M., 2004. Production of
lyptus. The maximal concentration of xylans + xylose in liquors can oligosaccharides by autohydrolysis of brewery’s spent grain. Bioresour.
be obtained with a P-factor of 800, as shown in Fig. 8. At that point, Technol. 91, 93–100.
xylans (expressed as xylose) and xylose content in spent liquors Food and Agriculture Organization (FAO). Statistics Division of the FAO (FAOSTAT).
http//www.faostat.fao.org (accessed 08.14.).
represented about 70–80% of the xylose in the raw material. Garrote, G., Domínguez, H., Parajó, J.C., 1999. Mild autohydrolysis: an
environmentally friendly technology for xylooligosaccharide production from
4. Conclusions wood. J. Chem. Technol. Biotechnol. 74, 1101–1109.
Garrote, G., Domínguez, H., Parajó, J.C., 2001. Kinetic modelling of corncob
autohydrolysis. Process. Biochem. 36, 571–578.
Xylans were almost fully hydrolyzed to oligomers and sugars Gullón, P., Pereiro, G., Alonso, J.L., Parajó, J.C., 2009. Aqueous pretreatment of
(xylans and arabans, xylose and arabinose) and to furfural, after agricultural wastes: characterization of soluble reaction products. Bioresour.
240, 90, and 40 min at 160, 170, and 180 ◦ C, respectively. Technol. 100, 5840–5845.
Kabel, M.A., Carvalheiro, F., Garrote, G., Avgerinos, E., Koukios, E., Parajó, J.C., Gírio,
The adopted model represented well the evolution of most com- F.M., Schol, H.A., Voragen, A.G.J., 2002. Hydrothermally treated xylan rich
ponents in liquors. The experimental data of xylans removal from by-products yield different classes of xylo-oligosaccharides. Carbohydr. Polym.
the raw material showed an almost perfect fit to the theoretical 50, 47–56.
Lau, C.S., Thoma, G.J., Clausen, E.C., Carrier, D.J., 2014. Kinetic modeling of xylose
ones at all temperatures. oligomer degradation during pretreatment in dilute acid or in water. Ind. Eng.
Furfural generated in liquors shows lower experimental values Chem. Res. 53, 2219–2228.
than theoretical ones from the model at long times of treatment. Li Jansson, Z., Brannvall, E., 2011. Characterisation of dissolved spruce xylan in
kraft cooking. Nord. Pulp Paper Res. J. 26, 380–385.
This behaviour might evidence that xylose or furfural, are degraded Mittal, A., Chatterjee, S.G., Scott, G.M., Amidon, T.E., 2009a. Modeling xylan
to other components. solubilization during autohydrolysis of sugar maple wood meal: reaction
Maximum concentrations of pentosans (xylans + arabans) in kinetics. Holzforschung 63, 307–314.
Mittal, A., Chatterjee, S.G., Scott, G.M., Amidon, T.E., 2009b. Modeling xylan
spent liquors were 15.9, 17.9 and 18.0% o.d.b. (oven-dry basis) at solubilization during autohydrolysis of sugar maple and aspen wood chips:
90, 40, and 20 min for 160, 170, and 180 ◦ C, respectively reaction kinetics and mass transfer. Chem. Eng. Sci. 64, 3031–3041.
An activation energy of 128.8 kJ mol−1 has been obtained for the Nabarlatz, D., Farriol, X., Montane, D., 2004. Kinetic modeling of the autohydrolysis
of lignocellulosic biomass for the production of hemicellulose-derived
fast hydrolysis of xylans from sugar cane bagasse. The maximal oligosaccharides. Ind. Eng. Chem. Res. 43, 4124–4131.
concentration of xylans + xylose in liquors was obtained with a P- Novo, L.P., Gurgel, L.V.A., Marabezi, K., Curvelo, A.A.S., 2011. Delignification of
factor of 800. sugarcane bagasse using glycerol–water mixtures to produce pulps for
saccharification. Bioresour. Technol. 102, 10040–10046.
Patil, R.A., 2012. Cleavage of Acetyl Groups for Acetic Acid Production in Kraft Pulp
Acknowledgements Mills. Theses and Dissertations.
http://digitalcommons.library.umaine.edu/etd/1857 (access 12.14.).
Prat, D., Hayler, J., Wells, A., 2014. A survey of solvent selection guides Green
The authors acknowledge the financial support from the Con-
Chem., 2014. Advance Article.
sejo Nacional de InvestigacionesCientíficas y Técnicas (CONICET), Qing, Q., Li, H., Kumar, R., Wyman, C.E., 2013. Xylooligosaccharides production,
Argentina and the Universidad Nacional de Misiones (UNaM), quantification, and characterization in context of lignocellulosic biomass
Misiones, Argentina. pretreatment (pages 391–415). In: Wyman, C.E. (Ed.), Aqueous Pretreatment of
Plant Biomass for Biological and Chemical Conversion to Fuels and Chemicals.
John Wiley & Sons, Ltd., United Kingdom, pp. 391–415.
Sasikumar, E., Viruthagiri, T., 2008. Optimization of process conditions using
References
response surface methodology (RSM) for ethanol production from pretreated
sugarcane bagasse Kinet. Modeling. Bioenerg. Res. 1, 239–247.
Aguilar, R., Ramirez, J.A., Garrote, G., Vazquez, M., 2002. Kinetic study of the acid Sixta, H., Potthast, A., Krotschek, A.W., 2006. In: Handbook of Pulp, Sixta, H (Eds.),
hydrolysis of sugar cane bagasse. J. Food. Eng. 55, 309–318. Chemical Pulping Processes, vol. 1. Wiley-VCH GmbH & Co. KGaA, Weinheim,
Allen, S.G., Kam, L.C., Zemann, A.J., Antal, M.J., 1996. Fractionation of sugar cane pp. 109–509.
with hot compressed, liquid water. Ind. Eng. Chem. Res. 35, 2709. Vallejos, M.E., Zambon, M.D., Area, M.C., Curvelo, A.A.S., 2012. Low liquid–solid
Amidon, T.E., Liu, S., 2009. Water-based woody biorefinery. Biotechnol. Adv. 27, ratio (LSR) hot water pretreatment of sugarcane bagasse. Green Chem. 14,
542–550. 1982–1989.
Area, C.M., Felissia, F.E., Vallejos, M.E., 2009. Ethanol-water fractionation of sugar Wang, Z., Xu, J., Cheng, J.J., 2011. Modeling biochemical conversion of
cane bagasse catalyzed with acids. Cellul. Chem. Technol. 43, 271– lignocellulosic materials for sugar production: a review. BioResources 6,
279. 5282–5306.
Ávila Rodrigues, F., Guirardello, R., 2008. Evaluation of a sugarcane bagasse acid Zeitsch, K.J., 2000. The Chemistry and Technology of Furfural and its Many
hydrolysis technology. Chem. Eng. Technol. 31, 883–892. By-Products. Elsevier, B.V. Dürener Str. 393, D-50935 Köln, Germany.
Bozell, J.J., Petersen, G.R., 2010. Technology development for the production of Zhang, T., Kumara, R., Wyman, C.E., 2013. Enhanced yields of furfural and other
biobased products from biorefinery carbohydrates—the US department of products by simultaneous solvent extraction during thermochemical
energy’s top 10 revisited. Green Chem. 12, 539–554. treatment of cellulosic biomass. RSC Adv. 3, 9809–9819.
Bujanovic, B.M., Goundalkar, M.J., Amidon, T.E., 2012. Increasing the value of a Zhuang, X., Yuan, Z., Ma, L., Wu, C., Xu, M., Xu, J., Zhu, S., Qi, W., 2009. Kinetic study
biorefinery based on hot-water extraction: lignin products. Tappi J. 11, 19–26. of hydrolysis of xylan and agricultural wastes with hot liquid water.
Canilha, L., Santos, V.T.O., Rocha, G.J.M., Almeida, E., Silva, J.B., Giulietti, M., Silva, Biotechnol. Adv. 27, 578–582.