See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/282762642

Ethanol-water fractionation of sugar cane bagasse catalyzed with acids

Article  in  Cellulose Chemistry and Technology · July 2009

CITATIONS READS
23 616

3 authors:

María Cristina Area Fernando Felissia

Instituto de Materiales de Misiones (UNaM-CONICET) National University of Misiones
228 PUBLICATIONS   1,192 CITATIONS    67 PUBLICATIONS   562 CITATIONS   

SEE PROFILE SEE PROFILE

María Evangelina Vallejos

62 PUBLICATIONS   940 CITATIONS   

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

BIO-PRODUCTS AND BIO-MATERIALS FROM THE BIOREFINERY OF AGRO INDUSTRIAL AND FOREST INDUSTRIAL WASTE View project

SOSTENIBILIDAD DE LA INDUSTRIA DE PULPA Y PAPEL View project

All content following this page was uploaded by María Cristina Area on 19 November 2015.

The user has requested enhancement of the downloaded file.

 CELLULOSE CHEMISTRY AND TECHNOLOGY

ETHANOL-WATER FRACTIONATION
OF SUGAR CANE BAGASSE CATALYZED WITH ACIDS

CRISTINA M. AREA, FERNANDO E. FELISSIA* and MARIA E. VALLEJOS

Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET),

Programa de Investigación de Celulosa y Papel, Facultad de Ciencias Exactas, Químicas y
Naturales, Universidad Nacional de Misiones, Felix de Azara 1552 (3300) Posadas, Misiones,
Argentina
*Programa de Investigación de Celulosa y Papel, Facultad de Ciencias Exactas, Químicas y
Naturales, Universidad Nacional de Misiones, Felix de Azara 1552 (3300) Posadas, Misiones,
Argentina

Received May 21, 2009

The conditions for maximizing bagasse ethanol-water fractionation (in cellulose, hemicelluloses and lignin)
were established by the evaluation of different variables (time, temperature, catalyst). To this end, the
organic compounds of the fibrous material and liquors were quantified. Acetic (2 g/L) and sulfuric (0.5, 1.0
and 2.0 g/L) acids were used as catalysts. An alkaline extraction was applied as a pre-treatment, using 3.6
g/L NaOH, at 100 ºC, for 1 h. The effects of different conditions of the organosolv treatment on the kinetics,
composition of the fibrous material and residual liquor, upon the fractionation of sugar cane bagasse used in
this work, were investigated. The kinetic parameters were determined for delignification under six different
conditions. The organic compounds of the fibrous material were quantified and lignin (by UV-visible
spectroscopy) and carbohydrates, organic acids, furfural and HMF (by HPLC chromatography) were
evaluated in residual liquors. The incorporation of sulfuric acid at 160 ºC produced delignification degrees
similar to those obtained by the addition of acetic acid at 180 ºC, or in the fractionation without catalyst (85-
86%). The delignification values showed that fractionations could be stopped at 90 or 120 min, since, after
90 min, the delignification percentage decreases by only about 1%. The incorporation of sulfuric acid
extracted a large amount of xylose and produced further degradation of cellulose. Fractionations with acetic
acid did not differ largely from the auto-catalyzed ones.

Keywords: organosolv, fractionation, kinetics, sugar cane bagasse, acetic acid, sulfuric acid

INTRODUCTION
The sugar industry could become a bagasse is usually stock-piled, constituting
modern and efficient agro-industry by an environmental problem, due to the risk of
diversifying its production into large spontaneous combustion of stored bagasse.2
amounts of by-products and energy. Sugar However, out of the about 130 sugar cane
cane bagasse, the main by-product of the derivatives known, over half are derived
sugar cane industry, is a fibrous residue of from bagasse.3,4
sugar cane resulting from conventional Bagasse fractionation, performed for
milling. Sugar mills generate approximately separating its main components (cellulose,
270 kg of bagasse (50% moisture) per metric hemicelluloses and lignin) and for obtaining
ton of sugar cane. About 50% of this amount higher added-value products, has been tested
is sufficient to supply the energy required by under different conditions and processes.
the sugar and ethanol plants.1 The remaining Literature references to fractionations

Cellulose Chem. Technol., 43 (7-8), 269-277 (2009)

Cristina M. Area et al.
involve: acid hydrolysis with hydrochloric, groups in lignin with acid concentration
sulfuric,5-7 nitric8 and phosphoric acid;9 hot might be taken as an evidence of it.17
water treatment10 at 230-280 ºC; sequential Ethanol-water delignification is an
alkaline extraction with sodium hydroxide interesting process for treating sugar cane
and hydrogen peroxide,11 treatments with bagasse, as it allows the use of resources
ammonia12 and supercritical CO2 in solvent already existing in the sugar mill (ethanol
mixtures,13,14 as well as with ultrasound, and bagasse). Although the kinetics of the
sodium hydroxide and hydrogen peroxide.15 ethanol-water organosolv pulping of sugar
Most of the cited studies followed cane bagasse is thoroughly described in
exclusively the extraction of hemicelluloses literature,16,20-24 few investigations have
and cellulose fractions and did not evaluate made a characterization of the residual
the quantity or quality of the lignin fraction. liquor, as the authors’ aim is mainly pulp
Organosolv lignins present potential uses in production. Such a characterization would
the manufacture of phenol-formaldehyde permit to determine the type and quantity of
resins (as a source of phenols) and of the by-products that could be recovered from
biodegradable polyurethanes. the residual liquor. In addition, the
The organosolv processes use neutral or optimization of the ethanol-water process,
acid solvents, either with or without acids as for improving the product yields, product
catalysts. When using ethanol-water performance and operating costs has not
mixtures, the deacetylation of the hemi- been solved yet.
celluloses from the fibrous material In the present work, the conditions for
generates acetic acid, which acidifies the maximizing bagasse ethanol-water
medium throughout the process, called fractionation (in cellulose, hemicelluloses
“auto-catalyzed” process,16-18 of which Alcell and lignin) were established by the
is an example for the pulp production using evaluation of different variables (time,
an ethanol-water mixture.19 temperature, catalyst). Experiments were
It has been reported that, in the presence performed at temperatures lower than those
of low acid concentrations and low usually applied in conventional organosolv
temperatures, the alcoholic solutions assure processes, in an attempt to simplify the
the best conditions for maximum operation and to allow the utilization of more
delignification, with low cellulose inexpensive equipments. To evaluate the
degradation and lower formation of performance, the organic compounds present
condensation products.20 Both sulfuric and in residual liquors and in the fibrous material
hydrochloric acids have been used as were quantified.
catalysts in the ethanol-water fractionation of This information is essential for the
wheat straw.21,22 Although acetic acid is a technical and economic feasibility of the
natural catalyst of the process, few works production of non-conventional by-products
have reported its use in ethanol-water from sugar cane bagasse, by using
fractionation.18 environmentally compatible and economi-
The kinetics of organosolv delignifi- cally competitive technologies.
cation has been explained by a model with
two simultaneous pseudo-first-order MATERIALS AND METHOD
reactions: a faster or dominant reaction and a Sugar cane bagasse and ethanol were supplied
slower, residual one.20,23,24 The acid- by a local mill (San Javier Sugar Mill, Misiones,
Argentina). Bagasse pith was removed in two
catalyzed process rate seems to be controlled
stages. In the former, bagasse was wet-depithed
by the hydrolysis of the α-ether linkage of
to break its structure in a Bauer disc refiner, using
lignin, although other complex reactions, a plate gap of 0.005 inches (0.13 mm), after
such as condensation, partial hydrolysis of which the bagasse pith was removed by
the β-ether linkage, formaldehyde release screening, using a plate with 2 mm wide slits
and rearrangement of the free radicals also (Wenmber). Finally, depithed bagasse was
take place.23 The importance of the β-ether centrifuged. Acetic acid and sulfuric acid (A.C.S.
linkage hydrolysis is under discussion, while reagent grade) were used as catalysts.
the increase in the free phenolic hydroxyl Bagasse was delignified by an organosolv

270
 Bagasse
ethanol process carried out in a 7 L MK digester process was evaluated by the delignification
(M/K Systems, Inc., Maryland) with liquor degree, represented by Kappa number and yield.
circulation, under different conditions. Alkaline The Kappa number (TAPPI T236) is the volume
extraction was applied as a pre-treatment in the F8 (mL) of 0.1 N potassium permanganate solution
fractionation (called pre-F8) using 3.6 g/L NaOH, consumed by 1 g of oven-dry fibrous material
at 100 ºC, for 1 h. The ratios of liquor/bagasse under the conditions specified.
and ethanol/water remained constant at 14/1 The residual liquid contained carbohydrate
(v/w) and 50% (% v/v), respectively. The time degradation products, such as hydroxymethyl
necessary to reach the maximum temperatures furfural (HMF) and furfural, and other
was of 30 min. The variables involved were as components, such as organic acids. The organic
follows: maximum temperature, time at compounds in the residual liquors were
maximum temperature and catalyst. quantified according to the procedures for the
The extractives in alcohol-benzene (TAPPI determination of sugars, by-products and
T204), solubility in hot water (TAPPI T207), degradation products present in the liquid samples
solubility in 1% sodium hydroxide (TAPPI (NREL LAP-015), as shown in Figure 1.
T212), acetyl groups content (National The compositions of sugars (glucose, xylose,
Renewable Energy Laboratory, Laboratory arabinose), organic acids (acetic and formic
Analytical Procedure – NREL–LAP002) and acids), furfural and HMF were determined by
ashes at 525 °C (TAPPI T211), were determined HPLC (Waters Corp. Massachusetts, USA), on an
on the bagasse samples. Acid-insoluble lignin AMINEX-HPX87H (SEE) column, under the
(TAPPI T222), acid-soluble lignin (TAPPI T250) following conditions: 4 mM H2SO4 as eluent at a
and the structural carbohydrate content in flow rate of 0.6 mL/min, at 35 ºC, with Refractive
biomass were determined by HPLC with IR Index and Diode Array as detectors.
detection (NREL LAP-002), on both bagasse and The polyoses were converted into monomers
the fibrous material (Fig. 1). by multiplying by the hydrolysis factor (hexoses
During fractionation, the residual liquors were to hexosanes: 0.900, pentoses to pentosanes:
sampled at different time values. The dissolved 0.880, acetic acid to acetyl groups: 0.683). The
lignin was measured and the residual lignin (L) lignin from the residual liquors was quantified by
was determined as the lignin content in the UV (Techcomb 8500 II Spectrophotometer) at
fibrous material. 210 nm, on liquor aliquots diluted in ethanol. The
After fractionation, the fibrous materials were absorptivity determined and used in this work
washed to remove the residual liquor, their yields was of 78.2 L/g.cm. The value obtained was
being determined as percentages of oven-dry corrected by subtracting the absorptivity of
bagasse. The performance of the fractionation furfural, obtained by HPLC.

Figure 1: Procedure for the analysis of materials

The results (concentrations of carbohydrates, catalyst as independent variables. The statistical

organic acids, degradation products and lignin) software employed was Statgraphics and the level
were analyzed by multifactorial analysis of of significance applied was of 95%.
variance (ANOVA), with time, temperature and

271
Cristina M. Area et al.
RESULTS AND DISCUSSION where:
The chemical composition of the sugar -dL/dt = delignification rate
cane bagasse (mass percent on oven-dry k0 = delignification rate constant
bagasse) was the following: glucan – 43.1%; [Ethanol] = ethanol concentration in the
xylan – 23.8%; arabinan – 1.66% and lignin liquor
– 21.3% (Table 1). L = lignin content in the fibrous material (%
The conditions of fractionation F5 were o.d.b.)
the same as those for F1, except for the use of Under conditions of constant temperature
sulfuric acid instead of acetic acid. The and liquor composition, equation (1) takes
treatment turned out too strong, producing the following form:
the degradation of the fibrous material and
−
dL
= k 0′ L (2)
the darkening of the residual liquor dt
(condensation products). Fractionation F8
repeated the conditions of F7, yet pre-treating By integrating equation (2), one obtains:
the fibrous material with sodium hydroxide ln L = −k 0′ t + ln L0 (3)
to favour the access of the liquor. However,
the high yield obtained indicates that this where L0 is the initial lignin content of
pre-treatment was inefficient. The conditions bagasse.
of the F7 treatment with 0.5 g/L sulfuric acid According to this equation, in the plot of
(160 ºC, 120 min) produced a yield similar to the natural logarithm of residual lignin in the
that obtained under stronger conditions, with fibrous material vs. time, the slope of the
acetic acid. Table 2 shows the results for the straight line represents the delignification
liquors and fibrous materials during final reaction rate constant, valid for the
fractionation. fractionation conditions applied. The
The first-order kinetics was tested with reaction rate constants for short and long
respect to residual lignin, by calculating the delignification time periods are presented in
reaction rate constants under different Tables 3 and 4. Figures 2 and 3 show the
fractionation conditions. Assuming that the kinetics of the more efficient fractionations:
delignification rate is proportional to the F3 (at 180 ºC, catalyzed with acetic acid) and
product of the residual lignin by the F7 (at 160 ºC, catalyzed with sulfuric acid).
concentration of chemical reagents in the
liquor for a given temperature, the reaction
rate can be represented by the equation:

−
dL
= k 0 [Ethanol ] L
(1)
dt

Table 1
Chemical characterization of bagasse (% o.d.b.)

Alcohol-benzene extractives 2.12

Hot water solubility 2.73
1% sodium hydroxide solubility 34.2
Ash at 525 °C 1.53
Total lignin 21.3
Soluble lignin 1.51
Insoluble lignin 19.8
Total carbohydrates 70.2
Glucans 43.1
Xylans 23.8
Arabinans 1.66
Acetyls 1.66

272
 Bagasse

Table 2
Results of fractionation

Fractio- Catalyst Maximum Time at max. Catalyst Initial Final Kappa Yield
nation temperature temperature (g/L) pH pH (%)
(ºC) (min)
F1 Acetic acid 175 240 2.0 3.9 3.8 37.8 48.9
F2 Without 175 240 0.0 5.9 3.9 37.5 48.2
F3 Acetic acid 180 240 2.0 3.9 3.7 31.1 46.9
F4 Without 180 240 0.0 5.9 3.8 34.2 46.8
F5 Sulfuric acid 175 240 2.0 2.1 2.4 – –
F6 Sulfuric acid 150 120 0.5 2.4 3.0 58.6 52.3
F7 Sulfuric acid 160 120 0.5 2.4 3.0 23.5 45.4
F 8* Sulfuric acid 160 120 1.0 2.8 3.1 – 63.5
* NaOH-pre-treated material (Pre-F8)

Table 3
Kinetic parameters of the equation for short time periods (F1 at F4, F6 and F7)

Fractionation ln L0 L0 - k0 R2
F1 (0 to 40 min) 2.665 14.37 1.93 x 10-2 0.98
-2
F2 (0 to 40 min) 2.750 15.64 1.95 x 10 1.00
-2
F3 (0 to 40 min) 2.621 13.75 2.26 x 10 0.98
-2
F4 (0 to 40 min) 2.695 14.81 2.21 x 10 0.99
-2
F6 (0 to 40 min) 2.736 15.43 2.23 x 10 0.98
F7 (0 to 20 min) 2.272 9.694 4.19 x 10-2 0.85

Table 4
Kinetic parameters of the equation for long time periods (F1 at F4, F6 and F7)

Fractionation ln L0 L0 - k0 R2
F1 (60 to 240 min) 1.281 3.60 0.603 x 10-3 0.96
-3
F2 (60 to 240 min) 1.241 3.46 0.387 x 10 0.89
-3
F3 (60 to 240 min) 1.112 3.04 0.494 x 10 0.98
-3
F4 (60 to 240 min) 1.363 3.91 1.44 x 10 0.99
-3
F6 (60 to 120 min) 1.918 6.81 2.98 x 10 1.00
F7 (40 to 120 min) 1.346 3.84 3.05 x 10-3 0.83

273
Cristina M. Area et al.
3,0 3,0

y = -0,0225x + 2,7311
R2 = 0,9808 y = -0,0419x + 2,2715
2,5
2,5 R2 = 0,8501

2,0

lnL
lnL

2,0
y = -0,003x + 1,9071
R2 = 0,9964 1,5
y = -0,003x + 1,3457
R2 = 0,8342
1,5
1,0

1,0 0,5
0 10 20 30 40 50 60 70 80 90 100 110 120 130 0 10 20 30 40 50 60 70 80 90 100 110 120 130
min min

Figure 2: Kinetics of fractionation F3 Figure 3: Kinetics of fractionation F7

The calculated initial lignin L0 varied in and the delignification percentages at

the different fractionations, being 6-8% o.d.b different time values (all calculated from the
and 10-12% o.d.b. lower than the lignin kinetic equations) are shown in Table 5.
content of bagasse in the fractio-nations The results of delignification at 120 min
catalyzed with acetic and sulfuric acid, (Table 5) showed that the temperature had a
respectively (Tables 3 and 4), as the digester significant influence on the total amount of
reached the maximum temperature within 30 extracted lignin (p = 0000). Fractionation F6
min, and therefore, different levels of (at 150 ºC) was the most inefficient one.
delignification were reached under different Fractionations F7 (with sulfuric acid at 160
conditions. ºC) and F3 (with acetic acid at 180 ºC) were
The fractionations carried out at low the most efficient, presenting similar degrees
temperatures presented inferior initial of delignification (homogeneous groups in
reaction rates. The highest reaction rate the multiple-range test).
occurred at 160 ºC, with sulfuric acid in the The delignification values calculated
first 20 min, with a change in the slope from the kinetic equations showed that
between 40 and 120 min (Fig. 3). The fractionation could be stopped at 90 or at 120
highest speed in the long time periods min, with a difference of only 1% in the
corresponded to the reactions catalyzed with residual lignin from the fibrous material. The
sulfuric acid. carbohydrates remaining in the fibrous
The lignin content of the fibrous material material are characterized in Table 6.

Table 5
Lignin in the fibrous material and delignification percentages

Fractionation F1 F2 F3 F4 F6 F7
Insoluble lignin (% o.d.p.) 5.73 6.20 5.03 5.70 9.10 4.51
Soluble lignin (% o.d.p.) 0.69 0.61 0.55 0.63 0.49 0.25
Total lignin (% o.d.p.) 6.42 6.81 5.58 6.33 9.59 4.76
Total lignin (% o.d.b.) 3.14 3.28 2.61 2.96 5.01 2.16
Delignification at 90 min (%)* 84.0 84.3 86.3 83.9 75.5 86.3
Delignification at 120 min (%)* 84.3 84.5 86.5 84.6 77.6 87.5
Delignification at 240 min (%)* 85.4 85.2 87.3 87.0 – –
(% o.d.p.): on oven-dry pulp; (% o.d.b.): on oven-dry bagasse; * calculated from the kinetic equations

274
 Bagasse

Table 6
Remaining carbohydrates in the fibrous materials

Fractionation F1 F2 F3 F4 F6 F7
Insoluble lignin (% o.d.p.) 5.73 6.20 5.03 5.70 9.10 4.51
Soluble lignin (% o.d.p.) 0.69 0.61 0.55 0.63 0.49 0.25
Total lignin (% o.d.p.) 6.42 6.81 5.58 6.33 9.59 4.76
Total lignin (% o.d.b.) 3.14 3.28 2.61 2.96 5.01 2.16
Delignification at 90 min (%)* 84.0 84.3 86.3 83.9 75.5 85.7
Delignification at 120 min (%)* 84.3 84.5 86.5 84.6 77.6 86.0
Delignification at 240 min (%)* 85.4 85.2 87.3 87.0 – –
(% o.d.p.): on oven-dry pulp; (% o.d.b.): on oven-dry bagasse; * calculated from lignin content in spent liquors

Table 7
Composition of non-hydrolyzed liquor (% o.d.b.) at different fractionation time periods

Fractionation Time Glucose Xylose Arabinose Formic Acetic Furfural

(min) acid acid
F1 90 0.14 1.03 0.69 0.29 1.34 0.52
F1 180 0.10 2.85 0.21 0.67 1.75 1.93
F1 240 0.14 3.75 0.11 0.77 2.00 3.08
F2 90 0.14 0.97 0.64 0.20 1.71 0.38
F2 180 0.08 3.12 0.28 0.79 2.51 1.70
F2 240 0.11 4.30 0.16 0.57 2.84 2.81
F3 90 n.d. 1.47 0.38 0.39 1.60 0.99
F3 180 0.12 3.27 0.07 0.81 1.96 3.06
F3 240 0.33 3.53 n.d. 0.97 2.36 4.51
F4 90 0.14 1.05 0.25 0.25 2.14 0.70
F4 180 0.12 3.07 0.08 0.79 2.82 2.78
F4 240 0.34 4.11 0.24 0.95 3.18 3.86
F6 20 0.06 0.99 0.42 0.29 0.25 n.d.
F6 90 0.14 5.02 0.66 0.62 0.68 n.d.
F6 120 0.17 6.48 0.69 0.69 0.88 n.d.
F7 20 0.23 7.27 0.68 0.82 0.66 n.d.
F7 90 0.86 13.1 0.89 0.96 1.22 0.34
F7 120 1.36 14.5 1.40 1.14 1.77 0.78
n.d.: not detected; (% o.d.b.): on oven-dry bagasse

A total loss of arabinans and acetyl The generated acetic acid differed
groups (not detected in pulp hydrolysates) significantly under all fractionation
and of 90% xylans (xylan content in bagasse: conditions (p = 0.0001), the highest amount
25.0%) occurred in fractionations F1 to F4. corresponding to fractionation F4 and the
On the contrary, these components remained lowest – to F6. Fractionation F7 presented the
in the fibrous material after fractionations F6 largest amount of formic acid, arabinose,
and F7. Fractionation F7 produced the largest glucose and xylose in the spent liquors, while
xylan extraction. The sugars, organic acids fractionations F3 and F4 generated the largest
and furfural contents of the residual liquor at amount of furfural. The spent liquors of F6
various reaction time values are shown in and F7 showed a significant amount of
Table 7. xylose, as compared to all the others (p =

275
Cristina M. Area et al.
0000). subsequent increase in the acetic acid content
Acetic and formic acids, xylose and present in the liquor and a loss of pentosans.
furfural increased progressively in the liquor The conditions of F5 produced a high
throughout the fractionation time (p = 0000). degradation of the fibrous material. The
Xylose and formic acid contents increased alkaline pre-treatment of F8 caused
significantly in the liquor when sulfuric acid considerable deacetylation, with a
was present (p < 0.01). Arabinose and subsequent increase in the acetic acid content
glucose showed the same trend. The balance in the liquor and a loss of pentosans.
of the components in the residual liquor is Fractionation F7 caused a larger hydrolysis of
shown in Table 8. pentosans and increased the xylose content in
The conditions of F5 produced a high the spent liquor. The evolution of most
degradation of the fibrous material. The organic components in the residual liquor of
alkaline pre-treatment of F8 caused fractionations F6 and F7 (both with sulfuric
considerable deacetylation, with a acid) is shown in Figure 4.

Figure 4: Organic compounds in the residual liquor from fractionations F6 and F7

Table 8
Organic compounds in residual liquors (% o.d.b.)

Fractionation Glucose Xylose Arabinose Pentosans* Formic Acetic HMF** Furfural Lignin
acid acid
F1 0.14 3.75 0.11 7.64 0.77 2.00 n.d. 3.08 18.2
F2 0.11 4.30 0.16 6.75 0.57 2.84 n.d. 2.81 18.2
F3 0.33 3.53 n.d. 5.02 0.97 2.36 0.21 4.51 18.6
F4 0.34 4.11 0.24 3.45 0.95 3.18 n.d. 3.86 18.6
F5 1.93 1.29 n.d. 0.58 2.58 3.91 3.18 11.5 17.3
F6 0.17 6.48 0.69 16.6 0.69 0.88 n.d. n.d. 16.6
F7 1.36 14.5 1.40 7.79 1.14 1.77 n.d. 0.78 18.3
Pre-F8s – – – 1.49 – 4.53 n.d. – –
F8 0.35 1.60 1.37 6.50 0.85 0.34 n.d. 0.09 10.8
* (Pentoses in hydrolyzed liquor – Pentoses in liquor such as it is) x hydrolysis factor; ** 5-(Hydroxymethyl)furfural;
n.d.: not detected; (% o.d.b.): on oven-dry bagasse

CONCLUSIONS with acetic acid and without catalyst at 180

The use of sulfuric acid as a catalyst at ºC and 240 min (> 87%).
160 ºC and 120 min generates deligni- Under optimum conditions (fractionation
fication degrees similar to those obtained with sulfuric acid at 160 ºC), the

276
 Bagasse
delignification values (calculated from the Bioresource Technol., 86, 301 (2003).
11
kinetic equations) showed that fractionation J. X. Sun, X. F. Sun, R. C. Sun and Y. Q. Su,
can be stopped at 90 min, with an Carbohyd. Polym., 56, 195 (2004).
12
approximately 1% decrease in deligni- Z. Pernalete, F. Piña, M. Suárez, A. Ferrer and
C. Aiello, Bioagro, 20, 3 (2008).
fication, as compared to the treatment at 120 13
D. Pasquini, M. T. B. Pimenta, L. H. Ferreira
min. and A. A. S. Curvelo, J. Supercrit. Fluid., 34, 125
In all cases, there was a significant (2005).
increase in carbohydrates, organic acids and 14
D. Pasquini, M. T. B. Pimenta, L. H. Ferreira
furfural in the liquor with the fractionation and A. A. S. Curvelo, J. Supercrit. Fluid., 36, 31
time, except for arabinose, which decreased (2005).
15
as it was degraded to furfural. J. X. Sun, R. Sun, X. F. Sun and Y. Su,
The largest amount of xylose in the Carbohyd. Res., 339, 291 (2004).
16
liquors (14.5% o.d.b.) was obtained in the S. Aziz and K. Sarkanen, Tappi J., 72, 169
fractionation with sulfuric acid, which also (1989).
17
T. J. McDonough, Tappi J., 76, 186 (1993).
produced the largest cellulose degradation. 18
E. Muurinen, Academic Dissertation, Faculty
Fractionation at 160 ºC with sulfuric acid of Technology, University of Oulu, Linnanmaa,
extracted the largest amounts of Acta Universitatis Ouluensis, Technica, 2000,
carbohydrates and lignin, producing the F146.
largest hydrolysis of pentosans and a 19
P. E. Kendall and J. H. Lora, Tappi J., 74, 113
moderate degradation to furfural. (1991).
20
T. N. Kleinert, Tappi J., 58, 170 (1975).
21
ACKNOWLEDGEMENTS: The authors G. Papatheofanous, E. Billa, D. P. Koullas, B.
gratefully acknowledge the financial support Monties and E. G. Koukios, Bioresource
of the Productive Innovation Federal Projects Technol., 54, 305 (1995).
22
D. Sidiras and E. Koukios, Bioresource
(PFIP) 2006, Secretariate for Technology,
Technol., 94, 91 (2004).
Science and Productive Innovation of the 23
K. V. Sarkanen, Tappi J., 73, 215 (1990).
Ministry of Education, Science and 24
A. A. S. Curvelo and R. Pereira, 8th
Technology. They also acknowledge the International Symposium on Wood and Pulping
assistance of the technical staff: Sebastián Chemistry (ISWPC), Helsinki (Finland), 1995,
González, María Antonieta Klein, Hugo vol. 2, p. 473.
Ferreira, Christian Sanabria and Daniel Baez.

REFERENCES
1
E. Frollini and M. J. A. Pimenta, Anais Assoc.
Bras. Quím., 46, 43 (1997).
2
B. P. Lavarack, G. J. Griffin and D. Rodman,
Catal. Today, 63, 257 (2000).
3
W. Alonso Pippo, P. Garzone and G.
Cornacchia, Waste Manag., 27, 869 (2007).
4
A. Ashok Pandey, C. R. Soccol, P. Nigam and
V. T. Soccol, Bioresource Technol., 74, 69
(2000).
5
B. P. Lavarack, G. J. Griffin and D. Rodman,
Biomass Bioenerg., 23, 367 (2002).
6
J. E. Paiva, I. R. Maldonade and A. R. P.
Scamparini, Rev. Bras. Eng. Agríc. Ambient., 13,
75 (2009).
7
R. Aguilar, J. A. Ramírez, G. Garrote and M.
Vázquez, J. Food Eng., 55, 309 (2002).
8
A. Rodríguez-Chong, J. A. Ramírez, G. Garrote
and M. Vázquez, J. Food Eng., 61, 143 (2004).
9
S. Gamez, J. J. Gonzalez-Cabriales, J. A.
Ramirez, G. Garrote and M. Vazquez, J. Food
Eng., 74, 78 (2006).
10
M. Sasaki, T. Adschiri and K. Arai,

277

View publication stats