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Pre-extraction of hemicelluloses from bagasse fibers: Effects of dry-strength

additives on paper properties

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DOI: 10.1016/j.indcrop.2012.07.047

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 Industrial Crops and Products 43 (2013) 365–371

Contents lists available at SciVerse ScienceDirect

Industrial Crops and Products

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

Pre-extraction of hemicelluloses from bagasse fibers: Effects of dry-strength

additives on paper properties
Yahya Hamzeh a,∗ , Alireza Ashori b , Zeinab Khorasani a , Ali Abdulkhani a , Ali Abyaz a
a
Department of Wood and Paper Science and Technology, Faculty of Natural Resources, University of Tehran, Karaj, Iran
b
Department of Chemical Technologies, Iranian Research Organization for Science and Technology (IROST), Tehran, Iran

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

Article history: The aim of this study was to further evaluate the viability of the integrated pulp mill biorefinery concept.
Received 27 February 2012 On one side the properties of hot-water pre-extractions were studied, in order to determine the effect
Received in revised form 16 July 2012 of extraction on soda pulping and bleachability. On the other side, the performance of two dry-strength
Accepted 25 July 2012
agents on the paper properties obtained from extracted and un-extracted (control) samples were inves-
tigated. It was found that hemicelluloses removal of the depithed bagasse chips was 24.6% at 140 ◦ C for
Keywords:
10 min with a solid to liquor ratio (S:L) of 1:8 (w/w), and that mass removal increased with extraction time
Bagasse
and temperature. The hemicelluloses removal reached 65.5% at 170 ◦ C for 30 min. The residual extracted
Bleaching
Cationic starch
bagasse were subjected to soda pulping at 160 ◦ C for 1 h with 11, 14 and 17% active alkali charge and
Chitosan a S:L of 1:5 (w/w). Conventional elemental chlorine free bleaching (D0 ED1 ) sequence was also used to
Hot-water extraction compare the results with the un-extracted ones. Compared with the control sample, the overall pulp
Pulping yield for extracted bagasse increased considerably while Kappa number and rejects decreased moder-
ately. In addition, yield and Kappa number of the pulps improved with increasing alkali charge from 11%
to 17%. After pre-extraction, better brightness compared with the control pulp was also shown. However,
hot-water extraction was found to negatively impact some pulp properties including decreases in burst
and tensile indices while addition of chitosan and cationic starch could improve the strength proper-
ties. Overall, papers treated with chitosan gave superior mechanical properties compared to the papers
treated with cationic starch.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction During a typical chemical pulping process, 80–90% of the lignin

Hemicelluloses are the second major sugar fraction after cellu-
lose in lignocellulosic materials. They are hetero-polysaccharides,
which contain hexosan and pentosan monomer units. The amount
of hemicelluloses in wood is usually between 20% and 30%. Soft-
wood hemicelluloses consist of both pentosans and hexosans, while
hardwood hemicelluloses consist mainly of pentosans. Most hemi-
celluloses have a low degree of polymerization of around 100–200,
and they are branched and generally do not form crystalline regions
(Sjöström, 1993). Their complex character and linkage to lignin
presents a major hurdle. Hemicelluloses function as a bridge to con-
nect cellulose and lignin. The linkages between hemicelluloses and
cellulose are hydrogen bonds, while hemicelluloses are often linked
to lignin through covalent bonds. These linkages could be either of
ester or ether type or glycosidic bonds (Sun et al., 2004; Yoon et al.,
2008).
∗ Corresponding author. Tel.: +98 26 3224 9311.
E-mail address: hamzeh@ut.ac.ir (Y. Hamzeh).
and 50% of the hemicelluloses are removed (Sjöström, 1993). The
degraded hemicelluloses (mostly aldonic acids) in the waste pulp-
ing liquor are then combusted during the chemical recovery process
together with the lignin dissolved in the cooking liquor. However,
the heating value of wood hemicelulloses, about 13.6 MJ/kg, is only
about half of that of lignin (Amidon and Liu, 2009). It is thus not
effective to use hemicelluloses as a fuel. It is currently underuti-
lized by burning. Therefore, in the pulp mill biorefinery concept,
a more economical use of the hemicelluloses would be to extract
them prior to pulping, and then convert them to higher value-
added products such as ethanol, itaconic acid, or other chemicals
(Schacht et al., 2008; Amidon et al., 2008). In recent years, the
interest in the isolation of hemicelluloses from biomass has greatly
increased (Mao et al., 2008; Mittal et al., 2009; Ren et al., 2009;
Lu et al., 2012; Jahan et al., 2012). There are several pre-treatment
technologies suggested for removal of hemicelluloses from wood
(biomass) such as steam explosion, organic solvents, alkali, dilute
acid, enzyme treatment and water extraction (autohydrolysis). In
selecting the optimal methods to remove the hemicelluloses from
wood prior to pulping, both economical and technological aspects
have to be taken into account (Tunc and van Heiningen, 2008).

0926-6690/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.indcrop.2012.07.047
366 Y. Hamzeh et al. / Industrial Crops and Products 43 (2013) 365–371

Environmental effects are another big concern. Autohydrolysis is Table 1

Chemical compositions of depithed bagasse.
of interest because water is the only reagent making it an environ-
mentally friendly, inexpensive process compared to dilute mineral Components, % Depithed bagassea Depithed bagasseb
acid and alkaline pre-hydrolysis which require recovery or neu- Holocellulose 73.7 ± 4.3 71.03 ± 0.5
tralization/disposal of the alkali or acid. During the autohydrolysis ␣-Cellulose 40.5 ± 3.2 42.34 ± 0.36
process at elevated temperatures, acetic acid is released from the Hemicellulose 33.2 ± 5.3 28.60 ± 0.42
acetylated polysaccharides in the wood. This lowers the pH of Pentosans 13.7 ± 2.1 23.9 ± 0.21
Ash 4.8 ± 1.9 2.1 ± 0.03
the extract to a range of 3–4, allowing the removal of hemicellu-
Lignin
loses from the wood. In addition, the autohydrolysis process could Acid insoluble 27.7 ± 3.5 21.7 ± 0.35
remove the extractives compounds which are present in woody Acid soluble 0.47 ± 0.08 –
materials (Caparrós et al., 2008). The obtained solid fraction from Solubles in
Hot water 6.5 ± 0.6 7.42 ± 0.05
authohydrolysis process, characterized by its high content of lignin
1% NaOH 31.8 ± 4.3 32.3 ± 0.1
and cellulose, could be employed as raw material for pulp and E-Dc 3.8 ± 1.1 –
papermaking (Garrote et al., 2003; Lao, 2004), alcohol produc- Monosaccharides
tion (Chikako et al., 2005), ruminant feed (Howard et al., 1995), Arabinose 2.2 ± 0.5 –
etc. Mannose 5.7 ± 1.0 –
Galactose 2.6 ± 0.4 –
It has been demonstrated that the removal of hemicelluloses
Glucose 76.9 ± 5.2 –
from raw materials before pulping results in pulps that refine Xylose 14.5 ± 2.1 –
difficultly and forms a weaker paper than obtained pulps from un- Rhamnose 0.4 ± 0.4 –
extracted raw materials (Duarte et al., 2011; Jahan et al., 2012). a
Current study.
Enhancing the strength properties of biorefinery pulps via dry b
Agnihotri et al. (2010).
c
strength additives for conventional products make it easier to com- Ethanol-dichloromethane mixture.
mercialize the biorefinery concept in the pulp and paper industry.
Recently for sustainable use of forest and agricultural resources, the
reinforcement of the pulps made from hot-water extracted hard- All stock solutions used in this work were freshly prepared to
woods with polylactic acid as a renewable polymer and a designed avoid any possible degradation.
biorefinery product, in combination with cationic starch applied in
the wet-end have been reported and showed encouraging results
2.2. Methods
(Gong et al., 2012). According to Nicu et al. (2011), chitosan could
have a great potential for a wide range of applications in the paper-
2.2.1. Chemical characterization
making such as papermaking additive, for both internal and surface
The chemical compositions of bagasse fibers were carried out
applications, due to its biodegradability, biocompatibility, antimi-
following the appropriate Tappi standards (2002) and the other
crobial activity, nontoxicity and versatile chemical and physical
published procedures as indicated. The samples were subjected to
properties.
the following determinations: holocellulose (Zobel and McElwee,
In this paper, hot-water pre-extraction of bagasse (agro-waste)
1966), ␣-cellulose (T 203 cm-99), Klason lignin (T 222 om-02),
was carried out in order to recover the hemicelluloses based on
acid-soluble lignin (T 250 um-91), pentosans (T 223 cm-01),
a biorefinery concept. Subsequently, the extracted residues and
ethanol–benzene solubility (T 204 cm-97), 1% NaOH solubility (T
an un-extracted sample (control) were subjected to soda pulp-
212 om-98), hot-water solubility (T 207 cm-99), ash (T 211 om-
ing. In order to compensate the adverse effect of hemicelluloses
93) and polysaccharide (T 249 cm-00). Table 1 shows the mean
extraction on the paper properties, the effects of addition of dry-
and standard deviations of three replicate determinations of each
strength additives (namely chitosan and cationic starch) on some
sample.
mechanical properties were also investigated and compared with
the control. The cationic starch was selected as commonly applied
dry-strength additive in papermaking and chitosan was chosen as 2.2.2. Hot-water pre-extraction
an effective additive that can be adsorbed on lignocellulosic fibers in Depithed bagasse was contacted with water in an electrically
the absence of electrostatic attraction (Ashori et al., 2005; Myllytie heated oil bath containing 4 bombs of 2.5 L capacity. The bombs
et al., 2009). were rotated at 1 rpm. The extraction temperatures were 140, 155
and 170 ◦ C with hold times of 10, 20 and 30 min after the set tem-
perature was reached. The solid to liquor (S:L) ratio was fixed at
2. Materials and methods 1:8 (by weight) and held constant in all experiments. At the end of
treatment, the solid residue was recovered by filtration and washed
2.1. Materials with distilled water. The solid fraction was used for soda pulping
process.
Bagasse was collected from Khuzestan province (Iran) and cut to The severity factor was used to describe the synergic effect of
2–3 cm in length. It was washed, air-dried and screened through a time and temperature of treatment on extraction results as well
series of screens to remove dirt and pith. For the chemical anal- as for comparison with the obtained results in the other studies.
ysis, the depithed bagasse was then ground using a Wiley mill It calculated by means of Eq. (1) in which T representing reaction
and the fraction passing 2 mm holes was stored in plastic bags for temperature (◦ C), Tr is a reference temperature and ω is an empir-
experiments. ical parameter related to activation energy and temperature, and
Two dry-strength additives were used in this study: chitosan t is reaction time (min). According to literature for autohydrolysis
and cationic starch. High-molecular weight chitosan was a Sigma process of lignocellulosic materials at a constant temperature, the
Aldrich product (USA), a material with 85.4% deacetylation, and reference temperature and ω are 100 ◦ C and 14.75 ◦ C, respectively
molecular weight of 9 × 105 g/mol. The cationic starch used in (Ligero et al., 2011; Wang et al., 2011).
this study was made from potato and was obtained from Lyckeby   T − T 
Amylex Co. It contained about 17% amylase and 83% amylopectin r
Severity factor = Log10 t × exp (1)
and had a degree of substitution of 0.065. ω
 Y. Hamzeh et al. / Industrial Crops and Products 43 (2013) 365–371
2.2.3. Holocellulose determination
Holocellulose was measured following the procedure origi-
nally pioneered by Zobel and McElwee (1966). The carbohydrate
(holocellulose) fraction of the pre-extracted samples was isolated
by removing the lignin from the sample using the acid chlorite
method. Air-dried fiber (2.5 g) was placed into an Erlenmeyer flask,
and a quantity of stock solution A (made from acetic acid (0.5 mL),
NaClO2 (1 g) and distilled water (80 mL)) was added. The flask was
placed in a hot-water bath (70 ± 2 ◦ C). After 1 h additional portions
of solution B (made from NaClO2 (1 g) and acetic acid (0.5 mL)) were
added and the mixture swirled thoroughly. After heating for 6 h,
the contents of the flask were transferred to a tared coarse crucible
and the liquid removed by suction on a filter flask. The sample was
washed with 1% aqueous acetic acid solution (100 mL) and then
with acetone (2 × 5 mL). The crucible containing the holocellulose
was oven-dried at 105 ± 5 ◦ C before being weighed.
2.2.4. Pulping process
Pulping experiments were carried out with 150 g of OD dep-
ithed bagasse using the same reactor used in the autohydrolysis
process. The pulping conditions were as follows: initial S:L 1:5,
time to maximum temperature 90 min, maximum temperature
160 ◦ C and pulping time at maximum temperature 60 min. All the
above-mentioned conditions were kept constant for extracted and
un-extracted (control) bagasse. The amounts of active alkali (NaOH)
charge were 11, 14 and 17% based on OD bagasse. After cooking,
the pulps were thoroughly washed with fresh water on a fine fil-
ter, and then disintegrated in a hydropulper at 30,000 revolutions
and 0.5% consistency for 5 min. Disintegrated pulps were screened
with vibratory flat screen to determine the screened rejects (pulp
shives) and screened yield. For each raw material (pre-extracted
and control samples), the screened yield, reject and Kappa number
was determined. Further cookings were carried out using cooking
liquors of varying active alkali charge in order to determine the
optimum cooking conditions for maximizing the yield of screened
pulp.
2.2.5. Bleaching
The obtained pulps from extracted and un-extracted bagasse
with 17% active alkali were bleached by conventional elemental
chlorine free (ECF) bleaching sequences. In the first stage (D0 ) of
D0 ED1 bleaching sequences the ClO2 charge was 2% based on OD
pulp. The temperature was 70 ◦ C and the time was 60 min in the D0
stage. Pulp consistency was 10%. The initial pH was adjusted to 4
by adding dilute H2 SO4 . In the alkaline extraction (E) stage, NaOH
charge was 2% (on OD pulp). The temperature was 80 ◦ C for 60 min
and the pulp consistency was 10%. In the D1 stage, the end pH was
fixed at 4. The ClO2 charge in the D1 was 0.5% at a temperature of
80 ◦ C for 60 min. In each bleaching stage, following the addition of
the specified chemicals, the pulp was stirred with a glass rod to
ensure even mixing. The slurry (pulp mass and bleaching liquor)
was periodically mixed as bleaching proceeded. At the end of each
bleaching stage, the slurry was collected on a filter mesh and then
thoroughly washed with deionized water.
2.2.6. Application of dry-strength additives
The chitosan solution was prepared by dissolving in 1% acetic
acid at room temperature by stirring for 8 h, whereas the cationic
starch was prepared by suspending of starch powder in distilled
water and heating to 95 ◦ C on a water bath with periodic stirring
and then holding the suspension at this temperature for 30 min
after the onset of gelatinization. The solutions were then diluted
with distilled water prior to use. Chitosan were applied in dosages
of 0%, 0.25%, 0.5%, and 1.0%, while cationic starch was used in dosage
of 0%, 0.5%, 1%, and 1.5% based on OD weight of the pulp. Vari-
ous mixtures of both dry-strength additives were also applied to
367
compare the results. Different dosage solutions of polymers were
added to a 1% suspension of bleached pulp. The mixture was agi-
tated for 30 min at room temperature (25 ◦ C). The suspension was
then diluted with distilled water to 0.5%.
2.2.7. Sheet formation and paper testing
After mixing the pulp suspension for 20 min, handsheets
(60 g/m2 ) were made in a British handsheet former as per TAPPI
Standard T 205 sp-02. The samples were conditioned at 50 ± 2%
relative humidity and 23 ± 1 ◦ C temperature according to TAPPI T
402 sp-98 for at least 4 h. The handsheets were tested for tensile
index (T 494 om-01), tear index (T 414 om-04), burst index (T 403
om-02), and brightness (T 452 om-98).
3. Results and discussion
3.1. Chemical characterization of the raw material
The results on general chemical composition of depithed
bagasse fibers considered in this study are presented in Table 1.
The average holocellulose content of bagasse was found to be
73.7%, which is comparable with hardwoods (68–74%), softwoods
(70–81%) (Sjöström, 1993), however lower than the value (80.2%)
reported by Jiménez et al. (2007).
Alpha-cellulose content was determined to be 40.5%, which was
comparable with the value (42.3%) reported for depithed bagasse
(Agnihotri et al., 2010). Pentosan content determination measures
the total amount of pentose-based carbohydrate in a material. The
pentosans content was 13.7%, which was lower than the tropical
hardwoods (Jahan et al., 2009) and depithed bagasse (Agnihotri
et al., 2010). Pentosan content in softwoods is reported to be
about 7–10%, and in hardwoods about 19–25% (Sjöström, 1993).
The values obtained for acid insoluble lignin are higher than that
reported by Agnihotri et al. (2010) and Jiménez et al. (2007). The
ash content was found to be 4.8%, which is in the range of non-
wood plants (4.5–12.5%) and significantly high when compared
with those reported by Agnihotri et al. (2010) for depithed bagasse
and Jiménez et al. (2007) for bagasse. Such high ash content causes
problems in chemical recovery.
Table 1 shows that the 1% NaOH solubles were 31.8%, which
was comparable with the value (32.3%) reported for depithed
bagasse (Agnihotri et al., 2010) and lower than the reported data
for bagasse (Jiménez et al., 2007). Due to high 1% NaOH solubles,
it can be expected to provide a medium pulp yield. The hot-water
solubility of bagasse is slightly lower than the value reported for
depithed bagasse and higher than value reported for bagasse. Hot-
water soluble substances in the raw materials included starch and
proteins, which could consume pulping reagents. Generally, the
presence of extraneous materials in the raw materials reduces
pulping yield and necessitates the consumption of soda chemi-
cals for their removal. The differences between the values obtained
in the present study and those reported in the literature may be
due to the differences in analysis methods, raw materials (depithed
and undepited bagasse) and variety. The analysis of monosaccha-
ride composition allowed some propositions to be made about
hemicellulose composition. Accordingly, it contains a significant
proportion of glucose as backbone and a rather high proportion of
xylose, which may suggest the presence of significant amounts of
xyloglucans.
3.2. Autohydrolysis process
After the hot-water extraction, the treated bagasse chips were
washed with fresh water and the extraction yield and hemicel-
luloses removal (loss) were tested for 100 g OD bagasse. Table 2
shows the results of hot-water pre-extraction prior to pulping of
368 Y. Hamzeh et al. / Industrial Crops and Products 43 (2013) 365–371

Table 2
Effects of hot-water extraction conditions on extraction yield and hemicelluloses loss.

Temp., ◦ C Time, min Severity factor, Extraction Extraction Hemicelluloses Extracted Hemicelluloses
min liquid, pH yield, % in residual, % hemicellulosesa removal, %

10 2.2 4.2 96.8 67.7 8.2 24.6

140 20 2.5 4.1 95.8 66.8 9.7 29.2
30 2.6 4.1 95.7 66.8 9.8 29.4

10 2.6 4.0 94.5 66.2 11.1 33.6

155 20 2.9 3.9 94.0 65.8 11.8 35.7
30 3.1 3.8 92.9 65.2 13.2 39.5

10 3.1 3.8 86.4 62.0 20.1 60.6

170 20 3.4 3.6 83.1 64.0 20.5 61.8
30 3.5 3.4 79.2 65.6 21.8 65.5

30 2.1 4.3 73.3 – – –

120b
60 2.4 4.11 98.9 – – –

30 3.2 3.7 98.8 – – –

160b
60 3.5 3.53 86.8 – – –

150c 60 3.2 3.57 76.9 – 16 48.2

a
Extracted hemicelluloses calculated for 100 g OD bagasse.
b
Lei et al. (2010).
c
Jahan et al. (2009).

bagasse. For comparison, the reported results from previous studies
(Jahan et al., 2009; Lei et al., 2010) using hot-water pre-extraction
on bagasse are also presented. The hot-water extraction process
dissolves the hemicelluloses portion of the lignocellulosic biomass
and the cellulose remains largely intact in the extracted residual
(Inoue et al., 2008; Xiao et al., 2011). Thus, percentages of hemicel-
luloses removal were calculated as indicated in Table 2. It can be
clearly seen that, as the extraction temperature and time increase,
the yield of extracted bagasse decreases. The content of the hemi-
celluloses in bagasse is at high level (Table 1), and the chemical
groups of hemicelluloses are mainly monosaccharides. Hot-water
extraction may destroy acetyl and furfural acid substitutions on
hemicelluloses chemical structures, and generate acetic acid and
other low molecular organic acids as reflected by decreasing the
pH values of extract. The formation of organic acids may contribute
to the break of ether bonds located in fiber cell wall, and pro-
mote the removal of oligosaccharides. In the acidic environments,
polysaccharides can be further hydrolyzed to produce single sugars,
and some monosaccharide may further degraded into aldehydes
(Zhang and Yang, 2011). This makes autohydrolysis similar to acid
hydrolysis in the way that it leads to unwanted side reactions at
elevated temperatures, which lowers the overall yield of hemicel-
luloses recovery. In addition, the temperature significantly affects
the dielectric constant of the liquid solution; therefore water can
also play a role of acid at high temperature for sugars degrading
(Palmqvist and Hahn-Hägerdal, 2000).
Taking account of the severity factor, similar results for extrac-
tion liquid pH and extraction yield reported by Lei et al. (2010).
However, Jahan et al. (2009) reported slightly lower values for
extraction liquid pH and extraction yield at a comparable sever-
ity factor, presumably due to extraction pith containing bagasse
with higher hemicelluloses content (Fig. 1). Since, the main aim
of an integrated pulp mill biorefinery is co-production of pulp
and high-value hemicelluloses-based materials, the high degree
of hemicelluloses extraction is less desirable because it would
have more pronounced adverse effects on paper properties. There-
fore, the residual obtained under operation condition of 170 ◦ C for
10 min, which resulted in a moderate (60.6%) removal of hemicel-
luloses, was selected for pulping and bleaching study.
value of the process. The results of studies on soda pulping of pre-
extracted and un-extracted (control) of bagasse conducted during
this investigation are given in Table 3. The cook at 11% active alkali
gave pulps that had a high Kappa number, and contained too much
uncooked material that was difficult to disintegrate into fibers, so
it was not possible to make handsheets from them. Hence, the
amount of active alkali was chosen at 14%. Analysis of pulps pre-
pared using 14% active alkali showed that either lignin precipitation
had occurred, and/or lignin within the fiber walls had not been
sufficiently removed, as indicated by the high Kappa number. To
obtain bleachable-grade bagasse soda pulps, the charge of active
alkali used had to be increased. With increasing the active alkali
charge from 11% to 17%, the Kappa number decreased, screened
yield increased and screened rejects decreased. An increase in the
active alkali above 17% generally led to limited improvements in
the screened pulp yield and Kappa number. Kraft pulping with 17%
active alkali was sufficient to ensure almost complete elimination
of non-cellulosic matter.
Table 3 also shows the effect of pre-extraction on the soda pulp-
ing of bagasse. It is seen that the pre-extraction of bagasse resulted
in lower Kappa number of pulp for the control samples with con-
siderable lowering of pulp reject. Similar results were observed for
hot-water pre-extraction of bagasse followed by alkaline pulping
(Jahan et al., 2009). In the previous studies, a higher pulp viscos-
ity from extracted bagasse than that from untreated bagasse have
been reported that attributed to the removal of hemicelluloses

3.3. Pulping process

Fig. 1. Effects of severity factor on the extraction yield and extraction (extraction
For the current study, the main aim of pulping is to produce yield: , current study; , Lei et al. (2010); , Jahan et al. (2009) and extraction
bleached pulp from bagasse fibers that will upgrade the economic liquid pH: ♦, current study; , Lei et al. (2010); , Jahan et al. (2009)).
 Y. Hamzeh et al. / Industrial Crops and Products 43 (2013) 365–371 369

Table 3
Laboratory soda pulping results for pre-extracted and control bagasse samples.

Properties 11% active alkali 14% active alkali 17% active alkali

Extracted Control Extracted Control Extracted Control

Overall yield, %a 52.5 45.1 53.9 43.3 56.9 51.1

Screen yield, % 45.3 34.5 46.6 40.6 56.9 51.1
Reject, % 6.3 10.6 3.2 2.5 0.0 0.0
Kappa no. 40 54 26.6 28.4 18.6 19.3
a
Based on OD bagasse.

and higher ratio of cellulose to hemicelluloses in extracted bag-
gase (Jahan et al., 2009; Lei et al., 2010). Hemicelluloses compared
to cellulose have high accessibility to acidic or alkaline hydrol-
ysis. This is due to their amorphous structure and much lower
degree of polymerization. During the pre-hydrolysis, some hemi-
celluloses and lignin were removed and delignification was thus
improved. The extracted bagasse had a more open structure due
to the hemicelluloses and lignin removal (Jahan et al., 2012). After
pre-hydrolysis, lignin migrated to the surface of bagasse. There-
fore the delignification was faster for pulping of extracted samples.
So, pulping of extracted bagasse yielded a lower Kappa number
even with lower alkali charge. In general, the total pulp yield and
Kappa number decreased with increasing alkali charge and bleach-
able grade pulp obtained from both un-extracted and extracted
bagasse at 17% alkali charge, thus these pulps chosen for bleaching
study.
3.4. Bleaching and unrefined pulp properties
As mentioned earlier, the main objective of this part of the
study was to evaluate the effect of pre-extraction on the brightness
of pulps using an ECF bleaching method. In general, the bright-
ness of the extracted bagasse pulps was higher than those of
un-extracted ones due to lower hemicelluloses contents. It is an
important observation because it provides another advantage over
un-extracted pulp. After bleaching, the overall pulp yield, on the
basis of original material, became narrower between pre-extracted
and un-extracted bagasse. In addition, it was found that the pre-
extracted pulps could be easily bleached to 87.5% ISO brightness by
a D0 ED1 sequence.
In general, mechanical properties of pre-extracted pulps were
decreased. It is seen that the tensile and burst indices of pre-
extracted pulps were lower than un-extracted ones. However, no
differences in tear index were observed (Table 4), indicating that
the fiber strength remains unaffected, but the inter-fiber bonding
decreases with extraction. A similar phenomenon reported in sev-
eral studies and attributed to the removal of hemicelluloses from
the pre-hydrolyzed raw materials (Sousa et al., 2007; Duarte et al.,
2011). The extraction of hemicelluloses from lignocellulosic mate-
rials prior to pulping decreases the fiber–fiber bonding capacity,
consequently lowering the Scott bond, tensile and burst indices of
paper (Jahan et al., 2009).
3.5. Effect of dry strength additives on mechanical properties
Data on mechanical properties of papers made from un-treated
and treated pulps by adding diluted acidic chitosan solution and
cationic starch solution to the pulp suspension are presented
in Fig. 2. The improvement effects of used dry-strength addi-
tives were higher for pre-extracted bagasse. When high amount
of dry-strength additives employed, no significant differences in
mechanical properties observed between extracted and control
samples. Duarte et al. (2011) investigated the effect of surface com-
position on the fibers’ total surface charge and zeta potential using
a Mütek SZP 06. They observed that a change in hemicelluloses
content (achieved by modified pulping) from 20% to 15% did not
affect the zeta potential. Therefore, the surface absorption of pre-
extracted fibers is as well as control. In other words, pre-extracted
fibers can absorb same amount of dry-strength additives.
The results demonstrate that the addition of chitosan can con-
siderably increase mechanical properties. Chitosan application has
a unique effect on the mechanical properties; for instance, at 1% chi-
tosan, the increases in tensile and burst indices were about 27.5 and
13.3% more than the control (Fig. 2a). A similar trend was observed
for treated paper with cationic starch. However, the increase less
than 1% was low. This indicates that chitosan should be used based
on end-product quality requirements and the cost effectiveness of
the process. However, all mechanical properties increased when

Table 4
Results of D0 ED1 bleaching of obtained soda pulps from pre-extracted and control
bagasse.

Properties Extracted Control

Initial Kappa no. 18.6 19.3

Total ClO2 charge, % 2.5 2.5
Brightness, % 87.5 86.2
Bleaching yield, % 95.0 93.2
Overall yield, %a 56.9 51.1
Tensile index, N m/g 42.46 49.33
Tear index, mN m2 /g 4.14 4.06
Burst index, kPa m2 /g 2.62 2.78
Fig. 2. Effects of dry-strength additives on the mechanical properties of pre-
a
Based on OD bagasse. extracted and control handsheets.
370 Y. Hamzeh et al. / Industrial Crops and Products 43 (2013) 365–371

the chitosan was added to furnish. But, the effect of chitosan on

the properties of handsheets under pre-extraction condition was
better than un-extracted condition (Fig. 2b). This indicates that the
un-extracted condition is less suitable than the extracted method
when chitosan and cationic starch are used presumably, due to
higher porosity of extracted pulps increasing adsorption of dry-
strength additives on the fiber surfaces (Kontturi et al., 2008).
Dry-strength additives have positive effects on the mechanical
properties through improving inter-fiber bonding. The added chi-
tosan molecules were supposed to act as crosslinkers by binding to
neighboring cellulose fibers. It was also suggested that the inter-
action of chitosan with the fiber would lead to a further increase
in fiber–fiber bonding due to the explicit polycationic character
of the chitosan. Once binding and crosslinking between fibers has
occurred, the yet unbound parts of the chitosan molecule have the
required geometry to enhance more hydrogen bonding. As a result,
the chitosan would attach itself to larger segments of the cellu-
lose fiber and tend to shorten the distance between the individual
cellulose fibers (Ashori et al., 2005). Fig. 3 is an idealized represen- Fig. 3. Idealized representation of bond formation in the cellulosic fiber–chitosan
bonding system.
tation of the cellulosic fiber–chitosan system, showing the bonding
between two cellulose molecules and two chitosan molecules. In
addition, it is reported that there is an increase in the surface rough- of polymer was higher. The increase in mechanical properties was
ness as extraction takes place, which is reflected in the increase significantly lower than chitosan sized papers.
of the kink index. So, extracted fibers may absorb more additives
compared with control ones (Sousa et al., 2007; Lei et al., 2010; 4. Conclusions
Duarte et al., 2011).
Fig. 4 shows the mechanical properties of handsheets produced The main goal of current work was to evaluate the viabil-
by the mixtures of chitosan and cationic starch. The data demon- ity of the integrated pulp mill biorefinery concept. Based on the
strate that the addition of cationic starch in the concentration range experimental results the optimized conditions for hot-water pre-
0.5–1.5% increases both mechanical properties of the handsheets extraction of bagasse were found to be: maximum temperature
(Fig. 4a). At 0.5% cationic starch and chitosan, the increase in burst 170 ◦ C, heat-up time 90 min, time at maximum temperature 10 min
index was 3.5 and 5% respectively compared to the control (Fig. 4b). and S:L ratio 1:8 (w/w). At this condition hemicelluloses can be
As in the case of chitosan, the effect was higher when the dosage partly separated from bagasse fibers by hot-water pre-extraction

Fig. 4. Effect of mixtures of chitosan and cationic starch on the pre-extracted (a) and control (b) samples (0% , 0.5% , 1% ♦, 1.5% * cationic starch).
 Y. Hamzeh et al. / Industrial Crops and Products 43 (2013) 365–371
process. Pulping results showed that the extracted bagasse had
different behaviors in terms of bleaching and mechanical prop-
erties in comparison to the un-extracted bagasse. The optimal
pulping conditions for production of bleachable grade pulp from
extracted bagasse were: alkali charge 17%, maximum temperature
160 ◦ C, heat-up time 90 min, and holding time at maximum tem-
perature 60 min. Pre-extracted pulps can be easily bleached to a
brightness of 87.5% ISO using a 3-stage ECF bleaching technique.
The ECF (D0 ED1 ) sequence is simple, and only two main stages
of bleaching are involved using only one major bleaching chemi-
cal, together with one alkaline extraction stage. The pre-extraction
affected tensile and burst indices of the produced pulp because of
removal of considerable amount of hemicelluloses. However, no
significant differences in tear index were observed, indicating that
the fiber strength remains unaffected, but the inter-fiber bonding
decreases with extraction. Addition of chitosan and cationic starch
could improve strength properties in terms of tensile and burst
indices. However, pre-extracted samples had more improvement
compared to the un-extracted ones.
Acknowledgments
The first author gratefully acknowledges the financial support
(Grant # 89000873) from the Iran National Science Foundation
(INSF).
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