Journal of Korea TAPPI

Vol. 51. No. 2, 2019, 16-25p

ISSN (Print): 0253-3200
Printed in Korea http://dx.doi.org/10.7584/JKTAPPI.2019.04.51.2.16

Effect of Ultrasonic-assisted Ionic Liquid Pretreatment on the

Bleachability and Properties of Eucalyptus Kraft Pulp

Jianmin Peng, Letian Qi‡, Guihua Yang†, Ming He, Yu Xue, Jiuachuan Chen
Received November 4, 2018; Received in revised form March 26, 2019; Accepted March 27, 2019

ABSTRACT
In this work, the application of ionic liquid (IL) and ultrasonic (Ul) treatment on the
bleachability and properties of eucalyptus kraft pulp were investigated. The results
showed that ILs protected fibers from depolymerization by improving the pulp viscosity.
The combination of Ul and IL treatment notably reduced the kappa number and improved
tensile index, burst index, tear strength index and folding endurance of pulp. Ul and IL
treatment reduced the fines content, decrease the water retention value (WRV) and cause
the formation of crosslinks between fibers, especially in Ul+[TEA][HSO4] treatment. The
XRD and FT-IR analysis illustrated the combination of Ul and IL treatment disturbed the
amorphous region of pulp fiber by increasing of crystallinity and no chemical change ap-
peared in the treatment process. The Ul assisted IL treatment technology will have a
promising application due to its high efficiency and environmental protection character.

Keywords: Ionic liquid, ultrasonic, treatment, bleaching, eucalyptus kraft pulp

1. Introduction ber3) and stable nature of lignin chains4) require

Elemental chlorine free (ECF) bleaching technol-
1)
ogy apply ClO2 to instead of Cl2 gas in the process.
It avoids the formation of organochlorine com-
pounds and reduces the amount of effluent dis-
2)
charged, thereby widely adopted in industry.
However, the rigid structure of lignocellulosic fi-
high dosage of ClO2 during the bleaching process,
which unavoidably causing equipment corrosion
and reducing the physical properties of paper.5-7)
Therefore, it would be helpful to develop a treat-
ment technology loosening the lignocellulose fiber
structure, facilitating the bleaching chemicals to
access lignin compounds, and minimizing the im-

• State Key Laboratory of Biobased Material and Green Papermaking, Qilu University of Technology, Shandong Academy of
Sciences, Jinan, 250353. P. R. China
† Corresponding Author: E-mail: ygh@qlu.edu.cn
‡ Co-corresponding Author: E-mail: lqi01@qlu.edu.cn

16 펄프·종이기술 51(2) 2019

 Jianmin Peng·Letian Qi·Guihua Yang·Ming He·Yu Xue·Jiuachuan Chen
pact on the fibers strength. So far, various ap-
proaches were investigated for fiber pretreatment
such as enzyme, ionic liquid and ultrasonic treat-
8)
ment.
Ionic liquids (IL) are molten salts under mild con-
ditions. These novel solvents have various merits,
such as good solubility, non-volatile, chemical
stable, recyclable and tunable.9) It has shown par-
ticular ability to disturb the H-bond network of
the plant fiber. Imidazolium-based ILs were firstly
reported to dissolve cellulose through their strong
H-bond effect, among them [BMIM][Cl] presented
10)
good solubility. This dissolution endures a de-
crease in crystallization, and transformation from
Cellulose I into Cellulose II.11)
Several studies have been done to investigate the
effect of ILs with lignocellulosic fibers, and the re-
sults showing that ILs can enhancing the swell-
ing,12) increasing surface area and improving phys-
13)
ical strength of paper. On the other hand, ILs
were also applied in the separation of lignocellu-
losic components. Imidazolium based ILs have been
used on the production of high purity dissolved
pulp.14,15) Moreover, [BMIM][Cl] was used to remove
low molecular weight lignin compounds, from pulp
in order to improves the bleaching performance.16)
These literature studies indicated that ILs can be
designed to lose the rigid plant fiber structure,
modify cellulose structures and remove lignin
compounds. Therefore, it could assist bleaching
process and improve the physical properties of pa-
per. However, current studies majorly focused on
imidazolium-based ILs and limited to their com-
mercial availability, which inhibited further appli-
cations. Recently it has been reported that [TEA]
[HSO4] IL has shown great power to dissolve lignin
17)
even at high water loading up to 20 wt%. In ad-
dition, this type of IL can be produced at low
18)
cost, which is ideal for plant fiber treatment.
With these merits, [TEA][HSO4] might be suitable
for the application in bleaching process.
Ultrasonic (Ul) treatment was considered as a
suitable approach to loosen fiber structure.13) It has
been reported being an efficient technique for
hemicellulose extraction,19,20) fiber morphology
modifcation21) and fibers properties enhancement.
The WRV,22) drainability23,24) and accessibility22) of
fiber have been improved after Ul treatment.
Thereby, when applied along with IL treatment, Ul
could enhance the IL treatment effect.13) It was re-
ported that a combination of Ul and IL treatment
improves surface areas of fiber and enhanced the
physical strength of handsheets.25) However, the
effect of Ul assisted IL treatment on bleachability
of kraft pulp (KP) have not been investigated yet.
In this work, IL and Ul pretreatment was applied
under mild treatment conditions before the bleach-
ing of eucalyptus KP. Their effect on bleaching
performance was investigated by analyzing the fi-
ber qualities and physical strength of handsheets.
2. Materials and Methods
2.1 Materials
Eucalyptus globules wood was obtained from Asia
Symbol (Shandong) Pulp and Paper Co., Ltd.
(China). It was air-dried and then cut into pieces
in size of 3-4 cm. The kraft cooking of eucalyptus
used following process conditions: available alkali
21%, sulfidity 25%, maximum cooking temperature
170℃, and cooking time 90 min at 170℃. And
cooking liquor was filtrated and then kraft pulp
sealed into polyethylene bag.
Chemicals used in this work including grade and
source was listed as following:
1-butyl-3-methylimidazolium hydrogen sulfate
([BMIM][HSO4]) (analytically reagent (AR), 95%)
was purchased from Shanghai Rhawn Chemical
Co., Ltd. Triethylamine (AR, 99%) was purchased
from Tianjin Fuyu Fine Chemical Co., Ltd. Anhy-
drous magnesium sulfate (AR, 99%) and sodium
J. of Korea TAPPI Vol.51 No.2 Mar.-Apr. 2019 17
Effect of Ultrasonic-Assisted Ionic Liquid Pretreatment on the Bleachability and Properties of Eucalyptus Kraft Pulp
hydroxide (AR, 96%) were purchased from Tianjin
Da Mao Chemical Co. Chlorine dioxide (AR, 1 vol%)
was purchased from Shandong Dahua Special En-
vironmental Engineering Co., Ltd. Hydrogen per-
oxide (AR, 30%) and sulfuric acid (AR, 98%) were
purchased from Lai Yang Chemical Co., Ltd. So-
dium sulfide (AR, 98%) was purchased from Tianjin
Dingshengxin Chemical Industry Co., Ltd.
Triethylammonium hydrogen sulfate ([TEA]
[HSO4]) was synthesized as described by Brandt et
17)
al., where 5M H2SO4 aqueous solution were added
stepwise into triethylamine in round-bottom flask
under ice bath. The IL generated was dehydrated
under rotary evaporation followed by Schlenk line
at 70℃ for 24 h.
2.2 Ionic liquid and ultrasonic treatment
25 g oven dried KP was homogeneously mixed
with or without the presence of 2.5 g IL, then wa-
ter was added until to become pulp consistency of
10%. After that, the mixture was reacted in water
bath, with or without 250 W ultrasonic treatment
(KQ-250DV, Kun Shan Ultrasonic Instruments
Co., Ltd.) for 60 min.
2.3 Bleaching
(O)AD0EOPD1 bleaching sequence was used, where
treated KP was delignified with oxygen treatment
(O):0.5 MPa oxygen, 3% Na2O, and 100 for 60 min.
The treated pulp was rinsed with water and ad-
justed to 10% pulp consistency in polyethylene bag.
Followed by AD0EOPD1 bleaching, with the opti-
mized condition as following: (1) hot acid bleaching
(A): pH 3.5-4.5, 85℃, 120 min; (2) chlorine dioxide
bleaching (D0): ClO2 7 kg/t pulp, pH 2-3, 70℃,
30 min; (3) alkali extraction with oxygen and hy-
drogen peroxide (EOP): H2O2 12 kg/t pulp, MgSO4
6 kg/t, sodium hydroxide aqueous solution (5 wt%)
was used for adjustment pH to 11-12, 90℃,
60 min, oxygen pressure 400 kPa; (4) chlorine di-
oxide bleaching (D1): ClO2 8 kg/t pulp, pH 3.5-4.5,
18 펄프·종이기술 51(2) 2019
75℃, 120 min.
2.4 Characterization of pulps
Viscosity was determined according to the ISO
10650:1999 method, and degree of polymerization
(DP) of pulp was calculated based on the pulp vis-
cosity. The average degree of polymerization was
calculated from the intrinsic viscosity (η) using the
same manner in literature,26) which was shown in
Eq. 1.
DP0.905=0.75[η] [1]
Pulp yield were calculated as the mass ratio of
sample before and after bleaching. Kappa number
was determined according to the ISO 302:2004
method. The mass ratio of samples before and af-
ter treatment were calculated as pulp yield. The
water retention value (WRV) of fibers was deter-
mined according to the ISO 23714:2013 method.
Fiber quality including weight mean length, weight
mean width, and fines content was determined ac-
cording to the ISO 16065:2007 method using a fiber
quality analyzer (FQA-LDA02, OpTest Equipment
Inc., Canada).
2.5 Characterization of the handsheets
Handsheets were prepared according to Chen et
al.13) Treated pulp was dispersed with water and
formed 80 g/m2 handsheets, then kept at the stan-
dard conditions of 23℃ and 50% humidity prior to
testing. The tensile index, burst index, tear index,
folding endurance and brightness of handsheets
were measured according to the ISO methods
15754:2010, 2758:2014, 1974:2012, 5625:1997 and
2470:1999, respectively.
Changes in morphology of the fibers were ana-
lyzed by using a Regulus 8,220 FE-SEM (Hitachi
High-Technologies Corporation, Japan) operated
at 5 kV accelerating voltage, 2,000 times magnifi-
cation.
 Jianmin Peng·Letian Qi·Guihua Yang·Ming He·Yu Xue·Jiuachuan Chen

The Fourier transformed infrared (FT-IR) spectra
of the handsheets were recorded using a spectro-
photometer (IR Irdison-21, Shimadzu, Japan), with
-1 -1
resolution ratio of 4 cm , scanning speed 32 s
and scanning range of 4,000-500 cm-1.
The crystallinity of the pulp fiber was measured
by X-ray diffraction (XRD D8-DVANCE Bruker,
Germany). The measurements were conducted un-
der the conditions of X-Ray 40 kW and 35 mA with
the angle from 5 to 60°. The crystallinity was de-
27)
termined according to Segal et al.
3. Results and Discussion
3.1 Effect of IL and Ul treatment on the pulp
properties
The oxidation of bleaching process destroyed the
fiber structures and resulting in undesirable depo-
lymerization. The degree of polymerization (DP)
was determined basing on viscosity of pulp in this
work, where the viscosity and DP of unbleached
pulp was 619 mL/g and 884, respectively, and was
dropped to 481 mL/g and 669 after bleaching. As
can be seen in Table 1, both IL treatments slightly
increased the DP of pulp, illustrating a protection
of fibers during the process. In addition, both type
IL treatment reduced the kappa number, indicating
desirable lignin removal. Meanwhile, the yield of
pulp and water retention value (WRV) remain un-
changed.
Ultrasonic treatment also increased the pulp vis-
cosity and DP, however reduced the yield. This
could attribute to the mechanical breakage of Ul,
resulting in a loss of low-DP fibers during bleach-
ing process. This mechanical effect also contrib-
uted to fibrillation, which induced the improvement
in WRV and helped with lignin removal. While,
after Ul assisted IL treatment, the DP increased,
and yield of pulp remain unchanged. This phe-
nomenon, again, indicated the protection effect of
IL during the bleaching process. The Ul treatment
promoted the lignin removal effect of IL, as the
kappa number reduced notably. Interestingly, the
WRV of pulp reduced after Ul+IL treatment in
comparison with that in control and Ul test, refer-
ring to a lower degradation of fiber as shown in
viscosity data. This also pointed out an unexpected
inhibition in fiber swelling and modification on
microfiber structures. These results firstly identi-
fied a fiber protection effect of Ul assisted IL
treatment during the bleaching, indicting it might
be an ideal combination for bleaching process. It
seems that lower WRV value of the Ul+IL treated
pulp is due to the lower degradation of fiber i.e.
difference of viscosity of pulp.
3.2 Effect of IL and Ul treatment on fiber
structures
Although ILs were widely reported to dissolve
lignocellulose, both type ILs tested in this work
presented no visible effect on the fiber qualities in

Table 1. Effect of IL and Ul treatment on the pulp properties

Treatment Pulp viscosity Degree of Yield WRV
Kappa number
method (mL/g) polymerization (%) (g/g)
Control 481±1 669 96±0.30 2.25±0.08 1.99±0.06
[BMIM][HSO4] 507±2 709 96±0.25 0.92±0.08 2.00±0.04
[TEA][HSO4] 486±1 677 97±0.46 0.92±0.08 1.99±0.03
Ul 485±1 675 94±0.13 2.16±0.08 2.14±0.02
UI+[BMIM][HSO4] 514±4 720 97±0.24 0.76±0.08 1.96±0.02
UI+[TEA][HSO4] 493±3 688 96±0.22 0.76±0.08 1.87±0.01

J. of Korea TAPPI Vol.51 No.2 Mar.-Apr. 2019 19

Effect of Ultrasonic-Assisted Ionic Liquid Pretreatment on the Bleachability and Properties of Eucalyptus Kraft Pulp

Table 2. Effect of IL and Ul treatment on the fiber qualities

Weight mean length Weight mean width Fines content
Kink index Curl index
(mm) (μm) (%)
Control 0.586±0.002 14.0±0.1 20.25±0.10 55.4±0.35 15.7±0.15
[BMIM][HSO4] 0.583±0.001 14.0±0.2 20.46±0.17 55.6±0.20 14.8±0.10
[TEA][HSO4] 0.590±0.005 14.4±0.1 18.92±0.31 54.1±0.32 15.0±0.10
Ul 0.587±0.001 14.0±0.1 20.99±0.54 54.6±0.45 14.8±0.15
UI+[BMIM][HSO4] 0.596±0.004 13.9±0.2 16.79±0.95 55.3±0.50 15.5±0.25
UI+[TEA][HSO4] 0.596±0.002 14.6±0.2 15.04±0.76 53.2±0.46 16.0±0.35

Table 2, except [TEA][HSO4] slightly increased the
fiber width, and reduced the fines content and kink
index, which could contribute to the enhancement
28)
of paper strength.
Ul treatment also presented minor effect on the
fiber qualities, with slight increase in the fines
content value and reduction in curl index, which
indicated an improvement in fibrillation. According
to Table 2, for the Ul assisted IL treatments, no no-
table change was found in fiber length, width and
curl index, but the kink index of fibers decreased
by 4%, which can improve the strength properties
for paper.28) However, the combination of IL and Ul
treatment notably reduced the fines content of
pulp, especially in Ul assisted [TEA][HSO4] treat-
ment process, where fines content decreased by
28%. This phenomenon could possibly be caused by
the mechanical effect of ultrasonic treatment via
modifying the surface of fiber, which improved the
accessibility of IL. As a result, micro-fiber compo-
nents were modified, and fines content reduced.
3.3 Effect of IL and Ul treatment on the
physical properties of handsheets
It was reported that IL could break the hydrogen
bond between cellulose and lignin, resulting in an
improvement in brightness.16,17) Table 3 showed
that IL treatment slightly improved the brightness
of paper, but notably enhanced their physical
strengths. The tensile index, burst index, tear in-
dex and folding endurance of fibers were all im-
proved. The reason might be that aqueous IL solu-
tion partially dissolved and softened the surface of
plant fiber cell wall.21) The modification of fibers
via the swelling and fibrillation enhanced the in-
teractions and crosslinks between fibers, therefore
improved the physical strengths.29,30) The folding
endurance increased from 115 to 273 in [BMIM]
[HSO4] treatment, and to 333 in [TEA][HSO4]
treatment, which was about 3 times of the control
samples. Similarly, [TEA][HSO4] treated samples
presented a stronger tensile, burst and tear index.
It was reported that [TEA][HSO4] aqueous solution

Table 3. Effect of IL and Ul treatment on the properties of handsheets

Tensile index Burst index Tear index Folding endurance Brightness
(N·m·g-1) (kPa·m2·g-1) (mN·m2·g-1) (times) (%)
Control 4.35±0.01 4.055±0.022 6.746±0.22 115±7 75.2±0.2
[BMIM][HSO4] 4.60±0.03 4.433±0.021 7.274±0.05 273±13 75.8±0.1
[TEA][HSO4] 4.72±0.03 4.454±0.01 7.461±0.14 333±18 75.8±0.1
Ul 4.64±0.06 3.964±0.01 7.537±0.11 186±11 75.3±0.2
Ul+[BMIM][HSO4] 4.68±0.04 4.335±0.019 7.955±0.23 305±15 76.0±0.1
Ul+[TEA][HSO4] 5.09±0.07 4.196±0.013 8.058±0.04 369±14 76.0±0.1

20 펄프·종이기술 51(2) 2019

 Jianmin Peng·Letian Qi·Guihua Yang·Ming He·Yu Xue·Jiuachuan Chen
promoted lignin removal,17) which contributed to
the fibrillation and swelling. In addition, the
removal of lignin also improved the flexibility of
pulp fiber, which can contribute to the important
of paper strength.
Ul treatment also improved the tensile, tear and
folding strength properties of paper, but presented
lower reduction in burst strength. It provided the
similar effect in beating process, assisting the loose
of plant fiber.29) The modification on the surface of
fiber improved the accessibility, thereby enhanced
the physical strengths and brightness. Ul treat-
ment mechanically broke the fiber and reduced the
length of fiber, leading to a reduction in burst in-
dex. The combination of IL and Ul treatment nota-
bly improved the physical strength of paper. This
phenomenon was also reported by Chen et al.13)
where Ul improved the accessibility of IL. The
swelling of fiber improved, and crosslinks en-
hanced, both of which improved the strength of
paper via Ul and IL pretreatment.
3.4 Morphology of the handsheets
The morphology of fibers was shown in Fig. 1,
where IL treatment changed the morphology of the
fiber. Minor cracks were observed on the fiber wall
surface after the [BMIM][HSO4] treatment (Fig.
1-b), Meanwhile [TEA][HSO4] provided more better
separation influence, and a significant modification
on fiber could be viewed in Fig. 1-c. Formation of
adhesive microfibers on the pulp fiber surface were
observed. This refers to the fact that the fines
content value dropped after IL and Ul treatment,
while the yield of pulp and water retention value
remain unchanged. In addition, the viscosity of
pulp have slightly increased via Ul+IL treatment.
All these could possibly due to the formation of
microfibers, which has more surface area and in-
duces cross-links between fibers and resulting in
an enhancement of paper strength.
Fibers became more fibrillated with the assistance
a b
c d
e f
Fig. 1. SEM images of the treated and untreat-
ed pulp. Note: (a) control, (b) [BMIM]
[HSO 4 ], (c) [TEA][HSO 4 ]; (d) Ul,
(e) Ul+[BMIM][HSO4] and (f) Ul+[TEA]
[HSO4].
of Ul treatment. A sign of mechanical breakage
was observed in Fig. 1-d. Applying Ul combined
with IL treatment caused a notable modification on
fiber surface. And the fibrillation notably im-
proved, and more adhesive microfibers formed.
The morphology of handsheets backed up with
previous analysis, where ILs treatment changed
the fiber surface, provided more cross-links. Es-
pecially in Fig. 1-f, with Ul assisted [TEA][HSO4]
treatment, a lot of cross-links formed. In the Ul
assisted IL approach, Ul treatment provided me-
chanical breakages, improved the accessibility of
IL to fibers, thereby improved the IL treatment
performance. Thus, Ul assisted IL treatment nota-
bly improved physical properties of paper.
3.5 Fourier transform infrared (FT-IR)
analysis
Fourier transform infrared (FT-IR) spectroscopy
of the treated pulp were shown in Fig. 2, where the
J. of Korea TAPPI Vol.51 No.2 Mar.-Apr. 2019 21
Effect of Ultrasonic-Assisted Ionic Liquid Pretreatment on the Bleachability and Properties of Eucalyptus Kraft Pulp
treated pulp showed a similar spectrum, indicating
no significant change in functional group of the
pulp occurred during the treatment. The peak po-
sition and assignment bonds were listed as follows:
the broad absorption band at 3,400 cm-1 was asso-
ciated with H-bond OH groups on cellulose and
lignin;16) the peak detected at 2,940 cm-1 indicated
a symmetric C-H stretching vibration; the band at
-1
2,850 cm was attributed to the symmetric C-H
stretching vibration; the band at 1,670-1,720 cm-1
was attributed to the -COO stretching vibration;
the band at 1,506-1,596 cm-1 was attributed to the
vibration of aromatic ring; the peak around 1,160 cm-1
was attributed to the C-O-C bending vibrations in
cellulose, while the peak near 1,060 cm-1 was
C-O-C stretching vibration.
Compared to untreated pulp, the FT-IR spectra
of treated pulp in Fig. 2 observed no new peak,
which indicates no chemical change in the IL and
Ul treatment process. It should be mention that,
-1 16)
the intensity of H-bond peaks (3,400 cm )
strengthened after Ul and IL treatments. The hy-
-1 -1
drogen bonds (3,000 cm to 3,600 cm ) in polymer
was evaluated use the same manner as in litera-
31)
ture, and the area of hydrogen bonds after aque-
Fig. 2. FT-IR spectra analysis of the treated
and untreated sheet. Note: (a) control,
(b) Ul, (c) [BMIM][HSO 4 ], (d) Ul+
[BMIM][HSO4], (e) [TEA][HSO4] and (f)
Ul+[TEA][HSO4].
22 펄프·종이기술 51(2) 2019
ous Ul+IL treatment decreased to 17.62%
(Ul+[TEA][HSO4]) and 17.59% (Ul+[BMIM][HSO4]),
whereas the other functional groups in pulp were
nearly unchanged. Breaking down the hydrogen
bonds in lignin structure by Ul and IL treatments
reduced the intermolecular forces.16) This may con-
tribute to a better crosslink between fibers, im-
proving the physical properties of handsheets. This
is another evidence of this treatment has an effect
on lignocellulosic fibers, which supports the previ-
ous SEM results.
3.6 X-ray diffraction (XRD) analysis
As shown in Fig. 3, XRD results showed no new
diffraction peak in addition to the enhancement of
intensity. The crystallinity of cellulose I was calcu-
lated in this work. According to Table 4, the crys-
tallinity of control samples is 43.7%. Both [BMIM]
[HSO4] and [TEA][HSO4] treatment improved the
crystallinity of pulp. [TEA][HSO4] performed
slightly better, improved to 46.7%. Ul treatment
improved the crystallinity of fiber by 2.5-3.0%.
Among all the treatments, [TEA][HSO4]+Ul treat-
ment showed the highest crystallinity of 48.0%.
Higher crystallinity degree indicates the IL and Ul
Fig. 3. XRD analysis of the treated and un-
treated sheet. Note: (a) control (b) UI,
(c) [BMIM][HSO 4 ], (d) Ul+[BMIM]
[HSO 4 ], (e) [TEA][HSO4] and (f)
Ul+[TEA][HSO4].
 Jianmin Peng·Letian Qi·Guihua Yang·Ming He·Yu Xue·Jiuachuan Chen
Table 4. Effect of IL and Ul treatment on the
fiber crystallinity
Crystallinity (%)
Control 43.7
[BMIM][HSO4] 45.3
[TEA][HSO4] 46.7
Ul 46.3
Ul+[BMIM][HSO4] 47.7
Ul+[TEA][HSO4] 48.0
treatment promoted the dissolution of amorphous
region of fiber.21) [TEA][HSO4] could form strong
17)
hydroxyl bond with fiber, thereby disturbed the
H-bond network in amorphous region. In addition,
Ul mechanically loosened the fiber structure, im-
13)
proved the accessibility of ILs to the fibers.
Thereby, the combination of Ul and IL treating
technique contributed to the dissolving of amor-
phous region, increased the crystallinity, resulting
in the improvement in physical strength of paper.
4. Conclusions
Combination of IL and Ul treatment had obvious
influence on the bleachability of eucalyptus kraft
pulp. ILs treatment protected fibers from depo-
lymerization in the bleaching process by improving
the viscosity. The Ul assisted IL treatment notably
reduced the kappa number. Enhancement in phys-
ical strength of pulp was observed due to the sig-
nificant decrease of the fines content of the pulp
treated by combination of IL and Ul treatment.
Fines content of the pulp treated by Ul and
[TEA][HSO4] decreased by 28%, while the yield of
pulp remains unchanged. The modification of mi-
cro-fibers resulted in a formation of adhesive mi-
crofibers, improved fiber crosslinks. The XRD and
FT-IR analysis showed that the Ul assisted IL
treatment disturbed the amorphous region of pulp
fiber by increasing the crystallinity without any
effect properties and chemical structure of pulp fi-
bers. Thereby, the Ul assisted IL treatment tech-
nology has a promising application in pulping and
papermaking industry for its high efficiency and
environmental protection character.
Acknowledgement
The authors are grateful for the financial support
from the National Key Research and Development
Program of China (Grant no. 2017YFB0307900),
the financial support from the National Natural
Science Foundation of China (Grant no. 31770628),
the Taishan Scholars Program, Foundation (No.
ZR201711) of Key Laboratory of Pulp and Paper
Science and Technology of Ministry of Education/
Shandong Province of China，and a Project of
Shandong Province Higher Educational Science and
Technology Program (Grant no. J18KA111).
Literature Cited
1. Ouchi, A., Efficient total halogen-free photo-
chemical bleaching of kraft pulps using alka-
line hydrogen peroxide, Journal of Photo-
chemistry & Photobiology A Chemistry 200(2):
388-395 (2008).
2. Kaur, D., Bhardwaj, N. K., and Lohchab, R.
K., Environmental aspect of using chlorine di-
oxide to improve effluent and pulp quality
during wheat straw bleaching, Waste & Bio-
mass Valorization 10(5):1231-1239 (2019).
3. Yang, S., Lu, X., Zhang, Y., Xu, J., Xin, J.,
and Zhang, S., Separation and characteriza-
tion of cellulose I material from corn straw by
low-cost polyhydric protic ionic liquids, Cellu-
lose 25(6):3241-3254 (2018).
4. Abejón, R., Rabadán, J., Lanza, S., Abejón, A.,
Garea, A., and Irabien, A., Supported ionic
J. of Korea TAPPI Vol.51 No.2 Mar.-Apr. 2019 23
Effect of Ultrasonic-Assisted Ionic Liquid Pretreatment on the Bleachability and Properties of Eucalyptus Kraft Pulp
liquid membranes for separation of lignin
aqueous solutions, Processes 6(9):143 (2018).
5. Süss, H. U. and Schmidt, K., Peroxide appli-
cation in ECF sequences - A description of the
state-of-the-art, Appita Journal 53(2):116-
121 (2000).
6. Bajpai, P., Environmentally Benign Approaches
for Pulp Bleaching, Elsevier Science, Amster-
dam, Netherlands, pp. 377-395 (2005).
7. Heo, Y. D., Sung, Y. J., Joung, Y. J., Kim, D.
K., and Kim, T. Y., Changes in the properties
of cotton cellulose by hydrogen peroxide
bleaching, Journal of Korea TAPPI 45(3):59-
68 (2013).
8. Yu, X., Bao, X., Zhou, C., Zhang, L., Aea, Y.,
and Yang, H., Ultrasound-ionic liquid en-
hanced enzymatic and acid hydrolysis of bio-
mass cellulose, Ultrasonics Sonochemistry 41:
410-418 (2018).
9. Khan, A. S., Man, Z., Bustam, M. A., Nasrul-
lah, A., Ullah, Z., Sarwono, A. et al. Efficient
conversion of lignocellulosic biomass to
levulinic acid using acidic ionic liquids, Carbo-
hydr. Polym. 181:208-214 (2018).
10. Swatloski, R. P., Spear, S. K., and Holbrey, J.
D., and Rogers, R. D., Dissolution of cellulose
with ionic liquids, Journal of the American
Chemical Society 124(18):4974-4975 (2002).
11. Sun, L., Chen, J. Y., Jiang, W., and Lynch, V.,
Crystalline characteristics of cellulose fiber
and film regenerated from ionic liquid solu-
tion, Carbohydrate Polymers 118:150-155
(2015).
12. Zhang, Z., Chen, J., Pang, Z., Lucia, L. A.,
Li, F., and Yang, G., Ionic liquids as a new
platform for fiber brittleness removal, BioRe-
sources 10(4):6565-6575 (2015).
13. Chen, J., Jiang, Q., Yang, G., Wang, Q., and
Fatehi, P., Ultrasonic-assisted ionic liquid
treatment of chemithermomechanical pulp fi-
bers, Cellulose 24(3):1483-1491 (2017).
24 펄프·종이기술 51(2) 2019
14. Roselli, A., Hummel, M., Monshizadeh, A.,
Maloney, T., and Sixta, H., Ionic liquid ex-
traction method for upgrading eucalyptus
kraft pulp to high purity dissolving pulp, Cel-
lulose 21(5):3655-3666 (2014).
15. Christiane, L., Sari, A., Riku, T., Agnes, S.,
Herbert, S., and Ali, H., Simultaneous bench
scale production of dissolving grade pulp and
valuable hemicelluloses from softwood kraft
pulp by ionic liquid extraction, Carbohydrate
Polymers 136:402-408 (2016).
16. Pang, Z., Chen, J., Dong, C., and Yang, G.,
Highly selective and efficient extraction of lig-
nin in kraft pulp by aqueous ionic liquids for
enhanced bleaching properties, RSC Adv.
4(56):29897-29900 (2014).
17. Brandt, A., Gschwend, F., Fennell, P., Lam-
mens, T., Tan, B., and Weale, J., An econom-
ically viable ionic liquid for the pretreatment
of lignocellulosic biomass, Green Chemistry
19(13):3078-3102 (2017).
18. Chen, L., Sharifzadeh, M., Dowell, N. M.,
Welton, T., Shah, N., and Hallett, J. P., Inex-
pensive ionic liquids: [HSO4]--based solvent
production at bulk scale, Green Chemistry
16(6):3098-3106 (2014).
19. Sun, R. C., Sun, X. F., and Ma, X. H., Effect
of ultrasound on the structural and phys-
iochemical properties of organosolv soluble
hemicelluloses from wheat straw, Ultrasonics
Sonochemistry 9(2):95-101 (2002).
20. Ebringerová, A. and Hromádková, Z., Effect of
ultrasound on the extractibility of corn bran
hemicelluloses, Ultrasonics Sonochemistry
9(4):225-229 (2002).
21. Li, J., Zhang, X., Zhang, M., Xiu, H., and He,
H. Ultrasonic enhance acid hydrolysis selec-
tivity of cellulose with HCl-FeCl3 as catalyst,
Carbohydrates Polymer 117:917-922 (2015).
22. Tatsumi, D., Higashihara, T., Kawamura, S.,
and Matsumoto, T., Ultrasonic treatment to
 Jianmin Peng·Letian Qi·Guihua Yang·Ming He·Yu Xue·Jiuachuan Chen
improve the quality of recycled pulp fiber,
Journal of Wood Science 46(5):405-409
(2000).
23. Sun, Q. Y., Yang, G. H., Jiang, Q. M., Chen,
J. C., Wang, Q., and Kong, F. G., Influence of
treatment of xylanase combined with ultra-
sonic wave-assisted on the properties of CTMP
of fast-growing poplar. Paper & Paper Mak-
ing, 35(12):5-9 (2016).
24. Xu, Y. J., Yan, Y., Yue, X. P., Zhu, Z. F.,
Zhang, D. J., and Hou, G. Q., Effect of ultra-
sonic wave pretreatment on the fibrillation of
cellulose fiber, TAPPI J. 13(4):37-43 (2014).
25. Sun, Q., Yang, G., and Chen, J., Effect of
ultrasonic-assisted cold caustic extraction on
the properties of ctmp poplar fibers, Journal of
Korea TAPPI 49(4):5-15 (2017).
26. Mazumder, B. B., Ohtani, Y., Zhou, C., and
Sameshima, K., Combination treatment of ke-
naf bast fiber for high viscosity pulp, Journal
of Wood Science 46(5):364-370 (2000).
27. Segal, L., Creely, J. J., Martin, A. E. Jr., and
Conrad, C. M., An empirical method for esti-
mating the degree of crystallinity of native
cellulose using the x-ray diffractometer, Tex-
tile Research Journal 29(10):786-794 (1959).
28. Kim, A. R., Choi, K. H., and Cho, B. U., Ef-
fects of kneading treatment on the properties
of various pulp fibers, Journal of Korea TAPPI
47(3):47-54 (2015).
29. He, M., Lee, Y. K., and Won, J. M., Modifica-
tion of KOCC with ultrasonic wave treatment.
Journal of Korea TAPPI, 45(3): 44-48 (2013).
30. Nazhad, M. M., Karnchanapoo, W., and Palo-
kangas. A., Some effects of fibre properties on
formation and strength of paper, Appita Jour-
nal 56(1):61-65 (2003).
31. Rogovina, S. Z., Akopova, T. A., Vikhoreva, G.
A., and Gorbacheva, I. N., Solid state produc-
tion of cellulose-chitosan blends and their
modification with the diglycidyl ether of oli-
go(ethylene oxide), Polymer Degradation &
Stability 73(3):557-560 (2001).
J. of Korea TAPPI Vol.51 No.2 Mar.-Apr. 2019 25