Article

pubs.acs.org/IECR

Intensified and Short Catalytic Bleaching of Eucalyptus Kraft Pulp

Ghazaleh Afsahi,*,† Naveen Kumar Chenna,† and Tapani Vuorinen†
†
Department of Forest Products Technology, Aalto University School of Chemical Technology, P.O. Box 16300, 00076 Espoo,
Finland

ABSTRACT: Bleaching processes remove residual lignin and hexenuronic acid from cellulosic pulps. The reactions taking place
in several stages are slow and consume large amounts of chemicals. The present study demonstrates a novel three-stage pulp
bleaching sequence that combines a tertiary amine-catalyzed hypochlorite oxidation with subsequent treatments with ozone and
hydrogen peroxide. With this sequence, the residual lignin and hexenuronic acid contents of an oxygen-delignified eucalyptus
pulp were decreased by ≫90%, and a full brightness (88% ISO) was achieved. The total reaction time was only ∼1 h, which is
one-fifth of the retention time of the current industrial pulp bleaching sequences. The chemical need was low, and the viscosity of
the pulp remained high. This study may open new doors to future pulp bleaching with fewer and smaller bleaching towers and
diminished use of chemicals.

■ INTRODUCTION
Bleaching is one of the key processes in the pulp industry and
has been the focus of many studies since the 18th century.1−4
Increasing the brightness and its stability through removal of
hexenuronic acid (HexA) and lignin are the main goals of pulp
bleaching. The bleaching process is influenced by the applied
chemicals, the overall reaction time, and the bleaching
sequence. The application of multistage bleaching sequences
has been proven to be the most effective method in industry.3
From the beginning, a combination of bleaching and extraction
treatments has been used for bleaching chemical pulps. The
bleaching chemicals and the order in which they are used make
up the “bleaching sequence”. Bleaching processes generally
contain two phases within each sequence: (1) a delignification
segment, whose main function is to remove most of the residual
lignin; and (2) a brightening segment, whose principal function
is to increase the brightness of the pulp.3 To improve the
overall brightness of the pulp, it is important to apply chemicals
in each stage while taking into account the time period of each
reaction. In addition, the use of chemicals that minimize the
environmental impact is highly appreciated.
Therefore, as an important milestone, the elemental chlorine
free bleaching (ECF), based on use of chlorine dioxide (D),
was introduced to replace the elemental chlorine bleaching,
which was producing high amounts of organochlorine
compounds.2 ECF bleaching is today the dominant process
in the industry, and more than 70% of all bleached chemical
pulp is produced with this technology.3 However, several
factors, such as huge investments in bleaching towers and long
retention times form the downside of ECF bleaching
processes.3,4 Totally chlorine-free (TCF) bleaching processes
that were claimed to be less toxic5 were introduced later.4,5 In a
typical TCF bleaching process, the dominant reagents are
oxygen-based chemicals, such as ozone (Z), oxygen (O), and
hydrogen peroxide (P).6−9 Typical ECF and TCF bleaching
processes need approximately 4−8 h2 to reach an ∼90% pulp
brightness.
Chemical pulp bleaching is based on oxidation chemistry,
and the process is considered selective when the oxidants react
with the removable components, especially HexA and lignin,
without attacking cellulose. The use of oxidants in hardwood
kraft pulp bleaching can be minimized by applying an acid
pretreatment stage (A) that selectively hydrolyzes HexA at pH
3−4.10 This treatment, however, requires a long retention time
(at least 2 h) at a high temperature (85−100 °C). In modern
eucalyptus pulp mills, the bleaching sequences include a hot
acid stage, for example, A/D−EOP−D−P or D/A−EOP−D−P.10
Ozone is one of the most efficient oxidants to attack lignin
and HexA;11 however, the use of ozone may also lead to
oxidization of carbohydrates, forming carbonyl and carboxylic
acid structures within the polysaccharide chain.11,12 These
groups may initiate further degradation, chain cleavage, and loss
in pulp viscosity. Therefore, utilization of ozone in the
beginning of pulp bleaching where the degradation of cellulose
is suppressed over the reactions of lignin that is still present in
high contents has been suggested. Despite its limitations, ozone
has a certain position in industrial pulp bleaching.13 Ozone has
been a key oxidant in development of TCF bleaching
sequences, such as A−Ze−P, EOP−Z−P, etc. Ozone has also
been used in light ECF bleaching sequences, where it partly
replaces chlorine dioxide, for example, ZD−EOP−D, Ze−D−P,
D−Ze−DP, etc.14
Because of its high reactivity, ozone bleaching does not
require a high temperature and partial pressure.15 The reaction
time is very short, and therefore, large bleaching towers are not
needed for ozone.11 It is stable at low temperature but
decomposes slowly at higher temperatures.12 In contrast to
other bleaching chemicals, including chlorine dioxide, ozone
does not form chromophores, such as quinones as reaction
products.15 Ozone reacts with HexA and lignin through the
kinds of reactions that are illustrated in Scheme 1.15
Ozone reacts through its strong electrophilic character with
carbon−carbon double bonds in the lignin remaining after
Received: May 8, 2015
Revised: August 14, 2015
Accepted: August 14, 2015
Published: August 14, 2015

© 2015 American Chemical Society 8417 DOI: 10.1021/acs.iecr.5b01725

Ind. Eng. Chem. Res. 2015, 54, 8417−8421
Industrial & Engineering Chemistry Research
Scheme 1. Oxidation of Lignin with Ozone
pulping and other delignification processes.16 During ozone
treatment, new functional groups are formed in lignin; as a
consequence, its macromolecular structure gets altered. Most of
the phenolic groups in lignin are oxidized, and the hydro-
philicity of the polymer increases, making it soluble in water
under neutral condition.16 Ozone seems to be more efficient
than some other oxidants, such as chlorine dioxide, and
hydrogen peroxide to eliminate condensed phenolic structures
in residual kraft lignin.16
Recently, it was postulated that the depolymerization of
cellulose in an ozone treatment of pulp is due to secondary
reaction of the reactive oxygen species formed in the oxidation
of HexA and lignin.17 Thus, the viscosity of the pulp stayed at a
higher level when most of HexA was removed with an acid
treatment (A) prior to the ozone stage.
Hydrogen peroxide (H2O2) in alkali is an effective oxidant
that removes the partially oxidized components formed in the
preceding bleaching stages. H2O2 also reacts with chromo-
phoric compounds such as quinones and oxidizes them to gain
the brightness of the pulp.18 The formation of the perhydroxyl
anion, a highly nucleophilic intermediate, is responsible for the
oxidation of chromophores through the cleavage of the side
chains.19
Several parameters, such as chemical usage, bleaching yield,
water consumption, effluent load, treatability, brightness
stability, refinability, and strength of the pulp, together
determine the choice of the bleaching technology. Although
the chemical costs form one of the most important criteria,
lower investment costs may favor sequences with fewer
bleaching stages. In general, the order of using the various
chemicals is detrimental for the overall efficiency and costs. For
instance, the use of the strongest chemicals in the initial
bleaching may reduce the residual lignin and HexA contents to
such a low level that only one additional stage is needed to
reach full brightness.20 Although it is possible to bleach pulp in
either one or two stages, this does not deliver full bright-
ness.21,22
Recently, we reported on initial bleaching of a eucalyptus
kraft pulp with hypochlorite and a tertiary amine as a catalyst.23
Most of the HexA and a significant part of the residual lignin
were removed very rapidly with a small amount of the oxidant
under mild conditions. The present work deals with subsequent
bleaching of the catalytically oxidized pulp with ozone and
hydrogen peroxide. The performance of the short bleaching
sequence is discussed, and the influence of bleaching
parameters in each stage is evaluated.
■ EXPERIMENTAL SECTION
Materials. Oxygen-delignified eucalyptus pulp was obtained
from a Brazilian kraft pulp mill. The kappa number of the pulp
was 11.4; HexA content, 66 mmol/kg; and viscosity, 1130 mL/
g. An aqueous solution of NaOCl (3.5%) was purchased from
VWR. The concentration of NaOCl expressed as active
8418
Article
chlorine was measured before every experiment by iodometric
titration as described in the standard method SCAN-C 29:72.
1,4-diazabicyclo[2.2. 2]octane (DABCO, 98%) was purchased
from Sigma-Aldrich. KI solution, 0.2 M Na2S2O3 (99.9%,
VWR), and 2 M HCl (Merck) were used for quantification of
ozone by iodometric titration. The concentration of aqueous
solution of H2O2 (5%) was measured before every experiment
by iodometric titration as described in the standard method
SCAN-C 29:72.
Methods. The catalytic oxidations of the pulp were
performed at 3% consistency in a stirred Büchiglasuster batch
reactor (2 L) made of borosilicate glass.23 DABCO (0.1% on
pulp) was added to the pulp suspension (1 L) which was then
neutralized (pH 7) with 1 M H2SO4. The reactor vessel was
thermostated at 25 °C and NaOCl (1% on pulp) was added.
The concentration of residual active chlorine was monitored
during the treatment by taking 5 mL aliquots from the solution
and titrating them according to SCAN-C 29:72. The bleaching
experiment was interrupted after a reaction time of 10 min by
filtration and washing with cold, deionized water in a Büchner
funnel. A 10 mL aliquot of the undiluted filtrate was analyzed
for the residual active chlorine, and the measurement was
repeated twice to reduce the experimental error.
The catalytically oxidized pulp was then treated with ozone
under conditions resembling those in conventional high-
consistency ozone bleaching. To acidify the pulp suspension,
its consistency was decreased to 3%, then the acidity of the
suspension was adjusted to pH 3 with a few drops of 1 M
H2SO4. After that, the consistency was increased to ∼30%
through centrifugation, and the ozonation was performed in a
specially designed rotating vessel. The setup included an ozone
generator, a flow meter, and a round-bottomed rotating glass
reactor (1 L).24 Ozone was produced from oxygen gas by an
electric discharge method using a WEDECO GSO30 system.
Next, the acidified pulp after the first stage (20 g dry matter
content) was added to the reactor, and the gas from the ozone
generator was flowed (2.5 L/min) through the reactor for 1−3
min to get a target dosage of 0.3−0.5% ozone. The ozone
content of the gas inflow and outflow was measured by
iodometric titration. The ozone consumption was calculated as
the difference of the inflow and outflow.
The ozone (Z) step was performed at 0.3%, 0.4%, and 0.5%
ozone dosages (o.d.p). After the ozone treatment, the pulp was
washed first with hot water and then with cold deionized water
to stop the reaction. The pulp was then centrifuged and stored
in cold (5 °C) for the next step.
The final brightening was conducted with hydrogen peroxide
at 10% consistency in plastic bags placed in a water bath. First,
the pulp suspension was mixed with MgSO4·7H2O (0.2%) and
H2O2 (0.3−0.6%), after which 1 M NaOH was added to adjust
the pH to 11.2. The plastic bags were kept in a water bath at 85
°C for 1 h. During the bleaching, the pulp in the plastic bag was
kneaded every 15 min. In the end, the pulp fibers were
separated using a Büchner funnel and washed with cold
deionized water to stop the chemical reactions. Finally, the pulp
was centrifuged to ∼30% consistency, homogenized, and stored
in cold. Additional bleaching experiments were carried out by
varying the temperature (60−85 °C) and time (30−60 min).
Pulp sheets of each stage were prepared according to TAPPI
standard method T205, and kappa number (2 parallel
measurements) and viscosity (3 parallel measurements) of
the pulps were determined according to standard methods
SCAN-C 1:00 and SCAN-CM 15:99, respectively. The content
DOI: 10.1021/acs.iecr.5b01725
Ind. Eng. Chem. Res. 2015, 54, 8417−8421
Industrial & Engineering Chemistry Research Article

Table 1. Changes in Kappa Number, HexA, and Lignin Contents, Brightness and Viscosity of Oxygen Delignified Kraft Pulp
during Hcat−Z−P Bleaching Sequence
O3 (%)a H2O2 (%) pH T (°C) t (min) κ HexA (mmol/kg) lignin (%)b brightness (%) viscosity (mL/g)
ref 11.4 66 100 57 1129
Hcat 7 25 10 5.9 30 ± 0.1 64 69 1103 ± 10
Hcat−Z 0.3 (0.28) 2.5 25 1 3.3 ≤3 ± 0.12c 12 81
Hcat−Z 0.4 (0.32) 2.5 25 2 2.8 ≤3 ± 0.12c 10 82
Hcat−Z 0.5 (0.46) 2.5 25 3 2.5 ≤3 ± 0.12c 10 84
Hcat−Z−P 0.3 0.6 11.2 60 30 1.2 2.6 ± 0.1 9 85 1060 ± 15
Hcat−Z−P 0.3 0.6 11.2 60 60 1.1 2.5 ± 0.2 9 86 1015 ± 10
Hcat−Z−P 0.3 0.6 11.2 85 30 1 2.3 ± 0.1 9 87 1060 ± 12
Hcat−Z−P 0.5 0.3 11.2 85 60 1.3 1,1 ± 0.2 7 86 1090 ± 10
Hcat−Z−P 0.5 0.6 11.2 85 60 0.9 0,8 ± 0.1 6 88 1080 ± 15
a
Measured consumption in parentheses. bRelative content. cThe exact value could not be measured because of overlapping signals.

of HexA and aromatic lignin were quantified by UV resonance

Raman (UVRR) spectroscopy6 (two parallel measurements)
using a Renishaw 1000 UV Raman spectrometer (Gloucester-
shire, U.K.), which was connected to a Leica DMLM
microscope (Wetzlar, Germany) and an Innova 90C FreD
frequency-doubled Ar+ ion laser (Coherent Inc., Santa Clara,
California, U.S.A.). The excitation wavelength of the laser was
244 nm; power output, 10 mW; and measuring transmittance,
25%. The beam was directed through a 40× objective, and the
sample was rotated to prevent burning. The spectral resolution
was ∼7 cm−1, which is the separation ability for two bands close
to one another. A diamond crystal was measured every day
prior to sample measurements to ensure the repeatability and
comparability of the sample band locations. The Raman spectra
were linearly baseline-corrected to zero at two wave numbers
(800 and 2000 cm−1) in Grams AI spectroscopy software. The
spectra were normalized to cellulose peak at 1094 cm−1. Figure 1. UVRR spectra of oxygen-delignified eucalyptus kraft pulp
ISO brightness was measured using a Loretzen & Wettre SE (a) treated first with DABCO and HOCl (Hcat) (b) and then with
070R Elrepho spectrophotometer.25 different amounts of ozone (0.3 (c), 0.4 (d), and 0.5% (e) on pulp).

■ RESULTS AND DISCUSSION

The effects of several reaction parameters, including chemical
charges, pH, temperature, and time, on DABCO-catalyzed
bleaching of an oxygen delignified eucalyptus kraft pulp were
reported earlier.23 In this study, we repeated the catalytic stage
(Hcat) in the conditions that led to a maximal decrease in kappa
number and the most extensive removal of HexA and lignin
from the oxygen delignified pulp.23 The catalytic treatment
decreased the kappa number by half and led to a significant
decrease in the content of HexA and lignin in the pulp (Table 1
and Figure 1). Chenna et al.23 reported on similar changes in
the pulp under similar conditions.
The catalytic treatment also increased the brightness of the
pulp while the viscosity remained almost unaffected (Table 1),
which verified the earlier observed high selectivity of the
catalysis. Although the conditions of the initial bleaching
probably affect the bleachability in the later stages, this aspect
was not investigated in the preliminary work of Chenna et al.23
The lower the content of the residual lignin, the harder it is
to remove with oxidants.27 Therefore, we elected to apply
ozone, known for its high reactivity, in the second bleaching
stage.
One of the key parameters of ozone bleaching is the acidity
of the medium. Because the delignification in this stage has
been reported to be most efficient at pH 2−3,16 we elected to
carry out the ozonation at pH 3. Ozonation at both medium
and high consistency has been used in the laboratory and in
8419
pulp industry. For practical reasons, we elected to use high-
consistency ozonation in the laboratory experiments. It has also
been claimed that the high consistency and the acidic
conditions lead to minimal degradation of carbohydrates and
decomposition of ozone.16
The second bleaching stage lowered the kappa number by
half when the ozone charge was 0.4%. The final kappa number
depended slightly on the amount of ozone used (Table 1).
UVRR spectra of the pulps (Figure 1) confirmed that most of
the residual HexA (1655 cm−1) and lignin (∼1600 cm−1) were
oxidized in the ozone treatment almost independent of the
ozone dosage. An increase in the Raman scattering intensity at
∼1700 cm−1 was an indication of formed oxidized lignin
structures.
The ISO brightness was increased to 81−84%, depending on
the charge of ozone (Table 1). It is known that secondary
reactions of the reactive oxygen species formed during
ozonation may introduce carbonyl groups into cellulose.16
Because their presence interferes with the CED viscosity
measurement, we did not determine the viscosity for the ozone-
bleached pulps. To reach full brightness, we bleached the pulps
further with alkaline peroxide. Hydrogen peroxide acts as a true
bleaching agent that destroys many of the chromophores
present in pulp.27 The alkaline peroxide also oxidizes the
possible carbonyl groups in the pulp, thus stabilizing its
viscosity.24−26
DOI: 10.1021/acs.iecr.5b01725
Ind. Eng. Chem. Res. 2015, 54, 8417−8421
Industrial & Engineering Chemistry Research
Because we could not predict the behavior of the Hcat−Z
bleached pulp in the alkaline peroxide treatment beforehand,
we varied the charges of alkali and peroxide and reaction
temperature and time in the trials (Table 1).
The peroxide bleaching stage increased the brightness by 2−
6% units and led to 85−88% final brightness, depending on the
conditions in the ozone and peroxide bleaching stages. The
peroxide treatment decreased the kappa number by 1−2 units,
resulting in a final kappa number of ∼1 (Table 1). The UVRR
spectra of the peroxide-bleached pulps were indicative of
extremely low residual lignin and HexA contents (Figure 2).
Figure 2. UVRR spectra of oxygen-delignified eucalyptus kraft pulp
(a) treated first with DABCO and HOCl (Hcat) (b); then with ozone
(0.5%) (c); and finally, with 0.3% (d) and 0.6% (e) peroxide for 60
min at 85 °C.
The viscosity of the pulp remained almost unchanged
throughout the bleaching (Table 1). This finding was
somewhat unexpected because both the ozone and peroxide
stages are known for their ability to oxidize cellulose to some
extent.24 Recently, it was claimed that the viscosity drop in the
ozone stage is caused by the reactive oxygen species formed in
oxidation of HexA and lignin-derived muconic acids.17 Thus,
the stability of cellulose toward ozone after the catalytic
bleaching could be explained by the low HexA and residual
lignin contents.
Although the reaction temperature and time affected the
brightness gain in the peroxide stage (Table 1), the residual
lignin and HexA contents were hardly affected by these
parameters (Table 1 and Figure 3).
■
CONCLUSIONS
The experimental results presented here show that eucalyptus
kraft pulps can be bleached extremely efficiently by combining a
tertiary amine-catalyzed hypochlorite prebleaching with ozone
bleaching. Both stages are highly reactive, and therefore, only
very short reaction times are needed, even at low temperatures.
Although the brightness is already high after the ozone stage,
full brightness is easy to achieve with an additional treatment
with alkaline peroxide. After this short Hcat−Z−P sequence, the
residual lignin and HexA contents are on the same or lower
level as the best ECF bleached pulps. In addition, the pulp
viscosity remains at a high level that is not typical for pulps that
have been bleached with ozone and peroxide.
The novel bleaching sequence presented here has a high
potential to be developed toward an industrial bleaching
8420
Article
Figure 3. UVRR spectra of oxygen-delignified eucalyptus kraft pulp
(a) treated first with DABCO and HOCl (Hcat); then with ozone
(0.3%) (c); and finally, with 0.6% peroxide for 30 min at 60 °C (d);
for 60 min at 60 °C (e); and for 30 min at 85 °C (f).
technology for eucalyptus and other hardwood pulps. The main
benefits could be substantially lowered investment costs
because of the fewer stages and smaller reactor sizes and
lower operation costs because of the diminished need for
heating and chemicals. In the future, the applicability of similar
short sequences for bleaching of the less reactive softwood kraft
pulps should also be studied.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: ghazaleh.afsahi@aalto.fi.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This study was funded by a consortium of Andritz, Kemira,
Metsä Fiber, Stora Enso, and UPM. Christian Järnefelt, Mirja
Reinikainen and Rita Hatakka are acknowledged for their help
with the experiments.
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8421 DOI: 10.1021/acs.iecr.5b01725

Ind. Eng. Chem. Res. 2015, 54, 8417−8421