PEER-REVIEWED ECF BLEACHING

Bleaching of eucalyptus kraft pulps

with chlorine dioxide: Factors affecting
the efficiency of the final D stage
OLENA SEVASTYANOVA, ANNBRITT FORSSTRÖM, EVA WACKERBERG,
AND MIKAEL E. LINDSTRÖM

ABSTRACT: We investigated the bleaching efficiency of the final chlorine dioxide (D2) stage in the D0(EP)D1D2
bleaching sequence, focusing on the effect of pH in relation to the bleaching history of pulp samples. The samples
used were unbleached kraft Eucalyptus grandis pulps with kappa no. 14.8 and the same pulp oxygen-delignified to
kappa nos. 12 and 9.8. The samples were bleached according to the D0(EP)D1 sequence to a brightness of about 86%
ISO and then submitted to the final D2 stage under identical conditions (e.g., chlorine dioxide charge, time, tempera-
ture, and final pH). The target final brightness was 90.5% ISO. Changes in the kappa number, brightness, viscosity,
and contents of hexenuronic acid, 4-O-methylglucuronic acid, and the total amount of carboxylic acid (COOH) groups
in pulps were monitored during the bleaching sequence. The final brightness of eucalyptus kraft pulps increased
when the terminal pH of the D2 stage was raised from 3.0 to 6.5. The 90.5% ISO target brightness in the D2 stage was
achieved for all pulps within a pH range of 4.5–6.5, but this required adjusting final pH for individual samples. The
optimal pH value with respect to pulp viscosity was between 3 and 5. Despite dissimilar conditions applied in previ-
ous bleaching stages, the samples after the D1 stage revealed similar residual lignin contents as shown by kappa
number analysis. The content of hexenuronic acid in the samples, however, varied broadly, from 2 to 26 mmol/kg.
Conductometric titration showed different amounts of carboxylic acid groups in pulps after the D1 stage, of which
hexenuronic acid accounted for only a minor part. The variations in the fiber charge resulted from the different
bleaching conditions applied before the D2 stage. The fiber charge affected the alkali demand in the final D2 stage,
whereas variations in the alkali demand affected the initial pH and associated process kinetics. Lower total fiber
charge was found to be beneficial for improved final brightening and viscosity when bleached at higher final pH.
Application: This study will help pulp mill engineers to better understand how a pulp’s oxidative history may
affect the process kinetics in the final D bleaching stage. Fiber charge is important when selecting optimal pH for the
final brightening of eucalyptus kraft pulps.

ucalyptus kraft pulps are the most important source
E of bleached pulp in the world and market demand is
growing constantly [1]. Bleached eucalyptus kraft pulps
are largely used to manufacture tissue and printing and
writing (P&W) paper grades. The fundamental feature of
modern eucalyptus brown stock pulp is the high content
of hexenuronic acids (HexA), which is mostly responsible
for the kappa number in eucalyptus kraft pulps entering
the bleaching plant [2]. HexA also reacts with chlorine
dioxide (ClO2) and/or its intermediates, thereby influenc-
ing the bleachability [3, 4] and the formation of organic
chlorine compounds (AOX) [5]. The presence of HexA in
fully bleached pulps has a negative effect on the brightness
stability [6].
The standard brightness for market pulp nowadays is 90.5%
ISO. Four-stage elemental chlorine-free (ECF) bleaching se-
quences of the D0 (EOP)DD and D0 (EOP)DP types usually
guarantee a brightness above 90% ISO for eucalyptus kraft
pulps [1]. ECF bleaching, which is based on chlorine dioxide,
allows production of kraft pulps that meet the highest require-
ments for strength, brightness, brightness stability, and clean-
liness with a moderate demand for chemicals. In addition to
producing fewer chlorinated phenols and AOX compared to
chlorine bleaching, ClO2 is an efficient delignification agent
with high selectivity toward lignin, thus resulting in a high
carbohydrate yield in pulp [7]. However, ever-increasing de-
mand for paper with very high brightness and high brightness
stability requires further development of bleaching technolo-
gies. Other factors that necessitate continuing improvements
are bleaching chemical demand, bleaching yield, pulp quality
for a specific end-use, water consumption, and effluent load
including AOX level.
The efficiency and kinetics of chlorine dioxide delignifica-
tion have been studied extensively, and the optimum condi-
tions have been identified [8–10]. Generally, ClO2 reacts with
phenolic lignin end groups either by oxidative ring opening,
which affords muconic acid structures, or by demethylation,
which affords quinine structure [10–17]. The result is a mod-
ified lignin with partly oxidized aromatic rings. Subsequently,
the modified lignin is solubilized and removed in the extrac-
tion stage. The difficulties with the complete removal of re-
sidual lignin from the pulp could be related to lignin-carbohy-
MARCH 2012 | VOL. 11 NO. 3 | TAPPI JOURNAL 43
ECF BLEACHING
drate complexes (LCC). Despite substantial
amounts of carboxylic groups forming in lignin
by oxidative treatments, the chemical bonds
between lignin and carbohydrates likely pre-
vent dissolution of the residual lignin from the
pulp during bleaching [18, 19].
The last and most difficult-to-achieve bright-
ness points are gained in the final stage of a
bleaching sequence by removing the remaining
lignin and destroying any chromophores per-
sisting in the pulp after previous treatment. The
exact chemical structures of the remaining
chromophores in bleached pulps are not
known, as their low concentration complicates isolation or in
situ analysis. The question of whether they are of lignin or
carbohydrate origin is still a matter of debate. In some studies,
high amounts of hydroxyl-quinone structures have been de-
tected in both chlorine dioxide- and hydrogen peroxide–
bleached pulps [17, 20–22]. Such compounds are resistant to
the typical bleaching agents and are believed to be responsible
for the current brightness ceiling. The subsequent brightness
development and bleachability of a pulp could be greatly in-
fluenced by its previous pulping and bleaching history [10].
The outcome of chlorine dioxide bleaching is highly de-
pendent on pH, as it will affect the proportions of reactive
species present in the bleaching liquor and the set of reaction
pathways. The objective of the final D2 stage is to brighten the
pulp, which requires a different chemistry than the earlier
chlorine dioxide bleaching stages. As a result, the typical op-
timal conditions (e.g., pH, reaction time, and temperature) for
the D2 stage are different from the D0 stage [10, 23].
Our goal was to obtain a better understanding of the im-
portant factors that determine the bleaching efficiency of the
final chlorine dioxide stage when bleaching modern eucalyp-
tus kraft pulps to high brightness. We investigated the effi-
ciency of the final D stage in the D0 (EP)D1D2 sequence as a
function of final pH; it is discussed in relation to the bleaching
history of the pulp.
EXPERIMENTAL
Materials
An unbleached industrial hardwood kraft pulp (Eucalyptus
grandis, South America) with kappa no. 14.8 and brightness
of 40.2% ISO and an industrial oxygen-delignified pulp
(E. grandis, South America) with kappa no. 12 and brightness
of 55.8% ISO were used in this study. The pulps were stored
cold (4ºC) before use. Chlorine dioxide and hydrogen perox-
ide (H2O2) were provided by Eka Chemicals AB (Bohus, Swe-
den). All other chemicals used in this study were of analytical
grade.
Methods
Part of the industrial unbleached pulp was subjected to
oxygen delignification in the laboratory. The reaction was
performed in stainless steel autoclaves, internally coated with
44 TAPPI JOURNAL | VOL. 11 NO. 3 | MARCH 2012
1. Sample generation scheme.
Teflon, and heated in a polyethylene glycol bath under rotation
using the following conditions: 90 min reaction time, 12%
pulp consistency, 0.7 MPa oxygen pressure at a reaction
temperature of 95ºC. The sodium hydroxide (NaOH) charge
was 15 kg/o.d. ton of pulp. A solution of magnesium sulfate
(MgSO 4) was added to each sample in the amount
corresponding to 0.5% MgSO4/o.d. ton pulp to protect
carbohydrates in the pulp sample from degradation. This
resulted in laboratory oxygen-delignified pulp with kappa no.
9.8 (Lab O2, Fig. 1) and brightness of 60.3% ISO.
Unbleached and oxygen-delignified pulps were further
subjected to a D0 (EP)D1 bleaching sequence. The bleaching
stages were performed in polyethylene bags placed in a water
bath preheated to the required temperatures. The sample gen-
eration scheme is shown in Fig. 1.
Bleaching trials with smaller samples were carried out to
find the optimal bleaching parameters so that brightness of
86% ISO was achieved after the D1 stage (Table I). The same
bleaching protocols were followed for the production of larg-
er samples to provide sufficient material for the study of the
role of final pH on brightness development.
The samples bleached according to the D0 (EP)D1 bleach-
ing sequence in the laboratory, together with a sample col-
lected at the mill after the first D1 stage in a DHT(EOP)D1D2
bleaching sequence, were subjected to the final D2 bleaching
using identical conditions: 80ºC, 180 min., 7 kg/o.d. ton of ac-
tive chlorine (aCl). The final pH varied between 3 and 10. The
target brightness after the D2 stage was 90.5% ISO.
The following standard methods were used: ISO 5351:2004
(“Pulps—determination of limiting viscosity number in cupri-
ethylenediamine [CED] solution”) for viscosity; ISO 302
(“Pulps—Determination of kappa number”) for kappa num-
ber; and ISO 2470:1999 (“Paper, board and pulps—Measure-
ment of diffuse blue reflectance factor [ISO brightness]) for
brightness measurements. The HexA content in pulp samples
was determined using the method of Gellerstedt and Li [24].
The contribution to the kappa number from hexenuronic acid
groups in pulp xylan was calculated using the method of Li
and Gellerstedt [25]. The conductometric titration method of
Katz et al. [26] was used to determine the amount of carbox-
yl groups in the D1 pulps. The lignin kappa number was cal-
 ECF BLEACHING

Bleaching stage D0 (EP) D1

Pulp samples* 15L 12L 10L-1 10L-2 15L 12L 10L-1 10L-2 15L 12L 10L-1 10L-2

Kappa factor 0.2 0.1 0.1 0.1 - - - - - - - -

ClO2, kg/o.d. ton aCl 29.6 12 10 10 - - - - 20 12 12 12

H2SO4, kg/o.d. ton - 1.6 - 4 - - - - - - - -

NaOH, kg/o.d. ton 6 - - - 8 8 6 6 3.5 0.25 - -

H2O2, kg/o.d. ton - - - - 2.5 2.5 1.5 1.5 - - - -

Pulp consistency, % 10 10 10 10 10 10 10 10 10 10 10 10

Time, min 50 45 50 50 60 60 60 60 120 120 120 120

Temperature, ºC 60 60 60 60 120 120 120 120 80 80 80 80

Terminal pH 3.1 3.2 6.3 3.5 11.1 11.0 11.5 11.4 3.3 3.4 3.8 3.4

*Sample designations are shown in Fig. 1.

I. Optimized bleaching conditions for the D0(EP)D1 laboratory bleaching sequence to obtain 86% ISO brightness.

culated as the difference between the standard kappa number
and the kappa number from HexA. The uronic acid units in
pulp samples were quantified by methanolysis according to
the modified procedure of Li et al. [27].
RESULTS AND DISCUSSIONS
D0(EP)D1 and DHT(EOP)D1 bleaching
Brightness, viscosity, and kappa number composition
Figure 2 shows the composition of the measured kappa
number—lignin and HexA—of the original E. grandis pulp
samples used in the study. Hexenuronic acid accounts for up
to 50%–60% of kappa number and must be considered during
the bleaching with ClO2 as it consumes the bleaching chemi-
cal [28]. At the same time, the presence of HexA is undesirable
in the fully bleached pulps due to its negative effect on bright-
2. Kappa number composition of the original pulp samples:
Eucalyptus grandis unbleached (15L/Un, brightness 40.2% ISO),
oxygen delignified at the mill (12M/O-del., 55.8% ISO) and
oxygen delignified in the laboratory (10L/O-del., 60.3 % ISO).
ness stability [6].
For the pulp samples bleached in the laboratory, the tradi-
tional D0 stage with varying ClO2 charge was applied (see
Table I for conditions), whereas the industrial pulp was delig-
nified using the DHT stage performed at high temperature
(90ºC) and for a longer time.
The kappa factor for the D0 stage was 0.1 for the oxygen-
prebleached samples. The 15L pulp, which was directly sub-
jected to ECF bleaching, required a higher ClO2 charge and a
kappa factor of 0.2 was applied. The change in contents of
lignin and HexA for each stage was used to monitor the prog-
ress in bleaching in parallel to the brightness development
(Table II).
The degree of lignin removal after the extraction stages
([EP] or [EOP]) was calculated as a change in the lignin kappa
number. For the 15L pulp, with a higher kappa factor (0.2) in
the D0 stage, the degree of lignin removal was 72%. The de-
crease in lignin content was similar for 10L-2 and 12L samples
and was 68% and 69%, respectively. For the pulp 15L, the ex-
cess of ClO2 charged in D0 was consumed in reactions with
HexA (the content of which decreased by 69%). The HexA
content decreased by only 22% and 24% in the oxygen pre-
bleached samples 10L-2 and 12L, respectively. For the pulp
10L-1, 18% of HexA was still removed despite the high final
pH (6.3) in the D0 stage. This confirms the conclusion that
HexA can be oxidized in the D0 stage even at pH values above
4 [29]. On the other hand, for this pulp (10L-1) only 32% lignin
was removed as a result of higher-than-optimal pH.
The first DHT chlorine dioxide stage in the industrial ECF
bleaching sequence (12M) showed superior efficiency in re-
moving both lignin and HexA. As much as 83% of the lignin
and 84% of the HexA had already been removed after the
DHT(EOP) stage, bringing the kappa number down to 2.0.
All oxygen-delignified samples required a similar charge
MARCH 2012 | VOL. 11 NO. 3 | TAPPI JOURNAL 45
ECF BLEACHING

HexA
Residual Lignin
Bleaching Kappa Brightness Viscosity
Sample Kappa (corrected kappa
Stage Number (% ISO) (dm3/kg)
µmol/g Number number)
Units*
Un 14.8 85.3 7.4 7.4 40.2 1315
D0 6.5 26.15 2.3 4.2 58.4 1242
15L (EP) 4.4 27.2 2.3 2.1 73.6 1132
D1 1.1 2.35 0.2 0.9 86.0 1087
D2 0.6 - - 0.6 90.5 1077
O 9.8 69.65 6.0 3.8 60.3 1130
D0 7.7 56.94 4.9 2.8 76.1 1077
10L-1 (EP) 7.5 57.64 4.9 2.6 81.8 1104
D1 3.2 25.67 2.2 1.0 86.3 996
D2 1.8 12.9 1.1 0.7 89.8 976
O 9.8 69.65 6.0 3.8 60.3 1130
D0 7.0 54.59 4.7 2.3 74.9 1085
10L-2 (EP) 5.9 55.04 4.7 1.2 81.4 1013
D1 2.7 19.59 1.7 1.0 86.4 965
D2 1.4 8.5 0.7 0.7 90.3 949
O 12 72.2 6.2 5.8 55.8 1195
D0 7.9 54.6 4.7 3.2 66.8 n/a
12L (EP) 6.5 54.6 4.7 1.8 80.2 994
D1 2.9 22.9 2.0 0.9 86.5 968
D2 1.1 6.5 0.6 0.5 90.0 937
O 12.0 72.2 6.2 5.8 55.8 1195
DHT 2.0 11.5 1.0 1.0 74.2 n/a
12M (EOP) 2.0 11.0 1.0 1.0 79.3 946
D1 1.8 12.0 1.0 0.8 86.4 914
D2 0.7 3.68 0.3 0.4 90.8 904
*10 µmol of HexA corresponds to 0.86 kappa units [24].

II. Results of laboratory bleaching according to the D0(EP)D1D2 bleaching sequence. The final pH in D2 stage was around 4.5 for all
samples. The 12M sample was bleached according to DHT(EOP)D1 at the mill before D2 stage.

of chlorine dioxide (12 kg aCl/o.d. ton) in the D1 stage to reach
a target brightness of 86% ISO (Tables I and II). For sample
15L, bleached directly after the kraft cook, the charge of
20 kg aCl/o.d. ton was applied in D1 stage.
The focus of D1 stage is usually on brightness increase and
shive reduction, but some delignification takes place as well.
If present, HexA reacts with ClO2 throughout the entire
bleaching sequence. In general, an ISO-unit brightness
increase of 4%–7% was achieved in the D1 stage in this study,
but this brightness gain did not directly correlate with the
degree of delignification. The delignification rate was 17%,
50%, and 62% for pulp samples 10L-2, 12L, and 10L-1,
respectively, despite the identical ClO2 charge of 12 kg aCl/o.d.
ton in the D1 stage. For the 15L sample, only 57% of the lignin
present in the pulp was removed despite a much greater ClO2
charge (20 kg aCl/o.d. ton). The varied reactivity of residual
lignin was a consequence of previous oxidative treatments.
46 TAPPI JOURNAL | VOL. 11 NO. 3 | MARCH 2012
The reaction of HexA with ClO2 in the D1 stage, on the other
hand, depended directly on the chemical charge.
Approximately 91% HexA was removed from pulp for the 15L
sample bleached with 20 kg of ClO2. Pulp samples bleached
with 12 kg aCl/o.d. ton (10L-1, 10L-2, and 12L) showed the
same amount of HexA removal, roughly three kappa units
(32–35 µmoll/g pulp), which corresponded to a content
decrease of 55%–60%. For the industrial 12M sample having
quite low lignin and HexA content already after the extraction
stage, the main outcome of the D1 stage was the brightness
increase of 7.1% ISO units despite the moderate delignification
degree of 20%.
The viscosity of the pulp samples was affected negatively
by the oxygen delignification treatment. The severity of the
viscosity loss depended on the degree of delignification
(Table II). Chlorine dioxide is known to be a very selective
bleaching agent; the 15L samples bleached with ClO2 directly

3. Kappa number composition of pulp samples after D1 stage.
The brightness values for the samples 15L, 12L, 10L-1, 10L-2, and
12M were 86.0, 86.5, 86.3, 86.4, and 86.4% ISO, respectively.
after the kraft cook had higher viscosity throughout the entire
bleaching sequence (Table II).
The target brightness of 86% ISO after the D1 bleaching
stage resulted in similar lignin content for all five samples, as
measured by the kappa number method corrected to exclude
HexA contribution and in a range of 0.9–1.0 kappa number
units. HexA content varied significantly, ranging between 0.2
and 2.2 kappa number units (corresponding to 2.4–25.7
mmol/kg). As a result, the standard kappa nos. were between
1.1 and 3.2 (Fig. 3).
Effect of bleaching on the fiber charge
Accurate prediction of the pH in a D stage is important in pulp
bleaching because concentrations and reactivity of the various
species formed from ClO2 are functions of pH. Traditionally,
alkali is added to pulp to maintain a recommended final pH.
This relationship is not that straightforward and requires pre-
liminary optimization because the type of pulp, chlorine di-
oxide charge, and other parameters play a role [23].
Different buffering properties of D1-bleached samples be-
came obvious when the amount of added NaOH or sulfuric
acid (H2SO4) was optimized to achieve a certain final pH in
the D2 stage. Figure 4 shows an obviously lower alkali de-
mand for the industrial sample in comparison with the labo-
ratory-bleached samples.
Such behavior is related to different amounts of charged
groups present in the samples. Previous research [19,30] has
shown that unbleached kraft pulp fibers contain two types of
acidic groups with the dissociation constants pK1 ≈ 3.4 and
pK2 ≈ 5.5. The lower pKa was assigned to ironic acids in xylan
[31], whereas the weaker acid groups were associated with
the carboxylic groups in the residual lignin formed during
alkaline pulping [32]. Both oxygen delignification and bleach-
ing were shown to have a significant effect on the hydroxyl
and carboxyl groups content of residual lignin, with the num-
ber of phenolic hydroxyl groups steadily decreasing and the
number of carboxyl groups increasing during the course of
ECF BLEACHING
4. Terminal pH in D2 stage as a function of added NaOH or H2SO4
(amount of ClO2 used was 7 kg aCl/o.d. ton).
treatment [33]. In addition, oxidative treatments may lead to
the formation of carboxylic groups in carbohydrates at vary-
ing positions [34]. Therefore, the fact that the total fiber
charge decreases as bleaching proceeds indicates that any
carboxylic groups formed are effectively removed from the
pulp [35].
The xylan, containing acetyl and uronic acid groups, 4-O-
methylglucoronic and hexenuronic acids, are usually consid-
ered to be major sources of carboxylic groups in unbleached
hardwood kraft pulps and especially eucalyptus pulps [36].
As can be seen in Fig. 3, the lignin content measured in kappa
number units was practically the same for all D1 bleached
pulps, whereas the hexenuronic acid content varied signifi-
cantly. For bleached pulps, however, the difference in hexenu-
ronic acid content did not correlate to the alkali demand. The
pulp 15L bleached according to the D0 (EP)D1D2 sequence
directly after cooking had the lowest amount of HexA groups
after the D1 stage but consumed similar amounts of NaOH as
the oxygen prebleached pulps (10L-1, 10L-2 and 12L), with up
to 10 times higher HexA content.
The fiber charge originating from lignin can be obtained by
subtracting the contributions to total fiber charge from methyl-
glucuronic and hexenuronic acid groups (Figs. 5 and 6). Cal-
culated in this way, the charge contribution of lignin in
bleached pulps in most cases appears to be higher than the
contribution from acid groups in xylan. This contradicts the
general understanding that hexenuronic acid is the main
source of the negative charge in bleached eucalyptus pulps.
However, at least some of the COOH attributed to the lignin
fraction might also originate from oxidized polysaccharides.
Indeed, Buchart et al. [37], in their study on the carboxylic
acid profiles during conventional and SuperBatch cooking,
attributed approximately 12 µmol/g carboxylic groups to the
metasaccharinic acid formed during the cooking process. As
all bleached samples in our work originated from the same
brownstock pulp, it is logical to assume that the portion of
charge coming from the oxidized polysaccharides would be
similar for all of them. Additional oxidation of polysaccharides
MARCH 2012 | VOL. 11 NO. 3 | TAPPI JOURNAL 47
ECF BLEACHING
5. The total amount of carboxylic acid groups,
4-O-methylglucuronic and hexenuronic acid groups in pulp
samples after D1 stage.
6. Fiber charge corresponding to xylan fraction (HexA+MeGlcA)
and to lignin fraction for pulp samples after D1 stage (*includes
a contribution from oxidized polysaccharides).
during the bleaching with chlorine dioxide was expected to
be moderate because chlorine dioxide reacts very slowly with
polysaccharides [34]. This suggested conclusively that the
major variation in the fiber charge for D2 samples seems to
relate mostly to the content of acidic groups in residual lignin.
Although an oxygen prebleaching stage is known to oxi-
dize lignin [16], the pulp not oxygen delignified (15L) had the
highest lignin contribution to fiber charge. The higher ClO2
charge in the D0 stage could be one explanation. Lachenal and
Chirat [38] showed that the reaction of ClO2 did not lead to
the same degree of lignin dissolution beyond a certain level
of ClO2 consumption. It was suggested that excess ClO2 reacts
with the already-oxidized lignin. The oxidation equivalent of
modified lignin is lower than for the phenolic units, leading
to the underestimation of the lignin content in the bleached
pulps measured by the kappa number method [10, 17, 38, 39].
A tentative conclusion we reached is that, despite the
similar kappa number and brightness after the D1 stage, the
pulp samples had different amounts of residual lignin with
48 TAPPI JOURNAL | VOL. 11 NO. 3 | MARCH 2012
7. Final brightness of pulp samples after D2 stage.
varying degrees of oxidation due to the differences in
bleaching history.
Final bleaching with ClO2 (D2 stage)
Efficiency of D2 stage as a function of bleaching history
Despite the different bleaching histories, all samples entering
the final D2 stage had similar brightness levels of about 86%
ISO. Our aim was to investigate the brightening response of
these five pulp samples in the final D2 stage when bleached
under identical conditions: chlorine dioxide charge of 7 kg
aCl/o.d. ton, temperature 80ºC, reaction time 120 min, and
final pH optimized at 4.5. The target final brightness was
90.5% ISO.
Of note, due to varying fiber charge of the samples, in prac-
tice different amounts of alkali had to be added to the bleach-
ing liquor to achieve the final pH 4.5 (from 1.5 kg/o.d. ton for
the DHT(EOP)D1 sample to 3–3.5 kg/o.d. ton NaOH for labora-
tory-bleached samples). It is logical to assume that these vari-
ations in the alkali demand affected the initial pH and associ-
ated process kinetics.
As a result of bleaching under the above-mentioned condi-
tions, two pulp samples reached the target brightness—15L
(90.5% ISO) and 12M (90.8% ISO). The other three samples
had final brightness close to 90% ISO (Fig. 7). The actual
brightness increase was very similar for 15L and 12M pulp
samples: 4.5% and 4.4% ISO units, respectively. The maximum
difference in the bleaching efficiency was 1% ISO unit (Table
II and Fig. 7).
Figure 8 shows that the content of both lignin and HexA
decreased after the final bleaching stage. That means ClO2 and
other reactive species formed in the bleaching liquor were
consumed in the reactions with lignin, HexA, and chromo-
phores present in pulp. The maximum lignin removal, as mea-
sured by corrected kappa number, was in the range of only
30%–50%. A higher degree of delignification (45%–50%) was
observed for samples that were oxygen prebleached to a high-
er kappa no. 12. At the same time, HexA content decreased
by 50%–60% despite the fact that the pH of bleaching liquor

8. Kappa number composition of fully bleached pulp samples.
was quite high compared to the conditions for the first DHT or
ordinary D0 stages. For sample 15L, with only a trace amount
of HexA after D1 stage, HexA removal was complete but it did
not have a pronounced positive effect on the delignification,
which was still only 35%.
The role of pH has been studied extensively for decades,
since the introduction of ClO2 into industrial bleaching in the
1950s. Despite some controversy regarding most of the sug-
gested mechanisms for chlorine dioxide bleaching, the main
reactive species present in the liquor during the bleaching
process have been identified [8,10] (Eqs. [1–3]):
ClO2 + lignin → HClO2 + oxidized lignin (1)
HClO2 + lignin → HClO + oxidized lignin (2)
HClO + lignin → HCl + oxidized lignin
(and organochlorine) (3)
Inorganic species formed during the reaction of ClO2 with
pulp can also react with each other, regenerating the ClO2 or
forming the species that are unreactive with lignin and re-
sponsible for the loss of oxidizing power of ClO2 (Eqs. [4,5]):
HClO + 2HClO2 → 2ClO2 + H2O + Cl- + H+ (4)
2HClO2 + HClO2 → ClO3 + H+ (5)
The pH governs the proportion of each reactive component
present in the solution. Of all active species (ClO2, HClO2,
HClO/Cl2) present during the bleaching, only hypochlorous
acid (HClO) reacts with HexA. The consumption of this con-
stituent in reaction with HexA above a certain level would
affect the regeneration of ClO2 and the composition of the
bleaching liquor. For samples in the present study, the pres-
ence of HexA in amounts greater than 12 mmol/kg (1 kappa
number unit) seemed to affect the brightness development in
the D2 stage negatively.
Recent studies have paid attention to the effect of the initial
ECF BLEACHING
pH immediately before ClO2 addition on the efficiency of the
final chlorine dioxide brightening stage [40]. The addition of
a high charge of NaOH at the beginning of the chlorine diox-
ide reaction was shown to cause some decomposition of ClO2
through the following reaction, Eq. (6):
2ClO2 + 2OH - → ClO2- + ClO3- + H2O (6)
The reaction becomes faster and the equilibrium shifts to the
right as the pH increases because of increased concentration
of hydroxyl ions. Therefore, in our study, the bleaching condi-
tions were not identical despite the similar final pH of 4.5 in
the D2 stage as the different amounts of NaOH were added
before ClO2. The bleaching liquor for the industrial sample
12M had a starting pH of 11.2 (1.5 kg/o.d. ton NaOH). Other
samples required 3–3.5 kg/o.d. ton of NaOH to achieve the
terminal pH 4.5 and the initial pH of bleaching solutions was
around 11.8–11.9. The lower initial pH of the bleaching solu-
tion for 12M probably contributed to the better brightening
efficiency in D2 stage.
Efficiency of D2 stage as a function of final pH
The chemistry of chlorine dioxide bleaching is quite compli-
cated because many species, including chlorine, hypochlo-
rous, chlorous, and chloric acids form as intermediates and
the exact composition of the bleaching liquor is a function of
pH. It has been assumed that maximum brightness is obtained
in the pH range where minimum loss of active bleaching
chemicals occurs [10]. The adjustment of pH limits the side
reactions leading to the formation of inactive compounds.
Traditionally, the optimum end pH for the brightening stage
with ClO2 was suggested to range from 3.5–4 because those
terminal pH values reduce the amount of time undesirable
pH-dependent reaction pathways are dominant during the
final stages of bleaching.
In modern industrial practice, the typical terminal pH for
the final brightening stage of eucalyptus kraft pulp is 4.5–5.
Milanez and Colodette have shown that the final D stage can
be more efficient when operated at a pH as high as 5.5 [41].
Jiang and Berry recently suggested that near-neutral pH final
chlorine dioxide brightening with final pH close to 6 was op-
timum for some bleaching sequences [42]. They explained
the controversy in the various pH recommendations based on
the degradation of ClO2 at high starting concentration of hy-
droxyl ions (Eq. [6]) and identified a leveled-out concentration
of OH- ions throughout the brightening stage as an important
parameter for improved bleaching efficiency. At near-neutral
final pH, the best result was achieved by applying an appro-
priate buffer to the system. At the same time, it was shown
that with very low ClO2 charge in the final stage where the
alkali demand is lower, bleaching pulp under unbuffered con-
ditions could produce as good a result. Those observations
better explain the role of the type of pulp (fiber charge) and
chlorine dioxide charge in the relationship between the
added alkali and the optimal final pH in ClO2 bleaching.
MARCH 2012 | VOL. 11 NO. 3 | TAPPI JOURNAL 49
ECF BLEACHING
In the present study, the final pH in the D2 stage was varied
between 3 and 10 to investigate the role of pH in brightness
development and viscosity for fully bleached pulps
(Figs. 9 and 10). Figure 9 shows that in general for each
pulp, brightness increased as the final pH was increased from
3 to 6.5. The target brightness of 90.5% ISO after the D2 stage
could be achieved for each sample, but it required slightly
differing final pH values ranging from 4.5–6.5. However, if the
final pH was fixed, for instance at 4.5, the brightening effect
in the final D2 bleaching was not the same (Fig. 7). Final pH
between 3 and 5 was optimal with respect to viscosity for all
samples.
The main purpose of the final D2 stage is removal of chro-
mophores. In general, nucleophilic reagents are more effi-
cient in such reactions as they primarily attack positions in 9. Brightness as a function of final pH.
lignin carrying a positive charge, especially carbonyl carbon
atoms and β-(and δ) carbons at double bonds conjugated with rite has significantly better selectivity [23, 42]. The hypochlo-
carbonyl or carboxyl groups [34]. It has been suggested that rite formation seems to be responsible for the viscosity drop
ClO2- and ClO- are the main brightening reagents generated at higher final pH when a high alkali charge is required. Hart
in situ from chlorine dioxide at higher pH and, of these, chlo- and Connell, in their work on pH optimization in chlorine

NaOH Residual aCl

Pulp sample Final pH Brightness (% ISO)
(kg/o.d. ton) (kg/o.d. ton)

15L/D2-1 1 3.28 0 89.6

15L/D2-2 2 3.98 0.3 90.4
15L/D2-3 3 4.45 1.2 90.5
15L/D2-4 3.5 4.87 1.5 90.6
15L/D2-5 4 7.52 2.93 89.8
10L-1/D2-1 1 3.32 0 88.9
10L-1/D2-2 2 3.86 0.43 89.0
10L-1/D2-3 3 4.59 n/a 89.8
10L-1/D2-4 3.5 4.64 n/a 90.2
10L-1/D2-5 5 9.03 4.3 90.2
10L-2/D2-1 1 3.02 0 89.4
10L-2/D2-2 2 3.55 0 89.5
10L-2/D2-3 3 4 0 89.9
10L-2/D2-4 3.5 4.56 0.83 90.3
10L-2/D2-5 5 7.12 3.13 90.7
12L/D2-1 1.2 3.01 0 89.1
12L/D2-2 3.5 4.34 0.27 90.0
12L/D2-3 4.5 4.86 1.41 90.4
12L/D2-4 4.8 6.4 1.64 90.4
12L/D2-5 5 6.5 2.44 90.5
12M/D2-1 1.5 (H2SO4) 2.81 0 89.7
12M/D2-2 0 3.42 0.17 89.9
12M/D2-3 1 4.17 0 90.4
12M/D2-4 1.5 4.6 0 90.8
12M/D2-5 1.8 4.77 0.14 91.2
12M/D2-6 2.5 5.57 1.7 91.1
12M/D2-7 3 7.23 2.64 90.4
12M/D2-8 3.5 8.3 3.9 90.4
12M/D2-9 4 9.69 3.8 90.5

III. Conditions for the final D2 bleaching stage.

50 TAPPI JOURNAL | VOL. 11 NO. 3 | MARCH 2012

10. Viscosity as a function of final pH.
11. Hexenuronic acid content in pulp as a function of final pH in
D2 stage.
dioxide bleaching, observed that maximum brightness tends
to occur at the pH that provides a measured ClO2 residual of
about 0.1–0.2 g/L (1–2 kg/o.d. ton) [23]. This residual at high-
er pH corresponds mainly to measured chlorite, indicating
the importance of this specie in the brightening reactions.
Our results showed that the presence of residual correlates
well with increased brightness but the optimum concentra-
tion range differs for various pulps (Table III).
The industrial sample 12M seemed to have better bleach-
ability and achieved the maximum brightness, above 91% ISO.
From pulps used in this work, 12M pulp had lower incoming
viscosity, but the viscosity drop during the final D2 stage was
less significant at higher pH in comparison with other sam-
ples. This could be the result of lower initial pH due to less
alkali added for achieving a certain final pH level (Table III).
Indirect support for the changed composition of the
bleaching liquor can be seen in Figs. 11 and 12. The HexA
groups that usually degraded during the chlorine dioxide
treatment were present in significantly higher amounts in
pulps bleached at higher pH values. At pH above 5.5, the
hypochlorous acid was in equilibrium with the hypochlorite
ECF BLEACHING
12. Residual lignin content as a function of final pH in D2 stage.
ion whereas chlorine that actually reacted with HexA present
below that pH. The behavior of residual lignin differed for
pulps bleached in the laboratory and in the mill. For
laboratory-bleached samples, brightening seemed to take
place rather than delignification. For the 12M sample using
less amount of alkali, both reactions took place, which
explained the higher efficiency of the final D2 stage, especially
at increased final pH.
CONCLUSIONS
• In chlorine dioxide bleaching, the brightness of eucalyptus
kraft pulps increased when pH was raised from 3 to 6.5. The
target brightness of 90.5% ISO in the D2 stage was achieved
for all pulps within a pH range of 4.5–6.5, but this required
adjusting the final pH for individual samples.
• Differences in bleaching conditions affected the number of
charged groups in fibers and specifically the contents of
HexA and carboxyl groups attached to lignin.
• The fiber charge affected the alkali demand in the final D2
stage, whereas variations in the alkali demand affected the
initial pH and associated process kinetics.
• Lower total fiber charge was beneficial for brightening
efficiency and viscosity at higher final pH. TJ
ACKNOWLEDGEMENTS
The authors acknowledge Eka Chemicals AB, Bohus, Sweden
for the initiation and financial support of the study and Profes-
sor Ants Teder, Dr. Elisabet Brännvall, and Dr. Boris Zhmud
for their interest in the work and for fruitful discussions.
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ABOUT THE AUTHORS
The demand for eucalyptus kraft
pulp with very high brightness and
high brightness stability is increas-
ing while the cost efficiency, quality
of the product, and environmental
considerations are still major deci-
sion factors when choosing the best
bleaching technology. It is well
known that the outcome of bleach-
ing with chlorine dioxide is highly Sevastyanova
dependent on pH. The terminal pH
is used for the bleaching optimiza-
tion, and a certain amount of alkali is usually added to
pulp to maintain an optimal terminal pH. It has been
previously reported that the optimum final pH ap-
pears to be dependent on pulp composition and ClO2
dosage. In practice, though, a number of dedicated
tests would need to be carried out at a pulp mill for
each type of pulp to correlate the alkali charge with
the final pH and brightness for achieving optimum
bleaching efficiency. Such optimization would need to
be done at a variety of ClO2 dosages.
We wanted to understand the link between the
fiber charge, alkali demand, final pH, and the bright-
ness efficiency. The alkali demand for kraft pulps is
affected by fiber charge and variations in fiber charge
result from the different cooking and bleaching condi-
tions applied before the final bleaching. To minimize
the number of variables, we worked with the same
brown stock eucalyptus pulp, bleached according to
different conditions before the D2 stage.
We did not expect to see a quite big difference in
the alkali demand for our samples after D1 stage, in
the range 1.5–3.0 NaOH kg/o.d. ton. Also, this did not
correlate with a number of hexenuronic acid groups in
52 TAPPI JOURNAL | VOL. 11 NO. 3 | MARCH 2012
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Lindström Forsström Wackerberg
eucalyptus pulps. The oxidation of residual lignin and
possible oxidation of cellulose during the previous
bleaching made a significant contribution to the total
fiber charge. Such variations in the alkali demand
affected the initial pH (11.2 versus 11.9) and associated
process kinetics.
We found that the pulp with the lowest fiber charge
after D1 stage – and, as result, the lowest alkali
demand – demonstrated the best bleaching efficiency
and less viscosity drop at a higher final pH in D2 stage.
Therefore, fiber charge can be an important
parameter when optimizing the alkali charge and
choosing the optimal terminal pH for efficient chlorine
dioxide bleaching.
Sevastyanova is a research scientist in the Division of
Wood Chemistry and Pulp Technology and Lindström is
a professor of pulp technology and dean of the School
of Chemical Science and Engineering at KTH–The Royal
Institute of Technology, Stockholm, Sweden. Forsström
is senior research engineer, bleaching and fiber, and
Wackerberg is section manager, bleaching and fiber,
product RD&I, at EKA Chemicals AB, Bohus, Sweden.
Email Sevastyanova at olena@kth.se.
 ECF BLEACHING
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1442(2007). Press, Atlanta, 2005, p.17.
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Atlanta, 2000, p. 159.

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