Kraft pulping with sulfide pretreatment
Part 2. The influence of pretreatment and cooking conditions on the pulp properties,
bleachability in a TCF-sequence and strength properties
Leelo Olm, Disa Tormund, STFI, Stockholm, Sweden
Keywords: Modified kraft pulping, Pretreatment, Delignifica-
tion, Bleachability, Strength properties
SUMMARY: This paper describes the influence of the conditions
in the pretreatment (hydroxide ion concentration and temperatu-
re) and in the cooking stage (hydroxide ion concentration and
hydrosulfide ion concentration) and possible interaction effects
on the delignification and carbohydrate degradation in softwood
kraft pulping with sulfide pretreatment. In addition the bleachabi-
lity in an OZQP*-sequence and the strength properties of the
unbleached pulp with different hydroxide ion concentrations in
the pretreatment and cooking stages have been evaluated. The
cooking experiments were conducted at liquor-to-wood ratio 4:1.
The delignification during kraft pulping with sulfide pretreat-
ment within the investigated experimental domain is affected
mainly by the hydroxide ion concentrations in the pretreatment
and in the cooking stage and by an interaction effect between
these factors. The cooking time required to reach a certain kappa
number can be considerably reduced by increasing the hydroxide
ion concentration in the pretreatment with a low hydroxide ion
concentration in the cooking stage. The hydrosulfide ion concen-
tration in the cooking stage had a minor effect on the delignifica-
tion within the investigated experimental domain. The results
indicate that in industrial displacement kraft pulping it would be
advantageous to increase the hydroxide ion concentration in the
hot black liquor displacement and to decrease the hydroxide ion
concentration in the white liquor in order to produce a pulp with
high yield, good bleachability and high unbleached pulp strength.
The results of the experiments reported in this paper indicate
the importance of terminating the cook in the bulk delignification
phase. A long cooking time at a relatively low hydroxide ion con-
centration (residual alkali 0.15 mol/L), as when the cook is termi-
nated in the residual phase, leads not only to poorer brightness of
unbleached pulp and bleachability but also to a loss of strength
properties. The fact that the displacement kraft cooks are finished
in the bulk delignification phase may be the major advantage and
may explain the high strength potential and good bleachability of
the pulps obtained in industrial displacement kraft pulping.
ADDRESS OF THE AUTHORS: STFI, Box 5604, SE-114 86
Stockholm, Sweden
In modified kraft pulping, the concentration profiles of
the active pulping chemicals and the temperature are chan-
ged in order to improve the pulping selectivity, viscosity at
a given kappa number, and to allow extended delignifica-
tion without any loss in pulp quality (Hartler 1978,
Nordén, Teder 1979; Johansson et al. 1984). The changes
in concentration profiles have been proposed from the dif-
ferential equations describing the rate of delignification
(LeMón, Teder 1973, Olm, Tistad 1979; Axegård, Wikén
1983) in different delignification phases and carbohydrate
degradation by alkaline hydrolysis during a kraft cook
(Kubes et al. 1983). The rate equations of delignification
are based upon kinetic studies with a constant cooking
liquor composition with a high liquor-to-wood ratio. A
variation in the hydroxide ion and hydrosulfide ion con-
centrations also influences the ionic strength of the coo-
king liquor. The ionic strength is usually defined as a sum
of [Na+] and [K+] in the cooking liquor. A high ionic
strength has a substantial negative effect on the delignifi-
70
cation rate in the bulk phase of the kraft pulping (LeMòn,
Teder 1973; Holm, Warnquist 1994; Lindgren, Lindström
1996). A high ionic strength in the cooking liquor increa-
ses the rate of alkaline hydrolysis of carbohydrates and
thus reduces the pulp viscosity (Lindgren 1997;
Andersson, Olm 1998). In the above mentioned kinetics
equations, however, no consideration has been given to
changes in the ionic strength of the cooking liquor.
The selectivity of kraft pulping is also influenced by the
presence of dissolved wood substances in the cooking
liquor (Sjöblom et al. 1983, 1988; Sjöblom 1996; Anders-
son, Olm 1998). Sjöblom (1988) found that reducing the
concentration of dissolved lignin and the ionic strength in
the cooking liquor during the final part of kraft pulping
improved the pulping selectivity, defined as viscosity at a
given kappa number. The improved selectivity was attribu-
ted to the higher delignification rate with a lower amount
of dissolved wood substances in the cooking liquor
(Sjöblom 1996). Recently it has been reported that the
organic substances (analysed as UV-lignin) in black liquor
mainly have a negative influence on the brightness of
unbleached pulp (Andersson, Olm 1998). A slower delig-
nification when black liquor was added to the cooking
liquor was found to be an effect of higher ionic strength.
Earlier kinetic studies (Edwards et al. 1974) have indi-
cated a two-factor interaction effect between hydroxide ion
and hydrosulfide ion concentrations on the delignification
rate in the bulk delignification phase of the kraft pulping.
Recently interaction effects between hydroxide ion, hydro-
sulfide ion and sodium ion concentration on the amount of
residual lignin have been reported (Gustavsson et al.
1997). It was found that the influence of hydrosulfide ion
concentration on the amount of residual lignin was more
pronounced at low than at high hydroxide ion concentra-
tion in the cooking liquor, indicating an interaction effect.
The results also showed that the negative effect of sodium
ion concentration on the amount of residual lignin decrea-
sed with increasing hydroxide ion and increasing hydro-
sulfide ion concentrations in the cooking liquor. Modern
kraft pulping processes are complicated with several addi-
tions and withdrawals of white and black liquors. The pos-
sible interaction effects may have a great influence on pul-
ping results.
This paper deals with displacement kraft pulping of the
SuperBatch and RDH (Rapid Displacement Heating) types
simulated in the laboratory as kraft pulping with sulfide
pretreatment. The influences of the conditions in the pre-
treatment (hydroxide ion concentration and temperature)
and in the cooking stage (hydroxide ion concentration and
hydrosulfide ion concentration) on the delignification and
carbohydrate degradation were investigated. The cooking
experiments were conducted at a liquor-to-wood ratio of
Nordic Pulp and Paper Research Journal Vol 15 no. 1/2000
Table 1. Conditions in the pretreatment and cooking stage. Experimental ced with a cooking liquor. The pretreatment
design 2 4-1. liquor was analysed with respect to hydrox-
ide ion and hydrosulfide ion concentrations.
Variable Pretreatment stage Cooking stage
The cooking liquor composition was com-
[OH¯], mol/L 0.2 (-), 0.5 (0), 0.8 (+) 1.0 (-), 1.5 (0), 2.0 (+) pensated for the carry-over of chemicals
[HS¯], mol/L 0.3 0.2 (-), 0.3 (0), 0.4 (+) from the pretreatment to the cook. The
[CO32-], mol/L 0.1 – liqour-to-wood ratio in the cooking stage
[Na+], mol/L 1.3 3.0 was 4:1. After the cooking chemicals had
Temperature, °C 130 (-), 140 (0), 150 (+) 170 been charged, the autoclaves were placed in
Time, min 60, 55 0, 70, 180 a glycol bath for 10 minutes at 130°C and
heated at a rate of 2°C/min to the 170°C.
Table 2. Conditions in the pretreatment and cooking stage. Experimental The cooking time at 170°C was 70 and 180
design 2 4-2. minutes. After the cook, the chips were
washed with deionized water for 10 h. The
Variable Pretreatment stage Cooking stage pulp was then screened in a water jet defi-
[OH¯], mol/L 0.1 (-), 0.3 (0), 0.5 (+) 1,0 (-), 1.3 (0), 1.6 (+) brator (2 mm hole) followed by a Wennberg
[HS¯], mol/L 0.3 0.3 screen (0.2 mm slit) and dewatered to
[CO32-], mol/L 0.1 – approximately 25% dry content.
[Na+], mol/L 1.1 2.1 The pretreatment and cooking liquors
Temperature, °C 130 170 were prepared from technical grade NaOH
and Na2S.

4:1 and with a constant sodium ion profile. Since the pre-
treatments were conducted with inorganic aqueous sulfide
solution, a small amount of sodium carbonate was added
to the pretreatment liquor to simulate the buffer capacity of
black liquor. The objective was to clarify the possible
interaction effects of the process parameters studied on the
delignification and carbohydrate degradation. A statistical
experimental design was employd to reach this goal.
Another aim was to study the effect of the hydroxide ion
concentrations in the pretreatment and in the cooking stage
on the bleachability of the produced pulps in an OZQP*-
sequence and on the strength properties of the unbleached
pulp. An attempt has been made to propose profiles of
active cooking chemicals and temperature in order further
to improve of the selectivity of the modern softwood kraft
pulping and to produce softwood pulps with good bleacha-
bility and high strength properties.
Experimental
Wood
Industrial fresh pinewood chips (Pinus silvestris) were
used. The chips were screened on a disk screen and the
2–6 mm fraction was used in cooking experiments. Bark
and knots were removed by hand sorting. The lignin con-
tent on wood was 27.8%.
Cooking
The cooking experiments were carried out as two stage
cooks: a pretreatment and a cooking stage. Three hundred
grams of wood (o.d.) were charged in autoclaves and the
pretreatment liquor was added. The liquor-to-wood ratio
was 4:1. The autoclaves were placed in a glycol bath for
10 minutes at 100°C and heated at a rate of 2°C/min to the
pretreatment temperature. The pretreatment time was 60
minutes at 130°C or 55 minutes at 150°C. After it had
been cooled, a part of the pretreatment liquor was removed
until a liquor-to-wood ratio of 2:1 was reached and repla-
Experimental Design 1
A statistical experimental design, 24-1, was used to evalua-
te the influence of hydroxide ion concentration and tempe-
rature in the pretreatment and of hydroxide ion and hydro-
sulfide ion concentrations in the cooking stage on the
delignification and carbohydrate degradation. The sodium
ion concentration was controlled by the addition of analy-
tical grade Na-acetate. The conditions in the pretreatment
and cooking stage are given in Table 1.
Experimental Design 2
A statistical experimental design, 24-2, was used to evalua-
te the pulping selectivity, bleachability and strength pro-
perties for various hydroxide ion concentrations in the pre-
treatment and cooking stages. The sodium ion concentra-
tion was controlled by the addition of analytical grade
NaCl. The cooking time was varied to obtain a kappa
number of 20. The conditions in the pretreatment and coo-
king stage are given in Table 2.
TCF-bleaching
The pulps were bleached in an OZQP*-sequence, where
P* means a P-stage with MgSO4-addition. Oxygen blea-
ching was carried out in steel autoclaves. Ozone treatment
was performed in a rotating glass reactor. Peroxide blea-
ching and complexing agent stages were carried out in sea-
led polyethylene bags in thermostated water baths.
Deionized water was used in all bleaching experiments.
Bleaching conditions are given in Table 3.
Analyses
The hydroxide ion concentration was determined accor-
ding to SCAN-N 33:94 and the hydrosulfide ion concen-
tration according to SCAN-N 31:94. Wood/pulp properties
were determined as follows: wood dry content SCAN-CM
39:88, pulp dry content SCAN-C 3:78, kappa number
SCAN-C 1:77, viscosity SCAN-CM 15:88 and ISO-
brightness SCAN-C 11:75. The lignin content in the wood

Nordic Pulp and Paper Research Journal Vol 15 no. 1/2000 71

Table 3. Bleaching conditions.
Bleaching Charge, Addition, Temp, Pressure, Time, Concistency,
stage kg/t kg/t °C MPa min
O 20 (NaOH) 1 (Mg) 100 0,65 70
Z 5 – 20 atm var
Q1 2 (EDTA) – 70 atm 60
P* 5–40 0,5 (Mg) 80 atm 1440
(24 h)
residue after pretreatment was determined as the sum of
the Klason and acid-soluble part of the lignin (Theander,
Westerlund 1986). The carbohydrate composition of the
pulps was analysed according to Theander and Westerlund
(1986). The amount of hexenuronic acids (HexA) was
determined by enzymatic hydrolysis followed by capillary
electrophoresis (Dahlman et al. 1997). The strength pro-
perties of the unbleached pulps were determined according
to SCAN-C 24:67 after beating in a PFI-mill. The con-
sumption of bleaching chemicals was calculated as oxida-
tion equivalents, OXE (Grundelius 1992).
Results and discussion
I: Interaction effects of the conditions in the pretreatment
and cooking stages
The cooking experiments were carried out as two stage
cooks: a pretreatment and a cooking stage. The conditions
in the pretreatment and cooking stages are presented in
Table 1. A statistical experimental design, 24-1, was used to
find the most important process parameters. The relation
between the pulping results and the process parameters
was evaluated using a PLS (Partial Least Squares)-analysis
(Geladi, Kowalski 1986). The PLS-model was constructed
using process parameters, hydroxide ion concentration and
temperature in the pretreatment and hydroxide ion and
hydrosulfide ion concentrations in the cooking stage, as X-
matrix. The kappa number, the lignin content (% on
wood/pulp), the brightness of the unbleached pulp, the car-
bohydrate yield and the pulp viscosity constituted the Y-
matrix. The X- and Y-matrix data were mean-centred and
scaled before the PLS-calculations were carried out. The
responses were measured at cooking times of 70 and 180
minutes. In the studied experimental domain, the cooking
time of 70 minutes represents the
delignification in the bulk delignifi-
% on pulp cation phase. The cooking time of
180 minutes represents the delignifi-
12 cation in the residual phase and was
39 assumed to be an indication of the
10 amount of residual lignin. In the
10 PLS-model, two significant PLS-
components were obtained which
together explained a total of 94% of
the variance in the Y-matrix. The predictability (Q2) of the
regression model was 63%.
The influence on the delignification in cooking stage
The influence on the kappa number of hydroxide ion con-
centrations in the pretreatment and in the cooking liquor at
cooking times of 70 and 180 minutes is illustrated in Fig.
1. As shown in this figure, at low hydroxide ion concentra-
tion (1.0 mol/L) in the cooking liquor the kappa number at
70 minutes was reduced from 53 to 27 when the hydroxide
ion concentration in the pretreatment liquor was raised
from 0.2 to 0.8 mol/L. At high hydroxide ion concentra-
tions in the cooking liquor (2.0 mol/L), the kappa number
decrease was only five units, from kappa number 18 to 13.
This means that the hydroxide ion concentration in the
pretreatment liquor has a considerable influence on the
delignification at a low hydroxide ion concentration (1.0
mol/L) in the cooking liquor, but that, at a high hydroxide
ion concentration (2.0 mol/L) in the cooking liquor this
effect is reduced. This observation indicates a two-factor
interaction effect on the delignification between the
hydroxide ion concentrations in the pretreatment and in the
cooking liquor. When the comparison is made at 180
minutes, also presented in Fig. 1, the observed two-factor
interaction effect on the kappa number was less, but it was
still significant. At [OH¯]=1.0 mol/L in the cooking liquor,
the kappa number decreased from 21 to 12 and at
[OH¯]=2.0 mol/L from 9 to 7 when the hydroxide ion con-
centration in the pretreatment liquor was increased from
0.2 to 0.8 mol/L.
It has been suggested (Ljunggren 1980; Gierer, Norèn
1980) that the cleavage of β-arylether linkages in non-phe-
nolic lignin units is the rate-determing delignification reac-
tion in the bulk phase of the kraft pulping. The liberation

Kappa number, 70 min Kappa number, 180 min

60 22

20
50
18

16
40
14
30 12

10
20 0,8
0,8 8
0,6 0,6
1,0 1,0
1,2 1,2
1,4 0,4
1,4
1,6
0,4
[OH¯ ]PRE, mol/L 1,6
[OH¯ ]PRE, mol/L
1,8 1,8
0,2 2,0 0,2
2,0
[OH¯ ]COOK, mol/L [OH¯ ]COOK, mol/L
Fig. 1. Kappa number at 70 minutes and 180 minutes for different hydroxide ion concentrations in the pretreatment and cooking stages.

72 Nordic Pulp and Paper Research Journal Vol 15 no. 1/2000

of hydroxyl groups in the lignin matrix is of major impor-
tance since they contribute not only to the “peeling” of the
lignin macromolecule but also to the solubilisation and
dissolution of the lignin. Depolymerisation, the introduc-
tion of new phenolic groups and degradation by “peeling”
cause the dissolution of lignin in the bulk phase (Ljung-
gren 1980). A possible explanation of the observed two-
factor interaction effect, illustrated in Fig. 1, may be that at
a low hydroxide ion concentration in the cooking liquor
(1.0 mol/L) there is a deficiency of alkali in the pulping
system and that this retards the fragmentation and solubili-
sation of the lignin macromolecule. In this case, an increa-
se in the hydroxide ion concentration in the pretreatment
leads to an increase in the hydroxide ion concentration in
the cooking stage, with greater lignin dissolution as a
result. At a high hydroxide ion concentration in the coo-
king liquor (2.0 mol/L), the supply of alkali seems to be
adequate regardless of the hydroxide ion concentration in
the pretreatment.
The hydrosulfide ion concentration in the cooking liqu-
or was varied at a high level (0.2–0.4 mol/L) characteristic
of the industrial displacement kraft cook. No significant
effect of hydrosulfide ion concentration in the cooking
liquor on the delignification was observed at a cooking
time of either 70 or 180 minutes. This agrees with Sved-
man et al. (1995) and Olm et al. (2000) who found that the
hydrosulfide ion concentration in the cooking liquor has a
negligible effect on the delignification in kraft pulping
with pretreatment at a high hydrosulfide ion concentration
in the pretreatment/displacement liquor. During the pre-
treatment with sulfide-containing liquors, a significant
amount of phenolic β-arylether linkages are cleaved
(Kleen, Olm 1995). Presumably, the demand of hydrosulfi-
de ions in the cooking stage is reduced, and this may be
the explanation of the results obtained. A more pronounced
influence of the hydrosulfide ion concentration on the rate
of delignification in the bulk phase has been reported in
kinetic studies (LeMón, Teder 1973; Lindgren, Lindström
1996). The different results may be explained by the diffe-
rent experimental techniques used and by the different
experimental domains investigated. The results of the pre-
sent study imply that, with a high hydrosulfide ion concen-
tration in the pretreatment, its concentration in the cooking
stage can possibly be reduced. In a further development of
the industrial kraft pulping with pretreatment, there seems
to be no need to raise the hydrosulfide ion concentration in
the cooking stage.
Within the investigated experimental domain, the repon-
ses were not significantly influenced by the pretreatment
temperature (130°C–150°C). The kappa number or lignin
content in the pulp after a cooking time of 70 or 180 minu-
tes appeared to be rather independent of the pretreatment
temperature, in spite of the fact that the lignin content in
the wood residue after pretreatment was considerably
reduced by a high pretreatment temperature. Approxi-
mately 42% of the lignin originally in the wood was dis-
solved during the pretreatment and the lignin content
reached a value of 15% on wood when the pretreatment
temperature was raised from 130°C to 150°C with a high
hydroxide ion concentration (0.8 mol/L) in the pretreat-
Nordic Pulp and Paper Research Journal Vol 15 no. 1/2000
ment liquor. The results support the previous findings of
Olm et al. (2000) that the removal of this lignin in the pre-
treatment stage seems not to be rate-determining in the
cooking stage.
Brightness of unbleached pulp
It is well known that the brightness of an unbleached pulp
increases with decreasing lignin content on pulp/kappa
number and with increasing effective alkali charge/residual
alkali in the kappa number range below 35–40 (Norrström
1969; Carnö et al. 1975; Svedman et al.1995; Kettunen
1997; Sjöström 1998). Fig. 2 gives the brightness/kappa
number relationship for all the pulps studied. Two different
relationships were obtained, indicating that pulps produced
with a cooking time of 70 minutes in the bulk delignifica-
tion phase, reached a higher brightness value than pulps
produced with a cooking time of 180 minutes. The pulp
brightness at a kappa number of 20 was approximately 5
units higher when the cook was completed in the bulk
delignification phase (cooking time of 70 minutes) than
when it was completed in the residual phase (cooking time
of 180 minutes), Fig. 2. The difference in light absorption
coefficient, measured at 557 nm, was about 4 m2/kg (12.4
compared to 8.1 m2/kg). A possible explanation of this
observation may be that, when the cooking time is exten-
ded, the amount of condensed lignin structures and thus
the amount of chromophoric groups in the pulp increase.
Also a more extensive resorption of lignin and carbohydra-
tes is obtained (Surewicz 1962; Simonsson 1963; Sjöström
1999). The metal ion content in the pulps should be of the
same magnitude, since the same wood material and deioni-
sed water were used in the cooking experiments.
The influence on carbohydrate degradation
The carbohydrate degradation was followed as pulp yield
and pulp viscosity at cooking times of 70 and 180 minutes.
The carbohydrate yield and the pulp viscosity at a cooking
time of 70 minutes are presented in Fig. 3 as a function of
hydroxide ion concentration in the pretreatment and coo-
king liquor. Both the carbohydrate yield and the pulp vis-
Fig. 2. Relationship between brightness of unbleached pulp and
kappa number. Cooking times 70 and 180 minutes.
73
 Carbohydrate yield, % on wood Viscosity, mL/g
1200
46
1100
45
1000
44
900

43 800

42 700

600 0,8
41 0,8
0,6
0,6 1,0
1,0 1,2
1,2 1,4 0,4
1,4 0,4
[OH¯ ]PRE, mol/L 1,6 [OH¯ ]PRE, mol/L
1,6 1,8
1,8 2,0 0,2
2,0 0,2

[OH¯ ]COOK, mol/L [OH¯ ]COOK, mol/L

Fig. 3. Carbohydrate yield (% on wood) and pulp viscosity for different hydroxide ion concentrations in the pretreatment and cooking stages at 70
minutes.

cosity were affected by the hydroxide ion concentration in
the pretreatment and cooking stages. Results indicated a
more pronounced loss of pulp yield at cooking times of
180 minutes than at 70 minutes. Obviously, the carbohy-
drates are more labile towards high hydroxide ion concen-
tration during the latter part of the cook. This effect has
also been noticed in previous studies by Aurell and Hartler
(1965) and by Sjöblom et al. (1983) and it has been explai-
ned by the greater accessibility of the carbohydrates due to
the higher degree of delignification. The decrease in pulp
viscosity was of the same magnitude at cooking times of
70 and 180 minutes. In the studied experimental domain,
the carbohydrate yield and pulp viscosity were indepen-
dent of the pretreatment temperature. As expected, the
hydrosulfide ion concentration had no significant effect on
either the carbohydrate yield or the pulp viscosity.
II: Alkali profiling in kraft pulping with sulfide pretreatment
On the basis of the results described in the first part, five
pulps were produced with different hydroxide ion concen-
trations in pretreatment and cooking liquor (see Experi-
mental, Design 2) since these process variables had been
found to be of primary importance in a kraft cook with sul-
fide pretreatment. The ionic strength ([Na+]) was kept con-
stant in the pretreatment and in the cooking stage in all the
cooks, so that only the influence of hydroxide ion concen-
tration was studied. The kappa number of the studied pulps
was 18–21. The main cooking conditions and the results
are presented in Table 4.
In spite of the fact that the hydroxide ion concentration
in the beginning of the cooking stage was corrected for the
carry-over of alkali from the pretreatment to the cooking
stage, the residual alkali at the end of the cook varied
widely (compare cook LL with cook HL and cook LH
with cook HH in Table 4). The residual alkali was about
0.2–0.3 mol/L higher at a high (0.5 mol/L) hydroxide ion
concentration than at a low (0.1 mol/L) hydroxide ion con-
centration in the pretreatment liquor. With a high hydroxi-
de ion concentration in the pretreatment liquor, the wood
substances are dissolved and neutralised to the greater
extent during the pretreatment than at a low hydroxide ion
concentration. The consumption of alkali in the cooking
stage is reduced and this leads to a higher residual alkali in
the black liquor.
Cooking selectivity
The pulping selectivity was determined as pulp viscosity
and pulp yield at a given kappa number and is presented in
Fig. 4 as a function of residual alkali at the end of the coo-
king stage. A linear relationship was obtained between
pulp viscosity and residual alkali in the black liquor in
accordance with Kubes et al. (1983). The highest pulp vis-

Table 4. Cooking conditions and pulp properties. The pulp viscosity and pulp yield are corrected to the kappa number (K) 20. It
was assumed that the viscosity change per kappa number was 20 mL/g (according to experience at STFI) and yield change
0.15% on wood (Bergnor et al. 1988).

Cook/Pulp [OH¯], [OH¯], Cooking Residual Kappa Vis- Yield Bright-

Pretreatm/ Pretreat- Cooking time at alkali, number cosity K=20, ness,
Cooking ment, stage, 170°C, mol/L K=20, % on % ISO
mol/L mol/L min ml/g wood

LL 0.1 1 194 0.15 20 960 44.1 30.3

HL 0.5 1 104 0.34 20.8 940 44.3 33.1
MM 0.3 1.3 92 0.48 19 920 43.1 35.4
LH 0.1 1.6 84 0.61 18.2 910 43.5 37.3
HH 0.5 1.6 62 0.88 19.4 870 42.2 38.3

L low hydroxide ion concentration

H high hydroxide ion concentration
M medium hydroxide ion concentration

74 Nordic Pulp and Paper Research Journal Vol 15 no. 1/2000

 Fig. 5. Xylan yield (% on wood) and the content of hexenuronic acid
Fig. 4. The pulp yield and pulp viscosity at kappa number 20 as a in pulp (HexA) at kappa number 20 as a function of hydroxide ion
function of the residual alkali in the black liquor. concentration in the cooking stage.

cosity at kappa number 20 was attained, as expected, at the
lowest residual alkali, i.e. with a low hydroxide ion con-
centration in the pretreatment (0.1 mol/L) and cooking
stage (1.0 mol/L), LL cook.
The hydroxide ion concentration profile in LL cook,
which gave the highest pulp viscosity, resulted in the same
pulp yield as the HL cook, with a high hydroxide ion con-
centration in pretreatment and low in cooking stage, Fig. 4
and Table 4. With a low hydroxide ion concentration in the
pretreatment and cooking stages (0.1 and 1.0 mol/L
respectively) the cooking time needed to reach a kappa
number of 20 was almost doubled, 194 and 104 minutes,
respectively. The prolonged cooking time between hydrox-
ide ions and carbohydrates presumably counteracts the
positive effect of a reduced hydroxide ion concentration in
the cooking liquor. The same tendency can be observed in
the experimental data of Gustavsson et al. (1999). When
the hydroxide ion concentration was levelled out at a low
level (0.55 mol/L) the cooking time was prolonged (four
times) and pulp viscosity improved by 80 mL/g compared
with the high level (1.5 mol/L). The pulp yield was unaf-
fected by these changes in hydroxide ion concentration
level.
When a comparison is made at approximately the same
total hydroxide ion concentration (the sum of [OH¯] in
pretreatment and cooking stage), the HL cook (total
[OH¯]=1.5 mol/L) gives about 1 %-unit higher pulp yield
at kappa number 20 than the MM cook (total [OH¯]=1.6
mol/L), with a medium hydroxide ion level in the pretreat-
ment and cooking stages. The loss of pulp yield was cau-
sed mainly by a decrease in the xylan yield, Table 5. At
high hydroxide ion concentration, the xylan degradation is
more extensive and xylan sorption is retarded (Simonson
1963). The results thus suggest that in order to improve the
pulp yield in industrial displacement kraft pulping the
hydroxide ion concentration in the displacements with
black liquor may be increased and the white liquor charge
in the cooking stage reduced.
In the kraft process, the methylglucuronic acids groups
in xylan are partly converted into hexenuronic acid groups
(HexA) (Buchert et al. 1996, 1997). HexA contribute to
the kappa number (Gellerstedt, Li 1996) and affect the
consumption of bleaching chemicals (Vuorinen et al.
1996). Fig. 5 shows the xylan yield and HexA content in
pulp for various hydroxide ion concentrations in the pre-
treatment and cooking stage. The results in Fig. 5 and

Table 5. Carbohydrate composition of the pulps calculated according to Jansson (1974) and hexenuronic acid (HexA) con-
tent in pulp.

Cook/Pulp Carbo- Carbohydrate composition, Carbohydrate composition, HexA,

Pretreatm/ hydrate % on pulp % on wood µmol/g
Cook yield, Xylan Gluco- Cellulose Xylan Gluco- Cellulose pulp
% wood mannan mannan

LL 42.8 8.6 8.2 80.1 3,8 3,6 35,3 22

HL 43.0 8.1 8.0 80.7 3,6 3,6 35,8 20
MM 41.7 7.0 8.4 81.6 3 3,6 35,1 14
LH 41.9 5.8 9.4 82.1 2,5 4,1 35,4 10
HH 40.9 4.9 8.6 83.6 2,1 3,6 35,2 11

L low hydroxide ion concentration

H high hydroxide ion concentration
M medium hydroxide ion concentration

Nordic Pulp and Paper Research Journal Vol 15 no. 1/2000 75

Table 6. Physical properties of studied pulps at 2 000 revolutions in PFI-mill. Fiber length number after the oxygen stage
is given as length weighted average. and per ton of pulp. As shown in
Table 4, the brightness of the
Cook/Pulp SR-number Rewetted Zero-span Fibre length, WRV,
unbleached pulp increases with
Pretreatm/ Tensile Index, %
increasing hydroxide ion/residual
Cooking Nm/g mm
alkali concentration in the coo-
LL 16 158 2.36 166 king stage in agreement with
HL 16 165 2.42 165 previous studies (Norrström 1969;
MM 15.5 164 2.36 160 Carnö et al. 1975; Svedman et al.
LH 15.5 163 2.38 159 1995). The differences in unblea-
HH 15 167 2.45 153 ched pulp brightness were at most
L low hydroxide ion concentration
8 units, when the pulp produced
H high hydroxide ion concentration with a low hydroxide ion concen-
M medium hydroxide ion concentration tration in pretreatment and coo-
king liquor (0.1/1.0 mol/L, LL
pulp in Table 4) was compared
Table 5 clearly demonstrate that the xylan yield as well as with pulp produced with a high hydroxide ion concentra-
the content of HexA in pulp correlate with the hydroxide tion in the pretreatment and cooking liquor (0.5/1.6 mol/L,
ion concentration in the beginning of the cooking stage HH pulp in Table 4).
and not with the residual alkali at the end of the cooking Fig. 6 shows the brightness development as a function
stage, as suggested by Buchert et al. (1997). This agrees of the consumption of bleaching chemicals for the studied
with Simonson’s (1963) findings on xylan in studies of the pulps. In spite of the large differences in unbleached pulp
conventional kraft pulping. The dissolution of xylan brightness, the brightness development was affected little
reached a maximum during the early part of the constant by the hydroxide ion concentrations in the pretreatment
temperature period (Simonson 1963). and cooking stages. In the range of residual alkali between
The galactoglucomannan yield (% on wood) as well as 0.34 and 0.61 mol/L, the bleachability was almost unaffec-
the cellulose yield were apparently not affected by the ted by the hydroxide ion concentrations in the pretreatment
hydroxide ion concentration in the pretreatment and coo- and cooking stages. At lower residual alkali values (0.15
king stages, Table 5. mol/L), the bleachability was impaired, and at higher valu-
es (0.88 mol/L) it was improved. In a D(EOP)DD-sequen-
Bleachability in OZQP* ce also, the bleachability of the SuperBatch type of pulps
The bleachability was studied in a TCF-sequence has been found to be unaffected by the residual alkali in
according to the OZQP*-sequence (P* is a P-stage with the cooking liquor in the range of 0.5 to 0.7 mol/L (Sved-
MgSO4-addition). The chemical charges were kept con- man et al. 1995). These findings are contrary to those of
stant in all stages except in the final P*-stage. The kappa Sjöström (1999) where optima in the bleachability in
number after the oxygen stage was 10 and after the ozone OAZQP*- and OQPQP*- sequences were found at inter-
stage about 4. The bleachability was evaluated as the total mediate hydroxide ion concentrations in the cooking liqu-
consumption of bleaching chemicals (as OXE) per kappa or (residual akali 0.6 mol/L) for modified kraft pulps of the
ITC (IsoThermal Cooking) type.
The results indicate that a long cooking time at a relati-
vely low hydroxide ion concentration, i.e. when cooking is
terminated in the residual delignification phase, leads to a
low brightness ceiling value (maximum achievable bright-
ness value). Furthermore, the consumption of bleaching
chemicals to attain a certain brightness level increases in
agreement with Gustavsson et al. (1999). As shown in Fig.
6, the LL pulp (low hydroxide ion concentration in both
the pretreatment and cooking stages) did not reach an ISO-
brightness of 90% under bleaching conditions studied.

Fig. 6. Brightness as a function of the consumption of bleaching
chemicals, defined as OXE per ton of pulp and per kappa number
after the oxygen stage.
Strength properties
The tear strength of the chemical pulps is affected both by
the pulp yield and by the pulp viscosity. Generally, the tear
strength increases as the pulp yield decreases, since the
number of load-bearing fibres in the paper sheet increases
(Bovin, Teder 1972). The loss of pulp viscosity increases
with decreasing kappa number due to the higher effective
alkali charge and longer reaction time required. For a
given wood material and a given pulping and bleaching
process, there is a non-linear relationship between the tear

76 Nordic Pulp and Paper Research Journal Vol 15 no. 1/2000

Fig. 7. Tear index-tensile index relationship for the studied pulps.
index (at a certain tensile index) and the pulp viscosity
(Rydholm 1965). There is no well-defined limit below
which a large decrease in tear strength occurs. In addition
the tear strength of kraft pulp also increases with increa-
sing fibre strength (Page, MacLeod 1992; Page 1994) and
increasing fibre length (Seth, Page 1988).
Fig. 7 gives the tear index/tensile index relationship of
unbleached pulps produced in kraft cooks with pretreat-
ment at various hydroxide ion concentrations in the pretre-
atment and cooking stages. The HH pulp with a high
hydroxide ion concentration in the pretreatment and coo-
king stages (0.5 mol/L and 1.6 mol/L respectively) exhibi-
ted the highest tear index values at tensile index values
below 100 Nm/g. The LL pulp with a low hydroxide ion
concentration in the pretreatment and cooking stages (0.1
mol/L and 1.0 mol/L respectively) had a significantly
lower tear index level than all the other pulps. The lower
pulp yield and higher fibre strength may explain the higher
tear strength of HH than of LL pulp. The fibre strength
was evaluated as rewetted zero-span tensile index, since
rewetting minimises the influence of fibre-fibre bonds
(Mohlin, Alfredsson 1990). As shown in Table 6, the diffe-
rences in the zero-span tensile index of the studied pulps
are small, except for the LL pulp. The LL pulp had a signi-
ficantly lower fibre strength, 158 Nm/g compared to a
value of 167 Nm/g (at 2000 rev. in PFI-mill) for the HH
pulp. No significant effect of hydroxide ion concentration
on the fibre length was found in this study. In conventional
kraft pulps, an improvement in tear index with increasing
effective alkali charge has also been found (Paavilainen
1989). The differences in tear index caused by changes in
effective alkali charge were explained in terms of fibre
flexibility and fibre stiffness. It should be noted that HH
pulp with the lowest viscosity (Table 4) had the highest
tear index at a tensile index of 90 Nm/g. There seems to be
a tendency towards a higher tear index with decreasing
pulp viscosity. Similar observation has been made for the
RDH type of pulps (Andrews 1989).
The beatability expressed as tensile index as a function
of the number of revolutions in a PFI-mill is presented in
Fig. 8. The influence of hydroxide ion concentrations in the
Nordic Pulp and Paper Research Journal Vol 15 no. 1/2000
Fig. 8. The development of tensile index with number of revolutions
in PFI-mill for the studied pulps.
pretreatment and cooking stages on the tensile index deve-
lopment with increasing beating in PFI-mill was minor. As
expected, the HH pulp had a lower tensile index level than
the other pulps, due to the lower hemicellulose and higher
cellulose contents in pulp, Table 5. The LL pulp did not
have the best beatability in spite of the highest hemicellulo-
se content in the pulp and fibre swelling measured as Water
Retention Value, reported as WRV in Table 6.
The results of this study indicate that terminating the
cook in the residual phase, LL cook, may have a negative
influence not only on the bleachability but also on the
strength properties of the pulp. In Paavilainen’s (1989)
study (at kappa number 28), the pulp produced at 18%
effective alkali charge had a lower fibre strength (-15
Nm/g) and tear strength (-1.5 mNm2/g) than pulps produ-
ced at effective alkali charges of 21 and 24 % respectively
on wood. The differences in tear index for pulps produced
at the high effective alkali charges (21 and 24%) were
small. The present study as well as Paavilainen’s work deal
with the strength properties of unbleached pulp. Recently
the same tendency was found in a study of the strength pro-
perties of ECF-bleached pulps (Poukka et al. 1999). An
optimum in kappa number with respect to strength properti-
es was obtained at kappa number of 30–40. The kappa
range studied was 20–60 and the cooking time at 167°C
varied from 46 to 146 minutes. It is reasonable to assume
that the pulp with the lowest kappa number was finished in
the residual phase. These literature data support the obser-
vation made in the present study that continuing the kraft
cook into the residual delignification phase has a detrimen-
tal effect on the strength properties of the pulp.
Process considerations
In an industrial displacement kraft cook of the SuperBatch
or RDH type, the hydroxide ion concentration is low during
displacement with black liquor and high in the cooking
stage (Perala, Hiljanen 1992; Lönnberg et al. 1993;
Andersson, Olm 1998). The hydroxide ion concentration
remains on a relatively high level throughout the cooking
stage due to the neutralisation of lignin and carbohydrate
degradation products during the displacement with black
77
liquor and the high liquor-to-wood ratio (5.5:1) (Perala,
Hiljanen 1992). According to the results obtained in this
study, it would be advantageous to increase the hydroxide
ion concentration in the hot black liquor displacement and
to decrease it in the white liquor in displacement kraft pul-
ping of the SuperBatch or RDH type. Such a change in the
hydroxide ion concentration profile in the pretreatment and
cooking stages (cf. LH and HL cooks in Tables 4–6) will
lead to a slightly higher pulp viscosity at a given kappa
number. Also the pulp yield is improved. The pulp properti-
es such as beatability and fibre swelling will be improved
while the tear index at a given tensile index seems to be
unaffected. The bleachability in an OZQP*-sequence is not
influenced by this hydroxide ion concentration profile
change. Based on the experimental results (two-stage coo-
king) the initial hydroxide ion concentrations of 0.5–0.8
mol/L in the hot black liquor displacement and 0.8–1.0
mol/L in the cooking stage are reasonable when the target
kappa number is approximately 20. Such a change in alkali
profile will presumably require an extension of the cooking
time to target kappa number and may if necessary, be com-
pensated for by an increase in temperature in the cooking
stage.
The results of this study indicate the importance of ter-
minating the cook in the bulk delignification phase. If the
alkali profile in kraft cook is levelled out at a low hydroxi-
de ion concentration level (residual alkali approximately
0.15 mol/L), the cook will be completed in the residual
phase. As a consequence, the cooking time required to
reach a target kappa number is considerably extended. The
pulp viscosity at a given kappa number is improved, but no
increase in pulp yield was observed. The consumption of
bleaching chemicals to attain a certain brightness level was
increased and the brightness ceiling value was reduced in
bleaching with the OZQP*-sequence. The fibre strength
and the tear index at a given tensile index of the unbleached
pulp were also impaired. The beatability, tensile index at a
given revolutions in PFI-mill, was not affected by this
hydroxide ion concentration profile. Although only one
cook (LL cook) was terminated in the residual phase, litera-
ture data from other investigations (Paavilainen 1989;
Gustavsson et al. 1999; Poukka et al. 1999) support this
observation.
The industrial displacement kraft pulping of the
SuperBatch and RDH type are usually terminated in the
bulk delignification phase in contrast to conventional kraft
pulping, which are terminated in the residual delignification
phase when pulping to low kappa numbers. The fact that a
displacement kraft pulping is finished in the bulk delignifi-
cation phase may be the major advantage and may explain
the high strength potential and good bleachability obtained,
in spite of the high ionic strength and the high content of
organic black liquor substances.
Conclusions
The results show that the delignification in a kraft pulping
with sulfide pretreatment is affected by the hydroxide ion
concentrations in the pretreatment and in the cooking stage,
and by a two-factor interaction between these variables.
78
The cooking time required to reach a certain kappa number
(lignin content on pulp) can be reduced considerably by
increasing the hydroxide ion concentration in the pretreat-
ment and having a low hydroxide ion concentration in the
cooking stage. The hydrosulfide ion concentration in the
cooking stage had no significant influence on the delignifi-
cation within the experimental domain investigated.
The results suggest that the lower xylan yield and the
lower hexenuronic acid content in the pulp observed in
industrial displacement kraft pulps of the SuperBatch and
RDH types, compared to modified continuous and conven-
tional kraft pulps, are related to the high initial hydroxide
ion concentration in the beginning of the cooking stage.
The results indicate that in industrial displacement kraft
pulping it would be advantageous to increase the hydroxide
ion concentration in the hot black liquor displacement and
to decrease the hydroxide ion concentration in the white
liquor in order to produce a pulp with high yield, good ble-
achability and high unbleached pulp strength. Hydroxide
ion concentrations of 0.5–0.8 mol/L in the hot black liquor
displacement and 0.8–1.0 mol/L in the cooking stage are
reasonable when the target kappa number is approximately
20. For a higher target kappa number, the hydroxide ion
concentration in the cooking stage should be decreased.
The temperature in the hot black liquor displacement
should be high, approx. 150°C.
Results of this study suggest that the kraft cook should
be terminated in the bulk delignification phase. A long coo-
king time at a relatively low hydroxide ion concentration
(residual alkali 0.15 mol/L) leads to a low brightness of
unbleached pulp, to a high consumption of bleaching che-
micals to attain a certain brightness level and a low bright-
ness ceiling value. The fibre strength and the tear index at a
given tensile index of unbleached pulp were also impaired.
The fact that the displacement kraft cook is finished in the
bulk delignification phase may be its major advantage and
may explain the high strength potential and good bleacha-
bility achieved by the displacement kraft pulping, in spite
of the high ionic strength and high content of organic black
liquor substances. A more systematic study should be carri-
ed out in order to confirm this observation and clarify the
possible effects.
Acknowledgements
The authors thank Professors Ants Teder, Göran Gellerstedt,
Sten Ljunggren and also Elisabeth Bergnor-Gidnert, Marie
Bäckström and Helena Lennholm for valuable discussions
and criticism of the manuscript. The authors thank
Margareta Söderqvist-Lindblad for well-performed laboratory
work. Professor Anthony Bristow is thanked for the linguistic
revision of the manuscript.
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Manuscript received September 9, 1999
Accepted December 1999
79