Possibilities for Increasing the Effectiveness of

Oxygen Delignification of Hardwood Kraft Pulp

S. NENKOVA, I. VALCHEV and G. SIMEONOVA

This investigation clarifies the influence of operating parameters on the effectiveness of oxygen delignification of hardwood kraft pulp. It is estab-
lished that an increased temperature can accelerate considerably the oxygen-delignification process without significant effect on the strength proper-
ties of the pulp. The effect of pressure and the sodium hydroxide charge on the brightness and Kappa reduction is comparatively smaller. Increasing
the alkali charge worsens the selectivity of oxygen delignification. An equation describing the temperature–time dependence of the Kappa number is
developed, which also includes the influence of oxygen pressure and alkali charge. This simple expression can be used for simulation and control of
oxygen delignification.

La présente étude clarifie l’influence des paramètres d’exploitation sur l’efficacité de la délignification à l’oxygène de la pâte kraft de feuillus. Il a été
établi qu’en accroissant la température, on peut considérablement accélérer le processus de délignification à l’oxygène, sans effets importants sur la
résistance de la pâte. L’effet de la pression et de la charge d’hydroxyde de sodium sur la blancheur et la réduction de l’indice Kappa est
comparativement plus faible. Si l’on accroît la charge d’alcali, on aggrave la sélectivité de la délignification à l’oxygène. Nous avons dégagé une
équation décrivant la dépendance température–temps de l’indice Kappa, qui comprend aussi l’influence de la pression de l’oxygène et de la charge
d’alcali. Cette simple expression peut être utilisée pour simuler et contrôler la délignification à l’oxygène.

INTRODUCTION softwood kraft pulp.

S. Nenkova, I. Valchev and
G. Simeonova
The use of oxygen delignification in Metso introduced the two-stage
Dept. Pulp Paper Printings Arts pulp bleaching has grown considerably over the OxyTrac process [8,9], with an oxygen pres-
8 Kliment Ochridski Blvd. last 25 years [1–7]. The introduction of two- sure and temperature of 0.8–1 MPa and
1756 Sofia, Bulgaria stage oxygen delignification has further in- 80–85°C, respectively, during the first stage of
(nenkova@uctm.edu) creased the effectiveness of the process, and has 20–30 min retention time. During the second
allowed a 70% reduction in Kappa number for stage, the oxygen pressure is 0.3–0.5 MPa, the

324 JOURNAL OF PULP AND PAPER SCIENCE: VOL. 29 NO. 10 OCTOBER 2003
temperature 90–100°C and the reaction time autoclaves rotated at a constant rate in a In a previous investigation of the kinetics
60–80 min. polyglycol bath previously heated to the de- of oxygen delignification [15], it was found that
According to Kvaerner, the optimal con- sired temperature. The kinetics of the process the rate of delignification is well described by a
ditions for oxygen delignification during the was studied at different constant temperatures modified form of the topochemical kinetic
first stage are a lower oxygen pressure, of 85, 95, 102 and 110°C and reaction times equation of Prout–Tompkins. In this kinetic
0.3–0.35 MPa, a temperature of 80–85°C and a varying from 10 to 80 min. The oxygen pres- model, the rate of progress of the reaction is de-
reaction time of only 5 min. Their conclusion is sure was varied from 0.3 to 0.6 MPa, the so- termined by the size of the interface between
based on the kinetics of oxygen delignification dium hydroxide charge from 2.0 to 3.5% and the reacted and unreacted solid. According to
reported by Olm and Teder [10]. A high oxygen the pulp consistency from 8 to 14%. this model, the rate of delignification v is a
pressure of 0.6–0.8 MPa and a high temperature The Kappa number, brightness and vis- function of the amount of oxidized lignin that
of 100°C or higher during the second stage are cosity were measured according to SCAN subsequently becomes soluble, a, and of the
recommended. However, today, both stages are methods (SCAN-C 1:77 [12], SCAN-CM amount of residual undissolved lignin at any
run at the highest possible pressure to boost 38:87 [13] and SCAN 15:02 [14]). time, (1 - a):
c -1
kappa reduction [11]. This system is applied in Strength properties of the pulp were de- da
c +1
the industry under the name DUALOX, and its termined according to the ISO test procedures. v= = k ¢a c (1 - a ) c (1)
effectiveness is analogous to that of the dt
OxyTrac process. RESULTS AND DISCUSSION where a = (Kappain – Kappa)/ Kappain and k' is
The differences in the operating condi- The effects of oxygen delignification the rate constant.
tions of the two commercial two-stage oxygen temperature and reaction time on the pulp prop- The power factors (c – 1)/c and (c + 1)/c
delignification technologies suggest that fur- erties were studied in the first series of investi- determine the relative contributions by the dis-
ther study is needed. Therefore, the effect of op- gations. The bleaching was carried out at solved and undissolved parts of lignin, respec-
erating parameters on the effectiveness of temperatures of 85, 95, 102 and 110°C for tively, on the rate of delignification. Based on
oxygen delignification of hardwood kraft pulp 10–80 min at 2% sodium hydroxide charge, this topochemical mechanism, the rate of
was investigated in this paper. 10% consistency and an oxygen pressure of 0.6 delignification depends on the size and the state
MPa. of the changing reaction interface.
EXPERIMENTAL Figure 1 shows that a prolonged treat- The integrated form of Eq. (1) used for
An industrial unbleached kraft pulp ment and higher temperature leads to a higher the description of the experimental data is:
from beech and oak, of Kappa number 17.9, lignin removal, as expected. The effect of in- a c
brightness 33.1% ISO and viscosity 965 creasing the temperature from 95 to 110°C is = ( kt ) (2)
dm3/kg was used in this study. The oxygen the same as that of doubling the double reaction 1- a
delignification was carried out using laboratory time. where k = k'/ ÷ is an apparent rate constant and c

Fig. 1. Kinetic data of Kappa number (experimental data and calcu- Fig. 2. Kinetic curves of brightness.
lated curves according to Eq. 1).

Fig. 3. Kinetic curves of viscosity. Fig. 4. Correlation between Kappa number and viscosity.

JOURNAL OF PULP AND PAPER SCIENCE: VOL. 29 NO. 10 OCTOBER 2003 325
is a power factor. pre-exponential factor A includes the effect of show that the (delignification–cellulose degra-
After rearrangement of Eq. (2) and with all steric factors on the process (charge of re- dation) selectivity is not a function of tempera-
inclusion of the Arrhenius temperature depend- agents, their mixing, the pressure in the system, ture. This was earlier noted by Agarwal et al.
ency of the apparent rate constant, Eq. (3) is ob- etc.) and was found to be 5·104 min–1. Equation [5]. However, the selectivity decreases by in-
tained: (3) can be used for process control of the Kappa creasing the alkali charge, as can be seen by the
number. extra viscosity drop at the same Kappa number.
Kappa Figure 2 shows the effect of temperature The pulp strength properties do not
ìï é -1ü and retention time on the pulp brightness after change considerably over the studied tempera-
( )
-0 .59 ù ï
= Kappain í1 - ê1 + 5 ´ 10 4 e (-5833/ T )t ú ý oxygen delignification. When the temperature ture–time interval (Table I). The breaking
ïî ë û ïþ is increased from 85 to 110°C, the brightness length varies between 8750 and 8970 m and the
improves by 9% ISO after 60 min. This is ex- tear index from 7.6–8.1 mN×m2/g. This result,
(3) pected because a decrease in Kappa number combined with the temperature–time depend-
normally leads to an increase in the brightness ence of oxygen delignification, indicates that
where t is the reaction time in min, and T is the of the pulp. an increase in temperature can considerably ac-
temperature in K. The ratio obtained of the acti- The development of the pulp viscosity is celerate the bleaching process without affecting
vation energy of the process to the universal gas shown in Fig. 3. It can be seen that increasing the pulp strength properties.
constant, E/R, is 5833 K. The activation energy temperature and reaction time lead to an in- The effect of oxygen pressure, sodium
E is 48.2 kJ/mol and depends only on the nature creased viscosity loss of the bleached pulp. The hydroxide charge and pulp consistency on the
of the unbleached pulp. In a mill with relatively behaviour of the pulp viscosity in Fig. 3 is very delignification was studied at a constant tem-
constant pulping conditions and wood supply, similar to that of the Kappa number in Fig. 1. perature of 102°C and a retention time 60 min
the activation energy is practically constant. The Kappa number–viscosity and (Table II). The data show that an increase in ox-
The same is true for the coefficient ÷ in the Kappa number–brightness relationships are ygen pressure from 0.3 to 0.6 MPa leads to a
Prout–Tompkins equation, which is 0.59. The shown in Figs. 4 and 5. The results in Fig. 4 Kappa number reduction of 0.75 units, a vis-
cosity loss of ~30 dm3/kg, and a brightness in-
crease of nearly 2% without changing the pulp
Equation 4 strength. This indicates that the higher oxygen
pressure increases the bleaching processes only
ìï é -1ü
( )
-0 .59 ù ï slightly.
. ´ 10 4 e (-0.175C + 0.8P - 5833/ T )t
Kappa = Kappain í1 - ê1 + 216 ú ý The results in Table II obtained by vary-
îï ë û þï
ing the sodium hydroxide charge show that a

TABLE I
TEMPERATURE–TIME DEPENDENCE ON
OXYGEN-DELIGNIFIED PULP STRENGTH PROPERTIES
Breaking
Temperature, Reaction time, length, Tear index,
°C min m mN×m2/g
85 50 8830 7.60
60 8800 7.66
95 60 8850 7.70
80 8640 8.35
102 40 8760 7.36
60 8750 8.00
110 40 8970 7.66
60 8750 8.10

Fig. 5. Correlation between Kappa number and brightness.

TABLE II
EFFECT OF OXYGEN-DELIGNIFICATION CONDITIONS ON THE PULP PROPERTIES
AT TEMPERATURE 102°C AND REACTION TIME 60 min
Oxygen delignification conditions Pulp properties
Oxygen Breaking
NaOH charge, Pulp conc., pressure, Kappa number Viscosity, Brightness, length, Tear index,
% % MPa dm3/kg ISO% m mN×m2/g
0.3 11.0 816 47.2 8500 7.50
2.5 10 0.4 10.9 809 47.6 8510 7.52
0.5 10.7 799 48.4 8520 7.46
0.6 10.5 787 49.5 8520 7.45
2.0 10.7 818 48.7 8700 7.80
2.5 10 0.6 10.5 787 49.5 8530 7.50
3.0 10.3 755 50.7 8400 7.70
3.5 10.0 715 52.1 8340 7.75
8.0 10.5 – 49.3 – –
2.5 10.0 0.6 10.5 787 49.5 8530 7.50
12.0 10.7 – 48.7 – –
14.0 10.7 – 48.7 – –

326 JOURNAL OF PULP AND PAPER SCIENCE: VOL. 29 NO. 10 OCTOBER 2003
higher charge leads to more cellulose degrada- results in larger cellulose degradation at the Delignification”, J. Pulp Paper Sci. 25(10):
tion (a viscosity loss of almost 100 dm3/kg) as same Kappa number. This indicates that it is 361–366 (1999).
well as to a pulp strength loss, besides a Kappa most effective to increase the degree of oxygen 7. IRIBARNE J. and SCHROEDER L.R., “High-
Pressure Oxygen Delignification of Kraft Pulps:
reduction of 0.7 units. The breaking length delignification by optimization of the tempera-
Part I: Kinetics”, Tappi J. 80(10):241–250
drops from 8790 to 8340 m and the viscosity ture–time profile. (1997).
from 818 to 715 dm3/kg by increasing the so- 8. F I R M E N N A C H R I C H T E N - AU S L A N D
dium hydroxide charge from 2.0 to 3.5%. ACKNOWLEDGEMENTS (Schweden Sunds Defibrator – Umweltfreund-
Therefore, a high charge of sodium hydroxide This research was supported by the liches Bleichverfahren erhält 1997 den Product
reduces the oxygen-delignification selectivity Svilosa AD, Bulgaria in respect to optimization E x c e l l e n c e Awa r d ) , Wochenblatt für
and leads to lower pulp strength at the same de- of their two-stage oxygen delignification. Papierfabrication 126 (8):380 (1998).
gree of delignification. 9. TUOMI, A.,“Environmental Delignification”,
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modified form of the topochemical kinetic and MILLER W., “Kinetics of Oxygen
equation of Prout–Tompkins (Eq. 4). The tem-
perature–time dependence obtained of Kappa REFERENCE: NENKOVA, S., VALCHEV, I. and SIMEONOVA, G., Possibilities for Increasing
number may be used for simulation and control the Effectiveness of Oxygen Delignification of Hardwood Kraft Pulp, Journal of Pulp and Paper
of the oxygen-delignification stage. Science, 29(10):324–327 October 2003. Paper offered as a contribution to the Journal of Pulp
It was found that by increasing the tem- and Paper Science. Not to be reproduced without permission from the Pulp and Paper Technical
perature, the delignification and brightness of Association of Canada. Manuscript received May 14, 2002; revised manuscript approved for pub-
the oxygen-delignified pulp were considerably lication by the Review Panel June 18, 2003.
increased without changing the selectivity of KEYWORDS: KRAFT PULPS, HARDWOOD PULPS, OXYGEN, DELIGNIFICA-
the process. The Kappa-number reduction and TION, OPERATIONS, PARAMETERS, TEMPERATURE, PULP PROPERTIES,
brightness increase are less affected by increas- PRESSURE, SODIUM HYDROXIDE, ALKALI, KAPPA NUMBER, EQUATIONS,
ing the alkali charge and even less by the oxy- SIMULATION.
gen pressure. However, a larger alkali charge

JOURNAL OF PULP AND PAPER SCIENCE: VOL. 29 NO. 10 OCTOBER 2003 327