A chemical reactor analysis

of industrial oxygen
delignification
By A. Van Heiningen, D. Krothapalli, J. Genco and A. Justason
PERFORMANCE EVALUATI ON
96 104:12 (2003) T 331 Pulp & Paper Canada
been reported by the group of Bennington [3, 4].
The mass transfer rate in the high shear oxygen
mixer has been recently correlated by Rewatkar
and Bennington [5].
Modelling of the oxygen delignification tower
has been described in two earlier studies [6, 7]. In
the first by Kovasin et al. [6], the mass transfer is
not accounted for separately, but assumed to be
included in the softwood delignification kinetic
equations of Olm and Teder [8], which they used.
Since Olm and Teder used a laboratory through-
flow set-up at a liquor to pulp ratio of 200 L/kg,
and separate oxygenation of the liquor in a
packed bed, it is unlikely that the kinetics contain
any oxygen mass transfer limitation. The same
approach was taken in the second modelling
study by Agarwal et al [7] for oxygen delignifica-
tion of mixed southern hardwood pulp. In addi-
tion to delignification they also predicted the
pulp viscosity. Again it was assumed that effect of
mass transfer was accounted for implicitly in their
own laboratory-generated kinetics.
In the present paper the effect of mass trans-
fer of oxygen on delignification in an industrial
retention tower is simulated. The dissolved oxy-
gen content of the aqueous phase at the entrance
of the retention tower is determined by simulat-
ing the mass transfer and reaction processes in
the high shear mixer. The effect of the mass trans-
fer on the efficiency of delignification is calculat-
ed as function of NaOH charge, oxygen charge
and pressure, consistency and temperature. The
applicability of the analysis to industrial practice
is tested by comparing the predictions to actual
oxygen softwood delignification data taken at the
Irving mill at Saint John, NB.
THEORY
Tower as Plug Flow Reactor with Oxygen Mass
Transfer using the Film Theory (k
L
a): The pulp
suspension is assumed to pass through the reten-
tion tower by plug flow. The plug flow behaviour
can be modelled by dividing the tower in a large
number of layers each of volume (V), and each
layer represented by a Continuous Stirred Tank
Reactor (CSTR). The oxygen mass balance for
the pulp suspension in a single layer is:
Inflow Outflow + Transfer from Gas =
Accumulation + Disappearance by Reaction (1)
T THE RECENT International Pulp
Bleaching Conference, Rewatkar and
Bennington [1] stated that detailed
modelling of industrial oxygen delig-
nification systems is needed in order
to explain why they operate on average about
20% below their delignification potential, i.e.
compared to what can be obtained in laboratory
experiments. In this model the effect of mass
transfer of oxygen from the gas phase to the
pulp fibres must be included to obtain the mill
delignification rate. The importance of mass
transfer was also demonstrated in a recent labo-
ratory study of Berry et al. [2], who obtained a
range of delignification varying from 30-55%
depending on the mixing conditions.
Another important question which was raised at
the 2002 International Bleaching Conference and
in the excellent review of Bennington and Pineault
[3] of industrial oxygen delignification systems is:
What is the relative contribution to delignification
of the high shear oxygen mixer and that of the
retention tower? Also, how to explain the rough
trend found by Pineault and Bennington [3] that
mills with a lower oxygen charge have a higher
degree of delignification? Answers to these ques-
tions are of great importance considering the eco-
nomic and environmental benefits of decreasing
the kappa number entering the bleach plant by
operating an industrial oxygen delignification sys-
tem at its optimum conditions.
Oxygen delignification of pulp is a three-
phase reaction system, with pulp fibres, an aque-
ous phase and the oxygen gas phase. In this sys-
tem, oxygen dissolves in the aqueous phase, and
is then transported through the liquid to the pulp
fibres. Subsequently the dissolved oxygen diffuses
into the fibre wall and then reacts with residual
lignin. For a chemical reactor analysis of this sys-
tem one needs to know the solubility of oxygen in
the alkaline solution, the oxygen mass transfer
rate in the aqueous phase, the effective diffusion
coefficient of oxygen inside a fibre wall, and final-
ly the stoichiometry and chemical kinetics of the
oxygen delignification reactions. Presently all
these fundamental physical and chemical param-
eters are reasonably well known or may be estima-
ted with some confidence, except for the oxygen
mass transfer rate in the liquid phase of the reten-
tion tower. The only information on the latter has
A. JUSTASON
Irving Pulp and Paper Ltd.
Saint John,
NB
J. GENCO
University of Maine
Orono, ME,
USA
D. KROTHAPALLI
University of Maine
Orono, ME,
USA
A. VAN HEININGEN
University of Maine
Orono, ME, USA
avanheiningen@umche.maine.edu
A
Abstract: Industrial oxygen delignification is modelled by taking into account oxygen mass trans-
fer, pulp delignification kinetics and mixer performance. The efficiency of delignification is cal-
culated as function of NaOH charge, oxygen charge and pressure, consistency and temperature.
The simulation is tested by comparing the predictions to actual mill operation of a two-stage oxy-
gen delignification system at Irving Pulp and Paper, Saint John, NB, for softwood kraft pulp.
Since the process is at steady state, the accumulation term is
zero, and equation (1) becomes:
100 -- z
R

(c
O
2,in
c
O
2,out
) + (k
L
a)(c
O
2,sat
c
O
2,out
)(!V)
z
= r
O
2
(1 X
g
)(!V) (2)
where R is the pulp production rate (o.d. kg/s), z is the pulp
consistency (%), c
O
2,in
and c
O
2,out
are the dissolved oxygen con-
centration (moles O
2
/L liquid) in the pulp suspension respec-
tively entering and leaving V, (k
L
a) is the volumetric mass
transfer rate of oxygen to the liquid phase (L liquid/L contac-
tor/s), c
O
2,sat
is the oxygen concentration in the liquid in equi-
librium with the oxygen pressure which exists in V, r
O
2
is the
rate of oxygen consumption by the fibres (moles O
2
/L suspen-
sion/s) and X
g
is the gas void fraction inside contactor volume
V.
The oxygen consumption rate, r
O
2
, is related to the rate of
decrease of kappa number (1/s), ((dK)/(dt)), as:
1.5b
1
z dK
r
O
2
=

(3)
32 100 0.333z dt
where b
1
is the stoichiometric coefficient for the oxygen-lignin
reaction (g O
2
consumed/g lignin removed). The value of b
1
will
be taken as 1.0, giving nearly the same value of 0.14% oxygen
consumption per kappa unit reported by Pineault and Ben-
nington [3]. The numerical value of 1.5 in equation (3) derives
from the experience that one softwood kappa unit represents
1.5 grams of lignin in 1.0 kilogram of pulp.
The rate of decrease of kappa number, ((dK)/(dt)), is ob-
tained from the intrinsic delignification kinetics obtained by
Iribarne and Schroeder [9] as:
dK 3 10
6

= e
51000/(8.314T)
dt 60
([OH

]
out
)
0.7
(c
O
2,out
)
0.7
(K
out
)
2.0
(4)
where T is the temperature (K), [OH

]
out
is the hydroxide con-
centration (mol/L liquid) of the suspension leaving V, and
K
out
is the Kappa number of the pulp leaving V.
In order to calculate the change in alkali concentration over
volume V, the following equation is used:
1.5b
2
z
([OH

]
in
[OH

]
out
) =

(K
in
K
out
) (5)
40 100 z
where b
2
is the stoichiometric coefficient (g NaOH consumed/g
lignin removed) of the sodium hydroxide consumption by the
pulp. The value of b
2
will be taken as 0.90 based on recent mea-
surements by Violette [10] for softwood kraft pulp. This stoi-
chiometric coefficient is equivalent to 0.135% NaOH consumed
per kappa unit decrease.
The change in kappa number over volume V is obtained
from equation (4) for a CSTR, i.e.,
3 10
6
K
in
K
out
= e
51000/(8314T)
60
([OH

]
out
)
0.7
(c
O
2,out
)
0.7
(K
out
)
2.0
(!t) (6)
where t is the residence time (s) of the pulp suspension in vol-
ume V. It is calculated as:
(!V)(1 X
g
)z
!t = (7)
R(100 0.333z)
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Pulp & Paper Canada T 332 104:12 (2003) 97
c
O
2,out
O
2
uptake O
2
reacted
" k
L
a c
O
2,out
F
s
= F
u
=

F
r
=

(Kappa)
mixer
(W/m
3
) (s
1
) (mol/L)
c
O
2,sat O
2
charged O
2
dissolved
1 10
6
0.034 1.0 10
4
0.016 1.48 10
3
7.62 10
3
1.5 10
4
1 10
7
0.342 8.9 10
4
0.141 1.30 10
2
3.97 10
3
6.8 10
4
TABLE II. Effect of mixer dissipation power on oxygen dissolution and delignification in the mixer.
Variable Base Low High
NaOH Charge (%) 2.0 1.0 3.0
Oxygen Charge (%) 2.0 1.0 3.0
Pulp Consistency (%) 10 8 14
Oxygen Pressure at Mixer
Outlet and Tower Inlet (psia) 120 80 200
Temperature (C) 95 85 115
TABLE I. Base case and range of variables.
FIG. 1 (A, B). Development of fractional oxygen saturation
in the tower as a function of mixer power.
Finally, the change in oxygen pressure
(Pa) over volume V in the tower is
obtained from a hydraulic balance as:
100 9810(1 X
g
)(!H)
P
in
P
out
= (8)
100 0.333z
where His the height (m) of volume V.
Both H and V are obtained by dividing
respectively the total height and volume
of the retention tower by n
max
, the total
number of equal sized layers in which the
tower is divided. The saturated oxygen
concentration in the liquid, c
O
2,sat
, is ob-
tained from the average pressure inside
V, using the Henry coefficient reported
by Tromans [11].
The above set of equations can be
solved numerically when the inlet condi-
tions of the tower are known. The latter
can be calculated using equations (2), (5)
and (6) for the high shear oxygen mixer.
In this case the inlet conditions to the
mixer are all known (P
in
, K
in
, [OH

]
in
,
and c
O
2,in
= 0) and k
L
a for the mixer is ob-
tained from the correlation of Rewatkar
and Bennington [5]:
k
L
a = 1.7 10
4
"
1.0
(X
g
)
2.6
e
0.386z
(9)
where " is the power dissipation per unit
volume of the mixer (W/m
3
).
The inlet hydroxide concentration,
[OH

]
in
is obtained from the NaOH
charge, A
c
(% on pulp), as:
10z A
c
[OH

]
in
= (10)
40(100 z)
The gas volume fraction, X
g
, in the
mixer is calculated from the oxygen
charge p (% on pulp), temperature T (K),
pulp consistency z (%), and the oxygen
pressure P
O
2
(psia) using equation (11):
1.206zpT
X
g
= (11)
1.206zpT + 3.2(100 0.333z)P
O
2
Oxygen Mass transfer limitation in the
Fibre Wall: The above analysis assumes
that there is no mass transfer resistance
for oxygen to diffuse from the fibre sur-
face to the lignin reaction sites inside the
fibre wall. This can be verified by applying
the steady-state diffusion-reaction solu-
tion for a catalyst [13] to that of oxygen
delignification of a fibre wall. This pseudo
steady-state analysis is allowed because the
characteristic time scale for delignifica-
tion (of about an hour) is orders of mag-
nitude larger than that of diffusion
through the fibre wall (about 0.01 sec-
onds). The characteristic time for diffu-
sion in the fibre wall is estimated as W
2
/
(ECCSA D), where W is the fibre wall
thickness (3 10
6
m), D is the bulk diffu-
sion coefficient of oxygen in alkaline
liquor of 95C (1.32 10
-8
m
2
/s), and
ECCSA is the so called Effective Capillary
Cross Sectional Area (0.07, see reference
[12]), which accounts for the tortuosity
and limited open area for diffusion in the
fibre wall. Therefore, the diffusion limita-
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FIG. 2. Development of kappa number in the tower as a
function of mass transfer rate.
FIG. 4. Normalized delignification vs oxygen pressure.
FIG. 3. Normalized delignification vs pulp consistency.
FIG. 5. Normalized delignification vs temperature.
k
L
a(s
1
) 0.002 0.004 0.006 0.01 #
Kappa leaving tower 20.33 18.50 17.80 17.25 16.45
Delignification in tower (%) 22 29 32 34 37
(Delignification in tower)
K
L
a
59 79 86 92 100
(Delignification in tower)
K
L
a=infinity
TABLE III. Degree of delignification achieved in the tower.
tion in the fibre wall is negligible when the rate of oxygen con-
sumption by reaction is an order of magnitude smaller than the
rate of oxygen diffusion into the fibre, or when [13]:
(r
O
2
)W
2
M
W
= $ 0.15 (12)
(ECCSA)D(c
O
2,sat
)
where M
W
is the non-dimensional Weisz Modulus and (r
O
2
) is
the oxygen consumption rate per unit volume of fibre wall
(moles O
2
/L fibre wall/s). The saturated oxygen concentration,
C
O
2,sat
, at 95C and oxygen pressure of 120 psia is 6.363 10
3
moles O
2
/L liquid. The highest value of (r
O
2
) occurs at the
start of delignification, and can be calculated as:
1.5b
1
dK
(r
O
2
) = %
fw

(13)
32 dt t =0
where
fw
is the fibre wall density (0.46 kg pulp/L swollen fibre
wall) taken for softwood pulp. At the base case conditions (see
later; NaOH charge of 2%, 26 kappa pulp, 95C and an oxygen
pressure of 120 psia), the value for (r
O
2
) is 1.611 10
4
moles
O
2
/L fibre wall/s). Insertion in equation (12) gives a Weisz
Modulus, M
T
, of 2.5 10
4
, which is three orders of magnitude
smaller than 0.15. Therefore the intra-fibre diffusion resistance
is insignificant for oxygen delignification as was shown earlier by
Hsu and Shieh [14].
RESULTS, DISCUSSION
Base Case and Range of Operating Variables: The high shear
mixer and tower were simulated for a softwood line of 1,000
oven-dry tonnes/day (odt/d), a mixer with internal volume of
50 liter (resulting in a mixer residence time of 0.3-0.4 seconds),
and a tower of 3.8 m internal diameter and hydraulic height of
38 m, giving a residence time of about 60 minutes. The incom-
ing kappa number was chosen as 26, and the void fraction, X
g
,
in tower was fixed at 0.1. The temperature in the tower and mix-
er was assumed constant. This ignores the small temperature
increase in the tower of about 2-3C due to the exothermic re-
actions occurring during oxygen delignification. The base case
and range of the five operational variables are shown in Table I.
The parameters that were investigated in the simulation are
the power dissipation per unit volume of the mixer ("), and the
mass transfer rate in the tower (k
L
a). Two values of " were used:
1 10
6
and 1 10
7
W/m
3
. These values are within the range
quoted for industrial high shear mixers [15]. The range of k
L
a
in the tower was taken as 0.002 to 0.01 s
1
, based on laboratory
measurements by Rewatkar and Bennington [1].
Effect of Mixer Operation on Oxygen Dissolution and Pulp De-
lignification: The effect of the power dissipation, ", of the mix-
er on the development of the fractional oxygen saturation,
c
O
2
/c
O
2,sat
, in the tower for the base case with k
L
a = 0.004 s
1
is
shown in Fig. 1A and 1B. It can be seen that the effect of increas-
ing " by an order of magnitude, from 1 10
6
and 1 10
7
W/m
3
,
leads to a noticeable increase in dissolved oxygen concentration
during the first minutes of retention time (see Fig. 1A). How-
ever, at the outlet of the tower after a retention time of about 57
minutes, the difference is negligible (Fig. 1B). Even more
important, in terms of delignification the 10-fold increase in
mixer power leads to a negligible decrease in kappa number at
the outlet of the tower from 18.50 to 18.46.
The effect of the power dissipation of the mixer is shown in
Table II. It can be seen that the dissolved oxygen concentration
in the mixer, c
O
2,out
, increases almost linearly with the power
increase, but that even for " = 1 10
7
W/m
3
, the fractional sat-
uration, F
s
, is still only 0.141, or 14.1% of the saturated oxygen
concentration at the base case conditions. In other words the
mixer is not very effective in dissolving oxygen, even at the high-
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Pulp & Paper Canada T 334 104:12 (2003) 99
FIG. 6. Normalized delignification vs alkali charge. FIG. 7. Normalized delignification vs oxygen charge.
Mixer or Mixer Mixer Tower Mixer Tower
Tower #1 #2 #1 #3 #2
Inlet Pressure n.a. n.a. 163 n.a. 120
(psia)
Outlet Pressure 165 165 120 123 70
(psia)
Inlet Temperature n.a. n.a. 179 n.a. 207
(F)
Outlet Temperature 179 179 183 207 212
(F)
Oxygen Charge 1.5 0.5 n.a. 0.0 n.a.
(%)
NaOH Charge 3.6 0.0 n.a. 0.0 n.a.
(%)
Power Con- 75 73 n.a. 77 n.a.
sumption (hp)
Volume (m
3
) 0.040 0.040 137 0.040 379
Internal Diameter n.a. n.a. 2.44 n.a. 3.745
(m)
Hydraulic Height n.a. n.a. 29.3 n.a. 34.4
(m)
Mill Outlet 22 15
Kappa
Mill Outlet 29 22
Viscosity (cP)
TABLE IV. Simulation input and mill performance data.
est power input. The fractional uptake, F
u
,
which is the ratio of the amount of oxygen
dissolved plus reacted in the mixer rela-
tive to the amount of oxygen charged, is
again one order of magnitude smaller
than F
s
. The significance of this result is
that at best about 1% of the charged oxy-
gen is consumed or dissolved in the pulp
suspension in the mixer, and that essen-
tially all the gas volume charged is still
present at the inlet of the tower.
Another non-dimensional ratio listed
in Table II is F
r
. It is the ratio of the
amount of oxygen reacted relative to the
amount of oxygen dissolved in the mixer.
The small values show that the consump-
tion of oxygen by delignification reactions
can be neglected compared to the
amount dissolved in the pulp suspension.
This means that the amount of delignifi-
cation that takes place in the mixer is triv-
ial, as confirmed by the values of the
change in kappa number across the mix-
er, (Kappa)
mixer
, listed in Table II. The
over-all conclusion based on the present
simulation is that the mixer is neither a
reactor nor a device that dissolves oxygen
in the pulp suspension. It is interesting to
note that in the review of industrial delig-
nification systems by Bennington and
Pineault [3], where all major mixers were
represented, it was also found that despite
a wide range of gas void fractions (0.06 <
X
g
< 0.23) and power dissipation, there
was no trend observed in delignification
efficiency.
It has been reported by Bennington
[15] that a flow of fine bubbles intro-
duced in a pulp suspension of 14.1% con-
sistency flowing through a 30.5-cm-diame-
ter pipe coalesce to 10 cm bubbles after
passing through a downstream valve. A
similar observation of gas separation from
the pulp suspension was made for an
operating mill. Thus, since the quality of
the gas distribution may also not be main-
tained after the mixer, the question must
be asked whether the importance of the
gas mixer for efficient industrial oxygen
delignification has been much overstated.
However, it is clear that most of the oxy-
genation and essentially all the delignifi-
cation of the pulp suspension must occur
in the retention tower.
Effect of Tower Operation on Oxygen
Dissolution and Pulp Delignification: Sim-
ulation of the tower operation was per-
formed for the base case, " = 1 10
6
W/m
3
, and different values of k
L
a of 0.002
to 0.01 s
1
, selected based on laboratory
measurements by Rewatkar and Benning-
ton [1]. The development of the kappa
number in the tower at the different mass
transfer rates is shown in Fig. 2. It can be
seen that the kappa number of the pulp
entering the tower is indistinguishable
from the value of 26 entering the mixer.
Furthermore the figure shows that over
the range of values of k
L
a reasonable de-
lignifications are obtained after almost 60
minutes retention time. Also shown in
Fig. 2 is the kappa development for k
L
a
of infinity (actually a very large value of
10 s
1
). This line represents the situation
whereby there is no mass transfer limita-
tion for oxygen, i.e., the delignification is
purely controlled by chemical kinetics. It
can be seen that this curve displays the
characteristic behaviour of a continuously
decreasing rate of delignification as time
progresses. On the other hand, the shape
of the delignification curves for the values
of k
L
a of 0.002 to 0.01 s
1
display a small
inflexion point at roughly 5 minutes re-
tention time, signifying that initially in the
tower the delignification rate increases up
to about 5 minutes and then decreases.
This can be explained by the fact that ini-
tially the delignification rate is small be-
cause the liquid is not yet oxygenated.
This initial increase in dissolved oxygen
concentration is clearly seen in Fig. 1A.
The effect of k
L
a on the degree of de-
lignification achieved in the tower for the
base case is summarized in Table III. Table
III shows that at a k
L
a value of 0.004 s
1
,
the delignification in the tower is 79% of
that when there is no mass transfer limi-
tation. Therefore, these simulations sug-
gest that a value of k
L
a of 0.004 s
1
for
mass transfer in the tower may explain
why industrial oxygen delignification sys-
tems operate on average about 20% below
their delignification potential as indicated
by Rewatkar and Bennington [1].
Effect of Mass Transfer Rate in the Tow-
er on the Delignification: The tower mass
transfer rate, k
L
a, was varied from 0.002 to
0.01 s
1
. The results are displayed in Figs.
3-7 as the drop in kappa number achieved
in the tower, K
0
-K
top
, normalized with
respect to the kappa number drop
achieved in the tower at the base case con-
ditions (see Table I) when there are no
mass transfer limitations (i.e. when k
L
a
is infinite). The independent variable
in each of these figures is one of
the major operating variables, while k
L
a is
the parameter.
It can be seen in Fig. 3 that the delig-
nification increases significantly when the
consistency is increased from 8 to 14%.
The main reason for this is that the resi-
dence time of the pulp in the tower in-
creases almost linearly with consistency
(see equation (7)). Also the effect of in-
creasing mass transfer becomes more pro-
nounced at higher consistency.
The effect of oxygen pressure at the
bottom of the tower is shown in Fig. 4.
The delignification increases strongly with
increasing pressure because the oxygen
concentration in the liquid phase increas-
es (almost linearly at the lowest k
L
a) with
increasing oxygen pressure. The impact
of improved mass transfer is greatest at
the lowest oxygen pressures.
The influence of increasing the tem-
perature in Fig. 5 is most pronounced at
the highest mass transfer rate studied of
k
L
a equal to 0.01 s
1
. This can be under-
stood because at this condition the delig-
nification is mostly determined by intrin-
sic chemical kinetics, which increase
exponentially with temperature (see equa-
tion (6)).
The effect of alkali charge in Fig. 6 is
also significant, although not as large as
that of temperature in Fig. 5. In both
these figures it can be seen that the rela-
tive impact of the mass transfer rate in-
creases with increasing temperature and
alkali charge. The explanation is that the
relative saturation level of oxygen, F
s
,
becomes smaller because the more rapid
consumption of the oxygen increases the
driving force for transfer of oxygen from
the gas to the bulk of the liquid.
Figure 7 shows that the oxygen charge
has no effect on the relative delignifica-
tion. This is expected because of the mod-
el assumption that the gas void fraction in
the tower, X
g
, is constant at 0.1, irrespec-
tive of operating conditions. Thus the
only effect of a larger oxygen charge is
that the residence time of oxygen in the
tower becomes smaller. In all the simula-
tions sufficient oxygen was charged to
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100 104:12 (2003) T 335 Pulp & Paper Canada
k
L
a (sec
1
) k
L
a (sec
1
) k
L
a (sec
1
)
0.004 0.01 infinite
Mixed Gas Residence Kappa Fractional Kappa Fractional Kappa Fractional
reactor holdup time out Saturation out Saturation out Saturation
Sequence (%) (%) (%)
Mixer 1 0.114 0.39 33.99 0.461 33.99 0.461 33.99 0.461
sec
Mixer 2 0.146 0.38 33.98 1.3 33.98 1.3 33.98 1.3
sec
Reactor 1 0.1 25.81 27.25 31.5 24.67 61.7 22.52 100
min
Mixer 3 0.184- 0.359 27.24 42.7 24.66 75.3 22.51 100
0.19 sec
Reactor 2 0.1 65.395 16.42 40.7 13.74 77.1 12.53 100
TABLE V. Simulation results and actual mill performance data.
meet the stoichiometric demand for delig-
nification. Bennington and Pineault [3]
found that the delignification decreased
with increasing oxygen charge.
In summary, the results in Figs. 3-7
show that the delignification increases
with increase of all the major operating
variables, except for the oxygen charge.
The largest impact of improving the mass
transfer rate in the tower is obtained at
high consistency, temperature and alkali
charge and at low pressure.
Simulation of Industrial Two-Stage Delig-
nification: The two stage delignification
system at Irving Pulp and Paper, Saint
John, NB, was simulated for softwood
kraft pulp to validate the program. The
pulp is fed to two oxygen mixers in series,
followed by the first retention tower oper-
ating at high pressure and a relatively low
temperature. Subsequently the three-
phase (gas/pulp/liquor) slurry passes
through a third mixer followed by the sec-
ond retention tower operating at lower
pressure and high temperature. All the
alkali is added up front, while the oxygen
charge is distributed over the first two
mixers. No extra oxygen is added in the
third mixer. The inlet conditions are:
pulp feed rate of 850 odt/d, 10.5 % con-
sistency, kappa number of 34 and pulp vis-
cosity of 39cP.
The input data for the simulation and
the actual mill performance in terms of
kappa number and pulp viscosity are listed
in Table IV. The gas void fraction, X
g
, was
assumed to be 0.1 in both towers. The val-
ue of k
L
a in the towers was varied from
0.004 s
1
to infinity. Although not listed in
Table IV, the simulation also accounted for
delignification in 18.6 m
3
piping volume
before the first tower and in 15.1 m
3
pip-
ing volume between the first and second
tower. Furthermore, the simulation con-
sidered an extra alkali charge of 0.23%
associated with black liquor carry-over.
The results of the simulation are
shown in Table V. It can be seen that the
fractional saturation of the liquor with
oxygen after the first two mixers is very
low, only 1.3% of the saturation value.
Similarly, the delignification achieved in
the mixers is negligible. The kappa num-
ber after the first tower decreases with in-
creasing oxygen mass transfer in the tow-
er. When the mass transfer rate, k
L
a, is
infinity, the predicted kappa number of
22.52 approaches the measured value of
22. This suggests that the k
L
a value of the
first tower is very high and/or the initial
delignification kinetics of Iribarne and
Schroeder [9] are not representative for
this particular pulp. A high value of k
L
a is
consistent with good mass transfer char-
acteristics resulting from the large
height/diameter ratio of 12 for this tower.
Also the value of X
g
of 0.146 after the sec-
ond mixer is only slightly larger than 0.1
assumed for the tower. This leads to a
modest relative velocity between oxygen
and the pulp suspension, and thus mini-
mizes slugging in the tower. The average
fractional saturation of oxygen in the first
tower increases from 31.5% at k
L
a = 0.004
s
1
to 100% at k
L
a = #.
The simulation predicts that the major-
ity of the delignification occurs in the
second tower, despite the fact that the in-
trinsic delignification rate decreases sig-
nificantly with decreasing kappa number.
The explanation is that the residence time
and temperature in the second tower are
about 60 minutes and 210F, compared to
20 minutes and 181F in the first tower,
respectively. The outlet kappa number of
15 measured by the mill would be pre-
dicted by a k
L
a value in the towers of
between 0.004 and 0.01 s
1
. This is in the
region obtained by Rewatkar and Ben-
nington [1]. Therefore these results show
that the present simulation is able to pre-
dict the delignification of an industrial sys-
tem by accounting for the mass transfer in
the tower(s). However, more information
is needed about k
L
a and X
g
in the towers,
and how these parameters are affected by
design and operating variables. The pre-
diction of the pulp viscosity will be includ-
ed in future simulations.
CONCLUSIONS
The simulation suggests that industrial
oxygen mixers are not effective in dissolv-
ing oxygen, even at the highest power
input. It is also found that most of the
oxygenation and essentially all delignifi-
cation occurs in the retention tower. Since
the gas distribution may not be main-
tained after the mixer, delignification is
mostly determined by tower design and
operating parameters and not by the oxy-
gen mixer.
The simulations show that oxygen
mass transfer limitations in the tower may
explain why industrial oxygen delignifica-
tion systems operate on average about
20% below their delignification potential
as indicated by Rewatkar and Bennington
[1]. It is also shown that delignification in-
creases with all operating variables, except
oxygen charge.
For softwood kraft pulp the delignifi-
cation is reasonably well predicted for the
two-stage delignification system at the Irv-
ing mill in Saint John, NB. However,
more information is needed about k
L
a
and X
g
in the towers, and how these para-
meters are affected by design and operat-
ing variables.
LITERATURE
1. REWATKAR, V.B., C.P.J. BENNINGTON. Gas-Liquid
Mass Transfer in Pulp Retention Towers. Proc., TAPPI
International Pulp Bleaching Conference, 171-180
(2002).
2. BERRY, R.M., Z-H. ZHANG, M. FAUBERT, B. VAN
LIEROP, G. SACCIADIS. Recommendations from
Computer Modeling for Improving Single Stage Oxy-
gen Delignification Systems. Proc., PAPTAC Annual
Conference, Montreal, QC, B151-B161 (2002).
3. BENNINGTON, C.P.J., I. PINEAULT. Mass Transfer
in Oxygen Delignification Systems: Mill Survey Re-
sults, Analysis and Interpretation. Pulp Paper Can.
100(12): T395-T402 (December 1999).
4. BENNINGTON, C.P.J., G. OWUSU, D.W FRANCIS.
Gas-Liquid Mass Transfer in Pulp Suspension Mixing
Operations. Can. J. Chem. Eng 75:53-61 (1997).
5. REWATKAR, V.B., C.P.J. BENNINGTON. Gas-Liq-
uid Mass Transfer in Low and Medium Consistency
Pulp Suspensions. Can J. Chem.Eng 78:504-512 (2000).
6. KOVASIN, K., P. UUSITALO, M. VIILO. Dimen-
sioning of Oxygen Delignification Reactor. Inter-
national Oxygen Delignification Conference. Atlanta:
TAPPI Press, 223-230 (1987).
7. AGARWAL, S.B., B.J.W. COLE, J.M. GENCO. Medi-
um Consistency Oxygen Delignification Kinetics and
Reactor Design. AICHE Symposium Series 94(319): 32-
46 (1998).
8. OLM, L., A. TEDER. The Kinetics of Oxygen
Bleaching. Tappi J. 62(12): 43 (1979).
9. IRIBARNE, J., L.R. SCHROEDER. High- Pressure
Oxygen Delignification of Kraft Pulps. Tappi J. 80(10):
241-250 (1997).
10. VIOLETTE, S. Oxygen Delignification Kinetics
and Selectivity Improvement. Ph.D. Thesis, University
of Maine, Orono (2003).
11. TROMANS, D. Modeling Oxygen Solubility in
Bleaching Solutions. Proc., PACWEST Conference,
Whistler, BC (1999).
12. ZHANG, X.G., Y. NI, A.R.P. VAN HEININGEN.
Effect of Consistency on Chemical Pulp Ozonation;
Calculation of the Effective Capillary Cross-Sectional
Area (ECCSA) and Tortuosity () of the Fibre Wall.
Fifth European Workshop on LignoCellulosics and
Pulp, Aveiro, Portugal, 413-416 (1998).
13. LEVENSPIEL, O. The Chemical Reactor Omni
Book. Corvallis, OR: OSU Book Stores Inc., (1993).
14. HSU, C.L., J.S. HSIEH. Reaction Kinetics in Oxy-
gen Bleaching. AICHE J. 34(1), 116-122 (1988).
15. BENNINGTON, C.P.J. Mixing and Mixers. Pulp
Bleaching: Principles and Practice. Atlanta: TAPPI Press,
537-568 (1996).
PERFORMANCE EVALUATI ON
Pulp & Paper Canada T 336 104:12 (2003) 101
Reference: VAN HEININGEN, A., KROTHAPALLI, D., GENCO, J., JUSTASON, A. A chemi-
cal reactor analysis of industrial oxygen delignification Pulp & Paper Canada 104(12): T331-336
(December, 2003). Paper presented at the 89th Annual Meeting in Montreal, QC, on January 28
to 30 2003. Not to be reproduced without permission of PAPTAC. Manuscript received on April
21, 2003. Revised manuscript approved for publication by the Review Panel on May 13, 2003.
Keywords: DELIGNIFICATION, OXYGEN, KINETICS, MODELS, CHEMICAL REACTORS,
SODIUM HYDROXIDE, SIMULATION, PRESSURE, CONSISTENCY, TEMPERATURE, MASS
TRANSFER, MIXERS, PERFORMANCE EVALUATION.
Rsum: La dlignification loxygne industrielle est modlise en tenant compte du trans-
fert de masse de loxygne, de la cintique de la dlignification loxygne, et de la performance
du mlangeur. Lefficacit de la dlignification est calcule en fonction de la charge de NaOH et
de la charge doxygne ainsi que de la pression, de la concentration et de la temprature. La sim-
ulation est soumise lessai en comparant les prdictions lexploitation relle en usine dun sys-
tme de dlignification loxygne en deux tapes chez Irving Pulp and Paper, de Saint John, NB
avec de la pte kraft de rsineux.