U.S. patent application number 10/595860 was filed with the patent office on 2009-04-30 for method for oxygen delignification of cellulose pulp at high pressure in several steps.
Invention is credited to Lennart Gustavsson, Martin Ragnar, Jonas Saetherasen, Vidar Snekkenes.
Application Number | 20090107642 10/595860 |
Document ID | / |
Family ID | 34102164 |
Filed Date | 2009-04-30 |
United States Patent
Application |
20090107642 |
Kind Code |
A1 |
Snekkenes; Vidar ; et
al. |
April 30, 2009 |
METHOD FOR OXYGEN DELIGNIFICATION OF CELLULOSE PULP AT HIGH
PRESSURE IN SEVERAL STEPS
Abstract
The method is for the improved oxygen delignification of
cellulose pulp with a medium consistency of 8-16%. The fraction of
dissolved oxygen can be maintained at a high level throughout the
process by the use of high pressure, greater than 15.0 bar, and by
repeated agitative mixing while maintaining the high pressure, such
that as large a fraction as just over 20% of the total oxygen added
is dissolved in the fluid phase, and such that the amount of oxygen
in the fluid phase is maintained at a high level throughout the
complete high pressure section. By the establishment of retention
times between the remixing operations with successively increasing
retention times, while retaining a high pressure, an optimal
adaptation of the remixing is obtained at the time at which a
certain fraction of the oxygen dissolved in the fluid phase has
been consumed.
Inventors: |
Snekkenes; Vidar; (Karlstad,
SE) ; Saetherasen; Jonas; (Hammaro, SE) ;
Gustavsson; Lennart; (Karlstad, SE) ; Ragnar;
Martin; (Karlstad, SE) |
Correspondence
Address: |
JAMES EARL LOWE, JR.
15417 W NATIONAL AVE # 300
NEW BERLIN
WI
53151
US
|
Family ID: |
34102164 |
Appl. No.: |
10/595860 |
Filed: |
September 20, 2005 |
PCT Filed: |
September 20, 2005 |
PCT NO: |
PCT/SE05/01366 |
371 Date: |
May 17, 2006 |
Current U.S.
Class: |
162/17 |
Current CPC
Class: |
D21C 9/147 20130101 |
Class at
Publication: |
162/17 |
International
Class: |
D21C 3/02 20060101
D21C003/02 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 30, 2004 |
SE |
0403222-3 |
Claims
1. A method for continuous alkali oxygen delignification of
digested cellulose pulp and of cellulose pulp that has been washed
after digestion, comprising: storing pulp in a storage tower or
pulp chute at essentially atmospheric pressure, maintaining the
pulp at a medium consistency in a range of 8-16%, maintaining the
cellulose pulp to be delignified at a kappa value of at least 15
units, the oxygen delignification taking place in a reactor system
with several oxygen reactors with a predetermined retention time of
the cellulose pulp in the reactor system, adding alkali to the
cellulose pulp in order to obtain an initial pH exceeding 9.0,
adding oxygen to the cellulose pulp at an amount of 5-50 kg per ton
of pulp at a position before a first oxygen reactor in the reactor
system, and providing the pulp with a predetermined total retention
time greater than 45 minutes in the reactor system, in association
with an addition of chemicals and an initial mixing-in operation
for oxygen delignification, placing the cellulose pulp under
pressure in a high pressure section of the reactor system at an
initial pressure of greater than 15.0 bar, the pulp passing at
least two reactor volumes with intermediate remixing positions,
setting a final pressure after a final reactor volume at least 13
bar at an end of the high pressure section, where a retention time
t.sub.1 is a retention time in a reactor volume before a first
remixing position M.sub.1 such that, when a number of high-pressure
reactors is X, the retention time is t.sub.1-t.sub.x for each
reactor R.sub.1-R.sub.x such that t.sub.1<t.sub.2<. . .
t.sub.x.
2. The method according to claim 1, wherein the retention times
t.sub.1-t.sub.x in the reactors R.sub.1-R.sub.x in the high
pressure section are expressed as: t.sub.min=1 minute for t.sub.1,
after which (t.sub.x2*t.sub.x-1) and T.sub.max=X*10 minutes;
(t.sub.1=1-10 min., t.sub.2=2-20 min.; t.sub.3=4-30 min.;
t.sub.4=8-40 min.), where t.sub.x<t.sub.x+1,
3. The method according to claim 2, wherein oxygen is added to the
cellulose pulp immediately after the initial pressure of more than
15.0 bar has been established.
4. The method according to claim 3, wherein the pressure of the
pulp is reduced after the high-pressure section to a pressure that
lies under 10 -12 bar, and the pulp is heated by steam such that
the temperature of the pulp is raised by at least 5.degree. C. by
the addition of steam, followed by the heated pulp being led to a
reactor system in a low pressure section with a retention time that
exceeds the retention time in the high pressure section.
5. The method according to claim 4, wherein the remixing positions
are constituted by fluidizing mixers, either in a form of a
fluidizing pump, a fluidizing restriction, a fluidizing mixer or a
restriction in a flow that results in a fall in pressure of less
than 1 bar.
6. The method according to claim 1 wherein a stirrer is present in
at least one high pressure reactor, which stirrer acts in the
principal part of the reactor volume, either in a form of a
mechanical stirrer (S) or hydrodynamic stirrers that at least
circulate free fluid in the reactor.
7. The method according to claim 1 wherein at least one of the
oxygen and alkali additions are added to the cellulose pulp in
association with the remixing positions in the high pressure
section at an amount that is lower than the amount that is added at
the initial mixing-in operation, and at least one of the oxygen and
alkali additions are added batch-wise at a beginning of the low
pressure section.
8. The method according to claim 1 wherein the cellulose pulp is
dewatered before the oxygen delignification to a higher consistency
and the cellulose pulp is rediluted before the oxygen
delignification to a medium consistency with pure filtrate that has
been previously oxidized, and alkali in a form of oxidized white
liquor is used in the oxygen delignification.
Description
THE PRIOR ART
[0001] The first system with two-stage oxygen delignification was
tested in Moss in Norway, and the first commercial two-stage system
with remixing between the stages was subsequently implemented at
Tomakomai mill in Japan, the results of which were reported in the
Tappi Proceedings Sep. 8-10, 1992, Japan-Tokyo, pp. 23-31. The
principal aim of this remixing between the stages, between the
reactions, was to finely distribute residual chemicals in the pulp
suspension and to break up any large gas bubbles to finely divided
gas bubbles. Kvaerner Pulping (under its name at the time of "Kamyr
AB") took part in both of these systems, the one at Moss and the
one at Tomakomai, as supplier of MC-mixers and MC-pumps.
[0002] One of the first patents covering two-stage oxygen
delignification is displayed in U.S. Pat. No. 5,217,575, owned by
Kvaerner Pulping AB, where the principles of using an active
heating before the second stage are reported. It is there described
in figures that improved delignification is obtained through
successively increased external heating between the stages or
reactions, where the patent protects a more than approximately 20
degrees higher temperature in a second reactor. This, naturally,
excludes the exothermic heating that the oxygen reaction gives rise
to of itself. Typically, an exothermic reaction takes place, which
gives a temperature increase of 5-8.degree. C. in the region of
medium consistency, given an input kappa value of 25-30 units,
which exothermic reaction is thus not included. It is specified in
U.S. Pat. No. 5,217,575 that a pressure of approximately 5 bar is
established in the two reactors, which creates, in practical
application in such systems having only one pump before the first
reactor, a pressurisation of 5-8 bar in the first reactor and a
pressurisation of 4-6 bar in the second reaction due to the large
fall in pressure through the system that is caused by the viscously
flowing pulp of medium consistency. A fall in pressure of 0.05-0.1
bar per meter of pipe is typically developed in these systems. The
second mixer between the reactors was primarily intended to provide
a remixing of residual chemicals and thus not necessarily with the
addition of further chemicals, where the second stage becomes more
of an extended alkali extraction with residual chemicals from the
first stage.
[0003] A later system is revealed through, for example, the patent
SE505141 (equivalent to U.S. Pat. No. 6,221,206; U.S. Pat. No.
6,319,357 and U.S. Pat. No. 6,454,900) in which at least 25 kg of
alkali and 25 kg oxygen per tonne of pulp is to be initially added
batchwise in a system with two reactors placed in series. Only one
remixing takes place between the reactors, but this may take place
with the addition of a small amount of alkali. A higher pressure is
established in the first reactor in these systems with a highest
specified pressure of 10 bar and a lower pressure of a maximum of 5
bar in the second reactor. The same applicant, Sunds Defibrator,
now named "Metso Paper", has demonstrated in the subsequent patent
SE 510740 (equivalent to U.S. Pat. No. 6238517) a second variant
with 4-15 bar in the first reactor and 2-5 bar in the second
reactor, and the applicant has described a third and a fourth
variant in SE 507871 and SE 507870 with 3-10 bar in a first reactor
of upward flow and less than 2 bar in a second reactor of downward
flow. It can be seen from this plethora of variants from the same
applicant that the applicant has not realised the significance of
the maintained high pressure in a second reactor following a
remixing.
[0004] The maximal pressurisation of 12 bar follows the theories
that have been adhered to by, for example, Metso Paper, and that
are presented by Olm and Teder (Tappi Proceedings Seattle, 1979,
pages 169-179), in which it is reported that no advantageous
effects can be demonstrated at a higher pressure than 10-12 bar. It
must, however, be mentioned that these theories were established
principally after laboratory experiments in which autoclaves were
used in which only a small amount of pulp was bleached in a pulp
specimen that was placed in the autoclave and rotated continuously
or, laboratory mixers have been used that have contained a small
amount of pulp specimen under continuous stirring and often under
continuous pressurisation with externally added oxygen (something
that creates an unlimited access to oxygen).
[0005] Theories are presented in the patents WO97/17489 (STORA) and
U.S. Pat. No. 3,725,194 (SAPPI) concerning the positive effect of
applying high pressure during the oxygen delignification with the
aim of increasing the amount of oxygen that, at least initially,
can be dissolved in the liquid phase. A pressure of 15-20 is
applied in STORA's application, while SAPPI's patent describes
pressures of up to 400 psi (approximately 27 bar). Also these
solutions attempt to achieve an improved delignification in which
the fraction of oxygen that is dissolved in the fluid phase is
high.
[0006] A specific sequence O-C/D-O-D is patented in another patent,
SE 369746. The first and the second oxygen stages in this sequence
are carried out very aggressively at a pressure of 14 bar and
temperatures of 119.degree. C. and 130.degree. C.,
respectively.
[0007] A two-stage oxygen delignification is described also in EP
865531, where repeated mixing takes place between reactors. It is,
however, specified in this case that the pressure lies within the
interval from 20 psig to the maximum pressure of 180 psig (i.e.
from 1.37 to 12 bar). The significance of repeated mixing at high
pressure in order to optimise the fraction of dissolved oxygen has
not been recognised at all here. A mixer followed by a reactor
provided with a stirrer is shown in a variant shown in FIG. 4 of
the patent, which stirrer can contribute to a repeated stirring
effect in the reactor.
[0008] A process is suggested also in Camilla Roost's thesis, The
Impact of Extended Oxygen Delignification on the Process Chemistry
in Kraft Pulping, ISSN 1652-2443, May 2004, with two oxygen
reactors in which an optimisation has been attempted of the
two-stage technology according to U.S. Pat. No. 5,217,575 with
heating between the stages, and in this way a powerful
delignification system in which a pressure of 16 bar is established
in the first reactor and a pressure of 6 bar has been established
in the second reactor has been seen. Pressures of 6, 10 and 16 bar
in the first reactor have been tested during the optimisation, and
it has proved to be the case that the pressure, together with the
addition of alkali, is one of the most dominant parameters for good
delignification.
[0009] Other solutions have been presented with repeated remixing
during oxygen delignification. A system with three mixers in
series, in which a pressure of 120 psig (approximately 8.2 bar) is
established, is described in U.S. Pat. No. 5,460,696. The aim in
this case is to reduce a pH that is far too high if all alkali is
added batchwise at the beginning, and the repeated mixing takes
place with the aim of mixing alkali in gradually, as the alkali is
consumed.
[0010] Three mixers in sequence are shown in U.S. Pat. No.
4,384,920 and U.S. Pat. No. 4,363,697, where these mixer stations
are constituted by horizontal reactors with an internal feed screw
and stirring screw. The pulp is fed through the horizontal reactors
while a gas phase is established at the roof of the reactors. These
systems are clearly run at a moderate excess pressure.
[0011] A system is shown in U.S. Pat. No. 4,259,150 in which the
pulp is led directly from the digester, while maintaining full
digester pressure, through four mixers in series, for the addition
of oxygen. In-line drainers are used in this case to drain off
fluid with precipitated organic material, and this has the result
that the concentration successively rises. This system, however, is
very expensive since large quantities of oxygen are required since
the pulp suspension on exit from the digester contains a very large
fraction of oxidisable organic material in the fluid phase, and
significant amounts of fibre bundles for which the fibre removal
process, the digestion process, is incomplete, and the bundles have
a high content of lignin, accompany the pulp since no straining
operation precedes the oxygen treatment, which bundles of fibres
consume large quantities of oxygen. It is here claimed that it is
possible to adjust the digestion process such that the digested
pulp obtains an increased kappa value around 70, rather than the
normal value of 35, after which delignification can take place down
to a kappa value of 15. An improved selectivity can be obtained in
this manner, i.e. it is possible to reach the same kappa value but
with a higher pulp strength. This process is not one that has been
driven to a great degree, since most of the oxygen delignification
stages in the bleaching line act on cellulose pulp that has an
input kappa value of this level.
[0012] There have been executed innumerable experiments in which it
has been attempted to drive the delignification at medium
consistency further than what it has become clear is possible to
achieve in a mill environment. Verification of new processes often
takes place in laboratories using autoclaves or laboratory mixers,
which (in contrast to the continuous processes in a mill) often
takes place under continuous stirring of the pulp specimen and in
certain cases with pressurisation by oxygen from an external
source, which ensures an excess of oxygen during the complete
process, and in the presence of saturated oxygen in all parts of
the treated pulp specimen. It is often therefore possible to drive
the oxygen delignification further in laboratory specimens than in
a mill environment.
[0013] The mixing of the chemical, oxygen and alkali, has been
considered by some to be significant, and several solutions involve
at least one of the establishment of a high pressure and the
addition of surfactants in order to maintain the finely distributed
gas phase evenly distributed throughout the cellulose pulp during
the process. Theories have been presented in which a maximal
contact area is to be maintained between the gas phase and the
fluid phase, something that can take place through minimising the
size of the finely divided gas bubbles, such that the dissolving of
the oxygen in the gas phase into the fluid phase can be promoted
over a maximised transition surface. The physical process in which
the oxygen is dissolved proceeds, however, relatively slowly
compared with the rate of consumption of oxygen during the first
phases of the reaction, and it requires that the fluid phase that
locally surrounds the oxygen bubble has a lower level of dissolved
oxygen than is theoretically possible in the process conditions
that are prevalent. The oxygen is considered, however, to react
primarily with the lignin in the fibre (after the oxidisable
material in the fluid phase has reacted), and that the fluid phase
that has penetrated the fibre is not immediately surrounded by
oxygen bubbles, which ensures that the oxygen that is to react with
the fibre material (and to reduce the kappa value) must first pass
into solution from the gas phase to the fluid phase, and then
diffuse into the fibre in the fluid phase, and that all of this is
to take place without the dissolved oxygen being consumed first by
organic material in the fluid phase. This results in the fibre
having a constant low value of dissolved oxygen with which it can
react, something that is not advantageous for the process.
Aim and Purpose of the Invention
[0014] The present invention intends to improve the oxygen
delignification at medium consistency, in the region of pulp
consistency 8-16%, hereafter referred to as "MC", in a mill
environment such that delignification can be driven as far or
further than what is possible when testing in laboratories. It is
also possible with the invention to maximise in a mill environment
the fraction of dissolved oxygen in the fluid phase and to promote
the penetration of the oxygen-saturated fluid into the fibre if a
very high pressure is maintained, and to subject the pulp to a
repeated mixing at this high pressure.
[0015] The principles that are applied in the invention are the
establishment in a first high pressure section of a pressure that
is greater than the 12-15 bar that has been set in most commercial
systems as the maximum suitable operating pressure, and the
initiation at this higher pressure of remixing effects in the pulp
suspension, with or without the extra addition of chemicals, with
the aim of ensuring that the part of the oxygen that has been
dissolved in the fluid phase is held as high as possible throughout
the complete volume of the fluid and that the fibre is stirred in
this volume of fluid that has been saturated with oxygen such that
the fluid that has been saturated with oxygen can be allowed to
penetrate the fibre in a more effective manner. The remixing
effects are initiated according to the invention in a manner that
is adapted to the decreasing rate of reaction in the
delignification, such that these remixing operations take place
after successively greater retention times in the high pressure
section between the remixing operations.
[0016] It is typical that a pressure greater than 15-20 bar or
higher is established in this high pressure section.
[0017] Other advantages and aims are made clear by the following
description of embodiments.
DESCRIPTION OF DRAWINGS
[0018] FIG. 1 shows schematically a system for oxygen
delignification in which the method according to the invention can
be applied;
[0019] FIG. 2 shows in principle how oxygen is mixed in to be mixed
with the cellulose pulp as finely divided or as a dissolved
fraction during the process as described by FIG. 1;
[0020] FIG. 3 shows how oxygen is consumed in an alternative system
with three remixer positions during the high pressure phase and
with maintained pressure, and with a mixing effect in the final
reactor of the high pressure section;
[0021] FIG. 4 shows how the oxygen is consumed in a further
alternative system with only 14 kg of batchwise added oxygen and
two remixing positions placed close to each other;
[0022] FIG. 5 shows how oxygen is consumed in a two-reactor system
with a high pressure zone and a low pressure zone without repeated
remixing in the high pressure zone.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0023] FIG. 1 shows an oxygen delignification system between a
preceding wash WI and a subsequent wash W.sub.2/W.sub.3, with a
number of reactors R.sub.1, R.sub.2, R.sub.3 and R.sub.4 between
the washes.
[0024] The pulp is passed after the first wash W.sub.1 to an
atmospheric storage tower ST (or to an atmospheric pulp chute).
[0025] It is appropriate that the alkali that must be added
batchwise to the oxygen is added batchwise at the bottom of the
storage tower (NaOH.sub.MAIN) after which all subsequent pumps
(P1/P2) contribute to efficient mixing, since pumps are good mixers
of fluid additions such as, for example, alkali (NaOH).
[0026] The three first reactors R.sub.1, R.sub.2, and R.sub.3 are
part of a high pressure section that establishes its pressure by
two pumps P1 and P2 connected in series. The first pump P1 is a
fluidising MC-pump with degassing, which not only is necessary in
order to fluidise the MC-pulp such that it can be pumped, but also
is used to separate out air (Air) from the pulp, which air
otherwise would influence the process negatively from the point of
view of delignification (not a high level of oxygen or a content of
other residual gases) and reduce the opportunity of pressurising
the pulp in an optimal manner. Also the second pump may be a
fluidising MC-pump, but in this case without degassing, although it
is appropriate that it is a conventional centrifugal pump optimised
for pressurisation, since the pulp has already been fluidised and
degassed by the first pump. It is appropriate that the second pump
has a significantly higher pumping efficiency, normally a pumping
efficiency that lies 10-20% higher than that of the first pump.
[0027] The pumps P1, P2 establish initially in the high pressure
section R.sub.1-R.sub.3 a pressure that lies well over 15.0 bar,
typically in the interval 17-30 bar and preferably in the interval
17-25 bar. The pressure may be higher, but it is limited by
practical considerations to 17-20 bar with two pumps connected in
series. If a pressure level of, for example, 18 bar is to be
established after the pumps P1/P2, a suitable dimensioning and
choice of pumps can be carried out such that the first fluidising
MC-pump P1 establishes a pressure height of 6-8 bar (approximately
30-40%), and the subsequent centrifugal pump establishes a pressure
height of 12-14 bar (approximately 60-70%), i.e. approximately one
third of the total required pressure height is achieved in the
first MC-pump and the remaining pressure height in the second pump.
If a higher pressure is required, several pumps can be connected in
series, where also a third and final pump can be a centrifugal
pump.
[0028] It is preferable that oxygen is added after the
pressurisation by the pumps P1/P2 to the pressurised cellulose pulp
through a principal mixer M1. It is appropriate that the mixer M1
should be a high intensity mixer with retention times of at least
0.1-2.0 seconds, which mixes oxygen evenly into the cellulose pulp
in a powerful shear force field.
[0029] The pressurised pulp is led from the first principal mixer
Ml at a pressure of approximately 18 bar with the oxygen that has
been mixed into it to a first reactor R.sub.1 in which the pulp
flows upwards with a first retention time t.sub.1 in the reactor
R.sub.1.
[0030] After the pulp has passed through the first reactor R.sub.1
the pulp is led to a second remixing location in the form of the
mixer M2. This mixer may be of a simpler type than the principal
mixer M1, and the principal aim is to obtain a remixing effect in
order to increase the dissolved fraction of oxygen and to promote
the penetration of the saturated fluid phase into the cellulose
fibre. The fall in pressure across this mixer is to be kept as low
as possible, preferably well under 1 bar, and the mixer may in its
simplest form be a static mixer, possibly in the form of a
half-closed valve. The mixer M2 may also be a small and simple pump
(with a limited build-up of pressure that corresponds to the fall
in pressure in the pipes and system up to this point), or it may be
an agitation and fluidising mixer.
[0031] The pressurised pulp is led from the second remixing
location by the mixer M2 at a pressure of approximately 17 bar with
its remixed oxygen to a second reactor R.sub.2 in which the pulp
flows upwards with a second retention time t.sub.2 in the reactor
R.sub.2.
[0032] After the pulp has passed the second reactor R.sub.2 the
pulp is led to a third remixing position in the form of the mixer
M3. This mixer may be of the same type as the mixer M2 with the
same aim and the same fall in pressure.
[0033] The pressurised pulp is led from the third remixing location
at a pressure of approximately 16 bar with its remixed oxygen to a
third reactor R.sub.3 in which the pulp flows upwards with a third
retention time t.sub.3 in the reactor R.sub.3.
[0034] The high pressure section ends after the third reactor
R.sub.3 and a controlled and managed reduction in pressure is
thereafter carried out before the concluding low pressure section
in at least one final reactor R.sub.4.
[0035] The reduction in pressure can be implemented through at
least one valve, although it is preferable that several valves
V.sub.1, V.sub.2 and V.sub.3 are used, where it is ensured that the
fall in pressure is kept as low as possible across each valve in
order to avoid large and sudden falls in pressure that risk
unnecessarily the flashing out of gas in the form of large bubbles.
Several valves in series ensures that each valve also provides a
stirring mixing effect in the turbulence that is formed, which
partially counteracts the negative effects of the fall in pressure
by maintaining the oxygen evenly distributed in the form of small
bubbles.
[0036] The low pressure section is, however, to continue to have a
relatively high pressure in order to be able to maintain a finely
distributed residual amount of the oxygen in the cellulose pulp,
but it is to have a sufficiently low pressure such that the pulp
can be heated by the addition of direct steam(MP steam) from the
medium pressure steam network of the mill. The medium pressure
steam in these networks is normally held at a pressure of 10-12
bar, and a positive pressure difference of at least 1-2 bar is
required in order to be able to introduce steam into the pulp. The
pressure difference required depends on the particular mixer M4,
where this medium pressure steam is added to the pulp after the
establishment of the correct pressure following the controlled
pressure reduction after the valves V1-V3.
[0037] It is appropriate that a pressure less than 10-12 bar is
established after the high pressure section, the level being
determined by the pressure in the steam network for medium pressure
steam at the mill, and this pressure after the high pressure
section should be at least 1-2 bar lower than the pressure in this
steam network, with conventional mixing methods for the steam. If
the pressure difference is lower, an arrangement must be used for
the addition of steam in which steam is added into the pulp through
sluices without the risk of the pulp flowing out against the flow
of steam.
[0038] The addition of steam entails the raising of the temperature
of the cellulose pulp by at least 5.degree. C. followed by the
leading of the heated pulp to a reactor system in a low pressure
part, with a retention time t.sub.4 that exceeds the total
retention time (t.sub.1+t.sub.2+t.sub.3) in the high pressure
section.
[0039] The reactors R.sub.1, R.sub.2 and R.sub.3 in the high
pressure section are so dimensioned that the cellulose pulp is
given successively longer retention times for the cellulose pulp,
such that when the number of high pressure reactors is X, then the
retention time for the reactors t.sub.1-X is such that
t.sub.1<t.sub.2< . . . t.sub.X, where t.sub.1 is the
retention time in reactor R.sub.1, etc. This ensures adaptation to
the reaction process, in the form of consumption of the added
chemicals, something that occurs very rapidly initially and
subsequently falls essentially exponentially.
[0040] Suitable retention times in the reactors R.sub.1 to Rx in
the high pressure section can be approximately expressed as:
t.sub.min=1 minute for t.sub.1, after which (t.sub.X=2*t.sub.x-1)
and t.sub.max=X*10 minutes;
(t.sub.1=1-10, t.sub.2=2-20; t.sub.3=4-30;t.sub.4=8-40 min.,
etc),
where t.sub.X<t.sub.X+1.
[0041] With the aim of further improving the fraction of dissolved
oxygen in the complete fluid volume in the high pressure section, a
stirrer can be placed in at least one high pressure reactor that
acts in the main part of the reactor volume (it is to act in
greater than 50% of the reactor volume), either in the form of a
mechanical stirrer (S) or a hydrodynamic stirrer that at least
circulates free fluid in the reactor. This stirrer may be present,
for example, in the largest reactor in the high pressure section,
or in the reaction in which the consumption is most rapid (which is
the first reactor), or in all reactors. The mechanical stirrer can
be realised in the form of a rotating shaft with arms that extend
radially in the reactor, which stirrer is driven at a rather
moderate rate of revolution of 10-100 rpm and does not exert any
fluidising effect on the cellulose pulp.
[0042] The retention time in the heated low pressure section is
greater than the total time in the high pressure section. Given a
total retention time of at least 3-10 minutes in the high pressure
section, a suitable minimum retention time in the low pressure
section is at least 30 minutes, which gives a total retention time
of at least 40 minutes. The high pressure section for these minimum
conditions can consist of a first reactor with a retention time of
at least one minute, remixing, followed by a second reactor with a
retention time of at least 2 minutes and, after a further remixing,
a final third reactor in the high pressure section with a retention
time of at least 4 minutes.
[0043] The low pressure section may have a retention time in the
interval 30-120 minutes, preferably 60-90 minutes.
[0044] In a plant that delignifies 3,000 tonnes of MC-pulp at a
consistency of 10% every day, the flow through the process is just
over 18 cubic metres per minute. Pipes with a diameter of
approximately 1.2 metres are normally used for such a level of
production, and these contain approximately 1.1 cubic metres per
metre of pipe. A first reactor which has then be implemented in the
form of a single pipe with a retention time of 1 minute will then
be approximately 16 m long. It is often attempted to realise the
reactors as pipes, which is the principal reason for keeping the
retention times in the reactors low. A pipe of length 16 metres can
be formed in the shape of a U-bend in a vertical plane, or it can
be located in a horizontal plane.
[0045] The pressure in the cellulose pulp is released after the low
pressure section at the outlet from the reactor R4 and the pulp is
fed to an atmospheric pulp chute (or to a storage tower) that can
lead off residual gases, after which the pulp from which the
pressure has been released is pumped by pump P3 to the subsequent
washing system, which is shown in FIG. 1 in the form of a pressure
diffuser W.sub.2 and a washing press W.sub.3 placed in series. This
combination can become relevant if very high requirements are
placed on the cleanliness of the pulp, for example, if the pulp is
to be used as packaging for foodstuffs. It is, however, often
sufficient with a single washing machine, and this reduces the
investment costs. Washing filtrate F3 is led in a conventional
manner from the final wash W.sub.3 as washing fluid F2 for the next
to last wash W.sub.2, i.e. the washing filtrate is led as a
countercurrent flow relative to the flow of pulp. The washing
filtrate Fl from the wash W.sub.2 directly after the final reactor
R.sub.4 is led in an equivalent manner to a wash W.sub.1 before the
oxygen delignification as at least one of washing fluid and
dilution fluid for the storage tower ST after this wash W.sub.1.
The pulp that has been subject to oxygen delignification and washed
is then pumped by the pump P5 to subsequent bleaching stages in the
bleaching sequence.
[0046] FIG. 2 shows in principle how oxygen is consumed in a system
as portrayed in FIG. 1, with the amount of oxygen plotted along the
Y-axis and time plotted along the X-axis. The total batch of oxygen
that is added in the mixer M1 is here 20 kg per tonne of pulp,
which batch size lies in the upper region of the interval of 14-20
kg per tonne of pulp that is conventionally added batchwise to a
oxygen delignification stage. It is not normally possible to add
much more than 30-35 kg oxygen per tonne of pulp to a mixing-in
position at a pressure of 12 bar since such large quantities of gas
readily give rise to the formation of channels in subsequent
reactors, something that establishes a central flow through the
reactor with very high speed, and a retention time in the reactor
of only a fraction of the intended retention time. The high
pressure s that is applied according to the invention during the
remixing and in the subsequent reactor results also in the ability
to add greater amounts of gas without the risk of channels forming,
or with a heavily reduced risk of channels forming, compared with
systems having a lower pressure, given the same batchwise addition
of oxygen. The residual quantity of oxygen that has not been
consumed at any moment largely follows the line O.sub.2 RES.sub.TOT
and the consumption is initially very rapid. The symbols I, II and
III denote the retention times in the reactors R.sub.1, R.sub.2 and
R.sub.3, respectively.
[0047] The maximum amount that can be dissolved in the fluid phase
at the prevalent pressure is shown in FIG. 2 by the grey-shaded
region O2 Liq.sub.MAX. At a pressure of 20 bar, at 80.degree. C.
and at pH 10, approximately 0.5 kg of oxygen per cubic metre of
fluid can be dissolved in the fluid phase. (The amount at a
pressure of 10 bar is 0.25 kg). There is 9 cubic metres of fluid
per tonne of pulp at a pulp consistency of 10%, and this means that
a maximum of 4.5 kg of oxygen per tonne of pulp can be dissolved at
a pressure or 20 bar. The amount 4.5 kg of a total batch size of 20
kg is equivalent to as much as 22.5% of the total batch size. The
solubility of oxygen in the fluid phase is relatively low compared
with those of many other bleaching agents, such as chlorine dioxide
and other fluid-phase bleaching agents. The process in which oxygen
passes from the gas phase to the fluid phase is relatively slow,
but it can be accelerated through vigorous agitation in fluidising
mixers. For this reason, thus, the first mixer M1 should either be
a high-fluidising mixer with a relatively short retention time of
0.1-2.0 seconds, which vigorously agitates the mixture of pulp and
gas in an intensive field of shear forces applied in a thin flow
slit, or it should be a more moderate continuous agitation that
occurs for a longer period of 1-10 seconds.
[0048] Given an optimal mixing in the mixer M1, it is possible to
assume that the amount of oxygen that has been dissolved in the
fluid phase lies close to the amount that theoretically can be
dissolved in the fluid phase. The consumption of that amount of
oxygen that has been dissolved in the fluid phase, however, takes
place very rapidly and considerably more rapidly than the
transition of the oxygen from the gas phase to the fluid phase, and
the fraction of remaining dissolved oxygen in the fluid phase
follows the curve O.sub.2 Liq RES for this reason. The oxygen that
is to react with the fibre wall in the cellulose is, therefore,
depleted far too rapidly, and this results in the oxygen
delignification of the cellulose fibre occurring under conditions
that are by no means advantageous. A remixing in the mixer M2 is
for this reason activated, such that it is possible to increase the
fraction of oxygen that is dissolved in the fluid phase. Also this
dissolved quantity is consumed during the period II in the reactor
R.sub.2 and a further remixing with the mixer M3 for this reason
takes place, in order again to increase the fraction of oxygen that
is dissolved in the fluid phase. The oxygen that has been dissolved
by the mixer M3 is subsequently consumed during the period III in
reactor R.sub.3.
[0049] The system in FIG. 1 is of conventional type, and the
pressure thus falls through the system due to pressure loss in
pipes, etc. The pressure falls for this reason in FIG. 1 from
reactor R.sub.1 to R.sub.2 by approximately 1 bar, and it falls
from R.sub.2 to R.sub.3 with approximately 1 bar, exclusive of any
pressure fall that depends on loss of static height. There will
also be a pressure fall of 1 bar in a reactor with a height of 10
metres due to the difference in the static heights of the inlet and
the outlet of the reactor. A high starting pressure of 17 bar thus
gives approximately 16 bar in reactor R.sub.2 and 15 bar in reactor
R.sub.3. The fall in pressure through the high pressure section
(HP) of the system (corresponding to the reactors R.sub.1, R.sub.2,
R.sub.3) is to be minimised since the principle of the invention is
to maintain the pressure at a high level as far as possible
throughout the complete high pressure section HP, and to activate
the remixing operations at a maintained pressure in order to
maintain the fraction of oxygen that has been dissolved in the
fluid phase as high as possible as far as it is practically
possible.
[0050] The pressure in itself is important in order to facilitate
the transition from gas phase to fluid phase since it is possible
to maintain the area of contact between the gas phase and the fluid
phase at a high level if undissolved oxygen (distributed in the
suspension as either visible or invisible foam or bubbles) can be
maintained in the form of small bubbles and counteract the
aggregation of these into large aggregates of gas, which happens
if, among other effects, the pressure is reduced.
[0051] If the gas can be maintained in the form of bubbles with a
diameter of 0.1 mm instead of 1 mm, the area of contact between the
gas phase and the fluid phase can be increased by a factor of 100.
It is also possible to maintain small bubbles distributed through
the complete volume of the suspension, and they can penetrate fibre
walls more easily.
[0052] The pressure is reduced after the high pressure section HP
to a lower level in the low pressure section LP, to a pressure at
which medium pressure steam can be used to heat the pulp suspension
directly. At an appropriate pressure of 10 bar in the low pressure
section, only half of the quantity of oxygen that can be dissolved
at 20 bar can be held in solution. The remaining quantity of oxygen
at this process position, however, is relatively low, due to the
high consumption in the high pressure section. The amount of oxygen
that theoretically can be dissolved at a pressure of 10 bar,
however, does amount to 40-60% of the residual amount of oxygen
that remains, and for this reason it may be the case in certain
systems that it is desirable to add a small amount of further
oxygen before the low pressure section.
[0053] In summary, FIG. 2 shows how the fraction of oxygen
dissolved in the fluid phase can be maintained at a high level by
repeated remixing not only by remixing but also by retaining a high
pressure. Both of these conditions are necessary in order to be
able to dissolve a fraction as high as just over 20% of the total
addition of oxygen and maintaining the amount of oxygen in the
fluid phase at a high level throughout the complete high pressure
section.
[0054] Advantageous conditions for delignification of the fibre
wall at its contact with the fluid phase, which also penetrates
into and between the fibres, are in this way created.
[0055] FIG. 3 shows another variant in which three remixing
positions between four reactors are used, and a stirrer S is also
present in the final reactor, as is shown schematically in FIG. 1.
The same high pressure throughout the complete high pressure
section HP is established in this case, and this may be ensured
where required by mixers at the remixing positions that raise the
pressure. The mixers DUALOMIX.TM. from Kvaerner Pulping AB are
mixers of a type that can give a build-up of pressure in certain
applications (determined by the size and the flow) and with certain
designs of the mixer. It is possible as an alternative to insert
auxiliary pumps between the reactors. In this case, again, 20 kg of
oxygen has been added as a batch at the beginning, but the remixing
operations take place more frequently with shorter and successively
increasing retention times between the remixing positions.
[0056] FIG. 4 shows a variant with an initial batchwise addition of
oxygen of 14 kg, maintained pressure throughout the system and more
frequent remixing operations than in the variant shown in FIG. 2.
Otherwise this variant is the same as that shown in FIG. 2.
[0057] FIG. 5 shows how the oxygen would be consumed if the method
according to the invention were to be not applied in a two-reactor
system with a first high pressure section and a second low pressure
section, i.e. if remixing does not take place in the high pressure
section. The drawing makes it clear that the amount of oxygen
dissolved in the fluid phase falls rapidly to a very low amount,
and delignification of the fibre and the fibre wall takes place for
this reason in conditions that are far from ideal in the latter
part of the high pressure section.
[0058] The main part of the chemicals, both oxygen and alkali,
required is, in principle, to be added before the first reactor,
which quantities of chemicals are such that alkali is added to
obtain an initial pH that lies well over 9.0 and oxygen is added at
an amount of between 5 and 50 kg per tonne of pulp. The particular
amount added depends on the initial kappa value. When using pulp
with an initial kappa value of 40-50 units and with a reduction to
a kappa value of 8-10, the addition of oxygen can amount to 30-50
kg per tonne of pulp, i.e. an effect on the kappa value of 1-2 kg
per .DELTA.kappa and tonne of pulp. If the initial kappa value is
lower, the kappa factor typically lies between 1.5 and 3.0 kg per
.DELTA.kappa and tonne of pulp. Thus the invention is applied in an
oxygen delignification with a kappa factor addition of oxygen that
lies in the region 1.0-3.0 (kg oxygen per .DELTA.kappa and tonne of
pulp).
[0059] Alkali must be added such that the pH is maintained at a
final value of 10-10.5 such that the alkalinity is maintained at a
sufficiently high level during the complete process. This normally
means that 80-100% of the total amount of oxygen is added at the
first mixing-in position, while 70-90% of the total amount of
alkali is added at the same mixing-in position. In certain cases,
in particular primarily in cases in which the total retention time
is short, the complete amount of alkali can be added at this
position.
[0060] Normally, only alkali is added before the low pressure
section principally for long total retention times, together with a
small amount of oxygen if the retention time in the low pressure
section is long. It has proved to be the case in practice that the
vast majority of systems display improved delignification and an
improved strength of the pulp, i.e. an improved selectivity, if a
small amount (typically 10%-40% of the total amount) is added as a
batch at the second stage.
[0061] Adaptation of the strategy for additions takes place
depending on a number of factors, such as: [0062] the initial kappa
value, where a higher initial kappa value may entail a greater
number of addition points for alkali or oxygen; [0063] the total
kappa reduction during the oxygen delignification; [0064] the
current cellulose being used (deciduous wood, conifer wood, heavy
eucalyptus, etc., where short-fibred deciduous wood may require
more frequent or a greater number of remixing positions in the high
pressure section); [0065] the subsequent bleaching stages (the ECF
or the TCF sequence, the use of other alkali bleaching stages of
P-stage type, and the power and the number of alkali extraction
stages of E-/EO-/EOP-type); [0066] the properties desired for the
bleached pulp; [0067] requirements on the COD level of emissions
(this may require more severe conditions in the oxygen treatment
despite reduced selectivity, which may reduce the amount of
chlorine dioxide required in D-stages).
[0068] With the aim of obtaining an optimal effect on the cellulose
pulp, and of not consuming the chemicals on unnecessary organic
material in the fluid phase, the cellulose pulp may be dewatered to
give a higher consistency before the oxygen delignification and it
may be rediluted to a medium consistency before the oxygen
delignification using pure filtrate (filtrate that is obtained from
washing stages after the oxygen delignification or other clean
process water), which has preferably been oxidised before this in
an oxidising reactor Ox.R. The alkali that is added may, for the
same reason, be added in portions or totally in the form of
oxidised white liquor.
[0069] The invention may be varied in a number of ways within the
framework of the invention. For example, types of reactor other
than a tower of upward flow may be used, such as a tower of
downward flow, or simple pipes that have been laid in a horizontal
plane or in a U-bend in a vertical plane.
[0070] Batchwise addition of oxygen may be required at all mixing
positions in the system for certain pulps, such as deciduous wood
pulps, that are difficult to delignify. The use of more than three
reactors with preceding mixing operations for each in the high
pressure section may also be required, as may the use of more than
one reactor in the subsequent low pressure section. However, at
least one remixing position is to be established in the high
pressure section with a predetermined minimum time delay following
a preceding principal mixing position, together with a subsequent
low pressure section having at least one reactor.
[0071] The predetermined time delay between the mixing positions
may be adapted to the current consumption of oxygen dissolved in
the fluid phase or to the total amount of added oxygen, where it is
appropriate that a remixing operation can take place as soon as
possible after more than 30% of the oxygen that has been previously
added has been consumed. The preferred retention times for the pulp
in the reactors R1-R3 that have been specified are, however, useful
guidelines for the vast majority of processes, which guidelines
have been adapted to the rapid consumption at the beginning of the
process, a rate of consumption that gradually declines.
[0072] The invention may also be applied in a delignification
system with a short initial low pressure section in which a small
amount of oxygen, typically considerably less than 40% and
preferably less than 20% of the total that is added to the oxygen
stage, is added before or at the low pressure section with the aim
of oxidising the material that is present dissolved in the fluid
phase. It is possible in this manner to avoid unnecessary
consumption of the oxygen that is added at the subsequent high
pressure section by oxidisable material in the fluid phase, and
ensure a greater fraction being used for delignification of the
cellulose in the high pressure section.
[0073] It is preferable that also oxidised white liquor is used as
addition of alkali.
[0074] Oxygen delignification in a mill environment can be more
readily driven to lower kappa values with the method according to
the invention, and deciduous wood, for example, which in laboratory
trials can be delignified down to a is kappa value of 9, or lower,
can approach this potential reduction in kappa also in a mill
environment. The reduction in kappa value in a mill environment
can, in certain conditions, be improved by up to 3 kappa units
while retaining the strength of the pulp. It is alternatively
possible to obtain the same reduction in kappa value with a
considerably improved pulp strength, or intermediate variants
between these extreme alternatives may be achieved in which both
the strength of the pulp and the reduction in kappa value are
improved. The costs for the operation of the bleaching line, in
particular the costs for further bleaching agents in subsequent
bleaching stages, are considerably reduced if it is possible to
reduce the kappa value by a further 2-3 units in the oxygen
delignification at an early stage of the bleaching line.
* * * * *