U.S. patent application number 11/029732 was filed with the patent office on 2005-08-11 for bleaching of medium consistency pulp with ozone without high shear mixing.
This patent application is currently assigned to Arbozon Oy Ltd.. Invention is credited to De Vos, Rolf, Tikka, Panu.
Application Number | 20050173082 11/029732 |
Document ID | / |
Family ID | 34839849 |
Filed Date | 2005-08-11 |
United States Patent
Application |
20050173082 |
Kind Code |
A1 |
De Vos, Rolf ; et
al. |
August 11, 2005 |
Bleaching of medium consistency pulp with ozone without high shear
mixing
Abstract
Methods are disclosed for bleaching medium consistency cellulose
pulp including generating a stream of ozone-containing gas having
an ozone concentration of at least 10% by weight and radially
injecting the stream of ozone-containing gas into a stream of
cellulose pulp flowing through a reactor so as to provide a stream
of bleached cellulose pulp. A low to medium intensity mixer
operating at no more than 800 rpm may be used, downstream from the
injection site.
Inventors: |
De Vos, Rolf; (Landvetter,
SE) ; Tikka, Panu; (Rauma, FI) |
Correspondence
Address: |
LERNER, DAVID, LITTENBERG,
KRUMHOLZ & MENTLIK
600 SOUTH AVENUE WEST
WESTFIELD
NJ
07090
US
|
Assignee: |
Arbozon Oy Ltd.
Espoo
FI
|
Family ID: |
34839849 |
Appl. No.: |
11/029732 |
Filed: |
January 5, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
11029732 |
Jan 5, 2005 |
|
|
|
09763221 |
May 15, 2001 |
|
|
|
Current U.S.
Class: |
162/65 ; 162/243;
162/246; 422/225; 422/228 |
Current CPC
Class: |
D21C 9/153 20130101 |
Class at
Publication: |
162/065 ;
162/243; 162/246; 422/225; 422/228 |
International
Class: |
D21C 009/153 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 24, 1998 |
FI |
98/808 |
Claims
1. A method for bleaching medium consistency cellulose pulp
comprising providing a stream of ozone-containing gas and radially
injecting the stream of ozone-containing gas in a single ozone
addition step into a stream of cellulose pulp flowing through a
reactor so as to provide a stream of bleached cellulose pulp,
wherein said reactor operates in plug flow mode at a pressure of at
least 3 bar and at a temperature of 50.degree. C. or less and said
reactor does not include a high shear mixer.
2. The method of claim 1 wherein said ozone-containing gas has an
ozone concentration of at least 10 percent by weight.
3. The method of claim 1 wherein said ozone-containing gas has an
ozone concentration of at least 15 percent by weight.
4. The method of claim 1 wherein said ozone-containing gas has an
ozone concentration of at least 20 percent by weight.
5. The method of claim 1 including radially injecting said stream
of ozone-containing gas into said stream of cellulose pulp by means
of a plurality of porous metal injectors.
6. The method of claim 1 wherein the mean residence time of said
pulp in said reactor is between about 10 and about 150 s.
7. The method of claim 6 wherein the mean residence time of said
pulp in said reactor is between about 15 and about 40 s.
8. The method of claim 1 wherein the stream of ozone-containing gas
is generated from a mixture of pressurized oxygen and at least one
other gas or liquid.
9. A reactor for bleaching medium consistency pulp wherein said
reactor comprises a vessel, means for radially injecting an
ozone-containing gas into a stream of cellulose pulp flowing
through said vessel, and said reactor further comprising a mixer of
the rotatable helix screw type having a first pitch in the center
and a second pitch at the periphery, the second pitch being lower
than the first pitch, downstream from said injecting means.
10. The reactor of claim 9 wherein the first pitch is in the range
of 20 to 45 degrees and the second pitch is in the range of 5 to 30
degrees.
11. The reactor of claim 9 including baffles on the vessel inner
wall.
12. The reactor of claim 11 wherein said baffles are of the helix
type, having a negative pitch in respect to the mixer.
13. The reactor of claim 12 wherein said baffles have a pitch in
the range of 5 to 45 degrees.
14. The reactor of claim 11 wherein said baffles comprise flat disc
baffles dividing the reactor volume.
15. A method for bleaching medium consistency cellulose pulp
comprising providing a stream of ozone-containing gas and radially
injecting the stream of ozone-containing gas in a single ozone
addition step into a stream of cellulose pulp flowing through a
reactor so as to provide a stream of bleached cellulose pulp,
wherein said reactor operates in plug flow mode at a pressure of at
least 3 bar and at a temperature of 50.degree. C. or less and said
reactor includes a mixer operating at not more than 800 rpm
downstream from the injection site.
16. The method of claim 15 wherein said ozone-containing gas has an
ozone concentration of at least 10 percent by weight.
17. The method of claim 15 wherein said ozone-containing gas has an
ozone concentration of at least 15 percent by weight.
18. The method of claim 15 wherein said ozone-containing gas has an
ozone concentration of at least 20 percent by weight.
19. The method of claim 15 wherein said mixer includes a static
mixer.
20. The method of claim 15 wherein said mixer includes a dynamic
mixer.
21. The method of claim 15 wherein said mixer includes a rotatable
helical screw mixer.
22. The method of claim 15, including radially injecting said
stream of ozone-containing gas into said stream of cellulose pulp
by means of a plurality of porous metal injectors.
23. The method of claim 15 wherein the mean residence time of said
pulp in said reactor is between about 10 and about 150 s.
24. The method of claim 23 wherein the mean residence time of said
pulp in said reactor is between about 15 and about 40 s.
25. The method of claim 15 wherein the stream of ozone-containing
gas is generated from a mixture of pressurized oxygen and at least
one other gas or liquid.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation-in-part of U.S.
patent application Ser. No. 09/763,221, filed May 15, 2001, the
disclosure of which is incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to a method of bleaching
medium consistency pulp with an ozone-containing gas. More
particularly, the present invention relates to the proper
utilization of the very fast reaction of ozone, by providing
efficient but pulp-preserving mixing immediately on introducing a
substantial amount of ozone into the pulp.
BACKGROUND OF THE INVENTION
[0003] A number of methods for the bleaching of pulp with ozone are
known in the art. These methods have developed with the goal of
carrying out the bleaching stage with medium consistency pulp, i.e.
having a consistency of about 7 to 16 percent.
[0004] Generally, ozone bleaching of medium consistency (MC) pulp
according to current practice can be described as ozone generation
followed by compression before introducing the ozone containing gas
into the MC pulp flow. The gas-liquid-fiber suspension is thus
vigorously treated in one or several high shear mixers before the
suspension is led into a bleaching tower. The ozone may be
introduced at several points along the pulp stream. Vent gases must
be treated because of excess ozone which is carried over.
[0005] The principle thus described may well be a result of the
application of oxygen bleaching methods. Oxygen, however, operates
at a much slower rate, and the temperatures which are used are
significantly higher than those employed in ozone bleaching.
[0006] Typical and frequent problems arise from the difficulty in
keeping the suspension uniform. Segregation into two-phase flow
readily occurs, and the ozonization rate drops significantly (to 1
or even 0.1% of its optimum rate). This is a dominant problem,
which may be reduced by using a higher quality ozone, resulting in
less gas void and consequently less need for vigorous mixing. A
typical solution in the present state of the art is the use of more
than one mixer. This does not, however, eliminate the problem, and
by applying more shear forces to the pulp, the strength properties
of the resulting product are severely affected.
[0007] A basic problem with such mixers is the short residence
time, and if mixing time is increased, undesired backmixing may
occur.
[0008] After leaving the mixers, the gas-pulp suspension rapidly
segregates into two-phase flow having a relatively small gas-liquid
interface per unit volume. The chemical consequences of this are
low capacity and a non-uniform bleaching result. Obvious evidence
of this phenomenon is the significant ozone surplus often remaining
after the bleaching stage, representing both a hazard and an
economical loss.
[0009] A pulp bleaching method comprising introduction of high
pressure ozone in a carrier gas into a pulp stream with vigorous
mixing and subsequent removal of carrier gas is disclosed in, e.g.
European Patent No. 511 433. The major issue in this patent is the
removal of gas from the pulp after injection into the mixer and the
reaction is said to take place essentially within ten seconds in a
vertical reaction vessel situated immediately following the
fluidizing mixer. Gas at about 10 to 13 bar, containing about 3 to
10% ozone by weight (6.8 vol %) is used. Preferably, the gas-pulp
mixture is carried in a horizontal path following the vertical
reaction step to effect separation of the large amount of carrier
gas involved.
[0010] Austrian patent application no. 2203/92 describes a method
wherein medium consistency pulp is treated with an ozone-containing
gas comprising more than 120 g O.sub.3/normal m.sup.3 gas (5.6 vol
%) whereby the gas is introduced as fine bubbles with a low
differential pressure (preferably less than 1 bar). It is
considered that using gas with a high ozone content, a sufficient
amount of ozone can be suspended into the gas to achieve the
desired bleaching. Further, Austrian patent application no. 2203/92
discloses the use of mixers with or without fluidization effects,
and of an ozone reaction stage subsequent to the mixing stage, as
well as additional ozone addition stages, with degassing stages in
between. Characteristically, the highly concentrated ozone is
introduced in static mixers at several points, possibly removing
the inert carrier gas (normally oxygen) between stages, and the
final reaction between ozone and fiber takes place in a bleaching
reactor, typically of the traditional upflow type.
[0011] A common feature of several other publications disclosing
ozone bleach processes for medium consistency pulp is the use of
fluidizing mixers in connection with the injection of
ozone-carrying gas, and the use of subsequent, relatively extended
reaction stages and gas separation.
[0012] In chemical process terms, MC ozonization can be described
as ozone molecules in a gas phase that must be transported to the
vicinity of the fiber and react with the fiber or other substrates.
The ozone must diffuse through the gas-liquid interface, through
the liquid to the fiber. The applied mixing affects the size and
the relative velocity of the gas bubbles, as well as the amount of
fiber-liquid interface. The rate limiting step completely
dominating the interaction of ozone with the fiber material is the
transport of ozone through the gas-liquid interface. The gas-liquid
transfer rate in a given volume is heavily dependant on the bubble
size, i.e. gas-liquid surface area m.sup.2 gas/m.sup.3 suspension,
and on the partial pressure of ozone. Other rate limiting steps,
like diffusion in the fiber material itself, are determined by the
nature and the consistency of the pulp, which is primarily affected
by the temperature.
[0013] Due to its dependency on mass transfer, the reaction rate of
ozone is, theoretically and empirically, first order.
[0014] The high gas void, i.e. the low concentration of ozone
generated by most present ozone generators, limits the
possibilities to improve the situation. Reduced gas void in
subsequent generations of ozone generators will reduce the need for
mixing and reduce energy requirements, as well as the size of the
equipment. Higher ozone concentrations will also increase the
ozonization rate.
[0015] Consequently, the following are characteristics of efficient
process solutions:
[0016] the residence time distribution (RTD) must follow a
plug-flow pattern (in contrast, backmixing commonly occurs in
dynamic mixers), which requires a special reactor geometry to avoid
backmixing e.g. appropriate turbine and baffles. High intensity,
high shear mixing is detrimental;
[0017] mean residence time in transfer/mixer/reactor must match
transport and reaction times for complete conversion of ozone;
consequently reactor diameter, shape and rotation rate of a
possible turbine must match flow rate; and
[0018] all ozone should be introduced in one step.
[0019] A low intensity mixer is sufficient for bleaching using
moderate ozone concentrations, as long as the other criteria for
ozone use are fulfilled. As the ozone concentration increases, the
need for mixing decreases, and a static mixer is sufficient for
distributing the ozone in the pulp. At sufficiently high ozone
concentrations, a mixer is not necessary.
SUMMARY OF THE INVENTION
[0020] In accordance with the present invention, these and other
objects have now been realized by the invention of a method for
bleaching medium consistency cellulose pulp comprising providing a
stream of ozone-containing gas and radially injecting the stream of
ozone-containing gas representing a single ozone addition into a
stream of cellulose pulp flowing through a reactor, so as to
provide a stream of bleached cellulose pulp, the reactor being
operated in plug flow mode at a pressure of at least 3 bar and at a
temperature of 50.degree. C. or lower. Downstream from the ozone
injection site, a low to medium intensity dynamic mixer operating
at no more than 800 rpm may be used. The method according to the
invention may include the use of static mixers, e.g. baffles. These
may preferably be used at higher ozone concentrations. Preferably,
the ozone concentration is at least 10 percent by weight; more
preferably at least 15 percent by weight; and most preferably about
20 percent by weight. The expression "percent by weight" refers to
the weight of ozone in the feed gas mixture.
[0021] In a preferred embodiment the method includes generating the
stream of ozone-containing gas from a mixture of pressurized oxygen
and at least one other gas or liquid.
[0022] In accordance with one embodiment of the method of the
present invention, the method includes radially injecting the
stream of ozone-containing gas at a pressure of at least 7 bar into
the stream of cellulose pulp.
[0023] In accordance with another embodiment of the method of the
present invention, the method includes radially injecting the
stream of ozone-containing gas into the stream of cellulose pulp
from a plurality of nozzles adapted to direct the ozone.
[0024] High-concentration, high pressure ozone is introduced into
the pulp line, whereby conditions approaching plug flow are
achieved, a high concentration of ozone is reached with a mass
transfer area in the suspension which is sufficient for effective
delignification.
[0025] According to one aspect of the present invention, the ozone
is introduced using effective injection nozzles providing for the
efficient dispersion necessary for obtaining a uniform distribution
as well as sufficient mass transfer area to overcome the
rate-limiting mass transfer threshold present in methods according
to the prior art. Thus, the need for fiber-destroying high shear
fluidizing mixers is removed.
[0026] According to a further aspect of the invention, a reactor
for bleaching medium consistency pulp according to the above
defined method is provided. The reactor comprises a vessel and
means, for radically injecting ozone into a pulp stream flowing
through the vessel, e.g. nozzles.
[0027] According to another aspect of the present invention, a
dynamic low to medium intensity mixer is provided in the pulp
stream downstream of the ozone injection site. Such a mixer
delivers to the pulp stream amounts of energy which are well below
fluidization energies, and does not mechanically affect the
fiber.
[0028] Preferably, the low to medium intensity mixer is of the
helix screw type with high pitch in the center, preferably 20 to 45
degrees, and lower peripheral pitch, preferably 5-30 degrees.
[0029] Baffles can be either of the helix-type on the vessel inside
with a negative pitch, preferably 5-45 degrees with respect to the
mixer, or flat discs dividing the reactor volume, preferably in at
least 5 segments (compartments); or both baffle types at the same
time. If flat disc baffles are used, a double helix-mixer with
opposite signs on the pitch may be used.
[0030] According to another aspect of the present invention, a
static mixer is provided in the pulp stream immediately downstream
of the ozone injection site.
[0031] Preferably, the process is operated at temperatures below
25.degree. C. to reduce the decomposition of ozone to negligible
values. At temperatures above 40.degree. C., the self-decomposition
of ozone increases significantly, and the process according to the
invention should be operated at a temperature not higher than
50.degree. C.
[0032] Higher temperatures will lead to higher requirements of
ozone charge, but also to shorter residence times and smaller
bleaching reactors.
[0033] The mean residence time of the pulp in the reactor may vary
between about 10 to about 150 s, and longer time is required for
higher ozone charges and for lower ozone pressure and
concentration. Preferably, the mean residence time is between about
15 and about 40 s.
[0034] The mixing efficiency is not sensitive to the gas void level
and the reactor can handle gas voids from 10 to 50 vol %.
[0035] With the aid of recent technology, as disclosed, e.g., in
Swedish Patent Application No. 9502339-6, ozone with a
concentration of up to 18 to 20% by volume may be generated.
References to concentrations as high as 300 g O.sub.3/Nm.sup.3 have
been made in prior art publications (e.g. European Application No.
426,652, with a priority date of Oct. 30, 1989), but such
concentrations have not been technically feasible until recently.
Using a high ozone concentration (300 g/m.sup.3 and higher) and at
high pressure (10 bars and higher) together with a proper injection
technique, the reaction between ozone and fiber can now take place
at a rate such that the subsequent use of an upflow bleach tower is
not necessary. The gas pressure is obtained by using precompressed
oxygen, optionally mixed with other gases or liquids (e.g. argon)
to maintain a suitable conductivity for ozone generation.
[0036] Oxygen is the most common carrier gas used for ozone. Highly
concentrated ozone is usually considered to be an explosion hazard.
As the ozone generating technology has developed, the accepted
limit for stable oxygen-ozone mixtures has been repeatedly pushed
upwards, and it appears that no absolute concentration limit for
the safe handling of ozone has yet been established. Thus, use of
very high ozone concentrations may yet be possible, which further
facilitates use of methods according to the present invention.
According to the present invention, the concentration of ozone in
the gas introduced into the pulp stream is sufficient for achieving
bleaching without any fiber-destroying mechanical impact.
[0037] The initial distribution of highly concentrated ozone into
the pulp is of importance, for the selectivity, as the carbohydrate
component itself may be attacked by ozone if exposed for an
extended time. The absence of backmixing, as may occur in high
shear mixers, and the presence of plug flow conditions counteract
this phenomenon.
BRIEF DESCRIPTION OF THE DRAWING
[0038] The present invention will be more fully appreciated with
reference to the following detailed description, which in turn
refers to the drawing, in which;
[0039] FIG. 1 is a graphical comparison between the changes in
reaction rates against time in a prior art ozone pulp bleaching
process using a medium consistency mixer, and a process according
to the present invention.
DETAILED DESCRIPTION
[0040] The present invention may be appreciated with reference to
the following specific examples;
EXAMPLE 1
[0041] Ozone-carrying gas having a pressure of about 15 bar and an
ozone concentration of 14% by volume is introduced into a medium
consistency pulp line carrying 1000 tons/day by means of a collar
of radially arranged nozzles. Preferably, the nozzles are arranged
to direct the gas radially into the pulp flow, essentially in a
direction perpendicular to the pulp flow. A number of nozzles
sufficient for evenly distributing the gas must be used. On this
production scale, 186 nozzles with an inlet diameter of a maximum
of 1 mm may be used.
[0042] A sufficient mean residence time (10 to 40 seconds) must be
allowed before any other disturbing action to the pulp.
EXAMPLE 2
[0043] A medium intensity (low-shear) mixer is adapted into the
pulp stream of the previous example, preferably immediately
following the gas injection site. The mixer turbine is preferably a
double or multiple screw with blade angles and rotation rate
balanced to maintain the plug flow residence time distribution
(RTD) and giving good radial mixing efficiency. The center blade
has a steeper angle than the outer screw blade. Alternatively,
porous metal injector devices for introduction of ozone can be
arranged peripherically or on the turbine.
[0044] FIG. 1 shows a comparison between a system employing a
traditional medium consistency mixer with a very high capacity for
a short interval dropping rapidly to zero, compared to a system
according to the present invention, with a moderately high capacity
kept constant for a long period. The dotted line represents
state-of-the-art traditional medium consistency mixer technology.
The first, steep section shows the effect of the mixer with high
reaction and uniform distribution. The low rate section shows the
effect of the corruption of the gas-suspension interface. The
reaction takes place with a nonuniform distribution and the pulp is
mechanically stressed by high shear mixing.
[0045] The solid line represents a system according to the present
invention. Throughout the process, a moderately fast reaction is
taking place in a mildly stressed pulp and with a uniform
distribution of ozone.
1TABLE 1 Present Calculus Base Units Conventional Modern invention
Pulp production ton 1000 1000 1000 OD/day Consistency % 10 10 10
Ozone pressure bar 9 9 15 Ozone w % 10 14 20 concentration vol % 7
10 14 Ozone charge kg/ton 5 5 5 (3-5) OD pulp Ozone generator kg/h
208 208 208 Ozone volume flow m.sup.3/s 0.0146 Nozzle diameter m
0.001 Number of nozzles 186 Process Process .degree. C. 40 40 40
temperature Process pressure bar 7 7 15 Pulp Flow ton OD 42 42 42
pulp/h Volume Flow m.sup.3/h 375 375 375 MC pulp Ozone gas charge
m.sup.3/h at 234 165 53 actual press. Gas void* % 38 31 12
Equipment Ozone Ozone No ozone compressor compressor compressor 1-3
mixers 1+ mixers No mixer Bleach Bleach Small bleach tower tower
reactor *Note: Gas void is proportional to process problems
[0046] Table 1 shows a comparison in numbers between a typical
conventional MC bleaching system, a state-of-the-art system and a
system according to the present invention.
* * * * *