U.S. patent number 3,652,385 [Application Number 05/036,670] was granted by the patent office on 1972-03-28 for process for treating cellulosic materials from which metal ions have been removed with alkali and oxygen in the presence of complex magnesium salts.
This patent grant is currently assigned to Mo och Domsjo Aktiebolag. Invention is credited to Sture Erik Olof Noreus, Hans Olof Samuelson.
United States Patent |
3,652,385 |
Noreus , et al. |
March 28, 1972 |
**Please see images for:
( Certificate of Correction ) ** |
PROCESS FOR TREATING CELLULOSIC MATERIALS FROM WHICH METAL IONS
HAVE BEEN REMOVED WITH ALKALI AND OXYGEN IN THE PRESENCE OF COMPLEX
MAGNESIUM SALTS
Abstract
Cellulosic materials from which metal ions have been removed by
acids or complexing agents is delignified with alkali in the
presence of oxygen, and particularly air, and in the presence of
magnesium compounds such as, for instance, chelates of magnesium
and aliphatic alpha- and beta-hydroxycarboxylic acids. The
invention is of particular application to the reduction of lignin
content in cellulose pulps without causing deleterious degradation
of the cellulose, the magnesium compounds reducing or entirely
preventing attack of oxygen on the hemicellulose and cellulose
carbohydrates, without appreciably diminishing the oxidation of the
lignin and its dissolution in the course of the process. The
process is also useful to obtain a controlled dissolution of the
hemicellulose.
Inventors: |
Noreus; Sture Erik Olof
(Sundasen, SW), Samuelson; Hans Olof (Goteborg,
SW) |
Assignee: |
Mo och Domsjo Aktiebolag
(Ornskoldsvik, SW)
|
Family
ID: |
20269591 |
Appl.
No.: |
05/036,670 |
Filed: |
May 12, 1970 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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869875 |
Oct 27, 1969 |
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Foreign Application Priority Data
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May 13, 1969 [SW] |
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6780/69 |
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Current U.S.
Class: |
162/23; 8/116.1;
162/26; 162/72; 162/80; 162/90; 162/25; 162/65; 162/76 |
Current CPC
Class: |
D21C
9/1026 (20130101); D21C 9/1005 (20130101) |
Current International
Class: |
D21C
9/10 (20060101); D21c 003/00 () |
Field of
Search: |
;162/25,26,65,72,73,74,75,76,78,80,81,82,84,85,86,89,23,24,90
;8/109,111,116 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Bashore; S. Leon
Assistant Examiner: Scavone; Thomas G.
Parent Case Text
This application is a continuation-in-part of Ser. No. 869,875
filed Oct. 27, 1969.
Claims
We claim:
1. In the process for treating cellulosic materials with alkali in
the presence of oxygen, and particularly air, the improvement which
comprises pretreating the cellulosic material with a compound
selected from the group consisting of acids and complexing agents
for catalytically active heavy metal compounds to remove or
inactivate catalytically active metals or metal compounds, bringing
the concentration of cellulosic material to within the range from
about 30 to about 60 percent, and then delignifying the cellulosic
material with alkali in the presence of oxygen and a soluble
complex magnesium compound selected from the group consisting of a
magnesium salt of organic acids having from two to about 12 carbon
atoms and one carboxylic acid group and an alpha or beta hydroxyl
group or at least two carboxylic acid groups and no or from one to
about 10 hydroxyl groups, and a magnesium salt of polyphosphoric
acids, and charging the alkali in at least two increments during
the oxygen treatment, the complex magnesium compound being in an
amount sufficient to reduce or entirely prevent attack of oxygen on
the hemicellulose and cellulose carbohydrates, without appreciably
diminishing the oxidation of the lignin and its dissolution in the
course of the process.
2. A process according to claim 1, in which the pretreatment is
carried out with an acid solution containing an acid selected from
inorganic acids and organic acids.
3. A process according to claim 2, in which the acid is a mineral
acid.
4. A process according to claim 2, in which the acid is a sulfurous
acid.
5. A process according to claim 2, characterized in that the
pretreatment is effected with acid bleaching waste liquor.
6. A process according to claim 1, characterized in that the
pretreatment stage is effected in the presence of complexing agents
for catalytically active, heavy metal compounds, selected from
copper, cobalt, iron and manganese.
7. A process according to claim 1, in which the oxygen-treatment is
effected at a concentration of cellulosic material of from about 32
to about 40 percent.
8. A process according to claim 1, in which the oxygen treatment is
carried out in at least two stages, and alkali is added between
each stage and/or during each stage.
9. A process according to claim 1, in which alkali is added to the
pretreated cellulosic material, and then the material is
disintegrated by mechanical means prior to or during the oxygen
treatment.
10. A process according to claim 1, in which the pretreated
cellulosic material is disintegrated by mechanical means, and then
alkali is added.
11. A process according to claim 1, in which alkali is added to the
pretreated cellulosic material while it is being mechanically
disintegrated during the oxygen treatment.
12. A process according to claim 1, in which oxygen treatment is
carried out while the cellulosic material is being mechanically
disintegrated.
13. A process according to claim 1, in which alkali is added in an
atomized condition.
14. A process according to claim 1, in which alkali is added to the
pretreated cellulosic material, the material is mechanically
disintegrated during oxygen treatment, and atomized alkali is
supplied to the disintegrated material during the oxygen
treatment.
15. A process according to claim 1, in which the oxygen treatment
is carried out in the presence of a silicate compound.
16. A process according to claim 15, in which the silicate is an
alkali metal silicate.
17. A process according to claim 1, wherein the magnesium compound
is a chelate of magnesium and an aliphatic alpha- or
beta-hydroxycarboxylic acid.
18. A process according to claim 1, wherein the magnesium compound
is a magnesium salt of a dicarboxylic aliphatic acid.
19. A process according to claim 1, wherein the magnesium compound
is a magnesium polyphosphate.
20. A process according to claim 1, wherein the treatment is
carried out on lignin-bearing wood cellulose to remove lignin at
least in part.
21. A process according to claim 1, wherein the magnesium compound
is a chelate of magnesium and the complexing organic acid is
contained in waste liquor from a process in which cellulosic
material is treated with alkali.
22. A process according to claim 21, wherein a magnesium salt is
added to the waste liquor to form the complex magnesium salt in
situ in the liquor.
23. A process according to claim 1, wherein the partial pressure of
the oxygen at the beginning of the treatment is at least about 1
atm.
24. A process according to claim 1, wherein the treatment is
carried out at a temperature within the range from about 80.degree.
to about 140.degree. C.
25. A process according to claim 1, wherein the cellulosic material
prior to being treated is impregnated with an aqueous solution of a
complex magnesium salt or components which in the solution form a
complex magnesium salt.
26. A process according to claim 25, wherein a portion of the
solution is removed from the pulp prior to the treatment.
27. A process according to claim 1, wherein the quantity of alkali
calculated as NaOH is within the range from about 0.5 to about 12
percent based on the dry weight of the cellulosic material.
28. A process according to claim 1 wherein the content of magnesium
during the treatment is at least 0.005 up to about 1 percent
calculated as MgO on the dry weight of the pulp.
29. A process according to claim 1, wherein the magnesium compound
is a chelate of magnesium and
an aliphatic hydroxy acid having from two to about 12 carbon atoms
and from one to about 10 hydroxyl groups.
30. A process according to claim 29, wherein the acid is selected
from the group consisting of glycolic acid, lactic acid,
dihydroxy-butyric acid, aldonic acid, gluconic acid, mannonic acid,
tartaric acid and oxalic acid.
31. A process according to claim 1, wherein in addition the
delignification is controlled to obtain a controlled dissolution of
hemicellulose in cellulose pulp, either during or after
delignification, in the presence of the complex magnesium
compound.
32. A process according to claim 1, wherein the cellulosic material
is an unbleached, partially bleached or bleached cellulose sulfate
pulp, sulfite pulp or semichemical pulp derived from wood.
33. A process according to claim 1, wherein the process is
controlled to obtain a controlled dissolution of hemicellulose in a
low lignin or lignin-free cellulose pulp in the presence of the
complex magnesium salt.
Description
It is known that chemical and semichemical cellulose pulps can be
treated with oxygen in an alkaline medium in order to dissolve
lignin. The oxygen treatment is carried out at an elevated
temperature, of the order of 100.degree. C., and does not normally
require more than 1 hour. The amount of alkali required is of the
order of 4 to 5% NaOH based on the dry pulp. It is possible to
obtain a good reduction in lignin content in this way, but
unfortunately, at the same time hemicellulose is also dissolved,
and a significant decomposition of the cellulose takes place, as
evidenced by a lower viscosity value. Also, the strength properties
of paper manufactured from such treated pulp are poor.
It has been proposed (U.S. Pat. No. 3,384,533 dated May 21, 1968,
to Robert et al.) that the process be improved by carrying out the
treatment in the presence of a metal carbonate, such as barium
carbonate, calcium carbonate, magnesium carbonate or zinc
carbonate, in an amount within the range from about 0.5 to 3
percent by weight of the pulp. Of these chemicals, magnesium
carbonate gives the best results, when in an amount of
approximately 1 percent by weight of the pulp. However, magnesium
carbonate is quite expensive, and the treatment is costly. Calcium
carbonate, which is cheaper, is much less effective. In the case of
all of these salts, the difficulty is that a powdered
water-insoluble material must be charged to and mixed with the
aqueous cellulose pulp system, and it is accordingly hard to obtain
and maintain a homogeneous mixture, with uniform effect.
A further serious disadvantage is that a particularly complicated
apparatus is required to carry out the heterogeneous reaction if
the process is to be effected in a reasonable length of time.
In accordance with the present invention, a process is provided for
treating cellulosic materials with alkali in the presence of
oxygen, and in the presence of a magnesium compound, such as a
magnesium salt of an organic acid having from two to about 12
carbon atoms and either one carboxylic acid group and an alpha or
beta hydroxy group such as an aliphatic alpha- or
beta-hydroxycarboxylic acid, or a mixture of a magnesium salt and
an aliphatic alpha- or beta-hydroxycarboxylic acid or salt thereof,
or two or more carboxylic acid groups and no or from one to 10
hydroxyl groups such as a dicarboxylic acid or a mixture of a
magnesium salt and such acid or salt thereof. In this process, the
cellulose is subjected to a pretreatment in which catalytically
active metals and/or metal compounds are removed or deprived of
their catalytic activity, and the concentration of cellulose during
treatment with oxygen is from about 30 to about 60 percent,
preferably from 32 to 40 percent. Moreover, it is preferred that
alkali be added incrementally or continuously, so that, in addition
to the amount of alkali present at the beginning of the oxygen
treatment, more alkali is added in at least one additional stage
during the oxygen treatment.
It has been found that in this process it is possible in one stage
to reduce the lignin content by more than 50 percent without
causing deleterious degradation of the cellulose, or appreciable
loss of hemicellulose. In fact, the dissolution of hemicellulose
can be controlled so as to be insignificant or appreciable, as
desired, so that the process is also applicable to hemicellulose
dissolution. It has surprisingly been found that the protective
effect obtained when adding magnesium compounds to the system can
be increased to such an extent that the process can be effected in
practice at high-pulp concentrations if, prior to being treated
with oxygen, the cellulose is subjected to a pretreatment step in
which metals and/or metal compounds which catalyze the attack on
the cellulose and hemicellulose are removed or deprived of their
catalytic activity, and if, furthermore, alkali is not added in one
single charge, but a percentage of the total quantity of alkali
charged is initially introduced to the system, and more alkali is
added when the alkali previously charged to the system has been
either completely or partially consumed, so that a large excess of
alkali is not present during any stage of the process.
The process of the invention is applicable to unbleached, partially
bleached or bleached cellulose pulps, prepared from any cellulose
source by any pulping process, for example, sulfate pulp, sulfite
pulp and semichemical pulp. The invention is especially applicable
to cellulose pulps derived from wood, such as spruce pulp, pine
pulp, hemlock pulp, birch pulp, fir pulp, cherry pulp, sycamore
pulp, hickory pulp, ash pulp, beech pulp, poplar pulp, oak pulp,
and chestnut pulp, or of other ligno-cellulosic material such as
bamboo, bagasse straw and reeds. The invention is particularly
advantageous in the preparation of any pulp in which it is
especially desired to avoid degradation of the cellulose during
processing, such as most grades of paper pulp, and when it is
desired to obtain a uniform controlled degradation, such as in the
manufacture of viscose pulp of a desired viscosity.
In most cases where the starting cellulose pulp is free of lignin,
or where the lignin content is low, either naturally so, or because
it has been delignified, the process of the invention can be
applied to remove hemicellulose, and/or cause oxidation of end
groups of the cellulose, with a regulated diminution of the pulp
viscosity. In these processes, the magnesium compounds have the
property of protecting the cellulose and hemicellulose molecules
against uncontrolled degradation.
The process of the invention is particularly advantageous in the
alkaline treatment of lignin-containing wood cellulose in the
presence of oxygen, gas or air, for the purpose of removing lignin.
This process is referred to in the art as alkaline oxygen gas
bleaching. It is also applicable to the controlled dissolution of
hemicellulose in cellulose pulps, either during or after
delignification.
Tests have shown that it is also advantageous if the cellulose is
swelled in the alkali, and that, when an excess quantity of alkali
has been used, the surplus is removed in a manner known per se.
The following advantages are gained when applying the process of
the invention:
1. Uniform bleaching can be obtained without it being necessary to
agitate the cellulose, except possibly when mixing in the alkali,
or to subject it to a mechanical treatment other than that
necessary in loosening the fibers thereof;
2. The cellulose can be bleached in a continuous process;
3. The cellulose is easily, transported, e.g., by means of screw,
scraper or gas-carrier conveyor systems, and sluice valves and
other valve arrangements;
4. Liquids or liquid droplets, which cause uneven bleaching an
accumulation of cellulose in the bleaching apparatus, are
avoided;
5. The costs of the apparatus are much lower than when the process
is applied to a wood pulp suspension;
6. Reduced heat consumption;
7. The process is effected at lower oxygen-gas pressure at a given
same reaction time;
8. The bleaching chemicals used can be recovered in a high
concentration, rendering the process more economical.
One surprising advantage of the process of the invention is that it
gives a cellulose pulp having a very low content of extractive
substances, "resins," such as fats, sterols, hydrocarbons, waxes
and fatty alcohols, in the treated material, even in the case of
cellulose material which is very difficult to deresin by other
methods. An example of such materials is wood cellulose produced
from fresh wood, particularly hardwood, such as birch.
In order to obtain the aforementioned advantages, particularly
those under items 1 to 5, it has been found that the concentration
of cellulose during the oxygen treatment should not be less than 30
percent, based on the treating solution. At lower concentrations,
the cellulose may adhere to the apparatus, and is liable to dry
out, creating, among other things, danger of explosion. Tests have
shown that the protective effect afforded by additions of magnesium
compounds at low cellulose concentrations is completely
unsatisfactory. Among the disadvantages observed have been
reduction in viscosity and strength of paper produced from the
pulp.
The concentration of cellulose is here calculated in weight percent
of the material impregnated with the alkaline liquid. The lower
concentration limit is important, although to some extent dependent
on the nature of the cellulosic material and the apparatus
used.
One factor important to the result and to the continuity of the
process is that the alkaline liquid must be completely absorbed by
the cellulose and retained by the fiber, so that, consequently, no
free coherent liquid phase exists. The concentration must be so
high that no liquid droplets are forced out of the material whilst
it is in, for example, the bleaching tower or other positions in
the apparatus where the pulp is not worked mechanically but can be
compressed by its own weight.
Test have shown fully unsatisfactory results, both with regard to
bleaching and to the transport of the cellulose through the
apparatus, when the cellulose concentration falls below 30 percent.
The best results have been obtained with a concentration within the
range from about 32 to about 40 percent, for example an initial
concentration of 38 percent, and a final concentration of 33
percent. The pulp, however, can be worked to advantage within the
concentration range of 32 to 50 percent or, if a significant
reduction in viscosity is desired, at a concentration as high as 60
percent, i.e., within the range from about 30 to about 60 percent.
With regard to the operation and simplicity of the apparatus, it is
particularly suitable that the concentration of cellulose during
the final stage reaches at least 30 percent.
In accordance with one embodiment, which has been found to afford
great practical advantages, the oxygen treatment is effected in two
or more stages, wherein the alkali-containing liquid is added to
the system between and/or during the treatment stages. In many
instances, it is desirable to add the alkaline liquid to the
pretreated cellulosic material before the oxygen treatment is
begun. The alkaline liquid can suitably be added in excess
quantities, thereby obtaining uniform liquid impregnation. The
excess alkaline liquid is later removed in a known manner, for
example, by pressing, to obtain a concentration within the given
limits; after which the pulp is disintegrated, e.g., in a shredder,
in a manner to provide a porous pulp having a greater surface area.
Accessibility to the cellulose during the oxygen gas treatment is
in this way increased. The oxygen gas treatment can be effected to
advantage during the disintegration process, although the treatment
process may be begun instead after the pulp has been
disintegrated.
In accordance with another embodiment, the pretreated cellulosic
material, which may be dry or wet, is loosened by mechanical
treatment, whereafter alkaline liquid is added. In order to obtain
uniform impregnation, it is important that the material be in
motion when the alkaline liquid is added, for example is being
mechanically treated, or is falling freely, or is moving in a flow
of gas and/or steam. In accordance with a further embodiment, which
is to be preferred with respect to simplicity of apparatus, the
alkaline liquid is added to the pretreated cellulosic material
while the material is being disintegrated by mechanical treatment.
In this embodiment, the alkaline liquid is added during the oxygen
treatment, or simultaneously therewith. With respect to apparatus
costs, it is desirable that contemporaneous treatment with oxygen
gas be effected during the mechanical treatment process, which in
this instance, at the same time, constitutes a first step in the
oxygen treatment.
When carrying out the method of the invention, it is important that
the oxygen treatment be effected while the cellulosic material is
being disintegrated by mechanical treatment or afterwards.
In all instances where alkaline liquid is added to the cellulosic
material while the material is in high pulp concentration, it is
desirable that the alkaline liquid be added to the system in a
finely divided atomized form. The alkaline liquid can be charged to
the system by known devices, for instance stationary or rotary jets
or nozzles. The liquid can be charged, suitably together with steam
and/or with the oxygen necessary for the treatment. The manner in
which the liquid is charged is less important when the alkaline
liquid is added whilst the cellulosic material is being subjected
to mechanical treatment. If the liquid is charged while the
material is falling freely, or moving in a stream of gas and/or
steam, for example, in a so-called cyclone bed or a blower conduit,
atomization of the liquid is desirable, and the liquid is suitably
charged to the system in the form of an aerosol.
In one embodiment which has shown very good results, alkaline
liquid is supplied to the pretreated cellulosic material, and any
surplus of alkaline liquid removed, for instance by pressing, after
which the cellulosic material is loosened by mechanical treatment
during contemporaneous treatment with oxygen, and atomized alkaline
liquid is supplied to the loosened material without or preferably
during contemporaneous treatment with oxygen. The alkaline liquid
is added to the loosened material suitably in the form of an
aerosol, for example while the loosened material is introduced into
the upper end of a tower through which it continuously passes, and
is subjected to treatment with oxygen.
The quantity of alkali necessary to the process depends on the
quantity of lignin and hemicellulose which it is desired to remove.
Normally, the total alkali addition, calculated as NaOH is within
the range from about 0.5 to about 10 percent, based on the dry
weight of the cellulosic material. Charges within the range of 7 to
12 percent alkali are used when it is desired to liberate large
quantities of lignin and/or hemicellulose. In pulps of low lignin
content, the normal total charge lies within the range of 1 to 7
percent. The alkali normally used is sodium hydroxide, optionally
in admixture with sodium bicarbonate. A slurry of calcium
hydroxide, so-called lime milk, may also be used as an alkaline
medium in the process. This latter medium, however, may cause
deposits in the apparatus.
Observations have shown that for a predetermined degree of lignin
dissolution, the least amount of cellulose decomposition is
obtained when the quantity of alkali present at the beginning of
the oxygen treatment is the smallest possible in practice, and when
the major portion of the alkali is added incrementally or
continuously as the alkali initially charged to the system is
totally or partially consumed. When producing strong paper pulps,
it is suitable that from about 10 to about 50 percent of the total
quantity of alkali charged to the system is present at the
beginning of the treatment, and that the remainder of the alkali is
either added stepwise, in one or more stages, or continuously,
during the oxygen treatment, or whilst the cellulose passes through
apparatus in which no oxygen treatment takes place.
The oxygen may be in the form of oxygen and/or air, or mixtures of
oxygen with any inert gas, such as nitrogen, argon, helium and
krypton. In order to promote a rapid reaction between the cellulose
and the charged gas, the partial pressure of oxygen at the
beginning of the process should be at least one atmosphere. A
practical upper limit for the partial pressure of oxygen is 20
atmospheres above atmospheric; the higher the pressure, the more
rapid the chemical reactions. The high-pulp concentration and the
looseness of the material facilitates dissolution of the oxygen in
the cellulose fibers impregnated with alkaline liquid, whereby
lower pressures than these used when treating low pulp
concentrations can be applied. Normally, an oxygen gas pressure
within the range of from about two to about 10 atoms is preferred.
It is often convenient to charge a further quantity of oxygen gas
or air during the process, and to release gas mixtures enriched
with respect to inert gas during the process.
The reactions take place slowly at low temperatures, e.g.,
50.degree. C.. In order to shorten the reaction time, the treatment
is normally effected at a temperature within the range from about
80.degree. to about 130.degree. C. However, in those cases where a
significant reduction in viscosity of the pulp is required, a
somewhat higher temperature can be used, e.g., about 140.degree. C.
In the case of sulphate paper pulps, the treatment process is
carried out to advantage at temperatures of between 90.degree. and
110.degree. C. A lower temperature is chosen in the case of
sulphate paper pulps, provided that a significant reduction in the
hemicellulose content is not desired. The temperature may be
changed incrementally or continuously during the process.
Consequently, it is convenient to start at a low temperature. This
is particularly true for pulps containing hemicellulose, which, in
nonoxidized state, is attacked by alkali, e.g., sulphite pulps and
semichemical pulps.
Very short reaction times, e.g., in the region of 5 minutes, can be
used when working with high-oxygen gas pressures and high
temperatures. It has been found relatively simple to control the
process under these conditions, since the reaction practically
stops when the alkali is consumed. To avoid working at high
pressures, it is possible instead to use, for example, oxygen gas
at atmospheric pressure, wherewith treatment times of 10 hours and
more can be used. Normal reaction times range from 10 to 120
minutes.
The magnesium compounds employed in the process of the invention
have the important property of reducing or entirely preventing the
attack of oxygen on the carbohydrates present in the cellulose and
hemicellulose, without to any notably great extend affecting the
oxidation of lignin extent its dissolution. This protective effect
is most noticeable with regard to the attack of oxygen on the
cellulose molecule, and primarily the attack of oxygen along the
anhydroglucose chain of the cellulose molecule, an attack which
gives rise to a rapid lowering of pulp viscosity. Thus, in the
presence of the magnesium compounds of the invention, the treated
delignified pulp is found to have a higher viscosity than would be
obtained in their absence.
The soluble preferred complex or chelate salts contsitute a
preerred class of magnesium compounds, because they give most
effective protection with a minimum magnesium concentration.
It is known that aliphatic alpha-hydroxycarboxylic acids of the
type RCHOHCOOH and the corresponding beta-hydroxycarboxylic acids
RCHOHCH.sub.2 COOH have the property of forming chelates with
magnesium. These chelates are of the type:
In the above formula, n is zero or one. When n is zero, the acid is
an alpha-hydroxy acid, and when n is one, the acid is a
beta-hydroxy acid.
R in the above formula is hydrogen or an aliphatic radical which
may be a hydrocarbon radical having from one to about 10 carbon
atoms, or a hydroxy-substituted hydrocarbon radical having from one
to nine hydroxyl groups, and from one to about 10 carbon atoms.
Exemplary alpha- and beta-hydroxy carboxylic acids are glycolic
acid, lactic acid, glyceric acid, .alpha.,.beta.-dihydroxybutyric
acid, .alpha.-hydroxy-butyric acid, .alpha.-hydroxy-isobutyric
acid, .alpha.-hydroxy-n-valeric acid, .alpha. -hydroxy-isovaleric
acid, .beta.-hydroxy-butyric acid, .beta.-hydroxy-isobutyric acid,
.beta.-hydroxy-n-valeric acid, .beta.-hydroxy-isovaleric acid,
erythronic acid, threonic acid, trihydroxy-isobutyric acid, and
saccharinic acids and aldonic acids, such as gluconic acid,
galactonic acid, talonic acid, mannonic acid, arabonic acid,
ribonic acid, xylonic acid, lyxonic acid, gulonic acid, idonic
acid, altronic acid, allonic acid, ethenyl glycolic acid, and
.beta.-hydroxy-isocrotonic acid.
Also useful are organic acids having two or more carboxylic groups,
and no or from one to 10 hydroxyl groups, such as oxalic acid,
malonic acid, tartaric acid, malic acid, and citric acid, ethyl
malonic acid, succinic acid, isosuccinic acid, glutaric acid,
adipic acid, suberic acid, azelaic acid, maleic acid, fumaric acid,
glutaconic acid, citramalic acid, trihydroxy glutaric acid,
tetrahydroxy adipic acid, dihydroxy maleic acid, mucic acid,
mannosaccharic acid, isosaccharic acid, talomucic acid,
tricarballylic acid, aconitic acid, and dihydroxy tartaric
acid.
The polyphosphoric acids are also good complexing agents for
magnesium, and the magnesium salts of these acids are useful in the
process of the invention. Exemplary are disodium-magnesium
pyrophosphate, trisodium-magnesium tripolyphosphate and magnesium
polymetaphosphate.
Especially advantageous from the standpoint of cost are the acids
naturally present in waste liquors obtained from the alkaline
treatment of cellulosic materials. These acids represent the
alkali- or water-soluble degradation products of polysaccharides
which are dissolved in such liquors, as well as alkali- or
water-soluble degradation products of cellulose and hemicellulose.
The chemical nature of these degradation products are complex, and
they have not been fully identified. However, it is known that
saccharinic and lactic acids are present in such liquors, and that
other hydroxy acids are also present. The presence of C.sub.6
-isosaccharinic and C.sub.6 -metasaccharinic acids has been
demonstrated, as well as C.sub.4 - and C.sub.5 -metasaccharinic
acids. Glycolic acids and lactic acid are also probable degradation
products derived from the hemicelluloses, together with
beta-gamma-dihydroxy butyric acid.
Carbohydrate acid-containing cellulose waste liquors which can be
used include the liquors obtained from the hot alkali treatment of
cellulose, liquors from sulfite digestion processes, and liquors
from sulfate digestion processes, i.e., kraft waste liquor. The
waste liquors obtained in alkaline oxygen gas bleaching or alkaline
peroxide bleaching processes can also be used. In this instance,
the alkaline liquor can be taken out from the process subsequent to
completing the oxygen gas treatment stage, or during the actual
treatment process.
The complex magnesium salts can be formed first, and then added to
the cellulose pulp. They can also be formed in situ from a
water-soluble or water-insoluble magnesium salt, oxide or
hydroxide, in admixture with the complexing acid, and this mixture
can be added to the pulp. Preferably, the waste liquor employed as
the source of complexing acid or anhydride or salt thereof can be
mixed with a magnesium salt, oxide or hydroxide, before being
introduced to the process. It is also possible to add the magnesium
salt, oxide or hydroxide to the pulp, and then bring the pulp into
contact with the complexing acid or anhydride or salt thereof. It
is also possible to combine the complexing acid or anhydride or
salt thereof with the pulp, and then add the magnesium salt, oxide
or hydroxide, but this method may be less advantageous in
practice.
In whatever form the magnesium is added, whether as salt, oxide,
hydroxide, or complex salt, the amount of magnesium is calculated
as MgO.
A noticeable improvement is obtained when as little magnesium as
0.005% MgO, calculated on the dry weight of the pulp, is added. A
high proportion of magnesium, up to 1% MgO, calculated on the dry
weight of the pulp, has been employed without disadvantageous
effect. However, for economic reasons, it is usually desirable to
use as little magnesium as possible, and normally an amount within
the range from about 0.01 to about 0.5% MgO, calculated on the dry
weight of the pulp, is employed.
It has been found that less effective but in many cases adequate
protection against decomposition of the cellulose also can be
obtained if the alkaline liquid contains a solid magnesium
compound, e.g., magnesium carbonate, magnesium oxide and magnesium
hydroxide. In this latter instance, however, large amounts of
magnesium compounds are required, and the process becomes less
satisfactory economically. The addition and distribution of solid
compounds also involves technical complications. The amount of
magnesium compounds should in this instance be within the range
from about 0.5 to 2.0% calculated as MgO on the dry weight of the
pulp.
A negligible shielding effect is obtained when practicing the
process of the invention using magnesium silicate in solid form. On
the other hand, it has been found that an alkaline silicate, for
example, sodium silicate, or other compounds which stop free
radical reactions, for example, aromatic organic substances such as
benzene, can be added to advantage together with magnesium
compounds, preferably complex magnesium compounds, and that in this
way the protective effect against cellulose decomposition is
further increased. The quantity of sodium silicate or benzene
introduced to the system is within the range from about 0.05 to
about 3.0 percent, estimated on the dry weight of the cellulosic
material, preferably from 0.1 to 1.0 percent.
Upon conclusion of the alkaline-oxygen gas treatment, it is
possible to separate the magnesium-containing waste liquor and
recycle it for reuse. The consumption of magnesium salts is
negligible, and usually it is not even necessary to replenish the
magnesium content before recycling. However, additional magnesium
compound can be added before recycling, if necessary, to restore
the magnesium content, as MgO, and maintain a high enough level,
for instance, to prevent oxidative degradation of the cellulose or
hemicellulose. The consumption of magnesium salt has been noted to
be particularly low when waste liquor from a part of the
alkaline-oxygen gas treatment process is employed as the source of
complexing acid, and recycled for continued treatment of new
batches of pulp.
Some waste liquors are particularly high in magnesium ion because
of the nature of the pulp or of the pulping process. For example,
waste pulping liquors from unbleached pulps produced by the cooking
of wood with magnesium bisulfite or magnesium sulfite usually
contain enough magnesium ion so that no addition of magnesium
compound need be made. Such waste liquors can be used per se, in
the process of the invention, inasmuch as they already contain the
complexing acids, and a sufficient proportion of magnesium ion as
well.
As a source of magnesium, one may add any magnesium salts, oxide or
hydroxide, either to regenerate a spent treatment liquor, or to
prepare a waste liquor or other material for use in the process.
Any water-soluble magnesium compound can be used, such as, for
example, magnesium sulfate, magnesium chloride, magnesium bromide,
magnesium chlorate, magnesium potassium chloride, magnesium
formate, magnesium oxide, magnesium hydroxide, and magnesium
nitrate. If it is desired to recover the liquor after the
treatment, then it is usually preferable to employ magnesium
sulfate, so as to avoid the introduction of foreign anions into the
system. Magnesium compounds which have no deleterious anion or
which have an anion which is destroyed in the course of the
process, such as magnesium oxide, magnesium hydroxide, and
magnesium carbonate, are also advantageous. Since these are
water-insoluble, it is desirable, however, to combine these with
the complexing agent in the presence of water, and await their
dissolution, indicating that the complex has been formed, before
combining with the pulp, or before commencing the alkaline-oxygen
gas reaction. Any other water-insoluble magnesium compounds can be
used in this way, for instance, magnesium phosphate, magnesium
silicate and magnesium sulfide.
The pretreatment of the cellulose can be effected to advantage with
an acid aqueous solution containing one or more acids, e.g.,
mineral acids such as hydrochloric acid, nitric acid, phosphoric
acid, or sulphurous acid. The use of sulphurous acid is
particularly advantageous in the case of cellulose containing iron
compounds, while sulphuric acid is preferred with cellulose
containing copper and copper compounds. Progressive treatment with
several acid aqueous solutions provides an increased effect if for
example, both iron and copper compounds are present in the
material. The solution may have a pH of 1 or thereover, for
example, from 1.5 to 4, preferably 2 to 3.5. Mixtures of different
mineral acids may also be used, for example, mixtures containing
hydrochloric acid, sulphuric acid, and organic acids such as
formic, acetic, and trichloroacetic acids.
In accordance with a particularly suitable embodiment, the
pretreatment is effected with acid bleaching liquids used in the
bleaching process, or washing water obtained from acid bleaching
stages.
When practicing the pretreatment methods hitherto described, it is
suitable to wash the cellulosic material with water before the
alkaline liquid is charged to the system, wherewith a more
effective removal of the deleterious heavy metal compounds which
catalyze cellulose decomposition is obtained, than if the alkali
were charged directly subsequent to the acid treatment process.
In accordance with another embodiment, which can be applied in the
absence of or in combination with a pretreatment process in an acid
environment, the cellulosic material is subjected to a pretreatment
process in the presence of a complex builder for catalytically
active heavy metal compounds, such as those which contain copper,
cobalt, iron and manganese. Examples of such complexing agents are
ethylene diaminetetraacetic acid (EDTA), nitrilotriacetic acid
(NTA), diethylene-triaminepentaacetic acid (DTPA),
hydroxyethylimindiacetic acid,
hydroxyethylethylene-diaminetriacetic acid (HEDTA) and
polyphosphoric acid and salts of said acids. Amines, for example,
ethylene-diamine, have also been found to give good results,
particularly if cobalt is present. The complex builders can be used
at pH values of, for example, from 4 to 10, preferably 5 to 8. When
treating certain cellulosic materials, it has been found suitable
to add complexing agents having a low pH, e.g., from 2 to 5,
preferably 3 to 4, and then to raise the pH, e.g., by adding
alkali. It is also suitable when practicing this type of
pretreatment to wash the material prior to charging to the system
the alkali necessary for the oxygen treatment.
The pretreatment step can be carried out at any pulp concentration
whatsoever, for example, concentrations within the range from about
1to about 20 percent. For practical reasons, however, a
concentration of 5 to 10 percent is preferred. The temperature may
be room temperature, although an elevated temperature within the
range from 40.degree. to 70.degree. C., for example, gives a more
rapid treatment. In the presence of certain metal compounds, the
treatment time may be very short, for example, 2 minutes. A longer
reaction time from about 10 to about 60 minutes, is often
preferred, however, in order that an acceptable result can be
obtained. If high temperatures and/or long reaction time are used,
a pH of less than 1.5 should be avoided when pretreating with acid
solutions.
In order to further improve the process, surface tension reducing
substances, for example, nonionic or anionic wetting agents, or
mixtures thereof can be used during the oxygen treatment.
The process can also be applied to materials which have previously
been treated in a known manner with, for example, chlorine,
hydrochlorite or chlorine dioxide or a combination of such
bleaching agents. The process can be applied with particular
advantage to a weakly chlorinated cellulose pulp.
The pulp treated in accordance with the process of the invention
can be further processed in accordance with known methods, as
desired. It can, for example, be bleached with chlorine and/or
sodium hydrochlorite and/or chlorine dioxide, and it may also be
subjected to continued refinements, in accordance with known
procedures. In the case of sulphate pulp it has been shown to be
particularly advantageous to treat the pulp with a mixture of
chlorine and chlorine dioxide, followed by alkali extraction and
final bleaching with, for example, chlorine dioxide.
The following example in the opinion of the inventors represent
preferred embodiments of their invention.
EXAMPLE 1
Unbleached pine sulphate pulp was used in these experiments. The
pulp had the following analysis:
Kappa number 31.4 Viscosity 1192 cm..sup.3 /g. ac- Viscosity
cording to SCAN 177 cp. accord- ing to TAPPI
the pulp was pretreated with an acid residual liquid obtained from
a bleaching stage in which a mixture of chlorine and chlorine
dioxide had been used to bleach an acid alkali-treated pulp having
a kappa number of 17. The conditions in this bleaching stage were
as follows:
Pulp concentration % 6 Time, hours 3 Temperature .degree.C. 50
Charge % active chlorine (estimated on pulp) 4.3 Distribution
Cl.sub.2 /ClO.sub.2 (estimated as active chlorine) 85/15 Residual
chlorine % 0.1 Final pH 2.0
the unbleached pulp was treated with the residual acidic liquid,
under the following conditions:
Temperature .degree.C. 20 Time, min. 30 Pulp concentration % 6
Subsequent to this treatment step, the residual liquid was removed
by pressing, after which the pulp was washed with water. The pulp
and an aqueous solution of NaOH and magnesium complex were mixed
carefully to a 3 percent pulp concentration. The pulp was then
dewatered to a concentration of 34 percent. The content of NaOH in
the pulp was then 3.5 percent, calculated on the dry weight of the
pulp, and the content of magnesium complex 0.2 percent, calculated
as MgO. The magnesium complex was produced by dissolving magnesium
sulphate in a liquid containing complexing agents, in this
instance, liquor separated from cellulose pulp which had been
treated with oxygen gas and alkali was used as a complexing agent.
The pulp, which contained NaOH and magnesium complex, was then
loosened in peg shredder, after which it was introduced into a
pressure vessel which was heated by direct steam contact to
100.degree. C. The pressure vessel was then connected to an oxygen
gas tube, and the pressure adjusted to 8 kg./cm..sup.2. After 20
minutes reaction time, the pulp was washed with water. The pulp had
the following analysis:
Kappa number 16.4 Viscosity 852 cm..sup.3 /g. ac- cording to SCAN
viscosity 50 cp. accord- ing to TAPPI
The same starting pulp, treated with acid residual liquid, was
mixed with NaOH and magnesium complex in a similar manner, but with
the alkali charge divided so that only 1.5 percent, estimated on
dry weight of pulp, was charged at a 3 percent pulp concentration,
after which, after 5 minutes reaction time, at 34 percent pulp
concentration and 8 kg./cm..sup.2 oxygen pressure, a further
addition of 2.0% NaOH in atomized liquid form was made, without
magnesium complex. The reaction was continued for 15 minutes more,
after which the pulp was washed with water. The pulp had the
following analysis:
Kappa number 16.2 Viscosity 1003 cm..sup.3 /g. ac- cording to SCAN
Viscosity 81 cp. accord- ing to TAPPI
it is evident that the viscosity becomes very low, if all the
alkali is charged simultaneously with the oxygen-alkali treatment
at high-pulp concentration. By dividing the alkali charge, it is
possible to reduce the initial concentration of alkali, and
considerably improve the viscosity of the pulp.
EXAMPLE 2
Unbleached pine sulphate pulp was used in this experiment. The pulp
had the following analysis:
Kappa number 34.7 Viscosity 1181 cm..sup.3 /g. ac- cording to SCAN
Viscosity 170 cp. accord- ing to TAPPI
the pulp was treated with aqueous ethylene diamine tetraacetic acid
solution (EDTA), with agitation, and under the following
conditions:
Pulp concentration, % 5 Time, min. 30 Temperature .degree.C. 60
EDTA, % of pulp 0.2
After being treated, the pulp was washed with water, after which a
magnesium complex containing alkali was charged successively to the
system, and the pulp treated with oxygen gas, as described in
Example 1. The pulp obtained had the following analysis:
Kappa number 16.0 Viscosity 993 cm..sup.3 /g. ac- cording to SCAN
Viscosity 79 cp. accord- ing to TAPPI
a treatment process according to the invention using complexing
agent (EDTA) during the pretreatment thus has an effect which, from
the point of view of stabilizing the viscosity, is comparable with
a treatment using acidic water. Furthermore, a lower Kappa number
on the oxygen-alkali treated pulp was obtained, despite the fact
that the starting pulp had a higher Kappa number than the pulp used
in Example 1. This can be explained by the fact that an
acid-treated pulp consumes more alkali than a pulp which has not
been acid treated. Oxygen-alkali treatment of pulp which has not
been pretreated with EDTA resulted in the following analysis:
Kappa number 16.3 Viscosity 893 cm..sup.3 /g. ac- cording to SCAN
Viscosity 56 cp. accord- ing to TAPPI
a much poorer viscosity thus is obtained if the pulp is not
pretreated with EDTA, than if a corresponding
oxygen-alkali-treatment is effected on pulp which is pretreated
with EDTA.
EXAMPLE 3
The same EDTA-treated pulp as that used in Example 2 was used in
this experiment. The pulp was dewatered to a pulp concentration of
34 percent, after which the pulp was enclosed in a pressure vessel,
and heated with direct steam contact to 100.degree. C. The pressure
vessel was then connected to an oxygen gas tube, and the pressure
set at 8 kg./cm..sup.2. A solution containing NaOH magnesium
complex according to Example 1 and sodium silicate in a quantity
corresponding to 1.5% NaOH, calculated on the quantity of dry pulp,
was then charged, in atomized liquid form. The quantity of
magnesium complex was 0.1 percent, calculated as MgO, and the
quantity of sodium silicate was 0.3 percent, based on the amount of
dry pulp. After 5 minutes reaction time, more alkali solution was
introduced to the system, corresponding to 2.0% NaOH in atomized
liquid form. The reaction was then continued for another 20
minutes, after which the pulp was washed with water. The pulp had
the following analysis:
Kappa number 15.7 Viscosity 980 cm..sup.3 /g. ac- cording to SCAN
Viscosity 75 cp. accord- ing to TAPPI
good results with regard to Kappa number and viscosity thus can be
obtained according to the invention, even if the alkali addition is
made after the oxygen gas pressure is connected to the pressure
vessel.
EXAMPLE 4
unbleached pine sulfite pulp which after being digested to a pulp
concentration of 5 percent was washed with an aqueous solution
containing ethylene diamine of pH 8.1, the quantity of ethylene
diamine rising to 0.2 percent, estimated on the dry weight of the
pulp, was used for this experiment. The pulp had the following
analysis:
Kappa number 12.6 Viscosity 1144 cm..sup.3 /g. ac- cording to SCAN
Viscosity 142 cp. acord- ing to TAPPI
the liquid was removed by pressing, to obtain a dry content of 50
percent. The pulp was loosened in a peg shredder, after which 2.0%
NaOH in atomized liquid form was added to the pulp. The pulp was
then placed in a pressure vessel, and heated to 90.degree. C. with
direct steam, afterwhich the pressure vessel was connected to an
oxygen gas tube. The pressure was set at 4 kg./cm..sup.2. After 5
minutes reaction time, a further 3% NaOH in atomized form was added
to the pulp, after the oxygen gas overpressure had been
interrupted. The oxygen gas pressure was then reset to 4
kg./cm.sup.2, after which the reaction was continued for another 20
minutes. The pulp was then washed with water. The pulp had the
following analysis:
Kappa number 4.3 Viscosity 675 cm..sup.3 /g. ac- cording to SCAN
Viscosity 28 cp. accord- ing to TAPPI
the results show that a high-pulp concentration can be used when
delignifying viscose pulp according to the invention, and that it
is possible to obtain a controlled viscosity reduction, which is
very desirable in the manufacture of viscose pulp.
* * * * *