Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
WO 2023/006601
PCT/EP2022/070609
Method for producind recienerated cellulosic fibers
Field of the invention
The current disclosure relates to innovations in the field of the production,
use and
application of man-made cellulosic fibers. Particularly the current disclosure
relates to
processes for the production of regenerated cellulosic fibers which are
produced
according to a cold-alkali process, the thus produced fibers and their use.
Description of the Related Art
Man-made cellulosic fibers are manufactured fibers that are based on
cellulosic
matter as a source material.
In the context of the current disclosure the term "cellulose" denotes an
organic
compound derived from plant cell walls or synthetically produced. Cellulose is
a
polysaccharide and is unbranched. Typically, cellulose comprises several
hundred to
ten thousand [3-D-glucose molecules (I3-1,4-glycosidic bound) or cellobiose
units,
respectively. The cellulose molecules that are used by plants to produce
cellulose
fibers are also used in technical processes to produce regenerated cellulose.
The term "regenerated cellulose" denotes a class of materials manufactured by
the
conversion of natural or recycled cellulose to a soluble cellulosic derivative
or a
directly dissolved cellulose solution and subsequent regeneration, forming
shaped
bodies, such as fibers (e.g., rayon), films or foils (e.g., cellophane) or
bulk solids (e.g.
beads, powders or pellets).
The term "fibers", as it is used herein, denotes continuous filaments as well
as cut
staple fibers of any desired length.
Cellulosic fibers can also be in the form of a woven, knitted or non-woven
fabric
comprising the cellulosic fibers. Woven fabrics comprise textile planar
fabrics made
from at least two crossed thread systems, which can be referred to as warp-
and
weft-yarns. By contrast, the yarn in knitted fabrics follows a meandering path
(a
course), forming symmetric loops (also called bights) symmetrically above and
below
the mean path of the yarn.
CA 03226776 2024- 1- 23 SUBSTITUTE SHEET (RULE 26)
WO 2023/006601
PCT/EP2022/070609
2
The term "non-woven fabric" denotes fabrics that are neither woven nor
knitted. Non-
woven fabrics can be in the form of a fabric comprising randomly oriented
fibers
and/or cut yarns of finite length. Non-woven fabrics can also comprise endless
yarns,
e.g. produced by a melt-blown-process.
As viscose fibers, regenerated cellulosic fibers are denoted, which are
manufactured
by means of a wet spinning method which is called viscose-method. The starting
raw
material of the viscose-method is cellulose which is usually provided on the
basis of
wood. From this starting raw material a highly pure cellulose in form of
chemical pulp
is obtained. Additionally or as an alternative other cellulosic materials,
such as
bamboo, cotton linters, recycled cellulosic materials, reed, etc., or mixtures
of such
materials can be used as a starting raw material. In subsequent process
stages, the
pulp is first treated with caustic soda (NaOH), whereby alkali cellulose is
formed. In a
subsequent conversion of said alkali cellulose with carbon disulfide,
cellulose-
xanthogenate is formed. From this, by further supplying NaOH, the viscose-
spinning
solution is generated which is pumped through holes of shower-like spinning
nozzles
into a coagulation bath (also referred to as spin bath). There, one viscose-
filament
per spinning nozzle hole is generated by coagulation. To coagulate the
spinning
solution, an acidic coagulation bath is used. The thus generated viscose-
filaments
are subsequently post processed. The post processing usually comprises several
washing- and stretching steps and the filaments are cut to viscose-staple
fibers.
Several other post-processing steps, such as crimping, bleaching and/or
finishing
("soft finish") can be performed on the uncut and/or the cut fibers. In the
context of
this document, the term õviscose process" denotes such a xanthogenate process.
The term "Lyocell", as used herein, denotes a regenerated fiber type
comprising
cellulose, which is manufactured according to a direct solvent method. The
cellulose
for the lyocell-method is extracted from the raw material containing the
cellulose. The
thus obtained pulp may subsequently be dissolved in a suitable solvent under
dehydration without chemical modification. In large-scale industrial
implementation N-
methylmorpholine-N-oxide (NMMO) is currently used a solvent, nonetheless it is
known that other solvents, such as ionic liquids, can also be used for the
process.
The solution is then filtered and, for the production of fibers, subsequently
extruded
through spinning nozzles into an air gap where they are drawn and coagulated
by
means of a moist airstream and then are fed into a coagulation bath containing
an
CA 03226776 2024- 1-23
WO 2023/006601
PCT/EP2022/070609
3
aqueous NMMO-solution. Subsequently the fibers can be further processed, e.g.
washed, bleached, finished, crimped, cut to staple fibers, etc.
Another well-known process for the manufacturing of regenerated cellulose
fibers is
the carbamate-method, which is similar to the viscose-process but uses urea
instead
of carbon disulfide. Still another process, which is called modal-process, is
a modified
viscose-process for the production of higher quality fibers. For these
processes, also
an acidic coagulation bath is used.
Further, processes for manufacturing of cellulosic products are known that can
use
an alkaline spin bath comprising a salt. To prepare the spinning solution,
cellulose is
dissolved in an aqueous alkaline medium at a controlled temperature Such
processes are herein generally denoted as "cold-alkali process".
W02018/169479 discloses an example of a fiber produced by a cold-alkali
process.
The method comprises: providing a spinning dope comprising a solution of
cellulose
and an additive in an alkaline solvent, in which solvent cellulose is present
at a
concentration of from about 5 to 12 percent per weight by weight and the
additive is
present in the range of from 0.1 ¨ 10 percent per weight by weight calculated
on the
cellulose; contacting the cellulose spinning dope with an aqueous coagulation
bath
fluid having a pH value above 7 and comprising a salt; forming a regenerated
cellulosic fiber composition; and stretching and washing the fiber composition
in one
or more washing and stretching baths.
EP3231901A1 discloses a similar process, wherein a spin dope is prepared by
dissolving cellulose in an aqueous NaOH solution. The spin bath comprises a
coagulation liquid comprising an aqueous sodium salt solution.
EP3231899A1 discloses a method for preparing a spin dope by direct dissolution
of
cellulose in cold alkali.
W02020171767A1 discloses a process for forming a fiber tow involving a wet
spinning procedure comprising the steps of: dissolving cellulose pulp in an
alkaline
aqueous solvent to form a cellulose spin dope composition, spinning the
cellulose
spin dope composition in a coagulation bath having a pH of more than 7.0,
preferably
a pH of at least 10, to produce a fiber tow, and passing the produced fiber
tow
through a sequence of consecutive stretching and washing steps in which the
formed
fiber tow is washed with a washing liquid by a counter-current flow washing
procedure.
CA 03226776 2024- 1-23
WO 2023/006601
PCT/EP2022/070609
4
Especially fibers that are produced according to the cold-alkali process issue
numerous challenges to the post-processing of the fiber. Subsequent production
steps, such as carding, yarn spinning, textile production or fleece
production, require
staple fibers having, for example, a sufficiently high tenacity, low
brittleness and an
appropriate crimp.
Crimping the fibers is generally done by specially profiled rollers that press
the fiber
tow into a wavy pattern before they are cut to staple fibers in a cutter. The
fiber tow
has to be crimped as long as it is still in a sufficiently formable state. The
resulting
staple fibers have a characteristic appearance, wherein bundles of fibers can
be
identified that are arranged in an exactly parallel wavy pattern. The crimp of
all fibers
show the same length and curvature which gives them a regular appearance.
For many applications a more natural crimp would be preferred. As it is used
herein,
the term "natural crimp" designates a crimp pattern of fibers that comprises
waves of
different and randomly distributed curvature and length. Such fibers resemble
more
closely to crimp of some natural fibers, such as cotton of wool.
Summary
The present disclosure describes methods and apparatuses for producing
regenerated fibers and specifically for the post-processing of a fiber tow of
regenerated cellulosic fibers that allow for the production of naturally
crimped fibers
that are produced according to a cold-alkali process.
In a first aspect the present disclosure relates to a method for producing
regenerated
cellulosic fibers comprising extruding a spinning solution into a coagulation
bath
which contains a salt and preferably an alkali to produce a fiber tow, the
spinning
solution comprising cellulose dissolved in an aqueous solvent comprising NaOH
and
ZnO, the coagulation bath having a pH-value of at least seven, wherein the
method
comprises at least the following steps: cutting the fiber tow in an undried
state into cut
fibers, suspending the cut fibers and collecting them in form of a non-woven
fiber
layer, pressing the non-woven fiber layer, thereby imposing a natural crimp on
the
fibers. The method allows for the production of naturally crimped fibers
having
improved post-processing properties.
The person skilled in the art and having knowledge of the teachings disclosed
herein
is able to choose a suitable salt for use in the coagulation bath. The salt
facilitates a
CA 03226776 2024- 1-23
WO 2023/006601
PCT/EP2022/070609
coagulation of the spinning solution and preferably can be present in the
coagulation
bath in a ratio ranging from 10 percent per weight to 30 percent per weight.
Preferably, the salt is a sodium salt, e.g. sodium carbonate or sodium
sulfate. Further
suitable salts can be chosen by taking into account the Hofmeister series
(also known
5 as the lyotropic series), which classifies ions in order of their
precipitation capacities.
The salt should, for one thing, allow for a quick coagulation and secondly, it
should
facilitate recovery and recycling of the compounds. Alternative, but less
preferred
coagulation sodium salts include sodium salts wherein the counter ion is a
carboxylate (e.g. formate, acetate, propionate, butyrate or benzoate), an
aliphatic or
aromatic sulfonate (e.g. benzenesulfonate, toluenesulfonate, or
methanesulfonate),
an aliphatic or aromatic phosphonate ion or mixtures thereof. Preferably, the
anionic
counter ion has a dense electric charge, placing it in the beginning of the
Hofmeister
series. Anionic counter ions having a dense electric charge are characterized
as
strongly "salting out proteins, due to their ability to increase surface
tension and
organize water molecules in solvation shells around them. Further, the
coagulation
sodium salt is preferably a sodium salt precipitating as a hydrate. Preferably
the
molar ratio of water to sodium salt in the precipitated hydrate is at least
4:1.
In one embodiment, the method can comprise a step wherein the fibers in the
fiber
tow are stretched to essentially their final cellulose specific diameter and
oriented to
essentially their final state before being cut to staple fibers in an undried
state. This
allows for the production of fibers with good performance in terms of tensile
strengths
and elongation.
The term "stretched to essentially the final cellulose specific diameter", as
it is used
herein, is to be interpreted to that effect that downstream of this stretching
step no
further stretching steps are preformed on the fiber tow, i.e. the diameter of
the fibers
is held essentially constant until the fibers are either cut (after which a
small amount
of relaxation is unavoidable and sometimes even intended) or dried (where the
diameter of the fibers as it would be actually measured is reduced due to the
loss of
liquid, generally without any change of the stretch of the fibers).
The term "cellulose specific diameter", as it is used herein, denotes a
diameter in a
virtually washed and dried state, i.e. only comprising the dry cellulose. One
example
of a cellulose specific diameter which is used in connection with fibers is
the fiber
titer, which is defined as the weight of the cellulosic contents of the fiber
per unit of
length.
CA 03226776 2024- 1-23
WO 2023/006601
PCT/EP2022/070609
6
In case of fibers having a circular cross-section, the diameter corresponds to
the
diameter of the circular cross-section. As a generic definition, the diameter,
as it is
used herein, corresponds to the diameter of the largest circle that can be
inscribed
into the cross-section of the fiber (across the main axes). For example, the
diameter
of a fiber having an elliptic diameter would correspond to the lengths of the
minor axis
of the ellipse.
The term "oriented to essentially their final state", as it is used herein, is
to be
interpreted to that effect that the molecular orientation of the cellulose in
the fibers is
not actively changed in downstream processing steps, i.e. remains constant,
apart
from minor changes that may occur naturally or are a (generally unwanted) side
effect of other downstream post-processing steps.
The term "undried", as it is used herein, defines a state, where the wet fiber
has only
been dewatered with mechanical means, i.e. by squeezing, and has not undergone
any drying step. More specifically, the term designates a never-dried fiber,
i.e. a fiber
that has not undergone any drying step after extrusion.
According to a further embodiment, after leaving the coagulation bath, the
fiber tow is
routed into at least one conditioning bath, the conditioning bath comprising
from 10
percent per weight to 30 percent per weight a salt that facilitates a further
coagulation
of the spinning solution, the conditioning bath preferably being fluidly
separated from
a downstream washing line, wherein the fibers in the fiber tow are stretched
to
essentially their final cellulose specific diameter and oriented to
essentially their final
state in the at least one conditioning bath. The method allows for a cost-
effective fiber
production and reduces the complexity of threading the fiber tow at the
production
startup. It was surprisingly found that stretching the fibers to their final
cellulose
specific diameter and state within the conditioning bath allows for an
economic and
controllable production of fibers having adequate properties that allow, for
example, a
spinning of fibers to yarn. The process is scalable to large-industry scale.
The term "fluidly separated", as it is used herein, denotes systems that are
either
associated to completely separated circulation systems, or that are connected
via an
installation that significantly changes the properties of the liquid, e.g. by
adding
substances to and/or removing substances from the liquid or by concentrating
or
diluting the liquid.
CA 03226776 2024- 1-23
WO 2023/006601
PCT/EP2022/070609
7
The salt in the conditioning bath can preferably be identical to the salt that
is used in
the coagulation bath, or it can be chosen according to the same requirements
as the
salt in the coagulation bath that are outlined above.
In one further embodiment, the coagulation bath and the conditioning bath are
fluidly
connected, wherein the temperature of the coagulation bath and the temperature
of
the conditioning bath can preferably be independently set, adjusted and/or
maintained. This facilitates the setup of optimized process conditions that
allow for a
complete and advantageous orientation and a strong stretching of the fibers in
the
conditioning bath.
The term "fluidly connected", as it is used herein, denotes units (e.g. a
bath, such as
the coagulation bath or the conditioning bath, or a washing unit) that are
associated
to the same circulation system, without having interposed between them an
installation that significantly changes the properties of the liquid, e.g. by
adding
substances to and/or removing substances from the liquid or by concentrating
or
diluting the liquid. For example, one unit can be serially connected to
another unit and
being traversed by a liquid stream, e.g. in a countercurrent-arrangement or in
a
concurrent-arrangement. In another approach the fluidly connected units could
be
independently fed from the same reservoir.
Instead of only one conditioning bath, also a series of two or more
conditioning baths
could be applied. This would allow an individual adjustment of the temperature
of the
coagulation liquid and a stepwise stretching of the fibers at different
temperatures. On
one hand, this would increase the costs and the complexity of the production
process, on the other hand it could be possible to improve fiber properties.
According to another embodiment, the fiber tow is routed through a washing
line, the
washing line comprising at least one washing step, wherein the washing line is
preferable arranged downstream of the at least one conditioning bath, and
wherein
the tension of the fiber tow and the cellulose specific diameter of the fibers
are
preferably kept essentially constant in the washing line. This further
"fixates" the
orientation and the elongation of the molded bodies and allows for a good
performance of the molded bodies, e.g. in terms of strengths and
extensibility.
The method described herein can further be improved by any technically
feasible
combination of one or more of the following steps:
CA 03226776 2024- 1-23
WO 2023/006601
PCT/EP2022/070609
8
- Washing the fiber tow or the non-woven fiber layer preferably with water.
Washing the already cut fibers in form of a non-woven fiber layer can be
realized in a more economic way that it is possible with the uncut fiber tow.
- Neutralizing the fiber tow or the non-woven fiber layer with an acidic
liquid,
wherein the acidic liquid may preferably be selected from diluted acetic acid,
lactic acid, sulphuric acid or the like. Alkaline residues can so be
neutralized.
Preferably a second washing step can be done after the neutralizing step to
wash out the salts that formed during the neutralizing step.
- Bleaching the fiber tow or the non-woven fiber layer.
- Application of a crosslinking agent on the fiber tow or the non-woven fiber
layer, e.g. to reduce fibrillation.
- Application of a finishing agent, particularly a soft finish, onto the
fiber tow or
the non-woven fiber layer. The (soft) finishing, for example, improves the
spinnability of the fibers and the quality of the so produced products.
- Drying the non-woven fiber layer, preferably in a drum dryer or a conveyor
dryer. Already cut fibers are not subjected to a tensile stress during drying
(as
it would be in the case of drying the fiber tow before cutting) which can
improve the fiber quality.
- Squeezing the fiber tow or the non-woven fiber layer before and/or after
any
other processing step. Squeezing can, for example, be easily done by running
the non-woven fiber layer of cut fibers through pressing rollers. Especially
at
the beginning of the post-processing of the non-woven fiber layer the
additional pressing can change and further improve the extent and quality of
the crimp.
The steps listed above can be implemented in any technically reasonable and
useful
order, and the person skilled in the art, being aware of the current
teachings, is able
to implement numerous configurations without deviating from the current
disclosure.
In another preferred embodiment the post-processing further can comprise at
least
one step of opening the non-woven fiber layer to loosen up and/or at least
partially
separate the fibers. The opening can improve downstream post-processing steps,
such as drying and baling, and facilitates the opening of the baled fibers. On
the other
CA 03226776 2024- 1-23
WO 2023/006601
PCT/EP2022/070609
9
hand, the opening allows to provide a fiber layer with a higher density in the
upstream
post-processing steps, which can be then be implemented in a more economic
way.
In a second aspect, the present disclosure relates to a processing facility
for
producing regenerated cellulosic fibers comprising a spinneret for extruding a
spinning solution into a coagulation bath which contains a salt and preferably
an
alkali to produce a fiber tow, the spinning solution comprising cellulose
dissolved in
an aqueous solvent comprising NaOH and ZnO, the coagulation bath having a pH-
value of at least seven, wherein the processing facility comprises a cutter to
cut the
fiber tow in an undried state into cut fibers, a fleece-forming device for
suspending
the cut fibers and collecting them in form of a non-woven fiber layer, and at
least on
pressing device for pressing the non-woven fiber layer, thereby imposing a
natural
crimp on the fibers. The processing facility allows for the industrial
implementation
and scale-up of the methods disclosed herein. A crimping facility in the fiber-
tow line
is not needed.
In a preferred embodiment the facility further comprises at least one
stretching device
for stretching the fibers in the fiber tow to essentially their final
cellulose specific
diameter and orienting the cellulose in the fibers to essentially their final
state.
According to another embodiment, the facility further can comprise at least
one
conditioning bath downstream of the coagulation bath, the conditioning bath
comprising from 10 percent per weight to 30 percent per weight a salt that
facilitates
a further coagulation of the spinning solution, the conditioning bath
preferably being
fluidly separated from a downstream washing line, and at least one stretching
device
for stretching the fibers in the fiber tow to essentially their final
cellulose specific
diameter and orienting the cellulose in the fibers to essentially their final
state within
the at least one conditioning bath.
According to still another embodiment, the coagulation bath and the
conditioning bath
are fluidly connected, wherein the temperature of the coagulation bath and the
temperature of the conditioning bath can preferably be independently set,
adjusted
and/or maintained. By setting these parameters the coagulation speed can be
optimized to provide sufficiently strong and extensible fibers.
According to a further embodiment, the fiber tow is routed through a washing
line, the
washing line comprising at least one washing step, wherein the washing line is
preferable arranged downstream of the at least one conditioning bath, and
wherein
CA 03226776 2024- 1-23
WO 2023/006601
PCT/EP2022/070609
the tension of the fiber tow and the cellulose specific diameter of the fibers
are
preferably kept essentially constant in the washing line. Washing the fiber
tow in a
tensioned state (and preferably without stretching them any further) can
improve fiber
properties.
5 According to other embodiments, the processing facility may further
comprise one or
more treatment facilities, which are independently selected from a list
comprising:
- one or more washing devices for washing the fiber tow or the non-woven
fiber
layer,
- one or more further pressing devices for squeezing the fiber tow or the
non-
10 woven fiber layer,
- a neutralizer for neutralizing the cut or uncut fibers with an acidic
liquid,
- a bleaching facility for bleaching the cut or uncut fibers,
- a crosslinking facility for the application of a crosslinking agent on
the cut or
uncut fibers,
- a finishing facility for applying a finishing agent, particularly a soft
finish, to the
cut or uncut fibers,
- an opener for opening the non-woven fiber layer to loosen up and/or at
least
partially separate the cut fibers,
- a dryer, preferably a drum dryer or a conveyor dryer, to dry fibers.
This improves the scalability and allows for large-scale industrial
application. The
facilities listed above can be implemented in any technically reasonable and
useful
order and the person skilled in the art, being aware of the current teachings,
is able to
implement numerous configurations without deviating from the current
disclosure.
In a third aspect, the present disclosure relates to regenerated cellulosic
fibers
produced in a processing facility as described herein and/or produced by a
method
as described herein. The fibers can meet enhanced quality standards, both in
view of
requirements for further processing steps as well as in terms of properties of
intermediate- and end products comprising the fiber.
In another aspect the present disclosure relates to a product, particularly a
consumer
product or an intermediate product, comprising the regenerated cellulosic
fibers as
disclosed herein. Preferably, the product can be selected from a list
comprising
CA 03226776 2024- 1-23
WO 2023/006601
PCT/EP2022/070609
11
yarns, fabrics, textiles, home textiles, garments, nonwovens, hygiene
products,
upholstery, technical applications, such as filter material, paper.
Brief Description of the Drawings
Hereinafter, exemplary embodiments of the invention are described with
reference to
the drawings, wherein
Fig. 1 is a schematic and exemplified representation of a
fiber production
process according to the present disclosure focusing on the spinning
dope preparation and
Fig. 2 is a schematic and exemplified representation of processing facility
according to the present disclosure focusing on the post-processing of
the spun fibers.
Detailed Description of the Drawings
Fig. 1 shows a flowchart representing an exemplary fiber production process
according to the present disclosure. The diagram is a simplified
representation and
shows the process in a schematized manner.
The process can be sectioned into the following basic steps, which are denoted
in
with roman numbers in Fig. 1:
I. Supplying the raw material
For the process according to the present disclosure a broad range of possible
cellulosic raw materials can be used. Generally the intrinsic viscosity and
the degree
of polymerization of the cellulose used as a raw material is lower than it is
common
for the viscose- or lyocell-process. For example dissolving pulp (kraft or
sulphite) with
an intrinsic viscosity (measured in Cuen, according to SCAN-CM 15:99) of about
200
mL/g to 700 mL/g (degree of polymerization DP of 500 to 1900), preferably
between
about 250 and about 400 mL/g (DP or 600 to 950) can be used. Further,
recycling
pulp or cotton linters (preferably having the same DP as stated above) can be
used.
The recycling pulp can, for example, be derived from waste paper, recycled
viscose
textile material, recycled modal textile material, recycled lyocell textile
material an/or
recycled cotton fiber textile material. Blends of pulps of different origin,
such as
blends of virgin wood pulp with recycling pulp, are possible and may be even
desirable.
CA 03226776 2024- 1-23
WO 2023/006601
PCT/EP2022/070609
12
In Fig. 1 a staple of dissolving pulp 1 is exemplarily depicted as the raw
material
II. Pretreatment of the raw material
The cellulosic raw material can be subjected to a pretreatment, wherein the
degree of
polymerization is adjusted to a desired DP to adjust the viscosity of the
spinning dope
to a value that allows for filtering and spinning. The pretreatment can
comprise
subjecting the raw material to an acidic pulp treatment, wherein the DP-value
is
mainly influenced by the duration of the pretreatment and the concentration of
the
acid. In other cases the pretreatment can be omitted, if the DP-value is
already at the
desired value. For example, pulp derived from cellulosic regenerate fibers may
have
a DP that allows for a direct dissolution without a pretreatment
In a more specific example, an acidic pulp treatment with 1-10 percent per
weight
sulfuric acid at 50 C to 95 C for a duration from 5min to 2h can be used as a
pretreatment. As the profitability of the process is reduced by a long
duration of this
treatment step, it is generally preferable to minimize the duration of the
pretreatment
as far as possible. The person skilled in the art, who is aware of the
teachings of this
disclosure is able to find suitable parameters and optimize them without undue
burden.
The pretreatment further comprises washing the cellulosic material with water
and
pressing to reduce moisture content, e.g. to about 50 percent per weight of
the
cellulosic material.
In Fig. 1 a source for a pretreatment chemical 2, e.g. sulfuric acid, and a
pretreatment
vessel 3 are exemplarily depicted. After the pretreatment in pretreatment
vessel 3 the
cellulosic material can be squeezed and washed to reduce the amount of acid
that is
transported to the next step.
III. Preparation of the spinning dope
To prepare the spinning dope (also called spinning solution), the wet and
pretreated
pulp is first cooled to about 0 C (while freezing of the pulp should be
avoided), and an
aqueous solvent comprising NaOH and ZnO is prepared. Preferably the solvent is
adjusted to provide a spinning solution comprising 5 to 10 percent per weight
NaOH
and 0.8 to 3 percent per weight ZnO. The solvent is cooled down to a process
temperature, which preferably lies between -5 C and -10 C.
CA 03226776 2024- 1-23
WO 2023/006601
PCT/EP2022/070609
13
The pulp and the solvent are blended to dissolve the cellulose in the solvent.
To
improve the processability, the preparation of the spinning dope comprises a
mixing
step followed by a homogenization step. During the mixing step the blend is
mixed
with a high shear stress, which can be done in a high-shear mixer. This high
shear
stress mixing is preferably only performed for a rather short period of time,
for
example the mixing can be done for 1 ¨2 minutes. In the following
homogenization
step the blend is agitated with a lower shear intensity. The homogenization
step can
last longer than the mixing step, for example about 5 minutes.
During both the mixing and the homogenization step the temperature of the
mixture is
controlled, especially cooled. Preferably the temperature is kept below 0 C.
The
process temperature should never exceed 5 C, as the solution could then
thicken
and be irrecoverably lost.
The so prepared spinning solution is then filtered and de-aerated. For
example, the
spinning dope can be filtrated at least twice via a KK filter (Kolben-Korb-
Filter,
Lenzing Technik) with a mesh size of 15 micrometer.
For the de-aeration the spinning solution is exposed to reduced pressure. This
step is
per-se known from the viscose process. Other techniques for filtering and de-
aerating
the dope that can be used are known to the person skilled in the art.
The prepared spinning dope should be free of voids, have a homogenous
consistency and a proper viscosity that allows for an extrusion in the
spinneret used
in the following extrusion step.
In a preferred embodiment the ballfall-viscosity of the spinning dope should
be in the
range of about 30 to 200 s. The ballfall-viscosity can be measured according
to DIN
53015-2019. The viscosity of the spinning dope can be adjusted by several
different
means. For example, the viscosity can be adjusted by altering the DP-value of
the
cellulose, by changing the composition of the solvent and/or the concentration
of the
cellulose in the spin dope. For example, the concentration of the cellulose
can be in
the range of about 4 percent per weight to about 12 percent per weight,
particularly in
the range of about 5 percent per weight to about 8 percent per weight
preferably
about 6 percent to about 7 percent per weight.
The specific parameters of the mixing, homogenization and filtering steps can
be
found by the person skilled in the art, who is aware of the current
disclosure, by
routine work and experimentation.
CA 03226776 2024- 1-23
WO 2023/006601
PCT/EP2022/070609
14
In Fig. 1 a chemical repository 4 for the storage of the ingredients of the
solvent, a
solvent cooling device 5 for the cooling of at least parts of the solvent, a
pulp cooling
device 6, a mixing vessel 7 and a de-aerating filter 8 are exemplarily
depicted. The
mixing vessel 7 is provided with a cooling jacket 9.
IV. Extrusion into the coagulation bath
The spinning dope can be extruded through a nozzle directly into a coagulation
bath.
In case additives are added to the spinning dope, the dope can be homogenized
via
a static mixer to incorporate additives. Before the extrusion step, the dope
can
preferably be tempered to spinning temperature, for example to a temperature
in the
range of from 5 C to 30 C. For fiber production, a straightforward approach
could be
to use as the extrusion nozzle a spinneret comprising, for example, up to 150
cups
with a diameter of 12.5 to 16 mm, comprising up to 3000 holes with a diameter
of
about 40 to 75 micrometer, which corresponds to dimensions as they are known
per
se and commonly used in connection with the viscose spinning process.
Nonetheless, it was surprisingly found that in connection with the cold-alkali
process
broader diameters can improve process stability and facilitate the coagulation
and
stretching of the fibers. According to the present disclosure it is therefore
suggested
to use a spinneret comprising holes with a diameter of about 80-120 pm,
preferably
between 90 and 110 pm. For example, in an industrial scale production plant
one
spinneret could comprise up to 150 cups with a diameter of 12,5 to 16 mm,
comprising about 600 to 1400 holes with a diameter of about 80-120 pm,
preferably
between 90 and 110 pm. The relatively thick diameter of the spinning holes
causes
different course of coagulation, i.e. that the freshly extruded fibers first
only coagulate
at the outer surface, while the middle of the fiber stays in a liquid state
for a longer
time. This allows for a higher stretching and the stretching conditions can be
uphold
in a more stable way.
The coagulation bath comprises an alkali, preferably NaOH, and a salt,
preferably
sodium carbonate, Na2CO3, or sodium sulfate, Na2SO4. As an example, the
coagulation bath can comprise from 10 percent per weight to 30 percent per
weight
Na2003 or Na2SO4 and from 0 to 3 percent per weight NaOH, preferably from 0.1
to
3% and still more preferred from 0.2 to 0.7 percent per weight NaOH. In a
specific
example the coagulation bath can comprise about 22 percent per weight Na2CO3
and
about 0.5 percent per weight NaOH. The temperature of the coagulation bath
can, for
CA 03226776 2024- 1-23
WO 2023/006601
PCT/EP2022/070609
example, be adjusted to between 10 C and 30 C, and preferably be tempered at
about 20 C.
The optimal distance, that the freshly extruded fiber travels through the
coagulation
bath (i.e. the coagulation bath distance) depends, inter alia, on the
extrusion speed,
5 the pull-off speed, the composition and consistency of the spinning dope,
the
composition of the coagulation bath and the temperature. Without being
restricted to
these values, under most parameter conditions the optimal coagulation bath
distance
may be found within a range from about 10 cm to about 100 cm. Preferred values
for
the coagulation bath distance range from about 15 cm to about 60 cm.
10 The fiber tow is drawn out of the coagulation bath to a transporting
section, which can
comprise several godets and/or pulleys that transport the fiber tow through a
series of
post-processing stages. The pull-off force that is exerted on the freshly
extruded
fibers can be regulated by the extrusion speed and the speed of the first
transporting
unit (or godet), which preferably can be positioned outside of the coagulation
bath.
15 Due to the pull-off force, which is exerted on the freshly extruded
fibers by the first
transporting unit, the fibers get stretched already inside the coagulation
bath. Further
stretching steps can be during the following post processing of the fibers.
In Fig. 1 a coagulation bath 10 comprising a coagulation liquid 11, a
spinneret 12 and
a first godet 13 are exemplarily depicted. The spinneret 12 extrudes a number
of
fibers 14 (corresponding to the number of holes of the spinneret 12) into the
coagulation liquid 11. The freshly extruded fibers 14 are gathered together
into a fiber
tow 15 by the first godet 13. By adjusting the extrusion speed at the
spinneret 12 and
the speed of the godet 13 the amount of stretching, that is done directly
after
extrusion within the coagulation bath 10 can be set. Although an inclined
angle of the
spinneret 12 (and the freshly extruded fibers 14) is shown in Fig. 1, the
skilled
practitioner, who is aware of the current teaching, is able to apply other
spinning
configurations that are per se known in the field, e.g. from viscose
production.
V. Post-processing of the fiber tow
As it is used throughout this disclosure, the term "post-processing"
encompasses all
processing steps that are performed on the extruded fibers after they have
been
withdrawn from the coagulation bath. Post-processing steps can be applied to
the
fiber tow while it is transported on the transporting unit. Additionally, the
fiber tow can
CA 03226776 2024- 1-23
WO 2023/006601
PCT/EP2022/070609
16
be cut in a cutting apparatus and further post-processing steps can be
performed on
the cut fibers.
In Fig. 1 the post-processing is only schematically represented by the
respective
reference sign V.
Post-processing of the fibers can comprise, but are not restricted to, any
combination
of one or more of the following steps:
- washing of the fiber tow and/or the cut fibers,
- squeezing the fiber tow and/or the cut fibers to reduce the amount of
liquid
therein,
- neutralizing the fiber tow and/or the cut fibers with an acidic liquid,
- bleaching the fiber tow and/or the cut fibers,
- crosslinking the fiber tow and/or the cut fibers by applying a
crosslinking agent
on the fibers,
- applying a finishing agent ("soft finish") to the fibers of the fiber tow
and/or the
cut fibers,
- drying the cut fibers.
Immediately after the fibers in the fiber tow have been withdrawn from the
coagulation bath, they already have been stretched to a certain extent, but
may not
have reached their final elongation (and final cellulose specific diameter).
In a different approach, several successive stretching steps during the post-
processing can be implemented. For example a counter current flow washing can
be
implemented in the post processing, wherein the fibers in the fiber tow are
being
incrementally stretched during and/or in-between the several washing steps
until they
have reached their final extension.
According to another approach, the fiber tow can be led into a conditioning
bath
comprising from 10 percent per weight to 30 percent per weight a salt that
facilitates
a further coagulation of the spinning solution, the conditioning bath
preferably being
fluidly separated from any downstream washing facilities, and stretched to
essentially
the final cellulose specific diameter of the fibers and oriented to
essentially their final
state within the conditioning bath. The conditioning bath can comprise a
coagulation
liquid that is similar or identical to the coagulation bath liquid. The
coagulation speed
CA 03226776 2024- 1-23
WO 2023/006601
PCT/EP2022/070609
17
in the conditioning bath can be adjusted by the temperature of the liquid
therein,
which preferably can be controlled independently from the coagulation bath.
Following the second bath, the fiber tow can be washed in a downstream washing
line, where no additional stretching is applied to the fiber.
As the case may be (and according to the technical requirements), other post-
processing steps can be arranged in the processing line according to any
technically
useful configuration.
Fig. 2 is a schematic block-diagram showing an exemplary configuration of a
post-
processing facility for treating a fiber-tow which is produced according to
the current
disclosure, e.g. by the facility depicted in Fig. 1.
Fibers 14 are extruded by a spinneret 12 into a coagulation liquid 11 within a
coagulation bath 10 and gathered together into a fiber tow 15 by the first
godet 13
(similar to Fig. 1). From the first godet 13 the fiber tow is directed to a
second godet
18. Between the first godet 13 an the second godet 18 the fiber tow 15 is
diverted via
a guide 16, e.g. a roller, bar or the like, and submerged into a conditioning
bath 17
containing a coagulation liquid 11'. The coagulation liquid can be identical
or similar
to the coagulation liquid 11 in the coagulation bath 10. Preferably the
coagulation
liquid 11 in the coagulation bath 10 and the coagulation liquid 11' in the
conditioning
bath 17 are circulated in a common fluid cycle. Preferably the temperature of
the
coagulation liquid 11' in the conditioning bath 17 can be controlled
independently
from the temperature of the coagulation liquid 11 in the coagulation bath 10.
Generally a higher temperature is preferred for the coagulation liquid 11' in
the
conditioning bath 17. For example, the temperature of the coagulation liquid
11 in the
coagulation bath 10 can be adjusted to a value between about 10 C and about
20 C
and the temperature of the coagulation liquid 11' in the conditioning bath 17
can be
adjusted to a value between about 20 C and about 40 C.
Between the first godet 13 and the second godet 18 and essentially within the
conditioning bath 17 the fibers in the fiber tow are stretched to essentially
their final
cellulose specific diameter and oriented to essentially their final state.
In Fig. 2 only one conditioning bath is shown. Nonetheless it would be
possible to
install more than one conditioning bath, for example two successive
conditioning
baths or a series of consecutive conditioning baths. Preferably the
conditioning baths
share the same fluid circuit with the coagulation bath and have an essentially
CA 03226776 2024- 1-23
WO 2023/006601
PCT/EP2022/070609
18
identical or at least similar content of salt and/or alkali. The temperatures
of the
conditioning baths can either be the same or controlled independently, as the
case
may be. Depending on the configuration, the fibers can, for example, be
stretched in
a cascading style, i.e. consecutive conditioning baths have an increasing
stretching
rate. The fibers could also be stretched to essentially their final state in
an upstream
conditioning bath (or several upstream conditioning baths) and than be further
coagulated and "fixated" within one (ore more) downstream conditioning bath(s)
with
constant speed and stretch. The person skilled in the art and having knowledge
of the
teachings disclosed herein is able to optimize the number of conditioning
baths, their
temperatures and extension rated by routine tests and experiments without
deviating
from the scope of the current disclosure. The fiber parameters, such as
tensile
strength, elongation, crystallinity etc., can so be optimized in a methodical
manner.
From the second godet 18 the fiber tow 15 is directed to a washing line 19
which can
comprise several washing steps which are exemplarily depicted in Fig. 2 as
washing
steps 20 and 20'. As the case may be, the washing line 19 can also comprise
only
one washing step 20 or any number of washing steps exceeding two. Further, any
washing techniques for washing fiber tows, that are known per se in the art,
can be
used for in the washing line 19.
The transporting means for the fiber tow, such as rollers and godets or the
like, in the
washing line are operated at a constant speed so that the tension is kept
essentially
constant and no further stretching of the fibers in the fiber tow occurs. This
also
keeps the orientation of the fibers essentially at the state they were when
leaving the
second godet 18 after the stretching within the conditioning bath.
After the washing line 19 the fiber tow 15 is directed to a cutter 21, which
cuts the
fiber tow into staple fibers 22. During the washing steps 20 the consistency
of the
fibers has sufficiently settled so that the fibers essentially keep their
cellulose specific
diameter, elongation and orientation even if they are cut in wet or never-
dried state.
Therefore, it is not necessary to dry the fiber tow 15 before cutting, which
can reduce
costs and allows for the implementation of more efficient post-processing
steps.
In the lower part of Fig. 2 an exemplary post-processing facility for the cut
staple
fibers is shown. The cut staple fibers are transported (or fall) from the
cutter 21 to a
fleece-forming device 23 having a basin 24 filled with a liquid, e.g. water,
and a
conveyer belt 25. The conveyer belt 25 is permeable to liquid and a current is
maintained in the basin that transports the fibers that are suspended in the
liquid of
CA 03226776 2024- 1-23
WO 2023/006601
PCT/EP2022/070609
19
the basin to the conveyer belt 25, where they are collected and form a non-
woven
fiber layer 26 on the top surface of the conveyer belt 25. The surface of the
conveyor
belt is tilted and transports the newly formed non-woven fiber layer 26 out of
the liquid
and to further transport equipment (which is, for reasons of conciseness, not
shown
in Fig. 2). The freshly cut staple fibers 22 should be regularly distributed
across the
width of the fleece-forming device 23 so that the non-woven fiber layer 26 has
a
uniform width and consistency.
After leaving the fleece-forming device 23, the non-woven fiber layer 26 is
squeezed
in a first pressing device 27a to remove some of the liquid in the non-woven
fiber
layer 26. Several further pressing devices 27b to 27e can be arranged
downstream
between several processing steps. Especially the first pressing device 27a,
but also
the other pressing devices, create a natural crimp on the fibers in the non-
woven fiber
layer which is preferable for many fiber appliances.
The post-processing that is performed on the non-woven fiber layer 26, as it
is shown
in Fig. 2, comprises a neutralizer 28, a bleaching facility 29, a crosslinking
facility 30,
a finishing facility 31, an opener 32, a dryer 33 and a baling press 34.
In the neutralizer 28 the fibers that may still contain residues of alkali are
neutralized
with an acidic liquid, which can be selected from a list comprising diluted
acetic acid,
lactic acid, sulphuric acid or the like. Depending on the specific processing
conditions, a neutralizing step may not always be necessary.
The fibers in the non-woven fiber layer 26 are then bleached in bleaching
facility 29. If
appropriate, a further washing step (not shown in Fig. 2) can be implemented
between the neutralizer 28 and the bleaching facility 29. The used water of
this (and
any other) washing step can be forwarded to upstream washing steps and/or the
cutter 21 of the washing line 19 in the form of a countercurrent washing
system.
In the crosslinking facility 30 a crosslinking agent can be applied to the
fibers in order
to reduce fibrillation of the fibers and improve the processing and handling
of the
fibers in the textile chain.
In the finishing facility 31 a finishing agent or soft finish can be applied
to the fibers.
After dewatering the non-woven fiber layer 26 in the pressing device 27e the
non-
woven fiber layer 26 is fed into an opener 32, which loosens and opens the
structure
of the fiber layer 26 to improve the drying efficiency in the following dryer
33 and also
to improve the further processing of the finished staple fibers.
CA 03226776 2024- 1-23
WO 2023/006601
PCT/EP2022/070609
Reference signs:
dissolving pulp 1
source for a pretreatment chemical 2
5 pretreatment vessel 3
chemical repository 4
solvent cooling device 5
pulp cooling device 6
mixing vessel 7
10 de-aerating filter 8
cooling jacket 9
coagulation bath 10
coagulation liquid 11
spinneret 12
15 first godet 13
fibers 14
fiber tow 15
guide 16
conditioning bath 17
20 second godet 18
washing line 19
washing step 20
cutter 21
staple fibers 22
fleece-forming device 23
basin 24
conveyer belt 25
non-woven fiber layer 26
pressing device 27
neutralizer 28
bleaching facility 29
crosslinking facility 30
finishing facility 31
opener 32
dryer 33
baling press 34
CA 03226776 2024- 1-23
