U.S. patent application number 16/072514 was filed with the patent office on 2019-01-31 for wet spinning method for producing a lignin-containing fiber as a precursor for a carbon fiber.
This patent application is currently assigned to FRAUNHOFER-GESELLSCHAFT ZUR FORDERUNG DER ANGEWANDTEN FORSCHUNG E. V.. The applicant listed for this patent is FRAUNHOFER-GESELLSCHAFT ZUR FORDERUNG DER ANGEWANDTEN FORSCHUNG E. V.. Invention is credited to Jens ERDMANN, Johannes GANSTER, Andre LEHMANN, Robert PROTZ.
Application Number | 20190032250 16/072514 |
Document ID | / |
Family ID | 55300478 |
Filed Date | 2019-01-31 |
United States Patent
Application |
20190032250 |
Kind Code |
A1 |
GANSTER; Johannes ; et
al. |
January 31, 2019 |
WET SPINNING METHOD FOR PRODUCING A LIGNIN-CONTAINING FIBER AS A
PRECURSOR FOR A CARBON FIBER
Abstract
The invention relates to a method for producing a precursor
fiber which is suitable for further processing into carbon and
activated carbon fibers. The method is a wet spinning method in
which a spinning solution consisting of lignin or lignin
derivatives, cellulose carbamate, and alkali lye are pressed
through the holes of a nozzle and introduced directly into a
coagulation bath. The precursor fibers falling into the bath can
undergo different additional method steps: they can be stretched,
post-treated, dried at an increased temperature, and wound. Because
the precursor fibers constitute an inexpensive starting material,
the precursor fibers can be used in connection with the production
of carbon and activated carbon fibers.
Inventors: |
GANSTER; Johannes; (Potsdam,
DE) ; LEHMANN; Andre; (Potsdam, DE) ; PROTZ;
Robert; (Wolllin, DE) ; ERDMANN; Jens;
(Berlin, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
FRAUNHOFER-GESELLSCHAFT ZUR FORDERUNG DER ANGEWANDTEN FORSCHUNG E.
V. |
Munchen |
|
DE |
|
|
Assignee: |
FRAUNHOFER-GESELLSCHAFT ZUR
FORDERUNG DER ANGEWANDTEN FORSCHUNG E. V.
Munchen
DE
|
Family ID: |
55300478 |
Appl. No.: |
16/072514 |
Filed: |
January 26, 2016 |
PCT Filed: |
January 26, 2016 |
PCT NO: |
PCT/EP2016/051589 |
371 Date: |
July 25, 2018 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
D01F 2/24 20130101; D01F
9/16 20130101; D01F 9/17 20130101 |
International
Class: |
D01F 9/17 20060101
D01F009/17; D01F 2/24 20060101 D01F002/24 |
Claims
1-24. (canceled)
25. A method for producing a lignin-containing precursor fiber for
the production of carbon fibers and/or activated carbon fibers,
wherein a spinning solution containing A) at least one type of
lignin or lignin derivative , B) a cellulose carbamate, and C) a
solvent, is extruded through a holed spinning nozzle immersed in a
coagulation bath, wherein the lignin-containing precursor fiber
precipitates.
26. The method according to claim 25, wherein the at least one type
of lignin or the lignin present in the lignin derivative is
extracted from a coniferous wood, deciduous wood, or annual plant
source.
27. The method according to claim 25, wherein the lignin has a
weight-average molar mass between 500 g/mol and 20,000 g/mol.
28. The method according to claim 25, wherein the cellulose
carbamate has a DP.sub.Cuoxam determined by viscosimetry between
150 and 750, wherein the cellulose carbamate has a degree of
substitution between 0.1 and 1.0.
29. The method according to claim 25, wherein the cellulose
carbamate is present in a concentration of more than 6 wt. %,
relative to the spinning solution.
30. The method according to claim 25, wherein the solvent is
selected from the group consisting of alkali lyes; tertiary amine
oxides; ionic liquids selected from the group consisting of
imidazolium compounds, pyridinium compounds, and
tetraalkyl-ammonium compounds; and mixtures thereof.
31. The method according to claim 25, wherein the spinning solution
has a mass ratio of cellulose carbamate to the at least one type of
lignin or lignin derivative between 0.60 and 1.80.
32. The method according to claim 25, wherein the spinning solution
is produced by stirring or kneading the at least one type of lignin
or the lignin derivative as well as the cellulose carbamate in the
solvent at a temperature of less than 0.degree. C.
33. The method according to claim 25, wherein the spinning solution
further contains spinning auxiliaries selected from the group
consisting of inorganic substances, organic additives, and mixtures
thereof.
34. The method according to claim 25, wherein the spinning solution
is filtered before extrusion through the holed spinning nozzle into
the coagulation bath.
35. The method according to claim 25, wherein the holed spinning
nozzle has a spinning hole diameter of 50 to 500 .mu.m.
36. The method according to claim 25, wherein the coagulation bath
has a pH value between 1 and 7.
37. The method according to claim 25, wherein the coagulation bath
contains water and/or a solvent selected from alcohols, saturated
or unsaturated hydrocarbons, polar-aprotic compounds, water, acid,
acid salt, and mixtures thereof
38. The method according to claim 25, which further includes: the
precursor fiber precipitated in the coagulation bath is introduced
into a stretching bath and stretched to 110 to 500% of its length,
wherein the stretching bath contains water, air, or a mixture of
water and a solvent, (ii) the precursor fiber from (i) is washed
with distilled water, (iii) the precursor fiber from (ii) is dried
by heated rollers and/or by through-flow drying at a temperature
between 40 and 100.degree. C., and/or (iv) the precursor fiber from
(ii) or (iii) is rolled up.
39. The method according to claim 38, wherein the precursor fiber
is coated with a spinning oil before and/or after it is dried in
step (iii).
40. A precursor fiber having more than 5 wt. % of the at least one
type of lignin or lignin derivative, wherein the pre-cursor fiber
has a strength measured according to DIN 53 834 of at least 5
cN/tex and a modulus of elasticity of 350 cN/tex.
41. The precursor fiber according to claim 40, wherein the
precursor fiber has a nitrogen/carbon mass ratio of less than
0.06.
42. The precursor fiber according to claim 40, wherein the
precursor fiber has a round cross-section with a diameter of less
than 70 .mu.m.
43. A precursor fiber produced by the method of claim 25.
44. A method for producing a carbon fiber, in which a precursor
fiber according to claim 40 is stabilized at temperatures between
100 and 300.degree. C., pre-carbonized between 300 and 900.degree.
C., and carbonized between 900 and 2,000.degree. C. under inert
conditions.
45. The method according to claim 44, wherein the precursor fiber
is stabilized at temperatures between 100 and 300.degree. C. and
simultaneously is extended in the range between 0 and 300% relative
to its initial length, whereby the precursor fiber becomes
non-meltable and non-combustible and obtains an orientated
structure.
46. The method according to claim 44, wherein the stabilized,
orientated precursor fiber is pre-carbonized at temperatures
between 300 and 900.degree. C. and extended in the range between 0
and 300% relative to its initial length, thereby obtaining a carbon
proportion of more than 80 wt. % and an orientated structure.
47. A carbon fiber made from a lignin-containing precursor fiber,
containing a carbon proportion of more than 80 wt.
48. The carbon fiber produced by the method of claim 44.
Description
[0001] The invention relates to a method for producing a precursor
fiber which is suitable for further processing to form carbon
fibers and activated carbon fibers. The method is a wet spinning
method, in which a spinning solution of lignin or lignin
derivatives, cellulose carbamate and alkali lye is pressed through
the holes of a nozzle and introduced directly into a coagulation
bath. The precursor fiber being precipitated in the bath may be
subjected to different further method steps: It may be stretched,
after-treated, dried at elevated temperature and rolled up. Since
it constitutes a cost-effective starting material, it may
subsequently be used for producing carbon fibers and activated
carbon fibers.
[0002] Carbon fibers are high-performance reinforcing fibers which
have already been used for a long time for composite materials in
aircraft construction, high-performance vehicle construction
(Formula I, high-performance sailing vessels etc.), for sports
equipment and for wind power plants. A current challenge consists
in producing carbon fibers of medium quality and with low
production costs at the same time, so that they may also be used in
automobile manufacture. The important driving force for this is the
aim of providing electric vehicles which have a low weight but
nevertheless stable bodywork.
[0003] Carbon fibers are produced by heat treatment of organic
precursor fibers at temperatures above 1,000.degree. C. The first
industrial production of carbon fibers based on cellulose
precursors was effected by the continuous method developed and
patented by C. E. Ford and C. V. Mitchell (U.S. Pat. No.
3,107,152). The carbon fibers thus produced were first marketed
under the trade name "Thornel 25" with strengths of 1.25 GPa and
moduli of 172 GPa. Due to further developments, further carbon
fibers with improved properties could be produced. They had
strengths of up to 4.0 GPa and moduli of elasticity of up to 690
GPa.
[0004] Crucial for good fiber properties even then was already
special process control. The cellulose fibers were exposed to
temperatures of 2,500-3,000.degree. C. and deformed in the process
(so-called stretch graphitization). Graphite can be plastically
deformed and orientated along the fiber axis only at these high
temperatures.
[0005] In the production process according to Ford and Mitchell
however, only a carbon yield between 10 and 20 wt. % could be
achieved. In addition, the process was also very costly at 1,000
$/kg of carbon fiber due to the special method control. This
resulted in the method being uneconomical and the production of
carbon fibers based on cellulose being almost completely
stopped.
[0006] This development was accompanied by intensive research work
in the field of carbon fibers made of alternative starting
materials. It was here shown that carbon fibers based on
polyacrylonitrile (PAN) or based on copolymers of polyacrylonitrile
with the same property profile could be produced significantly more
cost-effectively. Even today PAN and PAN copolymers are still the
dominant starting materials for producing precursor filament yarns
and carbon fibers generated therefrom. This includes the
ultrahigh-modulus carbon fibers based on pitch. (J. P. Donnet et
al., Carbon fibers, third edition, Marcel Dekker, Inc. New York,
Basel, Hong Kong).
[0007] Although the production of carbon fibers on the whole has
become more favorable due to the substitution of cellulose with PAN
or pitch, the distribution of the production cost proportions is
uneven and strongly coupled to the price of crude oil. Both PAN and
pitch are completely petroleum-based. Their production and
isolation accounts for about half of the production costs of carbon
fibers.
[0008] It is therefore a current challenge to develop alternative
methods for producing carbon fibers which are just as
cost-effective or even more cost-effective and the production costs
of which do not correlate to the same extent with the price of
crude oil as for PAN-based carbon fibers. Lesser properties of the
resulting carbon fibers could also be accepted in favor of lower
production costs. In order to successfully occupy a new market
segment, the carbon fiber should however have at least a modulus of
elasticity of 170 GPa and a strength of 1.7 GPa.
[0009] The raw material investigated most intensively for producing
an alternative precursor for carbon fibers is the biopolymer
lignin. This offers the advantage of a very high carbon yield
(about 60 wt. %) compared to PAN (50 wt. %) or cellulose (20-30 wt.
%). Lignin is a polyaromatic polyol, which is a constituent of wood
and occurs in large quantities as a byproduct of cellulose
production. The chemical structure of lignin is determined by the
type of wood used in the cellulose process as well as the method of
cellulose digestion. The main proportion of lignin occurring is
currently only used energetically. An extremely cost-effective raw
material is available with lignin which is in practice not
fiber-forming in unmodified form.
[0010] Kadla (J. F. Kadla et al., Carbon, 40, 2913-2920, 2002)
describes by way of example one process variant for producing a
lignin-based precursor fiber for a carbon fiber. A commercially
available kraft lignin is processed here by melt-spinning to form a
lignin fiber. However, the disadvantage of this method proved to be
that a cost-intensive thermal pre-treatment of the lignin is
necessary. In addition, the carbon fibers, which were produced from
the melt-spun, lignin-containing precursors, had strengths of only
about 0.4 GPa and moduli in the range from 40 to 50 GPa. Hence,
they do not fulfil the mechanical characteristic values strived for
by automobile manufacture.
[0011] Kubo (Kubo et al., Carbon, 36, 1119-1124, 1998) and Sudo (K.
Sudo et al. J. Appl. Polymer Sci., 44, 127-134, 1992) disclose
further processes for melt-spinning of lignin.
[0012] In the latter, the non-melting, high-molecular constituents
have to be removed from the lignin in a pre-treatment step and the
carbon fibers produced by these processes are likewise
characterized by a low strength level and do not meet the
requirements.
[0013] The state of the art thus shows that the melt-spinning of
lignin-containing precursors is indeed possible in principle, but
requires costly method steps. The precursor fibers were converted
only discontinuously and as a monofilament to form carbon fibers by
means of melt-spinning methods, since it required a crosslinking
reaction of the lignin to transform the meltable precursor fibers
to a no longer melting state.
[0014] The use of solutions, which contain lignin and a
fiber-forming polymer, has the advantage that from the start they
are thus non-melting polymers. They permit more rapid conversion
and process steps for removing the meltability are not
necessary.
[0015] U.S. Pat. No. 3,461,082 describes such a process for
producing a lignin-containing precursor fiber. Here, a solution of
a polymer, such as PAN or viscose and lignin, is processed by the
dry spinning method. The spinning mass is conveyed through a
spinning nozzle and the band of filaments generated then enters a
spinning shaft exposed to a hot gas medium. The solvent thus
evaporates and the polymers are regenerated in fiber form and may
be further processed.
[0016] Once again, direct dependence on the oil price arises for
the use of PAN as a fiber-forming polymer. However, the use of
viscose likewise brings with it disadvantages, since viscose is
cellulose xanthate and this does not constitute a storage-stable
compound, since xanthate substituents may be split off at any time.
This does not meet the quality requirements which a conversion
process to the carbon fiber taking place subsequently places on the
precursor material.
[0017] Furthermore, it has to be assumed in the dry spinning method
that residues of the alkali lye used to dissolve the cellulose
xanthate remain in the fiber and hence inevitably lead to defects
during conversion to the carbon fiber, since the fiber may then
overheat locally.
[0018] Even if the viscose process is by far the most often used
method for producing cellulosic chemical fibers, the byproducts
there being produced, such as for example carbon disulfide,
hydrogen sulfide, heavy metals, are ecologically questionable and
the entire process is associated with high investment costs.
Therefore efforts have already been undertaken for years to
supersede the viscose method with alternative methods.
[0019] On the one hand, methods based on the direct dissolution of
cellulose in suitable, solvents, such as for example
N-methylmorpholine-N-oxide or ionic liquids, have been developed
for this. Cellulosic regenerated fibers containing lignin can also
be generated therefrom. However, such spinning solutions have been
further processed hitherto by the air-gap spinning method due to
their high viscosity. The high viscosity additionally required more
expensive process equipment, so that the spinning solution could be
conveyed, and it was necessary to filter the solution. Recovery of
the solvent has enormous significance in the direct dissolution
processes of cellulose. Due to the introduction of lignin/lignin
derivative into the spinning solution and the joint precipitation
process, after which the polymer solution has emerged from the
nozzle in fiber form, has passed the air gap and then entered the
precipitation bath, there is partial washing out of the
lignin/lignin derivative into the precipitation bath, into which
the solvent also diffuses. The proportion of lignin/lignin
derivative which transfers to the precipitation bath may be reduced
by suitable additives. However, both cases constitute an additional
cost for recycling of the solvent, whereby the increased process
costs have to be applied to the resulting carbon fiber and thus one
possible cost advantage is minimized.
[0020] EP 57 105, EP 178 292 and EP 2 110 468 describe a
possibilities exists of producing mouldings made of regenerated
cellulose by precipitating a solution of cellulose carbamate.
Cellulose carbamate is formed by reacting cellulose with urea, is
soluble in cold sodium hydroxide solution and may be regenerated in
acid, salt-containing aqueous solutions or heated sodium hydroxide
solution.
[0021] In addition to this way of generating regenerated fibers
from cellulose carbamate, cellulose carbamate may also be
transformed from NMMO by means of air-gap gap spinning, as in EP 1
716 273 B1. The structure formation of the regenerated fibers is
effected in this process in the air gap and leads to high-modulus
and high-strength fibers. The stability of the spinning solution
made of cellulose carbamate in NMMO is problematic, since there is
increased splitting of the carbamate substituents, whereby the
rheological properties of the spinning solution change permanently
and hence the spinning behavior. Furthermore, gaseous ammonia,
which escapes through the spinning nozzle and leads to spinning
instabilities, is produced as a cleavage product.
[0022] It was therefore the object of the present invention to
provide a method for producing a lignin-containing precursor fiber
which does not have the disadvantages of the above-mentioned
methods from the state of the art. This means that the spinning
solution does not contain cellulose xanthates or viscose and should
be able to be processed by the wet spinning method. In addition, no
costly pre-treatment steps should be necessary for producing the
spinnable solution. In addition to these prerequisites, the method
should be sustainable and cost-effective.
[0023] Furthermore, the object of the present invention is to
indicate a corresponding lignin-containing precursor fiber which
has high moduli of elasticity and strengths. In addition, the
present invention relates to the further processing of the
precursor fiber to form a carbon fiber as well as to a
correspondingly produced carbon fiber or activated carbon
fiber.
[0024] This object is achieved with regard to the method for
producing a lignin-containing precursor fiber having the features
of patent claim 1. Patent claim 15 relates to a correspondingly
produced precursor fiber. In addition, a method for producing a
carbon fiber from the precursor fiber is indicated by patent claim
19. A correspondingly produced carbon fiber is provided by patent
claim 22 and patent claim 24 shows uses of this carbon fiber. The
respective dependent claims show advantageous developments.
[0025] In the method of the invention for producing a
lignin-containing precursor fiber for the production of carbon
fibers and/or activated carbon fibers, a spinning solution
containing at least one type of lignin or lignin derivative as well
as a cellulose carbamate and a solvent, is extruded through a holed
spinning nozzle, which is immersed in a coagulation bath, wherein
the lignin-containing precursor fiber precipitates. The spinning
method of the invention is thus a wet spinning method.
[0026] Storage-stable precursor fibers with high filament numbers
could be generated by the method of the invention due to
surprisingly simple process steps.
[0027] It is particularly advantageous in the method of the
invention if the at least one type of lignin or the lignin present
in the lignin derivative is extracted from a coniferous wood,
deciduous wood or annual plant source, wherein the lignin
particularly preferably has a weight-average molar mass
distribution between 500 g/mol and 20,000 g/mol, particularly
preferably between 2,000 g/mol and 10,000 g/mol, most particularly
preferably between 4,000 g/mol and 10,000 g/mol. Likewise it is
preferred in the method of the invention if the lignin or lignin
derivative contains less than 1 wt. % of ash. This may be achieved
in that the corresponding lignin or lignin derivative is washed
intensively with water or optionally with acids.
[0028] Furthermore, it is advantageous if the cellulose carbamate
has a DP.sub.Cuoxam determined by means of viscosimetry between 150
and 750, particularly preferably a DP.sub.Cuoxam between 250 and
550. The cellulose carbamate preferably also has a degree of
substitution between 0.1 to 1.0, in particular between 0.2 and 0.6.
In a further preferred embodiment of the invention, cellulose
carbamate is used in a concentration of more than 6 wt. %,
particularly preferably of more than 8 wt. %, most particularly
preferably of more than 10 wt. %, relative to the spinning
solution. A nitrogen content of the precursor fiber, which has an
advantageous effect in the further processing of the fiber to form
a carbon fiber, is produced in this manner. Furthermore, it is
preferred that the spinning solution has a mass ratio of cellulose
carbamate to the at least one type of lignin or lignin derivative
between 0.60 and 1.80, particularly preferably between 0.80 and
1.20, most particularly preferably 1.00. In one embodiment of the
invention, the solvent is selected from the group consisting of
[0029] alkali lyes, in particular sodium hydroxide or potassium
hydroxide; [0030] tertiary amine oxides, in particular
N-methylmorpholine N-oxide; [0031] ionic liquids, preferably
selected from the group consisting of imidazolium compounds,
pyridinium compounds or tetraalkyl-ammonium compounds, particularly
preferably 1-butyl-3-methyl-imidazolium chloride,
1-butyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium
acetate; and/or [0032] mixtures thereof.
[0033] It is particularly preferred that the solvent consists
exclusively of alkali lyes, tertiary amine oxides, in particular
N-methylmorpholine N-oxide, and that the solvent does not contain
ionic liquids.
[0034] This has the advantage that there may be no undesirable side
reactions of the ionic liquid itself or of the ionic liquid with
the degradation products with cellulose carbamate. It may be
successfully avoided that an imidazolium cation of an ionic liquid
or degradation products thereof react with the reducing end of the
cellulose unit or/and other aldehyde groups along the cellulose
carbamate with formation of a C--C bond and that this undefined
substitution has an influence on the cellulose carbamate/cellulose
carbamate or cellulose carbamate/lignin interaction in the
precursor fiber formed. By excluding the ionic liquids from the
spinning solution, it may furthermore be prevented that there is
formation of disadvantageous temperature profiles in the fiber.
[0035] Furthermore, it is particularly preferred that the spinning
solution consists of at least one type of lignin or lignin
derivative as well as a cellulose carbamate and a solvent and that
it contains no ionic liquids, no cellulose, no further cellulose
derivatives and no other additives.
[0036] Furthermore, it is preferred for the method that the
spinning solution contains spinning auxiliaries selected from the
group consisting of inorganic substances, in particular ZnO,
organic additives, in particular quaternary ammonium compounds
(cationic, for example Berol Spin 641), alkyl ethers of
polyoxyethylene glycol (non-ionic, for example Berol Visco 32) or
sulfonated oils (anionic), or mixtures thereof.
[0037] The spinning solution may be produced by stirring or
kneading the at least one type of lignin or lignin derivative as
well as cellulose carbamate in the solvent at a temperature of less
than 5.degree. C., preferably of less than 0.degree. C. Stirring or
kneading is thus continued until the solution is homogeneous and
fiber-free. The spinning solution thus produced is filtered before
extrusion through the holed spinning nozzle into the coagulation
bath. Optionally present insoluble constituents may thus be
separated off.
[0038] In a preferred embodiment, the holed spinning nozzle has a
spinning hole diameter of 50 to 500 .mu.m, particularly preferably
50 to 100 .mu.m.
[0039] A further advantageous aspect of the method of the invention
makes provision that the coagulation bath preferably has a pH value
between 1 and 7, particularly preferably between 2 and 5. The
temperature of the spinning bath is preferably 5.degree. C. to
60.degree. C., particularly preferably 10 to 50.degree. C.
[0040] Furthermore, the coagulation bath, in which the fiber
precipitates after extrusion through the spinning nozzle, may
preferably contain water and/or a solvent selected from the group
of alcohols, saturated or unsaturated hydrocarbons, polar-aprotic
compounds, particularly preferably DMF, DMSO, DMAc, or mixtures
thereof, in particular in a proportion between 10 and 50 vol. % or
water, add, particularly preferably sulfuric acid, and salts,
particularly preferably selected from the group of sulfates,
chlorides, salts with lithium, sodium, potassium, caesium,
ammonium, magnesium, calcium, zinc, copper, nickel, cadmium, or
mixtures thereof as a cation, preferably in a concentration between
40 and 240 g/L, particularly preferably in a concentration between
60 and 240 g/L.
[0041] The composition of the coagulation bath thus preferably
depends on the composition of the spinning solution. If the
spinning solution contains polar, aprotic additives, such as for
example DMSO, DMF, DMAc, for viscosity regulation, the spinning
bath is preferably composed of water and/or alcohols, saturated or
unsaturated hydrocarbons, polar-aprotic compounds, particularly
preferably DMF, DMSO, DMAc, or mixtures thereof.
[0042] If spinning is carried out from an alkaline aqueous
solution, the spinning bath is preferably composed of water and/or
sulfuric acid and salt.
[0043] It is further preferred that the precursor fiber
precipitated in the coagulation bath is then introduced into a
stretching bath and stretched to 110 to 500%, preferably to 110 to
300%, of its length, wherein the stretching bath contains water,
air, or a mixture of water and a solvent, preferably at a
temperature of more than 60.degree. C., particularly preferably at
a temperature of more than 80.degree. C., most particularly
preferably at a temperature of more than 100.degree. C., or
consists thereof, that the precursor fiber washed using distilled
water, dried by heated rollers and/or by through-flow drying at a
temperature between 40 and 100.degree. C., preferably between 60
and 80.degree. C., and/or rolled up.
[0044] The extent of structural orientation, which is achieved by
stretching the precursor fiber, is thus unexpectedly high and
contributes to the extraordinarily good mechanical properties of
the resulting carbon fiber. In a further preferred variant of the
method of the invention, the precursor fiber is coated with a
spinning oil before and/or after it is dried.
[0045] Equally, it is preferred in the process if the precursor
fiber during stabilization is present in the form of a continuous
multi-filament yarn and the latter is continuously transported
through an oven. Hence, the precursor fibers may be transferred to
a non-meltable and non-combustible state at residence times between
10 to 100 minutes and oven temperatures between 100 and 350.degree.
C. By applying a mechanical tension, furthermore, extension of the
precursor fiber may be achieved and at the same time it is
prevented that the fiber sags loosely in the oven.
[0046] According to the invention, a precursor fiber for producing
carbon fibers is likewise indicated. The precursor fiber of the
invention is characterized by a content of at least one type of
lignin or lignin derivative of more than 5 wt %, preferably more
than 10 wt. %, particularly preferably between 30 and 80 wt % and
has a strength measured according to DIN 53 834 of at least 5
cN/tex, preferably of at least 10 cN/tex, particularly preferably
of at least 15 cN/tex, most particularly preferably of at least 20
cN/tex, as well as a modulus of elasticity of 350 cN/tex,
preferably of at least 550 cN/tex, most preferably of at least 750
cN/tex.
[0047] The precursor fibers of the invention surprisingly withstand
very high heating rates of up to 50.degree. C./minute which are
applied during stabilization of the precursor fiber. In addition,
they have an unexpectedly high carbon yield after carbonization to
form carbon fibers. Also the loop strength, buckling strength and
tensile strength, which lies in the range from 150 to 200 MPa, and
their extension at break properties are remarkable and surpass the
corresponding properties of comparable lignin precursor fibers from
the state of the art.
[0048] The precursor fiber according to the preceding claim
preferably has a nitrogen/carbon mass ratio of less than 0.06,
particularly preferably less than 0.04, most particularly
preferably less than 0.02.
[0049] It is additionally preferred if the precursor fiber has a
round cross-section with a diameter of less than 70 .mu.m.
[0050] The precursor fiber of the invention can be particularly
advantageously produced by a method described above.
[0051] According to the invention, likewise a method for producing
a carbon fiber is disclosed, in which the precursor fiber is
stabilized at temperatures between 100 and 300.degree. C. and
simultaneously is extended in the range between 0 and 300% relative
to its initial length, wherein the precursor fiber becomes
non-meltable and non-combustible and obtains an orientated
structure.
[0052] Then the stabilized, orientated precursor fiber may be
pre-carbonized at temperatures between 300 and 900.degree. C. and
may be extended in the range between 0 and 300% relative to its
initial length, wherein a carbon proportion of the fiber of more
than 80 wt. % and an orientated structure are obtained.
[0053] Optionally the carbon fiber thus obtained may also be
graphitized at temperatures of 2,000-3,000.degree. C.
[0054] In addition, the present invention provides a carbon fiber
from a lignin-containing precursor fiber which contains a carbon
proportion of more than 80 wt. %, preferably of more than 90 wt.
%.
[0055] In addition, the carbon fiber of the invention can
advantageously be produced by the previously described method for
producing a carbon fiber.
[0056] Furthermore, it is the object of the invention that the
carbon fiber, which was produced by the previously described method
for producing a carbon fiber, is used for producing a chemically
activated carbon fiber and/or for producing composite
materials.
[0057] The carbonized or graphitized carbon fiber may thus be
activated physically or chemically by heat treatment in oxidizing
atmosphere or plasma treatment or treatment with chemicals on the
surface.
EXAMPLE 1
[0058] 250 g of cellulose carbamate {DPCuox 258, N content 2.2%,
moisture content 10 wt. %}was dissolved together with 2,000 g of a
7 wt. % aqueous sodium hydroxide solution chilled at -4.degree. C.
with stirring within 90 minutes. 250 g of a kraft lignin {moisture
content 10 wt. %) were then added to the solution and the mixture
was stirred for a further 30 minutes. The solution was then
filtered chilled under exposure to pressure by means of nitrogen (2
bar) through a 10 .mu.m metal filter and for the dissolution stored
for 20 hours.
[0059] The low-viscosity spinning solution thus generated was
conveyed at a temperature of +5.degree. C. by means of a spinning
pump to the spinning nozzle (600 hole, 70 .mu.m), which projected
into an aqueous spinning bath tempered at 40.degree. C. comprising
80 g/l of sulfuric acid and 140 g/l of sodium sulfate. The
coagulated filaments were drawn off by means of a nozzle draft of
0.7 and fed to washing. The filaments were washed by means of
distilled water heated at 60.degree. C. and dried at 80.degree. C.
The filaments thus generated had a strength of 19 cN/tex, an
extension of 6% as well as a modulus of 923 cN/tex. The lignin
content of the filaments was 49 wt. %.
EXAMPLE 2
[0060] The continuous multi-filament yarn produced by the method
from Example 1, consisting of lignin and cellulose carbamate (50/50
mass %), was transported continuously through two tubular ovens
separated spatially from one another and exposed to heat. In the
first tubular oven through which air flows continuously, the
process of stabilization was carried out on the multi-filament yarn
and for this temperatures in the range from 100-300.degree. C. and
action times at corresponding temperatures of about 80 minutes were
applied. Due to different rates of the thread transport devices
upstream and downstream of the tubular oven, an extension of the
multi-filament yarn of 100% was realized during the action of heat.
The structure of the fiber material is thus orientated and thus
mechanical properties of the final C fibers significantly improved.
The resulting orientated and stabilized continuous multi-filament
yarn was then wound onto a bobbin core. The corresponding
multi-filament yarn is characterized by non-meltability,
non-combustibility, freedom from adhesion adequate loop strength
and buckling strength as well as tensile strength of about 200 MPa
and extensions at break of about 5%. In the second tubular oven
through which inert gas flows continuously, the process of
pre-carbonization was carried out and for this temperatures in the
range from 300-900.degree. C. and action times at corresponding
temperatures of 30 minutes applied. Due to different rates of the
thread transport devices upstream and downstream of the oven, an
extension of the multi-filament yarn of about 10% could be realized
during the action of heat. The resulting orientated and
pre-carbonized continuous filament yarn was then wound onto a
bobbin core. The corresponding multi-filament yarn is characterized
by a carbon proportion >80 wt. %. Finally, the process of
carbonization was effected in a further oven at temperatures of
900-1,600.degree. C., wherein an orientated carbonized
multi-filament yarn was obtained which is characterized by a carbon
proportion >90 wt. %.
EXAMPLE 3
[0061] 300 g of cellulose carbamate (DPCuox: 274, DS 0.3) are mixed
together with 300 g of Organosolv Lignin with 1,500 g of
ethylmethylimidazolium acetate as well as 500 g of dimethyl
sulfoxide and dissolved in a horizontal kneader at 110.degree. C.
within 2.5 hours. The resulting homogeneous, black solution is
completely fiber-free and has a viscosity of 65 Pa s at 50.degree.
C.
[0062] The filtered solution was conveyed by means of pressure and
gear pump through a 120-hole spinning nozzle (hole diameter 70
.mu.m) in a 10 vol. % aqueous coagulation bath containing
ethylmethylimidazolium acetate and precipitated. The filaments were
washed by means of distilled water heated at 60.degree. C. and
dried at 80.degree. C. The filaments thus generated had a strength
of 24 cN/tex, an extension of 8% as well as a modulus of 1,150
cN/tex. The lignin content of the filaments was 41 wt. %.
EXAMPLE 4
[0063] The continuous multi-filament yarn produced by the method
from Example 3, consisting of lignin and cellulose carbamate (50/50
mass %), was transported continuously through a tubular oven and
exposed to heat. During this process step (stabilization), the
multi-filament yarn was exposed in air atmosphere to temperatures
in the range from 100-300.degree. C. and action times at
corresponding temperatures of about 80 minutes. The multi-filament
yarn produced according to Example 3 could be extended during the
action of heat but only by 10% at most, whereby the structure of
the fiber material was orientated only inadequately. After the
subsequent process steps of pre-carbonization and carbonization
(analogously to Example 2), the mechanical properties of the final
C fibers based on the multi-filament yarn produced according to
Example 3 were only a fraction of the level which was achieved with
multi-filament yarns from Example 1.
* * * * *