EP3864202A1 - Procédé et dispositif de stabilisation de fibres ou de films précurseurs pour la fabrication de fibres ou de films de carbone - Google Patents

Procédé et dispositif de stabilisation de fibres ou de films précurseurs pour la fabrication de fibres ou de films de carbone

Info

Publication number
EP3864202A1
EP3864202A1 EP19786568.6A EP19786568A EP3864202A1 EP 3864202 A1 EP3864202 A1 EP 3864202A1 EP 19786568 A EP19786568 A EP 19786568A EP 3864202 A1 EP3864202 A1 EP 3864202A1
Authority
EP
European Patent Office
Prior art keywords
temperature
precursor fibers
fibers
gas atmosphere
process gas
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19786568.6A
Other languages
German (de)
English (en)
Inventor
Manuel CLAUSS
Andreas Keller
Volker BAUCH
Frank Hermanutz
Erik Frank
Gunter Fauth
Michael R. Buchmeiser
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centrotherm International AG
Original Assignee
Centrotherm International AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Centrotherm International AG filed Critical Centrotherm International AG
Publication of EP3864202A1 publication Critical patent/EP3864202A1/fr
Pending legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/005—Lignin
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
    • D01F9/17—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate from lignin
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • D01F9/225—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles from stabilised polyacrylonitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/12—Applications used for fibers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • Carbon fibers or carbon foils from different precursor materials. Since the processes for both fibers and foils are essentially the same, only the fiber is explained in more detail below. Carbon fibers are technically produced in several process steps.
  • the starting material is usually polyacrylonitrile or PAN for short, but other precursors, in particular lignin, cellulose and polyethylene, are also considered as alternatives for carbon fiber production.
  • the starting materials are shaped into so-called precursor fibers. These precursor fibers are subsequently converted into carbon fibers in two further work steps in separate plant areas.
  • the first step is called stabilization while the second is called carbonization. While carbonization usually takes place at high temperatures above 1300 ° C, the stabilization, which leads to stabilization or crosslinking of the precursor fibers, takes place at much lower temperatures, usually in the range from 200 ° C to 300 ° C. This step is necessary to change the molecular structures of the precursor fibers in such a way that the fibers can withstand the thermal stress during carbonization.
  • Stabilization is usually carried out in a convection oven with separately heated zones, in which the precursor fibers are heated to temperatures between 200 ° C and 300 ° C and react with the oxygen in the air at atmospheric pressure.
  • the process of stabilization creates gaseous reaction products, such as carbon dioxide, hydrocyanic acid, carbon monoxide and ammonia, which have to be removed and disposed of in a controlled manner. This results in complex and expensive exhaust gas treatment.
  • the stabilization step is currently the most expensive and time-consuming step in the production of a carbon fiber. Attempts to reduce the response time seem sensible, but they pose challenges.
  • the invention provides a method according to claim 1. Further refinements of the invention result, inter alia, from the subclaims.
  • a method for stabilizing precursor fibers for the production of carbon fibers has the following steps: continuous introduction, passage and execution of the precursor fibers into, through and out of a process chamber, setting a predetermined process gas atmosphere which differs in composition from the ambient air in the at least one process chamber, wherein the process gas atmosphere contains at least one reactive component and / or a catalyst with a predetermined partial pressure while the precursor fibers are in the process chamber, heating the same to at least a first temperature and maintaining the first temperature for a predetermined period of time .
  • the method enables stabilization under controlled and precisely defined process conditions and at temperatures that are in some cases higher than the usual temperatures of the prior art.
  • this component can be provided in a controlled manner in an advantageous manner for the process.
  • Correspondingly processed precursor fibers reproducibly showed a high density and uniformity, as a result of which the subsequently carbonized fibers had excellent strength values.
  • the pressure in the process chamber can be maintained at ambient pressure or a pressure between ambient pressure and at least 90%, preferably at least 95% of the ambient pressure, which reduces the requirements for sealing the process chamber against a vacuum system which is designed for lower pressures .
  • the precursor fibers are heated over at least one further intermediate temperature from the first temperature to that of the second temperature, where the temperature difference between successive stages is at least 5 ° C., in particular at least 10 ° C., and precursor fibers for a predetermined period of time are maintained at the at least one intermediate temperature.
  • a multi-stage temperature increase has proven to be particularly advantageous.
  • the second temperature is preferably at least 30 ° C., in particular at least 40 ° C. higher than the first temperature.
  • the precursor fibers are preferably kept for at least 10 minutes, preferably for at least 20 minutes, at the first temperature, the second temperature and at least one optional intermediate temperature.
  • the first temperature should be in the range of 220 to 320 ° C and the second temperature in the range of 280 to 400 ° C. Particularly good results were achieved when the first temperature was in the range 260 to 320 ° C and the second temperature was in the range 300 to 380 ° C.
  • the process gas atmosphere preferably contains oxygen as a reactive component with a partial pressure of 30 to 300 mbar, preferably 50 to 200 mbar. This can be done at atmospheric pressure or a slight negative pressure, for example by a corresponding mixture of pure nitrogen with ambient air (around 78% by volume nitrogen, around 21% by volume oxygen and around 1% by volume other gases such as argon and others) or reach pure oxygen.
  • the first temperature is preferably in the range 200-240 ° C. and the second temperature is preferably in the range 240-300 ° C.
  • the process gas atmosphere should be an acid atmosphere that promotes dehydration of cellulose.
  • An acidic component in the process gas is preferably controlled via the partial pressure in order to control the dehydration.
  • the process gas atmosphere should in turn preferably be an acid atmosphere which activates the latent hardener in the lignin.
  • the acidic component in the process gas can be controlled via the partial pressure in order to control the activation.
  • the hardener for cellulose and lignin fibers, it is also conceivable for the hardener to be supplied from the gas phase, in which case it is then preferably reactive formaldehyde. It may also be useful in the case of cellulose fibers to impregnate the fibers from the gas phase with sulfur-containing substances which have the aim of increasing the carbon yield of the fibers.
  • precursor fibers from mixtures of PAN and lignin with iodine could also be useful, which provide increased strength and increased orientation of the final carbon fiber.
  • the precursor fibers are preferably kept under a defined tension during the process.
  • a tension in the range between 0.5 and 10 N per 3k fiber bundle has proven to be suitable.
  • the process gas atmosphere is preferably exchanged continuously or intermittently during the stabilization process. This can ensure that the reactive and / or catalytic component is essentially available with a constant partial pressure throughout the process.
  • reaction products can be removed from a process area in a controlled manner. In particular, the process area can continuously through a corresponding gas flow. The flow rate depends on the dimensions of the process chamber and the amount and type of process material.
  • the precursor fibers are passed through a plurality of essentially parallel process chambers during the method, adjacent process chambers being connected at one end via a deflection unit such that the fibers remain in the process gas atmosphere.
  • FIG. 1 shows a schematic side view of a stabilization device according to the invention, a process unit being shown in section;
  • FIG. 2 shows a schematic plan view of the device according to FIG. 1, the process unit being shown again in section;
  • FIG. 3 A schematic cross-sectional view through a process unit of the device according to FIG. 1;
  • FIG. 4 A schematic side view of an alternative embodiment of a stabilization device according to the invention.
  • FIG. 5 shows an enlarged detailed view of a deflection unit according to the embodiment of FIG. 6.
  • FIGS. 1 and 2 A basic structure of a stabilization device 1 for precursor fibers 2 is shown in FIGS. 1 and 2.
  • the stabilization device 1 essentially consists of a central process unit 3 with an entrance-side lock unit 4 and an exit-side lock unit 5, as well as a fiber feed 7 and a fiber holder 8.
  • the fiber feed 7 and the fiber holder 8 are not part of the stabilization device 1 per se , since they only provide a fiber feed to the stabilization device 1 and a receptacle therefrom. They are suitable for supplying precursor fibers 2 continuously or for taking up the stabilized fibers.
  • the units 7, 8 are each suitable for a large number of precursor fibers 2 in parallel with one another. to be delivered or received in one plane, as indicated in the plan view in FIG. 2. Since such units are known and are known in different versions on the market, there is no further description of these units 7, 8.
  • the process unit 3 has an elongated process chamber 10, a heating unit 12 directly adjacent to, in contact with or within the process chamber 10, and an insulation 14 which surrounds the process chamber 10 and possibly the heating unit 14.
  • the process chamber can be designed as a vacuum chamber with an appropriate tightness. However, it can also be designed as an atmospheric chamber, which is preferably sufficiently gas-tight to prevent process gases from getting into the environment from the interior of the chamber and ambient air from entering the process atmosphere.
  • the process unit 3 has at least one pump, which is optionally designed as a vacuum pump, and a gas supply, both of which are connected to the process chamber 10 in a suitable manner. The pump and the gas supply are not shown since the respective structure is not essential for the invention.
  • the gas supply is designed such that it can deliver a process gas mixture with a reactive component and / or a catalytic component with a predetermined partial pressure within an otherwise preferably inert gas.
  • the pump if processes are to be carried out in atmospheric pressure or a slight negative pressure (in order to prevent the process gas atmosphere from escaping), essentially serves for the controlled discharge of the process gas and the resulting reaction products.
  • the pump can also be dispensed with entirely, and the discharge of gases can only be controlled via an outlet and the introduction of gases.
  • the pump should be designed accordingly in order to be able to set a desired pressure of, for example, 50 to 300 mbar within the process chamber 10.
  • the process chamber 10 has a rectangular cross-section, as can best be seen in FIG. 3. At its longitudinal ends, the process chamber 10 is connected to the lock units 4, 5, via which, as will be explained below, precursor fibers 2 can be introduced continuously into the process chamber 10.
  • the vacuum chamber 10 is constructed from a suitable heat-resistant material, which is preferably heat-resistant up to at least 400 ° C.
  • the process chamber 10 has, for example, a length of 2 m to 6 m, although other lengths are of course also conceivable.
  • the heating unit 12 has a plurality of individually controllable heating plates 20, which are only indicated schematically in the top view in FIG. 2. 1 and 3, the heating plates 20 are each arranged in pairs above and below the process chamber 10. The heating plates each cover the entire width of the process chamber 10 and the pairs are adjacent in the longitudinal direction. As a result, different heatable zones are formed. In the illustration in FIGS. 1 and 2, five pairs of heating plates 20 are shown, so that there are five different heatable zones. The number of pairs of heating plates and the zones formed thereby can differ from the number shown, at least two zones should be present. Instead of heating plates 20, as shown, revolving heating cassettes or other forms of heating elements could also be provided, as recognized by the person skilled in the art. As previously indicated, the heating plates 20 or other suitable heating elements can be arranged within the process chamber 10 in such a way that adjacent heating zones are provided in the longitudinal direction.
  • the heating plates 20 are designed such that they provide an essentially constant temperature in the process chamber 10 within the respective zone over the width of the process chamber and the length range covered. In particular, they are designed so that they can set a temperature in the range from 220 to 400 ° C.
  • the insulation 14 surrounds the process chamber 10 and the heating unit 12 in order to thermally isolate them from the environment, as is known in the art for continuous furnaces.
  • the lock units 4 and 5 can be of any design to have sufficient tightness to substantially prevent the passage of gases into or out of the process chamber at a certain process pressure. In the case of an atmospheric process pressure or a slight negative pressure, a gas curtain in the lock could possibly be sufficient to separate the ambient atmosphere from the process atmosphere.
  • Fig. 4 shows an alternative embodiment of a stabilization device 1 with three vertically superimposed process units 3, an entrance-side lock unit 4, an exit-side lock unit 5, a fiber feed 7, a fiber holder 8, and deflection units 40 and 4L.
  • the fiber feeder 7 and the fiber holder 8 are again strictly speaking, no part of the stabilization device 1, since they only provide a fiber feed to the stabilization device 1 and a receptacle therefrom. They are suitable for continuously supplying or absorbing precursor fibers 2.
  • the units 7, 8 are each suitable for supplying or receiving a plurality of precursor fibers 2 parallel to one another in one plane, as indicated in the top view in FIG. 2. Since such units are known and are known in different versions on the market, there is no further description of these units 7, 8.
  • three process units 3, which can have the same structure as in the first embodiment, are provided vertically one above the other.
  • the entrance-side lock unit 4 is attached to the left side of the lowermost process unit 3 and the exit-side lock unit 5 is attached to the right side of the upper process unit 3.
  • the lock units 4, 5 can in turn have essentially the same structure as in the first embodiment.
  • the right end of the lower process unit 3 is vacuum-tightly connected to the right end of the middle process unit 3 via the deflection unit 40.
  • the left end of the middle process unit 3 is in turn connected vacuum-tight to the left end of the upper process unit 3 via the deflection unit 42.
  • the steering units 40, 42 are constructed essentially the same and the steering unit 40 is explained in more detail below.
  • the deflection unit 40 has a gas- or vacuum-tight housing 45, which has two passages 47, 48 in a side wall of the housing 45, and transport and guide rollers 50.
  • the housing 45 has a suitable shape and size, which is at the ends of two superimposed process units 3 can be attached to connect them.
  • the bushings 47, 48 in the side wall are aligned with corresponding openings in the ends of the process units 3.
  • the deflection unit is connected to the respective ends of the process units 3 via bellows units 54 in order to enable a gas or vacuum-tight but flexible connection between the units. This is particularly advantageous since the process units 3 are heated during operation and can expand thermally. A flexible bellows connection as shown can prevent loads between the different units.
  • the transport and guide rollers 50 are offset from one another and one above the other such that the precursor fibers 2 can be passed through one of the passages 47, around the transport and guide rollers 50 and out of the other of the passages 48.
  • three transport and guide rollers 50 are provided, of which, for example, the upper and the lower are fixed, while the middle one is designed as a dancer roller, which can move, for example, horizontally, in order to tension the precursor fibers 2 adjust and / or absorb fluctuations in transport.
  • At least one of the transport and guide rollers 50 can be connected to a drive motor in order to be able to provide an active drive during the deflection.
  • the drive motor can be surrounding housing 45 or outside, in which case a vacuum-tight passage of the drive shaft should be provided in the latter case.
  • the transport and guide rollers 50 are offset from one another and arranged one above the other such that the precursor fibers 2 can be passed through one of the passages 47, around the transport and guide rollers 50 and out of the other of the passages 48.
  • three transport and guide rollers 50 are provided, of which, for example, the upper and the lower are fixed, while the middle one is designed as a dancer roller, which can move, for example, horizontally, in order to tension the precursor fibers 2 set and / or absorb fluctuations in transport.
  • At least one of the transport and guide rollers 50 can be connected to a drive motor in order to be able to provide an active drive during the deflection.
  • the drive motor can be inside the vacuum housing 45 or outside, in which case a gas or vacuum-tight passage of the drive shaft should be provided in the latter case.
  • oxygen is regarded as a reactive component and the partial pressure of the oxygen in an otherwise largely inert gas mixture (for example containing nitrogen) is preferably set to 5 to 60 mbar. This corresponds approximately to a pressure of 25 to 300 mbar ambient air. An oxygen partial pressure in the range from 10 to 40 mbar has so far been shown to be particularly advantageous.
  • a corresponding process gas mixture is applied to the process chamber 10 via the gas supply, which is sucked off again via the pump.
  • the extracted air is cleaned by means of an appropriate aftertreatment unit in order to separate or render harmless undesirable gases that arise during operation, such as CO, C0 2 , NH 3 or HCN, for example.
  • the fleece plates 20 are activated so that they generate a constant temperature in the process chamber 10 in their respective zone. For example, a temperature of 260 ° C is set in the first zone on the left. Temperatures of 320 ° C, 360 ° C, 380 ° C and 400 ° C are then set in the neighboring zones, for example. There is therefore a temperature jump of 60 ° C between the first two zones and a temperature jump of 40 ° C between the second and third zones. The temperature is constant over the last three zones.
  • the precursor fibers 2 are now guided through the process unit 3 at a predetermined speed, the speed being set such that the precursor fibers 2 each remain in the respective zones for a predetermined time.
  • the precursor fibers 2 are quickly heated to the appropriate temperature and kept at this temperature during the run.
  • the precursor fibers 2 in the example above are first heated to 260 ° C. in a controlled gas atmosphere in the process chamber 10 and are kept at this temperature for approximately 20 minutes before they are heated to 320 ° C. and again for approximately Maintained at this temperature for 20 minutes.
  • the precursor fibers 2 are then heated to 360 ° C. and kept at this temperature for about 20 minutes. Then they are treated at 380 and 400 ° C. for 20 minutes each. As the precursor fibers 2 pass through the heating zones in the process chamber 10, they are stabilized.
  • the inventors have found that in the controlled process gas atmosphere with a reactive and / or catalytic component with a predetermined partial pressure, higher temperatures than at atmospheric pressure in air can be used without the precursor fibers 2 burning or being thermally damaged. This made it possible to produce reproducibly uniformly stabilized precursor fibers 2 with a high density.
  • the inventors have found that at least a gradual temperature increase is advantageous, the first temperature for PAN fibers being in the range from 220 to 320 ° C. and the second temperature in the range from 280 to 400 ° C.
  • the second temperature represents the highest temperature within the process chamber 10, while lower temperatures can also be set before the first temperature.
  • the first temperature is preferably in the range from 260 to 320.degree. C. and the second temperature in the range from 300 to 400.degree. C., which is significantly higher than the temperatures of the prior art used to date.
  • the second temperature is preferably at least 30 ° C., preferably at least 40 ° C. higher than the first temperature.
  • the temperature can gradually be increased, the temperature difference between successive stages being at least 5 ° C., in particular at least 10 ° C., and precursor fibers being kept at the at least one intermediate temperature for a predetermined period of time.
  • the time period per temperature level should preferably be at least 5 minutes, although the time period can also be shorter in the case of small temperature jumps.
  • the dwell time depends on the length of the respective heating zone and the transport speed of the precursor fibers 2. While the length of the individual heating zones is specified, the length of stay can be set via the transport speed. Of course, heating zones can also be heated evenly in order to multiply the length of stay at a certain temperature.
  • the embodiment according to FIG. 6 enables a more flexible temperature setting with several heating zones with a smaller footprint.
  • two or more process units can also be provided one above the other, the precursor fibers 2 having to be fed in and out from the same side in the case of an even number of process units 3.
  • precursor fibers can be stabilized accordingly, whereby a different reactive and / or a catalytic component with a predetermined partial pressure, different temperature ranges and residence times can be used here.
  • Other, already sour Precursors containing substance such as lignin or cellulose do not necessarily require externally supplied oxygen for the stabilization, but the stabilization by externally supplied oxygen can be accelerated if necessary.
  • reactive substances and / or catalysts can be brought directly into the fibers in a controlled manner via the gas phase.
  • the first temperature is preferably in the range 200-240 ° C. and the second temperature is preferably in the range 240-300 ° C.
  • the process gas atmosphere should be an acid atmosphere which requires cellulose to be dehydrated.
  • An acidic component in the process gas is preferably controlled via the partial pressure in order to control the dehydration.
  • the process gas atmosphere should in turn preferably be an acid atmosphere which activates the latent hardener in the lignin.
  • the acidic component in the process gas can be controlled via the partial pressure in order to control the activation.
  • the hardener for cellulose and lignin fibers, it is also conceivable for the hardener to be supplied from the gas phase, in which case it is then preferably reactive formaldehyde. In the case of cellulose fibers, it may also be useful to impregnate the fibers from the gas phase with sulfur-containing substances which have the aim of increasing the carbon yield of the fibers.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Fibers (AREA)

Abstract

L'invention concerne un dispositif de stabilisation de fibres précurseurs pour la fabrication de fibres de carbone. Le procédé comporte les étapes suivantes consistant à : introduire en continu, guider et sortir les fibres précurseurs dans, à travers et hors d'une chambre de traitement ; régler une atmosphère de gaz de traitement prédéfinie se distinguant de l'air ambiant par la composition dans la ou les chambres de traitement, l'atmosphère de gaz de traitement contenant au moins un composant réactif et/ou un catalyseur présentant une pression partielle prédéfinie ; pendant que les fibres précurseurs se trouvent dans la chambre de traitement, réchauffer celles-ci à au moins une première température et maintenir la première température pour une durée prédéfinie.
EP19786568.6A 2018-10-10 2019-10-10 Procédé et dispositif de stabilisation de fibres ou de films précurseurs pour la fabrication de fibres ou de films de carbone Pending EP3864202A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102018217354 2018-10-10
PCT/EP2019/077438 WO2020074623A1 (fr) 2018-10-10 2019-10-10 Procédé et dispositif de stabilisation de fibres ou de films précurseurs pour la fabrication de fibres ou de films de carbone

Publications (1)

Publication Number Publication Date
EP3864202A1 true EP3864202A1 (fr) 2021-08-18

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EP19786568.6A Pending EP3864202A1 (fr) 2018-10-10 2019-10-10 Procédé et dispositif de stabilisation de fibres ou de films précurseurs pour la fabrication de fibres ou de films de carbone

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US3954947A (en) * 1972-11-17 1976-05-04 Union Carbide Corporation Rapid stabilization of polyacrylonitrile fibers prior to carbonization
US6733737B1 (en) * 2001-08-29 2004-05-11 Wright Materials Research Corp. Rapid oxidation/stabilization technique for carbon foams, carbon fibers and C/C composites
US7649078B1 (en) * 2005-03-29 2010-01-19 Ut-Battelle, Llc Apparatus and method for stabilization or oxidation of polymeric materials
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ZA202101791B (en) 2022-02-23
US20210355610A1 (en) 2021-11-18
CN112912547A (zh) 2021-06-04
WO2020074623A1 (fr) 2020-04-16
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