EP3143187B1 - Procédé de production de fibres de carbone à partir de fibres de cellulose - Google Patents

Procédé de production de fibres de carbone à partir de fibres de cellulose Download PDF

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Publication number
EP3143187B1
EP3143187B1 EP15721717.5A EP15721717A EP3143187B1 EP 3143187 B1 EP3143187 B1 EP 3143187B1 EP 15721717 A EP15721717 A EP 15721717A EP 3143187 B1 EP3143187 B1 EP 3143187B1
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EP
European Patent Office
Prior art keywords
cellulose
weight
additives
parts
fibers
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Application number
EP15721717.5A
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German (de)
English (en)
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EP3143187A1 (fr
Inventor
Sunghee Son
Klemens Massonne
Frank Hermanutz
Johanna SPOERL
Michael R. Buchmeiser
Ronald BEYER
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Deutsche Institute fuer Textil und Faserforschung Stuttgart
Original Assignee
Deutsche Institute fuer Textil und Faserforschung Stuttgart
Deutsche Institute fuer Textil und Faserforschung Denkendorf DITF
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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
    • D01F9/16—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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/06—Washing or drying
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods

Definitions

  • the invention relates to a method for producing carbon fibers from cellulose fibers, characterized in that cellulose fibers which have a water content of more than 30 parts by weight of water per 100 parts by weight of cellulose fiber and during their production no process measures for drying are brought into contact with a solution of additives and then the additized cellulose fibers, which contain at least 1 part by weight of additives per 100 parts by weight of cellulose, are converted into carbon fibers, the additives being inorganic salts in the form of phosphate, hydrogen phosphate, phosphite, hydrogen phosphite, sulphate or sulphite and their solution being a single additive or may contain a mixture of different additives.
  • Carbon fibers can be produced by pyrolysis of polyacrylonitrile fibers or cellulose fibers. As a renewable raw material, cellulose fibers are becoming increasingly important for the growing carbon fiber market.
  • Fanlong Zeng, Ding Pan and Ning Pan use viscose fibers to produce carbon fibers (Journal of Inorganic and Organometallic Polymers and Materials, Vol.15, No.2 June 2005 ).
  • dried cellulose fibers are treated with solutions of additives and then converted into carbon fibers.
  • Hui Li, Yonggang Yang, Yuefang Wen and Lang Liu impregnate the viscose fibers with an organic silicon compound before drying.
  • the cellulose fiber is usually treated with additives, here with an aqueous solution of ammonium sulfate and ammonium chloride, and finally carbonization.
  • Cellulose which has been dissolved in ionic liquid, is also according to CN 101871140 used to manufacture carbon fibers.
  • EP 1669480 A1 discloses a process for the production of yarns or fiber sheets made of carbon starting from a cellulose material which are impregnated with an aqueous emulsion of an organosilicon additive.
  • the carbon yield should be as high as possible, that is, the carbon of the starting fiber should be converted as completely as possible into the carbon fiber.
  • the carbon yield is not yet satisfactory. Part of the carbon in the cellulose is lost through breakdown into carbon monoxide and carbon dioxide.
  • the mechanical properties of the carbon fibers obtained from cellulose fibers should also be improved.
  • the object of the present invention was therefore an improved process for the production of carbon fibers from cellulose fibers.
  • Cellulose fibers are the starting material for the process.
  • Cellulose fibers are understood here to mean fibers which consist of more than 60% by weight, in particular more than 80% by weight, particularly preferably more than 90% by weight, of cellulose or modified cellulose.
  • the cellulose fibers consist of more than 98% by weight, very particularly preferably 100% by weight, of cellulose or modified cellulose.
  • Modified cellulose is understood to mean cellulose in which hydroxyl groups are etherified or esterified, e.g. B. it can be cellulose acetate, cellulose formate, cellulose propionate, cellulose carbamate or cellulose allophanate.
  • cellulose fibers which consist of cellulose in the minimum amounts specified above.
  • the cellulose fibers which are brought into contact with the solution of an additive have a water content of more than 30 parts by weight of water, in particular more than 50 parts by weight of water, particularly preferably more than 70 parts by weight of water per 100 parts by weight of cellulose fiber.
  • the water content is not higher than 500, in particular not higher than 300 parts by weight of water per 100 parts by weight of cellulose fiber.
  • the cellulose fiber having the above water content can be easily obtained, for example, by immersing a dried cellulose fiber in water. Both natural cellulose fibers and synthetic cellulose fibers are suitable for this.
  • Natural cellulose fibers are in particular cellulose fibers obtained from cotton.
  • synthetic cellulose fibers are used
  • synthetic cellulose fibers are used which were produced immediately beforehand by a spinning process.
  • the cellulose fibers obtained are washed with water in order to remove adhering solvent or adhering additives from the spinning bath.
  • the contact with water is carried out in such a way that the cellulose fiber absorbs water in the desired amount specified above.
  • the cellulose fiber can be immersed in water for a sufficient time or it can be passed through a sufficiently long water bath in a continuous process.
  • cellulose fibers In the production of the cellulose fibers, there are preferably no process measures for drying.
  • the cellulose fiber obtained in the spinning process is washed with water without prior drying and then, of course, again without prior drying, brought into contact with the solution of the additive. It is therefore a so-called "never dried" cellulose fiber.
  • the aqueous cellulose fibers are brought into contact with a solution of additives.
  • hydrophilic solvent in particular in water, hydrophilic organic solvents, for example alcohols or ethers, or mixtures thereof.
  • hydrophilic organic solvents for example alcohols or ethers, or mixtures thereof.
  • Particularly preferred hydrophilic solvents are water or mixtures of water with other hydrophilic organic solvents which are infinitely miscible with water, in the latter case the water content in the solvent mixture in a preferred embodiment being at least 50% by weight.
  • the solution contains a single additive or a mixture of different additives.
  • Particularly suitable additives are compounds which have a solubility in water of at least 10 parts by weight, preferably at least 20 parts by weight, in particular at least 30 parts by weight per 100 parts by weight of water under normal conditions (20 ° C., 1 bar).
  • the additives are preferably low molecular weight compounds which have a molecular weight of at most 1000 g / mol, particularly preferably at most 500 g / mol, in particular at most 300 g / mol.
  • the additives are inorganic salts in the form of phosphate, hydrogen phosphate, phosphite, hydrogen phosphite, sulfate or sulfite, it being possible for them to be metal salts, in particular alkali metal salts, or salts with organic cations.
  • the cations of the above inorganic salts can in particular be metal cations, preferably alkali metal cations such as Na + or K + , or ammonium (NH 4 + ). Examples are (NH 4 ) 2 HPO 4 , NH 4 SO 4 or NH 4 Cl.
  • additives are often additives which are also used as flame retardants. It can be assumed that these additives interact with the primary hydroxyl group of the glucose ring (ie the CH 2 OH group) and counteract the breakdown of cellulose into volatile carbon compounds during pyrolysis.
  • the total amount of all additives in the solution is e.g. B. 0.05 to 5 mol / per liter of solution, preferably 0.1 mol to 2 mol / per liter of solution.
  • the contact with the solution of the additives is carried out in such a way that the cellulose fiber absorbs additives in the desired amount.
  • the cellulose fiber can be immersed in the solution for a sufficient time or it can be passed through a sufficiently long solution bath in a continuous process.
  • the cellulose fiber is passed continuously through the solution of the additive.
  • the contact time of the cellulose fiber with the solution of the additives is preferably at least 0.5 seconds, particularly preferably at least 2 and very particularly preferably at least 10 seconds. Generally it is no longer than 100 seconds, preferably no longer than 30 seconds.
  • the additized cellulose fiber obtained contains at least 5 parts by weight of additives per 100 parts by weight of cellulose.
  • the additized cellulose fiber particularly preferably contains at least 1 part by weight, very particularly preferably at least 3 parts by weight of additives per 100 parts by weight of cellulose fiber.
  • the cellulose fiber contains not more than 30 parts by weight of additives, in particular not more than 10 or not more than 5 parts by weight of additives per 100 parts by weight of cellulose fiber.
  • the production of the cellulose fiber in the spinning process and subsequent further processing by washing the cellulose fiber and bringing the cellulose fiber into contact with the solution of the additives are preferably components of a continuous overall process. After its production, the cellulose fiber is generally fed to the individual further processing steps via movable rollers.
  • excess solvent can be removed from the solution of the additives by squeezing off and the cellulose fiber with the additive can be rolled up.
  • the additized cellulose fiber can be dried, e.g. B. at temperatures of 50 to 300 ° C. Such drying is recommended if the cellulose fiber with the additive is to be stored or transported before it is converted into a carbon fiber.
  • the additized cellulose fiber is converted into a carbon fiber by pyrolysis.
  • the pyrolysis is generally carried out at temperatures of 500 to 1600 ° C. You can, for example, under air or under protective gas, z. B. nitrogen or helium can be carried out. It is preferably carried out under a protective gas.
  • the cellulose fiber can be dried before pyrolysis. In the case of cellulose fibers that have already been dried and stored, drying can be repeated if necessary.
  • the temperature can be increased gradually or continuously.
  • drying in two or more stages is possible, for example at 50 to 100 ° C. in a first stage and at 100 to 200 ° C. in a second stage.
  • the contact time in the individual stages can be, for example, 5 to 300 seconds each and a total of 10 to 500 seconds during the drying.
  • a pyrolysis in which the temperature is continuously increased, e.g. B. starting at 200 ° C and finally reaching 1600 or 1400 or 1200 ° C.
  • the temperature increase can take place, for example, at 1 to 20 Kelvin / minute.
  • the cellulose fiber should preferably be exposed to a temperature in the range from 900 to 1600 ° C. for a period of 10 to 60 minutes.
  • the carbon yield in pyrolysis is generally 20 to 95% by weight; that is, the carbon fiber contains 20 to 95 percent by weight of the carbon contained in the cellulose fiber.
  • the carbon yield is in particular 70 to 95, particularly preferably 70 to 90, very particularly preferably 70 to 85% by weight.
  • the process according to the invention enables an increased carbon yield.
  • the carbon fiber obtained has very good mechanical properties, in particular good strength and elasticity.
  • a synthetic, tear-resistant cellulose fiber which is used for the production of car tires, is used as the cellulose fiber.
  • Such cellulose fibers are known as tire cord fibers.
  • the cellulose fiber in the example has not been dried since its manufacture, hence the name "never-dried tire cord fiber".
  • the cellulose fiber in the comparative example was dried; Cellulose fibers usually contain bound residual water, so the water content of dried cellulose fibers can e.g. B. up to 20 wt.%.
  • a never-dried tire cord fiber with a water content of 150% and a single filament titer of 2.2 dtex with 1000 filaments is presented.
  • the finishing and drying of the fibers takes place in a continuous process on godets.
  • Godets are rollers that enable the fibers to run continuously along the system. 4 of these godets are used.
  • the fibers are loaded with the additives via an immersion bath.
  • a tension-controlled winder spools up the finished and dried fiber material.
  • the first godet serves as an unwinding unit for the never dried tire cord fibers stored in water.
  • the fiber is wound around the godet twice, which corresponds to a contact time of 10 seconds.
  • the fiber is then passed through an immersion bath with an ammonium dihydrogen phosphate solution (concentration of ammonium hydrogen phosphate of 0.54 mol / l).
  • the dwell time here is about one second.
  • the material is now wound around the second godet six times. This step is used to drain excess equipment and to bring about a homogeneous distribution of the ammonium hydrogen phosphate in the fiber.
  • the contact time here is 72 seconds. This is followed by drying on the third godet heated to 80 ° C.
  • 10 windings correspond to a contact time of 100 seconds.
  • the fiber is now guided through a hot air duct at 150 ° C.
  • the dwell time is 12 seconds.
  • the dry thread is now wound 4 times around the last godet (contact time 24 seconds) before a tension-controlled winder winds the material with a pretension of 0.1 cN / tex.
  • the cellulose fiber equipped with the additive is then carbonized in two stages under protective gas. In the first stage, it is heated at 2 ° K / min to 260 ° C and, after a dwell time of 10 min, heated at 10k / min to 1400 ° C and then cooled.
  • the carbon yield is 80% by weight, the strength of the fiber 1.4 Gpa and the elongation at break 3.1%.
  • a dried tire cord fiber with a water content of less than 20% by weight and a single filament denier of 2.2 dtex with 1000 filaments is presented.
  • the test procedure corresponds to example 1.
  • the carbon yield is 65% by weight, the strength of the fiber is 1.1 Gpa and the elongation at break is 2.2%.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)
  • Inorganic Fibers (AREA)

Claims (12)

  1. Procédé de production de fibres de carbone à partir de fibres cellulosiques, caractérisé en ce que les fibres cellulosiques, qui ont une teneur en eau supérieure à 30 parties en poids d'eau sur 100 parties en poids de fibres cellulosiques et ne subissent aucune opération de procédé pour le séchage lors de leur production, sont mises en contact avec une solution d'additifs et les fibres cellulosiques pourvues d'additifs qui contiennent au moins 1 partie en poids d'additifs sur 100 parties en poids de cellulose sont ensuite transformées en fibres de carbone, dans lequel les additifs représentent des sels inorganiques sous forme de phosphate, d'hydrogénophosphate, de phosphite, d'hydrogénophosphite, de sulfate ou de sulfite, et leur solution peuvent contenir un unique additif ou un mélange de différents additifs.
  2. Procédé selon la revendication 1, caractérisé en ce que les fibres cellulosiques contiennent plus de 50 parties en poids d'eau, en particulier plus de 70 parties en poids d'eau sur 100 parties en poids de cellulose.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que les cations des sels inorganiques sont des cations de métal alcalin ou des ions ammonium (NH4 +).
  4. Procédé selon au moins l'une des revendications précédentes, caractérisé en ce que les sels inorganiques sont le (NH4)2HPO4 ou le (NH4)2SO4.
  5. Procédé selon au moins l'une des revendications précédentes, caractérisé en ce qu'il s'agit d'une solution des additifs dans de l'eau, un solvant organique hydrophile ou leurs mélanges.
  6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que la fibre cellulosique passe en continu à travers la solution de l'additif et que le temps de contact est d'au moins 2 secondes.
  7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que la fibre cellulosique obtenue pourvue d'additifs contient au moins 5 parties en poids d'additifs sur 100 parties en poids de cellulose.
  8. Procédé selon au moins l'une des revendications précédentes, caractérisé en ce que les fibres cellulosiques se composent à plus de 60 % en poids, en particulier à plus de 80 % en poids, de manière particulièrement préférée à plus de 90 % en poids, de cellulose ou de cellulose modifiée.
  9. Procédé selon la revendication 8, caractérisé en ce que les fibres cellulosiques se composent à plus de 98 % en poids, de manière tout particulièrement préférée à plus de 100 % en poids, de cellulose ou de cellulose modifiée.
  10. Procédé selon la revendication 9, caractérisé en ce que les groupes hydroxyle de la cellulose modifiée sont éthérifiés ou estérifiés.
  11. Procédé selon la revendication 10, caractérisé en ce que la cellulose modifiée représente l'acétate de cellulose, le formiate de cellulose, le propionate de cellulose, le carbamate de cellulose ou l'allophanate de cellulose.
  12. Procédé selon l'une des revendications 1 à 11, caractérisé en ce que la fibre cellulosique obtenue pourvue d'additifs est transformée par pyrolyse en une fibre de carbone.
EP15721717.5A 2014-05-16 2015-05-12 Procédé de production de fibres de carbone à partir de fibres de cellulose Active EP3143187B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP14168572 2014-05-16
PCT/EP2015/060479 WO2015173243A1 (fr) 2014-05-16 2015-05-12 Procédé de production de fibres de carbone à partir de fibres de cellulose

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EP3143187A1 EP3143187A1 (fr) 2017-03-22
EP3143187B1 true EP3143187B1 (fr) 2020-11-11

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US (1) US20170081787A1 (fr)
EP (1) EP3143187B1 (fr)
EA (1) EA201692291A1 (fr)
WO (1) WO2015173243A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016078960A1 (fr) 2014-11-20 2016-05-26 Basf Se Procédé de production de fibres de carbone à partir de fibres de cellulose contenant du phosphore
WO2017133995A1 (fr) 2016-02-01 2017-08-10 Basf Se Procédé de production lactames c4-c15
ES2954633T3 (es) * 2016-02-11 2023-11-23 Technikum Laubholz Gmbh Procedimiento de producción de fibras de carbono a partir de fibras de celulosa tratadas con sales de ácido sulfónico
DE102020113807A1 (de) * 2020-05-22 2021-11-25 centrotherm international AG Endlosfasern auf Basis von Cellulose und/oder Cellulosederivaten, Verfahren zu deren Herstellung sowie deren Verwendung

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1455531A (en) * 1975-01-02 1976-11-10 Toyo Boseki Process for preparing active carbon fibres machine for attaching components to a printed circuit board
EP1669480A1 (fr) * 2004-12-07 2006-06-14 Snecma Propulsion Solide Méthode pour obtenir des fils ou des feuilles à base de fibre de carbon à partir d'un précurseur cellulosique
RU2429316C1 (ru) * 2010-03-26 2011-09-20 Юрий Васильевич Карасев Способ непрерывного получения из гидратцеллюлозы углеродного волокна в виде однонаправленного жгута

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1455531A (en) * 1975-01-02 1976-11-10 Toyo Boseki Process for preparing active carbon fibres machine for attaching components to a printed circuit board
EP1669480A1 (fr) * 2004-12-07 2006-06-14 Snecma Propulsion Solide Méthode pour obtenir des fils ou des feuilles à base de fibre de carbon à partir d'un précurseur cellulosique
RU2429316C1 (ru) * 2010-03-26 2011-09-20 Юрий Васильевич Карасев Способ непрерывного получения из гидратцеллюлозы углеродного волокна в виде однонаправленного жгута

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Publication number Publication date
WO2015173243A1 (fr) 2015-11-19
US20170081787A1 (en) 2017-03-23
EA201692291A1 (ru) 2017-04-28
EP3143187A1 (fr) 2017-03-22

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