EP0313736B1 - Procédé de préparation de fibres de carbones - Google Patents

Procédé de préparation de fibres de carbones Download PDF

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Publication number
EP0313736B1
EP0313736B1 EP88112010A EP88112010A EP0313736B1 EP 0313736 B1 EP0313736 B1 EP 0313736B1 EP 88112010 A EP88112010 A EP 88112010A EP 88112010 A EP88112010 A EP 88112010A EP 0313736 B1 EP0313736 B1 EP 0313736B1
Authority
EP
European Patent Office
Prior art keywords
intermediate product
carbon
solvent
spun
pitch
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.)
Expired - Lifetime
Application number
EP88112010A
Other languages
German (de)
English (en)
Other versions
EP0313736A3 (en
EP0313736A2 (fr
Inventor
Herbert Dr. Beneke
Gerd Dr. Collin
Manfred Dipl.-Ing. Meinbreckse
Gerhard Dr. Wilhelm
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.)
Ruetgers Germany GmbH
Original Assignee
Ruetgerswerke 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 Ruetgerswerke AG filed Critical Ruetgerswerke AG
Publication of EP0313736A2 publication Critical patent/EP0313736A2/fr
Publication of EP0313736A3 publication Critical patent/EP0313736A3/de
Application granted granted Critical
Publication of EP0313736B1 publication Critical patent/EP0313736B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
    • D01F9/15—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from coal pitch

Definitions

  • the preliminary product is usually spun using an extruder, and the pitch thread is made infusible by oxidation, carbonized and optionally graphitized.
  • the bituminous substance can be cleaned by filtration or extraction with subsequent subsequent distilling off of the solvent (DE-A-19 25 609). This stage of the process is not critical and is technically mastered.
  • the polymerization is carried out at elevated temperature with or without a catalyst. The conditions should be chosen so that as little quinoline-insoluble (QI) as possible, but a high proportion of optically anisotropic material. The tendency to form QI can be reduced by prior hydrogenation (DE-C-32 31 682).
  • the catalysts, if used, must be removed completely from the mesophase pitch.
  • the hydrogenation can also be carried out by adding H donors such as, for example, phenols and alcohols.
  • H donors such as, for example, phenols and alcohols.
  • the mixture of pitch and phenols or alcohols freed from quinoline-insoluble substances is first pretreated under pressure in order to obtain a hydrogenated pitch, and the reaction product is then subjected to a further thermal treatment, if appropriate after removing oils or unreacted phenols or alcohols subjected to mesophase formation.
  • the mesophase pitches made of hydrogenated pitch have a lower softening point than those made of non-hydrogenated pitch with the same mesophase content.
  • the mesophase pitches are spun into fibers in the usual way, which are oxidized and carbonized.
  • this process step can be carried out under high vacuum or with the introduction of a carrier gas (DE-C-28 42 723).
  • a carrier gas DE-C-28 42 723
  • the solvent used must be removed completely by distillation from the carbon fiber precursor under mild conditions.
  • the residue is a highly viscous mass which melts at temperatures above approximately 250 ° C. and is spun at temperatures which are approximately 100 ° C. higher. Spinning temperatures up to about 400 ° C are quite common.
  • the preliminary product continues to polymerize, and there is a risk of solids forming which lead to thread breaks or even block the spinnerets.
  • the object is achieved according to the invention in that 2 to 10% by weight of a solvent which is insoluble or only insoluble in the precursor under normal conditions is added to the carbon fiber precursor immediately before spinning and under conditions under which the solvent is in the supercritical state, is mixed with it, the mixing time being at least 10 min.
  • a solvent which is insoluble or only insoluble in the precursor under normal conditions
  • the mixing time being at least 10 min.
  • high-boiling alcohols, water, etc. which are present in liquid form at 100 ° C. under normal pressure can be used as solvents. Due to its supercritical state, the solvent dissolves completely and homogeneously in the preliminary product.
  • the carbonized fibers are graphitized in an argon stream with a temperature increase of 25 ° C / min to 2500 ° C.
  • the tensile strength was 2.5 kN / mm2 with an elastic modulus of 0.4 MN / mm2. There are no visible gas or solid inclusions at the break points.
  • Example 2 The same carbon fiber precursor as in Example 1 is heated to 320 ° C and fed directly to the extruder with a die plate.
  • the toughness was so high that the shear pin of the extruder drive broke off. No bad luck came out of the nozzle plate.
  • Example 2 The experiment described in Example 2 was repeated at a temperature which was only 20 ° C. in each case. At a temperature of 400 ° C, pitch threads were spun at a take-off speed of 300 ° C / min. The fibers had a diameter of 15 ⁇ m. However, a thread break already occurred after 8 minutes. The experiment was continued. After 4 hours, however, the die plate had become clogged with solids, so that the experiment had to be stopped in order to clean the extruder and die plate.

Landscapes

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

Claims (3)

  1. Procédé de fabrication de fibres de carbone à partir de matières bitumineuses de point d'ébullition élevé à partir desquelles on prépare, par purification, polymérisation, éventuellement après hydrogénation et concentration, un précurseur de fibres de carbone qui est filé en fibres, oxydé, carbonisé et éventuellement graphitisé, caractérisé en ce qu'on ajoute au précurseur de fibres de carbone, juste avant le filage, 2 à 10% en poids d'un solvant qui, dans les conditions normales, n'est pas soluble ou est soluble seulement dans une très faible mesure dans le précurseur et que, dans les conditions où le solvant se trouve à l'état surcritique, on le mélange avec celui-ci, moyennant quoi le temps de mélange s'élève à au moins 10 min.
  2. Procédé selon la revendication 1, caractérisé en ce que le solvant est un alcool de point d'ébullition élevé.
  3. Procédé selon les revendications 1 et 2, caractérisé en ce que le mélange fini de précurseur de fibres de carbone et de solvant est filé en l'espace de 15 min. à une température de pas plus de 30°C au-dessus du point de fusion du précurseur.
EP88112010A 1987-10-28 1988-07-26 Procédé de préparation de fibres de carbones Expired - Lifetime EP0313736B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3736494 1987-10-28
DE19873736494 DE3736494A1 (de) 1987-10-28 1987-10-28 Verfahren zur herstellung von kohlenstoffasern

Publications (3)

Publication Number Publication Date
EP0313736A2 EP0313736A2 (fr) 1989-05-03
EP0313736A3 EP0313736A3 (en) 1990-01-10
EP0313736B1 true EP0313736B1 (fr) 1992-07-29

Family

ID=6339258

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88112010A Expired - Lifetime EP0313736B1 (fr) 1987-10-28 1988-07-26 Procédé de préparation de fibres de carbones

Country Status (5)

Country Link
US (1) US4902492A (fr)
EP (1) EP0313736B1 (fr)
JP (1) JPH01148815A (fr)
DE (2) DE3736494A1 (fr)
PL (1) PL150719B1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5308599A (en) * 1991-07-18 1994-05-03 Petoca, Ltd. Process for producing pitch-based carbon fiber
US8123934B2 (en) 2008-06-18 2012-02-28 Chevron U.S.A., Inc. System and method for pretreatment of solid carbonaceous material
US11434429B2 (en) * 2019-03-18 2022-09-06 Terrapower, Llc Mesophase pitch for carbon fiber production using supercritical carbon dioxide
US20220010462A1 (en) * 2020-07-13 2022-01-13 Carbon Holdings Intellectual Properties, Llc Systems and methods for manufacturing carbon fiber from coal

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3035308A (en) * 1957-01-24 1962-05-22 Siemens Planiawerke A G Fur Ko Production of graphitizable pitch coke and graphite products
BE759139A (fr) * 1970-02-20 1971-04-30 Mitsubishi Oil Co Procede de fabrication d'une fibre au carbone
FR2087413A5 (fr) * 1970-05-19 1971-12-31 Charbonnages De France
GB1356568A (en) * 1970-09-08 1974-06-12 Coal Industry Patents Ltd Manufacture of carbon fibres
US3919387A (en) * 1972-12-26 1975-11-11 Union Carbide Corp Process for producing high mesophase content pitch fibers
GB2037724B (en) * 1979-11-08 1982-12-15 Mitsui Coke Co Process for producing carbon fibres
JPS5876523A (ja) * 1981-10-29 1983-05-09 Nippon Oil Co Ltd ピツチ系炭素繊維の製造方法
JPS59155493A (ja) * 1983-02-23 1984-09-04 Mitsubishi Petrochem Co Ltd メソフエ−ズピツチの製造方法
US4631181A (en) * 1984-03-31 1986-12-23 Nippon Steel Corporation Process for producing mesophase pitch
JPS61103989A (ja) * 1984-10-29 1986-05-22 Maruzen Sekiyu Kagaku Kk 炭素製品製造用ピツチの製造法
JPS61108725A (ja) * 1984-10-30 1986-05-27 Teijin Ltd 新規構造を有するピツチ系炭素繊維の製造法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CRC Handbook of Chemistry and Physics; 61. Ausgabe(1980/81) CRC Press Inc. Seite F-90 *

Also Published As

Publication number Publication date
PL275508A1 (en) 1989-06-26
EP0313736A3 (en) 1990-01-10
DE3736494A1 (de) 1990-03-15
DE3873256D1 (de) 1992-09-03
EP0313736A2 (fr) 1989-05-03
JPH01148815A (ja) 1989-06-12
PL150719B1 (en) 1990-06-30
US4902492A (en) 1990-02-20

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