EP0238787B1 - Procédé de production d'un précurseur de fibres de carbone - Google Patents

Procédé de production d'un précurseur de fibres de carbone Download PDF

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Publication number
EP0238787B1
EP0238787B1 EP87100271A EP87100271A EP0238787B1 EP 0238787 B1 EP0238787 B1 EP 0238787B1 EP 87100271 A EP87100271 A EP 87100271A EP 87100271 A EP87100271 A EP 87100271A EP 0238787 B1 EP0238787 B1 EP 0238787B1
Authority
EP
European Patent Office
Prior art keywords
pitch
carrier
process according
gas
mixture
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
Application number
EP87100271A
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German (de)
English (en)
Other versions
EP0238787A2 (fr
EP0238787A3 (en
Inventor
Siegfried Prof. Dr. Peter
Herbert Dr. Beneke
Franz Oeste
Wolfgang Fexer
Wolfgang Jaumann
Manfred Meinbreckse
Joachim Kempfert
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 EP0238787A2 publication Critical patent/EP0238787A2/fr
Publication of EP0238787A3 publication Critical patent/EP0238787A3/de
Application granted granted Critical
Publication of EP0238787B1 publication Critical patent/EP0238787B1/fr
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C1/00—Working-up tar
    • C10C1/04—Working-up tar by distillation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C10C3/08—Working-up pitch, asphalt, bitumen by selective extraction
    • 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 invention relates to a method for producing a carbon fiber intermediate product from coal tar pitch.
  • the spinning temperatures are about 60 to 130 ° C above the softening point of the pitch used.
  • the pitch already decomposes, the pitch at least partially passing into the semi-coke stage and considerable amounts of gas being generated. This disrupts the spinning process. There are frequent thread breaks that make continuous spinning impossible.
  • pitches with the lowest possible softening point are required. Such pitches have a low content of components insoluble in quinoline or pyridine. Their average molecular weight is relatively low with a broad molecular weight distribution. This makes the process step to make the pitch fiber infusible before carbonization becomes more difficult.
  • DE-OS 35 09 861 describes a process for producing suitable carbon fiber precursors from aromatic, mineral oil-derived residual oils.
  • the residue is subjected to a two-stage heat treatment under pressures from 0.13 to 65 mbar in a falling film evaporator.
  • the temperatures, in particular in the second treatment stage are so high at 450 to 500 ° C. that the partial formation of coke structures cannot be prevented.
  • the known methods are very complex and often can only be carried out under laboratory conditions.
  • the object of the invention is therefore to produce a pitch material for carbon fiber production which has excellent spinnability, which can be made infusible in a short time, and from which carbon fibers of high strength with high modulus of elasticity can be produced, the disadvantages and Problems in the manufacture of the pitch material do not occur.
  • a coal tar pitch is solved by extraction at elevated temperature and pressure in a supercritical gas in the presence of an entrainer, with the exception of the components insoluble in quinoline, by lowering the pressure and / or increasing the temperature, the quinoline-soluble fraction or / and the toluene-soluble fraction is separated, one of these fractions or a mixture of both fractions is thermally treated at 380 to 450 ° C.
  • the following compounds or their mixtures can be used as supercritical gas: an aliphatic hydrocarbon, preferably having 2 to 5 carbon atoms and a halogen-containing hydrocarbon having 1 to 4 carbon atoms.
  • Suitable entraining agents are mono- or polynuclear hydrocarbons, which are optionally substituted with alkyl groups, in particular with 1 to 2 carbon atoms or an amino group, and can be both aromatic and fully or partially hydrogenated, mono- or di-core heterocyclic compounds, alkyl esters of aromatic acids with 1 up to 6 carbon atoms in the alcohol component or a mixture thereof.
  • the extraction stages are carried out at temperatures between 80 and 300 ° C, preferably between 120 and 250 ° C, at pressures from 80 to 300 bar, preferably from 150 to 250 bar.
  • the temperatures for the thermal treatment are high enough on the one hand to ensure a sufficient reaction rate, but on the other hand so low that no bulk mesophase tends to solidify.
  • the subsequent extraction stage for the removal of a predominant part of the isotropic pitch material also takes place at such low temperatures at which the pitch mesophase does not change. Since the mesophases consist only of plastically easily deformable spherules, which only flow together due to the shear forces in the extruder, the difference between the melting temperature and the spinning temperature can be reduced to 10 to 50 K without the withdrawal speed having to be reduced.
  • the extractant loaded with pitch is transferred to two successive regeneration autoclaves and gradually expanded to a pressure of 50 bar.
  • the temperature during regeneration is 150 ° C.
  • the cooling that occurs during relaxation due to the Joule-Thomson effect is compensated for by the addition of heat.
  • the regenerated mixture of extractant and entrainer is recycled.
  • the following pitch fractions are obtained in the regeneration autoclave after an extraction time of 5 h:
  • Fraction 2 is thermally treated at 400 ° C. under nitrogen at atmospheric pressure for 1.5 hours with stirring. This creates 50 vol .-% mesophase spherules. After cooling to 150 ° C. at a pressure of 130 bar, the mesophase pitch is extracted with a mixture of 30% by weight of propane and 70% by weight of toluene. A pitch with a mesophase content of 80% by volume, a content of pyridine-insoluble (PI) of 32% by weight, a melting point of 342 ° C. and an average molecular weight of about 1000 remains as the residue.
  • PI pyridine-insoluble
  • This pitch is at 370 ° C spun using an extruder with a spinneret plate with a hole diameter of 0.3 mm at a take-off speed of 1000 m / min.
  • the pitch fiber is heated in air at a heating rate of 20 K / min from 250 to 350 ° C. The final temperature is held for 5 minutes to make the fiber infusible.
  • the fiber is then carbonized at 1500 ° C. in an inert gas stream for 15 minutes.
  • the carbon fiber with a diameter of 9 ⁇ m has a strength of 2.47 kN / mm 2 , an elastic modulus of 158 kN / mm 2 and an elongation at break of 1.2%.
  • Fraction 3 is thermally treated at 430 ° C. under nitrogen at atmospheric pressure for one hour with stirring. This creates 60 vol .-% mesophase spherules. After cooling to 190 ° C extracted the mesophase pitch at a pressure of 130 bar with the same mixture as in the first extraction stage. This leaves a pitch with a mesophase content of 87% by volume, a pyridine-insoluble content of 44% by weight, a melting point of 357 ° C. and an average molecular weight of about 1100. This pitch is as described in Example 1 , spun at 380 ° C, made infusible and carbonized. The carbon fiber with a diameter of 7 gm has a strength of 2.58 kN / mm 2 , an elastic modulus of 153 kN / mm 2 and an elongation at break of 1.0%.

Claims (7)

1. Procédé pour la préparation d'un précurseur de fibres de carbone à partir de brai de goudron de houille, caractérisé en ce qu'un brai de goudron de houille est dissous par extraction à température et à pression accrues dans un gaz surcritique en présence d'un agent d'entraînement, à l'exception des constituants insolubles dans la quinoléine, que par réduction de la pression ou/et par augmentation de la température la fraction soluble dans la quinoléine ou/et la fraction soluble dans le toluène sont séparées, qu'une de ces fractions ou un mélange des deux fractions est traité thermiquement à une température de 380-450°C sous gaz inerte ou sous un gaz non oxydant à la pression atmosphérique jusqu'à ce que 40 à 65% en volume soient transformés en mésophases et que le brai isotrope est séparé par extraction du brai contenant les mésophases à l'aide d'un gaz surcritique par emploi d'un gaz d'entraînement, afin d'obtenir un brai anisotrope ayant une teneur en mésophases d'au moins 75% en volume, une teneur en matières insolubles dans la pyridine de 20 à 50% en poids, un poids moléculaire moyen de 900 à 1200 et un point de fusion de 330 à 360°C.
2. Procédé selon la revendication 1, caractérisé en ce qu'en tant que gaz surcritique, on utilise un des composés suivants ou leurs mélanges au-dessus de leur température critique et de leur pression critique: un hydrocarbure aliphatique comportant de préférence 2 à 5 atomes de carbone, un hydrocarbure oléfinique comportant de préférence 2 à 5 atomes de carbone, un hydrocarbure halogéné comportant notamment 1 à 4 atomes de carbone.
3. Procédé selon la revendication 1, caractérisé en ce qu'en tant que gaz surcritique, on utilise un gaz liquéfié (LPG).
4. Procédé selon les revendications 1 à 3, caractérisé en ce qu'en tant qu'agent d'entraînement, on utilise des hydrocarbures mono- ou polycycliques éventuellement substitués par des groupes alkyles ayant en particulier 1 à 2 atomes de carbone ou par un groupe amino et pouvant être aussi bien aromatiques que totalement ou partiellement hydrogénés, des composés hétérocycliques à 1 ou 2 cycles, en particulier des composés hétérocycliques azotés dans lesquels un noyau ou les deux noyaux sont hétérocycliques, des esters alkyliques d'acides aromatiques comportant de préférence 1 à 6 atomes de carbone dans le composant alcool ou leurs mélanges.
5. Procédé selon les revendications 1 à 3, caractérisé en ce qu'en tant qu'agent d'entraînement, on utilise du benzène de lavage.
6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que le brai est traité à des températures dans le domaine de 80°C à 300°C, de préférence de 120 à 250°C, avec un mélange constitué par un gaz surcritique et un agent d'entraînement sous-critique.
7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que le brai est traité à des pressions dans le domaine de 80 à 300 bars, de préférence de 150 à 250 bars avec un mélange constitué par un gaz surcritique et un agent d'entraînement sous-critique.
EP87100271A 1986-03-27 1987-01-12 Procédé de production d'un précurseur de fibres de carbone Expired EP0238787B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3610375 1986-03-27
DE19863610375 DE3610375A1 (de) 1986-03-27 1986-03-27 Verfahren zur herstellung eines kohlenstoffaser-vorprodukts und daraus hergestellte kohlenstoffasern

Publications (3)

Publication Number Publication Date
EP0238787A2 EP0238787A2 (fr) 1987-09-30
EP0238787A3 EP0238787A3 (en) 1987-12-16
EP0238787B1 true EP0238787B1 (fr) 1989-07-19

Family

ID=6297406

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87100271A Expired EP0238787B1 (fr) 1986-03-27 1987-01-12 Procédé de production d'un précurseur de fibres de carbone

Country Status (5)

Country Link
US (1) US4756818A (fr)
EP (1) EP0238787B1 (fr)
JP (1) JPS62243830A (fr)
DE (2) DE3610375A1 (fr)
PL (1) PL151114B1 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3741482A1 (de) * 1987-12-08 1989-08-10 Ruetgerswerke Ag Verfahren zur herstellung von kohlenstoffasern
US5032250A (en) * 1988-12-22 1991-07-16 Conoco Inc. Process for isolating mesophase pitch
AU651847B2 (en) * 1990-09-13 1994-08-04 Commonwealth Scientific And Industrial Research Organisation Process for refining pitch
WO1992005231A1 (fr) * 1990-09-13 1992-04-02 Commonwealth Scientific And Industrial Research Organisation Procede de raffinage du brai
CA2055092C (fr) * 1990-12-14 2002-01-15 Conoco Inc. Brais mesomorphes contenant des composes organometalliques pour le filage de fibres de carbone dans le brai
JP5262119B2 (ja) * 2008-01-10 2013-08-14 ソニー株式会社 負極および電池
RU2480509C1 (ru) * 2012-03-16 2013-04-27 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Башкирский государственный университет" Способ получения анизотропного волокнообразующего нефтяного пека экстракцией ароматическими и гетероциклическими соединениями
JP6437355B2 (ja) * 2015-03-17 2018-12-12 株式会社神戸製鋼所 炭素繊維の製造方法
JP6392701B2 (ja) * 2015-05-12 2018-09-19 株式会社神戸製鋼所 炭素繊維製造用原料ピッチ
US11434429B2 (en) * 2019-03-18 2022-09-06 Terrapower, Llc Mesophase pitch for carbon fiber production using supercritical carbon dioxide
CN113549466B (zh) * 2021-08-05 2022-09-20 广州市浩立生物科技有限公司 优质中间相沥青的制备方法
CN116606669A (zh) * 2023-05-31 2023-08-18 石河子大学 一种环烷基减压渣油脱沥青的溶剂及溶剂脱沥青的方法

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DE3509861A1 (de) * 1984-03-26 1985-10-03 Idemitsu Kosan Co. Ltd., Tokio/Tokyo Pechmaterial fuer einen kohlenstoffhaltigen formkoerper und verfahren zu seiner herstellung

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Publication number Priority date Publication date Assignee Title
DE3242629A1 (de) * 1981-11-18 1983-05-26 Nippon Oil Co., Ltd., Tokyo Ausgangspeche fuer kohlefasern
DE3509861A1 (de) * 1984-03-26 1985-10-03 Idemitsu Kosan Co. Ltd., Tokio/Tokyo Pechmaterial fuer einen kohlenstoffhaltigen formkoerper und verfahren zu seiner herstellung

Also Published As

Publication number Publication date
EP0238787A2 (fr) 1987-09-30
PL151114B1 (en) 1990-08-31
DE3610375A1 (de) 1987-10-01
US4756818A (en) 1988-07-12
JPS62243830A (ja) 1987-10-24
PL264837A1 (en) 1988-05-12
EP0238787A3 (en) 1987-12-16
DE3760336D1 (en) 1989-08-24

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