EP0238787B1 - Procédé de production d'un précurseur de fibres de carbone - Google Patents
Procédé de production d'un précurseur de fibres de carbone Download PDFInfo
- 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
Links
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%.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Fibers (AREA)
- Working-Up Tar And Pitch (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Claims (7)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19863610375 DE3610375A1 (de) | 1986-03-27 | 1986-03-27 | Verfahren zur herstellung eines kohlenstoffaser-vorprodukts und daraus hergestellte kohlenstoffasern |
DE3610375 | 1986-03-27 |
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 (13)
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 |
US20240217823A1 (en) * | 2022-12-29 | 2024-07-04 | Uop Llc | High performance (mesophase) carbon fiber feedstock production |
CN116606669B (zh) * | 2023-05-31 | 2024-07-02 | 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 |
Citations (2)
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 |
Family Cites Families (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US32120A (en) * | 1861-04-23 | Floor-clamp | ||
US2572583A (en) * | 1948-12-21 | 1951-10-23 | Phillips Petroleum Co | Improved liquid-liquid contacting process using di(beta-cyanoethyl)-amine |
US3087887A (en) * | 1959-12-21 | 1963-04-30 | Exxon Research Engineering Co | Method for manufacturing of specification paving and industrial asphalts |
US3202605A (en) * | 1962-06-06 | 1965-08-24 | Badger Co | Propane deaspihalting process |
DE1493190C3 (de) * | 1963-04-16 | 1980-10-16 | Studiengesellschaft Kohle Mbh, 4330 Muelheim | Verfahren zur Trennung von Stoffgemischen |
GB1482690A (en) * | 1974-12-19 | 1977-08-10 | Coal Ind | Hydrogenation of coal |
US4101416A (en) * | 1976-06-25 | 1978-07-18 | Occidental Petroleum Corporation | Process for hydrogenation of hydrocarbon tars |
JPS6041111B2 (ja) * | 1976-11-26 | 1985-09-13 | 新日鐵化学株式会社 | コ−クス製造原料の調整方法 |
US4208267A (en) * | 1977-07-08 | 1980-06-17 | Exxon Research & Engineering Co. | Forming optically anisotropic pitches |
DE2810332C2 (de) * | 1978-03-10 | 1982-08-05 | Rütgerswerke AG, 6000 Frankfurt | Verfahren zur Abtrennung von chinolinunlöslichen Bestandteilen aus Steinkohlenteerpech |
US4184942A (en) * | 1978-05-05 | 1980-01-22 | Exxon Research & Engineering Co. | Neomesophase formation |
US4219404A (en) * | 1979-06-14 | 1980-08-26 | Exxon Research & Engineering Co. | Vacuum or steam stripping aromatic oils from petroleum pitch |
DE3017876A1 (de) * | 1980-05-09 | 1982-05-19 | Peter, Siegfried, Prof.Dr., 8520 Erlangen | Verfahren zur abtrennung von feststoffen aus oelen |
US4354928A (en) * | 1980-06-09 | 1982-10-19 | Mobil Oil Corporation | Supercritical selective extraction of hydrocarbons from asphaltic petroleum oils |
US4402824A (en) * | 1981-03-25 | 1983-09-06 | Sumitomo Metal Industries, Limited | Process for refining coal-based heavy oils |
USRE32120E (en) | 1981-04-01 | 1986-04-22 | Phillips Petroleum Company | Hydrotreating supercritical solvent extracts in the presence of alkane extractants |
US4390411A (en) * | 1981-04-02 | 1983-06-28 | Phillips Petroleum Company | Recovery of hydrocarbon values from low organic carbon content carbonaceous materials via hydrogenation and supercritical extraction |
US4517072A (en) * | 1981-05-18 | 1985-05-14 | Domtar Inc. | Process for modifying coal tar materials |
US4497789A (en) * | 1981-12-14 | 1985-02-05 | Ashland Oil, Inc. | Process for the manufacture of carbon fibers |
US4482453A (en) * | 1982-08-17 | 1984-11-13 | Phillips Petroleum Company | Supercritical extraction process |
JPS5941387A (ja) * | 1982-08-30 | 1984-03-07 | Osaka Gas Co Ltd | ピッチの製造方法 |
US4503026A (en) * | 1983-03-14 | 1985-03-05 | E. I. Du Pont De Nemours And Company | Spinnable precursors from petroleum pitch, fibers spun therefrom and method of preparation thereof |
US4502943A (en) * | 1983-03-28 | 1985-03-05 | E. I. Du Pont De Nemours And Company | Post-treatment of spinnable precursors from petroleum pitch |
DE3335316A1 (de) * | 1983-09-29 | 1985-04-11 | Rütgerswerke AG, 6000 Frankfurt | Verfahren zur abtrennung harzartiger stoffe aus kohlestaemmigen schweroelen und verwendung der gewonnenen fraktion |
US4604184A (en) * | 1983-11-16 | 1986-08-05 | Domtar Inc. | Modified coal-tar pitch |
JPS60200816A (ja) * | 1984-03-26 | 1985-10-11 | Kawasaki Steel Corp | 炭素材料の製造方法 |
US4575412A (en) * | 1984-08-28 | 1986-03-11 | Kawasaki Steel Corporation | Method for producing a precursor pitch for carbon fiber |
US4578177A (en) * | 1984-08-28 | 1986-03-25 | Kawasaki Steel Corporation | Method for producing a precursor pitch for carbon fiber |
JPH0670220B2 (ja) * | 1984-12-28 | 1994-09-07 | 日本石油株式会社 | 炭素繊維用ピッチの製造法 |
-
1986
- 1986-03-27 DE DE19863610375 patent/DE3610375A1/de not_active Withdrawn
-
1987
- 1987-01-12 DE DE8787100271T patent/DE3760336D1/de not_active Expired
- 1987-01-12 EP EP87100271A patent/EP0238787B1/fr not_active Expired
- 1987-02-24 US US07/018,200 patent/US4756818A/en not_active Expired - Fee Related
- 1987-03-26 PL PL1987264837A patent/PL151114B1/pl unknown
- 1987-03-27 JP JP62071964A patent/JPS62243830A/ja active Pending
Patent Citations (2)
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 |
US4756818A (en) | 1988-07-12 |
DE3610375A1 (de) | 1987-10-01 |
PL264837A1 (en) | 1988-05-12 |
EP0238787A3 (en) | 1987-12-16 |
DE3760336D1 (en) | 1989-08-24 |
JPS62243830A (ja) | 1987-10-24 |
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