EP0313736A2 - Procédé de préparation de fibres de carbones - Google Patents
Procédé de préparation de fibres de carbones Download PDFInfo
- Publication number
- EP0313736A2 EP0313736A2 EP88112010A EP88112010A EP0313736A2 EP 0313736 A2 EP0313736 A2 EP 0313736A2 EP 88112010 A EP88112010 A EP 88112010A EP 88112010 A EP88112010 A EP 88112010A EP 0313736 A2 EP0313736 A2 EP 0313736A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- solvent
- precursor
- carbon fiber
- fibers
- spun
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title abstract 2
- 229910052799 carbon Inorganic materials 0.000 title abstract 2
- 239000000835 fiber Substances 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 238000009987 spinning Methods 0.000 claims abstract description 9
- 238000002844 melting Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 12
- 239000004917 carbon fiber Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000013067 intermediate product Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 6
- 239000011295 pitch Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011302 mesophase pitch Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000011337 anisotropic pitch Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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. 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 towards QI formation can be reduced by prior hydrogenation.
- the catalysts, if used, must be removed completely from the mesophase pitch.
- this process step can be carried out under high vacuum or with the introduction of a carrier gas.
- a carrier gas such as a nitrogen gas
- the solvent used must be removed completely by distillation from the carbon fiber precursor under mild conditions.
- the residue that remains is a highly viscous mass that melts at temperatures above about 250 ° C. and is spun at temperatures that are about 100 K 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 in that 2 to 10% by weight of a solvent which is insoluble or only very slightly soluble in the precursor under normal conditions is added to the carbon fiber precursor 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 very slightly soluble 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 flow with a temperature increase of 25 K / 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 bolt 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 of only 20 K each. At a temperature of 400 ° C, pitch threads were spun at a take-off speed of 300 K / 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 nozzle plate had clogged with solids, so that the experiment had to be stopped in order to clean the extruder and nozzle 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)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19873736494 DE3736494A1 (de) | 1987-10-28 | 1987-10-28 | Verfahren zur herstellung von kohlenstoffasern |
DE3736494 | 1987-10-28 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0313736A2 true EP0313736A2 (fr) | 1989-05-03 |
EP0313736A3 EP0313736A3 (en) | 1990-01-10 |
EP0313736B1 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) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8123934B2 (en) | 2008-06-18 | 2012-02-28 | Chevron U.S.A., Inc. | System and method for pretreatment of solid carbonaceous material |
Families Citing this family (2)
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 |
US11434429B2 (en) | 2019-03-18 | 2022-09-06 | Terrapower, Llc | Mesophase pitch for carbon fiber production using supercritical carbon dioxide |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2108079A1 (de) * | 1970-02-20 | 1971-10-21 | Mitsubishi Oil Co., Ltd., Tokio | Verfahren zur Herstellung von Kohlenstoffasern |
GB2037724A (en) * | 1979-11-08 | 1980-07-16 | Mitsui Coke Co | Process for producing carbon fibers |
EP0157615A2 (fr) * | 1984-03-31 | 1985-10-09 | Nippon Steel Corporation | Procédé de production d'un brai en phase méso et produits carbonés fabriqués à partir de celui-ci |
Family Cites Families (8)
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 |
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 |
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 |
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 |
-
1987
- 1987-10-28 DE DE19873736494 patent/DE3736494A1/de not_active Withdrawn
-
1988
- 1988-07-26 EP EP88112010A patent/EP0313736B1/fr not_active Expired - Lifetime
- 1988-07-26 DE DE8888112010T patent/DE3873256D1/de not_active Expired - Fee Related
- 1988-10-17 US US07/258,394 patent/US4902492A/en not_active Expired - Fee Related
- 1988-10-25 JP JP63267340A patent/JPH01148815A/ja active Pending
- 1988-10-26 PL PL1988275508A patent/PL150719B1/pl unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2108079A1 (de) * | 1970-02-20 | 1971-10-21 | Mitsubishi Oil Co., Ltd., Tokio | Verfahren zur Herstellung von Kohlenstoffasern |
GB2037724A (en) * | 1979-11-08 | 1980-07-16 | Mitsui Coke Co | Process for producing carbon fibers |
EP0157615A2 (fr) * | 1984-03-31 | 1985-10-09 | Nippon Steel Corporation | Procédé de production d'un brai en phase méso et produits carbonés fabriqués à partir de celui-ci |
Non-Patent Citations (1)
Title |
---|
CRC Handbook of Chemistry and Physics; 61. Ausgabe(1980/81) CRC Press Inc. Seite F-90 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8123934B2 (en) | 2008-06-18 | 2012-02-28 | Chevron U.S.A., Inc. | System and method for pretreatment of solid carbonaceous material |
Also Published As
Publication number | Publication date |
---|---|
PL150719B1 (en) | 1990-06-30 |
JPH01148815A (ja) | 1989-06-12 |
US4902492A (en) | 1990-02-20 |
EP0313736A3 (en) | 1990-01-10 |
PL275508A1 (en) | 1989-06-26 |
DE3736494A1 (de) | 1990-03-15 |
DE3873256D1 (de) | 1992-09-03 |
EP0313736B1 (fr) | 1992-07-29 |
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