EP0313736A2 - Process of preparation of carbon fibres - Google Patents
Process of preparation of carbon fibres 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.
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Kohlenstoffasern aus hochsiedenden bituminösen Stoffen wie beispielsweise Steinkohlenteerpech, Petrolpech, Rückstandsölen der Kohleverflüssigung und Synthesepechen.
Verfahren dieser Art sind an sich bekannt. Die bituminösen Stoffe werden gereinigt und gegebenenfalls nach einer Vorbehandlung polymerisiert. Dabei entsteht ein Mesophasenpech mit unterschiedlichen Mengen an anisotropen Pechbestandteilen, aus dem die leichter flüchtigen und die isotropen Bestandteile zumindest teilweise entfernt werden müssen, um ein Kohlenstoffaser-Vorprodukt mit hohem optisch anisotropem Anteil zu erhalten.
Dieses Vorprodukt muß folgenden Anforderungen genügen:
- a) Der Anteil an Feststoffen sollte gering sein, damit es beim Verspinnen nicht zu Fadenbrüchen kommt.
- b) Unter Spinnbedingungen darf es nicht zu einer Gasentwicklung kommen, um Fadenbrüche zu vermeiden.
- c) Die Viskosität sollte bei hohem Verkokungsrückstand niedrig sein, damit das Vorprodukt bei Temperaturen versponnen werden kann, die deutlich unter der Polymerisationstemperatur liegen.
Methods of this type are known per se. The bituminous substances are cleaned and, if necessary, polymerized after pretreatment. This creates a mesophase pitch with different amounts of anisotropic pitch constituents, from which the more volatile and the isotropic constituents have to be at least partially removed in order to obtain a carbon fiber precursor with a high optically anisotropic proportion.
This preliminary product must meet the following requirements:
- a) The proportion of solids should be low so that thread breaks do not occur during spinning.
- b) Under spinning conditions, there must be no gas development in order to avoid thread breaks.
- c) The viscosity should be low in the case of a high coking residue so that the preliminary product can be spun at temperatures which are significantly below the polymerization temperature.
Das Vorprodukt wird meist über einen Extruder versponnen, und der Pechfaden durch Oxidation unschmelzbar gemacht, carbonisiert und gegebenenfalls graphitiert.
Die Reinigung des bituminösen Stoffes kann durch Filtration oder Extraktion mit gegebenenfalls anschließendem Abdestillieren des Lösungsmittels erfolgen. Diese Verfahrensstufe ist nicht kritisch und wird technisch beherrscht.
Die Polymerisation wird bei erhöhter Temperatur mit oder ohne Katalysator durchgeführt. Die Bedingungen sind so zu wählen, daß möglichst wenig Chinolinunlösliches (QI) aber ein hoher Anteil an optisch anisotropem Material entsteht. Die Neigung zur QI-Bildung kann durch vorheriges Hydrieren vermindert werden. Die Katalysatoren müssen, soweit welche verwendet werden, restlos aus dem Mesophasenpech entfernt werden.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.
Um bereits bei der Polymerisation einen ausreichend hohen Anteil an anisotropem Material zu erhalten, kann dieser Verfahrensschritt unter hohem Vakuum oder unter Einleiten eines Trägergases durchgeführt werden. Die Neubildung von Chinolinunlöslichem läßt sich jedoch nicht vollständig vermeiden, so daß sich häufig an die Polymerisation noch eine Extraktionsstufe anschließen muß. Das verwendete Lösungsmittel muß unter schonenden Bedingungen restlos aus dem Kohlenstoffaser-Vorprodukt destillativ entfernt werden.
Als Rückstand verbleibt eine bei Temperaturen oberhalb etwa 250 °C schmelzende hochviskose Masse, die bei ca. 100 K höheren Temperaturen versponnen wird.
Spinntemperaturen bis etwa 400 °C sind durchaus üblich. Dabei polymerisiert das Vorprodukt weiter, und es besteht die Gefahr, daß sich Feststoffe bilden, die zu Fadenbrüchen führen oder sogar die Spinndüsen verstopfen. Hohe Fließpunkte sind aber notwendig, damit die Pechfäden bei dem bei Temperaturen oberhalb 200 °C beginnenden Oxydationsprozeß noch eine ausreichende Festigkeit besitzen und nicht verkleben. Dieses Problem ist bisher nicht zufriedenstellend gelöst. Es ist vielmehr als Hauptgrund dafür anzusehen, daß die Herstellung von Kohlenstoffasern aus Pech bisher sich großtechnisch nicht hat durchsetzen können.In order to obtain a sufficiently high proportion of anisotropic material already during the polymerization, this process step can be carried out under high vacuum or with the introduction of a carrier gas. However, the new formation of quinoline-insoluble matter cannot be completely avoided, so that an extraction step often has to follow the polymerization. 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. However, high pour points are necessary so that the pitch threads still have sufficient strength during the oxidation process that begins at temperatures above 200 ° C. and do not stick together. So far, this problem has not been solved satisfactorily. Rather, it can be seen as the main reason why the production of carbon fibers from pitch has so far not been able to establish itself on an industrial scale.
Es besteht daher die Aufgabe, ein Verfahren zur Herstellung von Kohlenstoffasern zu entwicklen, bei dem das hochschmelzende Vorprodukt bei vergleichbar niedrigen Temperaturen versponnen werden kann.It is therefore the task of developing a process for producing carbon fibers in which the high-melting intermediate product can be spun at comparatively low temperatures.
Die Aufgabe wird erfindungsgemäß dadurch gelöst, daß dem Kohlenstoffaser-Vorprodukt unmittelbar vor dem Verspinnen 2 bis 10 Gew.-% eines Lösungsmittels, das unter normalen Bedingungen in dem Vorprodukt nicht oder nur in sehr geringem Maße löslich ist, zugegeben und unter Bedingungen, unter denen das Lösungsmittel im überkritischem Zustand vorliegt, mit diesem vermischt wird, wobei die Mischzeit mindestens 10 min beträgt. Als Lösungsmittel können beispielsweise hochsiedende Alkohole, Wasser usw. verwendet werden, die unter 100 °C bei Normaldruck in flüssiger Form vorliegen. Durch seinen überkritischen Zustand löst sich das Lösungsmittel vollständig und homogen in dem Vorprodukt.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. For example, 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.
Überraschenderweise wurde gefunden, daß es auch innerhalb eines Zeitraumes von etwa 15 min beim Verspinnen nicht zu einer Entmischung kommt. Das Vorprodukt ließ sich länger als 60 min ohne Fadenbruch bei nicht mehr als 30 K über dem Schmelzpunkt liegenden Temperaturen zu 10 µm dicken Fasern verspinnen. Auch nach tagelangen Dauerversuchen zeigten die Spinndüsen keine Verstopfungen. Beim Oxydationsprozeß diffundiert der überwiegende Teil des Lösungsmittels aus der Faser, ohne daß in der Faser bleibende Gasblasen gefunden werden.Surprisingly, it was found that segregation does not occur within a period of about 15 minutes during spinning. The preliminary product could be spun for more than 60 minutes without breaking the thread at temperatures not more than 30 K above the melting point to give fibers 10 μm thick. Even after long-term tests, the spinnerets showed no blockages. In the oxidation process, the majority of the solvent diffuses out of the fiber without any gas bubbles remaining in the fiber being found.
Die Erfindung wird anhand des nachfolgenden Beispiels näher erläutert:The invention is illustrated by the following example:
100 Gew.-Teile eines Kohlenstoffaser-Vorprodukts aus Steinkohlenteer mit folgenden Eigenschaften:
Der Versuch wird nach 1 1/4 h abgebrochen. Bis zu diesem Zeitpunkt ist kein Fadenbruch aufgetreten. Die Pechfasern werden in Luft mit 3 K/min bis auf 150 °C und dann mit 1 K/min bis auf 300 °C erhitzt und diese Temperatur 30 min lang erhalten, um die Fasern durch Oxidation zu stabilisieren. Die stabilisierten Fasern werden anschließend in einer Stickstoffatmosphäre mit 5 K/min bis auf 1000 °C aufgeheizt und diese Temperatur 30 min lang gehalten, um die Fasern zu carbonisieren.100 parts by weight of a carbon fiber intermediate product from coal tar with the following properties:
The experiment is stopped after 1 1/4 hours. No thread breakage has occurred up to this point. The pitch fibers are heated in air at 3 K / min up to 150 ° C. and then at 1 K / min up to 300 ° C. and this temperature is maintained for 30 minutes in order to stabilize the fibers by oxidation. The stabilized fibers are then heated in a nitrogen atmosphere at 5 K / min up to 1000 ° C. and this temperature is maintained for 30 minutes in order to carbonize the fibers.
Die carbonisierten Fasern werden in einem Argonstrom mit einer Temperatursteigerung von 25 K/min bis 2500 °C graphitiert. Die Zugfestigkeit betrug 2,5 kN/mm² bei einem Elastizitäts-Modul von 0,4 MN/mm². An den Bruchstellen sind keine sichtbaren Gas- oder Feststoffeinschlüsse erkennbar.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.
Das gleiche Kohlenstoffaser-Vorprodukt wie in Beispiel 1 wird auf 320 °C erhitzt und direkt dem Extruder mit Düsenplatte zugeführt. Die Zähigkeit war so hoch, daß der Scherbolzen des Extruderantriebs abriß. Es trat kein Pech aus der Düsenplatte aus.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.
Der im Beispiel 2 beschriebene Versuch wurde bei jeweils nur 20 K erhöhter Temperatur wiederholt. Bei einer Temperatur von 400 °C gelang es, Pechfäden mit einer Abzugsgeschwindigkeit von 300 K/min zu spinnen. Die Fasern hatten einen Durchmesser von 15 µm. Nach 8 min trat jedoch bereits ein Fadenbruch auf. Der Versuch wurde fortgesetzt. Nach 4 h hatte sich die Düsenplatte jedoch mit Feststoffen zugesetzt, so daß der Versuch abgebrochen werden mußte, um Extruder und Düsenplatte zu reinigen.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 µm. 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.
Claims (3)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19873736494 DE3736494A1 (en) | 1987-10-28 | 1987-10-28 | METHOD FOR PRODUCING CARBON FIBERS |
DE3736494 | 1987-10-28 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0313736A2 true EP0313736A2 (en) | 1989-05-03 |
EP0313736A3 EP0313736A3 (en) | 1990-01-10 |
EP0313736B1 EP0313736B1 (en) | 1992-07-29 |
Family
ID=6339258
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88112010A Expired - Lifetime EP0313736B1 (en) | 1987-10-28 | 1988-07-26 | Process of preparation of carbon fibres |
Country Status (5)
Country | Link |
---|---|
US (1) | US4902492A (en) |
EP (1) | EP0313736B1 (en) |
JP (1) | JPH01148815A (en) |
DE (2) | DE3736494A1 (en) |
PL (1) | PL150719B1 (en) |
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 (en) * | 1970-02-20 | 1971-10-21 | Mitsubishi Oil Co., Ltd., Tokio | Process for the production of carbon fibers |
GB2037724A (en) * | 1979-11-08 | 1980-07-16 | Mitsui Coke Co | Process for producing carbon fibers |
EP0157615A2 (en) * | 1984-03-31 | 1985-10-09 | Nippon Steel Corporation | Process for producing mesophase pitch and carbon products produced from the mesophase pitch |
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 (en) * | 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 (en) * | 1981-10-29 | 1983-05-09 | Nippon Oil Co Ltd | Preparation of pitch carbon fiber |
JPS59155493A (en) * | 1983-02-23 | 1984-09-04 | Mitsubishi Petrochem Co Ltd | Preparation of meso phase pitch |
JPS61103989A (en) * | 1984-10-29 | 1986-05-22 | Maruzen Sekiyu Kagaku Kk | Production of pitch for manufacture of carbon product |
JPS61108725A (en) * | 1984-10-30 | 1986-05-27 | Teijin Ltd | Production of pitch carbon yarn having novel structure |
-
1987
- 1987-10-28 DE DE19873736494 patent/DE3736494A1/en not_active Withdrawn
-
1988
- 1988-07-26 DE DE8888112010T patent/DE3873256D1/en not_active Expired - Fee Related
- 1988-07-26 EP EP88112010A patent/EP0313736B1/en not_active Expired - Lifetime
- 1988-10-17 US US07/258,394 patent/US4902492A/en not_active Expired - Fee Related
- 1988-10-25 JP JP63267340A patent/JPH01148815A/en active Pending
- 1988-10-26 PL PL1988275508A patent/PL150719B1/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2108079A1 (en) * | 1970-02-20 | 1971-10-21 | Mitsubishi Oil Co., Ltd., Tokio | Process for the production of carbon fibers |
GB2037724A (en) * | 1979-11-08 | 1980-07-16 | Mitsui Coke Co | Process for producing carbon fibers |
EP0157615A2 (en) * | 1984-03-31 | 1985-10-09 | Nippon Steel Corporation | Process for producing mesophase pitch and carbon products produced from the mesophase pitch |
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 |
---|---|
EP0313736A3 (en) | 1990-01-10 |
US4902492A (en) | 1990-02-20 |
PL150719B1 (en) | 1990-06-30 |
EP0313736B1 (en) | 1992-07-29 |
JPH01148815A (en) | 1989-06-12 |
PL275508A1 (en) | 1989-06-26 |
DE3736494A1 (en) | 1990-03-15 |
DE3873256D1 (en) | 1992-09-03 |
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