EP0089840A1 - Procédé de préparation de brai ayant une anisotropie optique - Google Patents
Procédé de préparation de brai ayant une anisotropie optique Download PDFInfo
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- EP0089840A1 EP0089840A1 EP83301552A EP83301552A EP0089840A1 EP 0089840 A1 EP0089840 A1 EP 0089840A1 EP 83301552 A EP83301552 A EP 83301552A EP 83301552 A EP83301552 A EP 83301552A EP 0089840 A1 EP0089840 A1 EP 0089840A1
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- Prior art keywords
- pitch
- temperature
- quinoline
- content
- matter content
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 80
- 239000011295 pitch Substances 0.000 claims abstract description 233
- 239000007858 starting material Substances 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 239000011337 anisotropic pitch Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 239000000295 fuel oil Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 64
- 239000000047 product Substances 0.000 claims description 19
- 239000011261 inert gas Substances 0.000 claims description 11
- 239000011269 tar Substances 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 6
- 239000003245 coal Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims 1
- 239000012071 phase Substances 0.000 description 26
- 238000009987 spinning Methods 0.000 description 23
- 230000005484 gravity Effects 0.000 description 19
- 229920000049 Carbon (fiber) Polymers 0.000 description 18
- 239000004917 carbon fiber Substances 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 229910001873 dinitrogen Inorganic materials 0.000 description 11
- 239000000835 fiber Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000006068 polycondensation reaction Methods 0.000 description 11
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 238000009835 boiling Methods 0.000 description 8
- 238000004227 thermal cracking Methods 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000002074 melt spinning Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000010692 aromatic oil Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
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- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- -1 polycyclic aromatic compounds Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- 238000010926 purge Methods 0.000 description 1
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- 239000011299 tars and pitches Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
Images
Classifications
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- 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
- D01F9/155—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from petroleum pitch
-
- 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
- C10C3/002—Working-up pitch, asphalt, bitumen by thermal means
-
- 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 present invention relates to a process for producing an optically anisotropic carbonaceous pitch suitable for the production of carbon fibers and other carbonaceous materials having a high strength and high modulus of elasticity.
- composition and structure of optically anisotropic pitches suitable for the production of high-performance carbon fibers have not fully been elucidated.
- the relationship between physical properties of carbonaceous pitch and composition and structure thereof has been unclear.
- Known optically anisotropic pitches such as those disclosed in Japanese Patent Laid-Open Nos. 19127/1974, 89635/1975 and 118028/1975 are produced by only a step of subjecting isotropic pitches to thermal decomposition/polycondensation reaction to make them heavier.
- An optically anisotropic phase (hereinafter referred to as AP) correspond substantially to quinoline-insoluble matter (or pyridine-insoluble matter). If A P is increased to nearly 100%, the softening point of the pitch is raised remarkably and the spinning temperature is elevated to about 400°C or higher. Consequently, a gas is formed due to decomposition of the pitch and polymerization occurs during the spinning operation. Therefore, in these processes, the AP content is controlled below 90%, practically 50-70%, so as to prevent excessive spinning temperature elevation for preventing the remarkable thermal decomposition and thermal polymerization.
- pitch compositions obtained by the conventional processes are heterogeneous, since they are mixtures of AP and a considerable amount of an optically isotropic phase (hereinafter referred to as IP). Therefore, they have defects that the fibers are broken in the course of the spinning and the fibers have uneven thickness and low strength.
- pitches disclosed in Japanese Patent Publication No'. 8634/1974 has an AP content of 100%. However, this is a special pitch having a specified chemical structure of the molecules. Such a pitch is produced by simple thermal polymerization of an expensive pure substance such as chrysene, phenanthrene or tetrabenzophenazine. It has a relatively well-controlled structural molecular weight. On the other hand, pitches produced from ordinary mixed starting materials have generally quite high softening points.
- homogeneous, optically anisotropic pitches having an AP content of approximately 100% produced by the known processes are expensive and they have generally high softening points and, accordingly, the stable spinning of them is difficult.
- pitches having a low softening point are heterogeneous excluding those having special compositions and structures produced from special starting materials, and spinning of them is also difficult. As a result, it is difficult to obtain carbon fibers having excellent qualities.
- optically anisotropic pitches have a well-developed laminate structure of condensed polycyclic aromatic compounds and a high molecular orientation, and actually, there are various kinds of optically anisotropic pitches.
- those having a low softening point and suitable for the production of homogeneous carbon fibers have a special chemical structure and composition.
- the inventors found that compositions, structures and molecular weights of a component 0 (i.e., n-heptane-soluble component) and a component A (i.e., n-heptane-insoluble/benzene-soluble component) are quite important.
- a process for producing such optically anisotropic pitches is disclosed in the specification accompanying European Patent Application 81305427.7.
- AP formed in the initial stage of the thermal reaction stays in the reaction system for a long time and, therefore, polycondensation reaction proceeds excessively.
- AP formed in the initial stage of the thermal reaction consists of substances having softening points higher than those constituting AP formed thereafter.
- This process is characterized in that a starting material for the production of pitch is subjected to thermal decomposition/polycondensation, the reaction mixture is settled when the polycondensate having a given AP content has been obtained to deposit high-density A P to form a lower layer and the lower layer is separated from an upper layer (pitch mainly comprising IP of a low density).
- a main object of the present invention is to provide a process for producing an optically anisotropic carbonaceous pitch having a low softening point and suitable for the production of carbon materials, particularly carbon fibers, having a high strength and a high modulus of elasticity.
- Another object of the invention is to provide a process for producing a homogeneous optically anisotropic carbonaceous pitch having a high orientation and suitable for the production of carbon materials, particularly carbon fibers, having a high strength and a high modulus of elasticity.
- Still another object of the invention is to provide a process for producing an optically anisotropic carbonaceous pitch having an excellent spinnability which can be spun at a temperature sufficiently lower than that at which remarkable thermal decomposition/ polycondensation reaction occurs, resulting in carbon fibers having a high strength and a high modulus of elasticity.
- a further object of the invention is to provide a process for producing an optically anisotropic carbonaceous pitch capable of forming the optically anisotropic carbonaceous pitch having a stable, high quality irrespective of variation of properties of the starting material and, therefore, capable of producing a high-quality carbon material in an economically advantageous manner.
- the Figure is a graph showing changes in yield of a heat-settled lower layer AP 6 and a softening point 0 thereof with time of the thermal reaction for making the pitch heavier.
- the pitch was subject to an isothermal heat treatment for various times for making the same heavier and then the pitch was settled and the softening point of a lower layer (pitch of about 100% AP) was examined.
- the results are shown in an attached figure.
- a curve with symbols 0 shows a relationship between the heat reaction time and softening point of the lower layer (AP) after the heat-settling. It will be understood that the softening point is lowered initially with the thermal reaction time but is then elevated after 2 hr.
- a curve with symbols ⁇ shows a relationship between the thermal reaction time and yield of the heat-settled lower AP layer. It will be understood that yield of the lower AP layer is increased with the thermal reaction time. Further, it is shown that if the thermal reaction for making the pitch heavier is carried out for longer than about 2.5 h, the separation by the settling becomes difficult.
- AP formed in the initial stage of the above-mentioned thermal reaction may be removed by extraction with a solvent or filtration under heating under elevated pressure, in addition to the heat-settling process.
- both of the former processes are expensive and have practically difficult problems. The inventors considered, therefore, that the heat-settling process is the most excellent, inexpensive and easy process.
- the precipitate formed in the initial stage of the thermal reaction can be settled easily at a low settling temperature in a short settling time, since the softening point of the whole pitch system and viscosity thereof at a settling temperature are extremely low in the initial stage.
- the above-mentioned objects and other objects of the present invention can be attained by employing a process which comprises stopping the thermal reaction of a starting material for pitch for making the pitch heavier in the initial stage of the reaction, subjecting the pitch to a heat settling treatment to divide the pitch into two layers, removing and precipitated and concentrated lower heavy pitch layer and subjecting the residual upper layer to an after-treatment including the thermal reaction for making the same heavier.
- optically anisotropic phase refers to one form of pitch constituents which, when a section of a pitch mass solidified at around room temperature is polished and observed by means of a reflection-type polarizing microscope under crossed nicols, exhibits brilliance upon rotation of the sample or cross nicols, namely an optically anisotropic moiety.
- a moiety exhibiting no brilliance, i.e., having an optical isotropy, is called an optically isotropic phase (IP).
- IP optically isotropic phase
- AP comprises mainly molecules having such a chemical structure that the planarity of the polycyclic aromatic condensed rings are more highly developed than those of IP, the planar structures being aggregated and associated together to form a laminate structure.
- the optically anisotropic phase is considered to be in the form of a liquid crystal. Therefore, if it is extruded through a thin nozzle in the spinning step, the molecules are so arranged that the planar surfaces thereof are substantially in pal- lalel with the fiber axis. Consequently, the carbon fibers produced from the optically anisotropic pitch exhibit a high modulus of elasticity.
- the amount of AP or IP is determined by observing and taking a picture thereof by means of a polarizing microscope under crossed nicols and measuring an areal ratio of AP or IP. It is represented by vol.% in practice.
- vol.% may be considered to be substantially equal to a wt.% in the determination of these values.
- Optically anisotropic pitch defined in this specification is a pitch having an AP content of 100% or an extremely high AP content and containing IP in the form of globular particles or islands of indeterminate forms.
- the one which exhibits a high homogeneity in the actual melt spinning step has a sufficiently low IP content determined as described above.
- this pitch solid particles having a diameter of at least 1/tf are not substantially detected therein in the observation of the section thereof with a reflection-type microscope.
- the pitch does not substantially form bubbles due to a volatile matter at the melt-spinning temperature.
- Such a pitch is referred to as substantially homogeneous, optically anisotropic pitch.
- softening point of pitch refers to a temperature at which the pitch transfers from the solid state into a liquid state.
- the softening point is determined from a peak temperature of latent heat absorbed or released when the pitch is molten or solidified by means of a differential scanning calorimeter. This temperature coincides with that determined by the ring-and-ball method or micro melting point method with an error of + 10°C in each pitch sample.
- low softening point herein refers to a softening point in the range from 230 to 320°C. The softening point is closely related to the melt-spinning temperature of the pitch (not necessarily the temperature of the pitch at the nozzle but the highest necessary temperature of the pitch in the spinning machine).
- a viscosity suitable for the spinning is realized at a temperature about 60-100 0 C higher than the softening point, though it varies depending on variety of the pitch used. If the softening point is higher than about 320 0 C, the spinning is effected at a temperature higher than 380°C at which the thermal cracking and polycondensation occur. Therefore, cracked gas and unmelted matter are formed, thereby deteriorating the spinning properties. In addition, the pitch fibers thus obtained contain bubbles and solid foreign matters disadvantageously. If the softening point is lower than 230°C, an infusibilization treatment of pitch fiber at a low temperature for a long period of time is required. Therefore, the treatment becomes complicated and expensive in such a case unfavorably.
- a powdery pitch is charged in a cylindrical filter having an average pore diameter of 1 ⁇ .
- Heat extraction is effected with n-heptane in a Soxhlet extractor for 20 h.
- An n-heptane-soluble matter obtained as above will be referred to as component 0.
- it is heat-extracted with benzene for 20 h to obtain an n-heptane-insoluble/benzene-soluble matter which will be referred to as component A.
- the residual benzene-insoluble matter is treated by centrifugation according to JIS K-2425 with quinoline as solvent.
- a benzene-insoluble/quinoline-soluble matter (so-called ⁇ -resin) will be referred to as component B and a quinoline-insoluble matter will be referred to as component C.
- the fractionation may be effected by, for example, a method disclosed on page 45 of "Journal of Japan Petroleum Society" 20, (1) (1977).
- Component C may be extracted and analyzed by, in addition to the above-described process, a process of ASTM D-2318-76 (wherein the extraction and filtration are effected at 75°C), a boiling quinoline process (wherein the extraction and filtration are effected using boiling quinoline) and a boiling pyridine method (i.e. Soxhlet extraction using pyridine).
- ASTM D-2318-76 wherein the extraction and filtration are effected at 75°C
- a boiling quinoline process wherein the extraction and filtration are effected using boiling quinoline
- a boiling pyridine method i.e. Soxhlet extraction using pyridine
- heat settling herein means precipitation and aggregation of a high-specific gravity phase into the direction of gravity force by maintaining the pitch in a molten state at a temperature necessary and sufficient for the precipitation and aggregation of the high-specific gravity phase including AP and other infusible matters in a slightly or no turbulent flow. Therefore, this operation includes a standing method in a slightly turbulent stream, a heat centrifugal separation method and a liquid cyclone method.
- the process of the present invention wherein a starting material for pitch is heated to convert the same into a heavy product and to form or to increase and concentrate AP phase-forming components is characterized in that the pitch satisfying certain conditions obtained in the initial stage of the heat treatment is subjected to the easy and low-cost heat setting treatment to precipitate and concentrate components contained in the pitch in the initial stage as high-specific gravity components, since the incorporation of them in the final pitch product is undesirable. Then the lower layer is removed, an upper layer pitch containing components of a low specific gravity in a large amount is used as a starting material in the next step and the pitch is further subjected to a heat treatment including the conversion thereof into a heavy product.
- starting materials for the pitch there may be used various carbonaceous heavy oils, tars and pitches obtained in petroleum or coal industry.
- Preferred starting materials are those specified in the Specifications accompanying our European Patent Application No.82300420.5 and our Japanese Patent Application 135296/1981.
- the preferred starting materials are (1) oily products containing as main component a carbonaceous heavy oil having a boiling point of 250-540°C which products have an aromatic carbon fraction in the aromatic oil and resin in the n-heptane-soluble matter of at least 0.6 and a number-average molecular weight of up to 1,000 or (2) tarry substances mainly comprising components having a boiling point of at least 540°C which tarry substances have an aromatic carbon fraction in the aromatic oil and resin of at least 0.7 and a number-average molecular weight of up to 1,000.
- these starting materials for pitch are subjected to the thermal reaction at a temperature of 370-500°C, preferably 380-430 9 C, to effect mainly thermal cracking and thermal polycondensation and to convert the materials into heavy products and then volatile matters are removed from the cracked products, AP is formed and increased in amount and finally an optically anisotropic pitch is obtained.
- thermal reaction is stopped in the initial stage and the reaction mixture is transferred to the characteristic heat settling step.
- the time at which the pitch is transferred to the heat settling step is such that the pitch contains quinoline-insoluble matter and benzene-insoluble matter as minor components, has not so high softening point and contains two phases having different specific gravities in a molten state.
- the pitch to be subjected to the heat settling should have a quinoline-insoluble matter content of about 2-20 wt.%, a quinoline-soluble/benzene-insoluble matter content of about 5-40 wt.%, a softening point of up to 200°C and a relatively high specific gravity phase content of 5-50 wt.% (in a molten state at a temperature about 100°C higher than the softening point).
- the pitches having the above-described properties may be obtained by slightly heat-treating the above-mentioned starting materials under broad conditions without limiting the properties so strictly as shown above, or they can be obtained directly from other processes or other pitch makers.
- the pitch to be subjected to the heat settling is heat-treated excessively and its quinoline-insoluble matter content or benzene-insoluble matter content is far higher than the range shown above, the amount of the lower layer pitch to be discarded in the heat settling becomes large and finally, the yield of the intended product is lowered unfavorably. If the softening point is higher than about 200 0 C, a high temperature and long residence time are required in the heat settling step unfavorably.
- the pitch has (1) a quinoline-insoluble matter content or benzene-insoluble matter content lower than the above-mentioned range and (2) too low content of a high-specific gravity phase, the separation of the lower layer becomes insufficient or a large amount of the upper layer is discarded together with the lower layer in the heat settling step and the object of the present invention cannot be attained in many cases.
- the above-described carbonaceous material for pitch is prepared or got in the market and is subjected to the heat settling treatment.
- thermal reactions such as thermal cracking and thermal polymerization proceed slowly at a sufficiently mild temperature range in which the pitch can be kept in a molten, sufficiently fluid state. More concretely, a temperature in the range from 200 to 400°C is employed, though it varies depending on the softening point and viscosity of the pitch to be treated.
- This step is characterized in that the pitch per se can be settled directly in a molten state according to the precipitation due to gravitation, while a solvent or additive may be incorporated therein.
- a temperature as high as above 400°C is not preferred in this step, since at such a high temperature, troubles are caused in the system by bubbling or evaporation of products formed by the thermal cracking. Another reason therefor is that coking of the metal surface of the settling vessel would be caused, since the liquid phase is not stirred or the flow is only slight.
- a temperature lower than 200 0 C a sufficiently fluidity cannot be obtained even if the pitch subjected to the settling treatment has a softening point far lower than 200 0 C.
- problems are posed that a long residence time is required for the settling or that the phase separation does not occur at all, or that the lower layer cannot be taken out easily.
- the object can be attained by maintaining the pitch in a molten state at the above-mentioned temperature for a given time even without stirring.
- the pitch may be stirred slowly or the whole pitch may be allowed to flow in such a manner that the phase precipitation is not inhibited for the purpose of effecting the separation continuously or for the purpose of obtaining a uniform temperature distribution throughout the system.
- the separation of the phase having a higher specific gravity is effected for the purpose of concentrating and removing a major part of the phase having a higher specific gravity from the pitch. It is unnecessary to completely precipitate 100% of the phase as the lower layer or to completely remove 100% of the lower layer.
- the upper layer pitch obtained after the heat settling followed by the removal of the lower layer still contains only a small amount of the phase having a higher specific gravity.
- this phase does not exert significant influences on the final product, since it is one of the original constituents of the pitch.
- the higher the degree of concentration of the lower layer phase of a higher specific gravity the better in the heat settling step.
- a degree of concentration of about 70-90% is satisfactory in general.
- the amount of the phase having a higher specific gravity still remaining in the upper layer after the separation is preferably small. The object can be attained, however, if the amount is as small as 5-30% based on the amount thereof contained prior to the settling.
- Process for the preparation of the pitch to be subjected to the heat settling treatment is not particularly limited in the present invention. However, there may be mentioned two preferred processes for preparing the pitch by subjecting various carbonaceous heavy oils, tar or pitch obtained in petroleum or coal industry to the heat.treatment as described below.
- One of the processes comprises heating a starting material for the production of pitch to a temperature in the range from about 370 to 460°C, preferably 400 to 430°C while an inert gas is introduced above the pitch surface or in the liquid pitch phase to cause bubbling and to accelerate the removal of low molecular weight volatile matter, stopping the thermal reaction when the pi ⁇ tch residue having a globular AP content of 5-50%, a quinoline-insoluble matter content of 2-20 wt.% and a softening point of the pitch as a whole of up to 200°C has been obtained, and transferring the reaction product from the reaction vessel to the subsequent heat settling step.
- the heat settling is effected preferably at a temperature in the range from 250 to 400°C.
- the other improved process for preparing the pitch to be heat-settled comprises heating a starting material for the production of pitch to a temperature in the range from 370 to 460°C, preferably from 400 to 430°C to effect a thermal reaction without the introduction of inert gas or rather in a closed system.
- This process may be effected under elevated pressure without forcing to remove volatile matters but under accelerated reflux of the starting material or oil formed by the cracking.
- the starting material sealed or continuously introduced in a high pressure thermal reaction vessel or tube is heated to the above-mentioned temperature. The pressure is elevated by low molecular products formed by the thermal cracking.
- the reaction is continued while the pressure is controlled until a pitch having a quinoline-insoluble matter content of 2-10 wt.% a benzene-soluble matter content of at least 60 wt.% and a softening point of up to 150°C has been obtained.
- the pitch is taken out of the reaction tank and transferred to the subsequent heat settling step.
- the thermal reaction is carried out at the above-described reaction temperature under atmospheric pressure without particular acceleration of the removal or volatile matters but rather under the reflux of a major part of the starting material and low-molecular weight substances into the reaction system at the bottom of the reactor to control the quinoline-insoluble matter content of the resulting pitch to 2-10 wt.%, the benzene-soluble matter content to at least 60 wt.% and the softening point to up to 150°C.
- pressure exhibit no direct effect on the acceleration of the reaction and the pressure may be elevated for the purpose of inhibiting the removal of volatile matter in the cracking products or unreacted reaction material from the reaction system.
- liquid phase should be stirred sufficiently or allowed to flow in the preparation of the pitch to be subjected to the heat settling so that the two phases formed in this step are not separated clearly from each other and uniform temperature distribution can be obtained.
- pressure When the reaction is carried out in the closed system, pressure exhibit no direct effect on the acceleration of the reaction and the pressure may be elevated for the purpose of inhibiting the removal of volatile matter in the cracking products or unreacted reaction material from the reaction system.
- liquid phase should be stirred sufficiently or allowed to flow in the preparation of the pitch to be subjected to the heat settling so that the two phases formed in this step are not separated clearly from each other and uniform temperature distribution can be obtained.
- the process for producing the pitch to be subjected to the heat settling by the heat treatment in the above-mentioned closed system or in an atmospheric pressure system wherein the removal of volatile matters is not accelerated is characterized in that the pitch contains a large amount of low-molecular weight substances and, therefore, the subsequent heat settling can be effected at a lower temperature. More particularly, the object can be attained at a temperature of 150-400°C, preferably 200-350°C, under easy operating conditions without causing thermal reaction.
- Process for the after-treament is not particularly limited. Any process capable of increasing an A P content in the pitch while a softening point is not elevated significantly may be employed. After investigations, the inventors have found that two processes which will be described below are particularly preferred.
- One of the processes comprises subjecting the "pitch containing a large amount of the phase having a lower specific gravity" to the heat treatment to convert the same into heavy product at 300-420°C after the heat settling treatment. This treatment is continued until the I P content of the residual pitch has been reduced to less than 20%. Namely, this treatment is effected mainly for concentrating the AP-forming pitch contained in the "pitch containing a large amount o.f the phase having a lower specific gravity" obtained by the heat settling and also for forming fresh AP by the thermal chemical reaction.
- the lighter pitch obtained by the heat settling is subjected to the thermal reactions mainly comprising thermal cracking and thermal polycondensation reactions at a temperature of 350-420°C, preferably 370-420°C while an inert gas is introduced into the reaction system or under reduced pressure to convert the light pitch partially into heavy components and also to distill another part of the light pitch from the reaction system, whereby the pitch is made gradually heavier.
- the AP-forming components are concentrated.
- This thermal treatment is finished when an intended pitch having an AP content of at least 80%, a softening point in the range from 230-320°C and a quinoline-insoluble matter content of no higher than 70%, preferably no higher than 50 wt.% and particularly no higher than 40 wt.% is obtained.
- the other process for the heat treatment for converting the pitch into heavy product comprises dividing the reaction step into two steps, i.e., a thermal chemical reaction step and a distillation step in which the thermal reaction proceeds only slightly.
- the lighter pitch obtained by the heat settling is subjected to the thermal chemical reactions mainly comprising thermal cracking and thermal polycondensation at 370-420°C, preferably 390-400°C in a closed system or under such reflux conditions that the removal of volatile matter is not particularly accelerated.
- the resulting pitch is subjected to thermal cracking/ polycondensation reaction under mild conditions at a temperature in the range from 300-370°C, preferably 320-350°C and low-molecular substances are removed under reduced pressure or with introduction of an inert gas to obtain a pitch having an A P content of at least 80%, a softening point in the range from 230-320°C and a quinoline-insoluble matter content of no higher than 70 wt.%, preferably no higher than 50 wt.% and particularly no higher than 40 wt.%.
- pitches of various properties can be obtained by suitably combining the thermal chemical reaction temperature with residence time or conditions of the volatile matter-removing operation with the residence time.
- this process is characterized in that a stable operation can be effected under sufficiently broad conditions, a continuous or semi-continuous treatment is possible and an intended product can be obtained in a high yield.
- the thermal reaction at 370-420°C is omitted and the AP content of the pitch can be increased only by a low- temperature heat treatment carried out at a low temperature under reduced pressure or with introduction of an inert gas. More particularly, the light pitch obtained by the heat settling is treated at a temperature of 300-370°C, preferably 300-350°C under reduced pressure or with introduction of an inert gas for a long residence time.
- pitch having an AP content of at least 80% usually at least 90%, a softening point in the range from 230-320 0 C and a quinoline-insoluble matter content of no more than 40 wt.%.
- This process has an advantage that the operation in each step is easy, though it takes a long time for the treatment.
- the pitch is stirred sufficiently or the liquid phase is allowed to flow so as to maintain a uniform pitch temperature and to avoid the phase separation in the heat treatment for making the pitch heavier.
- the inert gas used in the above-mentioned step is one which does not remarkably chemically react with the pitch at a temperature around 400 0 C.
- Another process for the after-treatment of the light pitch obtained by the heat settling comprises subjecting the light pitch obtained by heat settling to the heat treatment for making the same heavier, stopping this treatment halfway, subjecting the pitch again to the heat settling and taking "pitch containing a large amount of a high-specific gravity phase" in the lower layer as the intended product.
- the heat treatment for making the pitch heavier is carried out in the same manner as above at the same temperature as above.
- the pitch having an AP content of at least 80%, a softening point of 230-320°C and a quinoline-insoluble matter content of no more than 70% is not approached directly by this treatment only.
- This treatment is stopped halfway when a pitch having an AP content of 20-70%, preferably 30-50%, a quinoline-insoluble matter content of up to 25 wt.%, preferably up to 20 wt.%, a quinoline-soluble/benzene-insoluble matter content of at least 25 wt.%, preferably at least 30 wt.% and a softening point of the pitch as a whole of up to 250°C has been obtained.
- the pitch is again subjected to the heat settling at a temperature in the range from 330 to 400°C to precipitate and aggregate AP spheres of a higher specific gravity and to form a lower layer.
- the lower layer pitch comprising substantially AP is separated from the upper layer pitch comprising mainly IP .
- the pitch thus obtained may be subjected further to a finishing treatment, if necessary.
- the optically anisotropic pitch obtained as above has an AP content of at least 80% usually at least 90%, a softening point in the range from 230 to 3200C and a quinoline-insoluble matter content of no more than 70 wt.%.
- the pitch obtained by this process has a higher AP content and lower softening point and it has higher spinnability and gives carbon fibers and graphite fibers having more excellent properties.
- the temperature, reactor, flowing method and stirring method may be the same as those described above and the residence time is shorter than the above.
- the second heat settling in this process may be effected in the same manner as in the first heat settling except that the temperature range is different.
- the second heat settling step is effected at a temperature of 330-400°C for maintaining the viscosity of the whole system sufficiently low and for precipitating spherical particles or masses of A P to.form the lower layer while the aggregation and aging of AP are accelerated, since the pitch subjected to the second heat settling treatment has been made considerably heavier. If a temperature below 320 0 C is employed in this step, the aggregation, precipitation and separation of lower layer AP become difficult. At a temperature above 410°C, a residence time of several minutes is required generally, though AP is separated in such a short time in some cases. If the residence time is as long as above, a violent thermal reaction occurs to elevate the softening point of the resulting pitch unfavorably.
- a pitch having about 20% AP content and softening point of 168°C was used as starting material, said A P comprising globular particles having a diameter of up to about 100 ⁇ .
- the pitch had a quinoline-insoluble matter content of 14.9 wt.% and a quinoline-soluble/benzene-insoluble matter content of 30.1 wt.%.
- 300 g of the starting pitch was charged in a 500 ml cylindrical glass vessel and left to stand in a nitrogen atmosphere in a muffle furnace at 360°C for 1 h. After cooling, the glass vessel was broken to obtain about 36 g of a lower layer, i.e., relatively brittle, dim pitch and about 260 g of an upper pitch layer.
- the lower layer pitch was optically anisotropic and comprised nearly 100% AP.
- This pitch had a quinoline-insoluble matter content of 65.6 wt.% and a softening point of 295 0 C. This pitch will be referred to as pitch a.
- the upper layer pitch comprised mainly IP containing about 10% of A P in the form of globular particles having a diameter of up to about 10)1. This pitch had a softening point of 156°C, a quinoline-insoluble matter content of 4 wt. % and a quinoline-soluble/benzene-insoluble matter content of 48.6 wt.%.
- pitch b 200 g of the upper layer pitch was allowed to react at 400°C for 4 h while 2l/min of nitrogen gas was introduced above the pitch surface in a 500-ml stainless steel reaction vessel.
- This pitch will be referred to as pitch b.
- the two pitch fibers obtained from the two pitches respectively were maintained in an oxygen stream at 200°C for 2 h and then in an oxygen stream at 240°C for 30 min, and heated to 1500°C at a temperature- elevation rate of 50°C/min in argon gas and immediately thereafter, they were left to cool to obtain carbon fibers. Diameters of 16 samples of each of the two carbon fibers were measured and then tensile strength and modulus in tension of them were determined. Averages of the values were calculated.
- the carbon fibers obtained from pitch a had an average diameter of 14 ⁇ , average strength of 16 GPa and average modulus of elasticity of 1.4 x 10 2 GP a.
- the carbon fibers obtained from pitch b had an average diameter of 8.7 ⁇ , average strength of 26 GPa and average modulus of elasticity of 2.3 x 10 2 GPa. Comparative Example 1
- Example 2 200 g of the same starting material as in Example 1 was allowed to react in a 500-ml stainless steel reaction vessel at 400°C for 4 h while a l/min of nitrogen gas was introduced above the pitch surface in the vessel.
- An optically anisotropic pitch having an AP content of about 95% was obtained.
- the pitch had a quinoline-insoluble matter content of 61.1 wt.%, a benzene-insoluble/quinoline-soluble matter content of 23.0 wt. % and a softening point of as high as 330 0 C.
- the pitch could not be spun with the same spinning apparatus as in Example 1.
- Example 2 300 g of the same starting material as in Example 1 was settled in the same manner as in Example 1. 200 g of an upper layer pitch was heat-treated for making the same heavier at 400°C for 2 h in a 500 mX stainless steel reaction vessel while 2 l/min of nitrogen gas was introduced therein to obtain 168.4 g of an intermediate pitch.
- the pitch had a softening point of 212°C, a quinoline-insoluble matter content of 9.5 wt.%, a benzene-insoluble matter content of 55.2 wt.% and an A P globular particle content of about 45%.
- the pitch was charged in a 200-ml glass cylindrical vessel and settled again at 380°C for 2 h to divide the pitch into upper and lower layers.
- the amount of the lower layer pitch was about 22 g. It had an AP content of 99%, a quinoline-insoluble matter content of 33.3 wt.% and a softening point of 244 0 C.
- the pitch could be spun with the same spinning apparatus as in Example 1 at 320°C without breaking of the fiber. for a long time.
- Example 2 200 g of the same starting material as in Example 1 was heat-treated for making the same heavier at 400°C for 2 h in a 500-ml stainless steel reaction vessel while 2 R/min of nitrogen gas was introduced therein to obtain 181.3 g of an intermediate pitch.
- the intermediate pitch had a softening point of 2240C, an AP globular particle content of about 45%, a quinoline-insoluble matter content of 23.0 wt.% and a quinoline-soluble/benzene-insoluble matter content of 30.1 wt.%.
- the intermediate pitch 100 g was charged in a 200-ml glass cylindrical vessel and settled at 3800C for 2 h to divide the pitch into upper and lower layers.
- the amount of the lower layer pitch was about 28 g. It had an AP content of approximately 100%, a softening point of 286°C, a quinoline-insoluble matter content of 74.2 wt.% and a quinoline-soluble/benzene-insoluble matter content of 1.4 wt.%.
- the pitch was spun in the same manner as in Example 1. The optimum spinning temperature was 370°C and the breaking occurred considerably frequently.
- a pitch having a boiling point of above 450°C (under atmospheric pressure) obtained by reduced pressure distillation of a tar obtained by catalytic cracking of petroleum was used as starting material. 20l of the pitch was heat-treated at 430°C for 2 h under a 30l/min nitrogen gas stream in a 50- stainless steel reaction tank to obtain the starting material used in Example 1.
- the pitch had a softening point of up to 100°C, a quinoline-insoluble matter content of about 2.4 wt.% and a benzene-soluble matter content of 86 wt.%.
- 400 g of the pitch was transferred to a 500 mf stainless steel reactor and treated at 360°C for about 5 h while 6l/min of nitrogen gas was introduced therein to obtain 152 g of residual pitch.
- This pitch had a softening point of 221°C, an AP content of about 40%, a quinoline-insoluble matter content of 8.7 wt.% and a quinoline-soluble/benzene-insoluble matter content of 42.4 wt.%.
- this pitch was charged in a 200-ml glass cylindrical vessel and settled at 380°C for 2 h. Upper and lower layers were formed clearly. 24 g of lower layer pitch was obtained.
- This pitch had a softening point of 261°C, an AP content of approximately 100%, a quinoline-insoluble matter content of 32.6% and a quinoline-insoluble/benzene-soluble matter content of 30.8%.
- the pitch could be spun at a spinning temperature of 350°C easily for longer than 30 min without breakage in the same manner as in Example 1.
- a residual pitch had an AP content of about 97%, a quinoline-insoluble matter content of 25.9 wt.%, a quinoline-soluble/benzene-insoluble matter content of 40.7 wt.% and a softening point of 271°C.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Working-Up Tar And Pitch (AREA)
- Inorganic Fibers (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP47903/82 | 1982-03-24 | ||
JP4790382A JPS58164687A (ja) | 1982-03-24 | 1982-03-24 | 光学的異方性ピツチの製造方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0089840A1 true EP0089840A1 (fr) | 1983-09-28 |
EP0089840B1 EP0089840B1 (fr) | 1989-11-29 |
Family
ID=12788346
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19830301552 Expired EP0089840B1 (fr) | 1982-03-24 | 1983-03-21 | Procédé de préparation de brai ayant une anisotropie optique |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0089840B1 (fr) |
JP (1) | JPS58164687A (fr) |
AU (1) | AU565830B2 (fr) |
CA (1) | CA1196596A (fr) |
DE (1) | DE3380898D1 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0138286A1 (fr) * | 1983-05-20 | 1985-04-24 | Fuji Standard Research Inc. | Procédé de fabrication de brai carboné |
EP0172955A1 (fr) * | 1984-08-28 | 1986-03-05 | Kawasaki Steel Corporation | Méthode pour la production d'un brai précurseur pour une fibre de carbone |
US4591424A (en) * | 1984-02-13 | 1986-05-27 | Fuji Standard Research, Inc. | Method of preparing carbonaceous pitch |
EP0250116A1 (fr) * | 1986-06-09 | 1987-12-23 | Conoco Inc. | Précipitation à pression de brai à mésophase |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2424954A1 (fr) * | 1978-05-05 | 1979-11-30 | Exxon Research Engineering Co | Procede de preparation de brais ayant une anisotropie optique |
EP0044714A2 (fr) * | 1980-07-21 | 1982-01-27 | Toa Nenryo Kogyo Kabushiki Kaisha | Procédé pour la production de brai mésophatique |
GB2086932A (en) * | 1980-11-05 | 1982-05-19 | Koa Oil Co Ltd | Process for producing mesocarbon microbeads of uniform particle-size distribution |
EP0055024A2 (fr) * | 1980-11-19 | 1982-06-30 | Toa Nenryo Kogyo Kabushiki Kaisha | Brai carboné, sa préparation et fibres de carbone à partir de ce brai |
EP0057108A2 (fr) * | 1981-01-28 | 1982-08-04 | Toa Nenryo Kogyo Kabushiki Kaisha | Procédé de préparation de brai carboné optiquement anisotrope |
-
1982
- 1982-03-24 JP JP4790382A patent/JPS58164687A/ja active Pending
-
1983
- 1983-03-11 CA CA000423409A patent/CA1196596A/fr not_active Expired
- 1983-03-21 DE DE8383301552T patent/DE3380898D1/de not_active Expired - Lifetime
- 1983-03-21 EP EP19830301552 patent/EP0089840B1/fr not_active Expired
- 1983-03-23 AU AU12755/83A patent/AU565830B2/en not_active Ceased
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2424954A1 (fr) * | 1978-05-05 | 1979-11-30 | Exxon Research Engineering Co | Procede de preparation de brais ayant une anisotropie optique |
EP0044714A2 (fr) * | 1980-07-21 | 1982-01-27 | Toa Nenryo Kogyo Kabushiki Kaisha | Procédé pour la production de brai mésophatique |
GB2086932A (en) * | 1980-11-05 | 1982-05-19 | Koa Oil Co Ltd | Process for producing mesocarbon microbeads of uniform particle-size distribution |
EP0055024A2 (fr) * | 1980-11-19 | 1982-06-30 | Toa Nenryo Kogyo Kabushiki Kaisha | Brai carboné, sa préparation et fibres de carbone à partir de ce brai |
EP0057108A2 (fr) * | 1981-01-28 | 1982-08-04 | Toa Nenryo Kogyo Kabushiki Kaisha | Procédé de préparation de brai carboné optiquement anisotrope |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0138286A1 (fr) * | 1983-05-20 | 1985-04-24 | Fuji Standard Research Inc. | Procédé de fabrication de brai carboné |
US4591424A (en) * | 1984-02-13 | 1986-05-27 | Fuji Standard Research, Inc. | Method of preparing carbonaceous pitch |
EP0172955A1 (fr) * | 1984-08-28 | 1986-03-05 | Kawasaki Steel Corporation | Méthode pour la production d'un brai précurseur pour une fibre de carbone |
EP0250116A1 (fr) * | 1986-06-09 | 1987-12-23 | Conoco Inc. | Précipitation à pression de brai à mésophase |
Also Published As
Publication number | Publication date |
---|---|
EP0089840B1 (fr) | 1989-11-29 |
DE3380898D1 (de) | 1990-01-04 |
JPS58164687A (ja) | 1983-09-29 |
AU1275583A (en) | 1983-09-29 |
CA1196596A (fr) | 1985-11-12 |
AU565830B2 (en) | 1987-10-01 |
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