WO2016181929A1 - 炭素繊維製造用原料ピッチ - Google Patents

炭素繊維製造用原料ピッチ Download PDF

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WO2016181929A1
WO2016181929A1 PCT/JP2016/063727 JP2016063727W WO2016181929A1 WO 2016181929 A1 WO2016181929 A1 WO 2016181929A1 JP 2016063727 W JP2016063727 W JP 2016063727W WO 2016181929 A1 WO2016181929 A1 WO 2016181929A1
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Prior art keywords
carbon fiber
coal
raw material
pitch
temperature
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PCT/JP2016/063727
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English (en)
French (fr)
Japanese (ja)
Inventor
眞基 濱口
祥平 和田
聡則 井上
聖昊 尹
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株式会社神戸製鋼所
国立大学法人九州大学
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Application filed by 株式会社神戸製鋼所, 国立大学法人九州大学 filed Critical 株式会社神戸製鋼所
Priority to CN201680024557.6A priority Critical patent/CN107532086B/zh
Priority to KR1020177031562A priority patent/KR102070167B1/ko
Priority to DE112016002135.6T priority patent/DE112016002135T5/de
Priority to US15/570,922 priority patent/US20180142158A1/en
Publication of WO2016181929A1 publication Critical patent/WO2016181929A1/ja

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    • 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
    • C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C10C3/08—Working-up pitch, asphalt, bitumen by selective extraction
    • 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
    • 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
    • C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
    • C10C3/026—Working-up pitch, asphalt, bitumen by chemical means reaction with organic compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch

Definitions

  • the present invention relates to a raw material pitch for carbon fiber production.
  • Carbon fiber is widely used as a reinforcing material for structural materials such as resin, concrete and ceramic.
  • carbon fiber is also used as, for example, a heat insulating material, activated carbon raw material, conductive material, heat transfer material, and the like.
  • Carbon fiber is generally produced by forming a synthetic resin such as polyacrylonitrile, pitch obtained from petroleum or coal into a fiber shape by spinning, and making the yarn infusible (air oxidation) and carbonized.
  • a synthetic resin such as polyacrylonitrile
  • pitch obtained from petroleum or coal into a fiber shape by spinning
  • yarn infusible air oxidation
  • carbonized carbonized.
  • coal pitch is a residue after removing volatile components such as naphthalene by distillation from coal tar, which is a liquid material by-produced when carbon is produced by carbonization to produce coke. Black material.
  • Such a coal pitch is a mixture of many compounds containing many aromatic compounds containing many benzene rings in their skeletons.
  • the main component is a polycyclic aromatic compound having a high degree of ring condensation, such as a methyl group, an ethyl group, or a propyl group.
  • the content of chains and oxygen-containing structures such as ether bonds and phenol groups is extremely small.
  • the oxygen content of the coal pitch is generally 1% by mass or less, and in many cases 0.5% by mass or less. is there.
  • coal pitch melts into a viscous liquid when heated to about 100 ° C. to 200 ° C., and can be spun by extruding it from a nozzle.
  • coal pitch is a by-product during coke production and is recovered as a residue.
  • spinning of metal impurities and solid carbon, and subsequent infusibilization and carbonization are performed. It contains various ingredients that inhibit it. For this reason, it is difficult to produce carbon fiber stably and efficiently from coal pitch.
  • these impurities can cause the defect of the carbon fiber manufactured, the tensile strength of the carbon fiber obtained is reduced.
  • the raw material pitch used for producing the carbon fiber is uniformly melted at a constant temperature during spinning.
  • the softening point of the raw material pitch is preferably 150 ° C. or higher so that the temperature of the infusibilization treatment for fixing the shape of the fiber on which the raw material pitch is spun can be increased, and the temperature at which no thermal decomposition reaction occurs during spinning 350 ° C. or lower is preferable so that spinning can be performed at
  • an object of the present invention is to provide a raw material pitch for producing carbon fibers that can produce carbon fibers having excellent tensile strength at a relatively low cost.
  • the invention made to solve the above-mentioned problems is a pitch for producing carbon fiber obtained from coal and melt-spun, and has an oxygen content of 1.0% by mass or more and a toluene-soluble component. It is a raw material pitch for carbon fiber production characterized by having a content of 20% by mass or more.
  • the carbon fiber production raw material pitch when the oxygen content is 1.0 mass% or more, oxygen forms crosslinks between molecules in the carbonization step. For this reason, the said raw material pitch for carbon fiber manufacture can inhibit the lamination
  • the carbon fiber raw material pitch is excellent in meltability and spinnability in the melt spinning process because the content of toluene-soluble component composed of a compound having a relatively small molecular weight is 20% by mass or more. . Therefore, by using the raw material pitch for producing carbon fibers, carbon fibers having excellent tensile strength can be produced at a relatively low cost.
  • the above coal may be bituminous coal or subbituminous coal.
  • the yield of the raw material pitch for carbon fiber production becomes relatively high.
  • the raw material pitch for carbon fiber production, and consequently the carbon fiber It can be manufactured at low cost.
  • the carbon fiber-producing raw material pitch is preferably a heat-treated component at a temperature of 150 ° C. or higher, which is a soluble component separated from a pyrolyzate in a coal solvent by solvent extraction at a temperature of less than 300 ° C.
  • the raw material pitch for carbon fiber production is obtained by heat-treating a soluble component separated from a thermal decomposition product in a solvent of coal by a solvent extraction treatment at a temperature of less than 300 ° C. at a temperature of 150 ° C. or more.
  • the oxygen content and the toluene soluble content can be easily and reliably within the above ranges.
  • the carbon fiber production raw material pitch, and hence the carbon fiber excellent in tensile strength can be produced at a relatively low cost.
  • the “oxygen content” means the content of oxygen atoms including not only oxygen molecules but also atoms bonded to other atoms, and specifically, according to JIS-M8813 (2004). Means the measured value.
  • the “toluene soluble content” is a value measured in accordance with JIS-K2207 (1996).
  • bituminous coal and “subbituminous coal” refer to coal having a coal quality defined in JIS-M1002 (1978).
  • carbon fiber can be produced at low cost by using the raw material pitch for producing carbon fiber of the present invention.
  • the raw material pitch for producing carbon fibers is a raw material pitch obtained from coal and for producing carbon fibers by melt spinning.
  • the carbon fiber production raw material pitch is preferably obtained from a thermal decomposition product in a coal solvent.
  • Coal contains more oxygen-containing structures such as alkyl side chains and more toluene-soluble matter than coal tar and petroleum production residues processed at relatively high temperatures. For this reason, the said raw material pitch for carbon fiber manufacture obtained from the thermal decomposition thing in the solvent of coal can be equipped with the characteristic which is demonstrated below.
  • the lower limit of the oxygen content in the carbon fiber production raw material pitch is 1.0% by mass, preferably 1.5% by mass, and more preferably 1.7% by mass.
  • the upper limit of the oxygen content is preferably 5.0% by mass, more preferably 4.0% by mass, and even more preferably 3.0% by mass.
  • the lower limit of the content of the toluene soluble component in the raw material pitch for carbon fiber production is 20% by mass, preferably 30% by mass, and more preferably 35% by mass.
  • an upper limit of the content rate of toluene soluble part 80 mass% is preferable, 60 mass% is more preferable, and 50 mass% is further more preferable.
  • the content of toluene-soluble components is less than the lower limit, the meltability and spinnability during melt spinning may be insufficient.
  • the content of the toluene-soluble component exceeds the above upper limit, the carbon fiber production cost may increase due to a decrease in the yield of the carbon fiber.
  • Examples of the coal used as the raw material pitch for carbon fiber production include anthracite, bituminous coal, subbituminous coal, lignite, etc., in descending order of the degree of coalification. preferable.
  • Bituminous coal and sub-bituminous coal have a relatively high content of toluene-soluble components and have an appropriate oxygen content. Therefore, by using bituminous coal and sub-bituminous coal as raw material coal, the oxygen content and toluene-soluble content are reduced.
  • the yield of the raw material pitch for producing carbon fibers within the above range can be increased.
  • the brown coal whose coalification degree is lower than subbituminous coal has the fault that the yield of carbon fiber from a raw material pitch becomes low because oxygen content rate is too large.
  • anthracite coal having a degree of coalification higher than that of bituminous coal has a drawback that it becomes difficult to melt-spin the raw material pitch because the oxygen content and the toluene soluble content are small.
  • the raw material pitch for producing the carbon fiber can be produced by the production method shown in FIG. Fig. 1
  • a method for producing a raw material pitch for carbon fiber production includes a step of forming ashless coal which is a pyrolyzate of coal by pyrolysis and extraction in a solvent of coal (pyrolysate formation step: step S1); The step of separating the ashless coal obtained in this pyrolyzate formation step into a soluble component and an insoluble component by a low-temperature solvent extraction process (separation step: step S2), and the soluble component obtained in this separation step A heat treatment step (heat treatment step: step S3).
  • step S1 the slurry obtained by mixing the raw coal and the solvent is heated to a temperature equal to or higher than the thermal decomposition temperature of the raw coal, and the soluble component of the pyrolyzed raw coal is extracted into the solvent.
  • Ashless coal is obtained by separating insoluble components at the decomposition temperature.
  • the “ashless coal” is a modified coal obtained by reforming coal and has an ash content of 5% or less, preferably 3% or less, more preferably 1% or less. “Ash” means a value measured in accordance with JIS-M8812 (2004).
  • the solvent is not particularly limited as long as it has a property of dissolving the raw material coal.
  • Aromatic compounds, tricyclic aromatic compounds such as anthracene, and the like can be used.
  • the bicyclic aromatic compound includes naphthalene having an aliphatic chain and biphenyl having a long aliphatic chain.
  • bicyclic to tricyclic aromatic compounds which are coal derivatives purified from coal carbonization products are preferred.
  • the bicyclic aromatic compound of the coal derivative is stable even in a heated state and has an excellent affinity with coal. Therefore, by using such a bicyclic aromatic compound as a solvent, the ratio of coal components extracted into the solvent can be increased, and the solvent can be easily recovered and reused by a method such as distillation. .
  • the lower limit of the slurry heating temperature is preferably 300 ° C, more preferably 350 ° C, and even more preferably 380 ° C.
  • the upper limit of the heating temperature of the slurry is preferably 450 ° C, more preferably 420 ° C. If the heating temperature of the slurry is less than the above lower limit, the bonds between the molecules constituting the coal cannot be sufficiently weakened. For example, when low grade coal is used as the raw coal, There is a possibility that the solidification temperature cannot be increased, and the yield may be low and uneconomical.
  • the extraction rate from coal in the pyrolysate formation step depends on the quality of the coal used as a raw material, but in the case of bituminous coal or sub-bituminous coal, for example, 20 mass% or more and 60 mass%. It is as follows.
  • Step S2 the ashless coal obtained in the pyrolyzate formation step of Step S1 is subjected to a low temperature solvent extraction treatment, whereby a relatively low molecular weight soluble component and a solvent extraction are extracted at low temperature. Separated into relatively high molecular weight insoluble components that are not. Thereby, the soluble component which can be melt-spun is obtained.
  • a slurry in which pulverized ashless coal is dispersed in a solvent is prepared, and this slurry is held within a predetermined temperature range for a certain period of time. Separate the solvent from which the dissolved components have been eluted.
  • the lower limit of the average particle size of ashless coal dispersed in the solvent is preferably 50 ⁇ m, more preferably 100 ⁇ m.
  • the upper limit of the average particle size of the ashless coal dispersed in the solvent is preferably 3 mm, and more preferably 1 mm.
  • the “average particle size” means a particle size at which the volume integrated value is 50% in the particle size distribution measured by the laser diffraction scattering method.
  • the lower limit of the mixing ratio of ashless coal with respect to the solvent of the slurry is preferably 3% by mass, and more preferably 5% by mass.
  • the upper limit of the mixing ratio of ashless coal to the solvent is preferably 40% by mass, and more preferably 30% by mass. If the mixing ratio of ashless coal to the solvent is less than the above lower limit, the production efficiency is low, which may be uneconomical. Conversely, when the mixing ratio of ashless coal with respect to the solvent exceeds the above upper limit, handling of the slurry and separation of insoluble components may be difficult.
  • the method for separating the solvent from which soluble components are eluted and the insoluble components there is no particular limitation on the method for separating the solvent from which soluble components are eluted and the insoluble components, and a known separation method such as a filtration method, a centrifugal separation method, a gravity sedimentation method, or a combination of these two methods is employed. It can. Among these, a combination of a centrifugal separation method and a filtration method that can continuously operate a fluid, is suitable for a large amount of processing at low cost, and can reliably remove insoluble components is preferable.
  • the solvent from the liquid (supernatant liquid) from which the insoluble components have been separated By removing the solvent from the liquid (supernatant liquid) from which the insoluble components have been separated in this way, the soluble components of ashless coal are separated and recovered, and by removing the solvent from the solids concentrate, Insoluble components are separated and recovered. It does not specifically limit as a method of removing a solvent from the said supernatant liquid and solid concentration liquid, A general distillation method, an evaporation method, etc. can be used. In particular, the removal of the solvent from the insoluble component is preferably performed by distillation in order to recover and reuse the solvent.
  • any solvent that can elute low molecular weight components of ashless coal may be used, and the same solvents as those used in the thermal decomposition product forming step can be used.
  • a solvent capable of obtaining a sufficient extraction rate at a low temperature, preferably room temperature is preferable, and examples of such a preferable solvent include pyridine, methylnaphthalene, tetrahydrofuran, anthracene and the like.
  • the optimum solvent extraction temperature in the separation process varies depending on the type of solvent.
  • the solvent extraction treatment temperature is preferably less than 300 ° C, more preferably 200 ° C or less, and further preferably 150 ° C or less.
  • the lower limit of the solvent extraction treatment temperature is not particularly limited, but normal temperature, for example, 20 ° C. is preferable.
  • the solvent extraction treatment temperature exceeds the above upper limit, the molecular weight of the soluble component to be extracted increases, so that the softening temperature becomes too high, and the spinning efficiency may be lowered during melt spinning.
  • cooling is required, and the cost may increase unnecessarily.
  • the lower limit of the extraction time in the separation step that is, the time maintained at the solvent extraction treatment temperature is preferably 10 minutes, and more preferably 15 minutes.
  • the upper limit of the extraction time is preferably 120 minutes, more preferably 90 minutes.
  • the lower limit of the extractability of soluble components from ashless coal in the separation step is preferably 10% by mass, more preferably 20% by mass, and even more preferably 30% by mass.
  • an upper limit of the extraction rate of the soluble component from ashless coal 90 mass% is preferable, 70 mass% is more preferable, and 50 mass% is further more preferable.
  • the extraction rate of soluble components from ashless coal in the separation step is less than the lower limit, the yield is low, and the production cost of the raw material pitch for producing carbon fibers may increase.
  • the extraction rate of the soluble component from the ashless coal in the separation step exceeds the upper limit, the softening temperature of the soluble component is increased, and the spinning efficiency may be decreased.
  • the soluble component obtained in the separation step of step S2 is heated to volatilize the low molecular weight component, and the carbon fiber is decomposed and removed in advance at a low temperature.
  • a raw material pitch for production is obtained.
  • the heat treatment is preferably performed in a non-oxidizing gas atmosphere.
  • a non-oxidizing gas atmosphere to prevent oxidative crosslinking, inconveniences such as an increase in softening temperature can be prevented.
  • the non-oxidizing gas is not particularly limited as long as the oxidation of pitch can be suppressed, but nitrogen gas is more preferable from the economical viewpoint.
  • the heat treatment is preferably performed in a reduced pressure state.
  • steam of a volatile component and the gas of a thermal decomposition product can be efficiently removed from pitch.
  • the lower limit of the heat treatment temperature in the heat treatment step is preferably 150 ° C, more preferably 170 ° C, and further preferably 200 ° C.
  • the upper limit of the heat treatment temperature is preferably 350 ° C, more preferably 320 ° C, and even more preferably 280 ° C.
  • the heat treatment temperature is less than the lower limit, volatile components in the insoluble component cannot be sufficiently removed, and the spinnability of the carbon fiber production raw material pitch becomes insufficient, and the spinning efficiency may decrease. There is.
  • the heat treatment temperature exceeds the upper limit, the energy cost may increase unnecessarily, the useful components may be thermally decomposed and the production efficiency of the carbon fiber may decrease, and the carbonization may proceed and spinning. May decrease.
  • the heat treatment temperature in the heat treatment step is preferably higher than the solvent extraction treatment temperature in the separation step of Step S2.
  • the heat treatment temperature is higher than the solvent extraction treatment temperature, volatile components having a boiling point higher than the solvent extraction treatment temperature can be removed from the pitch. Thereby, it can prevent that a void
  • the heat treatment temperature in the heat treatment step is more preferably higher than the melt spinning temperature.
  • the heat treatment temperature in the heat treatment step is higher than the melt spinning temperature, components that can be thermally decomposed during melt spinning can be previously thermally decomposed and removed in this heat treatment step.
  • the lower limit of the heat treatment time in the heat treatment step (the time for which the heat treatment temperature is maintained) is preferably 10 minutes, and more preferably 15 minutes.
  • the upper limit of the heat treatment time in the heat treatment step is preferably 120 minutes, more preferably 90 minutes.
  • the heat treatment time in the heat treatment step is less than the lower limit, the low molecular weight component may not be sufficiently removed.
  • the heat treatment time in the heat treatment step exceeds the upper limit, the treatment cost may be unnecessarily increased.
  • the lower limit of the softening temperature of the carbon fiber-producing raw material pitch obtained by heat-treating the soluble component is preferably 150 ° C, more preferably 170 ° C.
  • the upper limit of the softening temperature of the raw material pitch for carbon fiber production is preferably 280 ° C, and more preferably 250 ° C.
  • the softening temperature of the raw material pitch for carbon fiber production is less than the lower limit, the infusibilization temperature cannot be increased, and the infusibilization treatment may be inefficient.
  • the softening temperature of the raw material pitch for carbon fiber production exceeds the above upper limit, it is necessary to increase the melt spinning temperature, which may cause unstable spinning and increase the cost.
  • the “softening temperature” is a value measured by a ring and ball method in accordance with ASTM-D36.
  • the yield of the raw material pitch for carbon fiber production from the soluble component obtained in the separation step in the heat treatment step 80% by mass is preferable, and 85% by mass is more preferable.
  • the upper limit of the yield of the raw material pitch for producing carbon fibers from the soluble component in the heat treatment step is preferably 98% by mass, and more preferably 96% by mass.
  • the yield of the carbon fiber production raw material pitch from the soluble component in the heat treatment process exceeds the above upper limit, residual volatile components or components thermally decomposed at a low temperature in the carbon fiber production raw material pitch As a result, the spinnability of the pitch becomes insufficient, and the spinning efficiency may be reduced.
  • the carbon fiber production method using the carbon fiber production raw material pitch includes a step of melt spinning the carbon fiber production raw material pitch, a step of infusibilizing the filament obtained by the melt spinning, and an infusible yarn shape. And carbonizing the body.
  • the carbon fiber production raw material pitch is melt-spun using a known spinning device. That is, the raw material pitch in a molten state is formed into a thread by passing through a nozzle (die), and the shape of the raw material pitch is fixed to the thread by cooling.
  • a known nozzle may be used, and for example, a nozzle having a diameter of 0.1 mm to 0.5 mm and a length of 0.2 mm to 1 mm can be used.
  • the filamentous material obtained by melt spinning the raw material pitch is wound, for example, by a drum having a diameter of about 100 mm to 300 mm.
  • the lower limit of the melt spinning temperature is preferably 180 ° C, more preferably 200 ° C.
  • the upper limit of the melt spinning temperature is preferably 350 ° C, more preferably 300 ° C.
  • the melt spinning temperature is less than the above lower limit, the raw material pitch may not be sufficiently melted and stable spinning may not be possible.
  • the melt spinning temperature exceeds the above upper limit, the spun filaments may be disconnected due to thermal decomposition of components in the raw material pitch.
  • the lower limit of the linear speed of melt spinning is not particularly limited, but is preferably 100 m / min, and more preferably 150 m / min.
  • the upper limit of the melt spinning linear velocity is preferably 500 m / min, and more preferably 400 m / min.
  • the lower limit of the average diameter of the filaments spun in melt spinning is preferably 5 ⁇ m and more preferably 7 ⁇ m.
  • the upper limit of the average diameter of the filaments spun in melt spinning is preferably 20 ⁇ m and more preferably 15 ⁇ m.
  • the filament obtained in the melt spinning process is crosslinked and infusible by heating in an atmosphere containing oxygen.
  • an atmosphere containing oxygen air is generally used.
  • the lower limit of the infusibilization temperature is preferably 150 ° C, more preferably 200 ° C.
  • the upper limit of the infusibilization treatment temperature is preferably 300 ° C, and more preferably 280 ° C.
  • the lower limit of the infusibilization time is preferably 10 minutes, more preferably 20 minutes.
  • the upper limit of the infusibilization time is preferably 120 minutes, more preferably 90 minutes. If the infusibilization time is less than the lower limit, infusibilization may be insufficient. Conversely, when the infusibilization treatment time exceeds the above upper limit, the production cost of the carbon fiber may be unnecessarily increased.
  • carbon fibers are obtained by heating and carbonizing the filaments infusible in the infusibilization step.
  • the filamentous body is charged into an arbitrary heating device such as an electric furnace, the inside is replaced with a non-oxidizing gas, and then heated while blowing the non-oxidizing gas into the heating device.
  • an arbitrary heating device such as an electric furnace
  • the lower limit of the heat treatment temperature in the carbonization step is preferably 700 ° C, more preferably 800 ° C.
  • an upper limit of heat processing temperature 3000 degreeC is preferable and 2800 degreeC is more preferable. If the heat treatment temperature is less than the lower limit, carbonization may be insufficient. Conversely, when the heat treatment temperature exceeds the above upper limit, the production cost may increase from the viewpoint of improving the heat resistance of the equipment and fuel consumption.
  • the heating time in the carbonization step may be appropriately set depending on the characteristics required for the carbon material, and is not particularly limited, but the heating time is preferably 15 minutes or longer and 10 hours or shorter. If the heating time is less than the lower limit, carbonization may be insufficient. Conversely, when the heating time exceeds the above upper limit, the production efficiency of the carbon material may be reduced.
  • the non-oxidizing gas is not particularly limited as long as it can suppress the oxidation of the carbon material, but nitrogen gas is preferable from the economical viewpoint.
  • ash and the like in the slurry are not separated from the ashless coal in the thermal decomposition product forming step, and the ash and the like in the ashless coal in the next separation step. You may isolate
  • the heat treatment step may be omitted.
  • Example 1 As raw coal, an Australian bituminous coal with an oxygen content of 6.5% by mass on an anhydrous ashless basis was used. First, 1 kg of the above bituminous coal pulverized to 1 mm or less was mixed with 5 kg of methylnaphthalene, charged in an autoclave, held at 400 ° C. for 1 hour in a nitrogen atmosphere, and then cooled to obtain a thermal decomposition product. Next, 5 kg of methylnaphthalene is further added to this pyrolyzate, and the soluble component is extracted by stirring at an extraction temperature of 60 ° C. for 1 hour, followed by filtration. The obtained filtrate is distilled under reduced pressure to dissolve the soluble component. Separated. The soluble component was heat-treated in a nitrogen atmosphere at a heat treatment temperature of 230 ° C. for 1 hour to obtain a raw material pitch for carbon fiber production of Example 1.
  • Example 2 was experimentally manufactured under the same conditions as in Example 1 except that the extraction temperature was 80 ° C.
  • Example 3 was experimentally manufactured under the same conditions as in Example 1 except that the extraction temperature was 100 ° C.
  • Example 4 was experimentally manufactured under the same conditions as in Example 1 except that the heat treatment temperature was 250 ° C.
  • Example 5 was manufactured on the same conditions as Example 1 except that the extraction temperature was 80 ° C. and the heat treatment temperature was 250 ° C.
  • Example 6 was made on the same conditions as Example 1 except that the extraction temperature was 100 ° C. and the heat treatment temperature was 250 ° C.
  • Comparative Example 1 1 kg of the same bituminous coal crushed to 1 mm or less as in Example 1 was mixed with 5 kg of methylnaphthalene, charged in an autoclave, held at 400 ° C. for 1 hour in a nitrogen atmosphere, and then filtered ashless coal at a heat treatment temperature of 200 ° C.
  • the raw material pitch for carbon fiber manufacture of the comparative example 1 was obtained by heat-treating for 1 hour under nitrogen atmosphere.
  • Comparative Example 2 A commercially available hard pitch having an oxygen content of 0.9% by mass and a toluene soluble content of 64% by mass was prepared as a raw material pitch for carbon fiber production in Comparative Example 2, and this was prepared in a nitrogen atmosphere at a heat treatment temperature of 350 ° C.
  • the raw material pitch for carbon fiber manufacture of the comparative example 2 was obtained by heat-processing for 20 hours.
  • the carbon fiber which is comparatively excellent in tensile strength by making the oxygen content rate of the raw material pitch for carbon fiber production 1.0% by mass or more and the content rate of the toluene soluble content 20% by mass or more. It was confirmed that can be manufactured stably.
  • the raw material pitch for producing carbon fiber of the present invention is suitably used for producing carbon fiber.

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PCT/JP2016/063727 2015-05-12 2016-05-09 炭素繊維製造用原料ピッチ WO2016181929A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201680024557.6A CN107532086B (zh) 2015-05-12 2016-05-09 碳纤维制造用原料沥青
KR1020177031562A KR102070167B1 (ko) 2015-05-12 2016-05-09 탄소 섬유 제조용 원료 피치
DE112016002135.6T DE112016002135T5 (de) 2015-05-12 2016-05-09 Rohmaterialpech zur Kohlefaser-Herstellung
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018021386A1 (ja) * 2016-07-29 2018-02-01 株式会社神戸製鋼所 炭素繊維の製造方法
CN112105707A (zh) * 2017-12-22 2020-12-18 卡本控股知识产权有限责任公司 从煤生产碳纤维、树脂、石墨烯和其他高级碳材料的方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61287961A (ja) * 1985-06-17 1986-12-18 Asahi Chem Ind Co Ltd 炭素繊維用前駆体ピツチ
JPS6243461A (ja) * 1985-04-18 1987-02-25 Mitsubishi Oil Co Ltd 炭素繊維用原料ピツチ
JPH01282346A (ja) * 1988-05-10 1989-11-14 Toray Ind Inc ピッチ系炭素繊維製造方法
JPH023496A (ja) * 1988-06-14 1990-01-09 Sumitomo Metal Ind Ltd 高性能炭素繊維用原料の製造方法
JP2011089024A (ja) * 2009-10-22 2011-05-06 Osaka Gas Chem Kk 改質タール並びに改質タールの製造方法、生コークスの製造方法及びニードルコークスの製造方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3610375A1 (de) * 1986-03-27 1987-10-01 Ruetgerswerke Ag Verfahren zur herstellung eines kohlenstoffaser-vorprodukts und daraus hergestellte kohlenstoffasern
JPH0733514B2 (ja) * 1987-07-29 1995-04-12 日本カ−ボン株式会社 メソフェ−ズピッチの製造法
JP2808807B2 (ja) 1990-03-30 1998-10-08 三菱化学株式会社 炭素材用原料粉の製法
JPH0715099A (ja) 1993-06-22 1995-01-17 Mitsubishi Shindoh Co Ltd 回路基板およびその製造方法
CN100572503C (zh) * 2007-02-06 2009-12-23 湖南长岭石化科技开发有限公司 一种煤焦油的预处理方法
KR101372012B1 (ko) * 2012-03-02 2014-03-12 오씨아이 주식회사 고강도 고탄성 피치계 등방성 탄소섬유 및 그 제조 방법
CN102942945B (zh) * 2012-11-15 2014-05-28 四川创越炭材料有限公司 一种可溶性中间相沥青的制备方法
CN104232130B (zh) * 2013-06-09 2016-08-10 任相坤 一种针状焦的生产工艺

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6243461A (ja) * 1985-04-18 1987-02-25 Mitsubishi Oil Co Ltd 炭素繊維用原料ピツチ
JPS61287961A (ja) * 1985-06-17 1986-12-18 Asahi Chem Ind Co Ltd 炭素繊維用前駆体ピツチ
JPH01282346A (ja) * 1988-05-10 1989-11-14 Toray Ind Inc ピッチ系炭素繊維製造方法
JPH023496A (ja) * 1988-06-14 1990-01-09 Sumitomo Metal Ind Ltd 高性能炭素繊維用原料の製造方法
JP2011089024A (ja) * 2009-10-22 2011-05-06 Osaka Gas Chem Kk 改質タール並びに改質タールの製造方法、生コークスの製造方法及びニードルコークスの製造方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018021386A1 (ja) * 2016-07-29 2018-02-01 株式会社神戸製鋼所 炭素繊維の製造方法
CN112105707A (zh) * 2017-12-22 2020-12-18 卡本控股知识产权有限责任公司 从煤生产碳纤维、树脂、石墨烯和其他高级碳材料的方法
US11634331B2 (en) 2017-12-22 2023-04-25 Carbon Holdings Intellectual Properties, Llc Methods for producing advanced carbon materials from coal
US11767223B2 (en) 2017-12-22 2023-09-26 Carbon Holdings Intellectual Properties, Llc Methods for forming resins and other byproducts from raw coal
US11807537B2 (en) 2017-12-22 2023-11-07 Carbon Holdings Intellectual Properties, Llc Methods for producing carbon fiber from coal
US11975975B2 (en) 2017-12-22 2024-05-07 Carbon Holdings Intellectual Properties, Llc Systems for producing advanced carbon materials at carbon source locations

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CN107532086A (zh) 2018-01-02
KR102070167B1 (ko) 2020-01-29
CN107532086B (zh) 2021-04-06
US20180142158A1 (en) 2018-05-24
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