WO2016147743A1 - 炭素繊維の製造方法 - Google Patents

炭素繊維の製造方法 Download PDF

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WO2016147743A1
WO2016147743A1 PCT/JP2016/053664 JP2016053664W WO2016147743A1 WO 2016147743 A1 WO2016147743 A1 WO 2016147743A1 JP 2016053664 W JP2016053664 W JP 2016053664W WO 2016147743 A1 WO2016147743 A1 WO 2016147743A1
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temperature
heat treatment
coal
carbon fiber
pitch
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PCT/JP2016/053664
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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
仁 宮脇
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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 US15/557,506 priority Critical patent/US20180051397A1/en
Priority to KR1020177025776A priority patent/KR101943784B1/ko
Priority to CN201680014937.1A priority patent/CN107407012B/zh
Priority to DE112016001254.3T priority patent/DE112016001254T5/de
Publication of WO2016147743A1 publication Critical patent/WO2016147743A1/ja

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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
    • D01F9/15—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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods

Definitions

  • the present invention relates to a method for producing carbon fiber.
  • 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 produced by forming a synthetic resin such as polyacrylonitrile or pitch obtained from petroleum or coal into a fiber shape by spinning, and then infusing (air oxidation) and carbonizing the yarn.
  • 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 coal is produced by carbonization, and is a viscous black substance. .
  • Such a coal pitch is a mixture of many compounds containing many aromatic compounds containing many benzenes in their skeletons.
  • 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. Therefore, for example, metal impurities and solid carbon components that inhibit spinning and subsequent infusibilization and carbonization are prevented. It is difficult to produce carbon fibers stably and efficiently. Also, these impurities can cause defects in the produced carbon fiber.
  • the pitch used for the production of carbon fiber has a large carbon content and does not contain metal impurities or solid carbon.
  • the pitch used for producing the carbon fiber is uniformly melted at a constant temperature during spinning.
  • the softening point of the pitch is preferably 150 ° C. or higher so that the temperature of the infusibilization treatment for fixing the shape of the fiber spun with the pitch can be increased, and the spinning is performed at a temperature at which no thermal decomposition reaction occurs during spinning. It is preferably 300 ° C. or lower so that it can be used.
  • an object of the present invention is to provide a method capable of producing carbon fiber at a low cost.
  • the invention made to solve the above-mentioned problems is a process of separating ashless coal obtained from bituminous coal or subbituminous coal into soluble components and insoluble components by solvent extraction treatment, and heat-treating the soluble components
  • a method of producing a carbon fiber comprising: a step, a step of melt spinning the heat-treated soluble component, a step of infusifying the filament obtained by the melt spinning, and a step of carbonizing the infusible filament is there.
  • a soluble component mainly composed of a relatively low molecular weight organic substance is extracted from a ashless coal having a small content of impurities such as ash that inhibits spinning by a solvent extraction process, Pitch is obtained by removing from this soluble component volatile components that inhibit spinning by heat treatment and components that thermally decompose at low temperatures.
  • This pitch has few impurities and relatively high molecular weight components, and has a softening temperature that is suitable for melt spinning and can be infusibilized at a relatively high temperature. Therefore, the carbon fiber production method efficiently uses carbon fiber. Can be manufactured. Further, since the pitch can be obtained only by performing solvent extraction treatment and heat treatment, high-quality carbon fibers can be produced at a relatively low cost.
  • the solvent extraction temperature in the separation step is preferably less than 300 ° C.
  • the obtained pitch does not contain a relatively high molecular weight component and has a softening temperature at which melt spinning can be performed relatively easily. . Thereby, the production cost of carbon fibers can be further reduced by increasing the spinning efficiency.
  • the heat treatment temperature in the heat treatment step is preferably 150 ° C. or higher.
  • volatile components that inhibit spinning can be more reliably removed from the pitch, so that the efficiency of melt spinning can be improved.
  • an infusibilization treatment at a higher temperature is enabled.
  • the production cost of carbon fiber can be further reduced by increasing the efficiency of melt spinning and infusibilization.
  • the heat treatment temperature in the heat treatment step is preferably higher than the solvent extraction temperature in the separation step.
  • the heat treatment temperature in the heat treatment step is preferably higher than the spinning temperature in the melt spinning step.
  • the heat treatment temperature higher than the spinning temperature components that can be thermally decomposed from the pitch during spinning can be removed, and by further increasing the spinning efficiency, the production cost of the carbon fiber can be further reduced.
  • bituminous coal and “subbituminous coal” refer to coal having the quality defined in JIS-M1002 (1978).
  • “Ashless coal” refers to a modified coal obtained by reforming coal and having 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 carbon fiber production method of the present invention produces carbon fiber by melt spinning, infusibilization and carbonization of a pitch obtained by heat-treating a soluble component subjected to solvent extraction treatment from ashless coal.
  • a high-quality carbon fiber can be provided at a relatively low cost because the content of components that inhibit spinning in the pitch used is small and the spinning efficiency is high.
  • the method for producing carbon fiber includes a step of forming ashless coal by pyrolysis and solvent extraction treatment of bituminous coal or subbituminous coal (ashless coal formation).
  • Step S1 a process of separating ashless coal obtained from bituminous coal or subbituminous coal into a soluble component and an insoluble component by low-temperature solvent extraction treatment (separation step: step S2), and obtained A step of heat-treating the soluble component (heat treatment step: step S3), a step of melt-spinning the heat-treated soluble component (melt-spinning step: step S4), and a step of infusibilizing the filament obtained by this melt spinning ( Infusibilization step: Step S5) and a step of carbonizing the molded compound (carbonization step: Step S6).
  • a slurry obtained by mixing bituminous coal or subbituminous coal and a solvent is heated to a temperature higher than the pyrolysis temperature of bituminous or subbituminous coal, and pyrolytic bitumen.
  • Ashless coal is obtained by extracting soluble components of charcoal or subbituminous coal into a solvent.
  • Bituminous coal or subbituminous coal is superior in yield and pitch characteristics compared to other types of coal.
  • lignite and lignite have a high oxygen content and a low carbon content may cause a problem as a carbon fiber raw material.
  • what has a high degree of coalification like anthracite coal is not preferable because the yield of ashless coal is low.
  • the solvent is not particularly limited as long as it has a property of dissolving bituminous coal or subbituminous coal.
  • monocyclic aromatic compounds such as benzene, toluene, xylene, naphthalene, methylnaphthalene, dimethylnaphthalene, and the like.
  • Bicyclic aromatic compounds such as trimethylnaphthalene and the like can be used.
  • the bicyclic aromatic compound includes naphthalene having an aliphatic chain and biphenyl having a long aliphatic chain.
  • a bicyclic aromatic compound which is a coal derivative purified from a coal dry distillation product is preferable.
  • 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 470 ° C, more preferably 450 ° 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. On the other hand, when the heating temperature of the slurry exceeds the above upper limit, the thermal decomposition reaction of coal becomes very active and recombination of generated thermal decomposition radicals occurs, which may reduce the extraction rate.
  • the extraction rate from bituminous coal or subbituminous coal in the ashless coal formation process depends on the quality of bituminous coal or subbituminous coal as a raw material, for example, 40 It is set as mass% or more and 60 mass% or less.
  • step S2 the ashless coal obtained in the ashless coal formation step of step S1 is subjected to a low temperature solvent extraction process, so that a relatively low molecular weight soluble component and a solvent extraction can be extracted at a 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 soluble component of the ashless coal is separated and recovered, and the solvent is removed from the solid concentrate to thereby dissolve the ashless coal insoluble.
  • the 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.
  • the solvent used in the separation step is not particularly limited as long as it can elute low molecular weight components of ashless coal, and the same solvents as those used in the ashless coal formation step can be used.
  • a solvent capable of obtaining a sufficient extraction rate at a low temperature, preferably normal temperature is preferable, and examples of such a preferable solvent include pyridine, methylnaphthalene, tetrahydrofuran 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 processing 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 in step S4 may decrease.
  • the solvent extraction treatment temperature is less than the above lower limit, 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. If the extraction rate of soluble components from ashless coal in the separation step is less than the above lower limit, the yield may be low and the production cost may increase. On the contrary, when 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 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.
  • the upper limit of the heat treatment temperature is preferably 320 ° C, and more preferably 280 ° C. If the heat treatment temperature is less than the lower limit, the volatile components in the insoluble components cannot be sufficiently removed, the pitch spinnability becomes insufficient, and the spinning efficiency may be lowered. On the other hand, when the heat treatment temperature exceeds the upper limit, the energy cost may be unnecessarily increased, the useful components may be thermally decomposed and the production efficiency may be decreased, and the carbonization proceeds to lower the spinnability. There is a fear.
  • 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 is possible to prevent the formation of pores and the breakage of the filamentous body due to the volatile component coming out of the pitch formed in the filamentous shape in the spinning process of step S4.
  • the heat treatment temperature in the heat treatment step is more preferably higher than the melt spinning temperature in the melt spinning step in Step S4 described later.
  • the heat treatment temperature 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 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 pitch is preferably 280 ° C, more preferably 250 ° C. If the softening temperature of the pitch is less than the lower limit, the infusibilization temperature in the infusibilization step of Step S5 cannot be increased, and the infusibilization processing may become inefficient. On the contrary, if the softening temperature of the pitch exceeds the upper limit, it is necessary to increase the spinning temperature in the melt spinning step of step S4, which may cause spinning to become unstable and increase the cost.
  • the “softening temperature” is a value measured by a ring and ball method in accordance with ASTM-D36.
  • the lower limit of the yield of pitch from the soluble component obtained in the separation step in this heat treatment step is preferably 80% by mass, and more preferably 85% by mass.
  • the upper limit of the yield of pitch from the soluble component in the heat treatment step is preferably 98% by mass, and more preferably 96% by mass. If the yield of pitch from the soluble component in the heat treatment step is less than the lower limit, the yield may be unnecessarily lowered. Conversely, if the pitch yield from the soluble component in the heat treatment process exceeds the above upper limit, the spinnability of the pitch becomes insufficient due to the remaining volatile components in the pitch and components thermally decomposed at low temperatures, There is a possibility that the spinning efficiency is lowered.
  • the pitch obtained in the heat treatment process in step S3 is melt-spun using a known spinning device. That is, the molten pitch is formed into a thread shape by passing through a nozzle (cap), and the pitch shape is fixed to the thread shape 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 filaments obtained by melt spinning the pitch are wound up by a drum having a diameter of about 100 mm to 300 mm, for example.
  • 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 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 pitch fibers to be spun in melt spinning is preferably 7 ⁇ m and more preferably 10 ⁇ m.
  • the upper limit of the average diameter of pitch fibers spun in melt spinning is preferably 20 ⁇ m and more preferably 15 ⁇ m. If the average diameter of the pitch fibers is less than the lower limit, it may not be possible to spin stably. On the other hand, when the average diameter of the pitch fibers exceeds the upper limit, the flexibility of the pitch fibers may be insufficient.
  • the filament obtained in the melt spinning step of step S4 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.
  • step S6 Carbonization process
  • carbon fibers are obtained by heating and carbonizing the filaments infusible in the infusibility process of step S5.
  • 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 800 ° C, and more preferably 1000 ° C.
  • an upper limit of heat processing temperature 3000 degreeC is preferable and 2800 degreeC is more preferable.
  • the heat treatment temperature is less than the lower limit, carbonization may be insufficient.
  • 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 process may be appropriately set depending on the characteristics required of the carbon material, and is not particularly limited, but the heating time is preferably 15 minutes or more and 10 hours or less. 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.
  • Carbon fiber According to the carbon fiber manufacturing method of FIG. 1, carbon fibers obtained by melt spinning, infusibilization and carbonization of pitch, obtained by solvent extraction treatment of ashless coal obtained from bituminous coal or subbituminous coal. A carbon fiber using a pitch obtained by heat-treating the soluble component is produced.
  • a soluble component mainly composed of a relatively low molecular weight organic substance is extracted from a ashless coal having a small content of impurities such as ash that inhibits spinning by a solvent extraction process,
  • impurities such as ash that inhibits spinning by a solvent extraction process
  • the carbon fiber production method of the present invention does not require that ashless coal be produced from bituminous coal or subbituminous coal. That is, in the method for producing a carbon material of the present invention, ashless coal produced by a third party may be used as a starting material.
  • the carbon fiber manufacturing method may include a step of further graphitizing the carbon fiber by heating to a higher temperature than the carbonization step in a non-oxidizing atmosphere after the carbonization step.
  • Examples 1 to 4 of carbon fiber were made by trial production by the ashless coal forming step, separation step, heat treatment step, melt spinning step, infusibilization step, and carbonization step described below. Further, a comparative example 1 of carbon fiber was made as a prototype by omitting the heat treatment step from Example 1. Further, a comparative example 2 of carbon fiber was produced by melt spinning ashless coal.
  • Table 1 shows differences in manufacturing conditions between Examples 1 to 4 and Comparative Examples 1 and 2 and various measured values in the manufacturing process.
  • Ashless coal used as a raw material in Examples 1 to 4 and Comparative Example was produced using bituminous coal generally used as boiler fuel.
  • the yield of ashless coal based on raw coal was 48% by mass.
  • Example 1 The ashless coal was pulverized to an average particle size of 0.5 mm or less, and soluble components were extracted from 100 g of the ashless coal using 1 L of a solvent.
  • pyridine was used as the solvent
  • the solvent extraction temperature was 115 ° C.
  • the extraction time was 60 minutes.
  • Example 2 methylnaphthalene was used as the solvent
  • the solvent extraction temperature was 320 ° C.
  • the extraction time was 60 minutes.
  • Example 3 methylnaphthalene was used as the solvent, the solvent extraction temperature was 100 ° C., and the extraction time was 60 minutes.
  • Example 4 tetrahydrofuran was used as the solvent, the solvent extraction temperature was 65 ° C., and the extraction time was 60 minutes.
  • a soluble component is obtained by separating insoluble components from a slurry in which ashless coal is dispersed in a solvent and maintaining the extraction time at the solvent extraction temperature by vacuum filtration, and further distilling the solvent under reduced pressure. Was taken out.
  • the yield of the soluble component was 42% by mass in Example 1 and Comparative Example 1, 93% by mass in Example 2, 38% by mass in Example 3, and 36% by mass in Example 4. .
  • Heat treatment process Each soluble component obtained in the separation step was heat-treated in a nitrogen atmosphere to obtain a pitch.
  • the heat treatment conditions were a heat treatment temperature of 250 ° C. and a heat treatment time (holding time) of 1 hour.
  • the pitch yield in this heat treatment step that is, the ratio of the mass of the pitch after the heat treatment to the mass of the soluble component before the heat treatment was measured.
  • the yield in the heat treatment was 92% by mass in Example 1, 96% by mass in Example 2, 97% by mass in Example 3, and 98% by mass in Example 4.
  • the softening temperature was measured for the pitches of Examples 1 to 4 obtained by heat treatment, the pitch of Comparative Example 1 (soluble component not subjected to heat treatment) and the ashless coal of Comparative Example 2.
  • the softening temperature of the pitch was determined by the ring and ball method according to ASTM-D36, and the softening temperature of the ashless coal was determined by the Gieseller method according to JIS-M8801 (2004).
  • the softening temperature of the pitch was 205 ° C in Example 1, 259 ° C in Example 2, 194 ° C in Example 3, 188 ° C in Example 4, 195 ° C in Comparative Example 1, and 195 ° C in Comparative Example 2.
  • the softening temperature of the ashless coal was 245 ° C.
  • Examples 1 and 3 and 4 showed very good spinnability.
  • Example 2 the spinnability was slightly inferior, and in rare cases, disconnection (clogging with a nozzle) occurred.
  • Comparative Example 1 the formed filaments were frequently disconnected due to the generation of gas.
  • Comparative Example 2 the spinnability was considerably inferior, and frequent disconnection (clogging with a nozzle) occurred.
  • the filament formed in the melt spinning process was heat-treated in air to make it infusible.
  • the infusible treatment conditions were a treatment temperature of 250 ° C. and a treatment time of 1 hour.
  • the filaments infusible in the infusibilization step were carbonized in a nitrogen atmosphere.
  • the carbonization treatment temperature was 800 ° C.
  • the holding time was 30 minutes.
  • the tensile strengths of the carbon fibers obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were measured.
  • the tensile strength was measured according to JIS-R7606 (2000).
  • the tensile strength of the carbon fiber was 600 MPa in Example 1, 750 MPa in Example 2, 800 MPa in Example 3, and 850 MPa in Example 4.
  • Comparative Example 1 and Comparative Example 2 it was difficult to continuously and stably carry out melt spinning with a constant fiber diameter, and thus carbon fibers could not be obtained. Therefore, the measurement of the tensile strength of the comparative example 1 and the comparative example 2 was not implemented.
  • the carbon fiber production method of the present invention is suitably applied to the production of carbon fibers that require dimensional accuracy.

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PCT/JP2016/053664 2015-03-17 2016-02-08 炭素繊維の製造方法 WO2016147743A1 (ja)

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Application Number Priority Date Filing Date Title
US15/557,506 US20180051397A1 (en) 2015-03-17 2016-02-08 Method for producing carbon fibers
KR1020177025776A KR101943784B1 (ko) 2015-03-17 2016-02-08 탄소 섬유의 제조 방법
CN201680014937.1A CN107407012B (zh) 2015-03-17 2016-02-08 碳纤维的制造方法
DE112016001254.3T DE112016001254T5 (de) 2015-03-17 2016-02-08 Verfahren zum Herstellen von Kohlefasern

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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
WO2018154977A1 (ja) * 2017-02-24 2018-08-30 株式会社神戸製鋼所 多孔質炭素粒子の製造方法及び多孔質炭素粒子
WO2018186018A1 (ja) * 2017-04-07 2018-10-11 株式会社神戸製鋼所 多孔質炭素繊維シートの製造方法及び多孔質炭素電極の製造方法

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