WO2025013373A1 - 炭素材製造用バインダーピッチ及び炭素材の製造方法 - Google Patents

炭素材製造用バインダーピッチ及び炭素材の製造方法 Download PDF

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WO2025013373A1
WO2025013373A1 PCT/JP2024/015827 JP2024015827W WO2025013373A1 WO 2025013373 A1 WO2025013373 A1 WO 2025013373A1 JP 2024015827 W JP2024015827 W JP 2024015827W WO 2025013373 A1 WO2025013373 A1 WO 2025013373A1
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pitch
mass
binder pitch
softening point
carbon
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French (fr)
Japanese (ja)
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祐太朗 石川
信宏 西
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Resonac Corp
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Resonac Corp
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Priority to CN202480002387.6A priority Critical patent/CN119790110A/zh
Priority to JP2024548462A priority patent/JP7745774B2/ja
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • the present disclosure relates to a method for producing carbon materials such as graphite electrodes and binder pitch.
  • Carbon materials such as graphite electrodes used in electric furnaces that remelt iron are manufactured by kneading and shaping aggregates such as coke with pitch (called “binder pitch”) at a temperature above the softening point of the binder pitch, then firing and graphitizing it.
  • Carbon materials are required to have properties such as high mechanical strength, electrical conductivity, and thermal conductivity, so a high density is preferable.
  • the fired body due to the volatilization of low molecular weight components in the binder pitch during the firing process, the fired body has a porous structure. For this reason, the porosity is reduced by impregnating the fired body with pitch (called “impregnated pitch”) and re-firing it several times during the manufacturing process, resulting in a high density carbon material.
  • the carbonization yield of the binder pitch in the molded body during the sintering process is called the carbonization rate.
  • the higher this carbonization rate the higher the density of the resulting sintered body will be, which is preferable because it reduces the number of subsequent impregnations with impregnated pitch and re-sintering steps.
  • the higher the fixed carbon content of the pitch the higher the carbonization rate tends to be, so it is preferable to use such a pitch as the binder pitch.
  • a known method for increasing the fixed carbon content of binder pitch is to remove light components from the pitch by distillation, but this also increases the softening point.
  • a temperature about 50°C higher than the softening point is required, so a high softening point places a heavy burden on the equipment.
  • Patent Document 1 a method of adding cutback oil to pitch with a high fixed carbon content and high softening point
  • Patent Document 1 requires the addition of cutback oil, which has a relatively low boiling point, resulting in a problem of a lower initial boiling point of the resulting pitch. If the initial boiling point is too low, a large amount of light components volatilize during kneading, which causes a problem of an increase in viscosity during kneading and a decrease in kneadability. As such, it is difficult to achieve both good kneadability and a high carbonization rate solely from the perspective of the fixed carbon amount and softening point, which have been particularly important up until now.
  • This disclosure provides a binder pitch that can achieve both good kneadability and a high carbonization rate, and a method for producing a high-density carbon material using the binder pitch.
  • the binder pitch in the molded body softens and the viscosity decreases as the temperature rises. If the binder pitch flows out of the molded body at this time, the carbonization rate decreases.
  • it is considered effective to use a pitch that can maintain a relatively high viscosity even during firing.
  • such pitches generally have a high softening point, which causes a problem of reduced kneadability.
  • the inventors of the present invention considered that in order to suppress the flow-out of the binder pitch during firing without reducing kneadability, it is preferable to use a binder pitch whose viscosity is likely to decrease when the binder pitch is in a state where it is somewhat fluid, such as during kneading, and whose viscosity is maintained at a high level when the binder pitch is in a state where it is almost not fluid, such as during firing.
  • the inventors of the present invention have conducted extensive research by combining the fixed carbon content and softening point of the binder pitch, which have traditionally been considered important, with the new perspective of the rheological properties of the binder pitch. As a result, they discovered that even if the amount of fixed carbon was the same, a higher carbonization rate and a higher density carbon material could be obtained when a pitch with a higher Casson yield value was used as the binder pitch, leading to the present invention.
  • a binder pitch for producing carbon materials having a softening point of 70°C to 120°C, a fixed carbon content of 50.0 mass% or more, a quinoline insoluble content of 18.0 mass% or less, an initial boiling point of 320°C or more, and a Casson yield value at a softening point + 100°C of 0.18 Pa or more.
  • [3] A method for producing a carbon material using, as a binder pitch, pitch having a softening point of 70°C to 120°C, a fixed carbon content of 50.0 mass% or more, a quinoline insoluble content of 18.0 mass% or less, an initial boiling point of 320°C or more, and a Casson yield value at a softening point + 100°C of 0.18 Pa or more.
  • pitch having a softening point of 70°C to 120°C, a fixed carbon content of 50.0 mass% or more, a quinoline insoluble content of 18.0 mass% or less, an initial boiling point of 320°C or more, and a Casson yield value at a softening point + 100°C of 0.18 Pa or more.
  • the present disclosure it is possible to obtain a binder pitch that can achieve both good kneadability and a high carbonization rate. According to the present disclosure, it is possible to obtain a high-density carbon material.
  • FIG. 1 is a flow diagram showing a petrochemical process for thermally cracking naphtha or the like and a process for producing ethylene bottom oil.
  • FIG. 1 is a graph showing a change in viscosity when the shear rate is changed at a softening point of the binder pitch of Example 1 plus 100° C. (193° C.).
  • 1 is a Casson plot of the binder pitch of Example 1 (measurement temperature: 193° C.).
  • the binder pitch of one embodiment has a softening point of 70° C. to 120° C., a fixed carbon amount of 50.0% by mass or more, a quinoline insoluble matter amount of 18.0% by mass or less, an initial boiling point of 320° C. or more, and a Casson yield value at the softening point + 100° C. of 0.18 Pa or more.
  • the softening point, fixed carbon amount, quinoline insoluble matter, initial boiling point, and Casson yield value are measured by the method described in the Examples section.
  • the softening point of the binder pitch in one embodiment is 70°C or higher, preferably 80°C or higher, and more preferably 85°C or higher.
  • the softening point of the binder pitch in one embodiment is 120°C or lower, preferably 110°C or lower, and more preferably 100°C or lower. These upper and lower limit values can be combined in any manner. If the softening point is within the above temperature range, the binder pitch is sufficiently softened at the kneading temperature (e.g., 130°C to 170°C) and exhibits good kneadability, which is preferable.
  • the fixed carbon content of the binder pitch is 50.0% by mass or more, and more preferably 51.0% by mass or more. There is no particular limit to the upper limit of the fixed carbon content, but it is, for example, 75.0% by mass or 85.0% by mass.
  • the quinoline insolubles (QI) of the binder pitch is 18.0% by mass or less, preferably 15.0% by mass or less, and more preferably 10.0% by mass or less.
  • the quinoline insolubles of the binder pitch include the quinoline insolubles contained in the base pitch as well as the carbon powder added to the base pitch.
  • the carbon powder can be added, for example, in step 3 described below. It is preferable that the components detected as quinoline insolubles (QI) do not substantially contain mesophase spherulites that may be generated during the heat treatment of petroleum-based heavy oil. If the Casson yield value at the softening point of the binder pitch + 100°C is 0.18 Pa or more, the lower limit of the quinoline insolubles is not particularly limited, but is, for example, 1.0% by mass or 1.5% by mass.
  • the initial boiling point of the binder pitch in one embodiment is 320°C or higher, and preferably 340°C or higher. If the initial boiling point is 320°C or higher, the amount of light components volatilized at the kneading temperature (e.g., 130°C to 170°C) is small, so the viscosity of the pitch is less likely to increase during kneading, and kneading can be performed well. If the softening point of the binder pitch is in the range of 70°C to 120°C, the upper limit of the initial boiling point is not particularly limited, but is, for example, 400°C or 450°C.
  • the Casson yield value at the softening point of the binder pitch +100°C is 0.18 Pa or more, more preferably 0.20 Pa or more, and even more preferably 0.22 Pa or more.
  • "At the softening point of the binder pitch +100°C” means, for example, that when the softening point of the binder pitch is 93°C, the temperature at which the yield value is measured is set to 193°C. If the Casson yield value at the softening point +100°C is 0.18 Pa or more, this is preferable because it suppresses the loss of binder pitch from the molded body that may occur during firing and tends to increase the carbonization rate.
  • the upper limit of the Casson yield value at the softening point +100°C is not particularly limited, but is, for example, 1.5 Pa or 1.0 Pa.
  • the Casson yield value can be calculated by measuring the relationship between shear rate and shear stress at a measurement temperature and applying Casson formula (1) to a graph plotting both measured values in accordance with the method described in ASTM D5018-18. That is, when S is shear stress (Pa), D is shear rate (s -1 ), ⁇ 0 is Casson yield value (Pa), and ⁇ 0 is Casson viscosity (Pa ⁇ s), the Casson yield value can be calculated as the square of the y-intercept ( ⁇ 0 1/2 ) of the graph of S 1/2 against D 1/2 in Casson formula (1).
  • the method for producing the binder pitch for producing a carbon material is not particularly limited as long as it is a method that can obtain a binder pitch that satisfies predetermined physical property values, and examples thereof include the following production methods.
  • the method for producing the binder pitch for producing a carbon material according to one embodiment includes at least the following steps 1 to 3 in this order, and other steps may be added.
  • Step 1 heat treatment step: A step of heat treating petroleum-based heavy oil.
  • Step 2 distillation step: A step of distilling the heat-treated product obtained in step 1 to obtain a base pitch having a softening point of 60°C to 110°C, a fixed carbon content of 49.0 mass% or more, an initial boiling point of 320°C or more, and a quinoline insoluble matter (QI) of 1.0 mass% or less as a high-boiling point component.
  • Step 3 carbon powder mixing step: A step of adding carbon powder to the base pitch obtained in step 2 and mixing to obtain a binder pitch.
  • the petroleum heavy oil used as the raw material is not particularly limited as long as it can produce a base pitch having the desired characteristics in step 2, but it is preferable that it has the following composition. That is, the content of fractions having a boiling point of less than 150°C in the petroleum heavy oil is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less.
  • the content of fractions having a boiling point of 150°C or more and less than 450°C in the petroleum heavy oil is preferably 75% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more.
  • the content of fractions having a boiling point of 450°C or more and less than 550°C in the petroleum heavy oil is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less.
  • the content of fractions having a boiling point of 550°C or more in the petroleum heavy oil is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less.
  • the content of fractions in each temperature range here means the distillate amount in each temperature range when the distillation curve of the petroleum heavy oil is obtained.
  • the distillation curve can be calculated by selecting an appropriate method from JIS K 2254:2018, ASTM D7500-15, and ASTM D7169-16 depending on the type of petroleum heavy oil.
  • ethylene bottom oil light fraction An example of a petroleum heavy oil having the above composition is ethylene bottom oil light fraction.
  • naphtha etc. is generally thermally cracked at high temperatures, and the resulting pyrolysis product is distilled to separate it into various fractions such as ethylene, propylene and other olefins, aromatic compounds such as benzene, toluene and xylene, cracked gasoline, cracked kerosene, etc., which are then used as products.
  • the heavy fraction with the highest boiling point is called ethylene bottom oil, and is used as a raw material and fuel for carbon black etc. (see Figure 1).
  • Thermal cracking plants for naphtha etc. are often called ethylene plants, so the above-mentioned heavy fraction is called ethylene bottom oil.
  • ethylene bottom oil obtained by thermal cracking of naphtha-containing feedstock vary depending on the type of naphtha-containing feedstock, thermal cracking conditions, operating conditions of the refining distillation column, etc., but generally, the 50% distillation temperature is 200° C. to 400° C., the aromatic carbon content is 50 mass% or more, the flash point is 70° C. to 100° C., and the 50° C. kinematic viscosity is less than 40 mm 2 /s.
  • the above values may vary somewhat.
  • the ethylene bottom oil light fraction refers to a distillate obtained by distilling off an arbitrary proportion (for example, 5% by mass to 70% by mass) of light fractions from ethylene bottom oil by distillation or the like.
  • the high boiling point component obtained at this time is called the ethylene bottom oil heavy fraction.
  • Ethylene bottom oil, ethylene bottom oil heavy fraction, and other heavy oils may be added to the ethylene bottom oil light fraction as long as it falls within the range of the above-mentioned preferred composition.
  • the other heavy oils are not particularly limited, but examples include fluid catalytic cracking oil (FCC decant oil), atmospheric distillation residual oil, vacuum distillation residual oil, various petroleum heavy oils hydrotreated, cracked kerosene, and coal tar.
  • the sulfur and nitrogen contents in the pitch are preferably low because they cause puffing during firing.
  • these metal components evaporate during graphitization, and the density of the graphite electrode decreases, which may be undesirable in terms of product quality.
  • the other heavy oils are preferably low in sulfur, nitrogen, and metal components.
  • fluid catalytic cracking oil (FCC decant oil) and cracked kerosene are preferred.
  • fluid catalytic cracking oil (FCC decant oil) vary depending on the feedstock, operating conditions, etc., but generally have a 50% distillation temperature of 300°C to 450°C, a flash point of 60°C to 160°C, and a 40°C kinematic viscosity of less than 40 mm2 /s. However, since fluid catalytic cracking oil (FCC decant oil) is a complex mixture, the above values may vary somewhat.
  • the petroleum-based heavy oil is an ethylene bottom oil light fraction.
  • Cracked kerosene is a mixture of hydrocarbons, mainly containing 9 or more carbon atoms, produced in petrochemical processes, and is a fraction with a boiling point in the range of 90°C to 230°C at 1 atmosphere. However, because cracked kerosene is a mixture of hydrocarbons, the number of carbon atoms and boiling point may vary slightly.
  • cracked kerosene include, for example, xylene, styrene, allylbenzene, propylbenzene, methylethylbenzene, trimethylbenzene, methylstyrene, dicyclopentadiene, indane, indene, methylpropylbenzene, methylpropenylbenzene, ethylstyrene, divinylbenzene, methylindene, naphthalene, and methyldicyclopentadiene.
  • Step 1 is a step of heat treating petroleum heavy oil.
  • the heat treatment is preferably carried out in a closed vessel in a non-oxidizing gas atmosphere.
  • the non-oxidizing gas include nitrogen gas, argon, hydrogen gas, lower alkanes such as methane and ethane, and mixed gases of these non-oxidizing gases. Nitrogen gas is preferred from the viewpoint of cost and ease of handling.
  • the heat treatment temperature is preferably 380°C or higher, more preferably 400°C or higher, and even more preferably 410°C or higher.
  • the heat treatment temperature is preferably 500°C or lower, more preferably 480°C or lower, and even more preferably 450°C or lower. These upper and lower limit values can be combined as desired.
  • the preferred range is 380°C to 500°C, more preferably 400°C to 480°C, and even more preferably 410°C to 450°C.
  • the appropriate heat treatment time varies depending on the heat treatment temperature.
  • the heat treatment temperature is 380°C to 400°C, 8 to 48 hours are preferable, and 16 to 48 hours are more preferable, from the time the specified heat treatment temperature is reached (same below).
  • the heat treatment temperature is between 400°C and 430°C, 1 to 24 hours are preferable, and 3 to 16 hours are more preferable.
  • the heat treatment temperature is between 430°C and 500°C, 0.1 to 16 hours are preferable, and 0.5 to 8 hours are more preferable.
  • the upper and lower limits of the appropriate heat treatment time for each heat treatment temperature condition can be combined arbitrarily.
  • the pressure at the start of the heat treatment is preferably 0 MPaG, but there is no particular limit.
  • the pressure inside the sealed container rises due to hydrogen and lower alkanes such as methane and ethane that are generated by thermal decomposition that occurs during the heat treatment. There is no limit to the pressure inside the sealed container, and it is possible to release the pressure as necessary. However, carrying out the process under pressurized conditions is preferable because this tends to increase the yield of base pitch obtained in step 2.
  • the preferred pressure range when carrying out the process under pressurized conditions is, for example, about 0.1 MPaG to 15 MPaG.
  • a solid catalyst may be added during the heat treatment, but in that case, a step for removing the solid catalyst must be added before step 3.
  • Step 2 is a step of removing low boiling points by distilling the heat-treated product obtained in step 1, and obtaining a pitch (base pitch) having the desired characteristics as a high boiling point component.
  • the distillation method in step 2 may be any of atmospheric distillation, reduced pressure distillation (vacuum distillation), or a combination of atmospheric distillation and reduced pressure distillation, and can be appropriately selected. It is preferable that the internal temperature of the distillation apparatus does not exceed 360°C. If the temperature exceeds 360°C, reactions such as polymerization are likely to occur, and coking may occur on the inner wall of the distillation apparatus.
  • the lower limit temperature does not affect the characteristics of the pitch, but if the temperature is low, the distillation pressure must be lowered to distill off the low boiling points, so that 200°C or higher is preferable from the viewpoint of economy.
  • the pressure during distillation is preferably 100 PaA to 10,000 PaA, more preferably 500 PaA to 3,000 PaA, and even more preferably 800 PaA to 2,000 PaA.
  • the higher the distillation end point the higher the initial boiling point.
  • the distillation end point converted into normal pressure is preferably 320° C. or higher, more preferably 330° C. or higher.
  • the softening point of the base pitch of one embodiment obtained in step 2 is preferably 60°C or higher, more preferably 65°C or higher.
  • the softening point of the base pitch of one embodiment obtained in step 2 is preferably 110°C or lower, more preferably 100°C or lower. These upper and lower limit values can be arbitrarily combined.
  • a preferred range is 60°C to 110°C, more preferably 65°C to 100°C.
  • a softening point of 60°C to 110°C is preferable because the softening point of the resulting binder pitch will be 70°C to 120°C.
  • the softening point is measured by the method described in the Examples section.
  • the fixed carbon content of the base pitch of one embodiment obtained in step 2 is preferably 49.0% by mass or more, and more preferably 50.0% by mass or more. Although it depends on the type and amount of carbon powder added and mixed in step 3, if the fixed carbon content is 49.0% by mass or more, the fixed carbon content of the resulting binder pitch will be 50.0% by mass or more, which is preferable.
  • the upper limit of the fixed carbon content is not particularly limited, but is, for example, 75.0% by mass or 85.0% by mass. The fixed carbon content is measured by the method described in the Examples section.
  • the initial boiling point of the base pitch is preferably 320°C or higher, and more preferably 330°C or higher. Although it depends on the conditions of step 3, if the initial boiling point of the base pitch is 320°C or higher, the initial boiling point of the resulting binder pitch is also preferably 320°C or higher.
  • the upper limit of the initial boiling point of the base pitch in one embodiment is not particularly limited as long as the softening point of the resulting base pitch is 60°C to 110°C, but is preferably 450°C or lower, and more preferably 400°C or lower. These upper and lower limits can be combined in any combination.
  • the preferred range is 320 to 450°C, and more preferably 330 to 400°C.
  • the initial boiling point is measured by the method described in the Examples section.
  • the quinoline insolubles (QI) of the base pitch in one embodiment is preferably 1.0 mass% or less, more preferably 0.5 mass% or less, and even more preferably 0.1 mass% or less.
  • the lower limit of the QI of the base pitch is not particularly limited, but is, for example, 0.0 mass% or 0.001 mass%. The QI is measured by the method described in the Examples section.
  • Step 3 is a step of adding carbon powder to the base pitch obtained in step 2 and mixing it.
  • the carbon powder used improves the Casson yield value of the binder pitch without deteriorating the kneadability of the resulting binder pitch.
  • carbon powder having a particle size of about 1 nm to 20 ⁇ m can be used.
  • the particle size of particles of 10 nm or more is determined by a laser diffraction/scattering method.
  • the particle size of particles less than 10 nm means the arithmetic mean diameter measured by observation under an electron microscope.
  • graphite powder examples include artificial graphite powder, natural graphite powder, coke powder, and free carbon powder in coal tar (primary QI). Among these, artificial graphite powder and coke powder are preferred. Carbon powders and the like can also be used. The carbon powders can be used alone or in combination. In one embodiment, the carbon powder is artificial graphite powder.
  • the amount of carbon powder added is preferably 1.0 part by mass or more, more preferably 3.0 parts by mass or more, and even more preferably 5.0 parts by mass or more, relative to 100 parts by mass of base pitch.
  • the amount of carbon powder added is preferably 22.0 parts by mass or less, more preferably 18.0 parts by mass or less, and even more preferably 11.0 parts by mass or less, relative to 100 parts by mass of base pitch.
  • These upper and lower limit values can be arbitrarily combined.
  • the preferred range is 1.0 part by mass or more and 22.0 parts by mass or less, more preferably 3.0 parts by mass or more and 18.0 parts by mass or less, and even more preferably 5.0 parts by mass or more and 11.0 parts by mass or less, relative to 100 parts by mass of base pitch.
  • the quinoline insolubles in the obtained binder pitch will be 18.0 mass% or less, and the Casson yield value can be improved without deteriorating the kneadability, and therefore the carbonization rate can be improved.
  • the method for mixing the base pitch and carbon powder is not particularly limited, but a method that thoroughly disperses the carbon powder in the base pitch is preferred.
  • a method of mixing base pitch and carbon powder at a temperature equal to or higher than the softening point of the base pitch can be mentioned.
  • the mixing temperature is preferably 350°C or lower, more preferably 250°C or lower, and even more preferably 200°C or lower.
  • the mixing time is not particularly limited, but is, for example, 5 minutes to 24 hours. Although it depends on the mixing conditions, it is possible to well disperse the carbon powder in the base pitch within the above range.
  • the mixing atmosphere is not particularly limited, and it can be performed under air or a non-oxidizing gas atmosphere, but it is preferable to perform it under a non-oxidizing gas atmosphere from the viewpoint of minimizing the deterioration of the base pitch that may occur during mixing.
  • non-oxidizing gases include nitrogen gas, argon, hydrogen gas, lower alkane gas such as methane and ethane, and mixed gases of these non-oxidizing gases. Among these, nitrogen gas is preferable from the viewpoint of cost and ease of handling.
  • the mixing device is not particularly limited, but for example, a heatable mixer, kneader, etc. can be used.
  • mixing methods include dissolving the base pitch in a suitable solvent and mixing it with carbon powder. In this case, a process of removing the solvent by vacuum distillation or the like is required after mixing.
  • suitable solvents There are no particular limitations on suitable solvents as long as they can dissolve the base pitch well, but benzene, toluene, xylene, quinoline, pyridine, and mixtures thereof are preferred.
  • Fractions containing large amounts of benzene and toluene obtained in petrochemical processes can also be used. Examples of such fractions include cracked gasoline and cracked kerosene.
  • Cracked gasoline is a mixture of hydrocarbons, mainly containing 6 to 8 carbon atoms, produced in a petrochemical process, and is a fraction with a boiling point in the range of 65°C to 150°C at 1 atmosphere.
  • cracked gasoline is a mixture of hydrocarbons, the number of carbon atoms and boiling point may vary slightly.
  • cracked gasoline examples include, for example, benzene, toluene, ethylbenzene, xylene, styrene, and hexane.
  • Mixing using a solvent can be performed at room temperature or under heated conditions. When mixing at normal pressure, mixing is preferably performed below the boiling point of the solvent used. When mixing at a temperature above the boiling point of the solvent used, mixing can be performed under reflux conditions or under pressure using a sealed container. Although it depends on the mixing conditions, the mixing temperature is preferably 350°C or less, more preferably 250°C or less, and even more preferably 200°C or less. Although it depends on the mixing conditions, if it is 350°C or less, it is possible to minimize the deterioration of the base pitch that may occur during mixing.
  • the mixing time is not particularly limited, but is, for example, 5 minutes to 24 hours.
  • the carbon powder can be well dispersed in the base pitch.
  • the mixing atmosphere is not particularly limited, and can be performed under air or a non-oxidizing gas atmosphere, but it is preferable to perform it under a non-oxidizing gas atmosphere from the viewpoint of minimizing the deterioration of the base pitch that may occur during mixing.
  • non-oxidizing gases include nitrogen gas, argon, hydrogen gas, lower alkanes such as methane and ethane, and mixed gases of these non-oxidizing gases. Of these, nitrogen gas is preferred from the standpoint of cost and ease of handling.
  • the method for removing the solvent is not particularly limited, but a method that can efficiently remove the solvent without altering the base pitch is preferable.
  • Examples of such a solvent removal method include distillation.
  • the distillation method in this case may be normal pressure distillation, reduced pressure distillation (vacuum distillation), or a combination of normal pressure distillation and reduced pressure distillation, and can be selected as appropriate.
  • the internal temperature of the distillation apparatus does not exceed 360°C. This is because if it exceeds 360°C, reactions such as polymerization are likely to occur, and the base pitch may be altered.
  • the lower limit temperature and the pressure when performing reduced pressure distillation (vacuum distillation) do not affect the physical properties of the base pitch, so the conditions can be selected as appropriate depending on the type of solvent used.
  • ⁇ Method of manufacturing carbon material> pitch having a softening point of 70° C. to 120° C., a fixed carbon content of 50.0% by mass or more, a quinoline insoluble content of 18.0% by mass or less, an initial boiling point of 320° C. or more, and a Casson yield value of 0.18 Pa or more at a softening point +100° C.
  • the carbon material refers to various molded carbon materials such as graphite tubes, graphite crucibles, graphite boats, and graphite electrodes. The manufacturing process of exemplary carbon materials such as graphite electrodes will be described below. 1.
  • Kneading process A process of mixing and kneading needle coke and binder pitch together; 2. Molding process: A process of molding the mixture to obtain a molded body of a predetermined size and shape; 3. Firing process: A process of firing the molded body to obtain a fired body; 4. Impregnation process: A process of filling the fired body with impregnated pitch; 5. Re-firing process: A process of firing the fired body filled with impregnated pitch again to obtain a re-fired body; 6. Graphitization process: A process of graphitizing the re-fired body to obtain a graphitized body; 7. Processing process: A process of molding the graphitized body into a predetermined shape by cutting or the like to produce carbon materials such as graphite electrodes.
  • Kneading process The needle coke that has been crushed, classified, and blended in a predetermined particle size ratio is mixed and kneaded together with the binder pitch.
  • the blending amount of the binder pitch varies depending on the kneading method and the molding method, but is generally about 20 parts by mass to 30 parts by mass per 100 parts by mass of the needle coke.
  • the kneaded material may contain a puffing inhibitor such as iron oxide.
  • mixers or kneaders can be used for mixing and kneading. Specific examples include mixers and kneaders such as mixers and kneaders.
  • the kneading temperature varies depending on the binder pitch used, but is generally around 130°C to 170°C. After kneading, the kneaded product is cooled to a temperature suitable for subsequent molding (for example, 100°C to 130°C).
  • the binder pitch used has a softening point of 70°C to 120°C, a fixed carbon content of 50.0% by mass or more, a quinoline insoluble content of 18.0% by mass or less, an initial boiling point of 320°C or more, and a Casson yield value at softening point + 100°C of 0.18 Pa or more. Details of the pitch are as described above.
  • the kneaded material is molded to obtain a molded body of a desired size and shape.
  • the molding method can be appropriately selected from extrusion molding, molding, etc. depending on the target carbon material.
  • the target carbon material is a graphite electrode
  • extrusion molding into a cylindrical shape is generally used.
  • Firing process The molded body from the previous process is heated and fired at 700°C to 1000°C to obtain a fired body.
  • the firing process is preferably carried out in a non-oxidizing atmosphere of combustion exhaust gas.
  • the molded body softens at the beginning of the temperature rise, and at 200°C to 500°C, a large amount of decomposition gas is generated by thermal decomposition and polycondensation of the binder pitch, resulting in the formation of pores and volumetric shrinkage.
  • the binder pitch is carbonized.
  • Impregnation process In the firing process, generally, 35% to 45% of the mass of the binder pitch is lost as a volatile matter. At that time, a large number of pores are generated in the fired body. The impregnation process involves filling these pores with impregnation pitch. Impregnation is carried out, for example, by placing the fired body in an autoclave, degassing it under reduced pressure, and then injecting molten impregnation pitch into the pores at about 200°C and a gas pressure of about 1 MPa.
  • the softening point of the impregnated pitch used is preferably 80°C to 120°C.
  • the amount of fixed carbon is preferably 45.0% by mass or more, and more preferably 50.0% by mass or more.
  • Re-firing process The fired body filled with the impregnated pitch is fired again to obtain a re-fired body.
  • the re-firing process can be performed under the same conditions as the firing process.
  • the impregnation process and the re-firing process can be repeated as necessary.
  • the re-burned body is placed in a furnace (such as an Acheson furnace or an LWG furnace) surrounded by an insulating material, and the re-burned body is subjected to a heat treatment using packing coke or resistance heating of the re-burned body due to electrical current.
  • the graphitization temperature is 2000°C to 3000°C. This temperature is necessary to convert the amorphous carbon in the re-burned body into crystalline graphite. It is preferable to heat treat the re-burned body for several days to convert it into a graphitized body.
  • the graphitized body is machined, for example, by cutting, to form a carbon material of a predetermined shape, for example, a graphite electrode product.
  • the density (bulk density) of the graphite electrode varies depending on the electric furnace equipment used and the operating conditions of the electric furnace, but is preferably 1.5 g/cm 3 to 1.9 g/cm 3 .
  • FIG. 3 shows the measurement results of Example 1.
  • the yield value was calculated using Casson formula (1) based on the measured data.
  • FIG. 4 shows the Casson plot of Example 1.
  • the devices used for the measurement are as follows. Rotational viscometer (Brookfield, DV-II + Pro) Thermocell (Brookfield, HT-110115 ADP) Spindle (Brookfield, SC4-21) Chamber (Brookfield, HT-2DB-100)
  • ⁇ Method for measuring true density of pitch The true density of the pitch was measured by a constant volume expansion method using an Accupyk II 1340 (Micromeritics) at 25° C. using helium as a replacement gas.
  • the molded body was fired at about 1000 ° C. to produce a fired body.
  • the density of the molded body and the fired body was measured in accordance with JIS R 7222: 2017 "Method for measuring physical properties of graphite material 7. Method for measuring bulk density”.
  • the carbonization rate was calculated using formula (2).
  • the artificial graphite powder used was fine artificial graphite powder (UF-G5) (Resonac Corporation, particle size: 3 ⁇ m), and the carbon black powder used was carbon black (MA230) (Mitsubishi Chemical Corporation, particle size: 30 nm).
  • Example 1 3000 g of ethylene bottom oil light fraction was introduced into a 6.0 L capacity SUS autoclave. The autoclave was sealed under a nitrogen gas atmosphere, and the inside of the container was heated to 430 ° C. at a rate of 4 ° C. / min while stirring, and heat treatment was performed. After 6 hours had passed since the temperature reached 430 ° C., the heat-treated product was allowed to cool to room temperature and taken out. The heat-treated product was subjected to vacuum distillation using a vacuum distillation apparatus to distill off low boiling point components, and 720 g (yield 24%) of base pitch A was obtained as a high boiling point component.
  • the obtained base pitch A 110.4 g and artificial graphite powder: 9.6 g were placed in a metal beaker, heated to 140 ° C. in an oil bath, and heated and mixed for 30 minutes using a three-one motor to prepare 120 g of binder pitch, and various evaluations were performed.
  • Comparative Example 2 114 g of the base pitch A obtained in Example 1 and 6 g of carbon black powder were placed in a metal beaker, heated to 140° C. in an oil bath, and heated and mixed for 30 minutes using a Three-One Motor to prepare 120 g of binder pitch, and various evaluations were performed.
  • the obtained base pitch B 110.4 g and artificial graphite powder: 9.6 g were placed in a metal beaker, heated to 140°C in an oil bath, and heated and mixed for 30 minutes using a three-one motor to prepare 120 g of binder pitch, and various evaluations were performed.

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  • Compositions Of Macromolecular Compounds (AREA)
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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5679190A (en) * 1980-11-28 1981-06-29 Nippon Carbon Co Ltd Production of binder for carbonaceous material
JPS60179493A (ja) 1984-02-27 1985-09-13 Mitsubishi Petrochem Co Ltd エチレンヘビ−エンドの処理方法
JPS60240790A (ja) 1984-05-15 1985-11-29 Mitsubishi Petrochem Co Ltd エチレンヘビ−エンドの処理法
JPH02258892A (ja) * 1989-01-09 1990-10-19 Conoco Inc バインダピッチの調製方法
JPH05279668A (ja) * 1992-03-31 1993-10-26 Mitsubishi Kasei Corp バインダーピッチの製造方法
JPH05279669A (ja) * 1992-04-02 1993-10-26 Mitsubishi Kasei Corp バインダーピッチの製造方法
JPH05279667A (ja) * 1992-03-31 1993-10-26 Mitsubishi Kasei Corp バインダーピッチの製造方法
US6352637B1 (en) 1998-12-31 2002-03-05 Marathon Ashland Petroleum, Llc High coking value pitch
JP2013237747A (ja) * 2012-05-14 2013-11-28 Jfe Chemical Corp バインダーピッチおよびその製造方法
JP2016204546A (ja) * 2015-04-24 2016-12-08 Ｊｆｅケミカル株式会社 バインダーピッチ及びその製造方法
JP2017218486A (ja) * 2016-06-06 2017-12-14 Ｊｆｅケミカル株式会社 バインダーピッチ及びその製造方法
WO2022049953A1 (ja) * 2020-09-03 2022-03-10 昭和電工株式会社 ピッチの製造方法

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5679190A (en) * 1980-11-28 1981-06-29 Nippon Carbon Co Ltd Production of binder for carbonaceous material
JPS60179493A (ja) 1984-02-27 1985-09-13 Mitsubishi Petrochem Co Ltd エチレンヘビ−エンドの処理方法
JPS60240790A (ja) 1984-05-15 1985-11-29 Mitsubishi Petrochem Co Ltd エチレンヘビ−エンドの処理法
JPH02258892A (ja) * 1989-01-09 1990-10-19 Conoco Inc バインダピッチの調製方法
JPH05279668A (ja) * 1992-03-31 1993-10-26 Mitsubishi Kasei Corp バインダーピッチの製造方法
JPH05279667A (ja) * 1992-03-31 1993-10-26 Mitsubishi Kasei Corp バインダーピッチの製造方法
JPH05279669A (ja) * 1992-04-02 1993-10-26 Mitsubishi Kasei Corp バインダーピッチの製造方法
US6352637B1 (en) 1998-12-31 2002-03-05 Marathon Ashland Petroleum, Llc High coking value pitch
JP2013237747A (ja) * 2012-05-14 2013-11-28 Jfe Chemical Corp バインダーピッチおよびその製造方法
JP2016204546A (ja) * 2015-04-24 2016-12-08 Ｊｆｅケミカル株式会社 バインダーピッチ及びその製造方法
JP2017218486A (ja) * 2016-06-06 2017-12-14 Ｊｆｅケミカル株式会社 バインダーピッチ及びその製造方法
WO2022049953A1 (ja) * 2020-09-03 2022-03-10 昭和電工株式会社 ピッチの製造方法

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