WO2025013371A1 - バインダーピッチの製造方法 - Google Patents

バインダーピッチの製造方法 Download PDF

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WO2025013371A1
WO2025013371A1 PCT/JP2024/015540 JP2024015540W WO2025013371A1 WO 2025013371 A1 WO2025013371 A1 WO 2025013371A1 JP 2024015540 W JP2024015540 W JP 2024015540W WO 2025013371 A1 WO2025013371 A1 WO 2025013371A1
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Prior art keywords
pitch
mass
carbon
less
binder pitch
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French (fr)
Japanese (ja)
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祐太朗 石川
信宏 西
啓介 太田
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Resonac Corp
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Resonac Corp
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Priority to CN202480001950.8A priority Critical patent/CN119585399A/zh
Priority to JP2024547917A priority patent/JP7841604B2/ja
Publication of WO2025013371A1 publication Critical patent/WO2025013371A1/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

Definitions

  • the present disclosure relates to a method for producing binder pitch for carbon materials such as graphite electrodes.
  • 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.
  • Heavy residual oil (ethylene bottom oil), a by-product of the production of olefins such as ethylene and propylene by steam cracking or thermal cracking of petroleum hydrocarbons such as naphtha, is mostly used as fuel, with only a portion of it being used as a raw material for carbon black. Therefore, converting this ethylene bottom oil into a product with high added value is a challenge in the field. In order to solve this challenge, attempts have been made to utilize the characteristics of ethylene bottom oil, which contains a large amount of aromatic compounds, to produce binder pitch for carbon materials from ethylene bottom oil.
  • petroleum pitch produced from petroleum heavy oils such as ethylene bottom oil has a lower carbonization rate than coal tar pitch, which has the same softening point as the petroleum pitch, and the density of the carbon material obtained tends to be lower. Therefore, petroleum pitch is not currently used very often.
  • binder pitch some of the most important are the carbonization rate, softening point, and initial boiling point.
  • the softening point is too high, kneadability and moldability decrease, so it is preferable that it is about 120°C or lower.
  • the initial boiling point is too low, a large amount of light components volatilize during kneading, which causes an increase in viscosity during kneading and decreases kneadability and moldability, so it is preferable that it is about 320°C or higher.
  • one method of increasing the carbonization rate and initial boiling point of binder pitch is to remove light components in the pitch by distillation, etc., but this has the problem of increasing the softening point at the same time.
  • Patent Document 1 As a method for improving the carbonization rate while suppressing the rise in the softening point to some extent, there is a method of adding cutback oil to pitch with a relatively high carbonization rate and high softening point (Patent Document 1).
  • Patent Document 1 requires the addition of cutback oil, which has a relatively low boiling point, which results in a problem of a lower initial boiling point of the resulting pitch. As such, it is difficult to independently adjust these parameters with conventional methods.
  • This disclosure provides a method for producing pitch from petroleum heavy oil that has a high carbonization rate and excellent kneading stability, making it suitable as a binder pitch for carbon materials.
  • a step of heat treating petroleum heavy oil (step 1); a step (step 2) of distilling the heat-treated product obtained in step 1 to obtain, as a high-boiling point component, a base pitch having a softening point of 60° C. or more and 110° C. or less, a fixed carbon content of 50.0% by mass or more, an initial boiling point of 320° C. or more and 450° C.
  • a method for producing a binder pitch for carbon materials comprising the steps of: [2] The method for producing a binder pitch for carbon materials according to [1], wherein the 3% distillation temperature of the base pitch is 340° C. or higher and 470° C. or lower. [3] The method for producing a binder pitch for carbon materials according to [1] or [2], wherein the petroleum heavy oil is an ethylene bottom oil light fraction.
  • [4] The method for producing a binder pitch for carbon materials according to any one of [1] to [3], wherein the carbon powder is at least one selected from the group consisting of graphite powder, coke powder, carbon black powder, and free carbon powder in coal tar.
  • [5] The method for producing a binder pitch for carbon materials according to any one of [1] to [4], wherein the amount of the carbon powder added is 1.0 part by mass or more and 22.0 parts by mass or less with respect to 100 parts by mass of the base pitch.
  • [6] The method for producing a binder pitch for carbon materials according to any one of [1] to [5], wherein the softening point of the binder pitch for carbon materials obtained in step 3 is 80° C. or higher and 120° C. or lower, and the quinoline insoluble content is 18.0 mass% or less.
  • [7] The method for producing a binder pitch for carbon materials according to any one of [1] to [6], wherein the carbon material is a graphite electrode.
  • a pitch suitable as a binder pitch for carbon materials can be obtained from petroleum-based heavy oil. Specifically, a binder pitch for carbon materials with a high carbonization rate and excellent kneading stability can be obtained. By using this binder pitch in the production of carbon materials, a high-density carbon material can be obtained.
  • 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.
  • a method for producing binder pitch 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 50.0 mass% or more, an initial boiling point of 320°C to 450°C, 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 them 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 referred to 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, 3 to 48 hours are preferable, and 6 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.
  • a base pitch having physical properties particularly suitable for the production of carbon materials such as graphite electrodes can be obtained.
  • This base pitch can be used as a binder pitch and an impregnation pitch when producing carbon materials such as graphite electrodes.
  • 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.
  • additives such as solid catalysts may be added during the heat treatment of petroleum-based heavy oil, but in that case, an additive removal step must be added prior to 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 having desired properties as a high boiling point component.
  • the pitch having the desired properties is called "base pitch”.
  • 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 properties 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 60°C or higher, and more preferably 70°C or higher.
  • the softening point of the base pitch of one embodiment obtained in step 2 is 110°C or lower, and more preferably 100°C or lower. These upper and lower limit values can be combined as desired.
  • a preferred range is 60°C or higher and 110°C or lower, and more preferably 70°C or higher and 100°C or lower.
  • a softening point of 60°C or higher and 110°C or lower is preferable because the softening point of the resulting binder pitch is 80°C or higher and 120°C or lower.
  • the softening point is measured by the method described in the Examples section.
  • the fixed carbon content of the base pitch in one embodiment is 50.0% by mass or more, and more preferably 51.0% by mass or more.
  • 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 softening point of the base pitch may exceed 110°C, depending on the raw materials and heat treatment conditions in step 1, so the initial boiling point is preferably 450°C or lower.
  • the initial boiling point is measured by the method described in the Examples section.
  • the 3% distillation temperature of the base pitch in one embodiment is preferably 340°C or higher, more preferably 380°C or higher.
  • the 3% distillation temperature of the base pitch in one embodiment is preferably 470°C or lower, more preferably 450°C or lower. These upper and lower limits can be combined as desired.
  • a preferred range is 340°C or higher and 470°C or lower, more preferably 380°C or higher and 450°C or lower.
  • the 3% distillation temperature is 340°C or higher, the amount of light matter volatilized at the kneading temperature (e.g., 150°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.
  • the 3% distillation temperature exceeds 470°C, depending on the raw materials and heat treatment conditions in step 1, the softening point of the base pitch may exceed 110°C, so the 3% distillation temperature is preferably 470°C or lower.
  • the 3% distillation temperature is measured by the method described in the Examples section.
  • Step 3 is a step of adding and mixing carbon powder to the base pitch obtained in step 2.
  • the carbon powder used is one that improves the carbonization rate without deteriorating the kneadability and moldability 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 measured 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.
  • 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 carbonization rate can be improved without deteriorating the kneadability and moldability.
  • 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 include benzene, toluene, xylene, quinoline, pyridine, and mixtures thereof. Fractions that are rich in benzene and toluene obtained from 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 gas, 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.
  • the total content of carbon powder in the binder pitch of one embodiment obtained in step 3 is preferably 1.0 to 18.0 mass%, more preferably 3.0 to 15.0 mass%, and even more preferably 5.0 to 10.0 mass%.
  • the softening point of the binder pitch of one embodiment obtained in step 3 is preferably 80°C or higher, and more preferably 90°C or higher.
  • the softening point of the binder pitch of one embodiment obtained in step 3 is preferably 120°C or lower, and more preferably 110°C or lower. These upper and lower limit values can be combined as desired.
  • a preferred range is 80°C or higher and 120°C or lower, and more preferably 90°C or higher and 110°C or lower. If the range is 80°C or higher and 120°C or lower, the pitch can be sufficiently softened at the kneading temperature (e.g., 140°C to 180°C), and therefore exhibits good kneadability.
  • the softening point is measured by the method described in the Examples section.
  • the quinoline insoluble content of the binder pitch of one embodiment obtained in step 3 is preferably 18.0 mass% or less, more preferably 15.0 mass% or less, and even more preferably 10.0 mass% or less. If it is 18.0 mass% or less, the binder pitch can sufficiently wet the needle coke surface in the kneading step, which is one of the manufacturing steps of the graphite electrode, and therefore exhibits good moldability.
  • the quinoline insoluble content of the binder pitch of one embodiment obtained in step 3 is preferably 1.0 mass% or more, more preferably 3.0 mass% or more, and even more preferably 5.0 mass% or more.
  • the quinoline insoluble content of the binder pitch includes the quinoline insoluble content contained in the base pitch as well as the carbon powder added in step 3. The quinoline insoluble content is measured by the method described in the Examples section.
  • the carbon materials refer to various molded carbon materials such as graphite tubes, graphite crucibles, graphite boats, graphite electrodes, etc.
  • the general manufacturing process for graphite electrodes is described below.
  • 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 a graphite electrode.
  • 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, kneaders, and other mixers and kneaders.
  • the kneading temperature varies depending on the binder pitch used, but is generally around 140°C to 180°C. After kneading, the mixture is cooled to a temperature suitable for subsequent molding (for example, 100°C to 130°C).
  • the softening point of the binder 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.
  • 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, such as by cutting, to form a graphite electrode product of a predetermined shape.
  • 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 .
  • TI ⁇ Method for measuring toluene insoluble matter (TI)> The toluene insoluble matter (TI) was measured in accordance with the filtration method described in "14.2 Quantitative method for toluene insoluble matter in processed tar and tar pitch" of JIS K 2425:2006 "Test methods for creosote oil, processed tar and tar pitch”.
  • ⁇ 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 (1).
  • 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).
  • the base pitch was placed in a beaker and heated to a predetermined temperature in an oil bath to dissolve the base pitch. Carbon powder was added thereto and mixed using a three-one motor to prepare a binder pitch.
  • the type of carbon powder used, the amount of carbon powder added, the mixing temperature, and the mixing time are as described in the Examples and Comparative Examples.
  • 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 of base pitch (yield 24%) was obtained as a high boiling point component. The physical properties of the obtained base pitch are as shown in Table 1. 9.6 g of artificial graphite powder was added to 110.4 g of the base pitch, and 120 g of binder pitch was prepared by heating and mixing at 140 ° C. for 30 minutes using a three-one motor, and various evaluations were performed.
  • Example 2 6 g of carbon black powder was added to 114 g of the base pitch obtained in Example 1, and the mixture was heated and mixed at 140° C. for 30 minutes using a Three-One Motor to prepare 120 g of binder pitch, and various evaluations were performed.
  • Example 1 Comparing the electrode evaluation results of Example 1, Example 2, and Comparative Example 3, it can be seen that the carbonization rate is improved by adding carbon powder, and the density of the resulting sintered body is also improved.
  • Example 1 and Comparative Example 1 it can be seen that even if the same carbon powder is used, if the physical properties of the base pitch are not appropriate, the effect cannot be fully obtained. That is, the binder pitch of Comparative Example 1 has the same fixed carbon amount and true density as Example 1, but the initial boiling point of the base pitch is low. Therefore, the stability at the kneading temperature is low, and the viscosity increases during kneading (see Figure 2).
  • the base pitch of Comparative Example 2 has poor stability during kneading because the softening point, fixed carbon amount, and initial boiling point are not appropriate, and the carbonization rate and sintered body density are also significantly low. From the above, it is clear that it is important to add carbon powder to a base pitch having an appropriate softening point, fixed carbon amount, initial boiling point, and quinoline insoluble matter (QI).

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Citations (8)

* 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
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
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 (8)

* 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
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
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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