WO2023233847A1 - 石油系ピッチの製造方法及び石油系ピッチ - Google Patents

石油系ピッチの製造方法及び石油系ピッチ Download PDF

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Publication number
WO2023233847A1
WO2023233847A1 PCT/JP2023/015323 JP2023015323W WO2023233847A1 WO 2023233847 A1 WO2023233847 A1 WO 2023233847A1 JP 2023015323 W JP2023015323 W JP 2023015323W WO 2023233847 A1 WO2023233847 A1 WO 2023233847A1
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Prior art keywords
pitch
petroleum
mass
heat treatment
toluene
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Ceased
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PCT/JP2023/015323
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English (en)
French (fr)
Japanese (ja)
Inventor
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 EP23815608.7A priority Critical patent/EP4534629A1/en
Priority to CN202380020454.2A priority patent/CN118647691A/zh
Priority to US18/850,380 priority patent/US20250207034A1/en
Priority to JP2024524227A priority patent/JP7737554B2/ja
Publication of WO2023233847A1 publication Critical patent/WO2023233847A1/ja
Anticipated expiration legal-status Critical
Priority to JP2025126673A priority patent/JP2025160373A/ja
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C10C3/002—Working-up pitch, asphalt, bitumen by thermal means
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C10C3/06—Working-up pitch, asphalt, bitumen by distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/205—Preparation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C10C3/08—Working-up pitch, asphalt, bitumen by selective extraction
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step
    • C10G53/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step including only extraction steps, e.g. deasphalting by solvent treatment followed by extraction of aromatics
    • 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
    • C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
    • C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
    • C10G55/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one thermal cracking step
    • 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 invention relates to a petroleum-based pitch suitable for impregnated pitch used in the production of carbon materials such as graphite electrodes, and a method for producing the same.
  • Carbon materials such as graphite electrodes used in electric furnaces that remelt iron are made by kneading and forming aggregates such as coke and pitch (referred to as "binder pitch") at a temperature above the softening point of the binder pitch, and then firing. It is then produced by graphitizing. Since the carbon material is required to have properties such as high mechanical strength, high electrical conductivity and high thermal conductivity, it is preferable that the carbon material has high density. However, due to the volatilization of low molecular weight components in the binder pitch during the firing process, the fired body has a structure with many pores.
  • impregnated pitch is essential for producing high quality carbon materials.
  • ethylene bottom oil Some of the heavy residual oil (ethylene bottom oil) that is produced as a by-product when producing olefins such as ethylene and propylene by steam cracking or thermal cracking of petroleum hydrocarbons such as naphtha is used as a raw material for carbon black. The majority of it is used as fuel. Therefore, converting this ethylene bottom oil into products with high added value is a challenge in the technical field. In order to solve this problem, attempts have been made to utilize the characteristics of ethylene bottom oil, which contains a large amount of aromatic compounds, to produce impregnated pitch for carbon material production, binder pitch for carbon material production, etc. from ethylene bottom oil.
  • petroleum-based pitch produced from petroleum-based heavy oil such as ethylene bottom oil has a lower amount of fixed carbon than coal tar pitch produced from coal tar, so the resulting carbon material tends to have a lower density. It is in. Therefore, at present, petroleum-based pitches are not often used.
  • impregnability and fixed carbon content are some of the most important.
  • Various methods are known for improving the impregnating properties of coal tar pitch, and a representative example is a method of removing or reducing quinoline insoluble content (QI) in the pitch.
  • QI quinoline insoluble content
  • Coal tar pitch usually contains several mass % to several tens of mass % of QI derived from the primary QI contained in the raw material coal tar and the secondary QI that may be generated in the heat treatment process. Since this QI exists as solid fine particles even when the pitch is melted in the impregnation step, it significantly inhibits pitch from penetrating into the pores of the fired body. Therefore, it is desirable that the pitch impregnated with coal tar contains substantially no QI (Patent Document 1).
  • petroleum-based heavy oil especially ethylene bottom oil
  • Patent Document 2 JP-A-60-92388 (Patent Document 2), it is possible to produce petroleum-based pitch with a QI content of 1% by mass or less from petroleum-based heavy oil without a QI removal or reduction step, It has been reported that the obtained petroleum pitch can be suitably used as an impregnated pitch.
  • Patent Document 2 many of the petroleum-based pitches that have been reported so far, including the petroleum-based pitch described in Patent Document 2, have a lower amount of fixed carbon than coal tar pitch that has an equivalent softening point (Patent Document 2 and Non-patent document 1).
  • One method for increasing the amount of fixed carbon in petroleum-based pitch is to remove light components from the pitch by distillation or the like, but this also increases the softening point and viscosity, resulting in a decrease in impregnating properties. Therefore, using conventional methods, it is difficult to produce petroleum-based pitch that has both good impregnability and a high amount of fixed carbon.
  • An object of the present invention is to provide a petroleum-based pitch that has excellent impregnation into a fired body during the production of carbon materials such as graphite electrodes and has a high amount of fixed carbon, and a method for producing the same.
  • “petroleum-based pitch” refers to pitch manufactured from heavy oil derived from petroleum.
  • the present inventors have made extensive studies to achieve the above objective. Specifically, we investigated a method of subjecting heavy petroleum oil to relatively severe heat treatment within a range of conditions that do not cause QI. However, when the present inventors investigated this method, it was possible to obtain a petroleum-based pitch that did not contain QI and had a high amount of fixed carbon, but it became clear that its impregnability was extremely poor (in this specification (See Comparative Example 1, Comparative Example 3, and Comparative Example 4 in the book). This suggests that factors other than QI have a large influence on the impregnability of petroleum-based pitches manufactured using a manufacturing method that includes a process of heat-treating heavy petroleum oil under relatively harsh conditions. .
  • the present inventors have discovered that the toluene insoluble content (TI), which does not affect impregnability in coal tar pitch, is a petroleum-based pitch produced using a manufacturing method that includes a process of heat-treating petroleum-based heavy oil under relatively harsh conditions. It was discovered that the impregnating property was affected, and the results thereof were embodied in the present invention.
  • TI toluene insoluble content
  • the present invention includes a step of heat-treating petroleum heavy oil (step 1), a step of distilling the heat-treated product obtained in step 1 to obtain pitch 1 as a high boiling point component, and a step (step 2) of heat-treating petroleum-based heavy oil.
  • step 1) a step of heat-treating petroleum heavy oil
  • step 2 a step of heat-treating petroleum-based heavy oil.
  • step 3 A step (step 3) of reducing the toluene insolubles (TI) of the obtained pitch 1 and a step of distilling the component with reduced toluene insolubles (TI) obtained in step 3 to obtain pitch 2 as a high boiling point component.
  • the present invention has a quinoline insoluble content (QI) of 0.5% by mass or less, a toluene insoluble content (TI) of 3.0% by mass or less, a softening point of 60°C to 120°C, and a viscosity of 200mPa at 200°C. s or less, and relates to a petroleum-based pitch in which the amount of fixed carbon Y (mass %) satisfies formula (1). 80.0 ⁇ Y>0.2X+29.5 (1) Y: fixed carbon amount (mass%) X: Softening point (°C) (60 ⁇ X ⁇ 120)
  • the present invention relates to the following [1] to [10].
  • a method for producing petroleum pitch including at least the following steps 1 to 4.
  • Step 1 Heat-treating petroleum-based heavy oil
  • Step 2 Distilling the heat-treated product obtained in Step 1 to obtain pitch 1 as a high-boiling component
  • Step 3 Toluene-insoluble from pitch 1 obtained in Step 2 minutes (TI)
  • Step 4 of obtaining a component with reduced TI Distilling the component with reduced toluene insoluble matter (TI) obtained in step 3
  • [3] The method for producing petroleum pitch according to [1] or [2], wherein the heat treatment temperature in step 1 is 360°C to 500°C.
  • step 3 The removal of toluene-insoluble components (TI) in step 3 is performed by adding a solvent to the pitch 1 and extracting the solvent-soluble components of the pitch 1 into the solvent, and the solvent contains benzene, alkylbenzene, decomposition
  • the method for producing petroleum-based pitch according to any one of [1] to [3], which is at least one selected from the group consisting of gasoline and cracked kerosene.
  • the heat treatment time is 8 hours to 48 hours, and when the heat treatment temperature is over 390 ° C.
  • the heat treatment time is 0.5 hours to 24 hours
  • the quinoline insoluble content (QI) is 0.5% by mass or less
  • the toluene insoluble content (TI) is 3.0% by mass or less
  • the softening point is 60°C to 120°C
  • the viscosity at 200°C is 200 mPa ⁇ s or less.
  • a petroleum-based pitch that uses petroleum-based heavy oil as a raw material, has excellent impregnation properties into a fired body during production of carbon materials such as graphite electrodes, and has a high amount of fixed carbon.
  • This petroleum-based pitch can be easily impregnated into the fired body and has a high amount of fixed carbon, so that the quality of the obtained carbon material can be improved.
  • FIG. 2 is a flow diagram showing an example of a petrochemical process for thermally decomposing petroleum such as naphtha and a process for producing ethylene bottom oil.
  • FIG. 1 is a flow diagram illustrating an embodiment of a method for producing petroleum-based pitch.
  • FIG. 2 is a diagram showing the relationship between the softening point and fixed carbon content of various pitches produced from ethylene bottom oil under different production conditions.
  • the carbon material refers to various shaped carbon materials such as graphite tubes, graphite crucibles, graphite boats, and graphite electrodes.
  • the manufacturing process of a typical graphite electrode will be described below.
  • Kneading process Step of mixing and kneading needle coke and binder pitch together.
  • Molding step Step of molding the kneaded material to obtain a molded body of a predetermined size and shape.3.
  • Firing process Step of firing the molded body to obtain a fired body 4.
  • Impregnation step Step of filling the fired body with impregnated pitch5.
  • Re-firing process A process of re-firing the fired body filled with impregnated pitch to obtain a re-fired body6.
  • Graphitization step 7. Graphitization step of graphitizing the refired body. Processing process The process of forming a graphitized body into a predetermined shape by cutting etc. to make a graphite electrode.
  • Kneading process Needle coke, which has been pulverized, classified, and has a particle size blended at a predetermined ratio, and binder pitch are mixed and kneaded together.
  • the amount of binder pitch blended varies depending on the kneading method and molding method, but is generally about 20 parts by mass to 30 parts by mass per 100 parts by mass of needle coke.
  • the kneaded material may also contain a puffing inhibitor such as iron oxide.
  • a commercially available mixer or kneader 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 150°C.
  • the softening point of the binder pitch is preferably 130°C or lower, more preferably 110°C or lower. When kneading at around 150°C, it is difficult to sufficiently knead if the softening point of the binder pitch is higher than 130°C. After kneading, the kneaded material is cooled to a temperature (100° C. to 130° C.) suitable for subsequent molding.
  • the kneaded material is molded to obtain a molded body of a predetermined size and shape.
  • the molding method can be appropriately selected from extrusion molding, mold molding, etc. depending on the intended carbon material.
  • the target carbon material is a graphite electrode, extrusion molding into a cylindrical shape is common.
  • the molded body from the previous step is heated and fired at 700°C to 1000°C to obtain a fired body.
  • the firing step is preferably performed in a non-oxidizing combustion exhaust gas atmosphere.
  • the molded body softens in the early stages of temperature rise, and a large amount of decomposed gas is generated due to thermal decomposition and polycondensation of the binder pitch at 200°C to 500°C, resulting in the formation of pores and volumetric contraction.
  • the binder pitch carbonizes at 500°C to 600°C.
  • Impregnation Step During the calcination step, typically 35% to 45% of the weight of the binder pitch is lost as volatiles. At this time, a large amount of pores are generated in the fired body.
  • the impregnation step is to fill the pores with impregnated pitch. Impregnation is carried out by, for example, placing the fired body in an autoclave, degassing it under reduced pressure, and then injecting molten impregnated pitch into the pores at about 200°C and a gas pressure of about 1 MPa. .
  • Re-firing step The fired body filled with impregnated pitch is fired again to obtain a re-fired body. Re-firing can also be performed under the same conditions as the firing step. The impregnation step and the re-firing step may be repeated as necessary.
  • the refired body is placed in a furnace surrounded by an insulating material (Acheson furnace, LWG furnace, etc.), and the refired body is subjected to heat treatment using packing coke by energization or resistance heating of the refired body.
  • the graphitization temperature is 2000°C to 3000°C. This temperature is necessary to convert the amorphous carbon in the refired body to crystalline graphite.
  • the refired body is heat treated for several days to convert it into graphite.
  • the graphitized body is machined such as cutting to produce a graphite electrode product in 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 .
  • the method for producing petroleum pitch of one embodiment includes at least the following steps 1 to 4 in this order, and may include other steps.
  • a method for producing petroleum-based pitch according to another embodiment includes the following steps 1 and 2 in this order, and steps 3 and 4 can be omitted.
  • Step 1 Heat-treating petroleum-based heavy oil
  • Step 2 Distilling the heat-treated product obtained in Step 1 to obtain pitch 1 as a high-boiling component
  • Step 3 Toluene-insoluble from pitch 1 obtained in Step 2 minutes (TI)
  • Step 4 of obtaining a component with reduced TI Distilling the component with reduced toluene insoluble matter (TI) obtained in step 3
  • naphtha and other materials are generally thermally decomposed at high temperatures, and the resulting thermal decomposition products are distilled to produce ethylene, propylene, and other olefins, aromatic compounds such as benzene, toluene, and xylene, cracked gasoline, and cracked gasoline. It is separated into various fractions such as kerosene and made into products. Among these fractions, the heavy fraction with the highest boiling point is called ethylene bottom oil, and is used as a raw material for carbon black and other fuels (see Figure 1). Since pyrolysis plants for naphtha and the like are often referred to as ethylene plants, the aforementioned heavy fraction is referred to as ethylene bottom oil.
  • ethylene bottom oil obtained by thermal decomposition of naphtha-containing raw materials depend on the type of naphtha-containing raw material, thermal cracking conditions, operating conditions of the purification distillation column, etc., but generally the 50% distillation temperature is 200 ° C. -400°C, aromatic carbon content is 50% by mass or more, flash point is 70°C - 100°C, and kinematic viscosity at 50°C is less than 40 mm 2 /s.
  • ethylene bottom oil is a mixture of hydrocarbons, the above values may vary somewhat.
  • Petroleum-based heavy oil is ethylene bottom oil, ethylene bottom oil heavy fraction obtained by removing a desired proportion (for example, 5 to 70% by mass) of light components from ethylene bottom oil by distillation, or removed ethylene bottom oil light component. , other petroleum-based heavy oils, or a mixture thereof.
  • the petroleum-based heavy oil is ethylene bottom oil.
  • heavy oil such as coal tar may be added to petroleum-based heavy oil.
  • other petroleum-based heavy oils include, but are not particularly limited to, fluid catalytic cracking oil (FCC decant oil), atmospheric distillation residual oil, vacuum distillation residual oil, and the like.
  • FCC decant oil fluid catalytic cracking oil
  • atmospheric distillation residual oil atmospheric distillation residual oil
  • vacuum distillation residual oil and the like.
  • the sulfur content and nitrogen content in the pitch cause puffing during firing, so it is preferable that the content be as low as possible.
  • fluid catalytic cracking oil (FCC decant oil) is preferred as the other petroleum heavy oil.
  • the properties of fluid catalytic cracking oil (FCC decant oil) depend on the raw materials, operating conditions, etc., but generally the 50% distillation temperature is 300-450°C, the flash point is 60°C-160°C, and the temperature is 40°C.
  • the viscosity is less than 40 mm 2 /s.
  • fluid catalytic cracking oil (FCC decant oil) is a complex mixture, the above values may vary somewhat.
  • Step 1 is a step of heat treating petroleum heavy oil.
  • the heat treatment is preferably carried out in a non-oxidizing gas atmosphere in a closed container.
  • 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, but nitrogen gas is preferred from the viewpoint of cost and ease of handling.
  • the heat treatment temperature is preferably 360°C or higher, more preferably 390°C or higher, and even more preferably 410°C or higher.
  • the heat treatment temperature is preferably 500°C or lower, more preferably 450°C or lower. These upper limit values and lower limit values can be arbitrarily combined.
  • the heat treatment temperature is preferably 360°C to 500°C, more preferably 390°C to 500°C, even more preferably 410°C to 450°C.
  • Appropriate heat treatment time varies depending on the heat treatment temperature.
  • the heat treatment temperature is 360° C. to 390° C., it is preferably 8 hours or more, more preferably 16 hours or more from the time when the predetermined heat treatment temperature is reached (the same applies hereinafter).
  • the heat treatment time is preferably 48 hours or less.
  • the heat treatment temperature is 360° C. to 390° C., it is preferably 8 hours to 48 hours, more preferably 16 to 48 hours.
  • the heat treatment temperature is higher than 390° C. to 430° C., the heat treatment temperature is preferably 0.5 hours or more, more preferably 1 hour or more.
  • the heat treatment temperature is preferably 24 hours or less, more preferably 16 hours or less.
  • the heat treatment temperature is higher than 390°C to 430°C, it is preferably 0.5 to 24 hours, more preferably 1 to 16 hours.
  • the heat treatment temperature is higher than 430°C to 500°C, it is preferably 0.1 hour or more, more preferably 0.5 hour or more.
  • the heat treatment temperature is preferably 16 hours or less, more preferably 8 hours or less.
  • the heat treatment temperature is higher than 430°C to 500°C, it is preferably 0.1 hour to 16 hours, more preferably 0.5 hour to 8 hours.
  • the above upper limit value and lower limit value can be arbitrarily combined. By setting the heat treatment time within the above range, pitch with a sufficient amount of fixed carbon can be obtained.
  • the pressure at the start of heat treatment is preferably 0 MPaG, but is not particularly limited.
  • the pressure inside the closed container increases due to hydrogen and lower alkanes such as methane and ethane generated by thermal decomposition that occurs during heat treatment. Although there is no limit to the pressure inside the closed container, pressurized conditions are preferred since TI is likely to be produced under normal pressure and the final pitch yield will be reduced.
  • step 1 additives such as a solid catalyst may be added to the petroleum heavy oil.
  • the solid catalyst referred to here is a catalyst that does not dissolve in the reaction substrate (heavy petroleum oil) and does not decompose even at heat treatment temperatures, and specifically includes solid acid catalysts such as activated clay, silica alumina, and zeolite. It will be done. These solid acid catalysts are known to suppress the occurrence of fouling during heat treatment of petroleum-based heavy oil, as described in JP-A-60-179493 and JP-A-60-240790. Therefore, it is useful when heat treatment is performed under relatively severe reaction conditions for the purpose of increasing the amount of fixed carbon in pitch. Since the added solid catalyst can be removed as a solvent-insoluble component together with TI in step 3, it is not mixed into the pitch finally obtained in step 4.
  • Step 2 is a step of distilling the heat-treated product obtained in Step 1 to remove low boiling point substances and obtaining pitch 1 as a high boiling point component.
  • the pitch 1 obtained in step 2 is the petroleum pitch of one embodiment.
  • the distillation method in step 2 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 preferably does not exceed 360°C, although it depends on the distillation pressure. This is because if the temperature exceeds 360° C., TI is likely to be generated and the final pitch yield may decrease.
  • 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 remove low boiling point substances (light components), so from an economical point of view, a temperature of 200°C or higher is preferable. .
  • step 2 pitch 1 with a softening point of approximately 180°C or lower
  • the pressure during distillation is preferably 100 PaA to 10,000 PaA, more preferably 300 PaA to 5,000 PaA.
  • the softening point of pitch can be controlled by the amount of light matter removed. Generally, the greater the amount of light components removed, that is, the higher the end point of distillation, the higher the softening point.
  • the end point of distillation is preferably 450°C or lower, more preferably 420°C or lower, and even more preferably 400°C or lower.
  • Step 3 is a step of removing toluene insolubles (TI) from pitch 1 obtained in step 2 to obtain a component with reduced TI.
  • the method for removing TI is not particularly limited, but for example, an appropriate solvent is added to pitch 1 obtained in step 2, the solvent-soluble content of pitch 1 is extracted with the solvent, the solvent-insoluble content is separated and removed, and the TI is removed. Examples include methods for obtaining components with reduced .
  • the component with reduced TI includes the solvent soluble content and the solvent used.
  • the solvent-insoluble content includes TI and a solid catalyst added as necessary.
  • a suitable solvent is preferably a solvent that dissolves only toluene solubles (TS) without dissolving TI in the pitch.
  • TS toluene solubles
  • benzene, alkylbenzenes such as toluene and xylene, and mixtures thereof are preferred.
  • Benzene and alkylbenzene-rich fractions obtained from petrochemical processes can also be used. Such fractions include, for example, cracked gasoline and cracked kerosene.
  • Cracked gasoline is a mixture of hydrocarbons mainly having 6 to 8 carbon atoms produced through petrochemical processes, 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 to some extent.
  • cracked gasoline examples include benzene, toluene, ethylbenzene, xylene, styrene, and hexane.
  • Decomposed kerosene is a mixture of hydrocarbons mainly having 9 or more carbon atoms, produced through petrochemical processes, and is a fraction with a boiling point in the range of 90°C to 230°C at 1 atm. However, since cracked kerosene is a mixture of hydrocarbons, the number of carbon atoms and boiling point may vary somewhat.
  • the main components of decomposed kerosene include, for example, xylene, styrene, allylbenzene, propylbenzene, methylethylbenzene, trimethylbenzene, methylstyrene, dicyclopentadiene, indane, indene, methylpropylbenzene, methylpropenylbenzene, ethylstyrene, and divinyl.
  • examples include benzene, methylindene, naphthalene, and methyldicyclopentadiene.
  • the amount of the solvent added is preferably 25 parts by mass to 5,000 parts by mass, more preferably 300 parts by mass to 2,000 parts by mass, per 100 parts by mass of pitch 1. Although it varies somewhat depending on the extraction conditions, if the amount is 25 parts by mass or more, efficient extraction can be achieved. If it exceeds 5,000 parts by mass, the extraction efficiency will not change much, so from the viewpoint of economy and productivity, it is preferably 5,000 parts by mass or less.
  • the extraction temperature is not particularly limited. Although extraction can be carried out at room temperature, heating conditions are preferred as they provide better extraction efficiency. When extraction under heating conditions is performed at normal pressure, it is necessary to perform the extraction at a temperature below the boiling point of the solvent used. When heating at a temperature above the boiling point, the extraction can be carried out under reflux conditions or under pressure using a closed vessel.
  • the method for separating the solvent in which the solvent-soluble matter is dissolved and the solvent-insoluble matter is not particularly limited, and for example, centrifugation, filtration, or a combination thereof can be used.
  • Step 4 is a step in which light components are distilled off from the TI-reduced component obtained in Step 3 to obtain pitch 2 as a high boiling point component.
  • Pitch 2 obtained in step 4 is a petroleum-based pitch of one embodiment.
  • the distillation method in step 4 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 preferably does not exceed 360°C, although it depends on the distillation pressure. This is because when the temperature exceeds 360°C, the polycondensation reaction tends to proceed, and TI tends to be generated.
  • 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 remove low boiling point substances (light components), so from an economical point of view, a temperature of 200°C or higher is preferable. .
  • the pressure during distillation is preferably 100 PaA to 10,000 PaA, more preferably 300 PaA to 5,000 PaA.
  • the softening point of pitch can be controlled by the amount of light matter removed. Generally, the greater the amount of light components removed, that is, the higher the end point of distillation, the higher the softening point.
  • ethylene bottom oil as the petroleum-based heavy oil, in order to lower the softening point of pitch 2 to 120°C or less, it depends on the heat treatment conditions in step 1 and the distillation equipment, etc.
  • the end point is preferably 450°C or lower, more preferably 420°C or lower, and even more preferably 400°C or lower. Although it depends on the heat treatment conditions in Step 1, the distillation equipment, etc., the end point of distillation when converted to normal pressure is preferably 250°C or higher, more preferably 300°C or higher. If the end point of distillation is less than 250°C, a large amount of light components will volatilize at the impregnation temperature (for example, 200°C), and there is a concern that the viscosity of the pitch will abnormally increase during the impregnation process.
  • the petroleum pitch of one embodiment can be suitably used as an impregnated pitch used in the production of carbon materials.
  • the petroleum pitch of one embodiment can be suitably used as an impregnated pitch used in the manufacture of graphite electrodes.
  • the petroleum-based pitch of one embodiment can be used as a binder pitch used in the manufacture of graphite electrodes.
  • the petroleum-based pitch of one embodiment can also be used as an impregnating pitch and a binder pitch for manufacturing carbon materials other than graphite electrodes.
  • the quinoline insoluble content (QI) of the petroleum pitch in one embodiment is 0.5% by mass or less. Since the smaller the QI, the better the pitch impregnation properties are, it is preferably 0.3% by mass or less, more preferably 0.1% by mass or less.
  • the lower limit of QI is not particularly limited, but is, for example, 0.0% by mass or 0.001% by mass. The QI was measured by the method described in the Examples section.
  • the toluene insoluble content (TI) of the petroleum pitch in one embodiment is 3.0% by mass or less. Since the pitch impregnation property improves as the TI content decreases, the content is preferably 2.0% by mass or less, and more preferably 1.0% by mass or less.
  • the lower limit of TI is not particularly limited, but is, for example, 0.0% by mass or 0.1% by mass. The TI was measured by the method described in the Examples section.
  • the softening point of the petroleum pitch in one embodiment is 60°C to 120°C.
  • the softening point is 60°C or higher, preferably 70°C or higher, and more preferably 75°C or higher. These upper limit values and lower limit values can be arbitrarily combined.
  • the softening point is preferably 70°C to 110°C, more preferably 75°C to 100°C. The softening point was measured by the method described in the Examples section.
  • the viscosity of the petroleum pitch in one embodiment at 200° C. is 200 mPa ⁇ s or less.
  • the lower the viscosity, the better the pitch fluidity and impregnability, so the viscosity at 200° C. is preferably 100 mPa ⁇ s or less, more preferably 70 mPa ⁇ s or less, and even more preferably 40 mPa ⁇ s or less.
  • the lower limit of the viscosity at 200° C. is not particularly limited, but is, for example, 5 mPa ⁇ s or 10 mPa ⁇ s. The viscosity was measured by the method described in the Examples section.
  • the amount of fixed carbon in the petroleum pitch of one embodiment is preferably 47.0% by mass or more, and 48.0% by mass.
  • the content is more preferably at least 50.0% by mass, and even more preferably at least 50.0% by mass.
  • the amount of fixed carbon is preferably 80.0% by mass or less, preferably 70.0% by mass or less, and more preferably 65.0% by mass or less.
  • the amount of fixed carbon is preferably 47.0% to 80.0% by mass, more preferably 48.0% to 70.0% by mass, and even more preferably 50.0% to 65.0% by mass. preferable.
  • the amount of fixed carbon was measured by the method described in the Examples section.
  • FIG. 3 shows the relationship between the softening point and fixed carbon content of pitches prepared by heat-treating ethylene bottom oil under different heat treatment conditions and distilling the heat-treated products under different distillation conditions.
  • FIG. 3 shows that when the distillation conditions are changed under the same heat treatment conditions, the relationship between the softening point and the amount of fixed carbon can be approximated by a linear equation. It can be seen that although the value of the intercept changes depending on the heat treatment conditions, the value of the slope is 0.2 regardless of the heat treatment conditions. It can also be seen that the more severe the heat treatment conditions (high temperature and/or long time), the larger the value of the intercept, and that a pitch with a higher amount of fixed carbon can be obtained at the same softening point.
  • the petroleum pitch of one embodiment satisfies formula (1). That is, the value of the amount of fixed carbon Y (mass %) of the petroleum pitch exceeds the value calculated by substituting the softening point X (° C.) of the petroleum pitch into equation (1). Petroleum-based pitch that satisfies this condition has a larger amount of fixed carbon than pitch that has a similar softening point. 80.0 ⁇ Y>0.2X+29.5 (1) Y: fixed carbon amount (mass%) X: Softening point (°C) (60 ⁇ X ⁇ 120)
  • petroleum-based pitch can achieve both good impregnating properties and a high amount of fixed carbon, which has been difficult with conventional methods.
  • the method for producing petroleum-based pitch is not particularly limited as long as it yields a pitch that satisfies the properties shown above, but a production method including steps 1 to 4 above is preferred. If the pitch obtained in step 2 satisfies the characteristics shown above, steps 3 and 4 may be omitted.
  • ⁇ Preparation method of ethylene bottom oil light fraction Using 894 kg of ethylene bottom oil as a raw material, distillation and purification were carried out in a distillation facility with 15 theoretical plates (Sulzer packing) at a pot temperature of 101°C and an operating pressure of 533 to 1067 PaA, and 544 kg of heavy ethylene bottom oil was obtained as the pot residual liquid. Obtained. The initial boiling point of the heavy fraction of the obtained ethylene bottom oil was 218°C. Approximately 350 kg of components obtained as distillate fractions were used as ethylene bottom oil light fractions.
  • Example 1-1 3,000 g of ethylene bottom oil was introduced into a SUS autoclave with a capacity of 6 L. The container was sealed under a nitrogen gas atmosphere, and the temperature inside the container was raised to 430° C. at a rate of 5° C./min while stirring. One hour after the temperature reached 430°C, heating was terminated and the mixture was allowed to cool to room temperature (Step 1). The yield of the heat-treated product was 2,790 g. 600 g of the obtained heat-treated product was distilled under reduced pressure (distillation pressure: 667 PaA) so that the distillation end point was 355° C. in terms of normal pressure, to obtain 222 g of pitch 1 (step 2).
  • the resulting pitch 1 had a softening point of 110° C., a TI of 13.9% by mass, and a QI of 0.0% by mass.
  • 2,220 g of toluene was added to 222 g of pitch 1, and the mixture was heated and stirred at 130° C. for 1 hour. Thereafter, the mixture was separated into soluble and insoluble components by centrifugation (Step 3). Light components were distilled off from the obtained soluble components (components with reduced TI) by vacuum distillation (Step 4), and 184 g of Pitch 2 was obtained as a distillation residue (high boiling point components). (equivalent to a yield of 29%). The various tests described above were conducted using this pitch.
  • Example 2-1 3,000 g of light ethylene bottom oil was introduced into a 6 L SUS autoclave. The container was sealed under a nitrogen gas atmosphere, and the temperature inside the container was raised to 400° C. at a rate of 5° C./min while stirring. After 6 hours had passed since the temperature reached 400°C, heating was terminated and the mixture was allowed to cool to room temperature (Step 1).
  • the yield of the heat-treated product was 2,940 g. 2,940 g of the obtained heat-treated product was distilled under reduced pressure (distillation pressure: 667 PaA) so that the distillation end point was 390°C in terms of normal pressure, and 617 g of pitch was obtained (yield 21% based on the light content of the raw ethylene bottom oil). ) obtained (Step 2).
  • the characteristics of the obtained pitch are as shown in Table 1, and because the above-mentioned preferred pitch characteristics were satisfied, steps 3 and 4 were omitted. A filterability test was conducted using this pitch.
  • Example 2-2 Pitch was prepared according to the method described in Example 2-1, except that the heat treatment conditions and distillation conditions were changed as shown in Table 1.
  • the yield of pitch was 570 g (yield 19% based on the light content of the raw material ethylene bottom oil) (Step 2).
  • the characteristics of the obtained pitch are as shown in Table 1, and because the above-mentioned preferred pitch characteristics were satisfied, steps 3 and 4 were omitted. A filterability test was conducted using this pitch.
  • Example 2-3 Pitch was prepared according to the method described in Example 2-1, except that the heat treatment conditions and distillation conditions were changed as shown in Table 1.
  • the yield of pitch was 732 g (yield 24% based on the light content of the raw material ethylene bottom oil) (Step 2).
  • the characteristics of the obtained pitch are as shown in Table 1, and because the above-mentioned preferred pitch characteristics were satisfied, steps 3 and 4 were omitted. A filterability test was conducted using this pitch.
  • the petroleum-based pitches of the examples have both good impregnating properties and a high amount of fixed carbon, and are clearly suitable as impregnated pitches for producing carbon materials.

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  • General Chemical & Material Sciences (AREA)
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US18/850,380 US20250207034A1 (en) 2022-06-02 2023-04-17 Method for producing petroleum pitch and petroleum pitch
JP2024524227A JP7737554B2 (ja) 2022-06-02 2023-04-17 石油系ピッチの製造方法及び石油系ピッチ
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5764743U (https=) 1980-10-07 1982-04-17
JPS6092388A (ja) 1983-09-27 1985-05-23 リユートガースヴエルケ・アクチエンゲゼルシヤフト 石油化学精製による、不飽和化合物を含有する高級芳香族残渣から熱安定なピツチ及び油を製造する方法
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
JPS6397691A (ja) 1986-10-14 1988-04-28 Showa Denko Kk 炭素材用含浸ピツチの製造法
JPH10316972A (ja) * 1997-05-20 1998-12-02 Mitsubishi Chem Corp ニードルコークスの製造方法
JP2018053071A (ja) * 2016-09-28 2018-04-05 国立大学法人九州大学 高軟化点ピッチの製造方法
JP2021080143A (ja) * 2019-11-22 2021-05-27 Ｊｆｅケミカル株式会社 炭素材料原料用ピッチおよびその製造方法
WO2021181905A1 (ja) * 2020-03-12 2021-09-16 昭和電工株式会社 含浸ピッチの製造方法
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 (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5764743U (https=) 1980-10-07 1982-04-17
JPS6092388A (ja) 1983-09-27 1985-05-23 リユートガースヴエルケ・アクチエンゲゼルシヤフト 石油化学精製による、不飽和化合物を含有する高級芳香族残渣から熱安定なピツチ及び油を製造する方法
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
JPS6397691A (ja) 1986-10-14 1988-04-28 Showa Denko Kk 炭素材用含浸ピツチの製造法
JPH10316972A (ja) * 1997-05-20 1998-12-02 Mitsubishi Chem Corp ニードルコークスの製造方法
JP2018053071A (ja) * 2016-09-28 2018-04-05 国立大学法人九州大学 高軟化点ピッチの製造方法
JP2021080143A (ja) * 2019-11-22 2021-05-27 Ｊｆｅケミカル株式会社 炭素材料原料用ピッチおよびその製造方法
WO2021181905A1 (ja) * 2020-03-12 2021-09-16 昭和電工株式会社 含浸ピッチの製造方法
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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