WO2010110144A1 - ゴム配合油及び芳香族含有基油、並びにこれらの製造方法 - Google Patents

ゴム配合油及び芳香族含有基油、並びにこれらの製造方法 Download PDF

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WO2010110144A1
WO2010110144A1 PCT/JP2010/054544 JP2010054544W WO2010110144A1 WO 2010110144 A1 WO2010110144 A1 WO 2010110144A1 JP 2010054544 W JP2010054544 W JP 2010054544W WO 2010110144 A1 WO2010110144 A1 WO 2010110144A1
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Prior art keywords
base oil
oil
aromatic
mass
benzo
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PCT/JP2010/054544
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English (en)
French (fr)
Japanese (ja)
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俊男 吉田
徳 辻井
稔 井原
孝二 前山
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新日本石油株式会社
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Priority claimed from JP2009079063A external-priority patent/JP5417009B2/ja
Priority claimed from JP2009079082A external-priority patent/JP5390233B2/ja
Application filed by 新日本石油株式会社 filed Critical 新日本石油株式会社
Priority to SG2011054012A priority Critical patent/SG174122A1/en
Priority to CN2010800141368A priority patent/CN102365323B/zh
Publication of WO2010110144A1 publication Critical patent/WO2010110144A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/14—Hydrocarbons
    • 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/16—Oxygen-containing compounds
    • 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
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02—Petroleum fractions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/104—Aromatic fractions
    • C10M2203/1045—Aromatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/011—Cloud point
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/015—Distillation range
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/017—Specific gravity or density
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/54—Fuel economy

Definitions

  • the present invention relates to a rubber compounding oil, an aromatic-containing base oil, and methods for producing them.
  • Highly aromatic mineral oil has a high affinity with rubber components and is excellent in processability, softening properties, and economy of rubber compositions, and is therefore used in the production of rubber compositions such as natural rubber and synthetic rubber.
  • synthetic rubber such as SBR is blended with extender oil (extender oil) at the time of synthesis, and rubber processed products such as tires are processed oil (in order to improve processability and quality of the rubber processed product).
  • extender oil extender oil
  • Process oil for example, Patent Document 1
  • Patent Document 1 discloses that the aromatic hydrocarbon content (C A ) is 20 to 35% by weight, the glass transition temperature T g is ⁇ 55 ° C. to ⁇ 30 ° C., and the kinematic viscosity.
  • a petroleum-based process oil having a (100 ° C.) of 20 to 50 mm 2 / s and a polycyclic aromatic component amount (PCA) of 3% by weight or less in the petroleum-based process oil has been proposed.
  • PCA polycyclic aromatic component amount
  • Patent Document 2 a solvent extraction extract of desiccated oil, and the like is known (for example, Patent Document 2).
  • the solvent extraction extract of the vacuum distillation fraction is generally rich in polycyclic aromatics, and due to the above-mentioned regulations, it is becoming a situation where it cannot be used as a rubber compounding oil as it is.
  • a technique corresponding to such a situation there is also known a method for increasing the extract yield with the aim of reducing aromaticity by hydrogenation treatment of an aromatic compound and diluting effect of polycyclic aromatics.
  • these methods are concerned about deterioration in economic efficiency due to the addition of hydrogenation facilities, reduction in aromaticity, or deterioration in the yield of by-product lubricating base oil.
  • rubber compounded oils are required to have a high flash point (250 ° C. or higher) that is not covered by the hazardous materials No. 4 petroleums in order to improve handling and handling properties.
  • the rubber compounding oil is required to have a low glass transition point in order to improve the low temperature characteristics (low temperature elastic modulus, etc.) of the rubber.
  • Patent Documents 1 and 3 propose rubber compounding oils having low glass transition points of ⁇ 55 ° C. to ⁇ 30 ° C. and ⁇ 45 ° C. to ⁇ 20 ° C., respectively.
  • the glass transition point and the aromatic content generally exhibit contradictory properties, it is generally difficult to achieve both a high aromatic content and a low glass transition point.
  • a rubber compounding oil having an aromatic content of 50% by mass or more according to ASTM D 2007 and a glass transition point of ⁇ 45 ° C. or less has not been obtained (for example, see Examples and Comparative Examples in Patent Document 3).
  • the glass transition point of the rubber compounding oil is lowered, not only the aromatic content but also the flash point tends to be lowered.
  • a highly aromatic base oil containing a normal unrefined extract has a high pour point and a high glass transition point.
  • a lubricating base oil obtained by refining raffinate obtained by extracting a distillation under reduced pressure with a polar solvent has a low pour point but a low aromatic content and a high aniline point. Use in the extender oil used is difficult.
  • a production method (1) a method of hydrogenating an extract to reduce polycyclic aromatics, a production method (2) an extraction step with a polar solvent A method of increasing the yield of extract and diluting polycyclic aromatics, and a production method (3) a method of performing solvent extraction of a vacuum distillation fraction in two stages (Patent Document 2) are known. .
  • Patent Document 1 as a rubber compounding oil blended with a diene rubber, an aromatic hydrocarbon content (C A ) is 20 to 35% by weight, a glass transition temperature T g is ⁇ 55 ° C. to ⁇ 30 ° C., It has been proposed to use a petroleum-based process oil having a kinematic viscosity (100 ° C.) of 20 to 50 mm 2 / s and a polycyclic aromatic component amount (PCA) of 3% by weight or less.
  • PCA polycyclic aromatic component amount
  • JP 2004-155959 A Japanese Patent No. 3658155 International Publication No. 97/35462
  • the aromatic content of the resulting product tends to be reduced along with the deterioration of economics associated with the addition of hydrogenation equipment.
  • the production method (2) from the raffinate The yield of the resulting lubricating base oil tends to decrease and the aromatic content also decreases.
  • the density is less than 0.94 g / cm 3 , the polycyclic aromatics are small, and the yield of the extract that is a high aromatic content is increased, but the yield of raffinate is greatly increased. In addition to being low, the aromatic content tends to decrease.
  • each has a low glass transition point at a high flash point and a high total aromatic content, and a specific carcinogenicity.
  • the raffinate is useful as a non-carcinogenic highly aromatic base oil obtained from a rubber compounding oil or an extract useful as a base material, and also useful as a rubber compounding oil or a base material and lubricating base oil.
  • the present invention provides a rubber compounding oil having a high flash point and a low glass transition point while maintaining a high total aromatic content, and a sufficiently reduced content of a specific polycyclic aromatic compound, and its A first object is to provide a method for producing a rubber compounding oil.
  • the present invention provides a carcinogenicity while having a high flash point, a low glass transition point, and a high total aromatic content from raffinate and extract obtained by a polar solvent extraction method using a vacuum distillation fraction as a raw material.
  • a polar solvent extraction method using a vacuum distillation fraction as a raw material.
  • the total aromatic content according to ASTM D 2007 or ASTM D 2549 is 50% by mass or more, the flash point is 250 ° C. or more, and the difference between the pour point and the glass transition point is 45 ° C. or more.
  • a rubber compounding oil having a benzo (a) pyrene content of 1 mass ppm or less and a total content of specific aromatic compounds of the following 1) to 8) of 10 mass ppm or less.
  • the rubber compounding oil of the present invention has a high flash point and a low glass transition point while maintaining a high total aromatic content, and the content of a specific polycyclic aromatic compound is sufficiently reduced.
  • the rubber compounding oil of the present invention contains raffinate obtained by separating a vacuum distillation fraction of crude oil atmospheric distillation residue in a solvent extraction step or a refined oil thereof, and has a kinematic viscosity at 40 ° C. of 60 to 600 mm 2.
  • aniline point is 70 ° C. or higher
  • 10% point by GC distillation is 400-500 ° C.
  • 90% point is 500-600 ° C.
  • % C A by ASTM D 3238 is 3-20
  • glass transition point is ⁇ 30 ° C.
  • the solvent extraction step includes contacting the reduced-pressure distillation fraction with the polar solvent in the first extraction tower having a tower bottom temperature of 30 to 90 ° C. and a tower top temperature higher than the tower bottom temperature. And a first solvent extraction step for obtaining a first raffinate and a first extract, and a second extraction tower in which the tower bottom temperature and the tower top temperature are each 10 ° C. or more higher than the first extraction tower.
  • the present invention contains a raffinate obtained by separating a vacuum distillation fraction of crude oil atmospheric distillation residue in a solvent extraction step or a refined oil thereof, and has a kinematic viscosity at 40 ° C. of 60 to 600 mm 2 / s.
  • the aniline point is 70 ° C. or higher
  • the 10% point by GC distillation is 400 to 500 ° C.
  • the 90% point is 500 to 600 ° C.
  • the% C A by ASTM D 3238 is 3 to 20
  • the glass transition point is ⁇ 30 ° C. or lower.
  • the total aromatic content according to ASTM D 2007 or ASTM D 2549 is 50% by mass or more, the flash point is 250 ° C. or more, and the difference between the pour point and the glass transition point is 45 ° C. or more.
  • the content of pyrene is 1 mass ppm or less, and the total content of the specific aromatic compounds of the following 1) to 8) is 10 mass ppm or less, and the content of the aromatic-containing base oil (a) is Provided is a method for producing a rubber compounding oil having a content of more than 0 and 95% by mass or less and an aromatic-containing base oil (b) of 5% by mass to less than 100% by mass.
  • the rubber compounding oil obtained by the production method of the present invention has a high flash point and a low glass transition point while maintaining a high total aromatic content, and the content of a specific polycyclic aromatic compound is sufficiently reduced.
  • the rubber compounding oil containing the aromatic-containing base oil (b) of the present invention has a peculiar difference between the pour point and the glass transition point of 45 ° C. or more, particularly 60 ° C. or more. Is 50 mass% or more, and even if the pour point is 15 ° C. or more, a rubber compounding oil having a glass transition point of ⁇ 45 ° C. or less can be obtained.
  • purification such as a dewaxing process and a hydrogenation process, to aromatic-containing base oil (b)
  • the present invention provides the first distillation column having a column bottom temperature of 30 to 90 ° C. and a column top temperature higher than the column bottom temperature.
  • a first solvent extraction step in which a solvent is contacted to obtain a first raffinate and a first extract; and a tower bottom temperature and a tower top temperature that are 10 ° C. or more higher than the first extraction tower, respectively.
  • the first raffinate and the polar solvent are brought into contact with each other, and the second raffinate has a density of 0.94 g / cm 3 or more at 15 ° C. and a total aromatic content of 30% by mass or more.
  • An aromatic-containing group containing at least a part of the second extract, the second raffinate, or a refined oil thereof, wherein the total aromatic content is 30% by mass or more.
  • An oil production method is provided.
  • a high flash point, a low glass transition point, a high yield of an aromatic-containing base oil having a high total aromatic content and a sufficiently reduced content of a specific carcinogenic substance can be manufactured.
  • Such an aromatic-containing base oil can be suitably used as a rubber compounding oil or as a raw material thereof.
  • the present invention includes a base oil preparation step for obtaining a refined oil by subjecting the second raffinate to a refining treatment including a dewaxing treatment after the second solvent extraction step. It is preferable to produce an aromatic-containing base oil having an aniline point of 90 ° C or higher, a viscosity index of 90 or higher, and a flash point of 250 ° C or higher.
  • the second raffinate is subjected to a purification treatment including a dewaxing treatment to obtain a refined oil.
  • a purification treatment including a dewaxing treatment to obtain a refined oil.
  • the second raffinate is subjected to a purification treatment including a dewaxing treatment to obtain a refined oil. It is preferable to produce an aromatic-containing base oil having an A of 120 to 250 mm 2 / s, a 10% point of 450 to 520 ° C. and a 90% point of 540 to 600 ° C. by gas chromatography.
  • the aromatic-containing base oil obtained by the production method of the present invention contains at least a part of the second extract, has a kinematic viscosity at 40 ° C. of 200 mm 2 / s or more, a flash point of 250 ° C. or more, and a pour point of 30.
  • the aniline point is 90 ° C. or lower
  • the glass transition point is ⁇ 30 ° C. or lower
  • the difference between the pour point and the glass transition point is 50 ° C. or higher.
  • this aromatic containing base oil may consist of a 2nd extract.
  • the aromatic-containing base oil obtained by the production method of the present invention contains at least a part of the second extract, has a kinematic viscosity at 40 ° C. of 200 mm 2 / s or more and less than 500 mm 2 / s, and a glass transition point. Is preferably ⁇ 60 to ⁇ 40 ° C.
  • aromatic-containing base oils include, for example, natural rubber (NR), various butadiene rubbers (BR), various styrene-butadiene copolymer rubbers (SBR), polyisoprene rubber (IR), butyl rubber (BR), and these It can be particularly suitably used as a petroleum process oil or extender oil blended with a diene rubber such as an optional blend rubber, particularly a diene rubber containing at least one styrene-butadiene copolymer rubber.
  • this aromatic containing base oil may consist of a 2nd extract.
  • the aromatic-containing base oil obtained by the production method of the present invention contains at least a part of the second extract, has a kinematic viscosity at 40 ° C. of 500 mm 2 / s or more, and a glass transition point of ⁇ 50 to ⁇ 30 ° C. It is preferable that Such an aromatic-containing base oil can be particularly suitably used as, for example, a petroleum-based process oil or extender oil to be blended with the diene rubber as described above. In addition, this aromatic containing base oil may consist of a 2nd extract.
  • the aromatic-containing base oil obtained by the production method of the present invention has a benzo (a) pyrene content of 1 mass ppm or less and a total content of the specific aromatic compounds 1) to 8) shown below. It is preferable that it is 10 mass ppm or less.
  • Such an aromatic-containing base oil is one in which the content of a specific carcinogenic polycyclic aromatic compound is sufficiently reduced, so that a petroleum-based process oil or extender oil for rubber processed products such as tires or the like As the substrate, it can be particularly preferably used.
  • the present invention also provides an aromatic-containing base oil obtained by the production method having the above-described characteristics.
  • This aromatic-containing base oil has a high flash point, a low glass transition point, a high total aromatic content, and a sufficiently low content of carcinogenic substances. While having excellent characteristics as oil or its base material, it is sufficiently excellent in safety.
  • this invention provides the rubber compounding oil containing the aromatic containing base oil which has the said characteristic in the 3rd side surface.
  • a rubber compounding oil having a high flash point and a low glass transition point while maintaining a high total aromatic content, and having a sufficiently reduced content of a specific polycyclic aromatic compound, and its A method for producing a rubber compounding oil can be provided.
  • the rubber compounding oil of the present invention has a high aromatic content, it is extremely compatible with rubbers such as styrene-butadiene rubber or rubber materials.
  • rubbers such as styrene-butadiene rubber or rubber materials.
  • a rubber excellent in low temperature characteristics can be produced.
  • the flash point is high and the content of the carcinogenic polycyclic aromatic compound is sufficiently reduced, the safety is also high.
  • a rubber compounding oil having a viscosity of -30 ° C. and a kinematic viscosity (100 ° C.) of 20 to 50 mm 2 / s is used, for example, natural rubber (NR), various butadiene rubbers (BR), various styrene-butadiene copolymer rubbers (SBR).
  • a diene rubber such as polyisoprene rubber (IR), butyl rubber (BR) and an optional blend rubber thereof, particularly a diene rubber containing at least one styrene-butadiene copolymer rubber, and a rubber obtained thereby.
  • IR polyisoprene rubber
  • BR butyl rubber
  • an optional blend rubber thereof particularly a diene rubber containing at least one styrene-butadiene copolymer rubber, and a rubber obtained thereby.
  • the raffinate and extract obtained by the polar solvent extraction method using a distillation under reduced pressure as a raw material have a high flash point, a low glass transition point, and a high total aromatic content.
  • An aromatic-containing base oil in which the content of cancerous substances is sufficiently reduced can be provided.
  • the manufacturing method of the aromatic containing base oil which can manufacture such an aromatic containing base oil with a high yield can be provided.
  • the rubber compounding oil of the present embodiment is excellent in affinity with rubber, softening property, flash point and safety, and has various properties of the rubber composition such as low fuel consumption, grip properties, heat aging resistance and heat wear resistance. In order to achieve a high level, it is preferable to have the following properties.
  • Aromatic content according to ASTM D2007 usually 50 to 90% by weight, preferably 55% by weight or more, more preferably 57% by weight or more, particularly preferably 60% by weight or more, preferably 80% by weight or less, more preferably Is 70% by mass or less.
  • Saturation by ASTM D2007 (Claygel method): Usually 5 to 50% by mass, preferably 10% by mass or more, more preferably 20% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less.
  • Polar compound content according to ASTM D2007 (Clay gel method): usually 1 to 20% by weight, preferably 2% by weight or more, more preferably 5% by weight or more, preferably 15% by weight or less, more preferably 12% by weight or less, and further preferably Is 10% by mass or less.
  • Saturated / polar compound ratio by ASTM D2007 (Claygel method): usually 0.25 to 50, preferably 1 or more, more preferably 2.5 or more, more preferably 3 or more, preferably 20 or less, more Preferably it is 10 or less, More preferably, it is 5 or less.
  • the content of benzo (a) pyrene (BaP) is 1 mass ppm or less, and the total content of the specific aromatic compounds (PAH) of 1) to 8) shown below is 10 mass ppm or less. Thereby, it can be set as the rubber
  • benzo (a) pyrene means benzo (a) pyrene (BaP) of 1) above
  • specific aromatic compound means an aromatic compound (PAH) of 1) to 8) above.
  • PAH aromatic compound
  • the flash point is 250 ° C. or higher, preferably 260 ° C. or higher, more preferably 280 ° C. or higher, preferably 350 ° C. or lower, more preferably 320 ° C. or lower, and even more preferably 310 ° C. or lower.
  • the flash point in this specification means the flash point by the Cleveland open type (COC) measured based on JIS K2265.
  • the difference between the pour point and the glass transition point is 45 ° C. or higher, preferably 50 ° C. or higher, more preferably 60 ° C. or higher, further preferably 65 ° C. or higher, preferably 100 ° C. or lower, more preferably 80 ° C. or lower.
  • the pour point is preferably 30 ° C. or lower, more preferably 25 ° C. or lower, preferably ⁇ 10 ° C. or higher, more preferably 5 ° C. or higher, still more preferably + 10 ° C. or higher, and particularly preferably + 12.5 ° C. or higher.
  • the pour point in the specification means a pour point measured according to JIS K2269.
  • the glass transition point (T g ) is preferably ⁇ 30 ° C. or less, more preferably ⁇ 40 ° C. or less, further preferably ⁇ 45 ° C. or less, particularly preferably ⁇ 48 ° C. or less, and particularly preferably ⁇ 50 ° C. or less.
  • the temperature is preferably ⁇ 80 ° C. or higher, more preferably ⁇ 60 ° C. or higher, and still more preferably ⁇ 55 ° C. or higher.
  • Glass transition point (T g ) in the present specification refers to the glass transition region measured when the temperature is increased at a constant rate of temperature increase (10 ° C./min) with a DSC (differential scanning calorimeter). It means the glass transition point obtained from the calorie change peak.
  • the initial temperature is usually about 30 ° C. to 50 ° C. or lower than the expected glass transition point, and the temperature is raised after the initial temperature is maintained for a certain time. In this embodiment, specifically, it can be measured under the following conditions.
  • heat amount change peak can be determined by the method described in JISK7121.
  • the density at 15 ° C. is usually 0.9 g / cm 3 to 1.0 g / cm 3 , preferably 0.94 g / cm 3 or more, more preferably 0.945 g / cm 3 or more, preferably 0.98 g / cm 3. Or less, More preferably, it is 0.96 g / cm 3 or less.
  • the kinematic viscosity at 40 ° C. is usually 200 to 3000 mm 2 / s, preferably 300 mm 2 / s or more, more preferably 400 mm 2 / s, still more preferably 500 mm 2 / s or more, preferably 2000 mm 2 / s or less, More preferably, it is 1000 mm ⁇ 2 > / s or less, More preferably, it is 800 mm ⁇ 2 > / s or less.
  • the kinematic viscosity at each temperature referred to in this specification means the kinematic viscosity at each temperature measured according to JIS K2283.
  • the kinematic viscosity at 100 ° C. is usually 10 to 100 mm 2 / s, more preferably 15 mm 2 / s or more, further preferably 20 mm 2 / s or more, preferably 60 mm 2 / s or less, more preferably 50 mm 2 / s. More preferably, it is 32 mm 2 / s or less.
  • the aniline point is usually 50 to 100 ° C., preferably 60 ° C. or higher, more preferably 65 ° C. or higher, further preferably 70 ° C. or higher, preferably 90 ° C. or lower, more preferably 85 ° C. or lower.
  • the aniline point in this specification means an aniline point measured according to JIS K 2256-1985.
  • the nitrogen content is usually 0.01 to 0.2% by mass, preferably 0.03% by mass or more, more preferably 0.05% by mass or more, preferably 0.15% by mass or less, more preferably 0.1% by mass. % Or less.
  • the nitrogen content in this specification means the nitrogen content by the chemiluminescence method measured based on JISK2609.
  • % CN is usually 5 to 30, preferably 10 or more, more preferably 14 or more, preferably 25 or less, more preferably 20 or less.
  • % C A is generally 10 to 40, preferably 17 or more, more preferably 20 or more, preferably 35 or less, and more preferably 30 or less, still more preferably 25 or less.
  • % CP is usually 30 to 85, preferably 40 or more, more preferably 50 or more, preferably 73 or less, more preferably 66 or less.
  • % C P ,% CN and% C A in this specification are determined by methods (ndM ring analysis) based on ASTM D 3238-85, respectively. Means the percentage of paraffin carbons to total carbons, the percentage of naphthene carbons to total carbons, and the percentage of aromatic carbons to total carbons.
  • the total aromatic content is usually 30 to 90% by mass, preferably 40% by mass or more, more preferably 50% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less.
  • the total aromatic content in this specification means the content of aromatic fraction measured according to ASTM D 2007 or ASTM D 2549 unless otherwise specified. To do.
  • the rubber compounding oil of the present embodiment contains raffinate obtained by separating a vacuum distillation fraction of crude oil atmospheric distillation residue in a solvent extraction step or a refined oil thereof, and has a kinematic viscosity at 40 ° C. of 60 to 600 mm. 2 / s, aniline point is 70 ° C.
  • Aromatic-containing base oil (a) containing an aromatic-containing base oil at a temperature of °C or less, and an extract obtained by separating a vacuum distillation residue of atmospheric distillation residue oil in a solvent extraction step or a refined oil thereof An aromatic having a kinematic viscosity at 40 ° C. of 200 mm 2 / s or more, an aniline point of 90 ° C. or less, a density at 15 ° C.
  • base oil (a) the aromatic-containing base oil (a) (hereinafter referred to as base oil (a)) and the aromatic-containing base oil (b) (hereinafter referred to as base oil (b)) will be described.
  • the above base oil (a) is obtained by contacting the distillation under reduced pressure of crude oil atmospheric distillation residue with a polar solvent in the first extraction tower having a tower bottom temperature of 30 to 90 ° C. and a tower top temperature higher than the tower bottom temperature.
  • a second raffinate is brought into contact with a polar solvent to obtain a second extract having a density of 0.94 g / cm 3 or more at 15 ° C. and a total aromatic content of 30% by mass or more with the second raffinate.
  • the second raffinate obtained by the solvent extraction step is preferably an aromatic-containing base oil having a total aromatic content of 30% by mass or more obtained by purification treatment.
  • the base oil (a) is an aromatic-containing base oil obtained by subjecting the second raffinate to a refining process including a dewaxing process, and has a kinematic viscosity at 40 ° C. of 60 to 120 mm 2 / s and is a GC distillation.
  • the base oil (a1) having a 10% point of 400 to 460 ° C. and a 90% point of 500 to 540 ° C. and / or a kinematic viscosity at 40 ° C. of 120 to 250 mm 2 / s and a 10% point by GC distillation of 450 to
  • a base oil (a2) having a 520 ° C. and 90% point of 540 to 600 ° C. is preferred.
  • the base oil (b) has a kinematic viscosity at 40 ° C. of 200 mm 2 / s or more, a flash point of 250 ° C. or more, a pour point of 30 ° C. or less, an aniline point of 90 ° C. or less, and a glass transition point of ⁇ 30 ° C. It is preferably an aromatic-containing base oil having a difference between the pour point and the glass transition point of 45 ° C. or higher.
  • kinematic viscosity at ° C. is 200 mm 2 / s or more 500 mm 2 / s, a glass transition point of -60 ⁇ -40 ° C. aromatic-containing base oil (b1) and / or 40 ° C.
  • An aromatic-containing base oil (b2) having a kinematic viscosity of 500 mm 2 / s or more and a glass transition point of ⁇ 50 to ⁇ 30 ° C. is preferable.
  • the pour point of the base oil (a) is preferably ⁇ 10 ° C. or lower and may be lower than ⁇ 20 ° C. However, the pour point of the base oil (a) is more preferably ⁇ 10 to ⁇ 20 ° C. from the viewpoint of the production cost of the rubber compounding oil.
  • the base oil (a) having a pour point of ⁇ 10 ° C. or lower a rubber compounding oil having a lower glass transition point can be easily obtained.
  • the glass transition point of the base oil (a) is preferably ⁇ 30 ° C. or lower, more preferably ⁇ 50 ° C. or lower, preferably ⁇ 100 ° C. or higher, more preferably ⁇ 80 ° C. or higher, and further preferably ⁇ 70 ° C. or higher. . If the glass transition point is too high, it tends to be difficult to obtain a rubber compounding oil having a low glass transition point. If the glass transition point is too low, the manufacturing cost tends to increase because it is necessary to make the dewaxing conditions excessively strict. There is.
  • the aniline point of the base oil (a) is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, and still more preferably 100 ° C. or higher. From the viewpoint of facilitating production of a rubber compounding oil that has excellent compatibility with rubber and that has a suitable aniline point for maintaining the properties of the rubber composition, the temperature is preferably 120 ° C. or lower.
  • the composition of the base oil (a),% C A is preferably 3 to 20, more preferably 5 ⁇ 10,% C N is preferably 15 to 35, more preferably 20-30.
  • % C P in the base oil (a) is determined depending on% C A and% C N , and is preferably 45 to 82, more preferably 60 to 75, and still more preferably 65 to 70.
  • the nitrogen content of the base oil (a) is preferably 0.01% by mass or less, more preferably 0.008% by mass or less, and may be less than 0.001% by mass.
  • the manufacturing cost of the rubber compounding oil can be reduced by using a lubricating base oil having a low degree of purification, it is preferably 0.002% by mass or more, more preferably 0.003% by mass or more from the viewpoint of economy. is there.
  • the flash point of the base oil (a) is 250 ° C. or higher, preferably 255 ° C. or higher, from the viewpoint that the flash point of the rubber compounding oil is 250 ° C. or higher and is excluded from the scope of dangerous materials No. 4 petroleums. Since the flash point of the base oil (b) can be increased, it is not necessary to increase the flash point of the base oil (a) more than necessary, preferably 290 ° C. or less, more preferably 280 ° C. or less. It is.
  • the 90% point in the GC distillation of the base oil (a) is 500 ° C. or higher, preferably 500 to 600 ° C.
  • the base oil (a1) as one embodiment of the base oil (a) has a temperature of 510 to 550 ° C.
  • the base oil (a2) as another embodiment of the base oil (a) has a temperature of 550 to 590 ° C.
  • limiting in particular in the 10% point in GC distillation of base oil (a) Preferably the flash point of rubber compounding oil is 250 degreeC or more, and the point which can be excluded from a dangerous material 4th petroleum.
  • the temperature is 400 to 510 ° C, preferably 440 to 500 ° C.
  • base oil (a1) a 10% point in the GC distillation at 440 to 470 ° C. can be used, and as the base oil (a2), a 10% point in the GC distillation at 450 to 500 ° C. can be used.
  • the content of the above-mentioned 1) benzo (a) pyrene (BaP) is preferably 1 ppm by mass or less, and the above-mentioned specific aromatic compound (PAH) contained in 1) to 8)
  • the total amount is preferably 10 ppm by mass or less.
  • the kinematic viscosity at 40 ° C. of the base oil (a) is preferably 60 to 600 mm 2 / s, more preferably 60 to 300 mm 2 / s, and further preferably 70 to 200 mm 2 / s.
  • the kinematic viscosity at 40 ° C. is preferably 50 to 500 mm 2 / s in order to obtain a rubber compounding oil having a suitable kinematic viscosity. It is preferable to use a base oil (a1) of 60 to 80 mm 2 / s and / or a base oil (a2) of 120 to 250 mm 2 / s.
  • the total aromatic content of the base oil (a) is not particularly limited, and is usually 20% by mass or more, preferably 30% by mass or more, more preferably 35% by mass or more, preferably 50% by mass or less, more preferably 45% by mass. % Or less.
  • the total aromatic content of the base oil (a) is less than 20% by mass, it tends to be difficult to obtain a rubber compounding oil having high aromaticity.
  • the total aromatic content of the base oil (a) exceeds 50% by mass, the oxidative stability when used as a lubricating base oil will be reduced, and it will be used for both lubricating base oil and rubber compounding oil applications. Tends to be difficult and the overall economics of the oil refining process tend to decline.
  • the aniline point of the base oil (b) is preferably 40 to 90 ° C, more preferably 45 to 70 ° C, still more preferably 50 to 65 ° C. If the aniline point is within this range, even if a lubricating base oil having a high aniline point is blended, the rubber blended oil having an aniline point suitable for maintaining compatibility with rubber and maintaining the properties of the rubber composition. Can be easily manufactured.
  • composition of the base oil (b) is preferably 25 to 45, more preferably 30 ⁇ 40,% C N is preferably 5-20, more preferably 6-12. Further,% C P is determined depending on% C A and% C N and is preferably 35 to 70, more preferably 48 to 64. If composition of base oil (b) is the said range, even if it mix
  • the nitrogen content of the base oil (b) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and particularly preferably 0.15% by mass or more. .
  • the nitrogen content of the base oil (b) is high, the nitrogen content of the raffinate obtained by the solvent extraction step is low, and the refinement degree of the lubricating base oil is increased. Therefore, it is preferable to use the base oil (b) having a high nitrogen content as the rubber compounding oil because the entire vacuum distillation fraction can be effectively used.
  • the pour point of the base oil (b) is preferably 30 ° C or lower, more preferably 25 ° C or lower.
  • the pour point of the base oil (b) is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, further preferably 15 ° C. or higher, and particularly preferably 20 ° C. or higher.
  • the base oil (b) may be an unrefined extract having a high pour point, and preferably has a low glass transition point.
  • the difference between the pour point and the glass transition point of the base oil (b) (pour point-glass transition point) is preferably 45 ° C or higher, more preferably 50 ° C or higher, further preferably 55 ° C or higher, particularly preferably 60 ° C. Above, preferably 100 ° C. or lower, more preferably 80 ° C. or lower.
  • the glass transition point of the base oil (b) is preferably ⁇ 30 ° C. or lower, preferably ⁇ 60 ° C. or higher.
  • the glass transition point of the aromatic-containing base oil (b1) which is one embodiment of the base oil (b) is ⁇ 60 to ⁇ 40 ° C.
  • the glass transition point of the aromatic-containing base oil (b2) which is another embodiment Is ⁇ 50 to ⁇ 30 ° C.
  • the base oil (b) preferably has a content of 1) benzo (a) pyrene (BaP) of 1 ppm by mass or less, and the specific aromatic compound (PAH) of 1) to 8) above.
  • the total content of is preferably 10 mass ppm or less.
  • the flash point of the base oil (b) is not particularly limited, but is preferably 250 ° C. or higher, more preferably 250 ° C. or higher, so that the flash point of the rubber compounding oil is 250 ° C. or higher and excluded from the target of hazardous materials No. 4 petroleums. It is 270 ° C. or higher, more preferably 290 ° C. or higher, particularly preferably 300 ° C. or higher.
  • the total aromatic content of the base oil (b) is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 55% by mass or more, particularly preferably 60% by mass or more, and particularly preferably 65% by mass. It is above, Preferably it is 90 mass% or less, More preferably, it is 80 mass% or less, More preferably, it is 75 mass% or less.
  • the total aromatic content of the base oil (b) is less than 50% by mass, it tends to be difficult to obtain a rubber compounding oil having high aromaticity.
  • the total aromatic content exceeds 90% by mass, the extract Since the yield deteriorates, it is not preferable from the viewpoint of economy.
  • the first solvent extraction step and the second solvent extraction step for producing the base oil (a) and the base oil (b), and the produced base oil (a) and the base oil (b) are blended.
  • the first solvent extraction step in a first extraction tower having a tower bottom temperature of 30 to 90 ° C. and a tower top temperature higher than the tower bottom temperature, a vacuum distillation fraction of a crude oil atmospheric distillation residue, a polar solvent, To obtain a first raffinate and a first extract.
  • the first raffinate and the polar solvent are brought into contact with each other in the second extraction tower having a tower bottom temperature and a tower top temperature higher by 10 ° C. or more than the first extraction tower, respectively.
  • 2 raffinate and a second extract having a density of 0.94 g / cm 3 or more at 15 ° C. and a total aromatic content of 30% by mass or more are obtained. Details of each step will be described below.
  • FIG. 1 is a process diagram for explaining a first solvent extraction step and a second solvent extraction step in the method for producing a rubber compounding oil according to this embodiment.
  • a vacuum distillation fraction of crude oil atmospheric distillation residue is first extracted in the first extraction tower 30 having a tower bottom temperature of 30 to 90 ° C. and a tower top temperature higher than the tower bottom temperature.
  • the first raffinate and the first extract are separated by countercurrent contact with a polar solvent.
  • the polar solvent is supplied from the pipe 34 to the first extraction tower 30.
  • the vacuum distillation fraction is supplied to the first extraction tower 30 through the pipe 16.
  • the vacuum distillation fraction is a fraction obtained by introducing normal distillation residue of crude oil into a vacuum distillation apparatus.
  • the vacuum distillation fraction is not particularly limited, and a light lubricating oil fraction, a medium lubricating oil fraction, a heavy lubricating oil fraction, a mixture thereof, or a vacuum distillation fraction must be used. Can do. From the viewpoint of increasing the flash point of the finally obtained aromatic-containing base oil and obtaining an aromatic-containing base oil having an appropriate viscosity range without excessively increasing the viscosity, for example, 200 to 1500 N, preferably 250 to 1200 N, More preferably, a lubricating oil fraction of 300 to 600 N or 600 to 1200 N is used.
  • N means a neutral oil obtained from a vacuum distillation fraction. For example, if it is 300 N, the viscosity at 100 ° F. (37.8 ° C.) is 300 Seyvolt universal seconds. (SUS).
  • the vacuum distillation fraction is selected so that the base oil (a) has a viscosity of 200 to 1500 N, preferably 250 to 600 N or 600 to 1200 N, more preferably 300 to 450 N or 700 to 1000 N. It is preferable.
  • the bottom temperature of the first extraction tower 30 used in the first solvent extraction step is 30 to 90 ° C., preferably 50 to 70 ° C., more preferably 55 to 65 ° C.
  • the top temperature of the first extraction tower 30 is higher than the bottom temperature, preferably 10 to 50 ° C., more preferably 15 to 40 ° C., and further preferably 25 to 35 ° C.
  • the column top temperature is preferably 60 to 120 ° C, more preferably 80 to 100 ° C, and still more preferably 85 to 95 ° C.
  • the solvent ratio in the first solvent extraction step is preferably 0.5 to 3, more preferably 0.7 to 2, and still more preferably 1 to 1.5.
  • the “solvent ratio” means the volume ratio of the solvent to the raw material (solvent volume / raw material volume).
  • the polar solvent and the distillation under reduced pressure are in countercurrent contact within the first extraction tower 30, and the first extract and the polarity pass through the pipe 38 from the bottom of the first extraction tower 30.
  • a mixture with the solvent is obtained, and a mixture of the first raffinate and the polar solvent is obtained through the pipe 36 from the top of the column.
  • the mixture of the first extract and the polar solvent is fractionated into the first extract and the polar solvent in a fractionation tower (not shown).
  • the mixture of the first raffinate and the polar solvent may be fractionated into the first raffinate and the polar solvent in a fractionation tower (not shown). May be introduced.
  • the first extract and the first raffinate and the polar solvent fractionated are recovered and reused.
  • the polar solvent include polar solvents such as furfural, phenol, cresol, sulfolane, N-methylpyrrolidone, dimethyl sulfoxide, formylmorpholine, and glycol solvents.
  • furfural in that a general solvent base equipment for lubricating base oil can be used as it is.
  • the vacuum distillation fraction is separated into the first raffinate and the first extract.
  • the yield of the first raffinate obtained in the first solvent extraction step is preferably 50 to 90% by volume, more preferably 60 to 85% by volume, still more preferably 70 to 80% by volume based on the vacuum distillation fraction. %.
  • the yield of the first extract obtained in the first solvent extraction step is preferably 10 to 50% by volume, more preferably 15 to 40% by volume, still more preferably 20 to 30%, based on the vacuum distillation fraction. It is volume%.
  • the specific aromatic compound (PAH) described later is extracted on the first extract side by the first solvent extraction step, the second extract in the subsequent stage, the second raffinate, and the aromatic obtained therefrom.
  • the content of the specific aromatic compound (PAH) in the contained base oil can be sufficiently reduced.
  • a 1st extract contains a specific aromatic compound (PAH)
  • PAH specific aromatic compound
  • the total of the second raffinate and the second extract can be 70% by volume or more based on the distillation under reduced pressure, and the method for producing an aromatic-containing base oil of this embodiment is a resource. It can be said that it is extremely useful from the viewpoint of effective utilization of.
  • the first raffinate obtained in the first solvent extraction step or the mixture of the first raffinate and the polar solvent and the polar solvent are supplied from the pipe 36 and the pipe 44 to the second extraction tower 40.
  • the first raffinate and the polar solvent are brought into contact with each other.
  • the second extraction tower 40 has a tower bottom temperature and a tower top temperature that are 10 ° C. or more higher than the first extraction tower 30.
  • the bottom temperature of the second extraction column 40 used in the second solvent extraction step is 10 ° C. higher than the bottom temperature of the first extraction column 30 in the first solvent extraction step, preferably 10 to 50
  • the temperature is increased by a higher temperature, more preferably by 15 to 40 ° C., and further preferably by 20 to 30 ° C.
  • the bottom temperature of the second extraction tower 40 is preferably 40 to 140 ° C., more preferably 60 to 100 ° C., and still more preferably 80 to 95 ° C.
  • the top temperature of the second extraction tower 40 is preferably 10 to 50 ° C. higher, more preferably 15 to 40 ° C., and further preferably 25 to 35 ° C. higher than the tower bottom temperature.
  • the top temperature of the second extraction tower 40 is preferably 50 to 150 ° C., more preferably 80 to 140 ° C., and further preferably 110 to 130 ° C.
  • the solvent ratio in the second solvent extraction step is preferably 1 to 4, more preferably 1.3 to 3.5, and still more preferably 1.5 to 3.3.
  • the solvent ratio in the second solvent extraction step is preferably 1.5 times or more the solvent ratio in the first solvent extraction step.
  • the polar solvent and the first raffinate are in countercurrent contact inside the second extraction tower 40, and the second extract and the polarity are passed through the pipe 48 from the bottom of the second extraction tower 40.
  • a mixture with the solvent is obtained, and a mixture of the second raffinate and the polar solvent is obtained from the top of the column through the pipe 46.
  • the mixture of the second extract and the polar solvent is fractionated into the second extract and the polar solvent in a fractionation tower (not shown).
  • the mixture of the second raffinate and the polar solvent is fractionated into the second raffinate and the polar solvent in a fractionation tower (not shown).
  • the polar solvent separated from the second extract and the second raffinate is recovered and reused.
  • the first raffinate is separated into the second raffinate and the second extract.
  • the yield of the second raffinate obtained in the second solvent extraction step is preferably 50 to 90% by volume, more preferably 60 to 85%, based on the first raffinate introduced into the second extraction column 40.
  • the volume percentage is more preferably 70 to 85 volume%.
  • the yield of the second extract obtained in the second solvent extraction step is preferably 10 to 50% by volume, more preferably 15 to 40% by volume, and further preferably 15 to 30% by volume.
  • the raffinate obtained in the first solvent extraction step (preferably from which the polar solvent has been removed) is once stored in a tank or the like, and the extraction conditions are adjusted to the conditions of the second solvent extraction step.
  • the second solvent extraction step may be performed by introducing into the extraction tower 40. In this way, excessive capital investment can be made.
  • the second solvent extraction step it is possible to obtain the first raffinate and the second extract having a density at 0.9 ° C. of 0.94 g / cm 3 or more and a total aromatic content of 30% by mass or more. it can. If the density of the second extract at 15 ° C. is 0.94 g / cm 3 or more, the total aromatic content is high, the aniline point is sufficiently low, the flash point is high, and the difference between the pour point and the glass transition point is large. It is useful as a petroleum process oil or a base material thereof in the production process of rubber products such as tires using a diene rubber, or as an extender oil or a base material thereof in the production process of a diene rubber.
  • a highly aromatic base oil that is useful as a lubricating base oil, petroleum-based process oil, extender oil or its base material having a total aromatic content of 30% by mass or more is high. It can be obtained in a yield.
  • the density of the second extract at 15 ° C. is preferably 0.94 g / cm 3 or more, more preferably 0.95 to 1 g / cm 3 , and still more preferably 0.95 to 0.98 g / cm 3 .
  • the total aromatic content is preferably 30% by mass or more, more preferably 60% by mass or more, further preferably 80% by mass or more, and preferably 90% by mass or less.
  • the “total aromatic content” in the present specification is a value measured according to ASTM D2549.
  • the second extract preferably has a% C A measured by ASTM D2140 of preferably 15 to 35, more preferably 20 to 33, and still more preferably 22 to 32.
  • This second extract preferably has the following properties. Flash point: preferably 250 ° C. or higher, more preferably 260 ° C. or higher, preferably 310 ° C. or lower.
  • -Pour point preferably 30 ° C or lower, more preferably 10-30 ° C.
  • Aniline point preferably 90 ° C. or less, more preferably 40 to 80 ° C., still more preferably 50 to 70 ° C.
  • Glass transition point preferably ⁇ 30 ° C. or lower, more preferably ⁇ 40 ° C. or lower, and further preferably ⁇ 60 ° C. or higher.
  • Difference between pour point and glass transition point (pour point-glass transition point) preferably 45 ° C. or higher, more preferably 50 ° C.
  • -Benzo (a) pyrene content Preferably it is 1 mass ppm or less.
  • a lubricating base oil that is a refined oil can be obtained. It can.
  • the aromatic-containing base oil (lubricating base oil) thus obtained can be used as the base oil (a).
  • the base oil (a) may be a mixture of two or more aromatic-containing base oils (lubricant base oils) obtained as described above.
  • the base oil (a) thus obtained preferably has a total aromatic content of 30% by mass or more, more preferably 30 to 60% by mass.
  • the base oil (a) is preferably 200 to 1500 N, more preferably 250 N or more and less than 600 N base oil (a1) and / or 600 to 1200 N base oil (a2), more preferably 300 to 450 N base oil (a1). And / or 700 to 1000 N base oil (a2).
  • the distillation under reduced pressure to obtain 500N aromatic-containing base oil may contain a large amount of the above-mentioned 8 kinds of specific aromatic compounds (PAH), and also contains aromatics with high flash points with different viscosities. It tends to be difficult to obtain two or more base oils at the same time. For this reason, it is preferable to obtain an aromatic-containing base oil using a base oil (a1) of 300 to 450N and / or a base oil (a2) of 700 to 1000N.
  • PAH specific aromatic compounds
  • the total aromatic content is 30% by mass using at least one selected from the second extract and the second raffinate after the second solvent extraction step. You may have the base oil preparation process which obtains the aromatic containing base oil which is the above.
  • an aromatic-containing base oil having a total aromatic content of 30% by mass or more is obtained using at least one selected from the second extract and the second raffinate.
  • the second raffinate is subjected to refining treatment including dewaxing treatment, and the refined oil has a pour point of ⁇ 5 ° C. or lower, an aniline point of 90 ° C. or higher, a viscosity index of 90 or higher, and a flash point of 250 ° C. or higher.
  • (Dewaxed oil) may be obtained and used as an aromatic-containing base oil.
  • As the purification treatment dewaxing treatment and hydrofinishing are preferably performed.
  • the refined oil obtained by performing the above-described refining treatment can be suitably used as a lubricating base oil, a rubber compounding oil, or a base material thereof.
  • the kinematic viscosity when a 200 to 1500 N refined oil is obtained from the second raffinate, when the first and second solvent extraction steps are performed using a vacuum distillation fraction corresponding to this viscosity as a raw material, the kinematic viscosity at 40 ° C.
  • a second extract of preferably 200 mm 2 / s or more, more preferably 250 mm 2 / s or more, further preferably 5000 mm 2 / s or less, particularly preferably 2000 mm 2 / s or less.
  • the second raffinate and / or the refined oil thereof contains an aromatic-containing base oil having a total aromatic content of 30% by mass or more (hereinafter referred to as “aromatic-containing base oil a”), and / or.
  • aromatic-containing base oil b an aromatic-containing base oil having a total aromatic content of 30% by mass or more
  • a fraction is appropriately separated from the second raffinate and the second extract by appropriate distillation, and then a part of the second raffinate and a part of the second extract are respectively base oil. It is good also as (a) and base oil (b). Moreover, it is good also considering the 2nd raffinate and 2nd extract obtained by the 2nd solvent extraction process as base oil (a) and base oil (b) as it is, without performing a base oil preparation process.
  • the base oil (a) and the base oil (b) having the desired properties are co-produced by appropriately selecting the vacuum distillation fraction as the raw material according to the desired base oil (a) and the base oil (b). It is preferable to obtain as.
  • a refining step is performed to obtain a lubricating base oil having a base oil (a) of 300 N or more and less than 600 N, and a base oil (b) having a kinematic viscosity at 40 ° C. of 200 mm 2 / s or more and less than 500 mm 2 / s. It is possible to obtain one having a thickness of 250 to 350 mm 2 / s, more preferably 250 to 300 mm 2 / s.
  • a base oil (a) of 600 to 1200 N of lubricating oil base oil when obtaining a base oil (a) of 600 to 1200 N of lubricating oil base oil, the above-described first and second solvent extraction steps are carried out using a vacuum distillation fraction corresponding to this fraction as a raw material,
  • a base oil (a) is obtained as a base oil (a) of 600 to 1200 N
  • a base oil (b) has a kinematic viscosity at 40 ° C. of 500 to 5000 mm 2 / s, preferably 800 to 2000 mm. 2 / s, more preferably 900 to 1500 mm 2 / s can be obtained.
  • the base oil (a) of the present embodiment may be obtained by subjecting the second raffinate to a purification treatment including dewaxing, hydrofinishing, and the like.
  • the base oil (a) (lubricating base oil) thus obtained has a total aromatic content of 30% by mass or more, preferably 30 to 60% by mass.
  • the base oil (a) is preferably obtained as a lubricating base oil of 200 to 1500 N, more preferably 250 N or more and less than 600 N, or 600 to 1200 N, more preferably 300 to 450 N or 700 to 1000 N.
  • the base oil (a) 300N to 450N or 700 to 1000N is particularly preferable.
  • the base oil (a) is 600 to 1200 N, preferably 700 to 1000 N, it preferably further has the following properties in addition to the above specific properties.
  • Kinematic viscosity at 40 ° C . 120 to 250 mm 2 / s, preferably 150 to 200 mm 2 / s.
  • a base oil (a) and a base oil (b) having a specific aromatic compound (PAH) content of a predetermined amount or less can be obtained.
  • the “specific aromatic compound (PAH)” in the present specification means the following eight specific aromatic compounds (PAH).
  • the content of benzo (a) pyrene (BaP) in 1) is 1 ppm by mass or less, and eight types of 1) to 8) below are specified.
  • the sum total of content of an aromatic compound (PAH) can be 10 mass ppm or less.
  • PAH specific aromatic compounds
  • Base oil (a) and base oil (b) are suitable as a lubricant base oil, a rubber compounding oil, or a base material thereof.
  • the base oil (a) has a sufficiently reduced content of the specific aromatic compound (PAH), and has a flash point of 250 ° C. or higher and a pour point of ⁇ 5 ° C. or lower. It is also suitable. Further, since the total aromatic content is 30% by mass or more and the glass transition point is ⁇ 30 ° C. or less, it can be used as petroleum-based process oil or extender oil or its base material.
  • PAH specific aromatic compound
  • the base oil (b) has a sufficiently reduced content of the specific aromatic compound (PAH), has a flash point of 250 ° C. or higher, a total aromatic content of 30% by mass or more, and a glass transition point of ⁇ Since it is 30 ° C. or lower, it can be used as a petroleum-based process oil or extender oil or a base material thereof.
  • PAH specific aromatic compound
  • the base oil (a), the base oil (b) or a mixture thereof for example, by adjusting the glass transition temperature to ⁇ 55 to ⁇ 30 ° C. and the kinematic viscosity (100 ° C.) to 20 to 50 mm 2 / s, A petroleum process oil or extender oil particularly suitable for blending with a diene rubber can be obtained.
  • a tire produced by blending such a petroleum process oil or extender oil with a diene rubber can achieve both low fuel consumption and grip, and can improve heat aging resistance and wear resistance.
  • the aromatic content contains a high flash point, a low glass transition point, and a sufficiently low content of carcinogenic substances while having a high total aromatic content.
  • Base oil can be obtained in high yield.
  • it since it has properties suitable for lubricating base oil, petroleum-based process oil or extender oil or its base material, and can simultaneously produce a plurality of types of aromatic-containing base oils having different viscosities, Especially useful in industry.
  • the base oil (a) preferably has the following properties.
  • Pour point preferably ⁇ 5 ° C. or lower, more preferably ⁇ 10 ° C. or lower, still more preferably ⁇ 20 ° C. or higher.
  • Glass transition point preferably ⁇ 30 ° C. or lower, more preferably ⁇ 40 ° C. or lower, further preferably ⁇ 50 ° C. or lower, preferably ⁇ 60 ° C. or higher, more preferably ⁇ 100 ° C. or higher, more preferably ⁇ 80 ° C. or higher. Particularly preferred is ⁇ 70 ° C. or higher.
  • -Aniline point Preferably it is 70 degreeC or more, More preferably, it is 90 degreeC or more, More preferably, it is 105 degreeC or more, Preferably it is 120 degrees C or less. Viscosity index: preferably 90 or more, more preferably 95 or more, preferably 120 or less, more preferably 105 or less. Flash point: preferably 250 ° C. or higher, preferably 310 ° C. or lower.
  • ⁇ ASTM D 3238 by base oil composition % C P is preferably 60 ⁇ 70,% C N is preferably 20 ⁇ 30,% C A is preferably 5-10.
  • -Benzo (a) pyrene content Preferably it is 1 mass ppm or less.
  • -Total content of a specific aromatic compound (PAH) Preferably it is 10 mass ppm or less.
  • the base oil (a1) which is 300 N or more and less than 600 N, preferably 300 to 450 N, preferably has the following properties.
  • Kinematic viscosity at 40 ° C . preferably 60 to 120 mm 2 / s, more preferably 65 to 90 mm 2 / s, still more preferably 70 to 80 mm 2 / s.
  • 10% point by GC distillation preferably 400 to 460 ° C, more preferably 430 to 450 ° C. -90% point by GC distillation: preferably 500 to 540 ° C, more preferably 510 to 530 ° C.
  • the value of the gas chromatography in this specification is a value measured based on ASTM D2887.
  • the base oil (a2) 600-1200N, preferably 700-1000N aromatic-containing base oil preferably has the following properties in addition to the properties described above.
  • Kinematic viscosity at 40 ° C . preferably 120 to 250 mm 2 / s, more preferably 150 to 200 mm 2 / s.
  • 10% point by GC distillation preferably 450 to 520 ° C, more preferably 460 to 500 ° C. -90% point by GC distillation: preferably 540 to 600 ° C, more preferably 560 to 590 ° C.
  • Total aromatic content (ASTM D 2549): preferably 30% by mass or more, more preferably 35-60% by mass, still more preferably 40-50% by mass.
  • the second extract obtained by performing the first and second solvent extraction steps or an aromatic-containing base oil which is a refined oil thereof can be used.
  • the base oil (b) may be a mixture of two or more of the second extract obtained as described above or a refined oil thereof.
  • Base oil (b) is 40 kinematic viscosity 200 mm 2 / s or more 500mm less than 2 / s at ° C., a glass transition point kinematic viscosity at -60 ⁇ -40 ° C. of the base oil (b1) and / or 40 ° C. 500mm
  • the base oil (b2) is preferably 2 / s or more and a glass transition point of ⁇ 50 to ⁇ 30 ° C.
  • the base oil (b1) preferably has the following properties in addition to the properties described above.
  • Kinematic viscosity at 40 ° C . preferably 200 mm 2 / s or more and less than 500 mm 2 / s, more preferably 400 mm 2 / s or less, further preferably 350 mm 2 / s or less, particularly preferably 300 mm 2 / s or less.
  • Glass transition point preferably ⁇ 60 to ⁇ 40 ° C., more preferably ⁇ 55 to ⁇ 48 ° C.
  • Pour point preferably 0 to 30 ° C., more preferably 15 ° C. or higher, further preferably 20 ° C. or higher.
  • Difference between pour point and glass transition point preferably 60 ° C. or higher, more preferably 65 ° C. or higher, further preferably 70 ° C. or higher, preferably 100 ° C. or lower, more preferably 80 ° C. Less than.
  • Total aromatic content 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, preferably 90% by mass or less.
  • the base oil (b2) preferably has the following properties in addition to the properties described above.
  • Kinematic viscosity at 40 ° C . preferably 500 mm 2 / s or more, more preferably 800 mm 2 / s or more, further preferably 1000 mm 2 / s or more, preferably 5000 mm 2 / s or less, more preferably 2000 mm 2 / s or less, More preferably, it is 1500 mm ⁇ 2 > / s or less.
  • Glass transition point preferably ⁇ 50 to ⁇ 30 ° C., more preferably ⁇ 45 to ⁇ 35 ° C.
  • Total aromatic content 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, preferably 90% by mass or less.
  • the base oil (a) and the base oil (b) may be obtained by appropriately collecting a desired fraction by distillation. In this case, the viscosity of the vacuum distillation fraction as a raw material is not particularly limited.
  • the desired base oil (a) and the desired base oil (b) are co-products.
  • kinematic viscosity in 40 degreeC is 200 mm ⁇ 2 > / s as base oil (b1). It is preferable to obtain an extract (aromatic-containing base oil) of not less than 500 mm 2 / s, preferably 250 to 350 mm 2 / s, more preferably 250 to 300 mm 2 / s.
  • a vacuum distillation fraction corresponding to this fraction is used as a raw material.
  • an aromatic-containing base oil of 600 to 1200 N is obtained as the base oil (a2)
  • the kinematic viscosity at 40 ° C. of the base oil (b2) is 500 to 5000 mm 2 /
  • an extract (aromatic-containing base oil) of s preferably 800 to 2000 mm 2 / s, more preferably 900 to 1500 mm 2 / s.
  • the base oil (a) and the base oil (b) obtained as described above are blended at a predetermined ratio to prepare a rubber blending oil.
  • the base oil (a) is blended at a ratio of 95% by mass or less (excluding 0) and the base oil (b) at a ratio of 5% by mass or more based on the total amount of the rubber compounding oil.
  • the rubber compounding oil containing base oil (a) and base oil (b) can be obtained.
  • the compounding ratio of the base oil (a) is preferably 10 to 50% by mass, more preferably 20%, based on the total rubber compounding oil. -40 mass%. From the same viewpoint, the blending ratio of the base oil (b) is preferably 90 to 50% by mass, more preferably 80 to 60% by mass.
  • the base oil (a) preferably contains the base oil (a2).
  • the oil (b) preferably contains the base oil (b1) because the difference between the pour point and the glass transition point is particularly large, for example, 60 ° C. or higher.
  • the base oil (b) preferably includes the base oil (b1) and the base oil (b2).
  • the content ratio of the base oil (a) or the base oil (a2), the base oil (b1), and the base oil (b2) is preferably 10 to 40% by mass, 5 to 35% by mass, And 85 to 25% by mass, more preferably 20 to 30% by mass, 20 to 30% by mass, and 60 to 40% by mass.
  • base materials other than base oil (a) and base oil (b) can be mix
  • Example 1 Crude oil atmospheric distillation residue oil was distilled under reduced pressure using a normal vacuum distillation apparatus, and a fuel equivalent fraction, a fraction below 150N equivalent fraction, a 350N equivalent fraction and a 900N equivalent fraction were collected.
  • the collected fraction corresponding to 350N was treated with a polar solvent extraction apparatus as shown in FIG. Specifically, the 350N equivalent fraction is introduced into the first extraction tower 30 whose tower bottom temperature is lower than the tower top temperature, and the first solvent extraction is brought into contact with the polar solvent (furfural) and the 350N equivalent fraction. The process was performed.
  • a 350N equivalent fraction is separated from the first raffinate and polar solvent mixture obtained from the top portion of the first extraction tower 30 and the first extract and polarity obtained from the bottom portion. Separated into a mixture of solvents. Then, the polar solvent was collect
  • the first raffinate was introduced into the second extraction tower 40 where the tower bottom temperature was lower than the tower top temperature, and a second solvent extraction step was performed in contact with the polar solvent (furfural).
  • the first raffinate is separated into a mixture of the second raffinate and polar solvent obtained from the tower top portion and a mixture of the second extract and polar solvent obtained from the tower bottom portion. did.
  • the polar solvent was collect
  • the second raffinate had a total aromatic content of 30% by mass or more measured according to ASTM D2549. Further, the second extract had a density at 15 ° C. of 0.94 g / cm 3 or more and a total aromatic content measured according to ASTM D2549 of 30% by mass or more.
  • Table 1 shows production conditions and yields of the first solvent extraction step and the second solvent extraction step.
  • the above-mentioned second raffinate is purified by MEK dewaxing and hydrofinishing so that the pour point is ⁇ 10 ° C. or lower, and the aromatic-containing base oil having a total aromatic content of 30% by mass or more ( A lubricating base oil) was obtained. This was designated as base oil (A1). Moreover, the 2nd extract was used as base oil (B1) and (B3) component. Table 2 shows the properties of the base oil (A1), base oil (B1), and base oil (B3). The second extract was not purified.
  • the total content of benzo (a) pyrene and 8 types of specific aromatic compounds (PAH) was measured as follows. First, 1 g of each aromatic-containing base oil was dissolved in hexane in a 50 ml flask to prepare a 2% by mass sample solution. This sample solution was loaded onto 5% by mass water-containing silica gel, washed with hexane, and then the target component was eluted with a 1% by volume acetone / hexane solution. After the eluate was concentrated, a sample to which an internal standard was added was prepared, and identified and quantified with a general gas chromatograph mass spectrometer (GC-MS).
  • GC-MS general gas chromatograph mass spectrometer
  • Example 2 Crude oil atmospheric distillation residue oil was distilled under reduced pressure using a normal vacuum distillation apparatus, and a fuel equivalent fraction, a fraction below 150N equivalent fraction, a 350N equivalent fraction and a 900N equivalent fraction were collected.
  • the 900N equivalent fraction was introduced into the first extraction tower 30 instead of the 350N equivalent fraction, and the production conditions of the first and second solvent extraction steps were changed as shown in Table 3.
  • first and second raffinates and first and second extracts were produced.
  • manufacture was performed several times on the same conditions, and the manufactured goods of several lots were obtained.
  • Table 3 shows production conditions and yields of the first solvent extraction step and the second solvent extraction step.
  • the second raffinate in Example 2 also had a total aromatic content of 30% by mass or more measured according to ASTM D2549. Further, the second extract had a density at 15 ° C. of 0.94 g / cm 3 or more and a total aromatic content measured according to ASTM D2549 of 30% by mass or more.
  • Two types of second raffinate with different production lots are subjected to purification treatment by MEK dewaxing and hydrofinishing treatment so that the pour point is ⁇ 10 ° C. or less, and the total aromatic content is 30% by mass or more.
  • a variety of aromatic-containing base oils (lubricant base oils) were obtained. This was designated as base oil (A2) and base oil (A3).
  • the 2nd extract obtained at the 2nd solvent extraction process with the 2nd raffinate used for manufacture of base oil (A2) was made into base oil (B2).
  • the 2nd extract obtained at the 2nd solvent extraction process with the 2nd raffinate used for manufacture of base oil (A3) was made into base oil (B4).
  • Table 4 shows properties of the base oil (A2), base oil (A3), base oil (B2), and base oil (B4).
  • the total yield of the second raffinate and the second extract that are useful as a rubber compounding oil or a base material thereof is the same as that of the raw material oil of the first extraction tower.
  • the standard was 74 to 75% by volume (the yield of useful components).
  • the lubricating oil base oil (aromatic-containing base oil) useful as a rubber compounding oil or its base material can be manufactured with a high yield.
  • the base oils (A1), (A2), (A3), (B1), (B2), (B3) and (B4) of Examples 1 and 2 are all
  • the aromatic content was 30% by mass or more and the flash point was 250 ° C. or more. That is, in this example, by using a plurality of vacuum distillation fractions having different viscosities, a plurality of aromatic-containing base oils having different properties and different viscosities could be produced.
  • base oils (A1), (A2), (A3), (B1), (B2), (B3) and (B4) are carcinogenic benzo (a) pyrene and eight types of specific aromatics.
  • the total content of compound (PAH) was sufficiently reduced.
  • the base oil (B1) and the base oil (B2) have a difference between the pour point and the glass transition point of 50 ° C. or more, and the base oil (B1) has a specific property that the difference is 70 ° C. or more. Had. That is, it was confirmed that the base oil (B1) and the base oil (B2) both have a low glass transition point although the pour point is high.
  • the base oil (B1), base oil (B2), base oil (B3), and base oil (B4) of Examples 1 and 2 have an aromatic hydrocarbon content (C A ) of 20 to 35% by mass. high, since it has a moderate glass transition temperature T g, is blended into the rubber composition, it is possible to improve the tensile strength and wear resistance.
  • Example 3 The above base oils (A1), (A2), (B1) and (B2) were blended at the blending ratios shown in Table 5 to prepare rubber blending oils of Examples 3-1 to 3-4. Table 5 summarizes the properties of each rubber compounding oil.
  • the rubber compounding oils of Examples 3-1, 3-2, 3-3 and 3-4 all have a high aromatic content and flash point and are carcinogenic harmful substances. Was sufficiently reduced. Further, the difference between the pour point and the glass transition point was 45 ° C. or more.
  • the rubber compounding oils of Example 3-1 and Example 3-2 have a difference between the pour point and the glass transition point of 60 ° C. or more, and the total aromatic content according to ASTM D2549 or ASTM D2007 is 50% by mass or more. Despite the point being 15 ° C. or higher, it had a specific property that the glass transition point was ⁇ 45 ° C. or lower.
  • rubber compounding oils of Examples 3-1 to 3-4,% both by ASTM D3238 C A 20-35 a glass transition temperature T g is -55 ⁇ -30 ° C.
  • a kinematic viscosity (100 ° C.) is A process used for processing extender oil or diene rubber used in the production process of diene rubber because it is a petroleum process oil that is 20 to 50 mm 2 / s and does not substantially contain a specific aromatic compound (PAH).
  • PAH specific aromatic compound
  • the first raffinate thus obtained was purified by MEK dewaxing and hydrofinishing so that the pour point was ⁇ 10 ° C. or lower.
  • base oil (E1) and base oil (E2) two types of aromatic-containing base oils (lubricating base oils) having different production lots and having a total aromatic content of 30% by mass or more were obtained. This was designated as base oil (E1) and base oil (E2).
  • the extract was made into base oil (F).
  • Table 7 shows the properties of the base oil (E1), the base oil (E2), and the base oil (F).
  • the yield of the first raffinate based on the raw material introduced into the extraction tower was 60% by volume, and the yield of the first extract was 40% by volume.
  • the total content of the specific aromatic compound (PAH) that is carcinogenic in the aromatic-containing base oil (F) exceeded 10 ppm by mass.
  • This aromatic-containing base oil (F) is not suitable for use as a rubber blending oil as it is, and even when blended with another lubricating base oil, the blending ratio is usually 50% by mass or more. Can not do it.
  • This extract and the base oil (E1) of Reference Example 1 were blended at a mass ratio of 80:20 to prepare a rubber blended oil.
  • the rubber compounding oil had a pour point of 0 ° C. and a glass transition point of ⁇ 44.5 ° C., and the difference between the pour point and the glass transition point was 44.5 ° C.
  • a rubber compounding oil having a high flash point and a low glass transition point while maintaining a high total aromatic content, and having a sufficiently reduced content of a specific polycyclic aromatic compound, and its A method for producing a rubber compounding oil can be provided.
  • the raffinate and extract obtained by the polar solvent extraction method using a distillation under reduced pressure as a raw material have a high flash point, a low glass transition point, and a high total aromatic content.
  • An aromatic-containing base oil in which the content of cancerous substances is sufficiently reduced can be provided.
  • the manufacturing method of the aromatic containing base oil which can manufacture such an aromatic containing base oil with a high yield can be provided.

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JP7240202B2 (ja) 2019-02-28 2023-03-15 Ｅｎｅｏｓ株式会社 石油系芳香族含有油、ゴム組成物、タイヤ及びタイヤの製造方法

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