WO2019138948A1 - Lubricating oil composition and base oil - Google Patents

Lubricating oil composition and base oil Download PDF

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Publication number
WO2019138948A1
WO2019138948A1 PCT/JP2018/048554 JP2018048554W WO2019138948A1 WO 2019138948 A1 WO2019138948 A1 WO 2019138948A1 JP 2018048554 W JP2018048554 W JP 2018048554W WO 2019138948 A1 WO2019138948 A1 WO 2019138948A1
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base oil
oil
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lubricating oil
base
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PCT/JP2018/048554
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French (fr)
Japanese (ja)
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岳史 伊藤
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Ｊｘｔｇエネルギー株式会社
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Application filed by Ｊｘｔｇエネルギー株式会社 filed Critical Ｊｘｔｇエネルギー株式会社
Priority to CN201880088704.5A priority Critical patent/CN111727233A/en
Priority to JP2019564658A priority patent/JP7219232B2/en
Publication of WO2019138948A1 publication Critical patent/WO2019138948A1/en

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    • 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
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated

Definitions

  • the present invention relates to lubricating oil compositions and base oils.
  • Priority is claimed on Japanese Patent Application No. 2018-001962, filed on Jan. 10, 2018, the content of which is incorporated herein by reference.
  • Lubricants are oils used for lubrication and are used to lubricate many mechanical devices. By applying this lubricating oil to the moving parts of the machine, the friction between adjacent solids is reduced, and the generation of frictional heat and wear are suppressed. Thereby, the mechanical device can be kept operating stably.
  • various additives are added to a base oil (base oil).
  • Lubricants have the problem of oxidative degradation during use and storage.
  • antioxidants are conventionally added to lubricating oils as additives.
  • Phenolic compounds such as DBPC (2,6-di-tert-butyl-p-cresol) are widely used as antioxidants.
  • a base oil a mineral oil or synthetic oil having specific properties is adopted, and a lubricating oil composition formed by blending an amine antioxidant with this base oil has been proposed (see Patent Documents 1 and 2). .
  • JP-A-7-228882 Japanese Patent Application Laid-Open No. 7-258677
  • the present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a lubricating oil composition whose oxidation stability has been enhanced to prolong its life and a base oil used therefor. .
  • a first aspect of the present invention is a lubricating oil composition
  • a lubricating oil composition comprising a base oil and an antioxidant, wherein the base oil has an absorbance at a wavelength of 274 nm of 0.02 or more and 3.0 or less.
  • Lubricating oil composition is a lubricating oil composition.
  • the base oil preferably further has a sulfur content of 0.05% by mass or less.
  • the base oil further has a content ratio (% CA) of an aromatic hydrocarbon component of 1.0 or less.
  • the base oil preferably further has a viscosity index of 95 or more and 130 or less.
  • the base oil preferably further has a kinematic viscosity of 40 mm 2 / sec or more and 100 mm 2 / sec or less.
  • the antioxidant is preferably an aromatic amine antioxidant.
  • the lubricating oil composition according to the first aspect may further contain a rust inhibitor.
  • the lubricating oil composition according to the first aspect is suitable as a turbine oil for power generation.
  • a second aspect of the present invention is a base oil characterized in that the absorbance at a wavelength of 274 nm is 0.02 or more and 3.0 or less.
  • the content of sulfur is preferably 0.05% by mass or less.
  • the content ratio (% CA) of the aromatic hydrocarbon component is further preferably 1.0 or less.
  • the base oil according to the second aspect preferably further has a viscosity index of 95 or more and 130 or less.
  • the base oil according to the second aspect preferably further has a kinematic viscosity of 40 mm 2 / sec or more and 100 mm 2 / sec or less.
  • the base oil in this embodiment has a specific absorbance.
  • the base oil include those containing a mineral oil or a synthetic oil or a mixture of these oils.
  • mineral oils are preferred, and among these, paraffinic mineral oils are more preferred.
  • Refined base oils such as Group 3 (Classification of the American Petroleum Institute (API)) are widely used in high performance lubricating oils.
  • API American Petroleum Institute
  • the lubricating oil composition of the present embodiment is useful in that the range of feedstock selectivity is broadened.
  • the base oil in this embodiment has a specific absorbance, that is, an absorbance at a wavelength of 274 nm of 0.02 or more and 3.0 or less.
  • the lower limit of the absorbance is preferably 0.2 or more, 0.3
  • the upper limit value of the absorbance is preferably 2.8 or less, more preferably 1.5 or less, and still more preferably 0.95 or less.
  • the oxidation stability of the lubricating oil composition is enhanced, and the acid value serving as an indicator of the extent of the oxidative deterioration is further reduced for a long time (for example, 5000 The time can be maintained at less than 0.40 mg KOH / g), and a longer life can be achieved.
  • the base oil in this embodiment has a specific absorbance, that is, an absorbance at a wavelength of 274 nm of 0.02 to 3.0, and as another example, the lower limit of the absorbance is preferably 0.2 or more. 0.3 or more is more preferable, 0.8 or more is more preferable, 2.8 or less is preferable, 2.0 or less is more preferable, and 1.5 or less is more preferable. If the predetermined absorbance in the base oil is within the above range, the oxidation stability of the lubricating oil composition is enhanced, and the acid value serving as an index of the degree of oxidative deterioration progress is a reference value of 2.0 mg KOH / g The time which is kept below can be made longer, that is, the life can be extended.
  • the “base oil absorbance” refers to the absorbance at a wavelength of 274 nm, which is measured by the method according to JIS K 0115 (2014).
  • “Absorbance of base oil” includes both absorbance obtained by directly measuring base oil as a raw material and absorbance obtained by measuring a base oil separated from a lubricating oil composition.
  • the separation method of separating the base oil from the lubricating oil composition generally includes a method of extracting the lubricating oil composition using a polar solvent such as methanol. By extracting the lubricating oil composition using a polar solvent, it is possible to separate the base oil by separating the additives and the like.
  • the content of sulfur in the base oil in the present embodiment is preferably 0.05% by mass or less, more preferably 0.03% by mass or less, with respect to the total amount (100% by mass) of the base oil. % Or less is more preferable, 0.005% by mass or less is particularly preferable, 0.001% by mass or less is the most preferable, 0.0001% by mass or more is preferable, and 0.0002% by mass or more is more preferable. If the content ratio of sulfur in the base oil is equal to or less than the upper limit value of the preferable range described above, the risk of sulfur corrosion is further reduced, and an adverse effect on the oxidation stability is also suppressed.
  • “content ratio of sulfur content in base oil” can be measured by a method according to JIS K 2541-6 (2013).
  • 1.0 or less is preferable, as for the content rate (% CA) of the aromatic hydrocarbon component in the base oil in this embodiment, 0.7 or less is more preferable, 0.6 or less is more preferable, and 0.5 or less Particularly preferred. If the content ratio of the aromatic hydrocarbon component in the base oil is equal to or less than the upper limit value of the preferable range, oxidation deterioration with the passage of time is easily suppressed. In the lubricating oil composition of the present embodiment, the lower the content of the aromatic hydrocarbon component in the base oil, the better in terms of prolonging the life.
  • the “content ratio of the aromatic hydrocarbon component in the base oil” means the carbon number of the aromatic hydrocarbon component among all the components constituting the base oil relative to the total carbon number of all components constituting the base oil, Say the percentage of In the present invention, "the content ratio of the aromatic hydrocarbon component in the base oil” can be measured by the method according to ASTM D3238 (2017).
  • the viscosity index of the base oil in the present embodiment is preferably 130 or less, more preferably 128 or less, still more preferably 125 or less, and particularly preferably 120 or less.
  • the lower limit of the viscosity index of the base oil is preferably 95 or more, more preferably 97 or more, still more preferably 100 or more, and particularly preferably 104 or more. If the viscosity index of the said base oil is more than the lower limit of the said preferable range, the viscosity change by temperature will be easy to be suppressed, and if it is below the upper limit of the said preferable range, it will contribute to oxidation stability. A certain amount of components is secured, and oxidation deterioration with time is easily suppressed.
  • “the viscosity index of the base oil” can be measured by a method in accordance with JIS K 2283 (2000).
  • the lower limit of the 40 ° C. kinematic viscosity of the base oil is preferably 20 mm 2 / s or more, more preferably 25 mm 2 / s or more, and still more preferably 30 mm 2 / s or more. If the kinematic viscosity of the base oil at 40 ° C.
  • “40 ° C. kinematic viscosity of base oil” indicates a kinematic viscosity at a temperature of 40 ° C. measured by a method in accordance with JIS K 2283 (2000).
  • the base oil used in the present embodiment has an absorbance at a wavelength of 274 nm of 0.02 or more and 3.0 or less, and among those having such an absorbance, the content of sulfur is further 0.05% by mass or less, the aroma It is particularly preferable from the viewpoint of the oxidation stability and the width of the raw material selectivity to use one having a content of the group hydrocarbon component (% CA) of 1.0 or less and a viscosity index of 95 or more and 130 or less.
  • % CA group hydrocarbon component
  • the content of the base oil in the lubricating oil composition is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 96% by mass or more based on the total amount (100% by mass) of the lubricating oil composition. On the other hand, 99.9 mass% or less is preferable and 99.8 mass% or less is more preferable.
  • the antioxidant in the present embodiment is not particularly limited, and examples thereof include aromatic amine antioxidants, phenol antioxidants, sulfur antioxidants, sulfur and phosphorus antioxidants, and other antioxidants.
  • aromatic amine antioxidant examples include phenyl- ⁇ -naphthylamine, alkylated phenyl- ⁇ -naphthylamine, diphenylamine, alkylated diphenylamine and phenothiazine.
  • alkylated diphenylamine examples include p, p'-dioctyl diphenylamine and the like.
  • phenolic antioxidants examples include 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-4-ethylphenol, 4,4′-methylenebis (2,6-di- tert-Butylphenol), 4,4'-methylenebis (6-tert-butyl-o-cresol) and the like.
  • sulfur-based antioxidants include dibenzyl disulfide, dialkyl sulfides, sulfurized fats and oils, and the like.
  • sulfur and phosphorus antioxidants include zinc dialkyl dithiophosphate and zinc diallyl dithiophosphate.
  • Other antioxidants include N, N'-disalicylidene-1,2-diaminopropane, benzotriazole, 2 (n-dodecyldithio) benzimidazole, copper-based antioxidants, molybdenum-based antioxidants and the like.
  • the lubricating oil composition of the present embodiment only one antioxidant may be used, or two or more antioxidants may be used in combination.
  • the antioxidant is preferably at least one selected from the group consisting of an aromatic amine antioxidant and a phenolic antioxidant because oxidation stability is more easily improved, and among these, lubricating oil compositions are preferably used. It is particularly preferable to include at least an aromatic amine-based antioxidant because it is easy to achieve long life.
  • the content of the antioxidant in the lubricating oil composition is appropriately determined according to the type of the base oil or the antioxidant, and, for example, 0.1 mass based on the total amount (100 mass%) of the lubricating oil composition % Or more is preferable, 0.2 mass% or more is more preferable, 0.3 mass% or more is more preferable, 5 mass% or less is preferable, and 3 mass% or less is more preferable. If the content of the antioxidant is at least the lower limit value of the above-mentioned preferable range, the oxidation deterioration is less likely to occur, while, even if the upper limit value of the above-mentioned preferable range is exceeded, the oxidation prevention corresponding to the addition amount It becomes difficult to obtain the improvement effect.
  • rust inhibitor rust inhibitor
  • antifoam agent antifoam agent
  • friction modifier e.g., a friction modifier
  • viscosity index improver e.g., a metal Deactivators
  • pour point depressants e.g., pour point depressants
  • demulsifiers e.g., a metal detergent
  • ashless dispersants e.g., a metal detergent
  • antiwear agents or extreme pressure agents e.g., extreme pressure agents, corrosion inhibitors, etc.
  • the lubricating oil composition of the present embodiment may further contain a rust inhibitor (rust inhibitor) in addition to the base oil and the antioxidant.
  • a rust inhibitor for example, aliphatic amines, organic sulfonic acid metal salts, organic phosphoric acid metal salts, alkyl succinic acid esters, alkenyl succinic acid esters, succinic acid imides, sarcosinic acid derivatives, alkyl phenyl fatty acids, many And polyhydric alcohol esters.
  • the content of the rust inhibitor in the lubricating oil composition is appropriately determined according to the type of the base oil or the rust inhibitor, and is, for example, 0.01 mass based on the total amount (100% by mass) of the lubricating oil composition.
  • % Or more is preferable, 0.02 mass% or more is more preferable, 0.03 mass% or more is more preferable, 1 mass% or less is preferable, and 0.5 mass% or less is more preferable. If the content of the rust inhibitor is at least the lower limit value of the above-mentioned preferable range, an appropriate antirust effect is easily obtained, while if it exceeds the upper limit value of the above-mentioned preferable range, the oxidation stability is adversely affected. Become to exert.
  • a base oil having a specific absorbance and an antioxidant are combined.
  • the base oil contains a polycyclic aromatic hydrocarbon component having an absorbance at a wavelength of 274 nm of 0.02 or more and 3.0 or less, that is, having an absorption at a wavelength of 274 nm.
  • the determination of the polycyclic aromatic hydrocarbon component having absorption at a wavelength of 274 nm in such a base oil is difficult due to its small amount.
  • the oxidative stability is enhanced by the synergistic action of the polycyclic aromatic hydrocarbon component in a trace amount having a specific absorbance and the antioxidant. It is presumed that the life can be extended.
  • the lubricating oil composition of the present embodiment stable operation of a turbine or the like is enabled.
  • the lubricating oil composition is useful as various turbine oils.
  • the lubricating oil composition is suitable for use as a lubricant for infrastructure applications, and particularly suitable for use as a turbine oil for power generation, because the oxidative stability is maintained for a long time.
  • the base oil of the present embodiment has an absorbance of 0.02 or more and 3.0 or less at a wavelength of 274 nm.
  • the base oil having a content of sulfur of 0.05% by mass or less, and the content (% CA) of the content of an aromatic hydrocarbon component are 1. 0 or less is the base oil, the base oil viscosity index of 95 or more 130 or less, or 40 ° C.
  • kinematic viscosity of 20 mm 2 / sec or more 100 mm 2 / sec or less is base oil oxidation stability and material selectivity of the width It is preferable from the point of The detailed description about the said base oil is the same as ⁇ base oil> mentioned above.
  • the base oil of the present embodiment is solvent-depleted, solvent-extracted, hydrotreated, solvent dewaxed, catalytic dewaxed with respect to a fraction obtained by performing at least one of atmospheric distillation and vacuum distillation of crude oil. It can be obtained by combining and applying processes such as isomerization dewaxing, hydrorefining, acid washing and post-distillation. For example, by appropriately controlling the reaction temperature, the hydrogen pressure, the hydrogen / oil ratio, or the liquid hourly space at the time of the hydrotreating in plant production, the proportion of the trace sulfur and aromatic components of the base oil Can be adjusted.
  • the reaction temperature is preferably 270 ° C. to 500 ° C. during the hydrotreating.
  • Hydrogen pressure is preferably 5 MPa to 30 MPa, more preferably 10 MPa to 22 MPa;
  • hydrogen / oil ratio is preferably 10 NL / L to 2000 NL / L, more preferably 300 NL / L. L above 1000 NL / L or less;
  • the base oil of the present embodiment described above has a specific absorbance. Because of this, the base oil exhibits good oxidative stability and is suitable for long-term use or storage.
  • the base oils are particularly suitable for lubricating oils for infrastructure applications.
  • the absorbance at a wavelength of 274 nm, the content ratio of sulfur, the content ratio of an aromatic hydrocarbon component, the viscosity index, and the 40 ° C. kinematic viscosity of the base oil used in this example were measured by the methods described below.
  • the acid value was measured by the method shown below about a lubricating oil composition.
  • the lubricating oil composition was subjected to an accelerated deterioration test according to ASTM D 7873 (2013 e 2), and the acid value (mg KOH / g) of the accelerated deteriorated oil was measured according to JIS K 2501 (2003). Specifically, the lubricating oil composition is heated at 120 ° C. while blowing oxygen at a flow rate of 3.0 L / h in the presence of a copper and iron coil catalyst, and after a certain time, a small amount (20 g) of oil (20 g) Accelerated deterioration oil was sampled, and the acid value of this accelerated deterioration oil was measured.
  • the acid number 2 is an evaluation standard value when accelerated deterioration is made according to the TOST test (ISO 4263-1), which is defined by the quality regulations of turbine oil product standards such as ASTM D4304 or ISO 8068. .0 mg KOH / g was applied. The accelerated deterioration test was continued until it exceeded 2.0 mg KOH / g.
  • the base oils 1 to 8 and the base oils 10 to 11 used in the present embodiment are fractions obtained by performing at least one of atmospheric distillation and vacuum distillation on crude oil (paraffin-based crude oil or mixed base crude oil). On the other hand, it was obtained by performing a series of treatments such as solvent deasphalting, solvent extraction, hydrotreating, solvent dewaxing, catalytic dewaxing, isomerization dewaxing, hydrorefining, acid washing and post-distillation.
  • Each base oil was manufactured by appropriately controlling the reaction temperature, the hydrogen pressure, the hydrogen / oil ratio, and the liquid hourly space at the time of the hydrotreating in the plant production.
  • the base oil 9 used in the present example was manufactured based on GTL wax using natural gas as a raw material.
  • Base oil 1 The Middle East crude oil is subjected to an atmospheric distillation apparatus, and the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the vacuum distillation fraction obtained is subjected to a hydrocracking apparatus (reaction temperature 340 to 400 ° C., hydrogen pressure 10 to 15 MPa , The hydrogen / oil ratio is 450 to 650 NL / L, the liquid space velocity is controlled in the range of 1.0 to 2.0 h.sup.- 1 , and the resulting hydrocracked oil is distilled to remove the fuel fraction.
  • a hydrocracking apparatus reaction temperature 340 to 400 ° C., hydrogen pressure 10 to 15 MPa .
  • the hydrogen / oil ratio is 450 to 650 NL / L
  • the liquid space velocity is controlled in the range of 1.0 to 2.0 h.sup.- 1
  • the resulting hydrocracked oil is distilled to remove the fuel fraction.
  • an isomerization dewaxing unit (reaction temperature: 290 to 350 ° C., hydrogen pressure: 11 to 15 MPa, hydrogen / oil ratio: 400 to 600 NL / L, liquid space velocity: in the range of 1.0 to 2.0 h -1
  • the de-waxed oil obtained is subjected to distillation to remove the fuel fraction, and the hydrorefining apparatus (reaction temperature 270 to 330 ° C., hydrogen pressure 6 to 10 MPa, hydrogen / oil ratio 900 to 1500 NL / L) , range of the liquid hourly space velocity 1.0 ⁇ 2.0h -1 Subjected to the control) at the inner, subjected the resulting hydrotreated oil to a distillation apparatus, 40 ° C. kinematic viscosity was obtained as a fraction of 31.6mm 2 / s.
  • Base oil 2 The Middle East crude oil is subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the vacuum distillation fraction obtained is subjected to a hydrotreating apparatus (reaction temperature 280 to 330 ° C., hydrogen pressure 17 to 22 MPa And a hydrogen / oil ratio of 550 to 850 NL / L, and the liquid space velocity is controlled in the range of 0.5 to 1.0 h.sup.- 1 , and the obtained hydrotreated oil is subjected to solvent dewaxing (solvent is methyl ethyl ketone).
  • solvent dewaxing solvent is methyl ethyl ketone
  • Base oil 3 Middle East crude oil is subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the vacuum distillation fraction obtained is subjected to a hydrorefining apparatus (reaction temperature 260 to 330 ° C., hydrogen pressure 6 to 10 MPa, A hydrogen / oil ratio of 700 to 1,300 NL / L and a liquid space velocity of 1.0 to 2.0 h -1 are controlled, and the resulting hydrorefined oil is subjected to a hydrocracker (reaction temperature: 350 to The hydrocracked oil obtained at 400 ° C., a hydrogen pressure of 10 to 15 MPa, a hydrogen / oil ratio of 600 to 1000 NL / L, and a liquid hourly space velocity of 1.2 to 2.4 h ⁇ 1.
  • the fuel fraction is removed by distillation, and the mixture is then subjected to a vacuum distillation apparatus, and the resulting vacuum distillation fraction (viscosity grade VG46 equivalent fraction) is isomerized and dewaxed (reaction temperature 280 to 340 ° C., hydrogen pressure 11 ⁇ 15MPa, hydrogen / oil ratio 450 650NL / L, the liquid subjected space velocity in the control) in the range of 1.0 ⁇ 2.0 h -1, hydrogenation of the dewaxed oil obtained purifier (reaction temperature 280 ⁇ 340 ° C., the hydrogen pressure 7 ⁇ 11 MPa Hydrogen / oil ratio of 800-1300 NL / L, control of liquid space velocity in the range of 1.0-2.0 h.sup.- 1 ), and removing the fuel fraction by distillation of the resulting hydrogenated refined oil
  • the resultant was obtained as a fraction having a kinematic viscosity of 47.5 mm 2 / s at 40 ° C.
  • Base oil 4 The Middle East crude oil is subjected to an atmospheric distillation apparatus, and the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the vacuum distillation fraction obtained is subjected to a hydrocracking apparatus (reaction temperature 340 to 400 ° C., hydrogen pressure 10 to 15 MPa , The hydrogen / oil ratio is 450 to 650 NL / L, the liquid space velocity is controlled in the range of 1.0 to 2.0 h.sup.- 1 , and the resulting hydrocracked oil is distilled to remove the fuel fraction.
  • a hydrocracking apparatus reaction temperature 340 to 400 ° C., hydrogen pressure 10 to 15 MPa .
  • the hydrogen / oil ratio is 450 to 650 NL / L
  • the liquid space velocity is controlled in the range of 1.0 to 2.0 h.sup.- 1
  • the resulting hydrocracked oil is distilled to remove the fuel fraction.
  • an isomerization dewaxing unit (reaction temperature: 290 to 350 ° C., hydrogen pressure: 11 to 15 MPa, hydrogen / oil ratio: 400 to 600 NL / L, liquid space velocity: in the range of 1.0 to 2.0 h -1
  • the de-waxed oil obtained is subjected to distillation to remove the fuel fraction, and the hydrorefining apparatus (reaction temperature 270 to 330 ° C., hydrogen pressure 6 to 10 MPa, hydrogen / oil ratio 900 to 1500 NL / L) , range of the liquid hourly space velocity 1.0 ⁇ 2.0h -1 Subjected to the control) at the inner, subjected the resulting hydrotreated oil to a distillation apparatus, 40 ° C. kinematic viscosity was obtained as a fraction of 88.3mm 2 / s.
  • the Middle East crude oil is subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the vacuum distillation fraction obtained is subjected to a hydrorefining apparatus (reaction temperature 270 to 340 ° C., hydrogen pressure 7 to 12 MPa, A hydrogen / oil ratio of 900 to 1,400 NL / L and a liquid space velocity of 1.0 to 2.0 h -1 are controlled, and the resulting hydrorefined oil is subjected to a hydrocracker (reaction temperature: 360 to Hydrocracked oil obtained at 420 ° C., hydrogen pressure of 11 to 16 MPa, hydrogen / oil ratio of 700 to 1200 NL / L, and control of liquid hourly space velocity in the range of 0.8 to 1.8 h ⁇ 1 )
  • the fuel fraction is removed by distillation, and the mixture is then subjected to a vacuum distillation apparatus, and the obtained vacuum distillation fraction (viscosity grade VG32 equivalent fraction) is isomerized
  • Base oil 6 The Middle East crude oil is subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the vacuum distillation fraction obtained is subjected to a hydrocracking apparatus (reaction temperature 280 to 340 ° C., hydrogen pressure 7 to 12 MPa , The hydrogen / oil ratio is 400 to 700 NL / L, and the liquid space velocity is controlled within the range of 1.5 to 2.5 h.sup.- 1 , and the resulting hydrocracked oil is distilled to remove the fuel fraction.
  • a hydrocracking apparatus reaction temperature 280 to 340 ° C., hydrogen pressure 7 to 12 MPa .
  • the hydrogen / oil ratio is 400 to 700 NL / L
  • the liquid space velocity is controlled within the range of 1.5 to 2.5 h.sup.- 1
  • the resulting hydrocracked oil is distilled to remove the fuel fraction.
  • an isomerization dewaxing unit (reaction temperature: 290 to 350 ° C, hydrogen pressure: 7 to 10 MPa, hydrogen / oil ratio: 400 to 600 NL / L, liquid space velocity within the range of 1.5 to 2.5 h -1
  • the dewaxed oil obtained is subjected to distillation to remove the fuel fraction, and the hydrorefining apparatus (reaction temperature 250 to 310 ° C., hydrogen pressure 5 to 10 MPa, hydrogen / oil ratio 600 to 1000 NL / L) the liquid hourly space velocity in the range of 1.5 ⁇ 2.5 h -1
  • Subjected to the control subjecting the resulting hydrotreated oil to a distillation apparatus, 40 ° C. kinematic viscosity was obtained as a fraction of 29.9 mm 2 / s.
  • the Middle East crude oil is subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the vacuum distillation fraction obtained is subjected to a hydrocracking apparatus (reaction temperature 380 to 430 ° C., hydrogen pressure 13 to 17 MPa Hydrogen / oil ratio of 1000-1600 NL / L, control of liquid space velocity in the range of 0.6-1.6 h -1 ), and removing the fuel fraction by distillation of the obtained hydrocracked oil After that, an isomerization dewaxing unit (reaction temperature 300 to 350 ° C, hydrogen pressure 11 to 16MPa, hydrogen / oil ratio 1000 to 1600NL / L, liquid space velocity within the range of 0.6 to 1.6h -1 The dewaxed oil obtained is subjected to distillation to remove the fuel fraction, and the hydrorefining apparatus (reaction temperature 290 to 350 ° C., hydrogen pressure 8 to 12 MPa, hydrogen / oil ratio 1000 to 1600 NL / L)
  • Base oil 8 The Middle East crude oil is subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the vacuum distillation fraction obtained is subjected to a hydrocracking apparatus (reaction temperature 370 to 420 ° C., hydrogen pressure 12 to 16 MPa Hydrogen / oil ratio of 800 to 1,500 NL / L, and control of the liquid space velocity in the range of 0.8 to 1.8 h.sup.- 1 ), and removing the fuel fraction by distillation of the obtained hydrocracked oil After that, an isomerization dewaxing unit (reaction temperature: 290 to 350 ° C., hydrogen pressure: 11 to 15 MPa, hydrogen / oil ratio: 800 to 1,500 NL / L, liquid space velocity within the range of 0.8 to 1.8 h -1 The de-waxed oil obtained is subjected to distillation to remove the fuel fraction, and the hydrorefining apparatus (reaction temperature 290 to 350 ° C., hydrogen pressure 8 to 12
  • Base oil 9 An isomerization dewaxing unit (isomerization reaction temperature 300 to 320 ° C., hydrogen pressure 12 to 16 MPa, hydrogen) containing GTL wax (containing 40% by mass of normal paraffin of boiling range 480 to 570 ° C.) using natural gas as raw material (Controlled at a liquid space velocity of 1.2 to 1.6 h.sup.- 1 ), the obtained dewaxed oil is subjected to a distillation apparatus, and the kinematic viscosity at 40.degree. Obtained as a fraction of 5 mm 2 / s.
  • Base oil 10 The Middle East crude oil is subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the vacuum distillation fraction obtained is subjected to a hydrorefining apparatus (reaction temperature 220 to 280 ° C., hydrogen pressure 4 to 7 MPa, A hydrogen / oil ratio of 400 to 650 NL / L and a liquid hourly space velocity of 1.5 to 2.5 h -1 are controlled, and the resulting hydrorefined oil is subjected to a hydrogenolysis unit (reaction temperature: 330 to Hydrocracked oil obtained at 380 ° C., a hydrogen pressure of 8 to 13 MPa, a hydrogen / oil ratio of 400 to 800 NL / L, and a liquid hourly space velocity of 1.5 to 2.5 h ⁇ 1.
  • the mixture is subjected to a vacuum distillation apparatus, and the obtained vacuum distillation fraction (viscosity grade VG22 equivalent fraction) is isomerized and dewaxed (reaction temperature 260 to 320 ° C., hydrogen pressure 7) ⁇ 11MPa, hydrogen / oil ratio 400 ⁇ 650N / L, the liquid subjected space velocity in the control) in the range of 1.5 ⁇ 2.5 h -1, hydrotreater dewaxed oil obtained (reaction temperature 250 ⁇ 300 ° C., the hydrogen pressure 4 ⁇ 7 MPa,
  • the hydrogen / oil ratio is 500 to 1000 NL / L
  • the liquid space velocity is controlled in the range of 1.5 to 2.5 h.sup.- 1
  • the resulting hydrogenated refined oil is distilled to remove the fuel fraction.
  • the resultant was obtained as a fraction having a kinematic viscosity of 20.4 mm 2 / s at 40 ° C.
  • Base oil 11 Middle East crude oil is subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the obtained vacuum distillation fraction corresponding to 150 N is subjected to a furfural extraction apparatus (head temperature 110 to 130 ° C., bottom temperature Subjecting the raffinate fraction to a hydrorefining unit (reaction temperature 270-330 ° C., hydrogen pressure 4 to 6 MPa, hydrogen / The resulting hydrorefined oil is subjected to a solvent dewaxing apparatus (a mixed solvent of methyl ethyl ketone and toluene) at an oil ratio of 1500 to 2000 NL / L and a liquid space velocity controlled to a range of 1.0 to 2.0 h -1.
  • a solvent dewaxing apparatus a mixed solvent of methyl ethyl ketone and toluene
  • the lubricating oil compositions of the respective examples were produced by adding and mixing an antioxidant and a rust inhibitor to each of the base oils described above.
  • base oils 1 to 10 were used respectively.
  • As an antioxidant Irganox L06 manufactured by BASF and Arganox L57 manufactured by BASF, both of which are aromatic amine antioxidants, were used.
  • As a rust inhibitor Irgacore L12 manufactured by BASF Corp. was used.
  • the lubricating oil compositions of Examples 1 to 10 were prepared by adding Irganox L06 (0.3% by mass), Irganox L57 (0.2% by mass), and Irgacore L12 (to each base oil of the base oils 1 to 10). 0.1% by mass) was added and mixed.
  • the above parenthesis indicates the content of each component in the lubricating oil composition, and means the proportion of the total amount (100% by mass) of the composition.
  • Comparative example 1 A lubricating oil composition of Comparative Example 1 was prepared in the same manner as in Examples 1 to 10, except that the base oil was changed to base oil 11.
  • base oils base oil 1, base oil 3 and base oil 5 were used respectively.
  • antioxidant ANTAGE BHT manufactured by Kawaguchi Chemical Industry Co., Ltd., which is a phenolic antioxidant, was used.
  • rust inhibitor Irgacore L12 manufactured by BASF Corp. was used.
  • the lubricating oil compositions of Examples 11 to 13 contained ANTAGE BHT (1.0% by mass) and Irgacore L12 (0.1%) in the respective base oils (remaining parts) of base oil 1, base oil 3 and base oil 5. It prepared by adding and mixing with mass%).
  • the above parenthesis indicates the content of each component in the lubricating oil composition, and means the proportion of the total amount (100% by mass) of the composition.
  • Comparative example 2 A lubricating oil composition of Comparative Example 2 was prepared in the same manner as in Examples 11 to 13 except that the base oil was changed to base oil 11.
  • the lubricating oil compositions of Examples 1 to 3 to which the present invention is applied have an acid value of less than 2.0 mg KOH / g for an elapsed time of 6000 h. Was kept.
  • the lubricating oil composition of Example 4 to which the present invention was applied continued to be maintained for an elapsed time of 7000 hours or more and an acid value of less than 2.0 mg KOH / g.
  • an acid value of less than 2.0 mg KOH / g was maintained for an elapsed time of 2000 h.
  • Example 10 For the lubricating oil composition of Example 10 containing a base oil within the scope of the present invention, an acid value of less than 2.0 mg KOH / g was maintained for an elapsed time of 3000 h.
  • the elapsed time during which the acid value of less than 2.0 mg KOH / g was maintained was up to 1000 h.
  • the lubricating oil compositions of Examples 11 and 12 to which the present invention is applied maintain an acid value of less than 2.0 mg KOH / g for an elapsed time of 2000 h.
  • an acid value of less than 2.0 mg KOH / g was maintained until an elapsed time of 750 h.
  • the elapsed time during which the acid value of less than 2.0 mg KOH / g was maintained was up to 500 h.
  • the lubricating oil composition to which the present invention is applied has a higher oxidation stability and a longer life.

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Abstract

A lubricating oil composition comprising a base oil and an antioxidant, wherein a base oil having an absorbance of 0.02 to 3.0, inclusive, at a wavelength of 274 nm is used. Furthermore, one having a sulfur fraction content ratio of 0.05 mass% or less, an aromatic hydrocarbon component content ratio (%CA) of 1.0 or less, and a viscosity index of 95 to 130, inclusive, is selected as the base oil. According to such a lubricating oil composition, the oxidation stability can be enhanced and a longer life can be achieved.

Description

潤滑油組成物及び基油Lubricating oil composition and base oil
　本発明は、潤滑油組成物及び基油に関する。
　本願は、２０１８年１月１０日に日本に出願された、特願２０１８－００１９６２号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to lubricating oil compositions and base oils.
Priority is claimed on Japanese Patent Application No. 2018-001962, filed on Jan. 10, 2018, the content of which is incorporated herein by reference.
　潤滑油は、潤滑のために用いられる油であり、多くの機械装置の潤滑に用いられている。この潤滑油を、機械の可動部分に塗ることで、相接する固体の摩擦が低減し、摩擦熱の発生や摩耗が抑制される。これにより、機械装置を安定に運転し続けることができる。
　潤滑油には、ベースオイル（基油）に、様々な添加剤が加えられる。 Lubricants are oils used for lubrication and are used to lubricate many mechanical devices. By applying this lubricating oil to the moving parts of the machine, the friction between adjacent solids is reduced, and the generation of frictional heat and wear are suppressed. Thereby, the mechanical device can be kept operating stably.
To the lubricating oil, various additives are added to a base oil (base oil).
　潤滑油においては、使用中及び保管中に酸化劣化を生じるという問題がある。これを防止するため、従来、潤滑油には、添加剤として酸化防止剤が加えられている。酸化防止剤には、ＤＢＰＣ（２，６－ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール）等のフェノール系化合物が汎用されている。
　また、基油として、特定の性状を有する鉱油又は合成油を採用し、この基油にアミン系酸化防止剤を配合してなる潤滑油組成物が提案されている（特許文献１、２参照）。 Lubricants have the problem of oxidative degradation during use and storage. In order to prevent this, antioxidants are conventionally added to lubricating oils as additives. Phenolic compounds such as DBPC (2,6-di-tert-butyl-p-cresol) are widely used as antioxidants.
In addition, as a base oil, a mineral oil or synthetic oil having specific properties is adopted, and a lubricating oil composition formed by blending an amine antioxidant with this base oil has been proposed (see Patent Documents 1 and 2). .
特開平７－２２８８８２号公報JP-A-7-228882 特開平７－２５８６７７号公報Japanese Patent Application Laid-Open No. 7-258677
　ところで、潤滑油の中でも、インフラ用途の潤滑油（例えば発電用タービン油など）には、装置の安定稼働が特に求められ、長期にわたる酸化安定性が要求される。しかしながら、特許文献１、２に記載されたような従来の潤滑油組成物では、かかる要求に対して不充分である。 By the way, among lubricating oils, stable operation of the device is particularly required for lubricating oils for infrastructure applications (for example, turbine oil for power generation, etc.), and long-term oxidation stability is required. However, conventional lubricating oil compositions as described in Patent Documents 1 and 2 are insufficient for such a requirement.
　本発明は、上記事情に鑑みてなされたものであり、酸化安定性が高められて、より長寿命化が図られた潤滑油組成物、及びこれに用いる基油を提供することを課題とする。 The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a lubricating oil composition whose oxidation stability has been enhanced to prolong its life and a base oil used therefor. .
　本発明の第１の態様は、基油と酸化防止剤とを含有する潤滑油組成物であって、前記基油は、波長２７４ｎｍにおける吸光度が０．０２以上３．０以下であることを特徴とする潤滑油組成物である。 A first aspect of the present invention is a lubricating oil composition comprising a base oil and an antioxidant, wherein the base oil has an absorbance at a wavelength of 274 nm of 0.02 or more and 3.0 or less. Lubricating oil composition.
　第１の態様に係る潤滑油組成物において、前記基油は、さらに、硫黄分の含有割合が０．０５質量％以下であることが好ましい。又は、前記基油は、さらに、芳香族炭化水素成分の含有割合（％ＣＡ）が１．０以下であることが好ましい。又は、前記基油は、さらに、粘度指数が９５以上１３０以下であることが好ましい。又は、前記基油は、さらに、４０℃動粘度が２０ｍｍ２／ｓｅｃ以上１００ｍｍ２／ｓｅｃ以下であることが好ましい。 In the lubricating oil composition according to the first aspect, the base oil preferably further has a sulfur content of 0.05% by mass or less. Alternatively, it is preferable that the base oil further has a content ratio (% CA) of an aromatic hydrocarbon component of 1.0 or less. Alternatively, the base oil preferably further has a viscosity index of 95 or more and 130 or less. Alternatively, the base oil preferably further has a kinematic viscosity of 40 mm 2 / sec or more and 100 mm 2 / sec or less.
　第１の態様に係る潤滑油組成物において、前記酸化防止剤は、芳香族アミン系酸化防止剤であることが好ましい。
　第１の態様に係る潤滑油組成物は、さらに、さび止め剤を含有するものでもよい。
　第１の態様に係る潤滑油組成物は、発電用タービン油として好適なものである。 In the lubricating oil composition according to the first aspect, the antioxidant is preferably an aromatic amine antioxidant.
The lubricating oil composition according to the first aspect may further contain a rust inhibitor.
The lubricating oil composition according to the first aspect is suitable as a turbine oil for power generation.
　本発明の第２の態様は、波長２７４ｎｍにおける吸光度が０．０２以上３．０以下であることを特徴とする基油である。
　第２の態様に係る基油は、さらに、硫黄分の含有割合が０．０５質量％以下であることが好ましい。
　第２の態様に係る基油は、さらに、芳香族炭化水素成分の含有割合（％ＣＡ）が１．０以下であることが好ましい。
　第２の態様に係る基油は、さらに、粘度指数が９５以上１３０以下であることが好ましい。
　第２の態様に係る基油は、さらに、４０℃動粘度が２０ｍｍ２／ｓｅｃ以上１００ｍｍ２／ｓｅｃ以下であることが好ましい。 A second aspect of the present invention is a base oil characterized in that the absorbance at a wavelength of 274 nm is 0.02 or more and 3.0 or less.
In the base oil according to the second aspect, the content of sulfur is preferably 0.05% by mass or less.
In the base oil according to the second aspect, the content ratio (% CA) of the aromatic hydrocarbon component is further preferably 1.0 or less.
The base oil according to the second aspect preferably further has a viscosity index of 95 or more and 130 or less.
The base oil according to the second aspect preferably further has a kinematic viscosity of 40 mm 2 / sec or more and 100 mm 2 / sec or less.
　本発明によれば、酸化安定性が高められて、より長寿命化が図られた潤滑油組成物、及びこれに用いる基油を提供することができる。 According to the present invention, it is possible to provide a lubricating oil composition with enhanced oxidation stability and longer life and a base oil used therefor.
（潤滑油組成物）
　本実施形態の潤滑油組成物は、基油に特徴があり、基油と酸化防止剤とを少なくとも含有するものである。当該潤滑油組成物は、基油及び酸化防止剤に加え、必要に応じてその他成分を含有してもよい。 (Lubricating oil composition)
The lubricating oil composition of the present embodiment is characterized by a base oil, and contains at least a base oil and an antioxidant. The lubricating oil composition may contain other components as necessary in addition to the base oil and the antioxidant.
＜基油＞
　本実施形態における基油は、特定の吸光度を有する。
　当該基油としては、例えば、鉱油もしくは合成油又はこれらの混合油を含むものが挙げられる。当該基油の中でも、鉱油が好ましく、この中でもパラフィン系鉱油がより好ましい。
　グループ３（米国石油協会（American Petroleum Institute：API）の分類）のような高精製基油は、広く高性能な潤滑油に使用されている。しかし、それ以外でもグループ分類に関係無く、本実施形態によれば特定の吸光度を有する基油を採用することで、高い酸化安定性が発揮される。このため、本実施形態の潤滑油組成物は、原料選択性の幅が広がる点で有用である。 <Base oil>
The base oil in this embodiment has a specific absorbance.
Examples of the base oil include those containing a mineral oil or a synthetic oil or a mixture of these oils. Among the base oils, mineral oils are preferred, and among these, paraffinic mineral oils are more preferred.
Refined base oils such as Group 3 (Classification of the American Petroleum Institute (API)) are widely used in high performance lubricating oils. However, regardless of the group classification other than that, according to the present embodiment, by adopting a base oil having a specific absorbance, high oxidation stability is exhibited. For this reason, the lubricating oil composition of the present embodiment is useful in that the range of feedstock selectivity is broadened.
　本実施形態における基油は、特定の吸光度、すなわち、波長２７４ｎｍにおける吸光度が０．０２以上３．０以下であり、一例として、当該吸光度の下限値は、０．２以上が好ましく、０．３以上がより好ましく、当該吸光度の上限値は、２．８以下が好ましく、１．５以下がより好ましく、０．９５以下がさらに好ましい。
　当該基油における所定の吸光度が前記の範囲内であれば、潤滑油組成物の酸化安定性が高められて、酸化劣化進行程度の指標となる酸価を、より長時間低い値（例えば、５０００時間、０．４０ｍｇＫＯＨ／ｇ未満）に保つことができ、より長寿命化が図られる。 The base oil in this embodiment has a specific absorbance, that is, an absorbance at a wavelength of 274 nm of 0.02 or more and 3.0 or less. As one example, the lower limit of the absorbance is preferably 0.2 or more, 0.3 The above is more preferable, and the upper limit value of the absorbance is preferably 2.8 or less, more preferably 1.5 or less, and still more preferably 0.95 or less.
If the predetermined absorbance in the base oil is within the above range, the oxidation stability of the lubricating oil composition is enhanced, and the acid value serving as an indicator of the extent of the oxidative deterioration is further reduced for a long time (for example, 5000 The time can be maintained at less than 0.40 mg KOH / g), and a longer life can be achieved.
　又は、本実施形態における基油は、特定の吸光度、すなわち、波長２７４ｎｍにおける吸光度が０．０２以上３．０以下であり、他の例として、当該吸光度の下限値は、０．２以上が好ましく、０．３以上がより好ましく、０．８以上がさらに好ましく、当該吸光度の上限値は、２．８以下が好ましく、２．０以下がより好ましく、１．５以下がさらに好ましい。
　当該基油における所定の吸光度が前記の範囲内であれば、潤滑油組成物の酸化安定性が高められて、酸化劣化進行程度の指標となる酸価が、基準値である２．０ｍｇＫＯＨ／ｇ以下に保たれる時間をより長くできる、すなわち長寿命化が図られる。 Alternatively, the base oil in this embodiment has a specific absorbance, that is, an absorbance at a wavelength of 274 nm of 0.02 to 3.0, and as another example, the lower limit of the absorbance is preferably 0.2 or more. 0.3 or more is more preferable, 0.8 or more is more preferable, 2.8 or less is preferable, 2.0 or less is more preferable, and 1.5 or less is more preferable.
If the predetermined absorbance in the base oil is within the above range, the oxidation stability of the lubricating oil composition is enhanced, and the acid value serving as an index of the degree of oxidative deterioration progress is a reference value of 2.0 mg KOH / g The time which is kept below can be made longer, that is, the life can be extended.
　本発明において「基油の吸光度」は、ＪＩＳ　Ｋ　０１１５（２０１４）に準拠した方法により測定される、波長２７４ｎｍにおける吸光度を示す。
　「基油の吸光度」は、原料としての基油を直接に測定した吸光度、及び潤滑油組成物から分離した基油を測定した吸光度をいずれも包含する。
　潤滑油組成物から基油を分離する分離方法は、一般に、潤滑油組成物をメタノールのような極性溶媒を用いて抽出する方法が挙げられる。潤滑油組成物を、極性溶媒を用いて抽出することで、添加剤等が分離されることにより、基油を分取することが可能である。 In the present invention, the "base oil absorbance" refers to the absorbance at a wavelength of 274 nm, which is measured by the method according to JIS K 0115 (2014).
"Absorbance of base oil" includes both absorbance obtained by directly measuring base oil as a raw material and absorbance obtained by measuring a base oil separated from a lubricating oil composition.
The separation method of separating the base oil from the lubricating oil composition generally includes a method of extracting the lubricating oil composition using a polar solvent such as methanol. By extracting the lubricating oil composition using a polar solvent, it is possible to separate the base oil by separating the additives and the like.
　本実施形態における基油中の硫黄分の含有割合は、基油の総量（１００質量％）に対して０．０５質量％以下が好ましく、０．０３質量％以下がより好ましく、０．０１質量％以下がさらに好ましく、０．００５質量％以下が特に好ましく、０．００１質量％以下が最も好ましく、０．０００１質量％以上が好ましく、０．０００２質量％以上がより好ましい。
　当該基油中の硫黄分の含有割合が、前記の好ましい範囲の上限値以下であれば、硫黄腐食のリスクがより低減され、また、酸化安定性への悪影響も抑制される。
　本発明において「基油中の硫黄分の含有割合」は、ＪＩＳ　Ｋ　２５４１－６（２０１３）に準拠した方法により測定できる。 The content of sulfur in the base oil in the present embodiment is preferably 0.05% by mass or less, more preferably 0.03% by mass or less, with respect to the total amount (100% by mass) of the base oil. % Or less is more preferable, 0.005% by mass or less is particularly preferable, 0.001% by mass or less is the most preferable, 0.0001% by mass or more is preferable, and 0.0002% by mass or more is more preferable.
If the content ratio of sulfur in the base oil is equal to or less than the upper limit value of the preferable range described above, the risk of sulfur corrosion is further reduced, and an adverse effect on the oxidation stability is also suppressed.
In the present invention, “content ratio of sulfur content in base oil” can be measured by a method according to JIS K 2541-6 (2013).
　本実施形態における基油中の芳香族炭化水素成分の含有割合（％ＣＡ）は、１．０以下が好ましく、０．７以下がより好ましく、０．６以下がさらに好ましく、０．５以下が特に好ましい。
　当該基油中の芳香族炭化水素成分の含有割合が、前記の好ましい範囲の上限値以下であれば、経時に伴う酸化劣化が抑制されやすくなる。本実施形態の潤滑油組成物においては、長寿命化の点から、基油中の芳香族炭化水素成分の含有割合が低いほど好ましい。 1.0 or less is preferable, as for the content rate (% CA) of the aromatic hydrocarbon component in the base oil in this embodiment, 0.7 or less is more preferable, 0.6 or less is more preferable, and 0.5 or less Particularly preferred.
If the content ratio of the aromatic hydrocarbon component in the base oil is equal to or less than the upper limit value of the preferable range, oxidation deterioration with the passage of time is easily suppressed. In the lubricating oil composition of the present embodiment, the lower the content of the aromatic hydrocarbon component in the base oil, the better in terms of prolonging the life.
　「基油中の芳香族炭化水素成分の含有割合」とは、基油を構成する全成分の炭素数の合計に対する、基油を構成する全成分のうちの芳香族炭化水素成分の炭素数、の割合をいう。
　本発明において「基油中の芳香族炭化水素成分の含有割合」は、ＡＳＴＭ　Ｄ３２３８（２０１７）に準拠した方法により測定できる。 The "content ratio of the aromatic hydrocarbon component in the base oil" means the carbon number of the aromatic hydrocarbon component among all the components constituting the base oil relative to the total carbon number of all components constituting the base oil, Say the percentage of
In the present invention, "the content ratio of the aromatic hydrocarbon component in the base oil" can be measured by the method according to ASTM D3238 (2017).
　本実施形態における基油の粘度指数は、１３０以下が好ましく、１２８以下がより好ましく、１２５以下がさらに好ましく、１２０以下が特に好ましい。一方、基油の粘度指数の下限値は、９５以上が好ましく、９７以上がより好ましく、１００以上がさらに好ましく、１０４以上が特に好ましい。
　当該基油の粘度指数が、前記の好ましい範囲の下限値以上であれば、温度による粘度変化が抑えられやすくなり、一方、前記の好ましい範囲の上限値以下であれば、酸化安定性に寄与する成分が一定量確保され、経時に伴う酸化劣化が抑制されやすくなる。
　本発明において「基油の粘度指数」は、ＪＩＳ　Ｋ　２２８３（２０００）に準拠した方法により測定できる。 The viscosity index of the base oil in the present embodiment is preferably 130 or less, more preferably 128 or less, still more preferably 125 or less, and particularly preferably 120 or less. On the other hand, the lower limit of the viscosity index of the base oil is preferably 95 or more, more preferably 97 or more, still more preferably 100 or more, and particularly preferably 104 or more.
If the viscosity index of the said base oil is more than the lower limit of the said preferable range, the viscosity change by temperature will be easy to be suppressed, and if it is below the upper limit of the said preferable range, it will contribute to oxidation stability. A certain amount of components is secured, and oxidation deterioration with time is easily suppressed.
In the present invention, “the viscosity index of the base oil” can be measured by a method in accordance with JIS K 2283 (2000).
　本実施形態における基油の４０℃動粘度は、１００ｍｍ２／ｓ以下が好ましく、９５ｍｍ２／ｓ以下がより好ましく、９０ｍｍ２／ｓ以下がさらに好ましい。一方、基油の４０℃動粘度の下限値は、２０ｍｍ２／ｓ以上が好ましく、２５ｍｍ２／ｓ以上がよりに好ましく、３０ｍｍ２／ｓ以上がさらに好ましい。
　当該基油の４０℃動粘度が、前記の好ましい範囲の下限値以上であれば、油膜の形成能が高められやすくなり、一方、前記の好ましい範囲の上限値以下であれば、低温での粘度上昇が抑えられやすくなる。
　本発明において「基油の４０℃動粘度」は、ＪＩＳ　Ｋ　２２８３（２０００）に準拠した方法により測定される、温度４０℃における動粘度を示す。 100 mm < 2 > / s or less is preferable, as for the 40 degreeC dynamic viscosity of the base oil in this embodiment, 95 mm < 2 > / s or less is more preferable, and 90 mm < 2 > / s or less is more preferable. On the other hand, the lower limit of the 40 ° C. kinematic viscosity of the base oil is preferably 20 mm 2 / s or more, more preferably 25 mm 2 / s or more, and still more preferably 30 mm 2 / s or more.
If the kinematic viscosity of the base oil at 40 ° C. is equal to or more than the lower limit of the preferable range, the ability to form an oil film tends to be enhanced, while if it is equal to or less than the upper limit of the preferable range, the viscosity at low temperature The rise is likely to be suppressed.
In the present invention, “40 ° C. kinematic viscosity of base oil” indicates a kinematic viscosity at a temperature of 40 ° C. measured by a method in accordance with JIS K 2283 (2000).
　本実施形態で用いられる基油には、波長２７４ｎｍにおける吸光度が０．０２以上３．０以下であり、かかる吸光度を有するものの中でも、さらに、硫黄分の含有割合が０．０５質量％以下、芳香族炭化水素成分の含有割合（％ＣＡ）が１．０以下、及び粘度指数が９５以上１３０以下であるものを用いることが、酸化安定性、及び原料選択性の幅の点から特に好ましい。 The base oil used in the present embodiment has an absorbance at a wavelength of 274 nm of 0.02 or more and 3.0 or less, and among those having such an absorbance, the content of sulfur is further 0.05% by mass or less, the aroma It is particularly preferable from the viewpoint of the oxidation stability and the width of the raw material selectivity to use one having a content of the group hydrocarbon component (% CA) of 1.0 or less and a viscosity index of 95 or more and 130 or less.
　潤滑油組成物中の基油の含有量は、潤滑油組成物の総量（１００質量％）に対して、９０質量％以上が好ましく、９５質量％以上がより好ましく、９６質量％以上がさらに好ましく、一方、上限値は９９．９質量％以下が好ましく、９９．８質量％以下がより好ましい。 The content of the base oil in the lubricating oil composition is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 96% by mass or more based on the total amount (100% by mass) of the lubricating oil composition. On the other hand, 99.9 mass% or less is preferable and 99.8 mass% or less is more preferable.
＜酸化防止剤＞
　本実施形態における酸化防止剤は、特に制限されず、例えば、芳香族アミン系酸化防止剤、フェノール系酸化防止剤、硫黄系酸化防止剤、硫黄・りん系酸化防止剤、その他酸化防止剤が挙げられる。 <Antioxidant>
The antioxidant in the present embodiment is not particularly limited, and examples thereof include aromatic amine antioxidants, phenol antioxidants, sulfur antioxidants, sulfur and phosphorus antioxidants, and other antioxidants. Be
　芳香族アミン系酸化防止剤としては、フェニル－α－ナフチルアミン、アルキル化フェニル－α－ナフチルアミン、ジフェニルアミン、アルキル化ジフェニルアミン、フェノチアジン等が挙げられる。アルキル化ジフェニルアミンとしては、ｐ，ｐ’－ジオクチルジフェニルアミン等が挙げられる。 Examples of the aromatic amine antioxidant include phenyl-α-naphthylamine, alkylated phenyl-α-naphthylamine, diphenylamine, alkylated diphenylamine and phenothiazine. Examples of the alkylated diphenylamine include p, p'-dioctyl diphenylamine and the like.
　フェノール系酸化防止剤としては、２，６－ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール、２，６－ジ－ｔ－ブチル－４－エチルフェノール、４，４’－メチレンビス（２，６－ジ－ｔｅｒｔ－ブチルフェノール）、４，４’－メチレンビス（６－ｔｅｒｔ－ブチル－ｏ－クレゾール）等が挙げられる。 Examples of phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-4-ethylphenol, 4,4′-methylenebis (2,6-di- tert-Butylphenol), 4,4'-methylenebis (6-tert-butyl-o-cresol) and the like.
　硫黄系酸化防止剤としては、ジベンジルジサルファイド、ジアルキルサルファイド、硫化油脂等が挙げられる。
　硫黄・りん系酸化防止剤としては、ジアルキルジチオりん酸亜鉛、ジアリルジチオりん酸亜鉛等が挙げられる。
　その他酸化防止剤としては、Ｎ，Ｎ’－ジサリチリデン－１，２－ジアミノプロパン、ベンゾトリアゾール、２（ｎ－ドデシルジチオ）ベンズイミダゾール、銅系酸化防止剤、モリブデン系酸化防止剤等が挙げられる。 Examples of sulfur-based antioxidants include dibenzyl disulfide, dialkyl sulfides, sulfurized fats and oils, and the like.
Examples of sulfur and phosphorus antioxidants include zinc dialkyl dithiophosphate and zinc diallyl dithiophosphate.
Other antioxidants include N, N'-disalicylidene-1,2-diaminopropane, benzotriazole, 2 (n-dodecyldithio) benzimidazole, copper-based antioxidants, molybdenum-based antioxidants and the like.
　本実施形態の潤滑油組成物において、酸化防止剤は、１種のみが用いられてもよく、２種以上が組み合わされ用いられてもよい。
　酸化防止剤は、酸化安定性がより向上しやすいことから、芳香族アミン系酸化防止剤及びフェノール系酸化防止剤からなる群より選択される少なくとも１種が好ましく、この中でも、潤滑油組成物の長寿命化がより図られやすいことから、芳香族アミン系酸化防止剤を少なくとも含むことが特に好ましい。 In the lubricating oil composition of the present embodiment, only one antioxidant may be used, or two or more antioxidants may be used in combination.
The antioxidant is preferably at least one selected from the group consisting of an aromatic amine antioxidant and a phenolic antioxidant because oxidation stability is more easily improved, and among these, lubricating oil compositions are preferably used. It is particularly preferable to include at least an aromatic amine-based antioxidant because it is easy to achieve long life.
　潤滑油組成物中の酸化防止剤の含有量は、基油又は酸化防止剤の種類に応じて適宜決定され、例えば、潤滑油組成物の総量（１００質量％）に対して、０．１質量％以上が好ましく、０．２質量％以上がより好ましく、０．３質量％以上がさらに好ましく、５質量％以下が好ましく、３質量％以下がより好ましい。
　酸化防止剤の含有量が、前記の好ましい範囲の下限値以上であれば、酸化劣化をより生じにくくなり、一方、前記の好ましい範囲の上限値を超えても、その添加量に見合う酸化防止の向上効果が得られにくくなる。 The content of the antioxidant in the lubricating oil composition is appropriately determined according to the type of the base oil or the antioxidant, and, for example, 0.1 mass based on the total amount (100 mass%) of the lubricating oil composition % Or more is preferable, 0.2 mass% or more is more preferable, 0.3 mass% or more is more preferable, 5 mass% or less is preferable, and 3 mass% or less is more preferable.
If the content of the antioxidant is at least the lower limit value of the above-mentioned preferable range, the oxidation deterioration is less likely to occur, while, even if the upper limit value of the above-mentioned preferable range is exceeded, the oxidation prevention corresponding to the addition amount It becomes difficult to obtain the improvement effect.
　本実施形態の潤滑油組成物が含有してもよい、その他成分としては、例えば、さび止め剤（防錆剤）、泡消し剤（消泡剤）、摩擦調整剤、粘度指数向上剤、金属不活性剤、流動点降下剤、解乳化剤、金属系清浄剤、無灰分散剤、摩耗防止剤又は極圧剤、腐食防止剤などが挙げられる。 Other components that the lubricating oil composition of the present embodiment may contain include, for example, a rust inhibitor (rust inhibitor), an antifoam agent (antifoamer), a friction modifier, a viscosity index improver, a metal Deactivators, pour point depressants, demulsifiers, metal detergents, ashless dispersants, antiwear agents or extreme pressure agents, corrosion inhibitors, etc. may be mentioned.
　本実施形態の潤滑油組成は、基油及び酸化防止剤に加え、さらに、さび止め剤（防錆剤）を含有するものでもよい。
　さび止め剤としては、例えば、脂肪族アミン類、有機スルホン酸金属塩、有機リン酸金属塩、アルキルコハク酸エステル、アルケニルコハク酸エステル、コハク酸イミド類、サルコシン酸誘導体、アルキルフェニル脂肪酸類、多価アルコールエステル類などが挙げられる。
　潤滑油組成物中のさび止め剤の含有量は、基油又はさび止め剤の種類に応じて適宜決定され、例えば、潤滑油組成物の総量（１００質量％）に対して、０．０１質量％以上が好ましく、０．０２質量％以上がより好ましく、０．０３質量％以上がさらに好ましく、１質量％以下が好ましく、０．５質量％以下がより好ましい。
　さび止め剤の含有量が、前記の好ましい範囲の下限値以上であれば、適切な防錆効果が得られやすくなり、一方、前記の好ましい範囲の上限値を超えると、酸化安定性に悪影響を及ぼすようになる。 The lubricating oil composition of the present embodiment may further contain a rust inhibitor (rust inhibitor) in addition to the base oil and the antioxidant.
As the rust inhibitor, for example, aliphatic amines, organic sulfonic acid metal salts, organic phosphoric acid metal salts, alkyl succinic acid esters, alkenyl succinic acid esters, succinic acid imides, sarcosinic acid derivatives, alkyl phenyl fatty acids, many And polyhydric alcohol esters.
The content of the rust inhibitor in the lubricating oil composition is appropriately determined according to the type of the base oil or the rust inhibitor, and is, for example, 0.01 mass based on the total amount (100% by mass) of the lubricating oil composition. % Or more is preferable, 0.02 mass% or more is more preferable, 0.03 mass% or more is more preferable, 1 mass% or less is preferable, and 0.5 mass% or less is more preferable.
If the content of the rust inhibitor is at least the lower limit value of the above-mentioned preferable range, an appropriate antirust effect is easily obtained, while if it exceeds the upper limit value of the above-mentioned preferable range, the oxidation stability is adversely affected. Become to exert.
　以上説明した本実施形態の潤滑油組成物には、特定の吸光度を有する基油と、酸化防止剤と、が組み合わされている。かかる基油は、波長２７４ｎｍにおける吸光度が０．０２以上３．０以下である、すなわち、波長２７４ｎｍに吸収をもつ多環芳香族炭化水素成分を含有している。尚、かかる基油中の、波長２７４ｎｍに吸収をもつ多環芳香族炭化水素成分の定量は、微量のために難しい。
　本実施形態の潤滑油組成物においては、特定の吸光度を有する程度に微量の多環芳香族炭化水素成分と、酸化防止剤と、の相乗的な作用により酸化安定性が高められることで、より長寿命化が図られる、と推測される。 In the lubricating oil composition of the present embodiment described above, a base oil having a specific absorbance and an antioxidant are combined. The base oil contains a polycyclic aromatic hydrocarbon component having an absorbance at a wavelength of 274 nm of 0.02 or more and 3.0 or less, that is, having an absorption at a wavelength of 274 nm. The determination of the polycyclic aromatic hydrocarbon component having absorption at a wavelength of 274 nm in such a base oil is difficult due to its small amount.
In the lubricating oil composition of the present embodiment, the oxidative stability is enhanced by the synergistic action of the polycyclic aromatic hydrocarbon component in a trace amount having a specific absorbance and the antioxidant. It is presumed that the life can be extended.
　本実施形態の潤滑油組成物によれば、タービン等の安定稼働を可能とする。当該潤滑油組成物は、種々のタービン油として有用なものである。加えて、当該潤滑油組成物は、長期にわたって酸化安定性が保たれるため、インフラ用途の潤滑油に好適であり、発電用タービン油に特に好適である。 According to the lubricating oil composition of the present embodiment, stable operation of a turbine or the like is enabled. The lubricating oil composition is useful as various turbine oils. In addition, the lubricating oil composition is suitable for use as a lubricant for infrastructure applications, and particularly suitable for use as a turbine oil for power generation, because the oxidative stability is maintained for a long time.
（基油）
　本実施形態の基油は、波長２７４ｎｍにおける吸光度が０．０２以上３．０以下である。
　かかる吸光度を有するものの中でも、本実施形態の基油においては、さらに、硫黄分の含有割合が０．０５質量％以下である基油、芳香族炭化水素成分の含有割合（％ＣＡ）が１．０以下である基油、粘度指数が９５以上１３０以下である基油、又は４０℃動粘度が２０ｍｍ２／ｓｅｃ以上１００ｍｍ２／ｓｅｃ以下である基油が、酸化安定性及び原料選択性の幅の点から好ましい。
　当該基油についての詳細な説明は、上述した＜基油＞と同じである。 (Base oil)
The base oil of the present embodiment has an absorbance of 0.02 or more and 3.0 or less at a wavelength of 274 nm.
Among those having such absorbance, in the base oil of the present embodiment, the base oil having a content of sulfur of 0.05% by mass or less, and the content (% CA) of the content of an aromatic hydrocarbon component are 1. 0 or less is the base oil, the base oil viscosity index of 95 or more 130 or less, or 40 ° C. kinematic viscosity of 20 mm 2 / sec or more 100 mm 2 / sec or less is base oil oxidation stability and material selectivity of the width It is preferable from the point of
The detailed description about the said base oil is the same as <base oil> mentioned above.
　本実施形態の基油は、原油について、常圧蒸留及び減圧蒸留の少なくとも一方を行うことによって得られた留分に対し、溶剤脱れき、溶剤抽出、水素化処理、溶剤脱ろう、接触脱ろう、異性化脱ろう、水素化精製、酸洗浄、後蒸留などの各処理を組み合わせて施すことにより得られる。
　例えば、プラント製造での前記水素化処理の際における、反応温度、水素圧力、水素／オイル比、又は液空間速度を適宜制御することで、基油の微量な硫黄分、芳香族分などの割合を調整することができる。一例として、本実施形態の、波長２７４ｎｍにおける吸光度が０．０２以上３．０以下である基油を製造するために、前記水素化処理の際における、反応温度を好ましくは２７０℃以上５００℃以下、より好ましくは２９０℃以上４５０℃以下；水素圧力を好ましくは５ＭＰａ以上３０ＭＰａ以下、より好ましくは１０ＭＰａ以上２２ＭＰａ以下；水素／オイル比を好ましくは１０ＮＬ／Ｌ以上２０００ＮＬ／Ｌ以下、より好ましくは３００ＮＬ／Ｌ以上１０００ＮＬ／Ｌ以下；液空間速度を好ましくは０．１ｈ－１以上５．０ｈ－１以下、より好ましくは０．２ｈ－１以上３．０ｈ－１以下の範囲内で適宜制御する。 The base oil of the present embodiment is solvent-depleted, solvent-extracted, hydrotreated, solvent dewaxed, catalytic dewaxed with respect to a fraction obtained by performing at least one of atmospheric distillation and vacuum distillation of crude oil. It can be obtained by combining and applying processes such as isomerization dewaxing, hydrorefining, acid washing and post-distillation.
For example, by appropriately controlling the reaction temperature, the hydrogen pressure, the hydrogen / oil ratio, or the liquid hourly space at the time of the hydrotreating in plant production, the proportion of the trace sulfur and aromatic components of the base oil Can be adjusted. As an example, in order to produce the base oil having an absorbance at a wavelength of 274 nm of 0.02 to 3.0 according to this embodiment, the reaction temperature is preferably 270 ° C. to 500 ° C. during the hydrotreating. Hydrogen pressure is preferably 5 MPa to 30 MPa, more preferably 10 MPa to 22 MPa; hydrogen / oil ratio is preferably 10 NL / L to 2000 NL / L, more preferably 300 NL / L. L above 1000 NL / L or less; liquid the preferred space velocity 0.1 h -1 or 5.0 h -1 or less, more preferably controlled as appropriate within a range of 0.2 h -1 or 3.0 h -1 or less.
　上述した本実施形態の基油は、特定の吸光度を有する。このため、当該基油は、良好な酸化安定性を示し、長期間の使用又は保管に適する。当該基油は、インフラ用途の潤滑油用として特に好適である。 The base oil of the present embodiment described above has a specific absorbance. Because of this, the base oil exhibits good oxidative stability and is suitable for long-term use or storage. The base oils are particularly suitable for lubricating oils for infrastructure applications.
　以下、本発明の効果を実施例及び比較例を用いて詳細に説明するが、本発明は下記の実施例に限定されるものではない。
　本実施例で用いる基油について、波長２７４ｎｍにおける吸光度、硫黄分の含有割合、芳香族炭化水素成分の含有割合、粘度指数、４０℃動粘度を、それぞれ以下に示す方法により測定した。
　また、潤滑油組成物について、酸価を、以下に示す方法により測定した。 Hereinafter, the effects of the present invention will be described in detail using examples and comparative examples, but the present invention is not limited to the following examples.
The absorbance at a wavelength of 274 nm, the content ratio of sulfur, the content ratio of an aromatic hydrocarbon component, the viscosity index, and the 40 ° C. kinematic viscosity of the base oil used in this example were measured by the methods described below.
Moreover, the acid value was measured by the method shown below about a lubricating oil composition.
［波長２７４ｎｍにおける吸光度］
　基油についての波長２７４ｎｍにおける吸光度は、ＪＩＳ　Ｋ　０１１５（２０１４）に準拠して測定した。
　吸光度の測定試料は、基油３．０ｇを、ノルマルヘキサン（特級）３０ｍＬで希釈して調製した。測定セルには、厚さ１０ｍｍのものを用いた。測定装置には、株式会社日立ハイテクサイエンスのＵ－４１００形分光光度計を用いた。 [Absorbance at a wavelength of 274 nm]
The absorbance of the base oil at a wavelength of 274 nm was measured in accordance with JIS K 0115 (2014).
A sample for measurement of absorbance was prepared by diluting 3.0 g of the base oil with 30 mL of normal hexane (special grade). The measuring cell used had a thickness of 10 mm. As a measuring apparatus, a U-4100 spectrophotometer manufactured by Hitachi High-Tech Science Co., Ltd. was used.
［硫黄分の含有割合］
　基油についての硫黄分の含有割合（質量ｐｐｍ）は、ＪＩＳ　Ｋ　２５４１－６（２０１３）に準拠して測定した。 [Content ratio of sulfur content]
The sulfur content of the base oil (ppm by mass) was measured in accordance with JIS K 2541-6 (2013).
［芳香族炭化水素成分の含有割合］
　基油についての芳香族炭化水素成分の含有割合（％ＣＡ）は、ＡＳＴＭ　Ｄ３２３８（２０１７）に準拠して測定した。 [Content ratio of aromatic hydrocarbon component]
The content (% CA) of the aromatic hydrocarbon component in the base oil was measured in accordance with ASTM D3238 (2017).
［粘度指数］
　基油についての粘度指数は、ＪＩＳ　Ｋ　２２８３（２０００）に準拠して測定した。 [Viscosity Index]
The viscosity index of the base oil was measured in accordance with JIS K 2283 (2000).
［４０℃動粘度］
　基油についての４０℃動粘度（ｍｍ２／ｓ）は、ＪＩＳ　Ｋ　２２８３（２０００）に準拠して測定した。 [40 ° C kinematic viscosity]
The 40 ° C. kinematic viscosity (mm 2 / s) of the base oil was measured in accordance with JIS K 2283 (2000).
［酸価］
　潤滑油組成物について、ＡＳＴＭ　Ｄ７８７３（２０１３ｅ２）に準拠した加速劣化試験を行い、加速劣化油の酸価（ｍｇＫＯＨ／ｇ）をＪＩＳ　Ｋ２５０１（２００３）に準拠して測定した。
　具体的には、銅及び鉄のコイル触媒の存在下、流速３．０Ｌ／ｈの酸素を吹き込みながら、潤滑油組成物を１２０℃で加熱し、一定時間の経過後に少量（２０ｇ）の油（加速劣化油）を採取し、この加速劣化油の酸価を測定した。
　また、酸価の評価基準として、ＡＳＴＭ　Ｄ４３０４又はＩＳＯ８０６８等のタービン油製品規格の品質規定で定められている、ＴＯＳＴ試験（ＩＳＯ４２６３－１）により加速劣化させた際の評価基準値である酸価２．０ｍｇＫＯＨ／ｇを適用した。この２．０ｍｇＫＯＨ／ｇを超えるまで、当該加速劣化試験を継続して行った。 [Acid number]
The lubricating oil composition was subjected to an accelerated deterioration test according to ASTM D 7873 (2013 e 2), and the acid value (mg KOH / g) of the accelerated deteriorated oil was measured according to JIS K 2501 (2003).
Specifically, the lubricating oil composition is heated at 120 ° C. while blowing oxygen at a flow rate of 3.0 L / h in the presence of a copper and iron coil catalyst, and after a certain time, a small amount (20 g) of oil (20 g) Accelerated deterioration oil was sampled, and the acid value of this accelerated deterioration oil was measured.
In addition, as an acid number evaluation standard, the acid number 2 is an evaluation standard value when accelerated deterioration is made according to the TOST test (ISO 4263-1), which is defined by the quality regulations of turbine oil product standards such as ASTM D4304 or ISO 8068. .0 mg KOH / g was applied. The accelerated deterioration test was continued until it exceeded 2.0 mg KOH / g.
＜基油の製造＞
　本実施例で用いた基油１～８及び基油１０～１１は、原油（パラフィン基原油あるいは混合基原油）について、常圧蒸留及び減圧蒸留の少なくとも一方を行うことによって得られた留分に対し、溶剤脱れき、溶剤抽出、水素化処理、溶剤脱ろう、接触脱ろう、異性化脱ろう、水素化精製、酸洗浄、後蒸留の一連の処理を施すことによって得た。
　プラント製造での前記水素化処理の際、反応温度、水素圧力、水素／オイル比、液空間速度をそれぞれ適宜制御することで、各基油を製造した。 <Production of base oil>
The base oils 1 to 8 and the base oils 10 to 11 used in the present embodiment are fractions obtained by performing at least one of atmospheric distillation and vacuum distillation on crude oil (paraffin-based crude oil or mixed base crude oil). On the other hand, it was obtained by performing a series of treatments such as solvent deasphalting, solvent extraction, hydrotreating, solvent dewaxing, catalytic dewaxing, isomerization dewaxing, hydrorefining, acid washing and post-distillation.
Each base oil was manufactured by appropriately controlling the reaction temperature, the hydrogen pressure, the hydrogen / oil ratio, and the liquid hourly space at the time of the hydrotreating in the plant production.
　本実施例で用いた基油９は、天然ガスを原料としたＧＴＬワックスを基に製造した。 The base oil 9 used in the present example was manufactured based on GTL wax using natural gas as a raw material.
　以下、各基油の詳細な製造方法を記載する。 Hereafter, the detailed manufacturing method of each base oil is described.
　≪基油１≫
　中東原油を常圧蒸留装置に供し、得られた常圧蒸留残渣を減圧蒸留装置に供し、得られた減圧蒸留留分を水素化分解装置（反応温度３４０～４００℃、水素圧力を１０～１５ＭＰａ、水素／オイル比を４５０～６５０ＮＬ／Ｌ、液空間速度を１．０～２．０ｈ－１の範囲内で制御）に供し、得られた水素化分解油を蒸留にて燃料留分を除去後、異性化脱ろう装置（反応温度２９０～３５０℃、水素圧力を１１～１５ＭＰａ、水素／オイル比を４００～６００ＮＬ／Ｌ、液空間速度を１．０～２．０ｈ－１の範囲内で制御）に供し、得られた脱ろう油を蒸留にて燃料留分を除去後、水素化精製装置（反応温度２７０～３３０℃、水素圧力６～１０ＭＰａ、水素／オイル比を９００～１５００ＮＬ／Ｌ、液空間速度を１．０～２．０ｈ－１の範囲内で制御）に供し、得られた水素化精製油を蒸留装置に供し、４０℃動粘度が３１．６ｍｍ２／ｓの留分として得た。 «Base oil 1»
The Middle East crude oil is subjected to an atmospheric distillation apparatus, and the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the vacuum distillation fraction obtained is subjected to a hydrocracking apparatus (reaction temperature 340 to 400 ° C., hydrogen pressure 10 to 15 MPa , The hydrogen / oil ratio is 450 to 650 NL / L, the liquid space velocity is controlled in the range of 1.0 to 2.0 h.sup.- 1 , and the resulting hydrocracked oil is distilled to remove the fuel fraction. After that, an isomerization dewaxing unit (reaction temperature: 290 to 350 ° C., hydrogen pressure: 11 to 15 MPa, hydrogen / oil ratio: 400 to 600 NL / L, liquid space velocity: in the range of 1.0 to 2.0 h -1 The de-waxed oil obtained is subjected to distillation to remove the fuel fraction, and the hydrorefining apparatus (reaction temperature 270 to 330 ° C., hydrogen pressure 6 to 10 MPa, hydrogen / oil ratio 900 to 1500 NL / L) , range of the liquid hourly space velocity 1.0 ~ 2.0h -1 Subjected to the control) at the inner, subjected the resulting hydrotreated oil to a distillation apparatus, 40 ° C. kinematic viscosity was obtained as a fraction of 31.6mm 2 / s.
　≪基油２≫
　中東原油を常圧蒸留装置に供し、得られた常圧蒸留残渣を減圧蒸留装置に供し、得られた減圧蒸留留分を水素化処理装置（反応温度２８０～３３０℃、水素圧力を１７～２２ＭＰａ、水素／オイル比を５５０～８５０ＮＬ／Ｌ、液空間速度を０．５～１．０ｈ－１の範囲内で制御）に供し、得られた水素化処理油を溶剤脱ろう装置（溶剤をメチルエチルケトンとトルエンとの混合溶剤、一次溶剤比１．８～２．５、二次溶剤比０．６～１．０、脱蝋温度－１５～－２５℃の範囲内で制御）に供し、４０℃動粘度が３１．１ｍｍ２／ｓの留分として得た。 «Base oil 2»
The Middle East crude oil is subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the vacuum distillation fraction obtained is subjected to a hydrotreating apparatus (reaction temperature 280 to 330 ° C., hydrogen pressure 17 to 22 MPa And a hydrogen / oil ratio of 550 to 850 NL / L, and the liquid space velocity is controlled in the range of 0.5 to 1.0 h.sup.- 1 , and the obtained hydrotreated oil is subjected to solvent dewaxing (solvent is methyl ethyl ketone). Mixed with toluene and toluene, primary solvent ratio 1.8 to 2.5, secondary solvent ratio 0.6 to 1.0, dewaxing temperature controlled within the range of -15 to -25 ° C) The kinematic viscosity was obtained as a fraction of 31.1 mm 2 / s.
　≪基油３≫
　中東原油を常圧蒸留装置に供し、得られた常圧蒸留残渣を減圧蒸留装置に供し、得られた減圧蒸留留分を水素化精製装置（反応温度２６０～３３０℃、水素圧力６～１０ＭＰａ、水素／オイル比を７００～１３００ＮＬ／Ｌ、液空間速度を１．０～２．０ｈ－１の範囲内で制御）に供し、得られた水素化精製油を水素化分解装置（反応温度３５０～４００℃、水素圧力を１０～１５ＭＰａ、水素／オイル比を６００～１０００ＮＬ／Ｌ、液空間速度を１．２～２．４ｈ－１の範囲内で制御）に供し、得られた水素化分解油を蒸留にて燃料留分を除去後、減圧蒸留装置に供し、得られた減圧蒸留留分（粘度グレードＶＧ４６相当留分）を異性化脱ろう装置（反応温度２８０～３４０℃、水素圧力を１１～１５ＭＰａ、水素／オイル比を４５０～６５０ＮＬ／Ｌ、液空間速度を１．０～２．０ｈ－１の範囲内で制御）に供し、得られた脱ろう油を水素化精製装置（反応温度２８０～３４０℃、水素圧力７～１１ＭＰａ、水素／オイル比を８００～１３００ＮＬ／Ｌ、液空間速度を１．０～２．０ｈ－１の範囲内で制御）に供し、得られた水素化精製油を蒸留にて燃料留分を除去して、４０℃動粘度が４７．５ｍｍ２／ｓの留分として得た。 «Base oil 3»
Middle East crude oil is subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the vacuum distillation fraction obtained is subjected to a hydrorefining apparatus (reaction temperature 260 to 330 ° C., hydrogen pressure 6 to 10 MPa, A hydrogen / oil ratio of 700 to 1,300 NL / L and a liquid space velocity of 1.0 to 2.0 h -1 are controlled, and the resulting hydrorefined oil is subjected to a hydrocracker (reaction temperature: 350 to The hydrocracked oil obtained at 400 ° C., a hydrogen pressure of 10 to 15 MPa, a hydrogen / oil ratio of 600 to 1000 NL / L, and a liquid hourly space velocity of 1.2 to 2.4 h −1. The fuel fraction is removed by distillation, and the mixture is then subjected to a vacuum distillation apparatus, and the resulting vacuum distillation fraction (viscosity grade VG46 equivalent fraction) is isomerized and dewaxed (reaction temperature 280 to 340 ° C., hydrogen pressure 11 ~ 15MPa, hydrogen / oil ratio 450 650NL / L, the liquid subjected space velocity in the control) in the range of 1.0 ~ 2.0 h -1, hydrogenation of the dewaxed oil obtained purifier (reaction temperature 280 ~ 340 ° C., the hydrogen pressure 7 ~ 11 MPa Hydrogen / oil ratio of 800-1300 NL / L, control of liquid space velocity in the range of 1.0-2.0 h.sup.- 1 ), and removing the fuel fraction by distillation of the resulting hydrogenated refined oil The resultant was obtained as a fraction having a kinematic viscosity of 47.5 mm 2 / s at 40 ° C.
　≪基油４≫
　中東原油を常圧蒸留装置に供し、得られた常圧蒸留残渣を減圧蒸留装置に供し、得られた減圧蒸留留分を水素化分解装置（反応温度３４０～４００℃、水素圧力を１０～１５ＭＰａ、水素／オイル比を４５０～６５０ＮＬ／Ｌ、液空間速度を１．０～２．０ｈ－１の範囲内で制御）に供し、得られた水素化分解油を蒸留にて燃料留分を除去後、異性化脱ろう装置（反応温度２９０～３５０℃、水素圧力を１１～１５ＭＰａ、水素／オイル比を４００～６００ＮＬ／Ｌ、液空間速度を１．０～２．０ｈ－１の範囲内で制御）に供し、得られた脱ろう油を蒸留にて燃料留分を除去後、水素化精製装置（反応温度２７０～３３０℃、水素圧力６～１０ＭＰａ、水素／オイル比を９００～１５００ＮＬ／Ｌ、液空間速度を１．０～２．０ｈ－１の範囲内で制御）に供し、得られた水素化精製油を蒸留装置に供し、４０℃動粘度が８８．３ｍｍ２／ｓの留分として得た。 «Base oil 4»
The Middle East crude oil is subjected to an atmospheric distillation apparatus, and the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the vacuum distillation fraction obtained is subjected to a hydrocracking apparatus (reaction temperature 340 to 400 ° C., hydrogen pressure 10 to 15 MPa , The hydrogen / oil ratio is 450 to 650 NL / L, the liquid space velocity is controlled in the range of 1.0 to 2.0 h.sup.- 1 , and the resulting hydrocracked oil is distilled to remove the fuel fraction. After that, an isomerization dewaxing unit (reaction temperature: 290 to 350 ° C., hydrogen pressure: 11 to 15 MPa, hydrogen / oil ratio: 400 to 600 NL / L, liquid space velocity: in the range of 1.0 to 2.0 h -1 The de-waxed oil obtained is subjected to distillation to remove the fuel fraction, and the hydrorefining apparatus (reaction temperature 270 to 330 ° C., hydrogen pressure 6 to 10 MPa, hydrogen / oil ratio 900 to 1500 NL / L) , range of the liquid hourly space velocity 1.0 ~ 2.0h -1 Subjected to the control) at the inner, subjected the resulting hydrotreated oil to a distillation apparatus, 40 ° C. kinematic viscosity was obtained as a fraction of 88.3mm 2 / s.
　≪基油５≫
　中東原油を常圧蒸留装置に供し、得られた常圧蒸留残渣を減圧蒸留装置に供し、得られた減圧蒸留留分を水素化精製装置（反応温度２７０～３４０℃、水素圧力７～１２ＭＰａ、水素／オイル比を９００～１４００ＮＬ／Ｌ、液空間速度を１．０～２．０ｈ－１の範囲内で制御）に供し、得られた水素化精製油を水素化分解装置（反応温度３６０～４２０℃、水素圧力を１１～１６ＭＰａ、水素／オイル比を７００～１２００ＮＬ／Ｌ、液空間速度を０．８～１．８ｈ－１の範囲内で制御）に供し、得られた水素化分解油を蒸留にて燃料留分を除去後、減圧蒸留装置に供し、得られた減圧蒸留留分（粘度グレードＶＧ３２相当留分）を異性化脱ろう装置（反応温度２８０～３４０℃、水素圧力を１１～１５ＭＰａ、水素／オイル比を３５０～６５０ＮＬ／Ｌ、液空間速度を１．０～２．０ｈ－１の範囲内で制御）に供し、得られた脱ろう油を水素化精製装置（反応温度２９０～３５０℃、水素圧力９～１４ＭＰａ、水素／オイル比を９００～１４００ＮＬ／Ｌ、液空間速度を１．０～２．０ｈ－１の範囲内で制御）に供し、得られた水素化精製油を蒸留にて燃料留分を除去して、４０℃動粘度が３６．２ｍｍ２／ｓの留分として得た。 «Base oil 5»
The Middle East crude oil is subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the vacuum distillation fraction obtained is subjected to a hydrorefining apparatus (reaction temperature 270 to 340 ° C., hydrogen pressure 7 to 12 MPa, A hydrogen / oil ratio of 900 to 1,400 NL / L and a liquid space velocity of 1.0 to 2.0 h -1 are controlled, and the resulting hydrorefined oil is subjected to a hydrocracker (reaction temperature: 360 to Hydrocracked oil obtained at 420 ° C., hydrogen pressure of 11 to 16 MPa, hydrogen / oil ratio of 700 to 1200 NL / L, and control of liquid hourly space velocity in the range of 0.8 to 1.8 h −1 ) The fuel fraction is removed by distillation, and the mixture is then subjected to a vacuum distillation apparatus, and the obtained vacuum distillation fraction (viscosity grade VG32 equivalent fraction) is isomerized and dewaxed (reaction temperature 280 to 340 ° C., hydrogen pressure 11 ~ 15MPa, hydrogen / oil ratio 350 650NL / L, the liquid subjected space velocity in the control) in the range of 1.0 ~ 2.0 h -1, hydrogenation of the dewaxed oil obtained purifier (reaction temperature 290 ~ 350 ° C., the hydrogen pressure 9 ~ 14 MPa Hydrogen / oil ratio of 900-1400 NL / L, control of liquid space velocity in the range of 1.0-2.0 h.sup.- 1 , and removing the fuel fraction by distillation of the obtained hydrogenated refined oil to, 40 ° C. kinematic viscosity was obtained as a fraction of 36.2 mm 2 / s.
　≪基油６≫
　中東原油を常圧蒸留装置に供し、得られた常圧蒸留残渣を減圧蒸留装置に供し、得られた減圧蒸留留分を水素化分解装置（反応温度２８０～３４０℃、水素圧力を７～１２ＭＰａ、水素／オイル比を４００～７００ＮＬ／Ｌ、液空間速度を１．５～２．５ｈ－１の範囲内で制御）に供し、得られた水素化分解油を蒸留にて燃料留分を除去後、異性化脱ろう装置（反応温度２９０～３５０℃、水素圧力を７～１０ＭＰａ、水素／オイル比を４００～６００ＮＬ／Ｌ、液空間速度を１．５～２．５ｈ－１の範囲内で制御）に供し、得られた脱ろう油を蒸留にて燃料留分を除去後、水素化精製装置（反応温度２５０～３１０℃、水素圧力５～１０ＭＰａ、水素／オイル比を６００～１０００ＮＬ／Ｌ、液空間速度を１．５～２．５ｈ－１の範囲内で制御）に供し、得られた水素化精製油を蒸留装置に供し、４０℃動粘度が２９．９ｍｍ２／ｓの留分として得た。 «Base oil 6»
The Middle East crude oil is subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the vacuum distillation fraction obtained is subjected to a hydrocracking apparatus (reaction temperature 280 to 340 ° C., hydrogen pressure 7 to 12 MPa , The hydrogen / oil ratio is 400 to 700 NL / L, and the liquid space velocity is controlled within the range of 1.5 to 2.5 h.sup.- 1 , and the resulting hydrocracked oil is distilled to remove the fuel fraction. After that, an isomerization dewaxing unit (reaction temperature: 290 to 350 ° C, hydrogen pressure: 7 to 10 MPa, hydrogen / oil ratio: 400 to 600 NL / L, liquid space velocity within the range of 1.5 to 2.5 h -1 The dewaxed oil obtained is subjected to distillation to remove the fuel fraction, and the hydrorefining apparatus (reaction temperature 250 to 310 ° C., hydrogen pressure 5 to 10 MPa, hydrogen / oil ratio 600 to 1000 NL / L) the liquid hourly space velocity in the range of 1.5 ~ 2.5 h -1 Subjected to the control), subjecting the resulting hydrotreated oil to a distillation apparatus, 40 ° C. kinematic viscosity was obtained as a fraction of 29.9 mm 2 / s.
　≪基油７≫
　中東原油を常圧蒸留装置に供し、得られた常圧蒸留残渣を減圧蒸留装置に供し、得られた減圧蒸留留分を水素化分解装置（反応温度３８０～４３０℃、水素圧力を１３～１７ＭＰａ、水素／オイル比を１０００～１６００ＮＬ／Ｌ、液空間速度を０．６～１．６ｈ－１の範囲内で制御）に供し、得られた水素化分解油を蒸留にて燃料留分を除去後、異性化脱ろう装置（反応温度３００～３５０℃、水素圧力を１１～１６ＭＰａ、水素／オイル比を１０００～１６００ＮＬ／Ｌ、液空間速度を０．６～１．６ｈ－１の範囲内で制御）に供し、得られた脱ろう油を蒸留にて燃料留分を除去後、水素化精製装置（反応温度２９０～３５０℃、水素圧力８～１２ＭＰａ、水素／オイル比を１０００～１６００ＮＬ／Ｌ、液空間速度を０．６～１．６ｈ－１の範囲内で制御）に供し、得られた水素化精製油を蒸留装置に供し、４０℃動粘度が３２．８ｍｍ２／ｓの留分として得た。 «Base oil 7»
The Middle East crude oil is subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the vacuum distillation fraction obtained is subjected to a hydrocracking apparatus (reaction temperature 380 to 430 ° C., hydrogen pressure 13 to 17 MPa Hydrogen / oil ratio of 1000-1600 NL / L, control of liquid space velocity in the range of 0.6-1.6 h -1 ), and removing the fuel fraction by distillation of the obtained hydrocracked oil After that, an isomerization dewaxing unit (reaction temperature 300 to 350 ° C, hydrogen pressure 11 to 16MPa, hydrogen / oil ratio 1000 to 1600NL / L, liquid space velocity within the range of 0.6 to 1.6h -1 The dewaxed oil obtained is subjected to distillation to remove the fuel fraction, and the hydrorefining apparatus (reaction temperature 290 to 350 ° C., hydrogen pressure 8 to 12 MPa, hydrogen / oil ratio 1000 to 1600 NL / L) , Liquid space velocity 0.6 to 1.6 Subjected to the control) in the range of -1, subjecting the resulting hydrotreated oil to a distillation apparatus, 40 ° C. kinematic viscosity was obtained as a fraction of 32.8 mm 2 / s.
　≪基油８≫
　中東原油を常圧蒸留装置に供し、得られた常圧蒸留残渣を減圧蒸留装置に供し、得られた減圧蒸留留分を水素化分解装置（反応温度３７０～４２０℃、水素圧力を１２～１６ＭＰａ、水素／オイル比を８００～１５００ＮＬ／Ｌ、液空間速度を０．８～１．８ｈ－１の範囲内で制御）に供し、得られた水素化分解油を蒸留にて燃料留分を除去後、異性化脱ろう装置（反応温度２９０～３５０℃、水素圧力を１１～１５ＭＰａ、水素／オイル比を８００～１５００ＮＬ／Ｌ、液空間速度を０．８～１．８ｈ－１の範囲内で制御）に供し、得られた脱ろう油を蒸留にて燃料留分を除去後、水素化精製装置（反応温度２９０～３５０℃、水素圧力８～１２ＭＰａ、水素／オイル比を１０００～１５００ＮＬ／Ｌ、液空間速度を０．８～１．８ｈ－１の範囲内で制御）に供し、得られた水素化精製油を蒸留装置に供し、４０℃動粘度が３２．１ｍｍ２／ｓの留分として得た。 «Base oil 8»
The Middle East crude oil is subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the vacuum distillation fraction obtained is subjected to a hydrocracking apparatus (reaction temperature 370 to 420 ° C., hydrogen pressure 12 to 16 MPa Hydrogen / oil ratio of 800 to 1,500 NL / L, and control of the liquid space velocity in the range of 0.8 to 1.8 h.sup.- 1 ), and removing the fuel fraction by distillation of the obtained hydrocracked oil After that, an isomerization dewaxing unit (reaction temperature: 290 to 350 ° C., hydrogen pressure: 11 to 15 MPa, hydrogen / oil ratio: 800 to 1,500 NL / L, liquid space velocity within the range of 0.8 to 1.8 h -1 The de-waxed oil obtained is subjected to distillation to remove the fuel fraction, and the hydrorefining apparatus (reaction temperature 290 to 350 ° C., hydrogen pressure 8 to 12 MPa, hydrogen / oil ratio 1000 to 1500 NL / L) , a liquid hourly space velocity 0.8 ~ 1.8h - Subjected to the control) in the range of, subjecting the resulting hydrotreated oil to a distillation apparatus, 40 ° C. kinematic viscosity was obtained as a fraction of 32.1 mm 2 / s.
　≪基油９≫
　天然ガスを原料としたＧＴＬワックス（沸点範囲４８０～５７０℃留分のノルマルパラフィンを４０質量％含有）を、異性化脱ろう装置（異性化反応温度３００～３２０℃、水素圧１２～１６ＭＰａ、水素／オイル比を５００～７００ＮＬ／Ｌ、液空間速度１．２～１．６ｈ－１の範囲内で制御）に供し、得られた脱ろう油を蒸留装置に供し、４０℃動粘度が３３．５ｍｍ２／ｓの留分として得た。 «Base oil 9»
An isomerization dewaxing unit (isomerization reaction temperature 300 to 320 ° C., hydrogen pressure 12 to 16 MPa, hydrogen) containing GTL wax (containing 40% by mass of normal paraffin of boiling range 480 to 570 ° C.) using natural gas as raw material (Controlled at a liquid space velocity of 1.2 to 1.6 h.sup.- 1 ), the obtained dewaxed oil is subjected to a distillation apparatus, and the kinematic viscosity at 40.degree. Obtained as a fraction of 5 mm 2 / s.
　≪基油１０≫
　中東原油を常圧蒸留装置に供し、得られた常圧蒸留残渣を減圧蒸留装置に供し、得られた減圧蒸留留分を水素化精製装置（反応温度２２０～２８０℃、水素圧力４～７ＭＰａ、水素／オイル比を４００～６５０ＮＬ／Ｌ、液空間速度を１．５～２．５ｈ－１の範囲内で制御）に供し、得られた水素化精製油を水素化分解装置（反応温度３３０～３８０℃、水素圧力を８～１３ＭＰａ、水素／オイル比を４００～８００ＮＬ／Ｌ、液空間速度を１．５～２．５ｈ－１の範囲内で制御）に供し、得られた水素化分解油を蒸留にて燃料留分を除去後、減圧蒸留装置に供し、得られた減圧蒸留留分（粘度グレードＶＧ２２相当留分）を異性化脱ろう装置（反応温度２６０～３２０℃、水素圧力を７～１１ＭＰａ、水素／オイル比を４００～６５０ＮＬ／Ｌ、液空間速度を１．５～２．５ｈ－１の範囲内で制御）に供し、得られた脱ろう油を水素化精製装置（反応温度２５０～３００℃、水素圧力４～７ＭＰａ、水素／オイル比を５００～１０００ＮＬ／Ｌ、液空間速度を１．５～２．５ｈ－１の範囲内で制御）に供し、得られた水素化精製油を蒸留にて燃料留分を除去して、４０℃動粘度が２０．４ｍｍ２／ｓの留分として得た。 «Base oil 10»
The Middle East crude oil is subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the vacuum distillation fraction obtained is subjected to a hydrorefining apparatus (reaction temperature 220 to 280 ° C., hydrogen pressure 4 to 7 MPa, A hydrogen / oil ratio of 400 to 650 NL / L and a liquid hourly space velocity of 1.5 to 2.5 h -1 are controlled, and the resulting hydrorefined oil is subjected to a hydrogenolysis unit (reaction temperature: 330 to Hydrocracked oil obtained at 380 ° C., a hydrogen pressure of 8 to 13 MPa, a hydrogen / oil ratio of 400 to 800 NL / L, and a liquid hourly space velocity of 1.5 to 2.5 h −1. After removing the fuel fraction by distillation, the mixture is subjected to a vacuum distillation apparatus, and the obtained vacuum distillation fraction (viscosity grade VG22 equivalent fraction) is isomerized and dewaxed (reaction temperature 260 to 320 ° C., hydrogen pressure 7) ~ 11MPa, hydrogen / oil ratio 400 ~ 650N / L, the liquid subjected space velocity in the control) in the range of 1.5 ~ 2.5 h -1, hydrotreater dewaxed oil obtained (reaction temperature 250 ~ 300 ° C., the hydrogen pressure 4 ~ 7 MPa, The hydrogen / oil ratio is 500 to 1000 NL / L, the liquid space velocity is controlled in the range of 1.5 to 2.5 h.sup.- 1 , and the resulting hydrogenated refined oil is distilled to remove the fuel fraction. The resultant was obtained as a fraction having a kinematic viscosity of 20.4 mm 2 / s at 40 ° C.
　≪基油１１≫
　中東原油を常圧蒸留装置に供し、得られた常圧蒸留残渣を減圧蒸留装置に供し、得られた１５０Ｎ相当の減圧蒸留留分をフルフラール抽出装置（塔頂温度１１０～１３０℃、塔底温度６０～８０℃、溶剤比１．０～３．０の範囲内で制御）に供し、得られたラフィネート留分を水素化精製装置（反応温度２７０～３３０℃、水素圧力４～６ＭＰａ、水素／オイル比を１５００～２０００ＮＬ／Ｌ、液空間速度を１．０～２．０ｈ－１の範囲内で制御）に供し、得られた水素化精製油を溶剤脱蝋装置（メチルエチルケトンとトルエンの混合溶剤、一次溶剤比１．８～２．５、二次溶剤比０．６～１．０、脱蝋温度－１５～－２５℃の範囲で調整）に供し、４０℃動粘度が２６．７ｍｍ２／ｓの留分として得た。 «Base oil 11»
Middle East crude oil is subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the obtained vacuum distillation fraction corresponding to 150 N is subjected to a furfural extraction apparatus (head temperature 110 to 130 ° C., bottom temperature Subjecting the raffinate fraction to a hydrorefining unit (reaction temperature 270-330 ° C., hydrogen pressure 4 to 6 MPa, hydrogen / The resulting hydrorefined oil is subjected to a solvent dewaxing apparatus (a mixed solvent of methyl ethyl ketone and toluene) at an oil ratio of 1500 to 2000 NL / L and a liquid space velocity controlled to a range of 1.0 to 2.0 h -1. primary solvent ratio 1.8-2.5, secondary solvent ratio 0.6-1.0, subjected to adjustment) in the range of dewaxing temperature -15 ~ -25 ℃, 40 ℃ kinematic viscosity 26.7 mm 2 Obtained as a fraction of 1 / s.
　得られた各基油について、上述の方法により、波長２７４ｎｍにおける吸光度、硫黄分の含有割合、芳香族炭化水素成分の含有割合、粘度指数、４０℃動粘度をそれぞれ測定した。これらの測定結果を表１に示した。 The absorbance at a wavelength of 274 nm, the content of sulfur, the content of an aromatic hydrocarbon component, the viscosity index, and the 40 ° C. kinematic viscosity were measured for each of the obtained base oils by the above-described method. The measurement results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
＜潤滑油組成物の製造＞
　上述の各基油に、酸化防止剤とさび止め剤とを添加して混合することにより、各例の潤滑油組成物をそれぞれ製造した。 <Production of lubricating oil composition>
The lubricating oil compositions of the respective examples were produced by adding and mixing an antioxidant and a rust inhibitor to each of the base oils described above.
　（実施例１～１０）
　基油として、基油１～１０をそれぞれ用いた。
　酸化防止剤として、いずれも芳香族アミン系酸化防止剤であるＢＡＳＦ社製のＩｒｇａｎｏｘＬ０６、及び、ＢＡＳＦ社製のＩｒｇａｎｏｘＬ５７を用いた。
　さび止め剤として、ＢＡＳＦ社製のＩｒｇａｃｏｒｅＬ１２を用いた。 (Examples 1 to 10)
As base oils, base oils 1 to 10 were used respectively.
As an antioxidant, Irganox L06 manufactured by BASF and Arganox L57 manufactured by BASF, both of which are aromatic amine antioxidants, were used.
As a rust inhibitor, Irgacore L12 manufactured by BASF Corp. was used.
　実施例１～１０の各潤滑油組成物は、基油１～１０のそれぞれの基油（残部）に、ＩｒｇａｎｏｘＬ０６（０．３質量％）と、ＩｒｇａｎｏｘＬ５７（０．２質量％）と、ＩｒｇａｃｏｒｅＬ１２（０．１質量％）とを添加して混合することにより調製した。
　前記の括弧内は、潤滑油組成物中の各成分の含有量を示し、当該組成物の総量（１００質量％）に占める割合を意味する。 The lubricating oil compositions of Examples 1 to 10 were prepared by adding Irganox L06 (0.3% by mass), Irganox L57 (0.2% by mass), and Irgacore L12 (to each base oil of the base oils 1 to 10). 0.1% by mass) was added and mixed.
The above parenthesis indicates the content of each component in the lubricating oil composition, and means the proportion of the total amount (100% by mass) of the composition.
　（比較例１）
　基油を、基油１１へ変更した以外は、実施例１～１０と同様にして、比較例１の潤滑油組成物を調製した。 (Comparative example 1)
A lubricating oil composition of Comparative Example 1 was prepared in the same manner as in Examples 1 to 10, except that the base oil was changed to base oil 11.
　（実施例１１～１３）
　基油として、基油１、基油３及び基油５をそれぞれ用いた。
　酸化防止剤として、フェノール系酸化防止剤である川口化学工業株式会社製のＡＮＴＡＧＥ ＢＨＴを用いた。
　さび止め剤として、ＢＡＳＦ社製のＩｒｇａｃｏｒｅＬ１２を用いた。 (Examples 11 to 13)
As base oils, base oil 1, base oil 3 and base oil 5 were used respectively.
As an antioxidant, ANTAGE BHT manufactured by Kawaguchi Chemical Industry Co., Ltd., which is a phenolic antioxidant, was used.
As a rust inhibitor, Irgacore L12 manufactured by BASF Corp. was used.
　実施例１１～１３の各潤滑油組成物は、基油１、基油３及び基油５のそれぞれの基油（残部）に、ＡＮＴＡＧＥ ＢＨＴ（１．０質量％）と、ＩｒｇａｃｏｒｅＬ１２（０．１質量％）とを添加して混合することにより調製した。
　前記の括弧内は、潤滑油組成物中の各成分の含有量を示し、当該組成物の総量（１００質量％）に占める割合を意味する。 The lubricating oil compositions of Examples 11 to 13 contained ANTAGE BHT (1.0% by mass) and Irgacore L12 (0.1%) in the respective base oils (remaining parts) of base oil 1, base oil 3 and base oil 5. It prepared by adding and mixing with mass%).
The above parenthesis indicates the content of each component in the lubricating oil composition, and means the proportion of the total amount (100% by mass) of the composition.
　（比較例２）
　基油を、基油１１へ変更した以外は、実施例１１～１３と同様にして、比較例２の潤滑油組成物を調製した。 (Comparative example 2)
A lubricating oil composition of Comparative Example 2 was prepared in the same manner as in Examples 11 to 13 except that the base oil was changed to base oil 11.
＜評価＞
　調製された各潤滑油組成物について、上述の方法により酸価を測定し、長寿命性を評価した。酸価の測定結果を表２、３に示した。
　同じ経過時間で対比した場合、酸価の値が低いほど、酸化劣化を生じにくく、酸化安定性が高いことを意味する。
　酸価が２．０ｍｇＫＯＨ／ｇを超えるまでの経過時間が長いほど、酸化安定性が高く、長寿命であることを意味する。 <Evaluation>
For each of the prepared lubricating oil compositions, the acid value was measured by the method described above, and the long life was evaluated. The measurement results of the acid value are shown in Tables 2 and 3.
When compared at the same elapsed time, the lower the acid value, the less oxidative degradation is meant, and the higher the oxidative stability.
The longer the time elapsed until the acid value exceeds 2.0 mg KOH / g, the higher the oxidation stability and the longer the life.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２の結果から、芳香族アミン系酸化防止剤が添加されている場合、本発明を適用した実施例１～３の潤滑油組成物は、経過時間６０００ｈまで、酸価２．０ｍｇＫＯＨ／ｇ未満が保たれていた。同様に、本発明を適用した実施例４の潤滑油組成物は、経過時間７０００ｈ以上、酸価２．０ｍｇＫＯＨ／ｇ未満が保たれ続けていた。
　本発明の範囲内の基油を含有する実施例５～９の潤滑油組成物について、経過時間２０００ｈまで、酸価２．０ｍｇＫＯＨ／ｇ未満が保たれていた。
　本発明の範囲内の基油を含有する実施例１０の潤滑油組成物については、経過時間３０００ｈまで、酸価２．０ｍｇＫＯＨ／ｇ未満が保たれていた。
　一方、本発明の範囲外の基油を含有する比較例１の潤滑油組成物については、酸価２．０ｍｇＫＯＨ／ｇ未満が保たれていた経過時間は、１０００ｈまでであった。 From the results in Table 2, when an aromatic amine antioxidant is added, the lubricating oil compositions of Examples 1 to 3 to which the present invention is applied have an acid value of less than 2.0 mg KOH / g for an elapsed time of 6000 h. Was kept. Similarly, the lubricating oil composition of Example 4 to which the present invention was applied continued to be maintained for an elapsed time of 7000 hours or more and an acid value of less than 2.0 mg KOH / g.
For the lubricating oil compositions of Examples 5-9 containing a base oil within the scope of the present invention, an acid value of less than 2.0 mg KOH / g was maintained for an elapsed time of 2000 h.
For the lubricating oil composition of Example 10 containing a base oil within the scope of the present invention, an acid value of less than 2.0 mg KOH / g was maintained for an elapsed time of 3000 h.
On the other hand, for the lubricating oil composition of Comparative Example 1 containing a base oil outside the scope of the present invention, the elapsed time during which the acid value of less than 2.0 mg KOH / g was maintained was up to 1000 h.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表３の結果から、フェノール系酸化防止剤を用いた場合、本発明を適用した実施例１１、１２の潤滑油組成物は、経過時間２０００ｈまで、酸価２．０ｍｇＫＯＨ／ｇ未満が保たれていた。
　また、本発明の範囲内の基油を含有する実施例１３の潤滑油組成物については、経過時間７５０ｈまで、酸価２．０ｍｇＫＯＨ／ｇ未満が保たれていた。
　一方、本発明の範囲外の基油を含有する比較例２の潤滑油組成物については、酸価２．０ｍｇＫＯＨ／ｇ未満が保たれていた経過時間は、５００ｈまでであった。 From the results in Table 3, when a phenolic antioxidant is used, the lubricating oil compositions of Examples 11 and 12 to which the present invention is applied maintain an acid value of less than 2.0 mg KOH / g for an elapsed time of 2000 h. The
In addition, for the lubricating oil composition of Example 13 containing a base oil within the scope of the present invention, an acid value of less than 2.0 mg KOH / g was maintained until an elapsed time of 750 h.
On the other hand, for the lubricating oil composition of Comparative Example 2 containing a base oil outside the scope of the present invention, the elapsed time during which the acid value of less than 2.0 mg KOH / g was maintained was up to 500 h.
　すなわち、本発明を適用した潤滑油組成物は、酸化安定性が高められて、より長寿命化が図られたものであることが確認された。 That is, it was confirmed that the lubricating oil composition to which the present invention is applied has a higher oxidation stability and a longer life.

Claims (23)

  1. 　基油と酸化防止剤とを含有する潤滑油組成物であって、
    　前記基油は、波長２７４ｎｍにおける吸光度が０．０２以上３．０以下である、潤滑油組成物。     A lubricating oil composition comprising a base oil and an antioxidant,
    The lubricating oil composition, wherein the base oil has an absorbance of 0.02 or more and 3.0 or less at a wavelength of 274 nm.
  2. 　前記基油は、波長２７４ｎｍにおける吸光度が０．２以上２．８以下である、請求項１に記載の潤滑油組成物。 The lubricating oil composition according to claim 1, wherein the base oil has an absorbance of 0.2 to 2.8 at a wavelength of 274 nm.
  3. 　前記基油は、波長２７４ｎｍにおける吸光度が０．３以上２．８以下である、請求項１に記載の潤滑油組成物。 The lubricating oil composition according to claim 1, wherein the base oil has an absorbance of 0.3 to 2.8 at a wavelength of 274 nm.
  4. 　前記基油は、波長２７４ｎｍにおける吸光度が０．０２以上１．５以下である、請求項１に記載の潤滑油組成物。 The lubricating oil composition according to claim 1, wherein the base oil has an absorbance of 0.02 or more and 1.5 or less at a wavelength of 274 nm.
  5. 　前記基油は、波長２７４ｎｍにおける吸光度が０．３以上０．９５以下である、請求項１に記載の潤滑油組成物。 The lubricating oil composition according to claim 1, wherein the base oil has an absorbance of 0.3 or more and 0.95 or less at a wavelength of 274 nm.
  6. 　前記基油は、波長２７４ｎｍにおける吸光度が０．８以上２．８以下である、請求項１に記載の潤滑油組成物。 The lubricating oil composition according to claim 1, wherein the base oil has an absorbance of 0.8 to 2.8 at a wavelength of 274 nm.
  7. 　前記基油は、さらに、硫黄分の含有割合が０．０５質量％以下である、請求項１～６のいずれか一項に記載に記載の潤滑油組成物。 The lubricating oil composition according to any one of claims 1 to 6, wherein the base oil further has a sulfur content of 0.05% by mass or less.
  8. 　前記基油は、さらに、芳香族炭化水素成分の含有割合（％ＣＡ）が１．０以下である、請求項１～７のいずれか一項に記載の潤滑油組成物。 The lubricating oil composition according to any one of claims 1 to 7, wherein the base oil further has a content ratio (% CA) of an aromatic hydrocarbon component.
  9. 　前記基油は、さらに、粘度指数が９５以上１３０以下である、請求項１～８のいずれか一項に記載の潤滑油組成物。 The lubricating oil composition according to any one of claims 1 to 8, wherein the base oil further has a viscosity index of 95 or more and 130 or less.
  10. 　前記基油は、さらに、４０℃動粘度が２０ｍｍ２／ｓｅｃ以上１００ｍｍ２／ｓｅｃ以下である、請求項１～９のいずれか一項に記載の潤滑油組成物。 The lubricating oil composition according to any one of claims 1 to 9, wherein the base oil further has a kinematic viscosity of 40 mm 2 / sec or more and 100 mm 2 / sec or less.
  11. 　前記酸化防止剤は、芳香族アミン系酸化防止剤である、請求項１～１０のいずれか一項に記載の潤滑油組成物。 The lubricating oil composition according to any one of claims 1 to 10, wherein the antioxidant is an aromatic amine antioxidant.
  12. 　さらに、さび止め剤を含有する、請求項１～１１のいずれか一項に記載の潤滑油組成物。 The lubricating oil composition according to any one of claims 1 to 11, further comprising a rust inhibitor.
  13. 　発電用タービン油である、請求項１～１２のいずれか一項に記載の潤滑油組成物。 A lubricating oil composition according to any one of the preceding claims, which is a turbine oil for power generation.
  14. 　波長２７４ｎｍにおける吸光度が０．０２以上３．０以下である、基油。 Base oil whose absorbance at a wavelength of 274 nm is 0.02 or more and 3.0 or less.
  15. 　波長２７４ｎｍにおける吸光度が０．２以上２．８以下である、基油。 Base oil whose absorbance at a wavelength of 274 nm is 0.2 or more and 2.8 or less.
  16. 　波長２７４ｎｍにおける吸光度が０．３以上２．８以下である、基油。 Base oil whose absorbance at a wavelength of 274 nm is 0.3 or more and 2.8 or less.
  17. 　波長２７４ｎｍにおける吸光度が０．０２以上１．５以下である、基油。 Base oil whose absorbance at a wavelength of 274 nm is 0.02 or more and 1.5 or less.
  18. 　波長２７４ｎｍにおける吸光度が０．３以上０．９５以下である、基油。 Base oil whose absorbance at a wavelength of 274 nm is 0.3 or more and 0.95 or less.
  19. 　波長２７４ｎｍにおける吸光度が０．８以上２．８以下である、基油。 Base oil whose absorbance at a wavelength of 274 nm is 0.8 or more and 2.8 or less.
  20. 　さらに、硫黄分の含有割合が０．０５質量％以下である、請求項１４～１９のいずれか一項に記載の基油。 The base oil according to any one of claims 14 to 19, which further has a sulfur content of 0.05% by mass or less.
  21. 　さらに、芳香族炭化水素成分の含有割合（％ＣＡ）が１．０以下である、請求項１４～２０のいずれか一項に記載の基油。 The base oil according to any one of claims 14 to 20, wherein the content ratio (% CA) of the aromatic hydrocarbon component is 1.0 or less.
  22. 　さらに、粘度指数が９５以上１３０以下である、請求項１４～２１のいずれか一項に記載の基油。 The base oil according to any one of claims 14 to 21, which further has a viscosity index of 95 or more and 130 or less.
  23. 　さらに、４０℃動粘度が２０ｍｍ２／ｓｅｃ以上１００ｍｍ２／ｓｅｃ以下である、請求項１４～２２のいずれか一項に記載の基油。 The base oil according to any one of claims 14 to 22, which further has a kinematic viscosity of 40 mm 2 / sec or more and 100 mm 2 / sec or less.
PCT/JP2018/048554 2018-01-10 2018-12-28 Lubricating oil composition and base oil WO2019138948A1 (en)

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