WO2013147302A1 - Lubricant base oil and method for producing same - Google Patents
Lubricant base oil and method for producing same Download PDFInfo
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- WO2013147302A1 WO2013147302A1 PCT/JP2013/059947 JP2013059947W WO2013147302A1 WO 2013147302 A1 WO2013147302 A1 WO 2013147302A1 JP 2013059947 W JP2013059947 W JP 2013059947W WO 2013147302 A1 WO2013147302 A1 WO 2013147302A1
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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
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/02—Petroleum fractions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/16—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural parallel stages only
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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
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
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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
- C10M171/02—Specified values of viscosity or viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1022—Fischer-Tropsch products
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/302—Viscosity
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
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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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
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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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/16—Paraffin waxes; Petrolatum, e.g. slack wax
- C10M2205/163—Paraffin waxes; Petrolatum, e.g. slack wax used as base material
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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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/17—Fisher Tropsch reaction products
- C10M2205/173—Fisher Tropsch reaction products used as base material
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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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/065—Saturated Compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/071—Branched chain compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/36—Seal compatibility, e.g. with rubber
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2070/00—Specific manufacturing methods for lubricant compositions
Definitions
- the present invention relates to a lubricating base oil and a method for producing the same.
- a pour point is generally used as an evaluation index for low temperature viscosity characteristics of lubricating base oils and lubricating oils.
- a technique for evaluating low-temperature viscosity characteristics based on a lubricating base oil such as the content of normal paraffin or isoparaffin is also known.
- the low temperature fluidity of the lubricating base oil is better, but according to the study of the present inventor, the conventional lubricating base oil having the low temperature fluidity is a seal.
- the problem with sex More specifically, when the viscosity of the lubricating base oil is low, or when the sealing material is further contracted, the gap increases and oil leakage is likely to occur when pressure is applied to that portion.
- the present invention has been made in view of such circumstances, and an object of the present invention is to provide a lubricating base oil that can achieve both a low-temperature viscosity characteristic and a sealing property at a high level and a method for producing the same. .
- the present inventor firstly, as an approach different from the improvement of the low temperature viscosity characteristics of the lubricating base oil using the pour point as an index, the low temperature of the lubricating base oil using the SBV viscosity as an index. Attempts were made to achieve both viscosity characteristics and sealability. As a result, it was found that when the kinematic viscosity at 100 ° C., the viscosity index at -20 ° C. and the SBV viscosity at ⁇ 20 ° C. of the lubricating base oil satisfy specific requirements, the sealing property can be improved while sufficiently maintaining the low temperature viscosity characteristics, The present invention has been completed.
- the present invention provides a lubricating base oil shown in the following [1] to [12] and a manufacturing method of the lubricating base oil shown in the following [13] to [18].
- a lubricating base oil that is a hydrocarbon oil that satisfies any of the following conditions.
- the ratio of CH 2 carbon constituting the main chain in the hydrocarbon oil satisfying the condition (i) and occupying the total carbon constituting the lubricating base oil in 13 C-NMR analysis is The lubricating base oil according to any one of [1] to [3], which is 15% or more.
- the proportion of CH 2 carbon constituting the main chain in the hydrocarbon oil satisfying the condition (ii) and occupying in the total carbon constituting the lubricating base oil in 13 C-NMR analysis is The lubricating base oil according to any one of [1], [6], and [7], which is 20% or more.
- the hydrocarbon oil satisfies the condition (ii) and has a cycloparaffin content of 60% or less in FD-MS analysis, [1], [6], [7], [8 ]
- the hydrocarbon oil satisfies the condition (iii), and in 13 C-NMR analysis, the proportion of CH 2 carbon constituting the main chain in the total carbon constituting the lubricating oil base oil is The lubricating base oil according to any one of [1], [10], and [11], which is 15% or more.
- the hydrocarbon oil satisfies the condition (iii) and has a cycloparaffin content of 30% or less in the FD-MS analysis.
- [1], [10], [11], [12 ] The lubricating base oil as described in any one of the above.
- By fractional distillation of the refined oil the following (i), (ii) or (iii): (I) a hydrocarbon oil having a kinematic viscosity at 100 ° C.
- a method for producing a lubricating base oil comprising: [15] The lubricating base oil according to [14], wherein the lubricating base oil obtained in the third step satisfies the condition (i) and has a freezing point of ⁇ 20 to ⁇ 5 ° C. Production method.
- the third step includes at least one crystalline solid acidic substance selected from the group consisting of ZSM-22 type zeolite, ZSM-23 type zeolite, SSZ32 and ZSM-48 type zeolite, and an active metal.
- a method for producing a base oil. Any one of [14] to [18], wherein the hydrocarbon oil is obtained using GTL wax obtained from Fischer-Tropsch synthesis or slack wax obtained by solvent dewaxing as a raw material.
- the kinematic viscosity and the viscosity index in the present invention mean the kinematic viscosity and the viscosity index measured according to JIS K 2283-1993, respectively.
- the SBV viscosity referred to in the present invention is a method in which the viscosity is continuously measured by rotating the rotor at 0.3 rpm while cooling at a cooling rate of 1 ° C./hour according to the test method defined by ASTM D5133. The value to be measured.
- the freezing point as used in the field of this invention means the value measured by the following procedures. That is, a sample taken in a test tube is preheated to 46 ° C. and then cooled at 2.5 ° C./min. The cooling rate is 1 ° C. from a temperature 10 ° C. higher than the expected freezing point (measured once in advance). Change to / min and start measurement. By this method, it is possible to obtain a reproducible freezing point as compared with JIS. This freezing point is distinct from the pour point measured according to JIS K 2269-1987 (JIS method pour point).
- the pour point determined by JIS is suitable for measuring liquids having greatly different crystallization temperatures, such as petroleum-based lubricating base oils, which are multicomponent mixtures. .
- a single component of only paraffin as in the present invention does not flow by the JIS measurement method for evaluating the fluidity when tilted, but it is confirmed that it flows when an external force is applied. It does not show sex.
- This factor also has a compositional aspect, but the temperature decrease rate of 2.5 ° C./min also has an influence, and it is considered that the determination is made in a situation where crystallization does not proceed completely. Therefore, it is necessary to promote the fluidity of the base oil molecules and to obtain a freezing point closer to the true value by slowing the rate of temperature decrease.
- the ratio of CH 2 carbon constituting the main chain to the total carbon constituting the lubricating base oil can be determined, for example, by performing 13 C-NMR analysis under the following analysis conditions. That is, in the present invention, at the time of 13 C-NMR measurement, a sample obtained by diluting 0.5 g of a sample with 3 g of deuterated chloroform was used, the measurement temperature was room temperature, and the resonance frequency was 100 MHz. Moreover, the measuring method used the coupling method with a gate.
- the ratio of CH 2 to the total amount of constituent carbon of the lubricating base oil of the present invention is the ratio of the total integrated intensity due to the CH 2 main chain to the total integrated intensity of all carbon, as measured by 13 C-NMR. However, other methods may be used as long as an equivalent result is obtained.
- the ratio of the cycloparaffin content can be determined, for example, by performing FD-MS analysis under the following analysis conditions.
- the FD method is an ionization method in which a sample is applied on an emitter, the applied sample is heated by passing an electric current through the emitter, and the tunnel effect in a high electric field near the emitter surface and the whisker tip is used.
- JEOL JMS-AX505H was used, and measurement was performed under the conditions of an acceleration voltage (cathode voltage) of 3.0 kV and an emitter current of 2 mA / min.
- the type of compound in mass spectrometry is determined by the specific ions that are formed, and is usually classified by the z number.
- This z number is represented by the general formula C n H 2n + z for all hydrocarbon species. Since this saturated phase is analyzed separately from the aromatic phase, it is possible to measure the content of different cycloparaffins having the same stoichiometry.
- the cycloparaffin includes both one-ring cycloparaffin and two or more cycloparaffins.
- a lubricating base oil that can achieve both low temperature viscosity characteristics and sealing properties at a high level and a method for producing the same.
- Lubricating base oil that is a hydrocarbon oil that satisfies the condition (i)]
- the lubricating base oil according to the first embodiment of the present invention is carbonized with a kinematic viscosity at 100 ° C. of 3.0 to 5.0 mm 2 / s and an SBV viscosity at ⁇ 20 ° C. of 3,000 to 60,000 mPa ⁇ s. Hydrogen oil.
- the pour point used as an index of the low temperature viscosity characteristic of the lubricating base oil is to evaluate the ease of flow, in other words, the bulk viscosity.
- the SBV viscosity in the present invention is not a bulk viscosity but an evaluation of the ease of movement of the base oil at the molecular level. For example, at a temperature lower than the pour point, the lubricant base oil does not flow, but can move at the molecular level due to a shift between molecules constituting the base oil, etc., and can give an SBV viscosity.
- the lubricating base oil according to the present embodiment is based on the above-mentioned knowledge of the present inventor, and has a kinematic viscosity at 100 ° C. of 3.0 to 5.0 mm 2 / s and a lubricating oil base having a viscosity index of 145 or more.
- the oil by setting the SBV viscosity of the lubricating base oil at ⁇ 20 ° C. to 3,000 to 60,000 mPa ⁇ s, it is possible to improve the sealing performance while maintaining the low-temperature viscosity characteristics sufficiently. It has a great effect.
- the kinematic viscosity at 100 ° C. of the lubricating base oil according to this embodiment is 3.0 to 5.0 mm 2 / s, preferably 3.0 to 4.5 mm 2 / s, more preferably 3.2 to
- the thickness is 4.3 mm 2 / s, more preferably 3.4 to 4.1 mm 2 / s.
- the viscosity index of the lubricating base oil according to the present embodiment is 145 or more, preferably 147 or more, more preferably 148 to 160.
- the viscosity index is less than the above lower limit, energy saving performance is lowered, and when it exceeds the upper limit, the fluidity at normal temperature is lowered and it tends to be unusable as a lubricating base oil.
- the SBV viscosity at ⁇ 20 ° C. of the lubricating base oil according to this embodiment is 3,000 to 60,000 mPa ⁇ s, preferably 3,000 to 30,000 mPa ⁇ s, more preferably 3,000. ⁇ 15,000 mPa ⁇ s.
- the SBV viscosity at ⁇ 30 ° C. of the lubricating base oil according to this embodiment is preferably 50,000 to 500,000 mPa ⁇ s, more preferably 50,000 to 400,000 mPa ⁇ s, and still more preferably. 50,000 to 300,000 mPa ⁇ s.
- the kinematic viscosity at 40 ° C. of the lubricating base oil according to this embodiment is preferably 10 to 20 mm 2 / s, more preferably 12 to 16 mm 2 / s.
- the freezing point of the lubricating base oil according to the present embodiment is preferably ⁇ 20 to ⁇ 5 ° C., more preferably ⁇ 18 to ⁇ 8 ° C., and further preferably ⁇ 15 to ⁇ 10 ° C. If the freezing point is less than the above lower limit value, the energy saving property tends to be lowered, and if it exceeds the above upper limit value, the fluidity at normal temperature is lowered and the lubricating base oil tends not to be used.
- the proportion of CH 2 carbon constituting the main chain in the total carbon constituting the lubricating base oil is 15% or more. It is preferably 16% or more.
- the ratio is not less than the above lower limit, the traction coefficient of the lubricating base oil can be lowered (that is, low friction), which is preferable in terms of energy saving.
- the cycloparaffin content is preferably 50% or less, and more preferably 40% or less.
- the wear resistance of the lubricating base oil can be further improved.
- the urea adduct value of the lubricating base oil according to the present embodiment is preferably 4% by mass or less, more preferably 3.5%, from the viewpoint of improving the low temperature viscosity characteristics without impairing the viscosity-temperature characteristics at high temperatures. It is not more than mass%, more preferably not more than 3 mass%, particularly preferably not more than 2.5 mass%. Further, the urea adduct value of the lubricating base oil may be 0% by mass. However, it is possible to obtain a lubricating base oil having sufficient low-temperature viscosity characteristics and a higher viscosity index, and more preferably 0.1% by mass or more in terms of excellent economic efficiency by relaxing dewaxing conditions. Preferably it is 0.5 mass% or more, Most preferably, it is 0.8 mass% or more.
- the content of the saturated component in the lubricating base oil according to the present embodiment is preferably 90% by mass or more, more preferably 93% by mass or more, and still more preferably 95% by mass or more, based on the total amount of the lubricating oil base oil. Especially preferably, it is 99 mass% or more.
- the content of the saturated component satisfies the above conditions, viscosity-temperature characteristics and thermal / oxidation stability can be achieved, and when an additive is blended in the lubricating base oil, the addition The function of the additive can be expressed at a higher level while the agent is sufficiently and stably dissolved and retained in the lubricant base oil.
- content of the saturated part as used in the field of this invention means the value (unit: mass%) measured based on ASTM D 2007-93.
- the aromatic content in the lubricating base oil according to the present embodiment is preferably 5% by mass or less, more preferably 0.05 to 3% by mass, and still more preferably 0.1% based on the total amount of the lubricating base oil. To 1% by mass, particularly preferably 0.1 to 0.5% by mass. If the aromatic content exceeds the above upper limit, viscosity-temperature characteristics, thermal / oxidation stability, friction characteristics, volatilization prevention characteristics and low-temperature viscosity characteristics tend to be reduced. When an additive is blended with the additive, the effectiveness of the additive tends to decrease. Further, the lubricating base oil according to the present embodiment may not contain an aromatic component, but the solubility of the additive can be improved by setting the aromatic content to 0.05% by mass or more. It can be further increased.
- the aromatic content in the present invention means a value measured according to ASTM D 2007-93.
- the aromatic component usually includes alkylbenzene, alkylnaphthalene, anthracene, phenanthrene, and alkylated products thereof, as well as compounds in which four or more benzene rings are condensed, pyridines, quinolines, phenols, naphthols and the like. Aromatic compounds having atoms are included.
- the sulfur content in the lubricating base oil according to the present embodiment depends on the sulfur content of the raw material.
- a raw material that does not substantially contain sulfur such as a synthetic wax component obtained by a Fischer-Tropsch reaction or the like
- a lubricating base oil that does not substantially contain sulfur can be obtained.
- the sulfur content in the obtained lubricating base oil is usually 100 mass ppm. That's it.
- the sulfur content is preferably 10 mass ppm or less, from the viewpoint of further improving thermal and oxidation stability and reducing sulfur, and preferably 5 mass ppm or less. Is more preferably 3 ppm by mass or less, and particularly preferably 1 ppm by mass or less.
- the sulfur content in the obtained lubricating base oil is preferably 50 ppm by mass or less, and preferably 10 ppm by mass or less. More preferred.
- the sulfur content means a sulfur content measured according to JIS K 2541-1996.
- the pour point of the lubricating base oil according to the present embodiment is preferably ⁇ 5 ° C. or lower, more preferably ⁇ 10 ° C. or lower, and further preferably ⁇ 12.5 ° C. or lower.
- the pour point of the lubricating base oil according to this embodiment is preferably ⁇ 20 ° C. or higher, more preferably ⁇ 17.5 ° C. or higher, and still more preferably ⁇ 15 ° C. or higher.
- the pour point as used in the present invention means a pour point measured according to JIS K 2269-1987.
- the CCS viscosity at ⁇ 30 ° C. of the lubricating base oil according to the present embodiment is preferably 1500 mPa ⁇ s or less, more preferably 1200 mPa ⁇ s or less.
- the CCS viscosity of the lubricating base oil at ⁇ 35 ° C. is preferably 2500 mPa ⁇ s or less, more preferably 2000 mPa ⁇ s or less.
- the CCS viscosity at ⁇ 30 ° C. or ⁇ 35 ° C. exceeds the upper limit, the low temperature fluidity of the whole lubricating oil using the lubricating base oil tends to be lowered.
- the CCS viscosity at ⁇ 30 ° C. or ⁇ 35 ° C. means a viscosity measured in accordance with JIS K 2010-1993, respectively.
- ⁇ 15 of the lubricating base oil is preferably 0.815 or less, more preferably 0.810 or less.
- the density at 15 ° C. in the present invention means a density measured at 15 ° C. in accordance with JIS K 2249-1995.
- the NOACK evaporation amount of the lubricating base oil according to the present embodiment is preferably 8% by mass or more, more preferably 9% by mass or more, still more preferably 10% or more, and preferably 15% by mass or less. Preferably it is 14 mass% or less, More preferably, it is 13 mass% or less.
- the NOACK evaporation amount is the lower limit value, it tends to be difficult to improve the low temperature viscosity characteristics.
- the NOACK evaporation amount exceeds the upper limit value, when the lubricating base oil is used as a lubricating oil for an internal combustion engine, the amount of evaporation loss of the lubricating oil increases, and accordingly, catalyst poisoning is promoted. It is not preferable.
- the NOACK evaporation amount in the present invention means an evaporation loss amount measured according to ASTM D 5800-95.
- Lubricating base oil that is a hydrocarbon oil that satisfies the condition (ii)]
- the lubricating base oil according to the second embodiment of the present invention is a hydrocarbon oil having a kinematic viscosity at 100 ° C. of 5 to 9 mm 2 / s and an SBV viscosity at ⁇ 20 ° C. of 3,000 to 30,000 mPa ⁇ s. .
- the pour point used as an index of the low temperature viscosity characteristic of the lubricating base oil is to evaluate the ease of flow, in other words, the bulk viscosity.
- the SBV viscosity in the present invention is not a bulk viscosity but an evaluation of the ease of movement of the base oil at the molecular level. For example, at a temperature lower than the pour point, the lubricant base oil does not flow, but can move at the molecular level due to a shift between molecules constituting the base oil, etc., and can give an SBV viscosity.
- the lubricating base oil according to the present embodiment has been made based on the above-mentioned knowledge of the present inventor.
- the lubricating base oil having a kinematic viscosity of 5 to 9 mm 2 / s at 100 ° C.
- the lubricating base oil By setting the SBV viscosity at ⁇ 20 ° C. to 3,000 to 30,000 mPa ⁇ s, there is an unexpected remarkable effect that the sealability can be improved while sufficiently maintaining the low temperature viscosity characteristics.
- the kinematic viscosity at 100 ° C. of the lubricating base oil according to this embodiment is 5 to 9 mm 2 / s, preferably 5.5 to 8.5 mm 2 / s, more preferably 6 to 8 mm 2 / s. .
- the SBV viscosity at ⁇ 20 ° C. of the lubricating base oil according to this embodiment is 3,000 to 30,000 mPa ⁇ s, preferably 3,000 to 25,000 mPa ⁇ s, more preferably 3,000. ⁇ 20,000 mPa ⁇ s.
- the sealing property is insufficient
- the SBV viscosity exceeds the above upper limit value, the low temperature viscosity characteristics become insufficient.
- the SBV viscosity at ⁇ 25 ° C. of the lubricating base oil according to this embodiment is preferably 5,000 to 500,000 mPa ⁇ s, more preferably 5,000 to 400,000 mPa ⁇ s, and still more preferably. 5,000 to 300,000 mPa ⁇ s.
- the sealing property becomes insufficient
- the low temperature viscosity characteristic becomes insufficient.
- the kinematic viscosity at 40 ° C. of the lubricating base oil according to this embodiment is preferably 25 to 40 mm 2 / s, more preferably 28 to 35 mm 2 / s.
- the viscosity index of the lubricating base oil according to the present embodiment is 155 or more, preferably 157 or more, more preferably 158 to 165.
- the viscosity index is less than the lower limit, energy saving performance is lowered.
- the viscosity index is higher than the upper limit, the fluidity at normal temperature is lowered and the lubricating base oil tends not to be used.
- the freezing point of the lubricating base oil according to this embodiment is preferably ⁇ 15 to ⁇ 5 ° C., more preferably ⁇ 14 to ⁇ 7 ° C., and further preferably ⁇ 13 to ⁇ 8 ° C. If the freezing point is less than the above lower limit value, the energy saving property tends to be lowered, and if it exceeds the above upper limit value, the fluidity at normal temperature is lowered and the lubricating base oil tends not to be used.
- the proportion of CH 2 carbon constituting the main chain in the total carbon constituting the lubricating base oil is 20% or more. It is preferably 18% or more.
- the ratio is not less than the above lower limit, the traction coefficient of the lubricating base oil can be lowered (that is, low friction), which is preferable in terms of energy saving.
- the cycloparaffin content is preferably 60% or less, and more preferably 65% or less.
- the wear resistance of the lubricating base oil can be further improved.
- the urea adduct value of the lubricating base oil according to the present embodiment is preferably 4% by mass or less, more preferably 3.5%, from the viewpoint of improving the low temperature viscosity characteristics without impairing the viscosity-temperature characteristics at high temperatures. It is not more than mass%, more preferably not more than 3 mass%, particularly preferably not more than 2.5 mass%. Further, the urea adduct value of the lubricating base oil may be 0% by mass. However, it is possible to obtain a lubricating base oil having sufficient low-temperature viscosity characteristics and a higher viscosity index, and more preferably 0.1% by mass or more in terms of excellent economic efficiency by relaxing dewaxing conditions. Preferably it is 0.5 mass% or more, Most preferably, it is 0.8 mass% or more.
- the content of the saturated component in the lubricating base oil according to the present embodiment is preferably 90% by mass or more, more preferably 93% by mass or more, and still more preferably 95% by mass or more, based on the total amount of the lubricating oil base oil. Especially preferably, it is 99 mass% or more.
- the content of the saturated component satisfies the above conditions, viscosity-temperature characteristics and thermal / oxidation stability can be achieved, and when an additive is blended in the lubricating base oil, the addition The function of the additive can be expressed at a higher level while the agent is sufficiently and stably dissolved and retained in the lubricant base oil. Furthermore, it is possible to improve the friction characteristics of the lubricating base oil itself, and as a result, it is possible to achieve an improvement in friction reduction effect and an improvement in energy saving.
- the aromatic content in the lubricating base oil according to the present embodiment is preferably 5% by mass or less, more preferably 0.05 to 3% by mass, and still more preferably 0.1% based on the total amount of the lubricating base oil. To 1% by mass, particularly preferably 0.1 to 0.5% by mass. If the aromatic content exceeds the above upper limit, viscosity-temperature characteristics, thermal / oxidation stability, friction characteristics, volatilization prevention characteristics and low-temperature viscosity characteristics tend to be reduced. When an additive is blended with the additive, the effectiveness of the additive tends to decrease. Further, the lubricating base oil according to the present embodiment may not contain an aromatic component, but the solubility of the additive can be improved by setting the aromatic content to 0.05% by mass or more. It can be further increased.
- the sulfur content in the lubricating base oil according to the present embodiment depends on the sulfur content of the raw material.
- a raw material that does not substantially contain sulfur such as a synthetic wax component obtained by a Fischer-Tropsch reaction or the like
- a lubricating base oil that does not substantially contain sulfur can be obtained.
- the sulfur content in the obtained lubricating base oil is usually 100 mass ppm. That's it.
- the sulfur content is preferably 10 mass ppm or less, from the viewpoint of further improving thermal and oxidation stability and reducing sulfur, and preferably 5 mass ppm or less. Is more preferably 3 ppm by mass or less, and particularly preferably 1 ppm by mass or less.
- the sulfur content in the obtained lubricating base oil is preferably 50 ppm by mass or less, and preferably 10 ppm by mass or less. More preferred.
- the pour point of the lubricating base oil according to the present embodiment is preferably ⁇ 5 ° C. or lower, more preferably ⁇ 10 ° C. or lower, and further preferably ⁇ 12.5 ° C. or lower.
- the pour point of the lubricating base oil according to this embodiment is preferably ⁇ 20 ° C. or higher, more preferably ⁇ 17.5 ° C. or higher, and still more preferably ⁇ 15 ° C. or higher.
- the pour point is less than ⁇ 20 ° C., it becomes difficult to make the SBV viscosity at ⁇ 20 ° C. within the range of 3,000 to 30,000 mPa ⁇ s, and the sealing property tends to be insufficient.
- the CCS viscosity at ⁇ 30 ° C. of the lubricating base oil according to the present embodiment is preferably 950 mPa ⁇ s or less, more preferably 900 mPa ⁇ s or less.
- the CCS viscosity of the lubricating base oil at ⁇ 35 ° C. is preferably 1,600 mPa ⁇ s or less, more preferably 1,500 mPa ⁇ s or less.
- ⁇ 15 of the lubricating base oil is preferably 0.830 or less, more preferably 0.825 or less.
- Lubricating base oil that is a hydrocarbon oil that satisfies the condition (iii)]
- the lubricating base oil according to the third embodiment of the present invention has a kinematic viscosity at 100 ° C. of 2.0 to 3.0 mm 2 / s, a viscosity index of 130 or more, and an SBV viscosity at ⁇ 30 ° C. of 1,000 to 30. , 000 mPa ⁇ s hydrocarbon oil.
- the pour point used as an index of the low temperature viscosity characteristic of the lubricating base oil is to evaluate the ease of flow, in other words, the bulk viscosity.
- the SBV viscosity in the present invention is not a bulk viscosity but an evaluation of the ease of movement of the base oil at the molecular level. For example, at a temperature lower than the pour point, the lubricant base oil does not flow, but can move at the molecular level due to a shift between molecules constituting the base oil, etc., and can give an SBV viscosity.
- the lubricating base oil according to the present embodiment has been made based on the above-mentioned knowledge of the present inventor, and has a kinematic viscosity at 100 ° C. of 2.0 to 3.0 mm 2 / s and a lubricating oil base having a viscosity index of 130 or more.
- the oil by setting the SBV viscosity at ⁇ 30 ° C. of the lubricating base oil to 1,000 to 30,000 mPa ⁇ s, it is possible to improve the sealing property while maintaining the low-temperature viscosity characteristics sufficiently. It has a great effect.
- the kinematic viscosity at 100 ° C. of the lubricating base oil according to this embodiment is 2.0 to 3.0 mm 2 / s, preferably 2.1 to 2.9 mm 2 / s, more preferably 2.2 to 2.8 mm 2 / s.
- the viscosity index of the lubricating base oil according to the present embodiment is 130 or more, preferably 131 or more, more preferably 132 to 140.
- energy saving performance is lowered when the viscosity index is less than the lower limit, and when it exceeds the fluidity, the fluidity at normal temperature is lowered and the lubricating oil base oil cannot be used.
- the SBV viscosity at ⁇ 30 ° C. of the lubricating base oil according to the present embodiment is 1,000 to 30,000 mPa ⁇ s, preferably 1,000 to 20,000 mPa ⁇ s, more preferably 1,000. ⁇ 15,000 mPa ⁇ s.
- the sealing property is insufficient
- the SBV viscosity exceeds the upper limit value the low temperature viscosity characteristic becomes insufficient.
- the SBV viscosity at ⁇ 35 ° C. of the lubricating base oil according to this embodiment is preferably 3,000 to 500,000 mPa ⁇ s, more preferably 3,000 to 400,000 mPa ⁇ s, and still more preferably. 3,000 to 300,000 mPa ⁇ s.
- the SBV viscosity at ⁇ 40 ° C. of the lubricating base oil according to the present embodiment is preferably 5,000 to 750,000 mPa ⁇ s, more preferably 5,000 to 500,000 mPa ⁇ s, and still more preferably. 5,000 to 400,000 mPa ⁇ s.
- the sealing property at ⁇ 40 ° C. is less than the above lower limit, the sealing property is insufficient, and when it exceeds the upper limit, the low-temperature viscosity characteristics are insufficient.
- the kinematic viscosity at 40 ° C. of the lubricating base oil according to the present embodiment is preferably 7 to 12 mm 2 / s, more preferably 8 to 10 mm 2 / s.
- the freezing point of the lubricating base oil according to the present embodiment is preferably ⁇ 30 to ⁇ 10 ° C., more preferably ⁇ 29 to ⁇ 15 ° C., and further preferably ⁇ 28 to ⁇ 20 ° C. If the freezing point is less than the lower limit, the energy saving property tends to be lowered, and if the freezing point is exceeded, the fluidity at normal temperature is lowered and the lubricating base oil tends not to be used.
- the proportion of CH 2 carbon constituting the main chain in the total carbon constituting the lubricating base oil is 15% or more. It is preferably 15% or more.
- the ratio is not less than the above lower limit, the traction coefficient of the lubricating base oil can be lowered (that is, low friction), which is preferable in terms of energy saving.
- the cycloparaffin content is preferably 30% or less, and more preferably 25% or less.
- the wear resistance of the lubricating base oil can be further improved.
- the urea adduct value of the lubricating base oil according to the present embodiment is preferably 4% by mass or less, more preferably 3.5%, from the viewpoint of improving the low temperature viscosity characteristics without impairing the viscosity-temperature characteristics at high temperatures. It is not more than mass%, more preferably not more than 3 mass%, particularly preferably not more than 2.5 mass%. Further, the urea adduct value of the lubricating base oil may be 0% by mass. However, it is possible to obtain a lubricating base oil having sufficient low-temperature viscosity characteristics and a higher viscosity index, and more preferably 0.1% by mass or more in terms of excellent economic efficiency by relaxing dewaxing conditions. Preferably it is 0.5 mass% or more, Most preferably, it is 0.8 mass% or more.
- the content of the saturated component in the lubricating base oil according to the present embodiment is preferably 90% by mass or more, more preferably 93% by mass or more, and still more preferably 95% by mass or more, based on the total amount of the lubricating oil base oil. Especially preferably, it is 99 mass% or more.
- the content of the saturated component satisfies the above conditions, viscosity-temperature characteristics and thermal / oxidation stability can be achieved, and when an additive is blended in the lubricating base oil, the addition The function of the additive can be expressed at a higher level while the agent is sufficiently and stably dissolved and retained in the lubricant base oil. Furthermore, it is possible to improve the friction characteristics of the lubricating base oil itself, and as a result, it is possible to achieve an improvement in friction reduction effect and an improvement in energy saving.
- the aromatic content in the lubricating base oil according to the present embodiment is preferably 5% by mass or less, more preferably 0.05 to 3% by mass, and still more preferably 0.1% based on the total amount of the lubricating base oil. To 1% by mass, particularly preferably 0.1 to 0.5% by mass. If the aromatic content exceeds the above upper limit, viscosity-temperature characteristics, thermal / oxidation stability, friction characteristics, volatilization prevention characteristics and low-temperature viscosity characteristics tend to be reduced. When an additive is blended with the additive, the effectiveness of the additive tends to decrease. Further, the lubricating base oil according to the present embodiment may not contain an aromatic component, but the solubility of the additive can be improved by setting the aromatic content to 0.05% by mass or more. It can be further increased.
- the sulfur content in the lubricating base oil according to the present embodiment depends on the sulfur content of the raw material.
- a raw material that does not substantially contain sulfur such as a synthetic wax component obtained by a Fischer-Tropsch reaction or the like
- a lubricating base oil that does not substantially contain sulfur can be obtained.
- the sulfur content in the obtained lubricating base oil is usually 100 mass ppm. That's it.
- the sulfur content is preferably 10 mass ppm or less, from the viewpoint of further improving thermal and oxidation stability and reducing sulfur, and preferably 5 mass ppm or less. Is more preferably 3 ppm by mass or less, and particularly preferably 1 ppm by mass or less.
- the sulfur content in the obtained lubricating base oil is preferably 50 ppm by mass or less, and preferably 10 ppm by mass or less. More preferred.
- the pour point of the lubricating base oil according to this embodiment is preferably ⁇ 5 ° C. or lower, more preferably ⁇ 12.5 ° C. or lower, and further preferably ⁇ 15 ° C. or lower.
- the pour point of the lubricating base oil according to this embodiment is preferably ⁇ 27.5 ° C. or higher, more preferably ⁇ 25 ° C. or higher.
- the pour point is less than ⁇ 27.5 ° C., it becomes difficult to make the SBV viscosity at ⁇ 20 ° C. within the range of 3,000 to 60,000 mPa ⁇ s, and the sealing property tends to be insufficient.
- the CCS viscosity at ⁇ 30 ° C. of the lubricating base oil according to the present embodiment is preferably 1,000 mPa ⁇ s or less, more preferably 750 mPa ⁇ s or less.
- the CCS viscosity of the lubricating base oil at ⁇ 35 ° C. is preferably 1,300 mPa ⁇ s or less, more preferably 1,000 mPa ⁇ s or less.
- ⁇ 15 of the lubricating base oil is preferably 0.806 or less, more preferably 0.8058 or less.
- the NOACK evaporation amount of the lubricating base oil according to the present embodiment is preferably 20% by mass or more, more preferably 25% by mass or more, still more preferably 30% or more, and preferably 50% by mass or less. Preferably it is 48 mass% or less, More preferably, it is 46 mass% or less.
- the NOACK evaporation amount is the lower limit value, it tends to be difficult to improve the low temperature viscosity characteristics. Further, if the NOACK evaporation amount exceeds the upper limit value, when the lubricating base oil is used as a lubricating oil for an internal combustion engine, the amount of evaporation loss of the lubricating oil increases, and accordingly, catalyst poisoning is promoted. It is not preferable.
- a fifth step of obtaining a lubricating base oil that is a hydrocarbon oil that satisfies any of the following conditions: Is provided.
- a base oil fraction and a heavy fraction are fractionated from a hydrocarbon oil as a raw material (first step), and hydrogenation of the heavy fraction is performed.
- the cracked oil obtained by cracking is returned to the first step (second step). That is, only the heavy fraction is subjected to hydroisomerization dewaxing (third step) through hydrocracking, and the base oil fraction is hydroisomerized and dewaxed without hydrocracking. Therefore, as a whole of the oil to be treated subjected to hydroisomerization dewaxing, isomerization is difficult to proceed as compared with the conventional method for producing highly refined mineral oil.
- the base oil fraction is a fraction for obtaining a lubricating base oil through a dewaxing step, a hydrofinishing step and a second distillation step, and the boiling range thereof can be appropriately changed depending on the target product.
- a suitable boiling range of the base oil fraction in this embodiment is exemplified by 340 to 520 ° C.
- the heavy fraction is a heavy fraction having a boiling point higher than that of the base oil fraction.
- the boiling point of the heavy fraction is preferably higher than 520 ° C.
- the hydrocarbon oil may contain a light fraction (light fraction) having a boiling point lower than that of the base oil fraction in addition to the base oil fraction and the heavy fraction.
- the boiling point of the light component is preferably less than 340 ° C.
- hydrocarbon oils examples include hydrotreated or hydrocracked diesel oil, heavy diesel oil, vacuum diesel oil, lubricating oil raffinate, lubricating oil raw material, bright stock, slack wax (crude wax), waxy oil, deoiled oil
- hydrocarbon oils include wax, paraffin wax, microcrystalline wax, petrolatum, synthetic oil, Fischer-Tropsch synthetic reaction oil (hereinafter referred to as “FT synthetic oil”), high pour point polyolefin, and linear ⁇ -olefin wax. These can be used individually by 1 type or in combination of 2 or more types.
- hydrocarbon oils include vacuum gas oil, vacuum gas oil hydrocracked oil, atmospheric residue, atmospheric residue hydrocracked oil, vacuum residue, vacuum residue hydrocracked oil, slack wax, dewaxed oil. And at least one selected from the group consisting of paraffin wax, microcritalin wax, petratum and Fischer-Tropsch synthetic wax. More preferably, it is at least one selected from the group consisting of synthetic waxes.
- the hydrocarbon oil is preferably FT (Fischer-Tropsch) synthetic oil.
- the FT synthetic oil is a hydrocarbon oil synthesized from carbon monoxide and hydrogen by an FT synthesis reaction, and does not contain nitrogen. Therefore, when the hydrocarbon oil is an FT synthetic oil, there is no possibility of sulfur poisoning in hydrocracking and isomerization dewaxing described later, and various catalysts can be used.
- hydrocarbon oil containing a hydrocarbon derived from a petroleum raw material
- hydrocarbon oils include vacuum gas oil hydrocracked oil, atmospheric residue hydrocracked oil, vacuum residue hydrocracked oil, slack wax, dewaxed oil, paraffin wax, microcrystalline wax, and petratum. Can be mentioned.
- the first distillation step is a step of fractionating the base oil fraction and the heavy fraction from the hydrocarbon oil.
- the conditions of the fractionation step can be appropriately changed depending on the composition of the hydrocarbon oil.
- the fractionation step includes atmospheric distillation for distilling the light component from the hydrocarbon oil, and base oil fraction and heavy oil from the bottom oil of atmospheric distillation.
- the distillation is preferably performed by distillation under reduced pressure to fractionate the fractions.
- the heavy fraction fractionated in the first distillation step is subjected to a hydrocracking step.
- the hydrocracked oil obtained in the hydrocracking process is returned to the first distillation process.
- the type of the reactor used in the hydrocracking step is not particularly limited, and a fixed bed flow reactor filled with a hydrocracking catalyst is preferably used.
- a single reactor may be used, or a plurality of reactors may be arranged in series or in parallel. Further, the catalyst bed in the reactor may be single or plural.
- hydrocracking catalyst a known hydrocracking catalyst is used.
- a catalyst in which a metal belonging to Groups 8 to 10 of the periodic table of elements having hydrogenation activity is supported on an inorganic carrier having solid acidity (hereinafter, “ Hydrocracking catalyst A ”)) is preferably used.
- the hydrocracking catalyst A is preferably used because there is no risk of catalyst poisoning due to sulfur.
- Suitable inorganic supports having solid acidity constituting the hydrocracking catalyst A include zeolites such as ultrastable Y type (USY) zeolite, Y type zeolite, mordenite and ⁇ zeolite, and silica alumina, silica zirconia, and alumina. Examples thereof include those composed of one or more inorganic compounds selected from amorphous composite metal oxides having heat resistance such as boria.
- the carrier is more preferably a composition comprising USY zeolite and one or more amorphous composite metal oxides selected from silica alumina, alumina boria and silica zirconia. USY zeolite, alumina More preferred is a composition comprising boria and / or silica alumina.
- USY zeolite is obtained by ultra-stabilizing Y-type zeolite by hydrothermal treatment and / or acid treatment, and in addition to a micropore structure called micropores having a pore size originally possessed by Y-type zeolite of 2 nm or less. New pores having a pore diameter in the range of 10 nm are formed.
- the average particle size of the USY zeolite is not particularly limited, but is preferably 1.0 ⁇ m or less, more preferably 0.5 ⁇ m or less.
- the silica / alumina molar ratio is preferably 10 to 200, more preferably 15 to 100, and still more preferably 20 to 60.
- the support of the hydrocracking catalyst A preferably contains 0.1 to 80% by mass of crystalline zeolite and 0.1 to 60% by mass of amorphous composite metal oxide having heat resistance.
- the carrier of the hydrocracking catalyst A can be produced by molding a carrier composition containing the inorganic compound having solid acidity and a binder and then firing the carrier composition.
- the blending ratio of the inorganic compound having solid acidity is preferably 1 to 70% by mass, more preferably 2 to 60% by mass based on the mass of the whole carrier.
- the carrier contains USY zeolite
- the blending ratio of USY zeolite is preferably 0.1 to 10% by mass, and preferably 0.5 to 5% by mass based on the mass of the entire carrier. More preferred.
- the mixing ratio of USY zeolite and alumina boria is preferably 0.03 to 1 in terms of mass ratio.
- the mixing ratio of USY zeolite and silica alumina is preferably 0.03 to 1 in terms of mass ratio.
- the binder is not particularly limited, but alumina, silica, titania and magnesia are preferable, and alumina is more preferable.
- the blending amount of the binder is preferably 20 to 98% by mass, more preferably 30 to 96% by mass based on the mass of the whole carrier.
- the temperature at which the carrier composition is calcined is preferably in the range of 400 to 550 ° C., more preferably in the range of 470 to 530 ° C., and further in the range of 490 to 530 ° C. preferable. By baking at such a temperature, sufficient solid acidity and mechanical strength can be imparted to the carrier.
- the metals in Groups 8 to 10 of the periodic table having hydrogenation activity supported on the carrier include cobalt, nickel, rhodium, palladium, iridium, and platinum. Among these, it is preferable to use the metal chosen from nickel, palladium, and platinum individually by 1 type or in combination of 2 or more types. These metals can be supported on the above-mentioned carrier by a conventional method such as impregnation or ion exchange.
- the amount of metal to be supported is not particularly limited, but the total amount of metal is preferably 0.1 to 3.0% by mass with respect to the mass of the carrier.
- the periodic table of elements means a periodic table of long-period elements based on the provisions of IUPAC (International Pure Applied Chemistry Association).
- the conditions for contacting the base oil fraction and the hydrocracking catalyst A in the presence of hydrogen are not particularly limited, but the following reaction conditions can be selected.
- the reaction temperature include 180 to 400 ° C., preferably 200 to 370 ° C., more preferably 250 to 350 ° C., and particularly preferably 280 to 350 ° C.
- the reaction temperature exceeds 400 ° C., decomposition to light components proceeds and not only the yield of the base oil fraction decreases, but also the product tends to be colored and its use as a fuel oil base material tends to be limited. It is in.
- the reaction temperature is lower than 180 ° C.
- the hydrocracking reaction does not proceed sufficiently, and the yield of the base oil fraction decreases.
- the hydrogen partial pressure include 0.5 to 12 MPa, and 1.0 to 5.0 MPa is preferable.
- the liquid hourly space velocity of the heavy fraction include 0.1 ⁇ 10.0h -1 but is preferably 0.3 ⁇ 3.5 h -1.
- LHSV liquid hourly space velocity of the heavy fraction
- the base oil fraction may contain a sulfur content.
- a porous inorganic oxide comprising two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium as the hydrocracking catalyst, and the porous inorganic oxide
- hydrocracking catalyst B a catalyst having at least one metal selected from Group 6A and Group 8 elements supported on the periodic table. According to the hydrocracking catalyst B, a decrease in catalytic activity due to sulfur poisoning is sufficiently suppressed.
- a porous inorganic oxide comprising two or more selected from aluminum, silicon, zirconium, boron, titanium and magnesium as described above is used.
- the porous inorganic oxide is preferably at least two selected from aluminum, silicon, zirconium, boron, titanium and magnesium from the viewpoint that the hydrocracking activity can be further improved.
- An inorganic oxide (a composite oxide of aluminum oxide and another oxide) is more preferable.
- the aluminum content is preferably 1 to 97% by mass, more preferably 10 to 97% by mass in terms of alumina, based on the total amount of the porous inorganic oxide. %, More preferably 20 to 95% by mass.
- the aluminum content is less than 1% by mass in terms of alumina, physical properties such as carrier acid properties are not suitable, and sufficient hydrocracking activity tends not to be exhibited.
- the aluminum content exceeds 97% by mass in terms of alumina, the catalyst surface area becomes insufficient and the activity tends to decrease.
- the method for introducing silicon, zirconium, boron, titanium and magnesium, which are carrier constituent elements other than aluminum, is not particularly limited, and a solution containing these elements may be used as a raw material.
- silicon, silicon, water glass, silica sol, etc. for boron, boric acid, etc., for phosphorus, phosphoric acid and alkali metal salts of phosphoric acid, etc., for titanium, titanium sulfide, titanium tetrachloride and various alkoxide salts, etc.
- zirconium zirconium sulfate and various alkoxide salts can be used.
- the porous inorganic oxide preferably contains phosphorus as a constituent element.
- the phosphorus content is preferably 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, and further preferably 2 to 6% by mass, based on the total amount of the porous inorganic oxide. When the phosphorus content is less than 0.1% by mass, sufficient hydrocracking activity tends not to be exhibited, and when it exceeds 10% by mass, excessive decomposition may proceed.
- the raw materials of the carrier constituents other than the above-described aluminum oxide in a step prior to the firing of the carrier.
- the aluminum hydroxide gel containing these structural components may be prepared, and the said raw material may be added with respect to the prepared aluminum hydroxide gel.
- the above raw materials may be added in a step of adding water or an acidic aqueous solution to a commercially available aluminum oxide intermediate or boehmite powder and kneading them, but it is more preferable to coexist at the stage of preparing aluminum hydroxide gel.
- the porous inorganic oxide as the carrier carries one or more metals selected from Group 6A and Group 8 elements of the periodic table.
- these metals it is preferable to use a combination of two or more metals selected from cobalt, molybdenum, nickel and tungsten.
- suitable combinations include cobalt-molybdenum, nickel-molybdenum, nickel-cobalt-molybdenum, and nickel-tungsten. Of these, combinations of nickel-molybdenum, nickel-cobalt-molybdenum and nickel-tungsten are more preferred. In hydrocracking, these metals are used after being converted to a sulfide state.
- the total supported amount of tungsten and molybdenum is preferably 12 to 35% by mass, more preferably 15 to 30% by mass in terms of oxide. If the total supported amount of tungsten and molybdenum is less than 12% by mass, the active sites tend to decrease and sufficient activity cannot be obtained. On the other hand, if it exceeds 35% by mass, the metal is not effectively dispersed and sufficient activity tends not to be obtained.
- the range of the total supported amount of cobalt and nickel is preferably 1.0 to 15% by mass, more preferably 1.5 to 12% by mass in terms of oxide.
- the method of incorporating these active metals into the catalyst is not particularly limited, and a known method applied when producing an ordinary hydrocracking catalyst can be used.
- a method of impregnating a catalyst carrier with a solution containing a salt of an active metal is preferably employed.
- an equilibrium adsorption method, a pore-filling method, an incident-wetness method, and the like are also preferably employed.
- the pore-filling method is a method in which the pore volume of a support is measured in advance and impregnated with a metal salt solution having the same volume.
- the impregnation method is not particularly limited, and it can be impregnated by an appropriate method according to the amount of metal supported and the physical properties of the catalyst carrier.
- the number of types of hydrocracking catalyst B to be used is not particularly limited.
- one type of catalyst may be used alone, or a plurality of catalysts having different active metal species and carrier components may be used.
- a catalyst containing cobalt-molybdenum after the catalyst containing nickel-molybdenum, and nickel-cobalt-molybdenum after the catalyst containing nickel-molybdenum are used.
- a catalyst containing nickel-cobalt-molybdenum after the catalyst containing nickel-tungsten, and a catalyst containing cobalt-molybdenum after the catalyst containing nickel-cobalt-molybdenum may be further combined before and / or after these combinations.
- the content of aluminum oxide is included in the subsequent stage of the catalyst having an aluminum oxide content of 30% by mass or more and less than 80% by mass based on the total mass of the support.
- a catalyst having an amount in the range of 80 to 99% by mass may be used.
- a guard catalyst is used for trapping the scale component flowing in along with the base oil fraction as needed, or for supporting the hydrocracking catalyst B at the separation part of the catalyst bed.
- a demetallizing catalyst or an inert packing may be used. In addition, these can be used individually or in combination.
- the pore volume of the hydrocracking catalyst B by the nitrogen adsorption BET method is preferably 0.30 to 0.85 ml / g, more preferably 0.45 to 0.80 ml / g.
- the pore volume is less than 0.30 ml / g, the dispersibility of the supported metal becomes insufficient, and there is a concern that the active site is verified.
- the pore volume exceeds 0.85 ml / g, the catalyst strength becomes insufficient, and the catalyst may be pulverized or crushed during use.
- the average pore diameter of the catalyst determined by the nitrogen adsorption BET method is preferably 5 to 11 nm, and more preferably 6 to 9 nm. If the average pore diameter is less than 5 nm, the reaction substrate may not sufficiently diffuse into the pores, and the reactivity may be reduced. On the other hand, if the average pore diameter exceeds 11 nm, the pore surface area decreases, and the activity may be insufficient.
- the hydrocracking conditions are, for example, a hydrogen pressure of 2 to 13 MPa, a liquid space velocity (LHSV) of 0.1 to 3.0 h ⁇ 1 , a hydrogen oil ratio (hydrogen / oil ratio) of 150.
- a hydrogen pressure of 2 to 13 MPa
- a liquid space velocity LHSV
- hydrogen oil ratio hydrogen / oil ratio
- To 1500 NL / L preferably hydrogen pressure 4.5 to 12 MPa
- liquid space velocity 0.3 to 1.5 h ⁇ 1
- hydrogen oil ratio 380 to 1200 NL / L more preferably hydrogen
- the pressure is 6 to 15 MPa
- the space velocity is 0.3 to 1.5 h ⁇ 1
- the hydrogen oil ratio is 350 to 1000 NL / L.
- the reactivity tends to decrease or the activity rapidly decreases. is there.
- the hydrogen pressure and the hydrogen oil ratio exceed the above upper limit values, there is a tendency that excessive equipment investment such as a compressor is required.
- the lower the liquid space velocity tends to be advantageous for the reaction, but if the liquid space velocity is less than the above lower limit value, there is a tendency that an extremely large internal volume reactor is required and excessive equipment investment is required, When the liquid space velocity exceeds the above upper limit, the reaction tends not to proceed sufficiently.
- reaction temperature examples include 180 to 400 ° C., preferably 200 to 370 ° C., more preferably 250 to 350 ° C., and particularly preferably 280 to 350 ° C.
- reaction temperature exceeds 400 ° C.
- decomposition into light fractions proceeds and not only the yield of the base oil fraction decreases, but also the product is colored and its use as a fuel oil base material is restricted. There is a tendency.
- reaction temperature is lower than 180 ° C., the hydrocracking reaction does not proceed sufficiently, and the yield of the base oil fraction decreases.
- the heavy fraction is converted into hydrocarbons having a boiling point of approximately 520 ° C. or less by hydrocracking.
- a part of the heavy fraction is not sufficiently hydrocracked and remains as an undecomposed heavy fraction having a boiling point of 520 ° C. or higher.
- the composition of hydrocracked oil is determined by the hydrocracking catalyst used and the hydrocracking reaction conditions.
- the “hydrocracked oil” refers to the entire hydrocracked product containing an uncracked heavy fraction unless otherwise specified. If the hydrocracking reaction conditions are made stricter than necessary, the content of the undecomposed heavy fraction in the hydrocracked oil decreases, but the light fraction having a boiling point of 340 ° C. or less increases and a suitable base oil fraction (340 Yield of ⁇ 520 ° C. fraction). On the other hand, when the hydrocracking reaction conditions are milder than necessary, the uncracked heavy fraction increases and the base oil fraction yield decreases.
- this decomposition rate M2 / M1 is usually The reaction conditions are preferably selected so as to be 5 to 70%, preferably 10 to 60%, more preferably 20 to 50%.
- the dewaxing process will be described.
- the base oil fraction fractionated in the first distillation step is brought into contact with the hydrogenation catalyst in the presence of hydrogen (molecular hydrogen).
- hydrogen molecular hydrogen
- a known fixed bed reaction tower can be used as a reaction tower in the dewaxing step. More specifically, for example, a hydroisomerization catalyst is charged into a fixed bed flow reactor, and hydrogen (molecular hydrogen) and a base oil fraction are passed through the reactor to perform hydroisomerization. Can be implemented.
- hydroisomerization catalyst a catalyst generally used for hydroisomerization, that is, a catalyst in which a metal having a hydrogenation activity is supported on an inorganic carrier can be used.
- Examples of the metal having hydrogenation activity constituting the hydroisomerization catalyst include one or more metals selected from the group consisting of metals of Group 6, Group 8, Group 9 and Group 10 of the periodic table of elements. Used. Specific examples of these metals include noble metals such as platinum, palladium, rhodium, ruthenium, iridium and osmium, or cobalt, nickel, molybdenum, tungsten, iron, etc., preferably platinum, palladium, nickel, Cobalt, molybdenum and tungsten are preferable, and platinum and palladium are more preferable. These metals are also preferably used in combination of a plurality of types. In this case, preferable combinations include platinum-palladium, cobalt-molybdenum, nickel-molybdenum, nickel-cobalt-molybdenum, nickel-tungsten, and the like.
- noble metals such as platinum, palladium, rhodium, ruthenium, iridium and os
- the inorganic carrier constituting the hydroisomerization catalyst examples include metal oxides such as alumina, silica, titania, zirconia, and boria. These metal oxides may be one kind or a mixture of two or more kinds or a composite metal oxide such as silica alumina, silica zirconia, alumina zirconia, alumina boria and the like.
- the inorganic carrier is preferably a composite metal oxide having solid acidity such as silica alumina, silica zirconia, alumina zirconia, alumina boria, etc., from the viewpoint of efficiently proceeding hydroisomerization of normal paraffin.
- the inorganic carrier may contain a small amount of zeolite.
- the inorganic carrier may contain a binder for the purpose of improving the moldability and mechanical strength of the carrier. Preferred binders include alumina, silica, magnesia and the like.
- the content of the metal having hydrogenation activity in the hydroisomerization catalyst is about 0.1 to 3% by mass as a metal atom based on the mass of the support when the metal is the above-mentioned noble metal. preferable. Further, when the metal is a metal other than the noble metal, the metal oxide is preferably about 2 to 50% by mass based on the mass of the support.
- the content of the metal having hydrogenation activity is less than the lower limit, hydrorefining and hydroisomerization tend not to proceed sufficiently.
- the content of the metal having hydrogenation activity exceeds the upper limit, the dispersion of the metal having hydrogenation activity tends to be reduced, and the activity of the catalyst tends to be reduced, and the catalyst cost is increased.
- the hydroisomerization catalyst is selected from elements of Group 8 of the periodic table on a support made of a porous inorganic oxide composed of a material selected from aluminum, silicon, zirconium, boron, titanium, magnesium and zeolite.
- a catalyst formed by supporting one or more metals may be used.
- porous inorganic oxide used as a carrier for such a hydroisomerization catalyst examples include alumina, titania, zirconia, boria, silica, and zeolite, and among these, titania, zirconia, boria, silica, and zeolite. Among these, those composed of at least one kind and alumina are preferable.
- the production method is not particularly limited, but any preparation method can be adopted using raw materials in a state of various sols, salt compounds, etc. corresponding to each element.
- alumina gel and other hydroxides or in a suitable solution state It may be prepared by adding at any step.
- the ratio of alumina to other oxides can be any ratio with respect to the support, but preferably alumina is 90% by mass or less, more preferably 60% by mass or less, more preferably 40% by mass or less, preferably Is 10% by mass or more, more preferably 20% by mass or more.
- Zeolites are crystalline aluminosilicates, such as faujasite, pentasil, mordenite, TON, MTT, MRE, etc., which are ultra-stabilized by the prescribed hydrothermal treatment and / or acid treatment, or the alumina content in the zeolite What adjusted can be used.
- faujasite and mordenite particularly preferably Y type and beta type are used.
- the Y type is preferably ultra-stabilized, and the zeolite that has been super-stabilized by hydrothermal treatment forms new pores in the range of 20 to 100 mm in addition to the original pore structure called micropores of 20 mm or less.
- Known conditions can be used for the hydrothermal treatment conditions.
- the active metal of such a hydroisomerization catalyst one or more metals selected from Group 8 elements of the periodic table are used.
- these metals it is preferable to use one or more metals selected from Pd, Pt, Rh, Ir, Au, and Ni, and it is more preferable to use them in combination.
- Suitable combinations include, for example, Pd—Pt, Pd—Ir, Pd—Rh, Pd—Au, Pd—Ni, Pt—Rh, Pt—Ir, Pt—Au, Pt—Ni, Rh—Ir, Rh— Examples thereof include Au, Rh—Ni, Ir—Au, Ir—Ni, Au—Ni, Pd—Pt—Rh, Pd—Pt—Ir, and Pt—Pd—Ni.
- the total content of active metals based on the catalyst mass is preferably 0.1 to 2% by mass, more preferably 0.2 to 1.5% by mass, and 0.5 to 1.3% by mass as the metal. Even more preferred. If the total supported amount of the metal is less than 0.1% by mass, the active sites tend to decrease and sufficient activity cannot be obtained. On the other hand, if it exceeds 2% by mass, the metal is not effectively dispersed and sufficient activity tends not to be obtained.
- the method for supporting an active metal on a support is not particularly limited, and a known method applied when producing a normal hydroisomerization catalyst can be used. .
- a method of impregnating a catalyst carrier with a solution containing a salt of an active metal is preferably employed.
- an equilibrium adsorption method, a pore-filling method, an incident-wetness method, and the like are preferably employed.
- the pore-filling method is a method in which the pore volume of the support is measured in advance and impregnated with the same volume of the metal salt solution, but the impregnation method is not particularly limited, and the amount of metal supported Further, it can be impregnated by an appropriate method depending on the physical properties of the catalyst support.
- the following catalysts can also be used as the hydroisomerization catalyst.
- an organic template-containing zeolite containing an organic template and having a 10-membered ring one-dimensional pore structure is ion-exchanged in a solution containing ammonium ions and / or protons.
- a first step of obtaining a support precursor by heating a mixture containing the obtained ion-exchanged zeolite and a binder at a temperature of 250 to 350 ° C. in an N 2 atmosphere; and a platinum salt and / or A catalyst precursor containing a palladium salt is calcined at a temperature of 350 to 400 ° C. in an atmosphere containing molecular oxygen to obtain a hydroisomerization catalyst in which platinum and / or palladium is supported on a support containing zeolite. And obtaining a second step.
- the organic template-containing zeolite used in the present embodiment is a one-dimensional pore composed of a 10-membered ring from the viewpoint of achieving both high isomerization activity and suppressed decomposition activity in normal paraffin hydroisomerization reaction at a high level. It has a structure.
- zeolite examples include AEL, EUO, FER, HEU, MEL, MFI, NES, TON, MTT, WEI, * MRE, and SSZ-32.
- the above three letters of the alphabet mean the skeletal structure code given by the Structure Committee of The International Zeolite Association for each classified structure of molecular sieve type zeolite. To do.
- zeolites having the same topology are collectively referred to by the same code.
- zeolites having the above-mentioned 10-membered ring one-dimensional pore structure among the zeolites having the above-mentioned 10-membered ring one-dimensional pore structure, zeolites having a TON or MTT structure, and * MRE structures in terms of high isomerization activity and low decomposition activity ZSM-48 zeolite and SSZ-32 zeolite which are zeolites are preferred.
- ZSM-22 zeolite is more preferred as the zeolite having the TON structure
- ZSM-23 zeolite is more preferred as the zeolite having the MTT structure.
- the organic template-containing zeolite is hydrothermally synthesized by a known method from a silica source, an alumina source, and an organic template added to construct the predetermined pore structure.
- the organic template is an organic compound having an amino group, an ammonium group or the like, and is selected according to the structure of the zeolite to be synthesized, but is preferably an amine derivative. Specifically, at least one selected from the group consisting of alkylamine, alkyldiamine, alkyltriamine, alkyltetramine, pyrrolidine, piperazine, aminopiperazine, alkylpentamine, alkylhexamine and derivatives thereof is more preferable.
- the molar ratio ([Si] / [Al]) between silicon and aluminum constituting the organic template-containing zeolite having a 10-membered ring one-dimensional pore structure (hereinafter referred to as “Si / Al ratio”) is 10. Is preferably from 400 to 400, more preferably from 20 to 350.
- Si / Al ratio is less than 10
- the activity for the conversion of normal paraffin increases, but the isomerization selectivity to isoparaffin tends to decrease, and the increase in decomposition reaction accompanying the increase in reaction temperature tends to become rapid. Therefore, it is not preferable.
- the Si / Al ratio exceeds 400, it is difficult to obtain the catalyst activity necessary for the conversion of normal paraffin, which is not preferable.
- the organic template-containing zeolite synthesized preferably washed and dried usually has an alkali metal cation as a counter cation, and the organic template is included in the pore structure.
- the zeolite containing an organic template used in producing the hydroisomerization catalyst according to the present invention is in such a synthesized state, that is, calcination for removing the organic template included in the zeolite. It is preferable that the treatment is not performed.
- the organic template-containing zeolite is then ion-exchanged in a solution containing ammonium ions and / or protons.
- the counter cation contained in the organic template-containing zeolite is exchanged with ammonium ions and / or protons.
- a part of the organic template included in the organic template-containing zeolite is removed.
- the solution used for the ion exchange treatment is preferably a solution using a solvent containing at least 50% by volume of water, and more preferably an aqueous solution.
- the compound that supplies ammonium ions into the solution include various inorganic and organic ammonium salts such as ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium phosphate, and ammonium acetate.
- mineral acids such as hydrochloric acid, sulfuric acid and nitric acid are usually used as the compound for supplying protons into the solution.
- An ion-exchanged zeolite obtained by ion-exchange of an organic template-containing zeolite in the presence of ammonium ions releases ammonia during subsequent calcination, and the counter cation serves as a proton as a brane. Stead acid point.
- ammonium ions are preferred.
- the content of ammonium ions and / or protons contained in the solution is preferably set to be 10 to 1000 equivalents with respect to the total amount of counter cations and organic templates contained in the organic template-containing zeolite used. .
- the above ion exchange treatment may be performed on the powdery organic template-containing zeolite alone, and prior to the ion exchange treatment, the organic template-containing zeolite is blended with an inorganic oxide as a binder, molded, and obtained. You may perform with respect to the molded object obtained. However, if the molded body is subjected to an ion exchange treatment without firing, the molded body is likely to collapse and pulverize, so the powdered organic template-containing zeolite can be subjected to an ion exchange treatment. preferable.
- the ion exchange treatment is preferably performed by an ordinary method, that is, a method of immersing zeolite containing an organic template in a solution containing ammonium ions and / or protons, preferably an aqueous solution, and stirring or flowing the zeolite. Moreover, it is preferable to perform said stirring or a flow under a heating in order to improve the efficiency of ion exchange.
- a method in which the aqueous solution is heated and ion exchange is performed under boiling and reflux is particularly preferable.
- the solution it is preferable to exchange the solution once or twice or more during the ion exchange of the zeolite with the solution, and exchange the solution once or twice. It is more preferable.
- the organic template-containing zeolite is immersed in a solution containing ammonium ions and / or protons and heated to reflux for 1 to 6 hours. By heating and refluxing for ⁇ 12 hours, the ion exchange efficiency can be increased.
- a carrier precursor is obtained by heating a mixture containing ion-exchanged zeolite and a binder at a temperature of 250 to 350 ° C. in a nitrogen atmosphere.
- the mixture containing the ion exchange zeolite and the binder is preferably a mixture of the ion exchange zeolite obtained by the above method and an inorganic oxide as a binder and molding the resulting composition.
- the purpose of blending the inorganic oxide with the ion-exchanged zeolite is to improve the mechanical strength of the carrier (particularly, the particulate carrier) obtained by firing the molded body to such an extent that it can be practically used.
- the inventor has found that the choice of the inorganic oxide species affects the isomerization selectivity of the hydroisomerization catalyst.
- the inorganic oxide is at least one selected from a composite oxide composed of alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide, phosphorus oxide, and combinations of two or more thereof.
- Inorganic oxides are used.
- silica and alumina are preferable and alumina is more preferable from the viewpoint of further improving the isomerization selectivity of the hydroisomerization catalyst.
- the “composite oxide composed of a combination of two or more of these” is composed of at least two components of alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide, and phosphorus oxide.
- the composite oxide is preferably a composite oxide mainly composed of alumina containing 50% by mass or more of an alumina component based on the composite oxide, and more preferably alumina-silica.
- the mixing ratio of the ion exchange zeolite and the inorganic oxide in the above composition is preferably 10:90 to 90:10, more preferably 30:70 to 85 as a ratio of the mass of the ion exchange zeolite to the mass of the inorganic oxide. : 15.
- this ratio is smaller than 10:90, it is not preferable because the activity of the hydroisomerization catalyst tends to be insufficient.
- the ratio exceeds 90:10, the mechanical strength of the carrier obtained by molding and baking the composition tends to be insufficient, which is not preferable.
- the method of blending the above-mentioned inorganic oxide with the ion-exchanged zeolite is not particularly limited. The method performed can be adopted.
- the composition containing the ion-exchanged zeolite and the inorganic oxide or the viscous fluid containing the composition is molded by a method such as extrusion molding, and preferably dried to form a particulate molded body.
- the shape of the molded body is not particularly limited, and examples thereof include a cylindrical shape, a pellet shape, a spherical shape, and a modified cylindrical shape having a trefoil / four-leaf cross section.
- the size of the molded body is not particularly limited, but from the viewpoint of ease of handling, packing density in the reactor, etc., for example, the major axis is preferably about 1 to 30 mm and the minor axis is about 1 to 20 mm.
- the molded body obtained as described above is preferably heated to a temperature of 250 to 350 ° C. in a N 2 atmosphere to form a carrier precursor.
- the heating time is preferably 0.5 to 10 hours, and more preferably 1 to 5 hours.
- the heating temperature when the heating temperature is lower than 250 ° C., a large amount of the organic template remains, and the pores are blocked by the remaining template. It is considered that the isomerization active site is present near the pore pore mouse. In the above case, the reaction substrate cannot diffuse into the pore due to the clogging of the pore, and the active site is covered and the isomerization reaction does not proceed easily. The conversion rate of normal paraffin tends to be insufficient. On the other hand, when the heating temperature exceeds 350 ° C., the isomerization selectivity of the resulting hydroisomerization catalyst is not sufficiently improved.
- the lower limit temperature when the molded body is heated to form a carrier precursor is preferably 280 ° C or higher.
- the upper limit temperature is preferably 330 ° C. or lower.
- the micropore volume per unit mass of the hydroisomerization catalyst obtained through calcination after metal support described later is 0.02 to 0.11 cc / g, and the zeolite contained in the catalyst It is preferable to set the heating conditions so that the micropore volume per unit mass is 0.04 to 0.12 cc / g.
- a catalyst precursor in which a platinum salt and / or palladium salt is contained in the carrier precursor is heated to 350 to 400 ° C., preferably 380 to 400 ° C., more preferably 400 ° C. in an atmosphere containing molecular oxygen.
- a hydroisomerization catalyst in which platinum and / or palladium is supported on a support containing zeolite is obtained.
- under an atmosphere containing molecular oxygen means that the gas is in contact with a gas containing oxygen gas, preferably air.
- the firing time is preferably 0.5 to 10 hours, and more preferably 1 to 5 hours.
- platinum salts include chloroplatinic acid, tetraamminedinitroplatinum, dinitroaminoplatinum, and tetraamminedichloroplatinum. Since the chloride salt generates hydrochloric acid during the reaction and may corrode the equipment, tetraamminedinitroplatinum, which is a platinum salt in which platinum is highly dispersed other than the chloride salt, is preferable.
- the palladium salt examples include palladium chloride, tetraamminepalladium nitrate, and diaminopalladium nitrate. Since the chloride salt generates hydrochloric acid during the reaction and may corrode the equipment, tetraamminepalladium nitrate, which is a palladium salt in which palladium is highly dispersed other than the chloride salt, is preferable.
- the amount of the active metal supported on the support containing zeolite according to this embodiment is preferably 0.001 to 20% by mass, more preferably 0.01 to 5% by mass based on the mass of the support.
- the supported amount is less than 0.001% by mass, it is difficult to provide a predetermined hydrogenation / dehydrogenation function.
- the supported amount exceeds 20% by mass, lightening by decomposition of hydrocarbons on the active metal tends to proceed, and the yield of the target fraction tends to decrease, This is not preferable because the catalyst cost tends to increase.
- the hydroisomerization catalyst according to this embodiment is used for hydroisomerization of a hydrocarbon oil containing a large amount of a sulfur-containing compound and / or a nitrogen-containing compound, from the viewpoint of sustainability of catalyst activity, as an active metal, It is preferable to include a combination of nickel-cobalt, nickel-molybdenum, cobalt-molybdenum, nickel-molybdenum-cobalt, nickel-tungsten-cobalt and the like.
- the amount of these metals supported is preferably 0.001 to 50 mass%, more preferably 0.01 to 30 mass%, based on the mass of the carrier.
- the catalyst precursor is preferably calcined so that the organic template left on the carrier precursor remains.
- the micropore volume per unit mass of the resulting hydroisomerization catalyst is 0.02 to 0.11 cc / g, and the micropore volume per unit mass of zeolite contained in the catalyst It is preferable to set the heating conditions so that is 0.04 to 0.12 cc / g.
- the micropore volume per unit mass of the hydroisomerization catalyst is calculated by a method called nitrogen adsorption measurement. That is, for the catalyst, the physical adsorption / desorption isotherm of nitrogen measured at the liquid nitrogen temperature ( ⁇ 196 ° C.) is analyzed. Specifically, the adsorption isotherm of nitrogen measured at the liquid nitrogen temperature ( ⁇ 196 ° C.) The micropore volume per unit mass of the catalyst is calculated by analyzing by the ⁇ plot method. The micropore volume per unit mass of zeolite contained in the catalyst is also calculated by the above nitrogen adsorption measurement.
- micropore refers to a “pore having a diameter of 2 nm or less” defined by the International Pure and Applied Chemistry Union IUPAC (International Union of Pure and Applied Chemistry).
- Micropore volume V Z per unit mass of zeolite contained in the catalyst for example, if the binder does not have a micropore volume, the value of the micropore volume per unit mass of the hydroisomerization catalyst It can be calculated according to the following formula from V c and the content ratio M z (mass%) of the zeolite in the catalyst.
- V Z V c / M z ⁇ 100
- the hydroisomerization catalyst of this embodiment is preferably a catalyst that has been subjected to a reduction treatment after being charged into a reactor that performs a hydroisomerization reaction following the above-described calcination treatment.
- reduction treatment is performed for about 0.5 to 5 hours in an atmosphere containing molecular hydrogen, preferably in a hydrogen gas flow, preferably at 250 to 500 ° C., more preferably at 300 to 400 ° C. It is preferable that By such a process, the high activity with respect to dewaxing of hydrocarbon oil can be more reliably imparted to the catalyst.
- the hydroisomerization catalyst of this embodiment contains a zeolite having a 10-membered ring one-dimensional pore structure, a support containing a binder, and platinum and / or palladium supported on the support, and is a unit of catalyst.
- the zeolite contained is derived from an ion exchange zeolite obtained by ion exchange in a solution containing ammonium ions and / or protons, and the micropore volume per unit mass of the zeolite contained in the catalyst is 0.04. It may be from 0.12 cc / g.
- Said hydroisomerization catalyst can be manufactured by the method mentioned above.
- the micropore volume per unit mass of the catalyst and the micropore volume per unit mass of the zeolite contained in the catalyst are the blending amount of the ion exchange zeolite in the mixture containing the ion exchange zeolite and the binder, and the N of the mixture.
- the heating conditions under the two atmospheres and the heating conditions under the atmosphere containing the molecular oxygen of the catalyst precursor can be appropriately adjusted to be within the above range.
- the reaction temperature in the dewaxing step is preferably 200 to 450 ° C, more preferably 220 to 400 ° C.
- the reaction temperature is lower than 200 ° C.
- the isomerization of normal paraffin contained in the base oil fraction is difficult to proceed, and the wax component tends to be insufficiently reduced and removed.
- the reaction temperature exceeds 450 ° C., the decomposition of the base oil fraction becomes remarkable, and the yield of the lubricating base oil tends to decrease.
- the reaction pressure in the dewaxing step is preferably 0.1 to 20 MPa, more preferably 0.5 to 15 MPa.
- the reaction pressure is less than 0.1 MPa, the deterioration of the catalyst due to coke generation tends to be accelerated.
- the reaction pressure exceeds 20 MPa, the cost for constructing the apparatus tends to increase, and it tends to be difficult to realize an economical process.
- the liquid hourly space velocity for the base oil fraction of the catalyst is preferably 0.01 ⁇ 100 hr -1, more preferably 0.1 ⁇ 50 hr -1.
- the liquid space velocity is less than 0.01 hr ⁇ 1 , decomposition of the base oil fraction tends to proceed excessively, and production efficiency tends to decrease.
- the liquid space velocity exceeds 100 hr ⁇ 1 , isomerization of normal paraffin contained in the base oil fraction does not proceed easily, and the wax component tends to be insufficiently reduced and removed.
- Supply ratio of hydrogen to base oil fraction is preferably 100 ⁇ 1000Nm 3 / m 3, more preferably 200 ⁇ 800Nm 3 / m 3.
- the supply ratio is less than 100 Nm 3 / m 3 , for example, when the base oil fraction contains a sulfur content or a nitrogen content, hydrogen sulfide and ammonia gas generated by desulfurization and denitrogenation combined with the isomerization reaction are on the catalyst. Since the active metal is adsorbed and poisoned, it tends to be difficult to obtain a predetermined catalyst performance.
- the supply ratio exceeds 1000 Nm 3 / m 3 , a hydrogen supply facility with a large capacity is required, so that it is difficult to realize an economical process.
- the dewaxed oil obtained in the dewaxing process is subjected to a hydrofinishing process and subjected to a hydrofinishing process (hydrorefining process).
- the reactor used in the hydrofinishing process is not particularly limited, and a predetermined hydrorefining catalyst is charged into a fixed bed flow reactor, and molecular hydrogen and the dewaxed oil are circulated through the reactor.
- the hydrofinishing treatment can be suitably carried out.
- the hydrofinishing treatment (hydrorefining treatment) in the present invention means to improve the oxidation stability and hue of the lubricating oil, and the olefin hydrogenation and aromatic hydrogenation of the dewaxed oil are performed.
- hydrorefining catalyst for example, a support comprising one or more inorganic solid acidic substances selected from alumina, silica, zirconia, titania, boria, magnesia and phosphorus, and supported on the support, And a catalyst having at least one active metal selected from the group consisting of platinum, palladium, nickel-molybdenum, nickel-tungsten and nickel-cobalt-molybdenum.
- a suitable carrier is an inorganic solid acidic substance containing at least two kinds of alumina, silica, zirconia, or titania.
- the supported amount of active metal in the hydrotreating catalyst is preferably such that the total amount of metal is 0.1 to 25% by mass relative to the support.
- the average pore diameter of the hydrorefining catalyst is preferably 6 to 60 nm, and more preferably 7 to 30 nm. When the average pore diameter is smaller than 6 nm, sufficient catalytic activity tends to be not obtained, and when the average pore diameter exceeds 60 nm, the catalytic activity tends to decrease due to a decrease in the degree of dispersion of the active metal.
- the pore volume of the hydrotreating catalyst is preferably 0.2 mL / g or more. When the pore volume is less than 0.2 mL / g, the catalyst activity tends to be rapidly deteriorated.
- the specific surface area of the hydrotreating catalyst is preferably 200 m 2 / g or more.
- the specific surface area of the catalyst is less than 200 m 2 / g, the dispersibility of the active metal is insufficient and the activity tends to decrease.
- the pore volume and specific surface area of these catalysts can be measured and calculated by a method called the BET method based on nitrogen adsorption.
- the reaction conditions in the hydrofinishing step are preferably a reaction temperature of 200 to 300 ° C., a hydrogen partial pressure of 3 to 20 MPa, an LHSV of 0.5 to 5 h-1, and a hydrogen / oil ratio of 1000 to 5000 scfb, and a reaction temperature of 200 to 300 ° C. More preferably, the hydrogen partial pressure is 4 to 18 MPa, the LHSV is 0.5 to 4 h-1, and the hydrogen / oil ratio is 2000 to 5000 scfb.
- the reaction conditions it is preferable to adjust the reaction conditions so that the sulfur content and the nitrogen content in the hydrorefined oil are 5 mass ppm or less and 1 mass ppm or less, respectively.
- the refined oil obtained by the hydrofinishing process is subjected to the second fractionation process. Then, a desired lubricating oil fraction can be obtained by setting a plurality of cut points and distilling the hydrorefined oil under reduced pressure.
- the hydrorefined oil may contain light fractions such as naphtha and kerosene oil produced as a by-product of hydroisomerization or hydrofinishing treatment (hydrorefining treatment). For example, it can be recovered as a fraction having a boiling point of 350 ° C. or lower.
- the method for producing the lubricating base oil of the present invention is not limited to the above-described embodiment, and can be changed as appropriate.
- the method for producing a lubricating base oil of the present invention includes a distillation step of fractionating the dewaxed oil obtained by the above dewaxed oil production method to obtain a lubricating oil fraction, and the distillation base step. And a hydrofinishing step of hydrofinishing (hydrorefining treatment) of the lubricating oil fraction.
- the lubricant base oil according to the first to third embodiments and the lubricant base oil obtained by the production method according to the fourth embodiment have excellent low-temperature viscosity characteristics and sealing properties, and are used in various applications. It can be preferably used as a lubricating base oil.
- Lubricating oil base oils are specifically used in internal combustion engines such as gasoline engines for passenger cars, gasoline engines for motorcycles, diesel engines, gas engines, gas heat pump engines, marine engines, and power generation engines. (Lubricating oil for internal combustion engines), automatic transmissions, manual transmissions, continuously variable transmissions, final reduction gears, etc. Lubricating oils (drive transmission device oils), shock absorbers, hydraulic equipment for construction machinery, etc.
- Hydraulic oil compressor oil, turbine oil, industrial gear oil, refrigeration oil, rust prevention oil, heat medium oil, gas holder seal oil, bearing oil, paper machine oil, machine tool oil, slip guide surface oil , Electrical insulating oil, cutting oil, press oil, rolling oil, heat treatment oil, etc., and by using the lubricating base oil according to the present embodiment for these applications, It is possible at a high level both the Le resistance.
- the lubricant base oil according to each embodiment may be used alone, and the lubricant base oil according to each embodiment is used in combination with one or more other base oils. May be.
- the ratio of the lubricating base oil of the present invention in the mixed base oil is preferably 30% by mass or more. 50% by mass or more is more preferable, and 70% by mass or more is still more preferable.
- the other base oil used in combination with the lubricating base oil according to each embodiment is not particularly limited.
- the mineral base oil include solvent refined mineral oil having a kinematic viscosity at 100 ° C. of 1 to 100 mm 2 / s, Examples include hydrocracked mineral oil, hydrorefined mineral oil, and solvent dewaxing base oil.
- Synthetic base oils include poly ⁇ -olefins or hydrides thereof, isobutene oligomers or hydrides thereof, isoparaffins, alkylbenzenes, alkylnaphthalenes, diesters (ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridec Decyl adipate, di-2-ethylhexyl sebacate, etc.), polyol esters (trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol 2-ethylhexanoate, pentaerythritol pelargonate, etc.), polyoxyalkylene glycol, dialkyl Examples thereof include diphenyl ether and polyphenyl ether, and among them, poly ⁇ -olefin is preferable.
- an ⁇ -olefin oligomer or co-oligomer (1-octene oligomer, decene oligomer, ethylene-propylene co-oligomer, etc.) having 2 to 32 carbon atoms, preferably 6 to 16 carbon atoms, and those Of the hydrides.
- the production method of poly ⁇ -olefin is not particularly limited.
- Friedel-Crafts catalyst containing a complex of aluminum trichloride or boron trifluoride with water, alcohol (ethanol, propanol, butanol, etc.), carboxylic acid or ester is not particularly limited.
- a method of polymerizing ⁇ -olefin in the presence of a polymerization catalyst such as
- various additives can be blended in the lubricating base oil according to each embodiment or a mixed base oil of the lubricating base oil and other lubricating base oils as necessary.
- Such an additive is not particularly limited, and any additive conventionally used in the field of lubricating oils can be blended.
- Specific examples of such lubricating oil additives include antioxidants, ashless dispersants, metallic detergents, extreme pressure agents, antiwear agents, viscosity index improvers, pour point depressants, friction modifiers, oiliness agents. , Corrosion inhibitors, rust inhibitors, demulsifiers, metal deactivators, seal swelling agents, antifoaming agents, colorants and the like. These additives may be used individually by 1 type, and may be used in combination of 2 or more type.
- the lubricating base oil according to each embodiment can effectively exert the effect of adding a pour point depressant. Therefore, when the pour point depressant is contained in the lubricating base oil according to each embodiment or the mixed base oil of the lubricating base oil and other lubricating base oil, excellent low temperature viscosity characteristics (MRV viscosity at ⁇ 40 ° C. Is preferably 20,000 mPa ⁇ s or less, more preferably 15,000 mPa ⁇ s or less, and still more preferably 10,000 mPa ⁇ s or less).
- the MRV viscosity at ⁇ 40 ° C. means the MRV viscosity at ⁇ 40 ° C. measured according to JPI-5S-42-93.
- the MRV viscosity at ⁇ 40 ° C. is 12,000 mPa ⁇ s or less. More preferably, a lubricating oil composition having extremely excellent low-temperature viscosity characteristics of 10,000 mPa ⁇ s or less, more preferably 8,000 mPa ⁇ s, and particularly preferably 6500 mPa ⁇ s or less can be obtained.
- the blending amount of the pour point depressant is 0.05 to 2% by mass, preferably 0.1 to 1.5% by mass, based on the total amount of the composition.
- the MRV viscosity can be lowered.
- the pour point depressant has a weight average molecular weight of preferably 1 to 300,000, more preferably 50,000 to 200,000, and is particularly preferable.
- polymethacrylates are particularly preferable.
- Example 1-1 to 1-3 Comparative Examples 1-1 and 1-2
- lubricating base oils shown in Table 1 were prepared.
- the lubricating base oils of Examples 1-1 to 1-3 were obtained according to the manufacturing method of the lubricating base oil according to the fourth embodiment.
- the lubricating base oils of Comparative Examples 1-1 and 1-2 were obtained by a conventional method for producing a lubricating base oil.
- Examples 1-4 to 1-9, Comparative Examples 1-3 to 1-5 In Examples 1-4, 1-6, 1-8 and Comparative Examples 1-3, 1-5, the lubricating oil bases of Examples 1-1 to 1-3 or Comparative Examples 1-1 and 1-2, respectively. The oil was directly used as the sample oil. In Examples 1-5, 1-7 and 1-9 and Comparative Examples 1-4 and 1-6, each of Examples 1-1 to 1-3 or Comparative Examples 1-1 and 1-2 was used.
- a lubricating oil composition was prepared by adding 10% by mass and 5% by mass of a viscosity index improver (polymethacrylate type, Mw 350,000, effective concentration 50%) to obtain a sample oil.
- a viscosity index improver polymethacrylate type, Mw 350,000, effective concentration 50%
- JC08 Hot Mode Fuel Efficiency Evaluation Test For the lubricating oil compositions of Examples 1-5, 1-7, 1-9 and Comparative Examples 1-4, 1-6, a JC08 hot mode fuel efficiency evaluation test was performed according to the following procedure.
- the JC08 mode is a method for measuring the fuel consumption of automobiles set by the Ministry of Land, Infrastructure, Transport and Tourism (for details, see the Ministry of Land, Infrastructure, Transport and Tourism road safety vehicle detail specification [2009.07.30] Annex 42 Light / Medium Refer to the measurement method of car exhaust gas). JC08 is divided into a cold mode that starts when the engine is cold and a hot mode that measures when the engine is warm.
- Examples 2-1 and 2-2, Comparative Examples 2-1 and 2-3 lubricating base oils shown in Table 4 were prepared.
- the lubricating base oils of Examples 2-1 and 2-2 were obtained according to the manufacturing method of the lubricating base oil according to the fourth embodiment.
- the lubricating base oils of Comparative Examples 2-1 to 2-3 were obtained by a conventional method for producing a lubricating base oil.
- Examples 2-3 to 2-6, Comparative Examples 2-4 to 2-9 In Examples 2-3 and 2-5 and Comparative Examples 2-4, 2-6, and 2-8, the lubricating oil bases of Examples 2-1 and 2-2 or Comparative Examples 2-1 to 2-3 were used, respectively. The oil was directly used as the sample oil. In Examples 2-4 and 2-6 and Comparative Examples 2-5, 2-7, and 2-9, each of Examples 2-1 and 2-2 or Comparative Examples 2-1 to 2-3 was used. 0.8% by weight of package additives (breakdown: 60% by weight of antiwear agent, 25% by weight of antioxidant, 10% by weight of rust inhibitor and 5% by weight of metal deactivator) are added to the lubricating base oil. A lubricating oil composition was prepared and used as a sample oil.
- Examples 3-1 to 3-3, Comparative Examples 3-1 to 3-3 In Examples 3-1 to 3-3 and Comparative Examples 3-1 to 3-3, lubricating base oils shown in Table 7 were prepared. Here, the lubricating base oils of Examples 3-1 to 3-3 were obtained according to the manufacturing method of the lubricating base oil according to the fourth embodiment. On the other hand, the lubricating base oils of Comparative Examples 3-1 to 3-3 were obtained by a conventional method for producing a lubricating base oil.
- Example 3-4 to 3-6 Comparative Examples 3-4 to 3-6
- the lubricant base oils of Examples 3-1 to 3-3 or Comparative Examples 3-1 to 3-3 were respectively packaged.
- Additives (Breakdown: antiwear: 12% by mass, ashless dispersant: 50% by mass, pour point depressant: 1% by mass, antioxidant: 12% by mass, metallic detergent: 25% by mass) 8% by mass And 5 mass% of viscosity index improvers (polymethacrylate type, Mw 350,000, effective concentration 50 mass%) were added to prepare a lubricating oil composition.
Abstract
Description
[1]下記(i)、(ii)又は(iii):
(i)100℃における動粘度が3.0~5.0mm2/s、粘度指数が145以上且つ-20℃におけるSBV粘度が3,000~60,000mPa・sの炭化水素油、
(ii)100℃における動粘度が5~9mm2/s、粘度指数が155以上且つ-20℃におけるSBV粘度が3,000~30,000mPa・sの炭化水素油、
(iii)100℃における動粘度が2.0~3.0mm2/s、粘度指数が130以上且つ-30℃におけるSBV粘度が1,000~30,000mPa・sの炭化水素油、
のいずれかの条件を満たす炭化水素油である潤滑油基油。
[2]前記炭化水素油が、前記(i)の条件を満たし、且つ、-30℃におけるSBV粘度が5,000~500,000mPa・sである、[1]に記載の潤滑油基油。
[3]前記炭化水素油が、前記(i)の条件を満たし、且つ、凝固点が-20~-5℃である、[1]又は[2]に記載の潤滑油基油。
[4]前記炭化水素油が、前記(i)の条件を満たし、且つ、13C-NMR分析において、潤滑油基油を構成する全炭素に占める、主鎖を構成するCH2炭素の割合が15%以上である、[1]~[3]のいずれか一項に記載の潤滑油基油。
[5]前記炭化水素油が、前記(i)の条件を満たし、且つ、FD-MS分析において、シクロパラフィン分が50%以下である、[1]~[4]のいずれか一項に記載の潤滑油基油。
[6]前記炭化水素油が、前記(ii)の条件を満たし、且つ、-25℃におけるSBV粘度が5,000~500,000mPa・sである、[1]に記載の潤滑油基油。
[7]前記炭化水素油が、前記(ii)の条件を満たし、且つ、凝固点が-15~-5℃である、[1]又は[6]に記載の潤滑油基油。
[8]前記炭化水素油が、前記(ii)の条件を満たし、且つ、13C-NMR分析において、潤滑油基油を構成する全炭素に占める、主鎖を構成するCH2炭素の割合が20%以上である、[1]、[6]、[7]のいずれか一項に記載の潤滑油基油。
[9]前記炭化水素油が、前記(ii)の条件を満たし、且つ、FD-MS分析において、シクロパラフィン分が60%以下である、[1]、[6]、[7]、[8]のいずれか一項に記載の潤滑油基油。
[10]前記炭化水素油が、前記(iii)の条件を満たし、且つ、-35℃におけるSBV粘度が3,000~500,000mPa・sである、[1]に記載の潤滑油基油。
[11]前記炭化水素油が、前記(iii)の条件を満たし、且つ、凝固点が-30~-10℃である、[1]又は[10]に記載の潤滑油基油。
[12]前記炭化水素油が、前記(iii)の条件を満たし、且つ、13C-NMR分析において、潤滑油基油を構成する全炭素に占める、主鎖を構成するCH2炭素の割合が15%以上である、[1]、[10]、[11]のいずれか一項に記載の潤滑油基油。
[13]前記炭化水素油が、前記(iii)の条件を満たし、且つ、FD-MS分析において、シクロパラフィン分が30%以下である、[1]、[10]、[11]、[12]のいずれか一項に記載の潤滑油基油。
[14]基油留分及び該基油留分よりも重質の重質留分を含有する炭化水素油から、前記基油留分と前記重質留分とをそれぞれ分留する第1の工程と、
前記第1の工程で分留された重質留分を水素化分解し、得られる分解油を前記第1の工程に戻す第2の工程と、
前記基油留分を水素化異性化脱ろうして脱ろう油を得る第3の工程と、
前記脱ろう油を精製して精製油を得る第4の工程と、
前記精製油の分留により、下記(i)、(ii)又は(iii):
(i)100℃における動粘度が3.0~5.0mm2/s、粘度指数が145以上且つ-20℃におけるSBV粘度が3,000~60,000mPa・sの炭化水素油、
(ii)100℃における動粘度が5~9mm2/s、粘度指数が155以上且つ-20℃におけるSBV粘度が3,000~30,000mPa・sの炭化水素油、
(iii)100℃における動粘度が2.0~3.0mm2/s、粘度指数が130以上且つ-30℃におけるSBV粘度が1,000~30,000mPa・sの炭化水素油、
のいずれかの条件を満たす炭化水素油である潤滑油基油を得る第5の工程と、
を備える潤滑油基油の製造方法。
[15]前記第3の工程において得られる潤滑油基油が、前記(i)の条件を満たし、且つ、凝固点が-20~-5℃である、[14]に記載の潤滑油基油の製造方法。
[16]前記第3の工程において得られる潤滑油基油が、前記(ii)の条件を満たし、且つ、凝固点が-15~-5℃である、[14]に記載の潤滑油基油の製造方法。
[17]前記第3の工程において得られる潤滑油基油が、前記(iii)の条件を満たし、且つ、凝固点が-30~-10℃である、[14]に記載の潤滑油基油の製造方法。
[18]前記第3の工程は、ZSM-22型ゼオライト、ZSM-23型ゼオライト、SSZ32及びZSM-48型ゼオライトからなる群より選択される少なくとも1種の結晶性固体酸性物質と、活性金属として白金および/またはパラジウムを含む水素化異性化触媒の存在下、前記基油留分を水素化異性化脱ろうする工程である、[14]~[17]のいずれか一項に記載の潤滑油基油の製造方法。
[19]前記炭化水素油が、フィッシャートロプシュ合成から得られたGTLワックスあるいは、溶剤脱ろうによって得られたスラックワックスを原料として得られたものである、[14]~[18]のいずれか一項に記載の潤滑油基油の製造方法。 That is, the present invention provides a lubricating base oil shown in the following [1] to [12] and a manufacturing method of the lubricating base oil shown in the following [13] to [18].
[1] The following (i), (ii) or (iii):
(I) a hydrocarbon oil having a kinematic viscosity at 100 ° C. of 3.0 to 5.0 mm 2 / s, a viscosity index of 145 or more, and an SBV viscosity at −20 ° C. of 3,000 to 60,000 mPa · s;
(Ii) a hydrocarbon oil having a kinematic viscosity at 100 ° C. of 5 to 9 mm 2 / s, a viscosity index of 155 or more and an SBV viscosity at −20 ° C. of 3,000 to 30,000 mPa · s,
(Iii) a hydrocarbon oil having a kinematic viscosity at 100 ° C. of 2.0 to 3.0 mm 2 / s, a viscosity index of 130 or more and an SBV viscosity at −30 ° C. of 1,000 to 30,000 mPa · s,
A lubricating base oil that is a hydrocarbon oil that satisfies any of the following conditions.
[2] The lubricating base oil according to [1], wherein the hydrocarbon oil satisfies the condition (i) and has an SBV viscosity of 5,000 to 500,000 mPa · s at −30 ° C.
[3] The lubricating base oil according to [1] or [2], wherein the hydrocarbon oil satisfies the condition (i) and has a freezing point of −20 to −5 ° C.
[4] The ratio of CH 2 carbon constituting the main chain in the hydrocarbon oil satisfying the condition (i) and occupying the total carbon constituting the lubricating base oil in 13 C-NMR analysis is The lubricating base oil according to any one of [1] to [3], which is 15% or more.
[5] The hydrocarbon oil according to any one of [1] to [4], wherein the hydrocarbon oil satisfies the condition (i) and has a cycloparaffin content of 50% or less in FD-MS analysis. Lubricant base oil.
[6] The lubricating base oil according to [1], wherein the hydrocarbon oil satisfies the condition (ii) and has an SBV viscosity of 5,000 to 500,000 mPa · s at −25 ° C.
[7] The lubricating base oil according to [1] or [6], wherein the hydrocarbon oil satisfies the condition (ii) and has a freezing point of −15 to −5 ° C.
[8] The proportion of CH 2 carbon constituting the main chain in the hydrocarbon oil satisfying the condition (ii) and occupying in the total carbon constituting the lubricating base oil in 13 C-NMR analysis is The lubricating base oil according to any one of [1], [6], and [7], which is 20% or more.
[9] The hydrocarbon oil satisfies the condition (ii) and has a cycloparaffin content of 60% or less in FD-MS analysis, [1], [6], [7], [8 ] The lubricating base oil as described in any one of the above.
[10] The lubricating base oil according to [1], wherein the hydrocarbon oil satisfies the condition (iii) and has an SBV viscosity at −35 ° C. of 3,000 to 500,000 mPa · s.
[11] The lubricating base oil according to [1] or [10], wherein the hydrocarbon oil satisfies the condition (iii) and has a freezing point of −30 to −10 ° C.
[12] The hydrocarbon oil satisfies the condition (iii), and in 13 C-NMR analysis, the proportion of CH 2 carbon constituting the main chain in the total carbon constituting the lubricating oil base oil is The lubricating base oil according to any one of [1], [10], and [11], which is 15% or more.
[13] The hydrocarbon oil satisfies the condition (iii) and has a cycloparaffin content of 30% or less in the FD-MS analysis. [1], [10], [11], [12 ] The lubricating base oil as described in any one of the above.
[14] A first fraction in which the base oil fraction and the heavy fraction are each fractionated from a base oil fraction and a hydrocarbon oil containing a heavy fraction heavier than the base oil fraction. Process,
A second step of hydrocracking the heavy fraction fractionated in the first step and returning the resulting cracked oil to the first step;
A third step of hydroisomerizing and dewaxing the base oil fraction to obtain a dewaxed oil;
A fourth step of refining the dewaxed oil to obtain a refined oil;
By fractional distillation of the refined oil, the following (i), (ii) or (iii):
(I) a hydrocarbon oil having a kinematic viscosity at 100 ° C. of 3.0 to 5.0 mm 2 / s, a viscosity index of 145 or more, and an SBV viscosity at −20 ° C. of 3,000 to 60,000 mPa · s;
(Ii) a hydrocarbon oil having a kinematic viscosity at 100 ° C. of 5 to 9 mm 2 / s, a viscosity index of 155 or more and an SBV viscosity at −20 ° C. of 3,000 to 30,000 mPa · s,
(Iii) a hydrocarbon oil having a kinematic viscosity at 100 ° C. of 2.0 to 3.0 mm 2 / s, a viscosity index of 130 or more and an SBV viscosity at −30 ° C. of 1,000 to 30,000 mPa · s,
A fifth step of obtaining a lubricating base oil that is a hydrocarbon oil that satisfies any of the following conditions:
A method for producing a lubricating base oil comprising:
[15] The lubricating base oil according to [14], wherein the lubricating base oil obtained in the third step satisfies the condition (i) and has a freezing point of −20 to −5 ° C. Production method.
[16] The lubricant base oil according to [14], wherein the lubricant base oil obtained in the third step satisfies the condition (ii) and has a freezing point of −15 to −5 ° C. Production method.
[17] The lubricating base oil according to [14], wherein the lubricating base oil obtained in the third step satisfies the condition (iii) and has a freezing point of −30 to −10 ° C. Production method.
[18] The third step includes at least one crystalline solid acidic substance selected from the group consisting of ZSM-22 type zeolite, ZSM-23 type zeolite, SSZ32 and ZSM-48 type zeolite, and an active metal. The lubricating oil according to any one of [14] to [17], which is a step of hydroisomerizing and dewaxing the base oil fraction in the presence of a hydroisomerization catalyst containing platinum and / or palladium. A method for producing a base oil.
[19] Any one of [14] to [18], wherein the hydrocarbon oil is obtained using GTL wax obtained from Fischer-Tropsch synthesis or slack wax obtained by solvent dewaxing as a raw material. The manufacturing method of the lubricating base oil of description to term.
すなわち、試験管にとった試料を46℃まで予備加熱した後、2.5℃/分で冷却していき、予想の凝固点(事前に一度測定)よりも10℃高い温度から冷却速度を1℃/分に変更し測定を開始する。この方法により、JISに比べ再現性の凝固点を得る事が可能である。この凝固点はJIS K 2269-1987(JIS法流動点)により測定される流動点とは区別されるものである。なお、本発明者の検討によれば、JISで定める流動点は、多成分の混合物である石油系潤滑油基油のように、結晶化温度の大きく異なる液体を測定するのには適している。しかし、当該発明のようにパラフィンのみの単一成分では、傾けたときの流動性を評価するJISの測定方法では流動しないが、外的に力を与えると流動することか確認され、実際の流動性を現していない。この要因として組成的な面もあるが、2.5℃/分という温度低下速度も影響しており、結晶化が完全に進まない状況で判断していることも要因として考えられる。そのため、温度の降下速度を遅くすることで、基油分子の流動性を促進しより真値に近い凝固点をえることが必要である。 Moreover, the freezing point as used in the field of this invention means the value measured by the following procedures.
That is, a sample taken in a test tube is preheated to 46 ° C. and then cooled at 2.5 ° C./min. The cooling rate is 1 ° C. from a temperature 10 ° C. higher than the expected freezing point (measured once in advance). Change to / min and start measurement. By this method, it is possible to obtain a reproducible freezing point as compared with JIS. This freezing point is distinct from the pour point measured according to JIS K 2269-1987 (JIS method pour point). According to the study by the present inventor, the pour point determined by JIS is suitable for measuring liquids having greatly different crystallization temperatures, such as petroleum-based lubricating base oils, which are multicomponent mixtures. . However, a single component of only paraffin as in the present invention does not flow by the JIS measurement method for evaluating the fluidity when tilted, but it is confirmed that it flows when an external force is applied. It does not show sex. This factor also has a compositional aspect, but the temperature decrease rate of 2.5 ° C./min also has an influence, and it is considered that the determination is made in a situation where crystallization does not proceed completely. Therefore, it is necessary to promote the fluidity of the base oil molecules and to obtain a freezing point closer to the true value by slowing the rate of temperature decrease.
すなわち、本発明では、13C-NMRの測定の際に、サンプルとして試料0.5gに重クロロホルム3gを加えて希釈したものを使用し、測定温度を室温、共鳴周波数を100MHzとした。また、測定方はゲート付でカップリング法を使用した。
本発明の潤滑油基油の構成炭素の全量に占めるCH2の割合は、13C-NMRにより測定される、全炭素の積分強度の合計に対するCH2主鎖に起因する積分強度の合計の割合を意味するが、同等の結果が得られるのであればその他の方法を用いてもよい。 Further, the ratio of CH 2 carbon constituting the main chain to the total carbon constituting the lubricating base oil can be determined, for example, by performing 13 C-NMR analysis under the following analysis conditions.
That is, in the present invention, at the time of 13 C-NMR measurement, a sample obtained by diluting 0.5 g of a sample with 3 g of deuterated chloroform was used, the measurement temperature was room temperature, and the resonance frequency was 100 MHz. Moreover, the measuring method used the coupling method with a gate.
The ratio of CH 2 to the total amount of constituent carbon of the lubricating base oil of the present invention is the ratio of the total integrated intensity due to the CH 2 main chain to the total integrated intensity of all carbon, as measured by 13 C-NMR. However, other methods may be used as long as an equivalent result is obtained.
FD法とは、試料をエミッター上に塗布し、エミッターに電流を流すことで塗布した試料を加熱し、エミッター表面やウィスカー先端近傍の高電界におけるトンネル効果を利用したイオン化法である。本発明では、日本電子JMS-AX505Hを使用し、加速電圧(カソード電圧)3.0kV、エミッタ電流2mA/minの条件にて測定した。質量分析での化合物の種類は、形成される特有イオンにより決定され、通常、z数により分類される。このz数は全ての炭化水素種について一般式CnH2n+zで示される。この飽和物相は芳香族物相とは別途分析されるので、同じ化学両論の異なるシクロパラフィンの含有量を測定することが可能である。なお、シクロパラフィンには1環シクロパラフィン及び2環以上のシクロパラフィンの双方が包含される。 In addition, the ratio of the cycloparaffin content can be determined, for example, by performing FD-MS analysis under the following analysis conditions.
The FD method is an ionization method in which a sample is applied on an emitter, the applied sample is heated by passing an electric current through the emitter, and the tunnel effect in a high electric field near the emitter surface and the whisker tip is used. In the present invention, JEOL JMS-AX505H was used, and measurement was performed under the conditions of an acceleration voltage (cathode voltage) of 3.0 kV and an emitter current of 2 mA / min. The type of compound in mass spectrometry is determined by the specific ions that are formed, and is usually classified by the z number. This z number is represented by the general formula C n H 2n + z for all hydrocarbon species. Since this saturated phase is analyzed separately from the aromatic phase, it is possible to measure the content of different cycloparaffins having the same stoichiometry. The cycloparaffin includes both one-ring cycloparaffin and two or more cycloparaffins.
本発明の第1実施形態に係る潤滑油基油は、100℃における動粘度が3.0~5.0mm2/s且つ-20℃におけるSBV粘度が3,000~60,000mPa・sの炭化水素油である。 [First Embodiment: Lubricating base oil that is a hydrocarbon oil that satisfies the condition (i)]
The lubricating base oil according to the first embodiment of the present invention is carbonized with a kinematic viscosity at 100 ° C. of 3.0 to 5.0 mm 2 / s and an SBV viscosity at −20 ° C. of 3,000 to 60,000 mPa · s. Hydrogen oil.
ρ=0.0025×kv100+0.816 (1)
[式中、kv100は潤滑油基油の100℃における動粘度(mm2/s)を示す。] Further, the density (ρ 15 ) at 15 ° C. of the lubricating base oil according to the present embodiment is preferably not more than the value of ρ represented by the following formula (1), that is, ρ 15 ≦ ρ.
ρ = 0.0025 × kv100 + 0.816 (1)
[Wherein, kv100 represents the kinematic viscosity (mm 2 / s) of the lubricating base oil at 100 ° C. ]
ρ=0.0025×kv100+0.816 (1)
[式中、kv100は潤滑油基油の100℃における動粘度(mm2/s)を示す。] Further, the density (ρ 15 ) at 15 ° C. of the lubricating base oil according to the present embodiment is preferably not more than the value of ρ represented by the following formula (1), that is, ρ 15 ≦ ρ.
ρ = 0.0025 × kv100 + 0.816 (1)
[Wherein, kv100 represents the kinematic viscosity (mm 2 / s) of the lubricating base oil at 100 ° C. ]
本発明の第3実施形態に係る潤滑油基油は、100℃における動粘度が2.0~3.0mm2/s、粘度指数が130以上且つ-30℃におけるSBV粘度が1,000~30,000mPa・sの炭化水素油である。 [Third Embodiment: Lubricating base oil that is a hydrocarbon oil that satisfies the condition (iii)]
The lubricating base oil according to the third embodiment of the present invention has a kinematic viscosity at 100 ° C. of 2.0 to 3.0 mm 2 / s, a viscosity index of 130 or more, and an SBV viscosity at −30 ° C. of 1,000 to 30. , 000 mPa · s hydrocarbon oil.
ρ=0.0025×kv100+0.816 (1)
[式中、kv100は潤滑油基油の100℃における動粘度(mm2/s)を示す。] Further, the density (ρ 15 ) at 15 ° C. of the lubricating base oil according to the present embodiment is preferably not more than the value of ρ represented by the following formula (1), that is, ρ 15 ≦ ρ.
ρ = 0.0025 × kv100 + 0.816 (1)
[Wherein, kv100 represents the kinematic viscosity (mm 2 / s) of the lubricating base oil at 100 ° C. ]
本発明の第4実施形態に係る潤滑油基油の製造方法は、
基油留分及び該基油留分よりも重質の重質留分を含有する炭化水素油から、前記基油留分と前記重質留分とをそれぞれ分留する第1の工程と、
前記第1の工程で分留された重質留分を水素化分解し、得られる分解油を前記第1の工程に戻す第2の工程と、
前記基油留分を水素化異性化脱ろうして脱ろう油を得る第3の工程と、
前記脱ろう油を精製して精製油を得る第4の工程と、
前記精製油の分留により、下記(i)、(ii)又は(iii):
(i)100℃における動粘度が3.0~5.0mm2/s、粘度指数が145以上且つ-20℃におけるSBV粘度が3,000~60,000mPa・sの炭化水素油、
(ii)100℃における動粘度が5~9mm2/s、粘度指数が155以上且つ-20℃におけるSBV粘度が3,000~30,000mPa・sの炭化水素油、
(iii)100℃における動粘度が2.0~3.0mm2/s、粘度指数が130以上且つ-30℃におけるSBV粘度が1,000~30,000mPa・sの炭化水素油、
のいずれかの条件を満たす炭化水素油である潤滑油基油を得る第5の工程と、
を備える。 [Fourth Embodiment: Method for Producing Lubricating Base Oil]
The method for producing a lubricating base oil according to the fourth embodiment of the present invention,
A first step of fractionating the base oil fraction and the heavy fraction from a base oil fraction and a hydrocarbon oil containing a heavier fraction heavier than the base oil fraction,
A second step of hydrocracking the heavy fraction fractionated in the first step and returning the resulting cracked oil to the first step;
A third step of hydroisomerizing and dewaxing the base oil fraction to obtain a dewaxed oil;
A fourth step of refining the dewaxed oil to obtain a refined oil;
By fractional distillation of the refined oil, the following (i), (ii) or (iii):
(I) a hydrocarbon oil having a kinematic viscosity at 100 ° C. of 3.0 to 5.0 mm 2 / s, a viscosity index of 145 or more, and an SBV viscosity at −20 ° C. of 3,000 to 60,000 mPa · s;
(Ii) a hydrocarbon oil having a kinematic viscosity at 100 ° C. of 5 to 9 mm 2 / s, a viscosity index of 155 or more and an SBV viscosity at −20 ° C. of 3,000 to 30,000 mPa · s,
(Iii) a hydrocarbon oil having a kinematic viscosity at 100 ° C. of 2.0 to 3.0 mm 2 / s, a viscosity index of 130 or more and an SBV viscosity at −30 ° C. of 1,000 to 30,000 mPa · s,
A fifth step of obtaining a lubricating base oil that is a hydrocarbon oil that satisfies any of the following conditions:
Is provided.
本態様の水素化異性化触媒は、特定の方法によって製造されることでその特徴が付与される。以下、本態様の水素化異性化触媒について、その好ましい製造の態様に沿って説明する。 <Specific Embodiment of Hydroisomerization Catalyst>
The characteristics of the hydroisomerization catalyst of this embodiment are imparted by being produced by a specific method. Hereinafter, the hydroisomerization catalyst of this aspect is demonstrated along the aspect of the preferable manufacture.
VZ=Vc/Mz×100 Micropore volume V Z per unit mass of zeolite contained in the catalyst, for example, if the binder does not have a micropore volume, the value of the micropore volume per unit mass of the hydroisomerization catalyst It can be calculated according to the following formula from V c and the content ratio M z (mass%) of the zeolite in the catalyst.
V Z = V c / M z × 100
実施例1-1~1-3及び比較例1-1、1-2においては、それぞれ表1に示す潤滑油基油を調製した。ここで、実施例1-1~1-3の潤滑油基油は、上記第4の実施形態に係る潤滑油基油の製造方法に準じて得られたものである。一方、比較例1-1、1-2の潤滑油基油は、従来の潤滑油基油の製造方法によって得られたものである。各基油の各種性状、並びに荷重50N(平均ヘルツ圧0.60GPa),試料油温度50℃,周速1m/s,すべり率3%,27.4mmの鋼球とスチールディスクを用いた条件下で測定したトラクション係数を表1に示す。 [Examples 1-1 to 1-3, Comparative Examples 1-1 and 1-2]
In Examples 1-1 to 1-3 and Comparative Examples 1-1 and 1-2, lubricating base oils shown in Table 1 were prepared. Here, the lubricating base oils of Examples 1-1 to 1-3 were obtained according to the manufacturing method of the lubricating base oil according to the fourth embodiment. On the other hand, the lubricating base oils of Comparative Examples 1-1 and 1-2 were obtained by a conventional method for producing a lubricating base oil. Various properties of each base oil and conditions using steel balls and steel disks with a load of 50 N (average Hertz pressure 0.60 GPa), sample oil temperature 50 ° C., peripheral speed 1 m / s, slip rate 3%, 27.4 mm Table 1 shows the traction coefficients measured in (1).
実施例1-4、1-6、1-8及び比較例1-3、1-5においては、それぞれ実施例1-1~1-3又は比較例1-1、1-2の潤滑油基油をそのまま試料油とした。また、実施例1-5、1-7、1-9及び比較例1-4、1-6においては、それぞれ実施例1-1~1-3又は比較例1-1、1-2の各潤滑油基油に、パッケージ添加剤(内訳:無灰分散剤40質量%、金属系清浄剤40質量%、摩耗防止剤10質量%、酸化防止剤8質量%および金属不活性化剤2質量%)10質量%及び粘度指数向上剤(ポリメタクリレート系、Mw350,000、有効濃度50%)5質量%を添加して潤滑油組成物を調製し、試料油とした。また、比較例1-7として、市販の0W-20油を用意した。各潤滑油組成物の動粘度及び粘度指数を表2に示す。 [Examples 1-4 to 1-9, Comparative Examples 1-3 to 1-5]
In Examples 1-4, 1-6, 1-8 and Comparative Examples 1-3, 1-5, the lubricating oil bases of Examples 1-1 to 1-3 or Comparative Examples 1-1 and 1-2, respectively. The oil was directly used as the sample oil. In Examples 1-5, 1-7 and 1-9 and Comparative Examples 1-4 and 1-6, each of Examples 1-1 to 1-3 or Comparative Examples 1-1 and 1-2 was used. In addition to lubricating base oil, package additives (breakdown: ashless dispersant 40% by weight, metallic detergent 40% by weight, antiwear agent 10% by weight, antioxidant 8% by weight and metal deactivator 2% by weight) A lubricating oil composition was prepared by adding 10% by mass and 5% by mass of a viscosity index improver (polymethacrylate type, Mw 350,000, effective concentration 50%) to obtain a sample oil. As Comparative Example 1-7, a commercially available 0W-20 oil was prepared. Table 2 shows the kinematic viscosity and viscosity index of each lubricating oil composition.
実施例1-4~1-9及び比較例1-3~1-6の試料油について、以下の手順により、オイル漏洩試験を実施した。
200mlオートクレーブに試料油を100ml入れ、NBRのパッキンを用い、トルクレンチにより250N・mの締め付けトルクで組み上げる。上部には二方コックを用い、シール材にはテフロン(登録商標)パッキンを使用し、トルクレンチにより250N・mの締め付けトルクで組み上げる。組み上げ後、窒素ガスで200kPaに加圧しする。各資料油について同様の作業を実施し-30±1℃に制御された低温恒温槽に逆さまにセットする。結果は48時間後のNBRパッキンからの油の漏洩で評価し、漏洩のあったものは有、認められなかったものは無とした。
得られた結果を表2、3に示す。 [Oil leak test]
For the sample oils of Examples 1-4 to 1-9 and Comparative Examples 1-3 to 1-6, an oil leakage test was performed according to the following procedure.
Put 100ml of sample oil in a 200ml autoclave and assemble it with NBR packing and tightening torque of 250N · m with torque wrench. A two-way cock is used for the upper part, Teflon (registered trademark) packing is used for the sealing material, and a torque wrench is used to assemble with a tightening torque of 250 N · m. After assembly, the pressure is increased to 200 kPa with nitrogen gas. Carry out the same operation for each sample oil and place it upside down in a low temperature thermostat controlled at -30 ± 1 ° C. The results were evaluated by oil leakage from the NBR packing after 48 hours. Some were leaked and some were not.
The obtained results are shown in Tables 2 and 3.
実施例1-5、1-7、1-9及び比較例1-4、1-6の潤滑油組成物について、以下の手順により、JC08ホットモード燃費評価試験を実施した。
JC08モードは国土交通省が定めた自動車の燃費消費を測定する方法である(詳細は国土交通省 道路運送車両の保安基準の細目を定める告示[2009.07.30]別添42 軽・中量車排出ガスの測定方法参照)。JC08はエンジンが冷えた状態でスタートするコールドモードとエンジンが暖まった状態で測定するホットモードに分けられる。試験には2.5L、FFのガソリンエンジン車(トヨタエスティマ)を選定し、試験開始前にエンジン洗浄および新たに調合された試料油を充填し、シャシダイナモメータ上で試験自動車を60±2km/hの定速で15分間以上暖機運転させた後、速やかにアイドリング状態に戻して所定の走行パターンで運転し排気ガスより消費燃料を計算して燃費を算出した。得られた結果を表2、3に示す。 [JC08 Hot Mode Fuel Efficiency Evaluation Test]
For the lubricating oil compositions of Examples 1-5, 1-7, 1-9 and Comparative Examples 1-4, 1-6, a JC08 hot mode fuel efficiency evaluation test was performed according to the following procedure.
The JC08 mode is a method for measuring the fuel consumption of automobiles set by the Ministry of Land, Infrastructure, Transport and Tourism (for details, see the Ministry of Land, Infrastructure, Transport and Tourism road safety vehicle detail specification [2009.07.30] Annex 42 Light / Medium Refer to the measurement method of car exhaust gas). JC08 is divided into a cold mode that starts when the engine is cold and a hot mode that measures when the engine is warm. A 2.5-liter, FF gasoline engine car (Toyota Estima) was selected for the test, the engine was cleaned and filled with newly prepared sample oil before the start of the test, and the test car was placed on the chassis dynamometer at 60 ± 2 km / After warming up for 15 minutes or more at a constant speed of h, the engine was quickly returned to the idling state and operated in a predetermined traveling pattern, and fuel consumption was calculated from exhaust gas to calculate fuel consumption. The obtained results are shown in Tables 2 and 3.
実施例2-1、2-2及び比較例2-1~2-3においては、それぞれ表4に示す潤滑油基油を調製した。ここで、実施例2-1、2-2の潤滑油基油は、上記第4実施形態に係る潤滑油基油の製造方法に準じて得られたものである。一方、比較例2-1~2-3の潤滑油基油は、従来の潤滑油基油の製造方法によって得られたものである。各基油の各種性状、並びに荷重50N(平均ヘルツ圧0.60GPa),試料油温度50℃,周速1m/s,すべり率3%,27.4mmの鋼球とスチールディスクを用いた条件下で測定したトラクション係数を表4に示す。 [Examples 2-1 and 2-2, Comparative Examples 2-1 and 2-3]
In Examples 2-1 and 2-2 and Comparative Examples 2-1 to 2-3, lubricating base oils shown in Table 4 were prepared. Here, the lubricating base oils of Examples 2-1 and 2-2 were obtained according to the manufacturing method of the lubricating base oil according to the fourth embodiment. On the other hand, the lubricating base oils of Comparative Examples 2-1 to 2-3 were obtained by a conventional method for producing a lubricating base oil. Various properties of each base oil and conditions using steel balls and steel disks with a load of 50 N (average Hertz pressure 0.60 GPa), sample oil temperature 50 ° C., peripheral speed 1 m / s, slip rate 3%, 27.4 mm Table 4 shows the traction coefficient measured in (4).
実施例2-3、2-5及び比較例2-4、2-6、2-8においては、それぞれ実施例2-1、2-2又は比較例2-1~2-3の潤滑油基油をそのまま試料油とした。また、実施例2-4、2-6及び比較例2-5、2-7、2-9においては、それぞれ実施例2-1、2-2又は比較例2-1~2-3の各潤滑油基油に、パッケージ添加剤(内訳:摩耗防止剤60質量%、酸化防止剤25質量%、錆止め剤10質量%および金属不活性化剤5質量%)0.8質量%を添加して潤滑油組成物を調製し、試料油とした。 [Examples 2-3 to 2-6, Comparative Examples 2-4 to 2-9]
In Examples 2-3 and 2-5 and Comparative Examples 2-4, 2-6, and 2-8, the lubricating oil bases of Examples 2-1 and 2-2 or Comparative Examples 2-1 to 2-3 were used, respectively. The oil was directly used as the sample oil. In Examples 2-4 and 2-6 and Comparative Examples 2-5, 2-7, and 2-9, each of Examples 2-1 and 2-2 or Comparative Examples 2-1 to 2-3 was used. 0.8% by weight of package additives (breakdown: 60% by weight of antiwear agent, 25% by weight of antioxidant, 10% by weight of rust inhibitor and 5% by weight of metal deactivator) are added to the lubricating base oil. A lubricating oil composition was prepared and used as a sample oil.
実施例2-3~2-6及び比較例2-4~2-9の試料油について、以下の手順により、オイル漏洩試験を実施した。
200mlオートクレーブに試料油を100ml入れ、NBRのパッキンを用い、トルクレンチにより250N・mの締め付けトルクで組み上げる。上部には二方コックを用い、シール材にはテフロン(登録商標)パッキンを使用し、トルクレンチにより250N・mの締め付けトルクで組み上げる。組み上げ後、窒素ガスで300kPaに加圧しする。各資料油について同様の作業を実施し-30±1℃に制御された低温恒温槽に逆さまにセットする。結果は48時間後のNBRパッキンからの油の漏洩で評価し、漏洩のあったものは有、認められなかったものは無とした。
得られた結果を表5、6に示す。 [Oil leak test]
For the sample oils of Examples 2-3 to 2-6 and Comparative Examples 2-4 to 2-9, an oil leakage test was performed according to the following procedure.
Put 100ml of sample oil in a 200ml autoclave and assemble it with NBR packing and tightening torque of 250N · m with torque wrench. A two-way cock is used for the upper part, Teflon (registered trademark) packing is used for the sealing material, and a torque wrench is used to assemble with a tightening torque of 250 N · m. After assembly, the pressure is increased to 300 kPa with nitrogen gas. Carry out the same operation for each sample oil and place it upside down in a low temperature thermostat controlled at -30 ± 1 ° C. The results were evaluated by oil leakage from the NBR packing after 48 hours. Some were leaked and some were not.
The results obtained are shown in Tables 5 and 6.
実施例2-3~2-6及び比較例2-4~2-9の試料油について、以下の手順により、貯蔵安定性試験を実施した。
100mlのスクリュー管に2/3以上油をいれ、各々の試験管を0±1℃の冷蔵庫にいれ、48時間後の外観を確認する。外観に変化のない場合は変化無、曇りの生じたものは曇りと評価する。 [Storage stability test]
For the sample oils of Examples 2-3 to 2-6 and Comparative Examples 2-4 to 2-9, a storage stability test was performed according to the following procedure.
Add 2/3 or more oil into a 100 ml screw tube, put each test tube in a refrigerator at 0 ± 1 ° C., and check the appearance after 48 hours. When there is no change in the appearance, no change is observed.
実施例2-4、2-6及び比較例2-5、2-7、2-9の潤滑油組成物について、以下の手順により、省エネルギー性評価試験を実施した。
省エネルギー性は小型油圧ユニットを用いて評価した。小型油圧ユニットはポンプに可変容量型ピストンポンプを使用し、油量15L、油温80±2℃と低温始動時を考慮した0℃とし、市販の作動油(0W-20、40℃における動粘度:32.8mm2/s、粘度指数:125)を用いて吐出圧力を0.8から2.4MPaまで変化させたときのモーターの入力電力を測定した。ついで、実施例3、4及び比較例4~6の各潤滑油組成物を試料油としてモーターの入力電力を測定し、比較例7の試料油との消費電力の差異から省エネルギー性を評価した。
得られた結果を表5、6に示す。 [Energy saving evaluation test]
The lubricating oil compositions of Examples 2-4 and 2-6 and Comparative Examples 2-5, 2-7, and 2-9 were subjected to an energy saving evaluation test according to the following procedure.
Energy conservation was evaluated using a small hydraulic unit. The small hydraulic unit uses a variable displacement piston pump. The oil volume is 15 liters, the oil temperature is 80 ± 2 ° C, and 0 ° C is taken into account when starting at low temperatures. Commercial hydraulic oil (kinematic viscosity at 0W-20, 40 ° C) : 32.8 mm 2 / s, viscosity index: 125), and the input power of the motor was measured when the discharge pressure was changed from 0.8 to 2.4 MPa. Subsequently, the input power of the motor was measured using the lubricating oil compositions of Examples 3 and 4 and Comparative Examples 4 to 6 as sample oil, and the energy saving property was evaluated from the difference in power consumption with the sample oil of Comparative Example 7.
The results obtained are shown in Tables 5 and 6.
実施例3-1~3-3及び比較例3-1~3-3においては、それぞれ表7に示す潤滑油基油を調製した。ここで、実施例3-1~3-3の潤滑油基油は、上記第4実施形態に係る潤滑油基油の製造方法に準じて得られたものである。一方、比較例3-1~3-3の潤滑油基油は、従来の潤滑油基油の製造方法によって得られたものである。各基油の各種性状、並びに荷重50N(平均ヘルツ圧0.60GPa),試料油温度50℃,周速1m/s,すべり率3%,27.4mmの鋼球とスチールディスクを用いた条件下で測定したトラクション係数を表7に示す。 [Examples 3-1 to 3-3, Comparative Examples 3-1 to 3-3]
In Examples 3-1 to 3-3 and Comparative Examples 3-1 to 3-3, lubricating base oils shown in Table 7 were prepared. Here, the lubricating base oils of Examples 3-1 to 3-3 were obtained according to the manufacturing method of the lubricating base oil according to the fourth embodiment. On the other hand, the lubricating base oils of Comparative Examples 3-1 to 3-3 were obtained by a conventional method for producing a lubricating base oil. Various properties of each base oil and conditions using steel balls and steel disks with a load of 50 N (average Hertz pressure 0.60 GPa), sample oil temperature 50 ° C., peripheral speed 1 m / s, slip rate 3%, 27.4 mm Table 7 shows the traction coefficients measured in (1).
実施例3-4~3-6及び比較例3-4~3-6においては、それぞれ実施例3-1~3-3又は比較例3-1~3-3の潤滑油基油に、パッケージ添加剤(内訳:摩耗防止剤:12質量%、無灰分散剤:50質量%、流動点降下剤:1質量%、酸化防止剤:12質量%、金属系清浄剤:25質量%)8質量%及び粘度指数向上剤(ポリメタクリレート系、Mw350,000、有効濃度50質量%)5質量%を添加し、潤滑油組成物を調製した。 [Examples 3-4 to 3-6, Comparative Examples 3-4 to 3-6]
In Examples 3-4 to 3-6 and Comparative Examples 3-4 to 3-6, the lubricant base oils of Examples 3-1 to 3-3 or Comparative Examples 3-1 to 3-3 were respectively packaged. Additives (Breakdown: antiwear: 12% by mass, ashless dispersant: 50% by mass, pour point depressant: 1% by mass, antioxidant: 12% by mass, metallic detergent: 25% by mass) 8% by mass And 5 mass% of viscosity index improvers (polymethacrylate type, Mw 350,000, effective concentration 50 mass%) were added to prepare a lubricating oil composition.
実施例3-4~3-9及び比較例3-4~3-9の試料油について、以下の手順により、オイル漏洩試験を実施した。
すなわち、低温漏洩性試験として、実際のミッションを用い、ミッションに試料油を封入し低温保管して油の漏れ(にじみ)を評価した。得られた結果を表8、9に示す。 [Oil leak test]
For the sample oils of Examples 3-4 to 3-9 and Comparative Examples 3-4 to 3-9, an oil leakage test was performed according to the following procedure.
That is, as a low-temperature leakage test, an actual mission was used, sample oil was enclosed in the mission and stored at a low temperature, and oil leakage (bleeding) was evaluated. The obtained results are shown in Tables 8 and 9.
実施例3-4~3-9及び比較例3-4~3-9の試料油について、以下の手順により、貯蔵安定性試験を実施した。
100mlのスクリュー管に2/3以上油をいれ、各々の試験管を0±1℃の冷蔵庫にいれ、48時間後の外観を確認する。外観に変化のない場合は変化無、曇りの生じたものは曇りと評価する。 [Storage stability test]
For the sample oils of Examples 3-4 to 3-9 and Comparative Examples 3-4 to 3-9, a storage stability test was performed according to the following procedure.
Add 2/3 or more oil into a 100 ml screw tube, put each test tube in a refrigerator at 0 ± 1 ° C., and check the appearance after 48 hours. When there is no change in the appearance, no change is observed.
実施例3-4、3-6、3-8及び比較例3-4、3-6、3-8の潤滑油について、高圧摩擦試験機を用いて低温転がり軸受け試験を実施した。すなわち、常圧条件下、冷却ジャケットにより測定部位を0℃に冷却し、4時間温度を保持する。試験片としては円筒転がり軸受を用い、摩擦係数を評価した。得られた結果を表8、9に示す。表7中の摩擦係数が小さいことは、特に転がり初期の摩擦係数の低減に優れることを意味し、実機での低温始動性と相関がある。 [Low temperature rolling bearing test]
The lubricating oils of Examples 3-4, 3-6, 3-8 and Comparative Examples 3-4, 3-6, 3-8 were subjected to a low temperature rolling bearing test using a high pressure friction tester. That is, the measurement site is cooled to 0 ° C. with a cooling jacket under normal pressure conditions, and the temperature is maintained for 4 hours. A cylindrical rolling bearing was used as a test piece, and the friction coefficient was evaluated. The obtained results are shown in Tables 8 and 9. A small friction coefficient in Table 7 means that it is particularly excellent in reducing the friction coefficient at the beginning of rolling, and has a correlation with low temperature startability in an actual machine.
Claims (19)
- 下記(i)、(ii)又は(iii):
(i)100℃における動粘度が3.0~5.0mm2/s、粘度指数が145以上且つ-20℃におけるSBV粘度が3,000~60,000mPa・sの炭化水素油、
(ii)100℃における動粘度が5~9mm2/s、粘度指数が155以上且つ-20℃におけるSBV粘度が3,000~30,000mPa・sの炭化水素油、
(iii)100℃における動粘度が2.0~3.0mm2/s、粘度指数が130以上且つ-30℃におけるSBV粘度が1,000~30,000mPa・sの炭化水素油、
のいずれかの条件を満たす炭化水素油である潤滑油基油。 (I), (ii) or (iii) below:
(I) a hydrocarbon oil having a kinematic viscosity at 100 ° C. of 3.0 to 5.0 mm 2 / s, a viscosity index of 145 or more, and an SBV viscosity at −20 ° C. of 3,000 to 60,000 mPa · s;
(Ii) a hydrocarbon oil having a kinematic viscosity at 100 ° C. of 5 to 9 mm 2 / s, a viscosity index of 155 or more and an SBV viscosity at −20 ° C. of 3,000 to 30,000 mPa · s,
(Iii) a hydrocarbon oil having a kinematic viscosity at 100 ° C. of 2.0 to 3.0 mm 2 / s, a viscosity index of 130 or more and an SBV viscosity at −30 ° C. of 1,000 to 30,000 mPa · s,
A lubricating base oil that is a hydrocarbon oil that satisfies any of the following conditions. - 前記炭化水素油が、前記(i)の条件を満たし、且つ、-30℃におけるSBV粘度が5,000~500,000mPa・sである、請求項1に記載の潤滑油基油。 The lubricating base oil according to claim 1, wherein the hydrocarbon oil satisfies the condition (i) and has an SBV viscosity at -30 ° C of 5,000 to 500,000 mPa · s.
- 前記炭化水素油が、前記(i)の条件を満たし、且つ、凝固点が-20~-5℃である、請求項1又は2に記載の潤滑油基油。 The lubricating base oil according to claim 1 or 2, wherein the hydrocarbon oil satisfies the condition (i) and has a freezing point of -20 to -5 ° C.
- 前記炭化水素油が、前記(i)の条件を満たし、且つ、13C-NMR分析において、潤滑油基油を構成する全炭素に占める、主鎖を構成するCH2炭素の割合が15%以上である、請求項1~3のいずれか一項に記載の潤滑油基油。 The hydrocarbon oil satisfies the above condition (i), and in 13 C-NMR analysis, the proportion of CH 2 carbon constituting the main chain in the total carbon constituting the lubricating base oil is 15% or more. The lubricating base oil according to any one of claims 1 to 3, wherein
- 前記炭化水素油が、前記(i)の条件を満たし、且つ、FD-MS分析において、シクロパラフィン分が50%以下である、請求項1~4のいずれか一項に記載の潤滑油基油。 The lubricating base oil according to any one of claims 1 to 4, wherein the hydrocarbon oil satisfies the condition (i) and has a cycloparaffin content of 50% or less in FD-MS analysis. .
- 前記炭化水素油が、前記(ii)の条件を満たし、且つ、-25℃におけるSBV粘度が5,000~500,000mPa・sである、請求項1に記載の潤滑油基油。 The lubricating base oil according to claim 1, wherein the hydrocarbon oil satisfies the condition (ii) and has an SBV viscosity at -25 ° C of 5,000 to 500,000 mPa · s.
- 前記炭化水素油が、前記(ii)の条件を満たし、且つ、凝固点が-15~-5℃である、請求項1又は6に記載の潤滑油基油。 The lubricating base oil according to claim 1 or 6, wherein the hydrocarbon oil satisfies the condition (ii) and has a freezing point of -15 to -5 ° C.
- 前記炭化水素油が、前記(ii)の条件を満たし、且つ、13C-NMR分析において、潤滑油基油を構成する全炭素に占める、主鎖を構成するCH2炭素の割合が20%以上である、請求項1、6、7のいずれか一項に記載の潤滑油基油。 The hydrocarbon oil satisfies the above condition (ii), and in 13 C-NMR analysis, the proportion of CH 2 carbon constituting the main chain in the total carbon constituting the lubricating base oil is 20% or more. The lubricating base oil according to any one of claims 1, 6, and 7, wherein
- 前記炭化水素油が、前記(ii)の条件を満たし、且つ、FD-MS分析において、シクロパラフィン分が60%以下である、請求項1、6、7、8のいずれか一項に記載の潤滑油基油。 9. The hydrocarbon oil according to claim 1, wherein the hydrocarbon oil satisfies the condition (ii) and has a cycloparaffin content of 60% or less in FD-MS analysis. Lubricating base oil.
- 前記炭化水素油が、前記(iii)の条件を満たし、且つ、-35℃におけるSBV粘度が3,000~500,000mPa・sである、請求項1に記載の潤滑油基油。 The lubricating base oil according to claim 1, wherein the hydrocarbon oil satisfies the condition (iii) and has an SBV viscosity at -35 ° C of 3,000 to 500,000 mPa · s.
- 前記炭化水素油が、前記(iii)の条件を満たし、且つ、凝固点が-30~-10℃である、請求項1又は10に記載の潤滑油基油。 The lubricating base oil according to claim 1 or 10, wherein the hydrocarbon oil satisfies the condition (iii) and has a freezing point of -30 to -10 ° C.
- 前記炭化水素油が、前記(iii)の条件を満たし、且つ、13C-NMR分析において、潤滑油基油を構成する全炭素に占める、主鎖を構成するCH2炭素の割合が15%以上である、請求項1、10、11のいずれか一項に記載の潤滑油基油。 The hydrocarbon oil satisfies the above condition (iii), and in 13 C-NMR analysis, the proportion of CH 2 carbon constituting the main chain in the total carbon constituting the lubricating base oil is 15% or more. The lubricating base oil according to any one of claims 1, 10, and 11.
- 前記炭化水素油が、前記(iii)の条件を満たし、且つ、FD-MS分析において、シクロパラフィン分が30%以下である、請求項1、10、11、12のいずれか一項に記載の潤滑油基油。 The hydrocarbon oil according to any one of claims 1, 10, 11, and 12, wherein the hydrocarbon oil satisfies the condition (iii) and has a cycloparaffin content of 30% or less in an FD-MS analysis. Lubricating base oil.
- 基油留分及び該基油留分よりも重質の重質留分を含有する炭化水素油から、前記基油留分と前記重質留分とをそれぞれ分留する第1の工程と、
前記第1の工程で分留された重質留分を水素化分解し、得られる分解油を前記第1の工程に戻す第2の工程と、
前記基油留分を水素化異性化脱ろうして脱ろう油を得る第3の工程と、
前記脱ろう油を精製して精製油を得る第4の工程と、
前記精製油の分留により、下記(i)、(ii)又は(iii):
(i)100℃における動粘度が3.0~5.0mm2/s、粘度指数が145以上且つ-20℃におけるSBV粘度が3,000~60,000mPa・sの炭化水素油、
(ii)100℃における動粘度が5~9mm2/s、粘度指数が155以上且つ-20℃におけるSBV粘度が3,000~30,000mPa・sの炭化水素油、
(iii)100℃における動粘度が2.0~3.0mm2/s、粘度指数が130以上且つ-30℃におけるSBV粘度が1,000~30,000mPa・sの炭化水素油、
のいずれかの条件を満たす炭化水素油である潤滑油基油を得る第5の工程と、
を備える潤滑油基油の製造方法。 A first step of fractionating the base oil fraction and the heavy fraction from a base oil fraction and a hydrocarbon oil containing a heavier fraction heavier than the base oil fraction,
A second step of hydrocracking the heavy fraction fractionated in the first step and returning the resulting cracked oil to the first step;
A third step of hydroisomerizing and dewaxing the base oil fraction to obtain a dewaxed oil;
A fourth step of refining the dewaxed oil to obtain a refined oil;
By fractional distillation of the refined oil, the following (i), (ii) or (iii):
(I) a hydrocarbon oil having a kinematic viscosity at 100 ° C. of 3.0 to 5.0 mm 2 / s, a viscosity index of 145 or more, and an SBV viscosity at −20 ° C. of 3,000 to 60,000 mPa · s;
(Ii) a hydrocarbon oil having a kinematic viscosity at 100 ° C. of 5 to 9 mm 2 / s, a viscosity index of 155 or more and an SBV viscosity at −20 ° C. of 3,000 to 30,000 mPa · s,
(Iii) a hydrocarbon oil having a kinematic viscosity at 100 ° C. of 2.0 to 3.0 mm 2 / s, a viscosity index of 130 or more and an SBV viscosity at −30 ° C. of 1,000 to 30,000 mPa · s,
A fifth step of obtaining a lubricating base oil that is a hydrocarbon oil that satisfies any of the following conditions:
A method for producing a lubricating base oil comprising: - 前記第3の工程において得られる潤滑油基油が、前記(i)の条件を満たし、且つ、凝固点が-20~-5℃である、請求項14に記載の潤滑油基油の製造方法。 15. The method for producing a lubricant base oil according to claim 14, wherein the lubricant base oil obtained in the third step satisfies the condition (i) and has a freezing point of −20 to −5 ° C.
- 前記第3の工程において得られる潤滑油基油が、前記(ii)の条件を満たし、且つ、凝固点が-15~-5℃である、請求項14に記載の潤滑油基油の製造方法。 The method for producing a lubricating base oil according to claim 14, wherein the lubricating base oil obtained in the third step satisfies the condition (ii) and has a freezing point of -15 to -5 ° C.
- 前記第3の工程において得られる潤滑油基油が、前記(iii)の条件を満たし、且つ、凝固点が-30~-10℃である、請求項14に記載の潤滑油基油の製造方法。 15. The method for producing a lubricating base oil according to claim 14, wherein the lubricating base oil obtained in the third step satisfies the condition (iii) and has a freezing point of −30 to −10 ° C.
- 前記第3の工程は、ZSM-22型ゼオライト、ZSM-23型ゼオライト、SSZ32及びZSM-48型ゼオライトからなる群より選択される少なくとも1種の結晶性固体酸性物質と、活性金属として白金および/またはパラジウムを含む水素化異性化触媒の存在下、前記基油留分を水素化異性化脱ろうする工程である、請求項14~17のいずれか一項に記載の潤滑油基油の製造方法。 The third step includes at least one crystalline solid acidic substance selected from the group consisting of ZSM-22 type zeolite, ZSM-23 type zeolite, SSZ32 and ZSM-48 type zeolite, and platinum and / or active metal. The method for producing a lubricant base oil according to any one of claims 14 to 17, which is a step of hydroisomerizing and dewaxing the base oil fraction in the presence of a hydroisomerization catalyst containing palladium. .
- 前記炭化水素油が、フィッシャートロプシュ合成から得られたGTLワックスあるいは、溶剤脱ろうによって得られたスラックワックスを原料として得られたものである、請求項14~18のいずれか一項に記載の潤滑油基油の製造方法。 The lubrication according to any one of claims 14 to 18, wherein the hydrocarbon oil is obtained by using GTL wax obtained from Fischer-Tropsch synthesis or slack wax obtained by solvent dewaxing as a raw material. A method for producing an oil base oil.
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EP2835417A1 (en) | 2015-02-11 |
JP5957515B2 (en) | 2016-07-27 |
US20150060328A1 (en) | 2015-03-05 |
EP2835417B1 (en) | 2018-10-17 |
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