WO2013147305A1 - 潤滑油基油及びその製造方法 - Google Patents
潤滑油基油及びその製造方法 Download PDFInfo
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- WO2013147305A1 WO2013147305A1 PCT/JP2013/059972 JP2013059972W WO2013147305A1 WO 2013147305 A1 WO2013147305 A1 WO 2013147305A1 JP 2013059972 W JP2013059972 W JP 2013059972W WO 2013147305 A1 WO2013147305 A1 WO 2013147305A1
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- 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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- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
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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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/14—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel 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
- C10G67/02—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
- 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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- 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
- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
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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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- 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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- 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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- 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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- 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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- 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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- 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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- 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
- C10N2030/54—Fuel economy
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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
- 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 inventors, the conventional lubricating base oil having the low temperature fluidity is lubricated. There is room for improvement in terms of sex.
- 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 low-temperature viscosity characteristics and lubricity at a high level and a method for producing the same. .
- the present inventor first examined the reason why a lubricating base oil having a low pour point is inferior in lubricity.
- a lubricating base oil having a low pour point is inferior in lubricity.
- the structure of isoparaffin close to normal paraffin for example, the main chain is long and the degree of branching is small
- the content was also reduced, it was found that the lubricity tends to be impaired.
- the lubricating base oil and urea are contacted.
- lubricity is maintained while maintaining sufficient low-temperature viscosity characteristics. The inventors have found that it can be improved and have completed the present invention.
- the low temperature viscosity characteristics of the lubricating base oil and the lubricity can be achieved using the SBV viscosity as an index.
- 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.
- 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 SBV viscosity at ⁇ 20 ° C. of the lubricating base oil is set to 3,000-60,000 mPa ⁇ s, and the raffinate
- the present invention provides the lubricating base oil described in [1] to [4] below and the method for producing the lubricating base oil described in [5] to [10] below.
- Kinematic viscosity at 100 ° C. is 2.0 to 9 mm 2 / s
- viscosity index is 130 or more
- freezing point is ⁇ 30 to ⁇ 5 ° C.
- SBV viscosity at ⁇ 20 ° C. is 1,000 to 60,000 mPa ⁇ s.
- a freezing point of raffinate obtained by bringing the lubricating base oil into contact with urea and removing paraffin that can be included in urea.
- Kinematic viscosity at 100 ° C. is 3.0 to 5.0 mm 2 / s
- viscosity index is 145 or more
- freezing point is ⁇ 20 to ⁇ 5 ° C.
- SBV viscosity at ⁇ 20 ° C. is 3,000 to 60,000 mPa ⁇ s.
- a lubricating base oil which is a hydrocarbon oil of s
- Lubrication according to [1] wherein the freezing point of the lubricating base oil is 10 ° C.
- Oil base oil [3] Hydrocarbon having a kinematic viscosity at 100 ° C. of 5 to 9 mm 2 / s, a viscosity index of 155 or more, a freezing point of ⁇ 15 to ⁇ 5 ° C., and an SBV viscosity at ⁇ 20 ° C. of 3,000 to 30,000 mPa ⁇ s.
- a lubricating base oil that is an oil, Lubrication according to [1], wherein the freezing point of the lubricating base oil is 10 ° C.
- a lubricating base oil which is a hydrocarbon oil of s, Lubrication according to claim 1, wherein the freezing point of the lubricating base oil is at least 15 ° C higher than the freezing point of raffinate obtained by contacting the lubricating base oil with urea to remove paraffin that can be included in urea.
- Oil base oil [5] 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.
- the freezing point of the lubricating base oil obtained in the fifth step is a raffinate obtained by removing paraffin that can be included in urea by bringing the lubricating base oil into contact with urea.
- a method for producing a lubricating base oil which is a step of hydroisomerizing and dewaxing the base oil fraction so as to be higher by 10 ° C or more than a freezing point.
- the fifth step by kneading the refined oil, the kinematic viscosity at 100 ° C.
- the freezing point of the lubricating base oil obtained in the fifth step is a raffinate obtained by removing paraffin that can be included in urea by bringing the lubricating base oil into contact with urea.
- the kinematic viscosity at 100 ° C. is 5 to 9 mm 2 / s
- the viscosity index is 155 or more
- the freezing point is ⁇ 15 to ⁇ 5 ° C., and ⁇ 20 ° C.
- the freezing point of the lubricating base oil obtained in the fifth step is a raffinate obtained by removing paraffin that can be included in urea by bringing the lubricating base oil into contact with urea.
- 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 is a method for producing a base oil.
- 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. Refers to the measured value.
- a base oil fraction and a heavy fraction are fractionated from a hydrocarbon oil as a raw material (first step),
- the cracked oil obtained by hydrocracking the mass fraction 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.
- hydroisomerization dewaxing is performed so that the difference of the freezing point of the lubricating base oil and raffinate finally obtained may be 10 degreeC or more, and the obtained dewaxed oil is refined
- a refined oil can be obtained (fourth step), and a desired lubricating base oil can be effectively obtained by fractionating the refined oil (fifth step).
- hydrocracking and hydroisomerization dewaxing are generally performed on the entire raw material oil.
- the kinematic viscosity, viscosity index, freezing point at 100 ° C. The SBV viscosity at ⁇ 20 ° C. and the difference in freezing point between the lubricating base oil and the raffinate all make it difficult to obtain a lubricating base oil satisfying the above conditions, making it impossible to achieve both low temperature viscosity characteristics and lubricity.
- the conventional highly refined mineral oil producing method has a kinematic viscosity at 100 ° C. of 3 If it is within the range of 0.0 to 5.0 mm 2 / s, the freezing point is less than ⁇ 20 ° C., the SBV viscosity at ⁇ 20 ° C. is less than 3,000 mPa ⁇ s, and the difference in freezing point between lubricating oil and raffinate is less than 10 ° C. Cheap.
- the conventional method for producing highly refined mineral oil has a kinematic viscosity at 100 ° C. of 5 If it is in the range of ⁇ 9 mm 2 / s, the freezing point is less than ⁇ 15 ° C., the SBV viscosity at ⁇ 20 ° C. is less than 3,000 mPa ⁇ s, and the difference in freezing point between the lubricating oil and the raffinate is less than 10 ° C.
- the conventional highly refined mineral oil producing method has a kinematic viscosity at 100 ° C. of 2 If it is within the range of 0.0 to 3.0 mm 2 / s, the freezing point is less than ⁇ 30 ° C., the SBV viscosity at ⁇ 30 ° C. is less than 1,000 mPa ⁇ s, and the difference in freezing point between the lubricating oil and raffinate is less than 15 ° C. Cheap.
- a lubricating base oil and a method for producing the same that can achieve both low temperature viscosity characteristics and lubricity at a high level. Furthermore, the lubricating base oil of the present invention has the effect of exhibiting excellent fuel economy in JC08 cold mode due to its excellent low-temperature viscosity characteristics and lubricity.
- the lubricating base oil according to the first embodiment of the present invention has a kinematic viscosity at 100 ° C. of 2.0 to 9 mm 2 / s, a viscosity index of 130 or more, a freezing point of ⁇ 30 to ⁇ 5 ° C., and SBV at ⁇ 20 ° C.
- Preferred lubricant base oils include the following lubricant base oils A, B and C.
- the lubricating base oil A has a kinematic viscosity at 100 ° C. of 3.0 to 5.0 mm 2 / s, a viscosity index of 145 or more, a freezing point of ⁇ 20 to ⁇ 5 ° C., and an SBV viscosity at ⁇ 20 ° C. of 3,000 to A lubricating base oil that is a hydrocarbon oil of 60,000 mPa ⁇ s, wherein the freezing point of the lubricating base oil is brought into contact with the lubricating base oil and urea to remove paraffin that can be included in urea. It is higher by 10 ° C. or more than the freezing point of the raffinate obtained.
- Kinematic viscosity at 100 ° C. of the lubricating base oil A is 3.0 ⁇ 5.0mm 2 / s, preferably 3.2 ⁇ 4.3mm 2 / s, more preferably 3.4 ⁇ 4.1 mm 2 / S.
- the kinematic viscosity of the lubricating base oil A at 40 ° C. is preferably 10 to 20 mm 2 / s, more preferably 12 to 16 mm 2 / s.
- the viscosity index of the lubricating base oil A is 145 or more, preferably 147 or more, more preferably 148 to 160. When the viscosity index is less than the lower limit, energy saving performance is lowered. When 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 A is -20 to -5 ° C, preferably -18 to -8 ° C, more preferably -15 to -10 ° C.
- energy saving performance is lowered.
- the freezing point is exceeded, the fluidity at normal temperature is lowered and cannot be used as a lubricating base oil.
- the SBV viscosity of the lubricating base oil A at ⁇ 20 ° C. is 3,000 to 60,000 mPa ⁇ s, preferably 3,000 to 30,000 mPa ⁇ s, more preferably 3,000 to 15,000 mPa ⁇ s. -S.
- the sealing property at ⁇ 20 ° C. is less than the above lower limit value, the sealing property is insufficient, and when it exceeds the above upper limit value, the low temperature characteristic is insufficient.
- the SBV viscosity of the lubricating base oil A at ⁇ 30 ° C. is preferably 50,000 to 500,000 mPa ⁇ s, more preferably 50,000 to 400,000 mPa ⁇ s, and further preferably 50,000 to 300,000 mPa ⁇ s.
- the sealing property tends to be insufficient
- the low temperature characteristic tends to be insufficient.
- the freezing point of the lubricating base oil A is 10 ° C. or more, preferably 10-12, higher than the freezing point of raffinate obtained by bringing the lubricating base oil into contact with urea and removing paraffin that can be included in urea. ° C, more preferably 10-14 ° C higher. If the difference in freezing point is less than the above lower limit value, the lubricity becomes insufficient, and if it exceeds the above upper limit value, the fluidity as a base oil tends to be lowered and the use as a base oil tends to be difficult.
- the procedure for removing the paraffin that can be included in urea by bringing the lubricating base oil and urea into contact with each other to obtain raffinate can be exemplified as follows. 100 g of weighed sample oil (lubricating base oil) is placed in a round bottom flask, 200 g of urea, 360 ml of toluene and 40 ml of methanol are added and stirred at room temperature for 6 hours. As a result, white granular crystals are produced as urea adducts in the reaction solution. The reaction solution is filtered through a 1 micron filter to collect the produced white granular crystals, and the obtained crystals are washed 6 times with 50 ml of toluene.
- the recovered white crystals are put in a flask, 300 ml of pure water and 300 ml of toluene are added, and the mixture is stirred at 80 ° C. for 1 hour.
- the aqueous phase is separated and removed with a separatory funnel, and the toluene phase is washed three times with 300 ml of pure water.
- a desiccant sodium sulfate
- the ratio (mass percentage) of the urea adduct thus obtained to the sample oil is defined as “urea adduct value”.
- the proportion of CH 2 carbon constituting the main chain in the total carbon constituting the lubricating base oil is preferably 15% or more, More preferably, it is 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 proportion of CH 2 carbon constituting the main chain can be determined, for example, by performing 13 C-NMR analysis under the following analysis conditions.
- the ratio of CH 2 to the total amount of constituent carbon of the lubricating base oil means 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.
- other methods may be used as long as equivalent results are obtained.
- 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.
- the measuring method used the coupling method with a gate.
- the cycloparaffin content is preferably 50% or less, more preferably 40% or less.
- the wear resistance of the lubricating base oil can be further improved.
- the ratio of the cycloparaffin content can be obtained, 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.
- the cycloparaffin includes both one-ring cycloparaffin and two or more cycloparaffins.
- the urea adduct value of the lubricating base oil A is preferably 4% by mass or less, more preferably 3.5% by mass or less, from the viewpoint of improving the low temperature viscosity characteristic without impairing the viscosity-temperature characteristic at high temperature. More preferably, it is 3 mass% or less, Most preferably, it is 2.5 mass% or less. 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 A is preferably 90% by mass or more, more preferably 93% by mass or more, still more preferably 95% by mass or more, particularly preferably, based on the total amount of the lubricating oil base oil. 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 A is preferably 5% by mass or less, more preferably 0.05 to 3% by mass, and still more preferably 0.1 to 1% by mass based on the total amount of the lubricating base oil. Particularly preferred is 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 A 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 A is preferably ⁇ 5 ° C. or lower, more preferably ⁇ 12.5 ° 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 of the lubricating base oil A at ⁇ 30 ° C. is preferably 1,500 mPa ⁇ s or less, more preferably 1,200 mPa ⁇ s or less.
- the CCS viscosity of the lubricating base oil at ⁇ 35 ° C. is preferably 2,500 mPa ⁇ s or less, more preferably 2,000 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 A is preferably 8% by mass or more, more preferably 9% by mass or more, further preferably 10% or more, and preferably 15% by mass or less, more preferably 14% by mass. % Or less, more preferably 13% by 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.
- the lubricating base oil B has a kinematic viscosity at 100 ° C. of 3.0 to 5.0 mm 2 / s, a viscosity index of 145 or more, a freezing point of ⁇ 15 to ⁇ 5 ° C., and an SBV viscosity at ⁇ 20 ° C. of 3,000 to
- a lubricating base oil that is a hydrocarbon oil of 30,000 mPa ⁇ s, wherein the freezing point of the lubricating oil is obtained by contacting the lubricating base oil with urea to remove paraffin that can be included in urea. It is higher by 10 ° C. than the freezing point of raffinate.
- the kinematic viscosity at 100 ° C. of the lubricating base oil B 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 kinematic viscosity at 40 ° C. of the lubricating base oil B is preferably 25 to 40 mm 2 / s, more preferably 28 to 35 mm 2 / s.
- the viscosity index of the lubricating base oil B is 155 or more, preferably 157 or more, and more preferably 158 to 165.
- 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 cannot be used as a lubricating base oil.
- the freezing point of the lubricating base oil B is ⁇ 15 to ⁇ 5 ° C., preferably ⁇ 14 to ⁇ 7 ° C., more preferably ⁇ 13 to ⁇ 8 ° C. If the freezing point is less than the above lower limit value, the energy saving property is lowered, and if it exceeds the above upper limit value, the fluidity at normal temperature is lowered and it cannot be used as a lubricating base oil.
- the SBV viscosity of the lubricating base oil B at ⁇ 20 ° C. is 3,000 to 30,000 mPa ⁇ s, preferably 3,000 to 25,000 mPa ⁇ s, more preferably 3,000 to 20,000 mPa ⁇ s. -S.
- the sealing property is insufficient, and when it exceeds the above upper limit value, the low temperature characteristic is insufficient.
- the SBV viscosity at ⁇ 25 ° C. of the lubricating base oil B is preferably 5,000 to 500,000 mPa ⁇ s, more preferably 5,000 to 400,000 mPa ⁇ s, and further preferably 5,000 to 300,000 mPa ⁇ s.
- the sealing property tends to be insufficient
- the low temperature characteristic tends to be insufficient.
- the freezing point of the lubricating base oil B is 10 ° C. or more, preferably 10-20, higher than the freezing point of raffinate obtained by bringing the lubricating base oil into contact with urea and removing paraffin that can be included in urea. ° C, more preferably 10 to 15 ° C. If the difference in freezing point is less than the above lower limit value, the lubricity becomes insufficient, and if it exceeds the above upper limit value, the fluidity as a base oil tends to be lowered and the use as a base oil tends to be difficult.
- the proportion of CH 2 carbon constituting the main chain in the total carbon constituting the lubricating base oil is preferably 20% or more, More preferably, it is 20% 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 B is preferably 4% by mass or less, more preferably 3.5% by mass or less, from the viewpoint of improving the low temperature viscosity characteristic without impairing the viscosity-temperature characteristic at high temperature. More preferably, it is 3 mass% or less, Most preferably, it is 2.5 mass% or less. 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 B is preferably 90% by mass or more, more preferably 93% by mass or more, still more preferably 95% by mass or more, particularly preferably, based on the total amount of the lubricating oil base oil. 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 B is preferably 5% by mass or less, more preferably 0.05 to 3% by mass, and still more preferably 0.1 to 1% by mass based on the total amount of the lubricating base oil. Particularly preferred is 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.
- the lubricating base oil B may not contain an aromatic component, but the solubility of the additive can be further improved by setting the aromatic content to 0.05 mass% or more. it can.
- the sulfur content in the lubricating base oil B 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 B 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 B 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 60,000 mPa ⁇ s, and the sealing property tends to be insufficient.
- the CCS viscosity of the lubricating base oil B at ⁇ 30 ° C. 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.
- the density at 15 ° C. in the present invention means a density measured at 15 ° C. in accordance with JIS K 2249-1995.
- Lubricating base oil C has a kinematic viscosity at 100 ° C. of 2.0 to 3.0 mm 2 / s, a viscosity index of 130 or more, a freezing point of ⁇ 30 to ⁇ 10 ° C., and an SBV viscosity at ⁇ 30 ° C. of 1,000 to
- a lubricating base oil that is a hydrocarbon oil of 30,000 mPa ⁇ s or less, and the freezing point of the lubricating base oil removes paraffin that can be included in urea by bringing the lubricating base oil into contact with urea. Is higher than the freezing point of the raffinate obtained by the above.
- the kinematic viscosity at 100 ° C. of the lubricating base oil C 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 kinematic viscosity at 40 ° C. of the lubricant base oil C is preferably 7 to 12 mm 2 / s, more preferably 8 to 10 mm 2 / s.
- the viscosity index of the lubricating base oil C is 130 or more, preferably 131 or more, more preferably 132 to 140. When the viscosity index is less than the lower limit, energy saving performance is lowered. When the viscosity index is higher than the upper limit, the fluidity at normal temperature is lowered and cannot be used as a lubricating base oil.
- the freezing point of the lubricating base oil C is ⁇ 30 to ⁇ 10 ° C., preferably ⁇ 29 to ⁇ 15 ° C., more preferably ⁇ 28 to ⁇ 20 ° C. If the freezing point is less than the above lower limit value, the energy saving property is lowered, and if it exceeds the above upper limit value, the fluidity at normal temperature is lowered and it cannot be used as a lubricating base oil.
- the SBV viscosity of the lubricating base oil C at ⁇ 30 ° C. is 1,000 to 30,000 mPa ⁇ s, preferably 1,000 to 20,000 mPa ⁇ s, more preferably 1,000 to 15,000 mPa ⁇ s. -S.
- the SBV viscosity of the lubricating base oil C at ⁇ 35 ° C. 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 of the lubricating base oil C at ⁇ 40 ° C. 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.
- a value obtained by dividing the freezing point of the lubricating base oil from the freezing point of the raffinate obtained by bringing the lubricating base oil C and urea into contact with each other to remove paraffin that can be included in the urea is 10 ° C. or more, preferably It is 12 to 20 ° C, more preferably 15 to 19 ° C. If the difference in freezing point is less than the above lower limit value, the lubricity becomes insufficient, and if it exceeds the above upper limit value, the fluidity as a base oil tends to be lowered and the use as a base oil tends to be difficult.
- the proportion of CH 2 carbon constituting the main chain in the total carbon constituting the lubricating base oil is preferably 15% or more, More preferably, it is 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, 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 C is preferably 4% by mass or less, more preferably 3.5% by mass or less, from the viewpoint of improving the low temperature viscosity characteristic without impairing the viscosity-temperature characteristic at high temperature. More preferably, it is 3 mass% or less, Most preferably, it is 2.5 mass% or less. 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 C is preferably 90% by mass or more, more preferably 93% by mass or more, still more preferably 95% by mass or more, particularly preferably, based on the total amount of the lubricating oil base oil. 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 C is preferably 5% by mass or less, more preferably 0.05 to 3% by mass, and still more preferably 0.1 to 1% by mass based on the total amount of the lubricating base oil. Particularly preferred is 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 C may not contain an aromatic component, but the solubility of the additive can be further improved by setting the aromatic content to 0.05% by mass or more. it can.
- the sulfur content in the lubricating base oil C 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 C 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 C is preferably ⁇ 27.5 ° C. or higher, more preferably ⁇ 25 ° C. or higher.
- the pour point is less than ⁇ 27.5, 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 of the lubricating base oil C at ⁇ 30 ° C. 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 C 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, more preferably 48% by mass. % Or less, more preferably 46% by 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.
- the lubricating base oil according to the present embodiment (including the above lubricating base oils A, B, and C) is excellent in low temperature viscosity characteristics and lubricity, and is preferable as a lubricating base oil for various applications. Can be used.
- the use of the lubricating base oil according to the present embodiment specifically includes gasoline engines for passenger cars, gasoline engines for motorcycles, diesel engines, gas engines, gas heat pump engines, marine engines, power generation engines, and the like. Used in power transmission (lubricating oil for internal combustion engines), automatic transmission, manual transmission, continuously variable transmission, final reduction gear, etc.
- the lubricating base oil according to this embodiment may be used alone, or the lubricating base oil according to this embodiment may be 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 the present 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 the present 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, and 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 the present embodiment can effectively exhibit the effect of adding a pour point depressant. Therefore, when the pour point depressant is contained in the lubricating base oil according to the present 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. here means the MRV viscosity at ⁇ 40 ° C.
- the MRV viscosity at ⁇ 40 ° C. can be 12,000 mPa ⁇ s or less, more preferably 10,000 mPa ⁇ s.
- 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.
- the method for producing a lubricating base oil according to the second embodiment of the present invention includes: 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 the fractional distillation of the refined oil, the kinematic viscosity at 100 ° C.
- the freezing point of the lubricating base oil obtained in the fifth step is a raffinate obtained by removing paraffin that can be included in urea by bringing the lubricating base oil into contact with urea.
- the base oil fraction is hydroisomerized and dewaxed so as to be 10 ° C. or more higher than the freezing point.
- 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.
- Paraffin wax, microcritalin wax, petram and Fischer-Tropsch synthetic wax preferably at least one selected from the group consisting of synthetic wax, normal pressure residual oil, vacuum residual oil, vacuum gas oil, slack wax, and Fischer-Tropsch 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 FT synthetic oil, there is no risk 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 petratam. Can be mentioned.
- the first 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 step is subjected to the second step (hydrocracking step).
- the hydrocracked oil obtained in the second step is returned to the first step.
- 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 third step (dewaxing step) will be described.
- the base oil fraction fractionated in the first step is brought into contact with the hydrogenation catalyst in the presence of hydrogen (molecular hydrogen).
- hydrogen molecular hydrogen
- a base oil fraction is dewaxed by hydroisomerization, and a dewaxed oil is obtained.
- the freezing point of the lubricating base oil obtained in the fifth step described later is more than the freezing point of raffinate obtained by bringing the lubricating base oil and urea into contact with each other to remove paraffin that can be included in urea.
- the above base oil fraction is hydroisomerized and dewaxed so as to be higher by 10 ° C. or higher (15 ° C. or higher when the lubricating base oil C is produced).
- 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 fourth process (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-type reactor, and molecular hydrogen and the above dewaxed oil are circulated through this reactor.
- the hydrofinishing treatment (hydrorefining treatment) can be suitably carried out.
- the hydrofinishing treatment here means improving 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 step is subjected to the fifth step (fractional distillation step). 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 for fractionating the dewaxed oil obtained by the above-described method for producing a dewaxed oil to obtain a lubricating oil fraction, and the distillation base step. And a hydrofinishing step of hydrofinishing (hydrorefining treatment) of the lubricating oil fraction.
- Example 1 to 3 Comparative Examples 1 and 2
- lubricating base oils shown in Table 1 were prepared.
- the lubricating base oils of Examples 1 to 3 were obtained according to the manufacturing method of the lubricating base oil according to the above embodiment.
- the lubricating base oils of Comparative Examples 1 and 2 were obtained by a conventional method for producing a lubricating base oil.
- Table 1 shows the traction coefficients measured in (1).
- Example 4 to 6 and Comparative Examples 3 to 5 the package additives (breakdown: 40% by mass of ashless dispersant, metal-based cleaning agent) were added to each of the lubricating base oils of Examples 1 to 3 or Comparative Examples 1 and 2, respectively.
- 40% by weight of an agent, 10% by weight of an antiwear agent, 8% by weight of an antioxidant and 10% by weight of a metal deactivator and a viscosity index improver (polymethacrylate, Mw 350,000, effective concentration 50% by weight) ) 5% by mass was added to prepare a lubricating oil composition.
- Comparative Example 3 a commercially available 0W-20 oil was prepared.
- Table 2 shows the kinematic viscosity and viscosity index of each lubricating oil composition.
- JC08 cold mode fuel consumption evaluation test The lubricating oil compositions of Examples 4 to 6 and Comparative Examples 3 and 4 were subjected to a JC08 cold mode fuel consumption evaluation test 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, quickly returning to the idling state and operating once in a predetermined traveling pattern, and then in a room of 298 ⁇ 5K (25 ⁇ 5 ° C.) for 6 hours or more 36 It was left standing (soaked) for a period of time within a period of time, and then operated in a predetermined pattern, and fuel consumption was calculated by calculating fuel consumption from the operating exhaust gas. The obtained results are shown in Table 2.
- Example 7 and 8 Comparative Examples 6 to 8
- lubricating base oils shown in Table 3 were prepared.
- the lubricating base oils of Examples 7 and 8 were obtained according to the manufacturing method of the lubricating base oil according to the above embodiment.
- the lubricating base oils of Comparative Examples 6 to 8 were obtained by a conventional method for producing a lubricating base oil.
- Table 3 shows the traction coefficients measured in (1).
- Example 9 and 10 and Comparative Examples 9 to 11 In Examples 9 and 10 and Comparative Examples 9 to 11, the package additives (breakdown: 40% by mass of ashless dispersant, metal-based cleaning agent) were added to the lubricating base oils of Examples 7 and 8 or Comparative Examples 6 to 8, respectively. 40% by weight of an agent, 10% by weight of an antiwear agent, 8% by weight of an antioxidant and 10% by weight of a metal deactivator and a viscosity index improver (polymethacrylate, Mw 350,000, effective concentration 50% by weight) ) 5% by mass was added to prepare a lubricating oil composition. Table 2 shows the kinematic viscosity and viscosity index of each lubricating oil composition.
- JC08 cold mode fuel consumption evaluation test The lubricating oil compositions of Examples 9 and 10 and Comparative Examples 9 to 11 were subjected to a JC08 cold mode fuel consumption evaluation test 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 2.5L, FF gasoline engine car (Toyota Estima) was selected for the test, the engine was cleaned and filled with the newly prepared sample oil before the start of the test, and the test car was set to 60 ⁇ 2km / After warming up for 15 minutes or more at a constant speed of h, quickly returning to the idling state and operating once in a predetermined traveling pattern, and then in a room of 298 ⁇ 5K (25 ⁇ 5 ° C.) for 6 hours or more 36 It was left standing (soaked) for a period of time within a period of time and then operated in a predetermined pattern, and the fuel consumption was calculated by calculating the fuel consumption from the operating exhaust gas. Table 4 shows the obtained results.
- Example 11 to 13 Comparative Examples 12 to 14
- lubricating base oils shown in Table 5 were prepared.
- the lubricant base oils of Examples 11 to 13 were obtained according to the method for producing a lubricant base oil according to the above embodiment.
- the lubricating base oils of Comparative Examples 12 to 14 were obtained by a conventional method for producing a lubricating base oil.
- Table 1 shows the traction coefficients measured in (1).
- Examples 14 to 16, Comparative Examples 15 to 17 In each lubricant base oil, package additives (breakdown: antiwear agent: 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% by mass of a viscosity index improver (polymethacrylate type, Mw 350,000, effective concentration 50%) were added to prepare a lubricating oil composition.
- Table 6 shows the SBV viscosity of each lubricating oil composition at ⁇ 40 ° C.
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Abstract
Description
[1]100℃における動粘度が2.0~9mm2/s、粘度指数が130以上、凝固点が-30~-5℃、-20℃におけるSBV粘度が1,000~60,000mPa・sの炭化水素油である潤滑油基油であって、
前記潤滑油基油の凝固点が、前記潤滑油基油と尿素とを接触させて尿素に包摂され得るパラフィンを取り除くことによって得られるラフィネートの凝固点よりも10℃以上高い潤滑油基油。
[2]100℃における動粘度が3.0~5.0mm2/s、粘度指数が145以上、凝固点が-20~-5℃、-20℃におけるSBV粘度が3,000~60,000mPa・sの炭化水素油である潤滑油基油であって、
前記潤滑油基油の凝固点が、前記潤滑油基油と尿素とを接触させて尿素に包摂され得るパラフィンを取り除くことによって得られるラフィネートの凝固点よりも10℃以上高い、[1]に記載の潤滑油基油。
[3]100℃における動粘度が5~9mm2/s、粘度指数が155以上、凝固点が-15~-5℃、-20℃におけるSBV粘度が3,000~30,000mPa・sの炭化水素油である潤滑油基油であって、
前記潤滑油基油の凝固点が、前記潤滑油基油と尿素とを接触させて尿素に包摂され得るパラフィンを取り除くことによって得られるラフィネートの凝固点よりも10℃以上高い、[1]に記載の潤滑油基油。
[4]100℃における動粘度が2.0~3.0mm2/s、粘度指数が130以上、凝固点が-30~-10℃、-30℃におけるSBV粘度が1,000~30,000mPa・sの炭化水素油である潤滑油基油であって、
前記潤滑油基油の凝固点が、前記潤滑油基油と尿素とを接触させて尿素に包摂され得るパラフィンを取り除くことによって得られるラフィネートの凝固点よりも15℃以上高い、請求項1に記載の潤滑油基油。
[5]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、100℃における動粘度が2.0~9mm2/s、粘度指数が130以上、凝固点が-30~-5℃、-20℃におけるSBV粘度が1,000~60,000mPa・sの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、
前記第3の工程は、前記第5の工程で得られる前記潤滑油基油の凝固点が、前記潤滑油基油と尿素とを接触させて尿素に包摂され得るパラフィンを取り除くことによって得られるラフィネートの凝固点よりも10℃以上高くなるように、前記基油留分を水素化異性化脱ろうする工程である、潤滑油基油の製造方法。
[6]前記第5の工程が、前記精製油の分留により、100℃における動粘度が3.0~5.0mm2/s、粘度指数が145以上、凝固点が-20~-5℃、-20℃におけるSBV粘度が3,000~60,000mPa・sの炭化水素油である潤滑油基油を得る工程であり、
前記第3の工程は、前記第5の工程で得られる前記潤滑油基油の凝固点が、前記潤滑油基油と尿素とを接触させて尿素に包摂され得るパラフィンを取り除くことによって得られるラフィネートの凝固点よりも10℃以上高くなるように、前記基油留分を水素化異性化脱ろうする工程である、[5]に記載の潤滑油基油の製造方法。
[7]前記第5の工程が、前記精製油の分留により、100℃における動粘度が5~9mm2/s、粘度指数が155以上、凝固点が-15~-5℃、-20℃におけるSBV粘度が3,000~30,000mPa・sの炭化水素油である潤滑油基油を得る工程であり、る、請求項5に記載の潤滑油基油の製造方法。
[8]前記第5の工程が、前記精製油の分留により、100℃における動粘度が2.0~3.0mm2/s、粘度指数が130以上、凝固点が-20~-5℃、-30℃におけるSBV粘度が1,000~30,000mPa・sの炭化水素油である潤滑油基油を得る工程であり、
前記第3の工程は、前記第5の工程で得られる前記潤滑油基油の凝固点が、前記潤滑油基油と尿素とを接触させて尿素に包摂され得るパラフィンを取り除くことによって得られるラフィネートの凝固点よりも10℃以上高くなるように、前記基油留分を水素化異性化脱ろうする工程である、[5]に記載の潤滑油基油の製造方法。
[9]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、[5]~[8]のいずれか一項に記載の潤滑油基油の製造方法。
[10]
前記第1の工程における炭化水素油が、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、[5]~[9]のいずれか一項に記載の潤滑油基油の製造方法。
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2.0~9mm2/s、粘度指数が130以上、凝固点が-30~-5℃、-20℃におけるSBV粘度が1,000~60,000mPa・sの炭化水素油である潤滑油基油であって、該潤滑油基油の凝固点が、該潤滑油基油と尿素とを接触させて尿素に包摂され得るパラフィンを取り除くことによって得られるラフィネートの凝固点よりも10℃以上高いものである。
潤滑油基油Aは、100℃における動粘度が3.0~5.0mm2/s、粘度指数が145以上、凝固点が-20~-5℃、-20℃におけるSBV粘度が3,000~60,000mPa・sの炭化水素油である潤滑油基油であって、該潤滑油基油の凝固点が、該潤滑油基油と尿素とを接触させて尿素に包摂され得るパラフィンを取り除くことによって得られるラフィネートの凝固点よりも10℃以上高いものである。
秤量した試料油(潤滑油基油)100gを丸底フラスコに入れ、尿素200g、トルエン360ml及びメタノール40mlを加えて室温で6時間攪拌する。これにより、反応液中に尿素アダクト物として白色の粒状結晶が生成する。反応液を1ミクロンフィルターでろ過することにより、生成した白色粒状結晶を採取し、得られた結晶をトルエン50mlで6回洗浄する。回収した白色結晶をフラスコに入れ、純水300ml及びトルエン300mlを加えて80℃で1時間攪拌する。分液ロートで水相を分離除去し、トルエン相を純水300mlで3回洗浄する。トルエン相に乾燥剤(硫酸ナトリウム)を加えて脱水処理を行った後、トルエンを留去する。このようにして得られた尿素アダクト物の試料油に対する割合(質量百分率)を「尿素アダクト値」と定義する。
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。]
潤滑油基油Bは、100℃における動粘度が3.0~5.0mm2/s、粘度指数が145以上、凝固点が-15~-5℃、-20℃におけるSBV粘度が3,000~30,000mPa・sの炭化水素油である潤滑油基油であって、該潤滑油の凝固点が、該潤滑油基油と尿素とを接触させて尿素に包摂され得るパラフィンを取り除くことによって得られるラフィネートの凝固点よりも10℃以上高いものである。
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。]
潤滑油基油Cは、100℃における動粘度が2.0~3.0mm2/s、粘度指数が130以上、凝固点が-30~-10℃、-30℃におけるSBV粘度が1,000~30,000mPa・s以下の炭化水素油である潤滑油基油であって、該潤滑油基油の凝固点が、該潤滑油基油と尿素とを接触させて尿素に包摂され得るパラフィンを取り除くことによって得られるラフィネートの凝固点よりも15℃以上高いものである。
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。]
本発明の第2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、100℃における動粘度が2.0~9mm2/s、粘度指数が130以上、凝固点が-30~-5℃、-20℃におけるSBV粘度が1,000~60,000mPa・sの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、
前記第3の工程は、前記第5の工程で得られる前記潤滑油基油の凝固点が、前記潤滑油基油と尿素とを接触させて尿素に包摂され得るパラフィンを取り除くことによって得られるラフィネートの凝固点よりも10℃以上高くなるように、前記基油留分を水素化異性化脱ろうする工程である。
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。
VZ=Vc/Mz×100
実施例1~3及び比較例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1~3の潤滑油基油は、上記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、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。
実施例4~6及び比較例3、4においては、それぞれ実施例1~3又は比較例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質量%)5質量%を添加し、潤滑油組成物を調製した。また、比較例3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。
実施例4~6及び比較例3、4の潤滑油組成物について、以下の手順により、JC08コールド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1回運転した後、298±5K(25±5℃)の室内に6時間以上36時間以内の間停止させた状態で放置(ソーク)し、その後所定のパターンで運転し、運転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に示す。
実施例7、8及び比較例6~8においては、それぞれ表3に示す潤滑油基油を調製した。ここで、実施例7、8の潤滑油基油は、上記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6~8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3に示す。
実施例9、10及び比較例9~11においては、それぞれ実施例7、8又は比較例6~8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質量%)5質量%を添加し、潤滑油組成物を調製した。各潤滑油組成物の動粘度及び粘度指数を表2に示す。
実施例9、10及び比較例9~11の潤滑油組成物について、以下の手順により、JC08コールド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1回運転した後、298±5K(25±5℃)の室内に6時間以上36時間以内の間停止させた状態で放置(ソーク)し、その後所定のパターンで運転し、運転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4に示す。
実施例9、10及び比較例9~11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。
得られた結果を表4に示す。
実施例11~13及び比較例12~14においては、それぞれ表5に示す潤滑油基油を調製した。ここで、実施例11~13の潤滑油基油は、上記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12~14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。
各潤滑油基油に、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%)5質量%を添加し、潤滑油組成物を調製した。各潤滑油組成物の-40℃におけるSBV粘度を表6に示す。
実施例14~16及び比較例15~17の潤滑油組成物について、SRV摩擦試験機を用い、温度-30℃、荷重50N、周波数10Hz、振幅1mmでSRV摩擦試験を実施し、摩擦係数を測定した。得られた結果を表6に示す。
Claims (10)
- 100℃における動粘度が2.0~9mm2/s、粘度指数が130以上、凝固点が-30~-5℃、-20℃におけるSBV粘度が1,000~60,000mPa・sの炭化水素油である潤滑油基油であって、
前記潤滑油基油の凝固点が、前記潤滑油基油と尿素とを接触させて尿素に包摂され得るパラフィンを取り除くことによって得られるラフィネートの凝固点よりも10℃以上高い潤滑油基油。 - 100℃における動粘度が3.0~5.0mm2/s、粘度指数が145以上、凝固点が-20~-5℃、-20℃におけるSBV粘度が3,000~60,000mPa・sの炭化水素油である潤滑油基油であって、
前記潤滑油基油の凝固点が、前記潤滑油基油と尿素とを接触させて尿素に包摂され得るパラフィンを取り除くことによって得られるラフィネートの凝固点よりも10℃以上高い、請求項1に記載の潤滑油基油。 - 100℃における動粘度が5~9mm2/s、粘度指数が155以上、凝固点が-15~-5℃、-20℃におけるSBV粘度が3,000~30,000mPa・sの炭化水素油である潤滑油基油であって、
前記潤滑油基油の凝固点が、前記潤滑油基油と尿素とを接触させて尿素に包摂され得るパラフィンを取り除くことによって得られるラフィネートの凝固点よりも10℃以上高い、請求項1に記載の潤滑油基油。 - 100℃における動粘度が2.0~3.0mm2/s、粘度指数が130以上、凝固点が-30~-10℃、-30℃におけるSBV粘度が1,000~30,000mPa・sの炭化水素油である潤滑油基油であって、
前記潤滑油基油の凝固点が、前記潤滑油基油と尿素とを接触させて尿素に包摂され得るパラフィンを取り除くことによって得られるラフィネートの凝固点よりも15℃以上高い、請求項1に記載の潤滑油基油。 - 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、100℃における動粘度が2.0~9mm2/s、粘度指数が130以上、凝固点が-30~-5℃、-20℃におけるSBV粘度が1,000~60,000mPa・sの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、
前記第3の工程は、前記第5の工程で得られる前記潤滑油基油の凝固点が、前記潤滑油基油と尿素とを接触させて尿素に包摂され得るパラフィンを取り除くことによって得られるラフィネートの凝固点よりも10℃以上高くなるように、前記基油留分を水素化異性化脱ろうする工程である、潤滑油基油の製造方法。 - 前記第5の工程が、前記精製油の分留により、100℃における動粘度が3.0~5.0mm2/s、粘度指数が145以上、凝固点が-20~-5℃、-20℃におけるSBV粘度が3,000~60,000mPa・sの炭化水素油である潤滑油基油を得る工程であり、
前記第3の工程は、前記第5の工程で得られる前記潤滑油基油の凝固点が、前記潤滑油基油と尿素とを接触させて尿素に包摂され得るパラフィンを取り除くことによって得られるラフィネートの凝固点よりも10℃以上高くなるように、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5に記載の潤滑油基油の製造方法。 - 前記第5の工程が、前記精製油の分留により、100℃における動粘度が5~9mm2/s、粘度指数が155以上、凝固点が-15~-5℃、-20℃におけるSBV粘度が3,000~30,000mPa・sの炭化水素油である潤滑油基油を得る工程である、請求項5に記載の潤滑油基油の製造方法。
- 前記第5の工程が、前記精製油の分留により、100℃における動粘度が2.0~3.0mm2/s、粘度指数が130以上、凝固点が-20~-5℃、-30℃におけるSBV粘度が1,000~30,000mPa・sの炭化水素油である潤滑油基油を得る工程であり、
前記第3の工程は、前記第5の工程で得られる前記潤滑油基油の凝固点が、前記潤滑油基油と尿素とを接触させて尿素に包摂され得るパラフィンを取り除くことによって得られるラフィネートの凝固点よりも15℃以上高くなるように、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5に記載の潤滑油基油の製造方法。 - 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5~8のいずれか一項に記載の潤滑油基油の製造方法。
- 前記第1の工程における炭化水素油が、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5~9のいずれか一項に記載の潤滑油基油の製造方法。
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JP2018100329A (ja) * | 2016-12-19 | 2018-06-28 | 出光興産株式会社 | 鉱油系基油、潤滑油組成物、内燃機関、及び内燃機関の潤滑方法 |
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JP5957516B2 (ja) | 2016-07-27 |
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JPWO2013147305A1 (ja) | 2015-12-14 |
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US20150060327A1 (en) | 2015-03-05 |
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