JP7050544B2 - Wax isomerized oil manufacturing method - Google Patents

Description

The present invention relates to a method for producing a wax isomerized oil.

Conventionally, as a lubricating oil base oil, there is a wax isomerized oil in addition to a mineral oil-based base oil. Waxes that are the raw materials for wax isomerized oil include natural waxes such as petroleum slack wax obtained by removing hydrocarbon oil with a solvent, or those produced by Fischer-Tropsch synthesis using synthetic gas (FT wax). Examples include synthetic wax. Further, as a method for producing a high-quality lubricating oil base oil, for example, a method for hydrogenating and dewaxing a raw material oil derived from the above wax or the like is known (see, for example, Patent Document 1). ..

Japanese Patent Publication No. 2007-510798

As described above, the lubricating oil base oil produced by using the conventional raw material wax or the like can satisfy the requirements for improving fuel efficiency and reducing emissions to some extent, but according to the study by the present inventors. It was found that there is still room for improvement in terms of reduction of the traction coefficient even with the lubricating oil base oil.

Therefore, an object of the present invention is to provide a method for producing a wax isomerized oil having a low traction coefficient.

The present invention comprises a step of preparing an ethylene polymer wax, a step of hydrocracking the ethylene polymer wax with a hydrogenation decomposition catalyst to obtain a decomposition product, and a step of isomerizing and desorbing the decomposition product with a hydrogenation isomerization catalyst. Provided is a method for producing a wax isomerized oil, comprising a step of obtaining a hydrogenated wax isomerized oil by brazing.

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a method for producing a wax isomerized oil having a low traction coefficient.

Hereinafter, embodiments for carrying out the present invention will be described in detail.

The method for producing a wax isomerized oil according to the present embodiment is a step of preparing an ethylene polymer wax (first step) and a step of hydrocracking the ethylene polymer wax with a hydrogenation decomposition catalyst to obtain a decomposition product. (Second step) and a step (third step) of isomerizing and dewaxing the decomposition product with a hydrogenation isomerization catalyst to obtain a wax isomerized oil are provided.

The present inventors presume that the reason why the wax isomerized oil obtained by the production method according to the present embodiment exhibits a low traction coefficient is due to the specificity of its carbon number distribution.

That is, first, in the case of the conventional wax isomerized oil, the raw material wax such as wax obtained by FT synthesis is usually a hydrocarbon compound having an even number of carbon atoms (hydrocarbon compound having 2 n carbon atoms; n is 1 or more). (The same applies hereinafter) and a hydrocarbon compound having an odd number of carbon atoms (hydrocarbon compound having 2n + 1 carbon atoms), and the ratios of the two are almost the same. Further, even in the wax isomerized oil obtained by the conventional method for producing a base oil such as the production method described in Patent Document 1, the molecular structure of each hydrocarbon compound may change due to decomposition or isomerization, but as a whole. The ratio of either the hydrocarbon compound having 2n carbon atoms or the hydrocarbon compound having 2n + 1 carbon atoms does not become extremely large.

On the other hand, the raw material wax in the present embodiment is an ethylene polymer wax (that is, a wax which is a polymer of ethylene), and most of them are hydrocarbon compounds having an even number of carbon atoms (hydrocarbons having 2 n carbon atoms). Compound). Then, when the wax isomerized oil is produced by the method for producing the wax isomerized oil according to the present embodiment using the ethylene polymer wax as a raw material wax, the molecular structure is changed due to the isomerization (for example, normal paraffin having 2 n carbon atoms). (Production of isoparaffin having 2n + 1 carbon atoms by isomerization) can occur, but the obtained wax isomerized oil has a proportion of either a hydrocarbon compound having an even number of carbon atoms or a hydrocarbon compound having an odd number of carbon atoms. It shows a peculiar carbon number distribution that it is large. The wax isomerized oil according to the present embodiment exhibits a lower traction coefficient as compared with the conventional wax isomerized oil having the same viscosity and viscosity index because of the specificity of the carbon number distribution. it seems to do.

When the decomposition product obtained by hydrogenation decomposition is desorbed, the reason for isomerization dewaxing using a hydrogenation isomerization catalyst is to maintain the above-mentioned peculiar carbon number distribution as much as possible. .. This is because it is conceivable that a large amount of hydrocarbon compounds having an even number of carbon atoms having a strong intermolecular force are separated during dewaxing of decomposition products, for example, in solvent dewaxing, but hydrogenation isomerization. It is considered that such separation can be suppressed by isomerization and dewaxing using a catalyst.

Examples of the ethylene polymer wax prepared in the first step include ethylene oligomer wax obtained by oligomerizing ethylene. In the present embodiment, the "oligomer" means a polymer having a number average molecular weight (Mn) of 5000 or less. The Mn of the ethylene oligomer is preferably 3000 or less, more preferably 1000 or less. The lower limit of Mn of the ethylene oligomer is not particularly limited, but may be, for example, 200 or more, 250 or more, or 300 or more. Further, Mw / Mn indicating the degree of molecular weight distribution (dispersity) may be, for example, 1.0 to 5.0, or 1.1 to 3.0. When the Mn of the ethylene oligomer is 3000 or less, it is not necessary to tighten the isomerization conditions such as raising the reaction temperature in order to obtain the base oil having the target viscosity using the oligomer as a raw material, and the desired base oil is used. Can be obtained efficiently. It is also possible to prevent an increase in the traction coefficient due to excessive isomerization. On the other hand, when the Mn of the ethylene oligomer is 200 or more, the base oil having the target viscosity can be efficiently obtained.

The oligomers Mn and Mw can be determined as polystyrene-equivalent quantities based on a calibration curve prepared from standard polystyrene, for example, using a GPC apparatus.

The ethylene polymer wax used as the raw material wax usually contains normal paraffin. The content of normal paraffin in the ethylene polymer wax is not particularly limited, but may be, for example, 40% by mass or more, 50% by mass or more, and 60% by mass or more based on the total amount of ethylene polymer wax. May be. The upper limit of the content of normal paraffin is also not particularly limited, and may be, for example, 100% by mass or less, 90% by mass or less, or 85% by mass or less.

In the composition of the hydrocarbon compound contained in the ethylene polymer wax, the content of the hydrocarbon compound having an even number of carbon atoms is preferably 80% by mass or more, more preferably 90% by mass, based on the total amount of the ethylene polymer wax. As described above, from the viewpoint that the traction coefficient of the obtained wax isomerized oil can be reduced more effectively, it is more preferable that the hydrocarbon compound having an odd number of carbon atoms is not substantially contained.

The content of the above normal paraffin and the content of the hydrocarbon compound having an even number of carbon atoms were determined by performing gas chromatography analysis on the ethylene polymer wax under the following conditions, and the normal paraffin and the content of the hydrocarbon compound having an even number of carbon atoms in the total amount of the ethylene polymer wax. It means a value obtained by measuring and calculating the ratio of hydrocarbon compounds having an even number of carbon atoms. At the time of measurement, a mixed sample of normal paraffin having 5 to 50 carbon atoms is used as a standard sample, and each of the above ratios is the sum of the peak area values corresponding to the normal paraffin to the total peak area value of the chromatogram. Alternatively, it is obtained as a ratio of the total peak area values corresponding to the hydrocarbon compounds having an even number of carbon atoms. Here, in the case of a hydrocarbon compound having the same carbon number, the hydrocarbon compound having the highest boiling point (longest distillation time) is normal paraffin, so the above standard sample was measured when calculating the carbon number. The number of peaks existing between the peak corresponding to the distillation time of normal paraffin having n carbon atoms and the peak corresponding to the distillation time of normal paraffin having n-1 carbon atoms is n. It shall correspond to non-normal paraffin having the same carbon number as, and shall distinguish between normal paraffin and non-normal paraffin having the same carbon number.

(Gas chromatography conditions)
Column: Liquid phase non-polar column (length: 25 mm, inner diameter: 0.3 mmφ, liquid phase film thickness: 0.1 μm)
Heating conditions: 50 to 400 ° C (heating rate: 10 ° C / min)
Carrier gas: Helium (Line speed: 40 cm / min)
Split ratio: 90 / l
Sample injection amount: 0.5 μL (injection amount of sample diluted 20 times with carbon disulfide)
Detector: Hydrogen flame ionization detector (FID)

The method for producing the ethylene polymer wax is not particularly limited, but it can be obtained, for example, by polymerizing (oligomerizing) ethylene in the presence of an ethylene polymerization catalyst. As a specific embodiment, for example, a method of introducing ethylene into a reaction apparatus filled with a catalyst can be mentioned. The method of introducing ethylene into the reactor is not particularly limited.

Further, a solvent may be used in the polymerization reaction. Examples of the solvent include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane and decalin; aromatic hydrocarbon solvents such as tetralin, benzene, toluene and xylene. The catalyst can be dissolved in these solvents to carry out solution polymerization, slurry polymerization and the like.

The reaction temperature in the polymerization reaction is not particularly limited, but from the viewpoint of catalytic efficiency, for example, it may be −50 ° C. to 100 ° C., −30 ° C. to 80 ° C., or −20 ° C. to 70 ° C. It may be 0 ° C to 50 ° C, 5 ° C to 30 ° C, or 5 ° C to 15 ° C. When the reaction temperature is −50 ° C. or higher, precipitation of the polymer produced while maintaining the catalytic activity can be suppressed, and when the reaction temperature is 100 ° C. or lower, decomposition of the catalyst can be suppressed. Further, the reaction pressure is not particularly limited, but may be, for example, 100 kPa to 5 MPa. The reaction time is also not particularly limited, but may be, for example, 1 minute to 24 hours, 5 minutes to 60 minutes, 10 minutes to 45 minutes, or 20 minutes to 40 minutes. There may be.

The ethylene polymerization catalyst is not particularly limited, and examples thereof include a catalyst containing an iron compound represented by the following general formula (1).

In the formula (1), R represents a hydrocarbyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 12 carbon atoms, and a plurality of Rs in the same molecule may be the same or different. R'indicates a free radical having an oxygen atom and / or a nitrogen atom, and a plurality of R'in the same molecule may be the same or different. Y represents a chlorine atom or a bromine atom.

Examples of the hydrocarbyl group having 1 to 6 carbon atoms include an alkyl group having 1 to 6 carbon atoms and an alkenyl group having 2 to 6 carbon atoms. The hydrocarbyl group may be linear, branched or cyclic. Further, the hydrocarbyl group may be a monovalent group in which a linear or branched hydrocarbyl group and a cyclic hydrocarbyl group are bonded.

As the alkyl group having 1 to 6 carbon atoms, a linear alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group and an n-hexyl group; iso. -Propyl group, iso-butyl group, sec-butyl group, tert-butyl group, branched pentyl group (including all structural isomers), branched hexyl group (including all structural isomers), etc. A branched chain alkyl group having 3 to 6 carbon atoms; a cyclic alkyl group having 1 to 6 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group can be mentioned.

Examples of the alkenyl group having 2 to 6 carbon atoms include a linear alkenyl group having 2 to 6 carbon atoms such as an ethenyl group (vinyl group), an n-propenyl group, an n-butenyl group, an n-pentenyl group and an n-hexenyl group; Carbons such as iso-propenyl group, iso-butenyl group, sec-butenyl group, tert-butenyl group, branched pentenyl group (including all structural isomers), branched chain hexenyl group (including all structural isomers) Branched chain alkenyl group of number 2 to 6; cyclic alkenyl group having 2 to 6 carbon atoms such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclopentadienyl group, cyclohexenyl group, cyclohexadienyl group and the like can be mentioned. ..

Examples of the aromatic group having 6 to 12 carbon atoms include a phenyl group, a toluyl group, a xylyl group, and a naphthyl group.

In formula (1), a plurality of Rs and R'in the same molecule may be the same or different, but may be the same from the viewpoint of simplifying the synthesis of the compound.

The free radical having an oxygen atom and / or a nitrogen atom may be a free radical having 0 to 6 carbon atoms having an oxygen atom and / or a nitrogen atom, and may be, for example, a methoxy group, an ethoxy group, an isopropoxy group, or a nitro group. And so on.

Specific examples of such an iron compound include compounds represented by the following formulas (1a) to (1h). These iron compounds may be used alone or in combination of two or more.

In the iron compound represented by the general formula (1), the compound constituting the ligand (hereinafter, also referred to as a diimine compound) dehydrates and condenses, for example, dibenzoylpyridine and aniline compound in the presence of an acid. Can be obtained by

A preferred embodiment of the method for producing a diimine compound is a first step of dissolving 2,6-dibenzoylpyridine, an aniline compound and an acid in a solvent and dehydrating and condensing the mixture under heating and refluxing the solvent, and a reaction mixture after the first step. It is provided with a second step of performing separation / purification treatment to obtain a diimine compound.

As the acid used in the first step, for example, an organoaluminum compound can be used. Examples of the organic aluminum compound include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, and methylaluminoxane. And so on.

As the acid used in the first step, a protonic acid may be used in addition to the above-mentioned organoaluminum compound. Protonic acid is used as an acid catalyst to donate protons. The protonic acid used is not particularly limited, but is preferably an organic acid. Examples of such a protonic acid include acetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid and the like. When these protonic acids are used, it is preferable to remove the water with a Dean-Stark water separator or the like from the viewpoint of suppressing the by-product of water. It is also possible to carry out the reaction in the presence of an adsorbent such as molecular sieves. The amount of the protonic acid added is not particularly limited and may be any catalyst amount.

Examples of the solvent used in the first step include a hydrocarbon solvent and an alcohol solvent. Examples of the hydrocarbon solvent include hexane, heptane, octane, benzene, toluene, xylene, cyclohexane, methylcyclohexane and the like. Examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol and the like.

The reaction conditions in the first step can be appropriately selected depending on the type and amount of the raw material compound, the acid and the solvent.

The separation / purification treatment in the second step is not particularly limited, and examples thereof include silica gel column chromatography and a recrystallization method. In particular, when the above-mentioned organoaluminum compound is used as the acid, it is preferable to mix the reaction solution with a basic aqueous solution to decompose and remove aluminum, and then purify the compound.

The mixing method of the diimine compound and iron is not particularly limited, and for example,
(I) A method of adding and mixing an iron salt (hereinafter, also referred to simply as "salt") to a solution in which a diimine compound is dissolved.
(Ii) A method of physically mixing a diimine compound and a salt without using a solvent,
And so on.

Further, the method for extracting the complex from the mixture of the diimine compound and iron is not particularly limited, and for example,
(A) When a solvent is used in the mixture, the solvent is distilled off and the solid matter is filtered off.
(B) A method for filtering out the precipitate formed from the mixture,
(C) A method of adding a poor solvent to the mixture to purify the precipitate and filter it.
(D) A method for taking out the solvent-free mixture as it is,
And so on. After that, a cleaning treatment with a solvent capable of dissolving the diimine compound, a cleaning treatment with a solvent capable of dissolving the metal, a recrystallization treatment using an appropriate solvent, or the like may be performed.

Examples of iron salts include iron (II) chloride, iron (III) chloride, iron (II) bromide, iron (III) bromide, iron (II) acetylacetone, iron (III) acetylacetone, and iron (II) acetate. ), Iron acetate (III), and the like. Those salts having a ligand such as a solvent and water may be used. Among these, the salt of iron (II) is preferable, and iron (II) chloride is more preferable.

Further, the solvent for bringing the diimine compound into contact with iron is not particularly limited, and either a non-polar solvent or a polar solvent can be used. Examples of the non-polar solvent include hydrocarbon solvents such as hexane, heptane, octane, benzene, toluene, xylene, cyclohexane and methylcyclohexane. Examples of the polar solvent include polar protic solvents such as alcohol solvents and polar aprotic solvents such as tetrahydrofuran. Examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol and the like. In particular, when the mixture is used as it is as a catalyst, it is preferable to use a hydrocarbon solvent that does not substantially affect the ethylene polymerization reaction.

Further, the mixing ratio of the diimine compound and iron when they are brought into contact with each other is not particularly limited. The ratio of the dimin compound / iron may be 0.2 / 1 to 5/1, 0.3 / 1 to 3/1, or 0.5 / 1 to 2/1 in terms of molar ratio. , 1/1 may be used.

The two imine sites in the diimine compound are preferably E-forms, but may contain Z-form-containing diimine compounds as long as they both contain E-form diimine compounds. Since the diimine compound containing the Z-form is difficult to form a complex with a metal, it can be easily removed by a purification step such as solvent washing after forming the complex in the system.

The ethylene polymerization catalyst containing the iron compound represented by the general formula (1) may further contain an organoaluminum compound in order to allow the polymerization reaction to proceed more efficiently. Examples of the organoaluminum compound include trimethylaluminum and methylaluminoxane. At this time, the content ratio of the iron compound represented by the general formula (1) to the organoaluminum compound is a molar ratio when the number of moles of the iron compound is G and the number of moles of aluminum atoms of the organoaluminum compound is H. G: H = 1:10 to 1: 1000, 1:10 to 1:800, 1:20 to 1:600, 1:20 to 1: It may be 500. Within the above range, it is possible to suppress factors of cost increase while exhibiting more sufficient polymerization activity.

When methylaluminoxane is used as the organoaluminum compound, a commercially available product diluted with a solvent can be used as the methylaluminoxane, or a product obtained by partially hydrolyzing trimethylaluminum in a solvent can also be used. Further, at the time of partial hydrolysis of trimethylaluminum, modified methylaluminoxane which is co-hydrolyzed by coexisting trialkylaluminum other than trimethylaluminum such as triisobutylaluminum can also be used. Further, if unreacted trialkylaluminum remains during the above partial hydrolysis, the unreacted trialkylaluminum may be removed by distillation under reduced pressure or the like. Further, modified methylaluminoxane obtained by modifying methylaluminoxane with an active proton compound such as phenol or a derivative thereof may be used.

When trimethylaluminum and methylaluminoxane are used in combination as the organic aluminum compound, the content ratio of trimethylaluminum and methylaluminoxane in the ethylene polymerization catalyst is H1 for the _number of moles of trimethylaluminum and the number of moles of aluminum atoms in methylaluminoxane. In the case of H ₂ , the molar ratio may be H ₁ : H ₂ = 100: 1 to 1: 100, 50: 1 to 1:50, or 10: 1 to 1:10. May be. Within the above range, it is possible to suppress factors of cost increase while exhibiting more sufficient catalytic efficiency.

Further, the ethylene polymerization catalyst containing the iron compound represented by the general formula (1) may further contain a boron compound as an arbitrary component.

The boron compound has a function as an auxiliary catalyst for further improving the catalytic activity of the iron compound represented by the above formula (1) in the ethylene polymerization reaction.

Examples of the boron compound include arylboron compounds such as trispentafluorophenylboran. Further, as the boron compound, a boron compound having an anionic species can be used. For example, aryl borate such as tetrakispentafluorophenyl borate and tetrakis (3,5-trifluoromethylphenyl) borate can be mentioned. Specific examples of arylborates include lithium tetrakispentafluorophenylborate, sodium tetrakispentafluorophenylborate, N, N-dimethylanilinium tetrakispentafluorophenylborate, trityltetrakispentafluorophenylborate, and lithium tetrakis (3,5-tri). Fluoromethylphenyl) borate, sodium tetrakis (3,5-trifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (3,5-trifluoromethylphenyl) borate, trityltetrakis (3,5-trifluoromethyl) Phenyl) Borate and the like. Among these, N, N-dimethylanilinium tetrakispentafluorophenylborate, trityltetrakispentafluorophenylborate, N, N-dimethylanilinium tetrakis (3,5-trifluoromethylphenyl) borate or trityltetrakis (3,5) -Trifluoromethylphenyl) borate is preferred. These boron compounds may be used alone or in combination of two or more.

When the organoaluminum compound and the boron compound are used in combination in the ethylene polymerization catalyst, the content ratio of the organoaluminum compound and the boron compound is the molar ratio when the number of moles of the organoaluminum compound is H and the number of moles of the boron compound is J. H: J = 1000: 1 to 1: 1 may be used, 800: 1 to 2: 1 may be used, or 600: 1 to 10: 1 may be used. Within the above range, it is possible to suppress factors of cost increase while exhibiting more sufficient catalytic efficiency.

The ethylene polymerization catalyst containing the iron compound represented by the above formula (1) is further represented by the following general formula (2) from the viewpoint of ensuring more sufficient catalytic efficiency (hereinafter, may be referred to as a ligand). May be contained.

In the formula (2), R'' indicates a hydrocarbyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 12 carbon atoms, and a plurality of R''s in the same molecule may be the same or different. '''' Indicates a free radical having 0 to 6 carbon atoms having an oxygen atom and / or a nitrogen atom, and a plurality of R''''s in the same molecule may be the same or different.

Examples of the hydrocarbyl group having 1 to 6 carbon atoms include an alkyl group having 1 to 6 carbon atoms and an alkenyl group having 2 to 6 carbon atoms. The hydrocarbyl group may be linear, branched or cyclic. Further, the hydrocarbyl group may be a monovalent group in which a linear or branched hydrocarbyl group and a cyclic hydrocarbyl group are bonded.

As the alkyl group having 1 to 6 carbon atoms, a linear alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group and an n-hexyl group; iso. -Propyl group, iso-butyl group, sec-butyl group, tert-butyl group, branched pentyl group (including all structural isomers), branched hexyl group (including all structural isomers), etc. A branched chain alkyl group having 3 to 6 carbon atoms; a cyclic alkyl group having 1 to 6 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group can be mentioned.

Examples of the alkenyl group having 2 to 6 carbon atoms include a linear alkenyl group having 2 to 6 carbon atoms such as an ethenyl group (vinyl group), an n-propenyl group, an n-butenyl group, an n-pentenyl group and an n-hexenyl group; Carbons such as iso-propenyl group, iso-butenyl group, sec-butenyl group, tert-butenyl group, branched pentenyl group (including all structural isomers), branched chain hexenyl group (including all structural isomers) Branched chain alkenyl group of number 2 to 6; cyclic alkenyl group having 2 to 6 carbon atoms such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclopentadienyl group, cyclohexenyl group, cyclohexadienyl group and the like can be mentioned. ..

Examples of the aromatic group having 6 to 12 carbon atoms include a phenyl group, a toluyl group, a xylyl group, and a naphthyl group.

In the formula (2), a plurality of R ″ and R ″ in the same molecule may be the same or different, but may be the same from the viewpoint of simplifying the synthesis of the compound.

The free radical having an oxygen atom and / or a nitrogen atom may be a free radical having 0 to 6 carbon atoms having an oxygen atom and / or a nitrogen atom, and may be, for example, a methoxy group, an ethoxy group, an isopropoxy group, or a nitro group. And so on.

Specific examples of such a ligand include compounds represented by the following formulas (2a) to (2d). These ligands can be used alone or in combination of two or more.

Further, in the iron compound represented by the general formula (1) and the compound represented by the general formula (2) contained in the ethylene polymerization catalyst according to the present embodiment, R of the general formula (1) and the general formula ( The R'' of 2), the R'of the general formula (1) and the R'''of the general formula (2) may be the same or different, but the iron represented by the general formula (1) may be different. From the viewpoint of maintaining the same performance as the compound, they are preferably the same.

When the above-mentioned ligand is contained in the ethylene polymerization catalyst according to the present embodiment, the content ratio of the iron compound and the ligand is not particularly limited. The ligand / iron compound ratio is preferably 1/100 to 100/1, more preferably 1/20 to 50/1, still more preferably 1/10 to 10/1, and particularly preferably 1/5 in terms of molar ratio. It is ~ 5/1, very preferably 1/3 ~ 3/1. When the ratio of the ligand / iron compound is 1/100 or more, the effect of adding the ligand can be sufficiently exerted, and when the ratio is 100/1 or less, the effect of adding the ligand can be exerted and the cost can be suppressed. ..

The method for producing the above-mentioned ethylene polymerization catalyst is not particularly limited. For example, when the above-mentioned ethylene polymerization catalyst contains an iron compound represented by the above-mentioned general formula (1) and an organoaluminum compound, the general formula (1) is used. A method of adding and mixing a solution containing an organoaluminum compound to a solution containing an iron compound represented by the above, and a method of adding and mixing a solution containing an iron compound represented by the general formula (1) to a solution containing an organoaluminum compound. The method of doing this can be mentioned. Further, for example, when the above-mentioned boron compound and the compound represented by the general formula (2) are further contained in addition to the iron compound represented by the general formula (1) and the organoaluminum compound, all of these components are further contained. May be contacted all at once, or may be contacted in any order. As a method for producing an ethylene polymerization catalyst according to the present embodiment, for example,
(A) A method in which a solution containing an iron compound represented by the general formula (1) and a solution containing a boron compound are mixed and then brought into contact with an organic aluminum compound (B) An iron compound represented by the general formula (1). Method of contacting a boron compound after mixing the solution containing the above and the solution containing the organic aluminum compound (C) After mixing the solution containing the boron compound and the solution containing the organic aluminum compound, the general formula (1) is used. Method for contacting the iron compound to be prepared (D) Method for contacting the organic aluminum compound after mixing the solution containing the iron compound represented by the general formula (1) and the solution containing the ligand (E) General formula (1) ), After mixing the solution containing the iron compound and the solution containing the organic aluminum compound, the method of contacting the ligand (F) After mixing the solution containing the organic aluminum compound and the solution containing the ligand, the general formula Method for contacting the iron compound represented by (1) (G) After mixing the solution containing the iron compound represented by the general formula (1) and the solution containing the boron compound, the solution containing the organic aluminum compound is added. , Mixing, and then contacting the ligand (H) After mixing the solution containing the iron compound represented by the general formula (1) and the solution containing the boron compound, the solution containing the ligand is added and mixed, and then. Method for contacting an organic aluminum compound (I) After mixing a solution containing an iron compound represented by the general formula (1) and a solution containing an organic aluminum compound, a solution containing a boron compound is added and mixed, and then a ligand is used. (J) After mixing the solution containing the iron compound represented by the general formula (1) and the solution containing the organic aluminum compound, the solution containing the ligand is added and mixed, and then the boron compound is contacted. Method (K) A method (L) in which a solution containing an iron compound represented by the general formula (1) and a solution containing a ligand are mixed, then a solution containing an organic aluminum compound is added and mixed, and then a boron compound is brought into contact with the solution (L). ) A method in which a solution containing an iron compound represented by the general formula (1) and a solution containing a ligand are mixed, a solution containing a boron compound is added and mixed, and then an organic aluminum compound is brought into contact with the (M) boron compound. A method in which a solution containing an organic aluminum compound and a solution containing an organic aluminum compound are mixed, a solution containing an iron compound represented by the general formula (1) is added and mixed, and then a ligand is brought into contact with the solution (N) A solution containing a boron compound. And the solution containing the organic aluminum compound, then the solution containing the ligand is added and mixed, and then one Method for contacting iron compound represented by general formula (1) (O) After mixing a solution containing a boron compound and a solution containing a ligand, a solution containing an iron compound represented by the general formula (1) is added. , And then the method of contacting the organic aluminum compound (P) After mixing the solution containing the boron compound and the solution containing the ligand, the solution containing the organic aluminum compound is added and mixed, and then the general formula (1) is used. Method for contacting the represented iron compound (Q) After mixing the solution containing the organic aluminum compound and the solution containing the ligand, the solution containing the iron compound represented by the general formula (1) is added and mixed, and then the solution is added. Method for contacting a boron compound (R) After mixing a solution containing an organic aluminum compound and a solution containing a ligand, a solution containing a boron compound is added and mixed, and then an iron compound represented by the general formula (1) is obtained. Method of contacting (S) A method of contacting a boron compound with a solution containing an iron compound represented by the general formula (1), and then adding and mixing the solution containing an organic aluminum compound (T) with the general formula (1). Examples thereof include a method in which a boron compound is brought into contact with a solution containing the iron compound represented by the compound, and then a solution containing trimethylaluminum is added and mixed to bring the methylaluminoxane into contact.

The above-mentioned ethylene polymer wax can be used as a raw material, and the raw material can be hydrogenated and decomposed by a hydrogenation decomposition catalyst in the second step to obtain a decomposition product. Examples of the hydrocracking catalyst include catalysts containing Group 6 metals, Group 8-10 metals, and mixtures thereof. Preferred metals include nickel, tungsten, molybdenum, cobalt and mixtures thereof. The hydrocracking catalyst can be used in an embodiment in which these metals are supported on a heat-resistant metal oxide carrier, and the metal usually exists as an oxide or a sulfide on the carrier. When a metal mixture is used, it may exist as a bulk metal catalyst in which the amount of metal is 30% by mass or more based on the total amount of the catalyst. Examples of the metal oxide carrier include oxides such as silica, alumina, silica-alumina, and titania, and alumina is particularly preferable. Preferred alumina is γ-type or β-type porous alumina. The amount of metal supported is preferably in the range of 0.5 to 35% by mass based on the total amount of the catalyst. When a mixture of Group 9-10 metal and Group 6 metal is used, either Group 9 or Group 10 metal is present in an amount of 0.1 to 5% by mass based on the total amount of the catalyst. The Group 6 metal is preferably present in an amount of 5 to 30% by mass. The amount of metal carried may be measured by atomic absorption spectroscopy, inductively coupled plasma emission spectroscopy or other methods specified by ASTM for individual metals.

The acidity of the metal oxide carrier can be controlled by the addition of additives, control of the properties of the metal oxide carrier (eg, control of the amount of silica incorporated into the silica-alumina carrier), and the like. Examples of additives include halogens, especially fluorine, phosphorus, boron, itria, alkali metals, alkaline earth metals, rare earth oxides, and magnesia. Cocatalysts such as halogen generally increase the acidity of metal oxide carriers, while weakly basic additives such as yttrium or magnesia tend to weaken the acidity of such carriers.

Regarding the hydrocracking treatment conditions, the treatment temperature is preferably 150 to 450 ° C., more preferably 200 to 400 ° C., and the hydrogen partial pressure is preferably 1400 to 20000 kPa, more preferably 2800 to 14000 kPa, and the liquid space. The rate (LHSV) is preferably 0.1 to 10 hr ^-1 , more preferably 0.1 to 5 hr ^-1 , and the hydrogen / oil ratio is preferably 50 to 1780 m ³ / m ³ , more preferably 89 to. It is 890 m ³ / m ³ . The above conditions are an example, and it is preferable to appropriately select the hydrodecomposition treatment conditions according to the differences in raw materials, catalysts, devices, and the like.

In the third step, the decomposition product obtained in the second step can be isomerized and dewaxed to obtain a lubricating oil base oil which is a wax isomerized oil. The isomerization dewaxing is to desorb the raw material by hydrogenation isomerization by contacting the ethylene polymer wax with a hydrogenation isomerization catalyst in the presence of hydrogen (molecular hydrogen). The hydrogenation isomerization here includes, in addition to the isomerization of normal paraffin to isoparaffin, the conversion of olefins to paraffin by hydrogenation and the conversion of alcohols to paraffin by dehydrogenation groups.

The hydrogenation isomerization catalyst may contain either crystalline or amorphous material. Examples of the crystalline material include a molecular sieve containing aluminosilicate (zeolite) or siliconoaluminophosphate (SAPO) as a main component and having a 10- or 12-membered ring passage. Specific examples of zeolite include ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, ferrierite, ITQ-13, MCM-68, MCM-71 and the like. Further, as an example of aluminophosphate, ECR-42 can be mentioned. Examples of molecular sheaves include zeolite beta and MCM-68. Among these, it is preferable to use one or more selected from ZSM-48, ZSM-22 and ZSM-23, and ZSM-48 is particularly preferable. The molecular sieve is preferably in the hydrogen form. The reduction of the hydrogenation isomerization catalyst can occur in situ during the hydrogenation isomerization, but a hydrogenation isomerization catalyst that has been subjected to a reduction treatment in advance may be subjected to the hydrogenation isomerization.

Examples of the amorphous material of the hydrogenation isomerization catalyst include alumina doped with a group 3 metal, fluoride alumina, silica-alumina, and fluoride silica-alumina.

Preferred embodiments of hydrogenation isomerization catalysts include bifunctionality, i.e., fitted with at least one Group 6 metal, at least one Group 8-10 metal, or a metal hydrogenated component that is a mixture thereof. Be done. Preferred metals are Group 9-10 noble metals such as Pt, Pd or mixtures thereof. The amount of these metals attached is preferably 0.1 to 30% by mass based on the total amount of the catalyst. Examples of the catalyst preparation and metal mounting method include an ion exchange method and an impregnation method using a degradable metal salt.

When a molecular sieve is used, it may be composited with a binder material having heat resistance under hydrogenation isomerization conditions, or may be without a binder (self-bonding). Binder materials include silica, alumina, silica-alumina, a combination of two components of silica with other metal oxides such as titania, magnesia, tria, zirconia, silica-alumina-tria, silica-alumina-magnesia, etc. Examples thereof include inorganic oxides such as a combination of three components of oxides such as. The amount of molecular sieve in the hydrogenation isomerization catalyst is preferably 10 to 100% by mass, more preferably 35 to 100% by mass, based on the total amount of the catalyst. The hydrogenation isomerization catalyst is formed by a method such as spray drying or extrusion. The hydrogenation isomerization catalyst can be used in a sulfided or non-sulfided embodiment, and the sulfided embodiment is preferable.

Regarding the hydrogenation isomerization conditions, the temperature is preferably 250 to 400 ° C., more preferably 275 to 350 ° C., and the hydrogen partial pressure is preferably 791 to 20786 kPa (100 to 3000 psig), more preferably 1480 to 17339 kPa (200 to 17339 kPa). 2500 psig), the liquid space velocity is preferably 0.1 to 10 hr ^-1 , more preferably 0.1 to 5 hr ^-1 , and the hydrogen / oil ratio is preferably 45 to 1780 m ³ / m ³ (250 to 10000 scf). / B), more preferably 89 to 890 m ³ / m ³ (500 to 5000 scf / B). The above conditions are an example, and it is preferable to appropriately select hydrogenation isomerization conditions according to differences in raw materials, catalysts, devices, and the like.

The production method according to the present embodiment may include a step of fractionating the raw material wax (raw material distillation step) before subjecting the ethylene polymer wax to the above-mentioned second step. By subjecting the fraction obtained through the raw material distillation step to the second step and the third step as the oil to be treated, a wax isomerized oil having a desired viscosity grade can be efficiently obtained.

The boiling point range of the distillate in the raw material distillation step can be adjusted as appropriate. As the boiling point range of the fraction, for example, a fraction having a boiling point range of 250 to 500 ° C. can be fractionated. Further, when obtaining a wax isomerized oil corresponding to 70 Pale, SAE10 or VG6, for example, the boiling point range of the fraction can be set as follows.

70Pale: Fraction with boiling point range of 300 to 460 ° C SAE10: Fraction with boiling point range of 360 to 500 ° C VG6: Fraction of 250 to 440 ° C

For example, a boiling point range of 250 to 500 ° C. indicates that the initial distillate point and the end point are within the range of 250 to 500 ° C.

The distillation conditions in the raw material distillation step are not particularly limited as long as the desired fraction can be fractionated from the ethylene polymer wax. For example, the raw material distillation step may be a step of fractional distillation by vacuum distillation, or may be a step of fractional distillation by combining atmospheric distillation (or distillation under pressure) and vacuum distillation. Further, for example, in the raw material distillation step, it may be fractionated as a single fraction from the ethylene polymer wax, or may be fractionated as a plurality of fractions according to the viscosity grade.

The wax isomerized oil in which the normal paraffin contained in the decomposition product is isomerized to isoparaffin by the above-mentioned third step may be subjected to hydrorefining if desired, and is divided into fractions having a desired viscosity grade. It may be retained.

Hydrorefining, for example, hydrogenates the olefins in the wax isomerized oil, improving the oxidative stability and hue of the lubricating oil. Hydrorefining can be carried out, for example, using a hydrorefining catalyst.

The hydrorefining catalyst is preferably one in which a group 6 metal, a group 8-10 metal or a mixture thereof is supported on a metal oxide carrier. Preferred metals include precious metals, especially platinum, palladium and mixtures thereof. When a metal mixture is used, it may exist as a bulk metal catalyst in which the amount of metal is 30% by mass or more with respect to the catalyst. The metal content of the catalyst is preferably 20% by mass or less for non-precious metals and 1% by mass or less for noble metals. Further, the metal oxide carrier may be either amorphous or crystalline oxide. Specific examples thereof include low acid oxides such as silica, alumina, silica-alumina and titania, and alumina is preferable. From the viewpoint of saturation of aromatic compounds, it is preferable to use a hydrorefining catalyst in which a metal having a relatively strong hydrogenation function is supported on a porous carrier.

Preferred hydrorefining catalysts include mesoporeal materials belonging to M41S class or line catalysts. The catalyst of the M41S system is a mesoporous material having a high silica content, and specific examples thereof include MCM-41, MCM-48 and MCM-50. Such a hydrorefining catalyst has a pore size of 15 to 100 Å, and MCM-41 is particularly preferable. MCM-41 is an inorganic porous non-layered phase with a hexagonal arrangement of uniformly sized pores. The physical structure of the MCM-41 is like a bundle of straws with straw openings (cell diameters of pores) in the range of 15-100 angstroms. MCM-48 has cubic symmetry and MCM-50 has a layered structure. MCM-41 can be produced with pore openings of different sizes in the mesoporeity range. The mesoporous material may have a metal hydrogenating component which is at least one of Group 8, Group 9 or Group 10 metals, and the metal hydrogenating component is preferably a noble metal, particularly a Group 10 noble metal, and Pt. , Pd or mixtures thereof are most preferred.

Regarding the conditions of hydrorefining, the temperature is preferably 150 to 350 ° C., more preferably 180 to 250 ° C., the total pressure is preferably 2859 to 20786 kPa (about 400 to 3000 psig), and the liquid space velocity is preferably 0. .1 to 5 hr ^-1 , more preferably 0.5 to 3 hr ^-1 , and the hydrogen / oil ratio is preferably 44.5 to 1780 m ³ / m ³ (250 to 10,000 scf / B). The above conditions are an example, and it is preferable to appropriately select the hydrorefining conditions according to the difference in the raw material and the processing apparatus.

When the wax isomerized oil is fractionated into a fraction having a desired viscosity grade, the distillation conditions are not particularly limited, but for example, atmospheric distillation (or under pressure) for distilling a light fraction from the wax isomerized oil is performed. Distillation) and vacuum distillation for fractionating a desired fraction from the bottom oil of the atmospheric distillation.

In distillation, a plurality of lubricating oil fractions are obtained by setting a plurality of cut points and distilling the bottom oil obtained by atmospheric distillation (or distillation under pressure) of wax isomerized oil under reduced pressure. be able to. For example, in order to obtain a wax isomerized oil corresponding to 70 Pale, which is suitable as a lubricating oil base oil for ATF and shock absorbers, the boiling point range at normal pressure is set to a kinematic viscosity of 2.7 mm ² / s at 100 ° C. Method of recovering the fraction at 330 to 410 ° C; In order to obtain a lubricating oil base oil corresponding to SAE-10 suitable as a lubricating oil base oil for engine oils satisfying the specifications of API Group III, the kinematic viscosity at 100 ° C. 4 A method of recovering a distillate having a boiling point range of 410 to 460 ° C. at normal pressure with a target value of 0.0 mm ² / s; kinematic viscosity 2.0 mm at 100 ° C. to obtain a wax isomerized oil corresponding to VG6. Examples thereof include a method of recovering a distillate having a boiling point range of 330 ° C. or lower with ² / s as a target value.

The wax isomerized oil according to the present embodiment exhibits a lower traction coefficient as compared with the conventional wax isomerized oil having the same viscosity and viscosity index.

The viscosity grade of the wax isomerized oil according to the present embodiment is not particularly limited, but its kinematic viscosity at 100 ° C. is preferably 1.5 mm ² / s or more, more preferably 1.8 mm ² / s or more, and further. It is preferably 2.0 mm ² / s or more. On the other hand, the upper limit of the kinematic viscosity at 100 ° C. is not particularly limited, but is preferably 20 mm ² / s or less, more preferably 15 mm ² / s or less, still more preferably 10 mm ² / s or less, and particularly preferably 4 mm ² / s. It is as follows.

In the present embodiment, wax isomerized oil having a kinematic viscosity at 100 ° C. in the following range can be separated by distillation or the like and used.
(I) Wax isomerized oil having a kinematic viscosity of 1.5 mm ² / s or more and less than 2.3 mm ² / s, more preferably 1.8 mm to 2.1 mm ² / s at 100 ° C. (II) kinematic viscosity at 100 ° C. 2.3 mm ² / s or more and less than 3.0 mm ² / s, more preferably 2.4 to 2.8 mm ² / s wax isomerized oil (III) has a kinematic viscosity of 3.0 to 20 mm ² / at 100 ° C. s, more preferably 3.2 to 11 mm ² / s, even more preferably 3.5 to 5 mm ² / s, particularly preferably 3.6 to 4 mm ² / s wax isomerized oil.

In the present embodiment, the traction coefficient of the wax isomerized oil uses a steel ball and a steel disk as test pieces under the conditions of a load of 20 N, a test oil temperature of 25 ° C., a peripheral speed of 0.52 m / s, and a slip rate of 3%. Be measured.

The wax isomerized oil according to this embodiment can achieve a low traction coefficient. The traction coefficient of the wax isomerized oil according to the present embodiment can be appropriately selected according to the viscosity grade. For example, the traction coefficient of the wax isomerized oil (I) is preferably 0.0026 or less. More preferably, it is 0.0024 or less. The traction coefficient of the wax isomerized oil (II) is preferably 0.0026 or less, more preferably 0.0025 or less. The traction coefficient of the wax isomerized oil (III) is preferably 0.0027 or less, more preferably 0.0025 or less. When the traction coefficient is within the above numerical range, low friction can be ensured, which is preferable from the viewpoint of energy saving. On the other hand, the lower limit of the traction coefficient is not particularly limited, but may be, for example, 0.001 or more.

The viscosity index of the wax isomerized oil according to the present embodiment can be appropriately selected according to the viscosity grade. For example, the viscosity index of the isomerized oil (I) is preferably 105 to 150, more preferably 110 to 140, and even more preferably 115 to 135. The viscosity index of the isomerized oil (II) is preferably 120 to 160, more preferably 125 to 150, and even more preferably 130 to 150. The viscosity index of the isomerized oil (III) is preferably 140 to 180, more preferably 145 to 170. When the viscosity index is within the above range, excellent viscosity-temperature characteristics can be ensured, which is preferable from the viewpoint of energy saving. The viscosity index referred to in the present invention means a viscosity index measured in accordance with JIS K 2283-1993.

The density (ρ ₁₅ , unit: g / cm ³ ) of the wax isomerized oil according to the present embodiment at 15 ° C. can be appropriately selected according to its viscosity grade. For example, the ρ ₁₅ of the isomerized oil (I) is preferably 0.820 g / cm ³ or less, more preferably 0.810 g / cm ³ or less, and further preferably 0.800 g / cm ³ or less. The ρ ₁₅ of the isomerized oils (II) and (III) is preferably 0.840 g / cm ³ or less, more preferably 0.830 g / cm ³ or less, still more preferably 0.820 g / cm ³ or less. When the density at 15 ° C. is within the above range, it is excellent in viscosity-temperature characteristics and thermal / oxidation stability, as well as anti-volatile properties and low-temperature viscosity characteristics, and when an additive is added to the wax isomerized oil. , The efficacy of the additive can be sufficiently ensured. The density at 15 ° C. in the present invention means the density measured at 15 ° C. in accordance with JIS K 2249-1995.

The pour point of the wax isomerized oil according to the present embodiment can be appropriately selected according to its viscosity grade. For example, the pour point of the isomerized oil (I) is preferably −10 ° C. or lower, more preferably −20 ° C. or lower, still more preferably −30 ° C. or lower. The pour point of the isomerized oil (II) is preferably −10 ° C. or lower, more preferably −15 ° C. or lower, still more preferably −20 ° C. or lower. The pour point of the isomerized oil (III) is preferably −10 ° C. or lower, more preferably −15 ° C. or lower. When the pour point of the isomerized oil is within the above numerical range, the low temperature fluidity of the lubricating oil using the isomerized oil can be sufficiently ensured, which is preferable from the viewpoint of energy saving. The pour point referred to in the present invention means a pour point measured in accordance with JIS K 2269-1987.

The cloud point of the wax isomerized oil according to the present embodiment depends on its viscosity grade, but for example, the cloud point of the wax isomerized oil (I) is preferably −15 ° C. or lower, more preferably −17. It is 5 ° C or lower. The cloud point of the wax isomerized oil (II) is preferably −10 ° C. or lower, more preferably -12.5 ° C. or lower. The cloud point of the wax isomerized oil (III) is preferably −10 ° C. or lower. When the cloud point of the wax isomerized oil is within the above numerical range, the low temperature fluidity of the lubricating oil using the wax isomerized oil can be sufficiently ensured, which is preferable from the viewpoint of energy saving. The cloud point referred to in the present invention means a cloud point measured in accordance with "4. Cloud point test method" of JIS K 2269-1987.

Further, when gas chromatography analysis is performed on the wax isomerized oil according to the present embodiment, the carbon number distribution of the hydrocarbon compound contained in the wax isomerized oil can be appropriately selected according to the viscosity grade. .. For example, the carbon number distribution in the wax isomerized oil (I) is preferably 10 to 35, more preferably 15 to 30. The carbon number distribution in the wax isomerized oil (II) is preferably 12 to 40, more preferably 15 to 35. The carbon number distribution in the wax isomerized oil (III) is preferably 15 to 50, more preferably 18 to 45.

Further, when gas chromatography analysis is performed on the wax isomerized oil according to the present embodiment, the average carbon number of the hydrocarbon compound contained in the wax isomerized oil can be appropriately selected according to the viscosity grade. .. For example, the average carbon number of the wax isomerized oil (I) is preferably 15 to 25, more preferably 18 to 22. The average carbon number of the wax isomerized oil (II) is preferably 15 to 30, more preferably 20 to 25. The average carbon number of the wax isomerized oil (III) is preferably 20 to 40, more preferably 25 to 30. When the carbon number distribution and / or the average carbon number is within the above numerical range, a low traction coefficient can be better achieved, which is preferable from the viewpoint of energy saving.

As described above, the wax isomerized oil according to the present embodiment is obtained by using an ethylene polymer wax as a raw material, and most of the constituent hydrocarbon compounds of the ethylene polymer wax have an even number of carbon atoms. It is a hydrocarbon compound. Therefore, the wax isomerized oil has an uneven content balance between the hydrocarbon compound having an even number of carbon atoms and the hydrocarbon compound having an odd number of carbon atoms. In the composition of the hydrocarbon compound contained in the wax isomerized oil, the specific content of the hydrocarbon compound having an even number of carbon atoms is not particularly limited, but is, for example, based on the total amount of wax isomerized oil. , 50% by mass or less, 45% by mass or less, or 43% by mass or less.

The above-mentioned carbon number distribution, average number of carbon atoms, and content of the hydrocarbon compound having an even number of carbon atoms are values obtained by performing gas chromatography analysis on the wax isomerized oil under the same conditions as the above-mentioned raw material wax. Is. At the time of measurement, a mixed sample of normal paraffin having 5 to 50 carbon atoms was measured as a reference sample under the same conditions, and the carbon number distribution of the wax isomerized oil and the components for each carbon number were referred to with reference to the obtained chromatogram. Measure the ratio. From this measurement result, the sum of the products of the component ratio for each carbon number and the carbon number is obtained, and this is taken as the average carbon number. In calculating the carbon number, as described above, in the case of a hydrocarbon compound having the same carbon number, the hydrocarbon compound having the highest boiling point (longest distillation time) is normal paraffin, so the above reference sample. The peak exists between the peak corresponding to the distillation time of the hydrocarbon compound having n carbon atoms and the peak corresponding to the outflow time of the hydrocarbon compound having n-1 carbon atoms when measured. Is defined as a non-normal paraffin having n carbon atoms.

The wax isomerized oil according to the present embodiment has excellent energy saving properties and can be preferably used as a lubricating oil base oil for various purposes. Specific examples of the use of the wax isomerized oil according to the present embodiment include internal combustion engines such as gasoline engines for passenger cars, gasoline engines for two-wheeled vehicles, diesel engines, gas engines, gas heat pump engines, marine engines, and power generation engines. Lubricating oil (lubricating oil for internal combustion engine), lubricating oil used for drive transmission devices such as automatic transmissions, manual transmissions, stepless transmissions, and final speed reducers (oil for drive transmission devices), shock absorbers, Hydraulic hydraulic oil, compressor oil, turbine oil, industrial gear oil, refrigerating machine oil, rust preventive oil, heat transfer oil, gas holder seal oil, bearing oil, papermaking machine oil, machine tools used in hydraulic equipment such as construction machinery. Examples thereof include oil, slip guide surface oil, electrically insulating oil, cutting oil, pressing oil, rolling oil, heat-treated oil and the like. By using the wax isomerized oil according to the present embodiment for these purposes, it becomes possible to achieve improvement in characteristics such as energy saving of each lubricating oil.

In the above applications, the wax isomerized oil according to the present embodiment may be used alone as the lubricating oil base oil, and the wax isomerized oil according to the present embodiment may be used as one or 2 of other base oils. It may be used in combination with seeds or more. When the wax isomerized oil according to the present embodiment is used in combination with another base oil, the ratio of the wax isomerized oil according to the present embodiment to the mixed base oil thereof may be 30% by mass. It is more preferably 50% by mass or more, and even more preferably 70% by mass or more.

The other base oil used in combination with the wax isomerized oil according to the present embodiment is not particularly limited, and examples of the mineral oil-based base oil include mineral oils classified into Group I to Group III of the API classification. Will be.

The synthetic base oil includes poly-α-olefin or hydride thereof, isobutene oligomer or hydride thereof, isoparaffin, alkylbenzene, alkylnaphthalene, and diester (ditridecylglutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditri). Decyl adipate, di-2-ethylhexyl sebacate, etc.), polyol ester (trimethylolpropane caprilate, trimethylolpropane pelargonate, pentaerythritol 2-ethylhexanoate, pentaerythritol pelargonate, etc.), polyoxyalkylene glycol, dialkyl Examples thereof include diphenyl ether and polyphenyl ether, and among them, poly α-olefin is preferable. The poly-α-olefin is typically an α-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 the like. The hydride of is mentioned.

The method for producing the poly α-olefin is not particularly limited, and for example, a Friedel-Crafts catalyst containing a complex of aluminum trichloride or boron trifluoride with water, an alcohol (ethanol, propanol, butanol, etc.), a carboxylic acid or an ester. A method of polymerizing α-olefin in the presence of a polymerization catalyst such as the above can be mentioned.

Further, if necessary, various additives can be added to the wax isomerized oil according to the present embodiment or the mixed base oil of the wax isomerized oil and another base oil. The additive is not particularly limited, and any additive conventionally used in the field of lubricating oil can be blended. Specific examples of the lubricating oil additive include an antioxidant, an ashless dispersant, a metal-based detergent, an extreme pressure agent, an anti-wear agent, a viscosity index improver, a flow point lowering agent, a friction modifier, and an oil-based agent. , Corrosion inhibitor, rust preventive, anti-embroidery agent, metal deactivating agent, seal swelling agent, antifoaming agent, colorant and the like. These additives may be used alone or in combination of two or more.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Measurement of number average molecular weight (Mn) and weight average molecular weight (Mw)]
Two columns (Polymer Laboratories, trade name: PL gel 10 μm MIXED-B LS) were connected to a high-temperature GPC device (Polymer Laboratories, trade name: PL-20) to form a differential refractive index detector. 5 ml of orthodichlorobenzene solvent was added to 5 mg of the sample, and the mixture was heated and stirred at 140 ° C. for about 1 hour. The sample thus dissolved was measured at a flow rate of 1 ml / min and a column oven temperature of 140 ° C. The molecular weight was converted based on a calibration curve prepared from standard polystyrene, and the polystyrene-equivalent molecular weight was obtained.

[Calculation of catalyst efficiency]
The catalyst efficiency was calculated by dividing the weight of the obtained oligomer by the number of moles of the charged catalyst.

[Example 1]
Under a nitrogen stream, an iron compound (50 mg) represented by the formula (1a) and a ligand (19 mg) represented by the formula (2a) were introduced into a 500 mL eggplant flask, and dry toluene (200 mL) was added. A hexane solution of methylaluminoxane (3.64 M solution, 11 mL) was added to this toluene solution to prepare a solution (A).

A hexane solution of dried toluene (8 L) and methylaluminoxane (3.64 M solution, 2.8 mL) was introduced into a 20 L autoclave equipped with an electromagnetic induction stirrer that had been sufficiently dried at 110 ° C. under reduced pressure in advance under a nitrogen stream. , The temperature was adjusted to 30 ° C.

The solution (A) was introduced into the autoclave to prepare an ethylene polymerization catalyst. The content ratio of methylaluminoxane in the obtained ethylene polymerization catalyst was 500 equivalents with respect to the number of moles of the iron compound.

1 MPa of ethylene was continuously introduced at 30 ° C. into the autoclave into which the solution (A) was introduced. After 9 hours, the introduction of ethylene was stopped, unreacted ethylene was removed, and ethanol (100 mL) was added to inactivate the ethylene polymerization catalyst. The autoclave was opened, the contents were transferred to a 20 L eggplant flask, and the solvent was distilled off under reduced pressure to obtain a semi-solid ethylene oligomer wax (WAX1). The catalytic efficiency (CE) was 60824 kg Olig / Fe mol. The Mn of the obtained WAX1 was 490, Mw was 890, and Mw / Mn was 1.8. Table 1 shows the results obtained by gas chromatography analysis regarding the normal paraffin content of the obtained WAX1 and the content of the hydrocarbon compound having an even number of carbon atoms (even carbon number content).

The WAX1 obtained above was separated by distillation to obtain a fraction having a boiling point range of 350 to 450 ° C. The obtained fraction was hydrolyzed in the presence of a hydrocracking catalyst under the conditions of a reaction temperature of 350 ° C., a hydrogen partial pressure of 5 MPa, and a space velocity of 1.0 LHSV to obtain a decomposition product. As the hydration decomposition catalyst, a catalyst in which 3% by mass of nickel and 15% by mass of molybdenum were supported on an amorphous silica-alumina carrier (silica: alumina = 20: 80 (mass ratio)) was used in a sulfided state. The obtained decomposition product was subjected to conditions of a reaction temperature of 330 ° C., a hydrogen partial pressure of 5 MPa, and a space velocity of 1.0 LHSV using a zeolite-based hydrogenation isomerization catalyst adjusted to have a noble metal content of 0.1 to 5% by mass. The hydrogenation isomerization was carried out in the above to obtain a wax isomerized oil. Subsequently, the obtained wax isomerized oil was distilled under reduced pressure to obtain a wax isomerized oil equivalent to 70 Pale. Table 2 shows the properties of the obtained wax isomerized oil. In Table 2, the "carbon number distribution", "average carbon number" and "even carbon number content" were obtained by performing gas chromatography analysis on the obtained wax isomerized oil. , "Traction coefficient" is a value measured under the conditions of a load of 20 N, a test oil temperature of 25 ° C., a peripheral speed of 0.52 m / s, and a slip ratio of 3% using a steel ball and a steel disk as test pieces (hereinafter). The same is true).

[Comparative Example 1-1]
An FT wax (WAX2) having a paraffin content of 93% by mass and a carbon number distribution from 18 to 60 was used as a raw material wax. Table 1 shows the results obtained by gas chromatography analysis regarding the normal paraffin content of WAX2 and the content of the hydrocarbon compound having an even number of carbon atoms (even carbon number content).

Using the above WAX2, a wax isomerized oil was obtained by the same method as in Example 1. Table 2 shows the properties of the obtained wax isomerized oil.

[Comparative Example 1-2]
WAX1 was separated by distillation to obtain a distillate having a boiling point range of 250 to 500 ° C. The obtained fraction was hydrolyzed in the presence of a hydrocracking catalyst under the conditions of a reaction temperature of 350 ° C., a hydrogen partial pressure of 5 MPa, and a space velocity of 1.0 LHSV to obtain a decomposition product. As the hydration decomposition catalyst, a catalyst in which 3% by mass of nickel and 15% by mass of molybdenum were supported on an amorphous silica-alumina carrier (silica: alumina = 20: 80 (mass ratio)) was used in a sulfided state. Subsequently, the obtained decomposition product was distilled under reduced pressure to obtain a fraction equivalent to 70 Pale. The fraction was subjected to solvent dewaxing using a mixed solvent of methyl ethyl ketone-toluene 1: 1 under the conditions of a solvent / oil ratio of 4 times and a filtration temperature of -25 ° C. to obtain a wax isomerized oil. Table 2 shows the properties of the obtained wax isomerized oil.

[Example 2]
In Example 2, WAX1 was separated by distillation and a distillate having a boiling point range of 420 to 500 ° C. was used, and a wax isomerized oil equivalent to SAE10 was obtained by vacuum distillation of the obtained wax isomerized oil. Obtained a wax isomerized oil by the same method as in Example 1. Table 3 shows the properties of the wax isomerized oil obtained in Example 2.

[Comparative Example 2-1]
In Comparative Example 2-1 a wax isomerized oil was obtained by the same method as in Example 2 except that WAX2 was used. Table 3 shows the properties of the wax isomerized oil obtained in Comparative Example 2-1.

[Comparative Example 2-2]
In Comparative Example 2-2, a wax isomerized oil was obtained by the same method as in Comparative Example 1-2, except that a fraction equivalent to SAE10 was obtained by vacuum distillation of the decomposition product. Table 3 shows the properties of the wax isomerized oil obtained in Comparative Example 2-2.

[Example 3]
In Example 3, WAX1 was separated by distillation, a distillate having a boiling point range of 300 to 440 ° C. was used, and the obtained wax isomerized oil was distilled under reduced pressure to obtain a wax isomerized oil equivalent to VG6. A wax isomerized oil was obtained by the same method as in Example 1 except for the above. Table 4 shows the properties of the wax isomerized oil obtained in Example 3.

[Comparative Example 3-1]
In Comparative Example 3-1 a wax isomerized oil was obtained by the same method as in Example 3 except that WAX2 was used. Table 4 shows the properties of the wax isomerized oil obtained in Comparative Example 3-1.

[Comparative Example 3-2]
In Comparative Example 3-2, a wax isomerized oil was obtained by the same method as in Comparative Example 1-2, except that a fraction equivalent to VG6 was obtained by vacuum distillation of the decomposition product. Table 4 shows the properties of the wax isomerized oil obtained in Comparative Example 3-2.

Claims (1)

The process of preparing ethylene polymer wax and
A step of hydrogenating and decomposing the ethylene polymer wax with a hydrogenation decomposition catalyst to obtain a decomposition product, and a step of obtaining a decomposition product.
A step of isomerizing and dewaxing the decomposition product with a hydrogenation isomerization catalyst to obtain a wax isomerized oil.
Equipped with
In the composition of the hydrocarbon compound contained in the ethylene polymer wax, the content of the hydrocarbon compound having an even number of carbon atoms is 80% by mass or more based on the total amount of the ethylene polymer wax . How to make oil.