WO2014157385A1 - Huile de base d'huile lubrifiante et procédé pour la produire - Google Patents

Huile de base d'huile lubrifiante et procédé pour la produire Download PDF

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WO2014157385A1
WO2014157385A1 PCT/JP2014/058634 JP2014058634W WO2014157385A1 WO 2014157385 A1 WO2014157385 A1 WO 2014157385A1 JP 2014058634 W JP2014058634 W JP 2014058634W WO 2014157385 A1 WO2014157385 A1 WO 2014157385A1
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oil
base oil
zeolite
catalyst
lubricating base
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PCT/JP2014/058634
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English (en)
Japanese (ja)
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一生 田川
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Ｊｘ日鉱日石エネルギー株式会社
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Publication of WO2014157385A1 publication Critical patent/WO2014157385A1/fr

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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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1022—Fischer-Tropsch products
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10—Lubricating oil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/17—Fisher Tropsch reaction products
    • C10M2205/173—Fisher Tropsch reaction products used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/071—Branched chain compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • 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
    • C10N2040/02—Bearings
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • 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
    • C10N2040/06—Instruments or other precision apparatus, e.g. damping fluids
    • 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
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
    • 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
    • C10N2040/255—Gasoline engines
    • 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.
  • Patent Document 1 includes hydroisomerization treatment for isomerizing normal paraffin contained in a raw material into isoparaffin, hydroisomerization dewaxing treatment for removing a wax content in a lubricating base oil, and the like. It is disclosed.
  • the present inventor first examined the cause of insufficient low temperature viscosity characteristics of the GTL base oil.
  • white turbidity may occur, but the present inventor has found that the causative substance of the white turbidity contributes to the deterioration of the low temperature viscosity characteristics of the GTL base oil.
  • the causative substance of white turbidity is a paraffin component having a low degree of isomerization generated by hydroisomerization or hydroisomerization dewaxing.
  • solvent dewaxing treatment can be considered as a method for removing the causative substance of white turbidity.
  • solvent dewaxing treatment not only the low-isomerization paraffin content but also the paraffin content with a similar molecular structure (that is, isoparaffin which is not the causative agent of white turbidity) is separated in principle. There is a problem that the rate decreases.
  • the present invention has been made in view of such circumstances, and a method for producing a lubricating base oil capable of obtaining a GTL base oil having good low-temperature viscosity characteristics in a high yield, as well as the production method. It aims at providing the lubricating base oil obtained.
  • the present invention uses a synthetic wax obtained by a gas-to-liquid process or a lubricating oil fraction separated from the synthetic wax as a raw material, and normal paraffin contained in the raw material is isomerized into isoparaffin.
  • a method for producing a lubricating base oil is provided.
  • the cloud point in the present invention means a cloud point measured according to “4. Cloud point test method” of JIS K 2269-1987.
  • the isomerized oil obtained in the first step is subjected to urea dewaxing treatment so that the cloud point of the obtained lubricating base oil is less than ⁇ 5 ° C.
  • the paraffin component having a low degree of isomerization which is a substance, can be selectively separated from the isomerized oil. Therefore, a GTL base oil having sufficiently improved low-temperature viscosity characteristics can be obtained in a high yield.
  • the isomerized oil has a 10 wt% boiling point of 500 ° C. or higher in a gas chromatographic distillation test, a kinematic viscosity at 100 ° C. of 9 mm 2 / s or higher, a viscosity index of 160 or higher, and a pour point of ⁇ 5 ° C.
  • the average carbon number is 48 or more and the tertiary carbon ratio by 13 C-NMR is 7% or more.
  • the 10 wt% boiling point in the gas chromatographic distillation test means a 10 wt% boiling point measured according to JIS K 2254-1998.
  • the kinematic viscosity and the viscosity index mean a kinematic viscosity and a viscosity index measured in accordance with JIS K 2283-1993, respectively.
  • the pour point means a pour point measured according to “3. Pour point test method” of JIS K 2269-1987.
  • the average carbon number is determined by measuring the normal paraffin standard substance by gas chromatogram and comparing the retention time of each standard substance with the retention time of the evaluation oil to calculate the concentration of each carbon number as 100%. It means the value calculated as the average number of carbons.
  • 13 the ratio of tertiary carbon by C-NMR refers to the ratio of the tertiary carbon which is obtained by performing a 13 C-NMR analysis under the following conditions.
  • the ratio of tertiary carbon by 13 C-NMR is the ratio of tertiary carbon to the total carbon in the hydrocarbons constituting the isomerized oil (percentage of carbon atoms due to> CH— accounting for all carbon atoms). Yes, meaning the proportion of carbon atoms due to branching or naphthenes.
  • 13 C-NMR ratio of the tertiary carbon by the 13 measured by C-NMR is meant the percentage of the total integrated intensity attributed to tertiary carbon to the sum of integrated intensity of total carbon, equivalent Other methods may be used as long as the result is obtained.
  • the catalyst used for the hydroisomerization treatment in the first step is at least one crystallinity selected from the group consisting of ZSM-22 type zeolite, ZSM-23 type zeolite, SSZ32 and ZSM-48 type zeolite.
  • a catalyst containing a solid acidic substance and platinum and / or palladium as active metals is preferred.
  • the present invention also provides a lubricating base oil having a cloud point of less than ⁇ 5 ° C. obtained by the production method of the present invention.
  • the lubricating base oil of the present invention has excellent low-temperature viscosity characteristics because the paraffin content having a low isomerization degree, which is a causative substance of white turbidity, is sufficiently reduced.
  • a method for producing a lubricating base oil capable of obtaining a GTL base oil having good low-temperature viscosity characteristics in a high yield, and a lubricating base oil obtained by the producing method. Provided.
  • a method for producing a lubricating base oil uses a synthetic wax obtained by a gas-to-liquid (GTL) process or a lubricating oil fraction separated from the synthetic wax as a raw material, and is contained in the raw material.
  • the raw material used for the first step is a synthetic wax obtained by the GTL process or a lubricating oil fraction separated from the synthetic wax. These raw materials usually contain a hydrocarbon compound having 18 to 60 carbon atoms.
  • the above synthetic wax includes Fischer-Tropsch (FT) wax, GTL wax and the like.
  • FT Fischer-Tropsch
  • Such a synthetic wax or a lubricating oil fraction separated from the synthetic wax usually does not contain a nitrogen content, so that sulfur poisoning can be suppressed in hydrocracking and hydroisomerization dewaxing.
  • the means for separating the lubricating oil fraction from the synthetic wax is not particularly limited, and examples thereof include atmospheric distillation and vacuum distillation.
  • the “treatment for isomerizing normal paraffin contained in the raw material to isoparaffin” in the first step is a treatment mainly intended for isomerization such as hydroisomerization treatment, hydroisomerization dewaxing treatment, etc.
  • hydrocracking with isomerization is also included.
  • any one of hydrocracking, hydroisomerization or hydroisomerization dewaxing may be performed, or two or more may be performed in combination.
  • the type of the reactor used for the hydrocracking treatment 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 further 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
  • composition of the hydrocracked oil obtained by hydrocracking treatment is determined by the hydrocracking catalyst used and the hydrocracking reaction conditions.
  • hydrocracked oil refers to the entire hydrocracked product containing an uncracked heavy fraction unless otherwise specified.
  • the hydrocracking reaction conditions are stricter than necessary, the content of the undecomposed heavy fraction in the hydrocracked oil will decrease, but the light fraction with a boiling point of 340 ° C or less will increase, and it will be suitable as a lubricating base oil.
  • the yield of min (340-520 ° C. fraction) decreases.
  • the hydrocracking reaction conditions are milder than necessary, the undecomposed heavy fraction increases and the yield of the fraction suitable as a lubricating oil base oil decreases.
  • this decomposition rate M2 / M1 is usually It is preferable to select the reaction conditions so that it is 5 to 70%, preferably 10 to 60%, more preferably 20 to 50%.
  • a reaction tower for hydroisomerization or hydroisomerization dewaxing a known fixed bed reaction tower can be used. More specifically, for example, a hydroisomerization catalyst is charged into a fixed bed flow reactor, and hydrogen (molecular hydrogen) and hydrocracked oil are allowed to flow through the reactor. Wax 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 Group 6, Group 8, Group 9 and Group 10 metals 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, or 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 hydroisomerization catalyst 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, It is preferable to use a catalyst containing platinum and / or palladium as a metal.
  • the above-mentioned preferable hydroisomerization catalyst is characterized by being produced by a specific method.
  • the hydroisomerization catalyst of this aspect is demonstrated along the aspect of the preferable manufacture.
  • 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 codes given by the Structure Committee of The International Zeolite Association for each classified molecular sieve type structure. 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 decomposition reaction tends to increase rapidly as the reaction temperature increases. 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 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 in order to increase the efficiency of ion exchange, 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 or new. It is more preferable.
  • the solution is exchanged once, for example, the organic template-containing zeolite is immersed in a solution containing ammonium ions and / or protons, and this is 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.
  • a suitable amount of liquid such as water
  • a suitable amount of liquid such as water
  • 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 microisomer volume per unit mass of the hydroisomerization catalyst obtained through calcination after metal support described later is 0.02 to 0.11 cm 3 / g, and is contained in the catalyst.
  • the heating conditions are preferably set so that the micropore volume per unit mass of the zeolite is 0.04 to 0.12 cm 3 / 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 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 cm 3 / g
  • the micropores per unit mass of zeolite contained in the catalyst The heating conditions are preferably set so that the volume is 0.04 to 0.12 cm 3 / 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 template-containing zeolite is derived from an ion-exchanged 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 0.00. It may be 04 to 0.12 cm 3 / 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 of the hydroisomerization treatment or hydroisomerization dewaxing treatment 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.
  • reaction pressure in the hydroisomerization treatment or hydroisomerization dewaxing treatment is preferably 0.1 to 20 MPa, more preferably 0.5 to 15 MPa.
  • reaction pressure is less than 0.1 MPa, the deterioration of the catalyst due to coke generation tends to be accelerated.
  • reaction pressure exceeds 20 MPa, the cost for constructing the apparatus tends to be high, and it tends to be difficult to realize an economical process.
  • liquid hourly space velocity relative to the catalyst of the process oil is preferably 0.01 ⁇ 100 hr -1, more preferably 0.1 ⁇ 50 hr -1.
  • 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 the process oil 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 isomerized oil obtained in the first step may be subjected to a hydrofinishing step as necessary.
  • the reactor used in the hydrofinishing process is not particularly limited, and a predetermined hydrorefining catalyst is charged into a fixed bed flow reactor, and molecular hydrogen and the dewaxed oil are circulated through the reactor.
  • the hydrofinishing treatment (hydrorefining treatment) can be suitably carried out.
  • the hydrofinishing treatment here means improving the oxidation stability and hue of the lubricating oil, and 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, LHSV of 0.5 to 5 h ⁇ 1 , a hydrogen / oil ratio of 1000 to 5000 scfb, and a reaction temperature of 200 ° C. 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 so that the sulfur content and the nitrogen content in the hydrofinished oil obtained by the hydrofinishing step are 5 ppm by mass or less and 1 ppm by mass or less, respectively.
  • the isomerized oil (including hydrocracked oil, dewaxed oil, and hydrorefined oil) obtained through the first step may be further subjected to a fractionation step.
  • a desired lubricating oil fraction can be obtained by setting a plurality of cut points and distilling the hydrorefined oil under reduced pressure.
  • light fractions such as naphtha and kerosene produced as a by-product of hydrocracking, hydroisomerization, hydroisomerization dewaxing, and hydrofinishing (hydrorefining) are used. These light particles can be recovered, for example, as a fraction having a boiling point of 350 ° C. or lower.
  • Isomerized oil has a 10 wt% boiling point in a gas chromatographic distillation test of 500 ° C. or higher, a kinematic viscosity at 100 ° C. of 9 mm 2 / s or higher, a viscosity index of 160 or higher, a pour point of ⁇ 5 ° C. or lower, and an average carbon number. It is preferably 48 or more, and the ratio of tertiary carbon by 13 C-NMR is 7% or more.
  • the 10 wt% boiling point of the isomerized oil in the gas chromatographic distillation test is preferably 500 ° C. or higher, more preferably 505 ° C. or higher, and preferably 550 ° C. or lower, more preferably 540 ° C. or lower.
  • the kinematic viscosity at 100 ° C. of the isomerized oil is preferably 9 mm 2 / s or more, more preferably 9.2 mm 2 / s or more, and further preferably 9.5 mm 2 / s or more.
  • the kinematic viscosity at 100 ° C. is preferably 30 mm 2 / s or less, more preferably 28 mm 2 / s or less, and still more preferably 25 mm 2 / s or less.
  • the viscosity index of the isomerized oil is preferably 160 or more, more preferably 163 or more, and preferably 180 or less, more preferably 175 or less.
  • the pour point of isomerized oil is preferably ⁇ 5 ° C. or lower, more preferably ⁇ 7.5 ° C. or lower, and preferably ⁇ 17.5 ° C. or higher, more preferably ⁇ 15 ° C. or higher.
  • the average carbon number of the isomerized oil is preferably 40 or more, more preferably 42 or more, and preferably 60 or less, more preferably 58 or less.
  • the ratio of tertiary carbon of the isomerized oil by 13 C-NMR is preferably 7% or more, more preferably 7.2% or more, and preferably 10% or less, more preferably 9.0% or less. is there.
  • urea dewaxing treatment is performed on the isomerized oil to obtain a lubricating base oil having a cloud point of less than ⁇ 5 ° C.
  • the following method can be exemplified.
  • the weighed lubricating base oil is placed in a round bottom flask, urea, toluene and methanol are added and stirred at room temperature for 6 hours.
  • white granular crystals are produced as inclusion compounds of urea in the reaction solution.
  • the resulting white granular crystals and the filtrate are separated.
  • a urea dewaxed oil is obtained.
  • the cloud point can be controlled by carrying out this operation once in advance, confirming the amount of wax, and adjusting the amount of urea relative to that amount.
  • the cloud point of the lubricating base oil obtained in the second step is less than ⁇ 5 ° C., preferably ⁇ 7.5 ° C. or less, more preferably ⁇ 10 ° C. or less.
  • the proportion of CH 2 carbon constituting the main chain in the total carbon constituting the lubricating base oil is 7.0% or more. Preferably, it is 7.2% 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 of the present invention is the ratio of the total integrated intensity due to the CH 2 main chain to the total integrated intensity of all carbon, as measured by 13 C-NMR.
  • other methods may be used as long as an equivalent result is obtained.
  • the measuring method used the coupling method with a gate.
  • the cycloparaffin content is preferably 40% or more and 70% or less, and more preferably 40% or more and 60% or less.
  • the wear resistance of the lubricating base oil can be 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. Since this saturated phase is analyzed separately from the aromatic phase, it is possible to measure the content of different cycloparaffins having the same stoichiometry.
  • the cycloparaffin includes both one-ring cycloparaffin and two or more cycloparaffins.
  • the content of the saturated component in the lubricating base oil according to the present embodiment is preferably 100 to 95% by mass, more preferably 100 to 97% by mass, and still more preferably 100 to 100% by mass based on the total amount of the lubricating base oil. It is 98 mass%.
  • the content of the saturated component satisfies the above conditions, viscosity-temperature characteristics and thermal / oxidation stability can be achieved, and when an additive is blended in the lubricating base oil, the addition The function of the additive can be expressed at a higher level while the agent is sufficiently and stably dissolved and retained in the lubricant base oil.
  • content of the saturated part as used in the field of this invention means the value (unit: mass%) measured based on ASTM D 2007-93.
  • the aromatic content in the lubricating base oil according to the present embodiment is preferably 0.0 to 1.0% by mass, more preferably 0.0 to 0.75% by mass, based on the total amount of the lubricating base oil. More preferably, it is 0.3 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 this embodiment may not contain an aromatic component, but the solubility of the additive can be increased by setting the aromatic content to 0.3 mass% or more. It can be further increased.
  • the aromatic content here means a value measured in accordance with ASTM D 2007-93.
  • the aromatic component 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 and naphthols. Aromatic compounds having atoms are included.
  • the lubricating base oil according to the present embodiment is excellent in low-temperature viscosity characteristics, and has an effect that viscosity resistance and stirring resistance can be significantly reduced.
  • the BF viscosity at ⁇ 20 ° C. can be made 10,000 mPa ⁇ s or less.
  • the BF viscosity at ⁇ 20 ° C. means a viscosity measured according to JPI-5S-26-99.
  • the lubricating base oil of the present invention and the manufacturing method thereof are not limited to the above-described embodiment, and can be appropriately changed.
  • a distillation step may be provided before the first step, between the first step and the second step, or at any part or all after the second step.
  • the hydrofinishing process mentioned above may be performed between a 1st process and a 2nd process, or may be performed after a 2nd process.
  • the lubricating base oil according to this embodiment has good low-temperature viscosity characteristics, it can be preferably used as a lubricating base oil for various applications.
  • 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.
  • Hydraulic oil compressor oil, turbine oil, industrial gear oil, rust oil, heat medium oil, heat carrier oil, gas holder seal oil, bearing oil, paper machine oil, machine tool oil used in hydraulic equipment such as machines , Slip guide surface oil, electrical insulating oil, cutting oil, press oil, rolling oil, heat treatment oil and the like.
  • the lubricating base oil according to the present embodiment may be used alone, or the lubricating base oil according to the present embodiment may be used in combination with one or more other base oils. Also good.
  • the ratio of the lubricating base oil which concerns on this embodiment in those mixed base oils is 30 mass% or more Is preferably 50% by mass or more, and more preferably 70% by mass or more.
  • 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 dewaxed 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 ester (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 oil as necessary.
  • Such an additive is not particularly limited, and any additive conventionally used in the field of lubricating oils can be blended.
  • Specific examples of such lubricating oil additives include antioxidants, ashless dispersants, metallic detergents, extreme pressure agents, antiwear agents, viscosity index improvers, pour point depressants, friction modifiers, oiliness agents. , Corrosion inhibitors, rust inhibitors, demulsifiers, metal deactivators, seal swelling agents, antifoaming agents, colorants and the like. These additives may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Solution C A solution obtained by diluting 4.18 g of 1,6-hexanediamine (organic template) with 32.5 mL of ion-exchanged water.
  • Solution D 18 g of colloidal silica (Ludox AS-40 manufactured by Grace Davison) diluted with 31 mL of ion-exchanged water.
  • solution A was added to solution B and stirred until the aluminum component was completely dissolved.
  • the mixture of the solutions A, B and C was poured into the solution D with vigorous stirring at room temperature.
  • 0.25 g of ZSM-22 powder separately synthesized and not subjected to any special treatment after synthesis was added as a “seed crystal” for promoting crystallization, thereby obtaining a gel.
  • the gel obtained by the above operation is transferred to a stainless steel autoclave reactor having an internal volume of 120 mL, and the autoclave reactor is rotated on a tumbling apparatus at a rotation speed of about 60 rpm in an oven at 150 ° C. for 60 hours.
  • the hydrothermal synthesis reaction was performed. After completion of the reaction, the reactor was cooled and opened, and dried overnight in a dryer at 60 ° C. to obtain ZSM-22 having a Si / Al ratio of 45.
  • ZSM-22 containing organic template> ZSM-22 obtained above was subjected to ion exchange treatment with an aqueous solution containing ammonium ions by the following operation.
  • the ZSM-22 obtained above was placed in a flask, 100 mL of 0.5N ammonium chloride aqueous solution per 1 g of ZSM-22 zeolite was added, and the mixture was refluxed with heating for 6 hours. After cooling this to room temperature, the supernatant was removed and the crystalline aluminosilicate was washed with ion-exchanged water. The same amount of 0.5N-ammonium chloride aqueous solution as above was added again, and the mixture was refluxed with heating for 12 hours. Thereafter, the solid content was collected by filtration, washed with ion-exchanged water, and dried overnight in a dryer at 60 ° C. to obtain ion-exchanged NH 4 type ZSM-22.
  • This ZSM-22 is ion-exchanged in a state containing an organic template.
  • NH 4 type ZSM-22 obtained above and alumina as a binder were mixed at a mass ratio of 7: 3, and a small amount of ion-exchanged water was added thereto and kneaded.
  • the obtained viscous fluid was filled into an extrusion molding machine and molded to obtain a cylindrical molded body having a diameter of about 1.6 mm and a length of about 10 mm. This molded body was heated at 300 ° C. for 3 hours under an N 2 atmosphere to obtain a carrier precursor.
  • Tetraamminedinitroplatinum [Pt (NH 3 ) 4 ] (NO 3 ) 2 was dissolved in ion-exchanged water corresponding to the previously measured water absorption of the carrier precursor to obtain an impregnation solution.
  • This solution was impregnated into the above carrier precursor by an initial wetting method, and supported so that the amount of platinum was 0.3% by mass relative to the mass of the ZSM-22 type zeolite.
  • the obtained impregnated product (catalyst precursor) was dried overnight at 60 ° C. and then calcined at 400 ° C. for 3 hours under air flow to obtain hydroisomerization catalyst A-1. .
  • the micropore volume per unit mass of the obtained hydroisomerization catalyst was calculated by the following method. First, in order to remove water adsorbed on the hydroisomerization catalyst, pretreatment was performed to evacuate at 150 ° C. for 5 hours. The pretreatment hydroisomerization catalyst was subjected to nitrogen adsorption measurement at a liquid nitrogen temperature ( ⁇ 196 ° C.) using BELSORP-max manufactured by Nippon Bell Co., Ltd. The measured nitrogen adsorption isotherm was analyzed by the t-plot method, and the micropore volume (cm 3 / g) per unit mass of the hydroisomerization catalyst was calculated to be 0.055. It was.
  • V Z V c / M z ⁇ 100
  • V c the micropore volume per unit mass of the hydroisomerization catalyst
  • M z the content ratio (mass%) of the zeolite contained in the catalyst.
  • Example 1 GTL wax containing 40% by weight of normal paraffin from a boiling point range of 480 to 570 ° C. is subjected to an isomerization reaction temperature of 310 ° C., a hydrogen pressure of 15 MPa, a hydrogen / oil ratio of 500 NL / L, and a liquid space velocity of 1.5 h ⁇ 1 . Hydroisomerized with The hydroisomerization catalyst A-1 was used as the hydroisomerization catalyst.
  • the reaction temperature is a temperature at which the conversion rate becomes substantially 100%.
  • the content of the fraction having a boiling point range of 490 to 540 ° C., which is the main target fraction was 60% by volume.
  • the product oil thus obtained was fractionated by distillation to obtain isomerized oil A shown in Table 1.
  • 100 g of the weighed isomerized oil A was put in a round bottom flask, 200 g of urea, 360 ml of toluene and 40 ml of methanol were added and stirred at room temperature for 6 hours. This produced white granular crystals as urea adducts in the reaction solution.
  • the reaction solution was filtered through a 1 micron filter to separate the produced white granular crystals and the filtrate.
  • the solvent was removed from the obtained filtrate to obtain 95 g of urea dewaxed oil.
  • Example 1 A lubricating base oil was produced in the same manner as in Example 1 except that the solvent dewaxing treatment was performed instead of the urea dewaxing treatment in Example 1.
  • the solvent dewaxing treatment was performed as follows. A 50/50 mixed solvent of toluene and methyl ethyl ketone (MEK) was used as a solvent, and the mixed solvent and isomerized oil B were mixed and cooled at ⁇ 15 ° C. The solvent / oil volume ratio was 2.0. After precipitation of the wax by cooling, the mixture was stirred for 1 hour while maintaining a low temperature, further filtered while maintaining the temperature, and the solvent was removed from the obtained filtrate to obtain a solvent dewaxed oil.
  • MEK methyl ethyl ketone
  • Example 2 A GTL wax containing 40% by weight of normal paraffin from a boiling point range of 480 to 570 ° C. is subjected to an isomerization reaction temperature of 310 ° C., a hydrogen pressure of 15 MPa, a hydrogen / oil ratio of 500 NL / L, and a liquid space velocity of 1.5 h ⁇ 1 . Hydroisomerized with The hydroisomerization catalyst A-1 was used as the hydroisomerization catalyst.
  • the reaction temperature is a temperature at which the conversion rate becomes substantially 100%.
  • the content of the fraction having a boiling point range of 490 to 540 ° C., which is the main target fraction was 60% by volume.
  • the product oil thus obtained was fractionated by distillation to obtain isomerized oil B shown in Table 1.
  • 100 g of the weighed isomerized oil B was placed in a round bottom flask, 200 g of urea, 360 ml of toluene and 40 ml of methanol were added and stirred at room temperature for 6 hours. This produced white granular crystals as urea adducts in the reaction solution.
  • the reaction solution was filtered through a 1 micron filter to separate the produced white granular crystals and the filtrate.
  • the solvent was removed from the obtained filtrate to obtain 94 g of urea dewaxed oil.
  • Example 2 A lubricating base oil was produced in the same manner as in Example 2 except that solvent dewaxing treatment was performed instead of urea dewaxing treatment in Example 2.
  • the solvent dewaxing treatment was performed as follows. A 50/50 mixed solvent of toluene and methyl ethyl ketone (MEK) was used as the solvent, and the mixed solvent and the lubricating base oil were mixed and cooled at -12.5 ° C. The solvent / oil volume ratio was 3.0. After precipitation of the wax by cooling, the mixture was stirred for 1 hour while maintaining a low temperature, further filtered while maintaining the temperature, and the solvent was removed from the obtained filtrate to obtain a solvent dewaxed oil.
  • MEK methyl ethyl ketone
  • Table 2 shows various properties of the lubricating base oil (urea dewaxed oil or solvent dewaxed oil) obtained in Examples 1 and 2 and Comparative Examples 1 and 2.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Lubricants (AREA)

Abstract

L'invention concerne un procédé de production d'huile de base d'huile lubrifiante, le procédé comprenant : une première étape d'obtention d'une huile isomérisée au moyen d'une cire synthétique obtenue par un procédé de transformation de gaz en liquide ou une fraction d'huile lubrifiante séparée de ladite cire synthétique, comme matière première, et l'isomérisation des paraffines normales contenues dans ladite matière première en isoparaffines ; et une seconde étape d'obtention d'une huile de base d'huile lubrifiante ayant un point de trouble inférieur à -5 °C en soumettant ladite huile isomérisée à un traitement de déparaffinage à l'urée.
PCT/JP2014/058634 2013-03-29 2014-03-26 Huile de base d'huile lubrifiante et procédé pour la produire WO2014157385A1 (fr)

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JP6992958B2 (ja) 2016-03-25 2022-02-04 出光興産株式会社 潤滑油組成物、内燃機関、及び内燃機関の潤滑方法
CN107474878A (zh) * 2017-09-29 2017-12-15 江苏天时新材料科技有限公司 一种基础油的加工方法
JP2020158784A (ja) * 2020-06-30 2020-10-01 出光興産株式会社 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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WO2008123246A1 (fr) * 2007-03-30 2008-10-16 Nippon Oil Corporation Huile de base lubrifiante, son procédé de fabrication et composition d'huile lubrifiante
WO2010041590A1 (fr) * 2008-10-07 2010-04-15 新日本石油株式会社 Procédé de production d'une composition d'hydrocarbures, composition d'hydrocarbures, huile de base lubrifiante et composition d'huile lubrifiante

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