CN101563441A - Low sulphur, low sulphated ash, low phosphorus and highly paraffinic lubricant composition - Google Patents
Low sulphur, low sulphated ash, low phosphorus and highly paraffinic lubricant composition Download PDFInfo
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- CN101563441A CN101563441A CNA2007800466334A CN200780046633A CN101563441A CN 101563441 A CN101563441 A CN 101563441A CN A2007800466334 A CNA2007800466334 A CN A2007800466334A CN 200780046633 A CN200780046633 A CN 200780046633A CN 101563441 A CN101563441 A CN 101563441A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/17—Fisher Tropsch reaction products
- C10M2205/173—Fisher Tropsch reaction products used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/067—Unsaturated Compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/071—Branched chain compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/04—Detergent property or dispersant property
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/42—Phosphor free or low phosphor content compositions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/43—Sulfur free or low sulfur content compositions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/45—Ash-less or low ash content
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
Abstract
The present invention relates to a lubricant composition having a sulphur content of from 0.01 to 0.3 wt. %, a phosphorus content of from 0.01 to 0.1 wt. % and a sulphated ash content of from 0.1 to 1.2 wt. %, based on the total weight of the lubricant composition, which comprises a base oil or base oil blend, wherein the lubricant composition has a kinematic viscosity at 100 DEG C of more than 5.0 mm<2>/s (cSt), a cold cranking simulated dynamic viscosity at -15 DEG C according to ASTM D 5293 of less than 9500 mPas (cP) and a mini rotary viscosity test value of less than 60000 mPas at -20 DEG C according to ASTM D 4684, and wherein the base oil or base oil blend comprises a continuous series of iso-paraffins having n, n+1, n+2, n+3 and n+4 carbon atoms. The invention relates further to the use of the lubricant composition, for the reduction of piston ring deposits in an internal combustion engine.
Description
Technical field
The present invention relates to a kind of lubricant compositions.More specifically, relate to the lubricant compositions of low-sulfur, sulfate ash and phosphorus and highly paraffinic, and described lubricant compositions is used for reducing the sedimental purposes of piston ring at oil engine.
Background technology
In nearest decades, the oil engine that is used to transport and the application of other energy producing unit have become general.Especially, the compression-ignition engine that is also referred to as " diesel motor " after the Rudolf Diesel that invented first self-igniton engine in 1892 is used for the main type of engine that passenger vehicle and the whole world is used for heavy-duty applications and is used for fixing the formula generating because of their energy-efficient and accounts for main positions in Europe.
In compression-ignition engine, fuel/air mixture is by being compressed until because compression causes temperature to raise lights, rather than by independent ignition source for example the sparking plug in the petrol engine light.
In the last few years, developed wherein owing to specific power output increases to 60kW/ and rise the so high apical ring groove temperature of causing and to surpass 250 ℃ compression-ignition engine.These engines have the feasible no longer heat dissipation via passing through engine body or cylinder head and refrigerant or lubricant heat exchange of so high energy output.
The problem of these engines be the settling that forms on piston and the casing surface for example the amount of cigarette ash and greasy dirt increase.This may cause for example ring bonding or the ultimate failure and their operational issue of piston ring conversely.Other problem is the lubricating component that enters engine from the gas of combustion processes.The result is the enhanced oxidation and the fouling of employed lubricating oil.If this has shortened required replacing interval or has not changed the deposition that may cause mud in lubrication failure and the engine.Therefore, need to reduce the settling that in diesel engine exhaust, on piston and cylinder, forms.
In addition, because the consideration of environment is mounted to exhaust gas aftertreatment vehicle usually to reduce its particulate matter and NO
xDischarging.
But the concentration of sulfate ash, sulphur and the phosphorus of the conventional lubricant compositions that uses may have a negative impact to these finishing apparatuss in the oil engine.Sulfate ash is the overall weight percent of ash content in the lubricant compositions.
The concentration of considering sulfate ash, sulphur and the phosphorus of lubricant compositions may have a negative impact to exhaust gas aftertreatment, wishes that exploitation wherein has the lubricant compositions of sulfate ash, sulphur and/or the phosphorus concentration of reduction.Sulfate ash content in the lubricant compositions relates to total metal contents in soil wherein.Can measure sulfate ash according to ASTM D874 expediently.Normally use therein any metal detergent additives of the main source of sulfate ash and zinc dithiophosphate anti-wear additive in the lubricant compositions.But the amount of metal detergent additives has a negative impact to its detergency in the reduction lubricant compositions.
Therefore the utmost point wishes to develop the lubricant compositions with low sulfation ash content, sulphur and phosphorus concentration, described lubricant compositions also has good detergency and produces for example piston cleanliness of favourable Engine Cleanliness Level, particularly in being exposed to the engine of temperature.
The applicant has found unexpectedly that at present the settling on piston, piston ring groove and the cylinder wall is compared with the mineral oil based lubricant and significantly reduced when using lubricant compositions based on the sulfate ash with reduction, sulphur and the phosphorus concentration of the highly paraffinic base oil that is derived from the fischer-tropsch process to lubricate compression-ignition engine.In addition, have been found that lubricant compositions stands fouling and oxidation still less and therefore allows use more of a specified duration.
Summary of the invention
Therefore, the present invention relates to a kind of lubricant compositions, described lubricant compositions has the sulfate ash content in the phosphorus content of the sulphur content of lubricant compositions gross weight 0.01-0.3wt%, 0.01-0.1wt% and 0.1-1.2wt%, described lubricant compositions comprises base oil or base oil blend, and the kinematic viscosity of wherein said lubricant compositions under 100 ℃ is greater than 5.0mm
2/ s (cSt), according to ASTM D 5293 the cold start-up under-15 ℃ simulation dynamic viscosity be lower than 9500mPas (cP) and according to the miniature rotary viscosity test value of ASTM D 4684 under-20 ℃ be lower than 60000mPas and wherein said base oil or base oil blend comprise have n, the continuous sequence isoparaffin of n+1, n+2, n+3 and n+4 carbon atom.
The base oil of lubricant compositions or base oil blend preferably have the pour point that is lower than-39 ℃ and at 100 ℃ of following 3.8-8.5mm
2The kinematic viscosity of/s (cSt) and wherein lubricant compositions have at 100 ℃ of following 9.3-16.3mm
2The kinematic viscosity of/s (cSt).Still more preferably, base oil or base oil blend comprise the saturates of 98wt% and the naphthenic hydrocarbon that wherein said saturates cut comprises 10-40wt% at least.Again more preferably, described saturates cut comprises the naphthenic hydrocarbon greater than 12wt%.
Base oil component comprise have n, the continuous sequence isoparaffin of n+1, n+2, n+3 and n+4 carbon atom.This base oil can be Fisher-Tropsch derived base oil expediently, those disclosed among WO-A-02/070627, WO-A-2005/003067, WO-A-00/14188, WO-A-00/14187, WO-A-00/14183, WO-A-00/14179, WO-A-00/08115, WO-A-99/41332, EP-A-1029029, WO-A-01/18156 and the WO-A-01/57166 for example, prerequisite is viscosity and the cryogenic properties that base oil allow to obtain lubricant compositions, promptly wherein the kinematic viscosity of lubricant compositions under 100 ℃ greater than 5.0mm
2/ s (cSt), be lower than 9500mPas (cP) and be lower than 60000mPas in the cold start-up under-15 ℃ simulation dynamic viscosity according to the miniature rotary viscosity test value of ASTM D 4684 under-20 ℃ according to ASTM D 5293.
The implication of " Fisher-Tropsch derived " is that base oil is or comes from the synthetic product of fischer-tropsch condensation course.Can respective explanations term " non-Fisher-Tropsch derived ".Fischer-tropsch derived fuel also can be described as GTL (cyclostrophic liquid) fuel.
In the presence of the catalyzer that is fit to and usually at high temperature under (for example 125-300 ℃, preferred 175-250 ℃) and/or the high pressure (for example 5-100 crust, preferred 12-50 clings to), Fischer-Tropsch reaction changes into the more hydrocarbon of long-chain (normally paraffinic hydrocarbons) with carbon monoxide and hydrogen:
N (CO+2H
2)=(-CH
2-) n+nH
2The O+ heat.
In case of necessity, the hydrogen of use can not be 2: 1 with the carbon monoxide ratio.Carbon monoxide and hydrogen itself can be derived from organic or inorganic, natural or synthetic source, normally from Sweet natural gas or from organic derived methane.
The example of fischer-tropsch base process is " The Shell Middle Distillate SynthesisProcess ", the SMDS that describes among people's (seing before) such as van der Burgt (the Shell intermediate oil is synthetic).This process (being also referred to as Shell " cyclostrophic liquid " or " GTL " technology sometimes) is produced the intermediate oil range product by Sweet natural gas (mainly the being methane) synthetic gas of deriving is changed into heavy long chain hydrocarbon (paraffinic hydrocarbons) wax, can make this heavy long chain hydrocarbon (paraffinic hydrocarbons) wax hydrocracking and fractionation for example can be used for gas oil in the diesel fuel composition to produce liquid transportation fuels subsequently.
By the fischer-tropsch process, Fisher-Tropsch derived base oil basically not or contain can not detection level sulphur and nitrogen.Containing these heteroatomic compounds trends towards as the poisonous substance of Fischer-Tropsch catalyst and is therefore removed from raw material of synthetic gas.In fuel composition of the present invention, this can produce other benefit aspect catalyst performance effect.
Lubricant compositions can be used for by being lubricated to mechanical engine parts, particularly internal combustion type (for example ignition) engine parts oil addition.It is not the additional base oil that is derived from the fischer-tropsch process that lubricant compositions preferably contains what be lower than 10wt%.Again more preferably, lubricant compositions does not contain additional base oil.
Preferably, lubricant compositions is to comprise following material or by mixing the multistage general crankcase lubricant composition that following material makes: (a) base oil with lubricant viscosity of main amount comprises at least 50wt%, more preferably 60wt%, still more preferably 70wt%, more preferably 80wt%, also more preferably 90wt% and the most preferably Fisher-Tropsch derived base oil of 99wt% again at least at least; With a spot of: (b) dispersion agent ashless dispersant for example; (c) metal detergent, for example calcium and/or magnesium purification agent; (e) be selected from one or more other lubricant additive components of antioxidant, anti-wear agent and friction modifier; (f) viscosity modifier.
Typical fischer-tropsch product contain have n, the continuous sequence paraffinic hydrocarbons of n+1, n+2, n+3 and n+4 carbon atom.With as described below make isomerization of paraffinic hydrocarbons with the survey stick nature that obtains to be fit to as lubricating oil.
Base oil or base oil blend preferably contain greater than the paraffinicity of 80wt% paraffinic hydrocarbons with greater than the saturates content of 98wt%.Preferably, base oil or base oil blend contain the saturates of 98wt% and the naphthenic hydrocarbon that wherein said saturates cut comprises 10-40wt% at least.
Base oil can be the blend of the base oil fraction of single base oil fraction or different viscosity.More preferably, the saturates cut comprises the naphthenic hydrocarbon greater than 12wt%.
Aspect other, the present invention relates to the purposes that the lubricant compositions of the present invention that comprises base oil or base oil blend and one or more additives is used for reducing at oil engine piston ring fouling, and the kinematic viscosity of wherein said lubricant compositions under 100 ℃ is greater than 5.0mm
2/ s (cSt), be lower than 9500mPas (cP) and be lower than 60000mPas and wherein said base oil or base oil blend by the synthetic hydrocarbon-fraction acquisition of wax paraffinic hydrocarbons fischer-tropsch in the cold start-up under-15 ℃ simulation dynamic viscosity according to the miniature rotary viscosity test value of ASTM D 4684-20 ℃ under according to ASTM D 5293.
The present invention relates to lubricant, to be used for lubricated wherein burning be that compression-ignition engine intermittently is the purposes of the engine of diesel motor, reciprocator, Wankel engine and similar Design.As mentioned above, the applicant has been found that and uses the lubricant that comprises Fisher-Tropsch derived base oil to cause the obvious and beat all collaborative increase of piston cleanliness.
The engine of bag of the present invention to be used lubricates, and promptly lubricant forms film so that the direct contact between them minimizes between the surface of the parts that move mutually.This lubricant film reduces friction, wearing and tearing and the too much generation of heat between the moving parts.In addition as moving fluid, lubricant delivery from the lubricating component surface because the heat of the friction of motion mutually between parts or between parts and oil film.Usually, oil engine contains crankcase, cylinder head and cylinder.Lubricant is present in the crankcase usually, and in crankcase, bent axle, bearing and the lower submerged of bar that piston is connected to bent axle are in lubricant.The rapid movement of these parts cause lubricant to splash and lubricating piston-ring and cylinder face between surface in contact.This lubricant film also as the sealing between piston ring and the cylinder wall so that the combustion volume in the cylinder separate with space in the crankcase.
Do not wish to be fettered, it is believed that the existence of residual lubricant film reduces the temperature of piston and cylinder face, thereby reduce the formation of cigarette ash and mud by any concrete theory.In addition, use base oil or base oil blend to allow preparation to have the lubricant compositions of the viscosity modifier of reduction amount.WO-A-02/123887 discloses the lubricant compositions with low-sulfur and phosphorus ash oontent.Have been found that not all composition according to the document all can provide and the filling according to the carbon residue content that is lower than 4.8wt% of Nissan TD25 detergency test (Japanese AutomobileStandards Organization (JASO) M336:1998) and/or according to the inverted draw cut that Nissan TD25 detergency test (Japanese AutomobileStandards Organization (JASO) M336:1998) is lower than 50vol% of required low temperature and viscometric properties combination.When in lubricant compositions, using base oil of the present invention or base oil blend, unexpectedly realized this combination.
Base oil preferably have greater than the paraffinicity of 80wt% paraffinic hydrocarbons, greater than the saturates content of 98wt% and contain have n, the Fisher-Tropsch derived base oil of the continuous sequence isoparaffin of n+1, n+2, n+3 and n+4 carbon atom, wherein n is 15-35.
Base oil preferably contains the preferred saturates of 98wt% at least in addition, more preferably the saturates of 99.5wt% and most preferably 99.9wt% at least at least.Saturates cut in the base oil preferably contains the naphthenic hydrocarbon of 10-40wt%.Again preferably, the content of naphthenic hydrocarbon is lower than 30wt% and more preferably less than 20wt%.The content of preferred naphthenic hydrocarbon is 12wt% and more preferably 15wt% at least at least.These base oil additional features be the weight ratio of the 1-ring naphthenic hydrocarbon naphthenic hydrocarbon that contains two or more rings relatively greater than 3, be preferably greater than 5.Have been found that this ratio compatibly is lower than 15.
Can use any suitable method to measure naphthenic hydrocarbon in base oil or the base oil blend and have the content and the existence of continuous sequence of the sequence isoparaffin of n, n+1, n+2, a n+3 and n+4 carbon atom.Particularly suitable method may further comprise the steps: at first by use high performance liquid chromatography (HPLC) method IP368/01 with the base oil sample be separated into polarity (aromatic hydrocarbons) mutually and nonpolar (saturates) mutually, wherein use pentane to substitute hexane that described method stipulates as mobile phase.Use Finnigan MAT90 spectrometer analysis saturates and the aromatic fraction that is equipped with field desorption(FD)/field ionization (FD/FI) interface subsequently, wherein FI (" soft " ionization techniques) is used for from carbon number and the not enough aspect of hydrogen semi-quantitative determination of hydrocarbon types.Measure the kind of compound in the mass spectroscopy classifies and classifies by " z number " usually by formed characteristic ion.This is by being used for the general formula C of all hydrocarbon species
nH
2n+zProvide.Because saturates separates analysis mutually with aromatic hydrocarbons, may measure content with identical stoichiometric different rings alkane.(poly 32 to use business software; Can be from Sierra Analytics LLC, 3453 Dragoo Park Drive, Modesto, CaliforniaGA95350USA obtains) handle mass spectrometric result with the relative proportion of measuring each hydrocarbon kind and the molecular-weight average and the polydispersity of saturates and aromatic fraction.
The content of the preferred compound aromatic hydrocarbon of base oil composition is lower than 1wt%, more preferably less than 0.5wt% with most preferably be lower than 0.1wt%, sulphur content is lower than 20ppm and nitrogen content is lower than 20ppm.The pour point of base oil preferably is lower than-30 ℃ and more preferably less than-40 ℃.Viscosity index preferably is higher than 120.Having been found that novel base oils has usually is lower than 140 viscosity index.The kinematic viscosity of base oil under 100 ℃ is preferably 4.0-8mm
2/ s (cSt) and Noack volatility preferably are lower than 14wt%.
Aforesaid base oil is compatibly by the hydroisomerization of Fisher-Tropsch derived paraffin wax, preferred for example solvent or the catalytic dewaxing acquisition of dewaxing of carrying out some kinds subsequently.
In this manual, the base oil that is derived from fischer-tropsch wax as described herein will be called Fisher-Tropsch derived base oil.
Base oil or base oil blend preferably can be obtained by the method that may further comprise the steps:
(a) hydrocracking/hydroisomerization fischer-tropsch product, described fischer-tropsch product have at least 60 or the compound of more a plurality of carbon atoms be at least 0.2 with weight ratio with compound of at least 30 carbon atoms, wherein in the fischer-tropsch product at least the compound of 30wt% have at least 30 carbon atoms
(b) be separated into the product of step (a) at least a or pluralities of fuel cut and base oil precursor fraction and
(c) base oil precursor fraction that obtains in the step (b) is implemented catalytic dewaxing step and randomly
(d) product that obtains in the step (c) is separated at least a or multiple base oil fraction and than low boiler cut.
Preferably, the fischer-tropsch product that uses in the step (a) contains at least 50wt% and the more preferably compound with at least 30 carbon atoms of 55wt% at least, wherein the fischer-tropsch product have at least 60 or the compound of more a plurality of carbon atoms and weight ratio with compound of at least 30 carbon atoms be at least 0.4 and wherein the fischer-tropsch product comprise C with ASF-α value (the Anderson-Schulz-Flory chainpropagation factor) of at least 0.925
20+ cut.
For example, the example that can be used to prepare the fischer-tropsch process of above-mentioned Fisher-Tropsch derived base oil is the so-called commercialization slurry attitude phase distillate technology of Sasol, intermediate oil synthesis method and " AGC-21 " Exxon Mobil method of Shell.These and other process for example is described in greater detail among EP-A-776959, EP-A-668342, US-A-4943672, US-A-5059299, WO-A-9934917 and the WO-A-9920720.
Usually these fischer-tropsch synthesis products will comprise and have 1-100 and even greater than the hydrocarbon of 100 carbon atoms.This hydrocarbon product will comprise n-paraffin, isoparaffin, oxidation products and unsaturated product.If base oil is a kind of of required iso-paraffinic products, the Fischer-Tropsch derived feed of then using the phase counterweight may be favourable.The Fischer-Tropsch derived feed of phase counterweight contains at least 30wt%, preferred 50wt% at least and the more preferably compound with at least 30 carbon atoms of 55wt% at least.In addition, Fischer-Tropsch derived feed have at least 60 or the weight ratio of the compound of more a plurality of carbon atoms and compound preferably at least 0.2 with at least 30 carbon atoms, be more preferably at least 0.4 and be at least 0.55 most preferably.Preferred Fischer-Tropsch derived feed contains the C with ASF-α value (the Anderson-Schulz-Flory chainpropagation factor) of at least 0.925, preferred at least 0.935, more preferably at least 0.945 even more preferably at least 0.955
20+ cut.The arbitrary process that such Fischer-Tropsch derived feed can be passed through the fischer-tropsch product of the aforesaid phase counterweight of generation obtains.
Not all fischer-tropsch process all produces so heavy product.The example of the fischer-tropsch process that is fit to has been described among the WO-A-9934917.Fisher-Tropsch derived base oil will not contain or contain considerably less sulfur-bearing and nitrogen compound.This product for the Fischer-Tropsch reaction that is derived from the impure hardly synthetic gas of use is typical.Sulphur and nitrogen level will be usually less than limit of detection, and be current, and described limit of detection is 5mg/kg for sulphur and is 1mg/kg for nitrogen.
Described method will generally include that fischer-tropsch is synthetic, hydroisomerisation step and optional depression of pour point step, wherein said hydroisomerisation step and the optional following enforcement of depression of pour point step:
(a) hydrocracking/hydroisomerization fischer-tropsch product, (b) product with step (a) is separated at least a or multiple distillate fuel fraction and base oil or base oil middle runnings.
If the viscosity of the base oil that obtains in the step (b) and pour point, then do not need other processing as required and described oil can be used as base oil of the present invention.In case of necessity, in step (c), suitably further reduce the pour point of base oil middle runnings, to obtain to have the oil of preferred low pour point by making the oily catalytic dewaxing that obtains in the step (b).Can separate the product of the suitable boiling range of corresponding required viscosity from middle base oil fraction or from pressed oil by distillation, and obtain the required viscosity of base oil.Distillation can compatibly be the underpressure distillation step.
Preferably enforcement in the presence of hydrogen and catalyzer of the hydroconversion/hydroisomerisation of step (a) reaction, described catalyzer can be selected from known those of this reaction of being suitable for of those skilled in the art, hereinafter will describe wherein some in more detail.Can the known any catalyzer that is suitable for the isomerization paraffin molecules in this area on the catalyzer principle.Usually, the hydroconversion/hydroisomerisation catalysts of Shi Heing is to comprise those of the hydrogenation component of carrier band on refractory oxide carrier (for example mixture of two or more of soft silica-aluminum oxide (ASA), aluminum oxide, fluorided alumina, molecular sieve (zeolite) or these).A class preferred catalyst of using in hydroconversion/hydroisomerisation step of the present invention is to comprise platinum and/or the palladium hydroconversion/hydroisomerisation catalysts as hydrogenation component.Hydroconversion/hydroisomerisation catalysts very preferably comprises platinum and the palladium of carrier band on soft silica-aluminum oxide (ASA) carrier.The amount of platinum and/or palladium compatibly is 0.1-5.0wt%, is 0.2-2.0wt% with being more suitable for, calculates with element form with based on total weight of carrier.If the two all exists, then the weight ratio of platinum and palladium can change in grace period, but compatibly is 0.05-10, is 0.1-5 with being more suitable for.The example of noble metal catalyst on the ASA that is fit to is for example disclosed in WO-A-9410264 and EP-A-0582347.Other noble metal-based catalysts that is fit to for example platinum on the fluorided alumina carrier for example is disclosed among the US-A-5059299 and WO-A-9220759.The hydroconversion/hydroisomerisation catalysts that second class is fit to is to comprise at least a group vib metal (preferred tungsten and/or molybdenum) and at least a non-noble metal group VIII metal (preferably nickel and/or cobalt) as those of hydrogenation component.Two kinds of metals can exist with oxide compound, sulfide or their array configuration.The amount of group vib metal compatibly is 1-35wt%, is 5-30wt% with being more suitable for, calculates with element form with based on total weight of carrier.The amount of non-noble metal group VIII metal compatibly is 1-25wt%, and preferably 2-15wt% calculates with element form with based on total weight of carrier.Found that particularly suitable this class hydrogenation conversion catalyst is to comprise the nickel of carrier band on fluorided alumina and the catalyzer of tungsten.
Above-mentioned non-noble metal-based catalysts is preferably used with their sulfur form.In order to keep the sulfur form of catalyzer during use, need to exist some sulphur in the raw material.There are preferably 10mg/kg and the more preferably sulphur of 50-150mg/kg at least in the raw material.
Can comprise for example iron, nickel and I B-group metal copper for example of the non-noble metal group VIII metal of carrier band on acid carrier with the preferred catalyst that the unvulcanised form is used.Preferably exist copper to suppress hydrogenolysis of paraffins to methane.Catalyzer have by the water absorption measurement preferably 0.35-1.10ml/g pore volume, by BET nitrogen determining adsorption 200-500m preferably
2The surface-area of/g and the bulk density of 0.4-1.0g/ml.Support of the catalyst is preferably made by soft silica-aluminum oxide, and wherein aluminum oxide can exist with 5-96wt%, preferred 20-85wt%.SiO
2The dioxide-containing silica of form is 15-80wt% preferably.The tackiness agent that carrier also can contain a small amount of for example 20-30wt% is aluminum oxide, silicon-dioxide, IVA family metal oxide and multiple clay, magnesium oxide etc. for example, preferred aluminum oxide or silicon-dioxide.At Ryland, Lloyd B., Tamele, M.W., and Wilson, J.N., Cracking Catalysts, Catalysis: VII volume, Ed.Paul H.Emmett, Reinhold Publishing Corporation, New York, the preparation of soft silica-aluminum oxide micro-sphere body has been described in 1960, the 5-9 pages or leaves.By metal being flooded altogether from solution to carrier, descending dry and under 200-550 ℃, in air, calcine to prepare catalyzer at 100-150 ℃.Group VIII metal amount is about 15wt% or still less, preferred 1-12wt%, and I B-group metal exists with still less amount usually, for example the weight ratio of relative group VIII metal is 1: about 1: 20 of 2-.
Provided typical catalyzer below:
Ni， 2.5-3.5wt％
Cu， 0.25-0.35wt％
Al
2O
3-SiO
2， 65-75wt％
Al
2O
3(tackiness agent), 25-30wt%
Surface-area 290-325m
2/ g
Pore volume (Hg) 0.35-0.45ml/g
Bulk density 0.58-0.68g/ml
Another kind of suitable hydroconversion/hydroisomerisation catalysts is based on those of molecular sieve material, compatibly comprises at least a group VIII metal component, preferred Pt and/or Pd as hydrogenation component.Then, the zeolite of Shi Heing and other alumino-silicate materials comprise zeolite beta, zeolite Y, super steady Y, ZSM-5, ZSM-12, ZSM-22, ZSM-23, ZSM-48, MCM-68, ZSM-35, SSZ-32, ferrierite, mordenite and silicon-dioxide-aluminate or phosphate for example SAPO-11 and SAPO-31.
The example of the hydroisomerization/hydroisomerisation catalysts that is fit to has for example been described in WO-A-9201657.The combination of these catalyzer also is possible.Fit closely hydroconversion/hydroisomerisation process is those that may further comprise the steps: first step, wherein use zeolite beta or ZSM-48 catalyst based; With second step, wherein use ZSM-5, ZSM-12, ZSM-22, ZSM-23, ZSM-48, MCM-68, ZSM-35, SSZ-32, ferrierite, mordenite catalyst based.In next one group, ZSM-23, ZSM-22 and ZSM-48 are preferred.Described the example of these processes in US-A-20040065581, its disclosed process comprises the first step catalyzer that comprises platinum and zeolite beta and comprises the second step catalyzer of platinum and ZSM-48.These processes can produce the base oil product that does not need other dewaxing step.
Wherein make the fischer-tropsch product experience at first that use comprises first hydroisomerisation step of the amorphous catalyst of silica-alumina carriers as mentioned above, experience uses the combination of second hydroisomerisation step of the catalyzer comprise molecular sieve also to be confirmed to be the preferred method of the base oil that uses among preparation the present invention subsequently.More preferably implement first and second hydroisomerisation step in the crossfire mode.Most preferably in the single reaction vessel of the bed that comprises above-mentioned amorphous and/or crystal catalyst, implement two steps.
In step (a), in the presence of the catalyzer, under high temperature and high pressure raw material is contacted with hydrogen.Temperature will be 175-380 ℃ usually, preferably be higher than 250 ℃ and more preferably 300-370 ℃.Pressure is 10-250bar and preferred 20-80bar normally.Can be with the gas hourly space velocity supply hydrogen of 100-10000Nl/l/hr, preferred 500-5000Nl/l/hr.Can be with 0.1-5kg/l/hr, preferably be higher than 0.5kg/l/hr and more preferably less than the weight hourly space velocity supply hydrocarbon feed of 2kg/l/hr.The ratio of hydrogen and hydrocarbon feed can be 100-5000Nl/kg and 250-2500Nl/kg preferably.
Be defined as in the step (a) at every turn by the time boiling point be higher than 370 ℃ raw material reaction and become the transformation efficiency of weight percentage that boiling point is lower than 370 ℃ cut and be 20wt% at least, be preferably 25wt% at least, but preferably be not more than 80wt%, more preferably no more than 65wt%.The raw material that uses in the above-mentioned definition is the total hydrocarbon feed that adds step (a), therefore also comprise in the step (b) can obtainable high boiling fraction any optional recycle.
In step (b), preferably the product with step (a) is separated into one or more distillate fuel fraction and has the base oil or the base oil precursor fraction of required viscometric properties.If pour point is not within the required range, then by the dewaxing step (c), preferably further reduce the base oil pour point by catalytic dewaxing.In this embodiment, making the more wide-boiling cut dewaxing of the product of step (a) may be further advantage.Can advantageously from the gained dewaxed product, isolate a kind of and multiple base oil by distillation subsequently with required viscosity.Dewaxing preferably by as the catalytic dewaxing for example described among the WO-A-02/070629 implement.Final boiling point to the raw material of the step that dewaxes (c) can be the final boiling point of the product of step (a), or lower in case of necessity.Therefore, the present invention also relates to be used for prepare as mentioned above base oil, separate base oil and add necessary additive and other component to obtain the method for lubricant compositions.
Compatibly, base oil or base oil blend have at 100 ℃ of following 3-25mm
2The kinematic viscosity of/s.Preferably, it has at 100 ℃ of following 3-15mm
2/ s, more preferably 3.5-9.5mm
2/ s, more preferably 3.75-8.5mm still
2The kinematic viscosity of/s.Preferably, base oil has the pour point that is lower than-39 ℃ and at 100 ℃ of following 3.8-8.5mm
2The kinematic viscosity of/s (cSt) and wherein lubricant compositions have at 100 ℃ of following 9.3-16.3mm
2The kinematic viscosity of/s (cSt).Still more preferably, it has under 100 ℃ and is lower than 15.5mm
2/ s, more preferably less than 14mm
2/ s, most preferably be lower than 13mm
2The kinematic viscosity of/s.
The pour point of base oil preferably is lower than-30 ℃.Measure by ASTM D92, the flash-point of base oil is preferably greater than 120 ℃, more preferably even greater than 140 ℃.
The base oil that uses in the lubricant compositions in bag of the present invention has the viscosity index of 100-600, more preferably the viscosity index of 110-200 and even the more preferably viscosity index of 120-150.
Lubricant compositions of the present invention can only comprise the combination of paraffinic base oil or aforesaid paraffinic base oil and ester or as an alternative with the combination of another additional base oil as base oil component.Additional base oil will compatibly account for the 20wt% that is lower than of total fluid preparation, more preferably less than 10wt%, again more preferably less than 5wt%.The example of these base oils is mineral based paraffinic and naphthenic base oils and synthetic base oil, for example poly-alpha olefins alkene, polyalkylene glycol etc.Consumption is subjected to nitrous oxide to be reached and reduces restriction.Preferably, lubricant also comprises the saturated cyclic hydrocarbons in the amount of total lubricant 5-10wt%, because this has improved the low temperature compatibility of different components in the lubricant.
Lubricant compositions of the present invention can also comprise as disclosed any one or the multiple additives according to general formula I of the 8-10 page or leaf of WO-A-2005/123887.These preferred amounts of one or more compounds with general formula I are 0.01-10.00wt%, in the lubricant compositions gross weight.
Lubricant compositions preferably contains one or more zinc dithiophosphates (preferred zinc dialkyl dithiophosphate) and/or one or more salicylate purification agents (more preferably alkaline-earth metal salicylate) in addition.
Lubricant compositions preferably has the sulfate ash content in lubricant compositions gross weight 0.6-1.0wt% in addition.Lubricant compositions preferably has the sulphur content in lubricant compositions gross weight 0.12-0.20wt% in addition.
Lubricant compositions preferably has the TBN value of the 5.0-12.0mg.KOH/g that measures by ASTM D2896 in addition.
Lubricant of the present invention preferably contains the viscosity modifier of the amount of 0.01-30wt% in addition.Viscosity index improver (being also referred to as VI improving agent, viscosity modifier or viscosity modifier) provides high temperature and low temperature operability to lubricant.These additives provide shear stability and acceptable at low temperatures viscosity at high temperature.The other preferred package of the lubricant that uses in the bag of the present invention contains at least a other additional lubricant component (for example polarity and/or nonpolar lubricant base oil) of significant quantity and performance additive such as but not limited to metal and ashless oxidation retarder, metal and ashless dispersant, metal and ashless detergent, corrosion inhibition and rust-preventive agent, metal passivator, metal and nonmetal, low ash content, phosphorous and without phosphorus, sulfur-bearing and sulfur-bearing anti-wear agent not, metal and nonmetal, phosphorous and without phosphorus, sulfur-bearing and no sulphur extreme-pressure additive, anti-jamming dose, pour point depressant, wax modifiers, viscosity modifier, sealing compatilizer, friction modifier, oiliness improver, stainproofing agent, chromogenic reagent, defoamer, emulsion splitter and other normally used additive-package.About the summary of multiple normally used additive, with reference to the Lubricants and RelatedProducts of D.Klamann, Verlag Chemie, Deerfield Beach, FL; ISBN 0-89573-177-0 and Noyes Data Corporation of Parkridge, " the Lubricant Additives " of the M.W.Ranney that N.J. (1973) publishes.
The present invention be more particularly directed to lubricant compositions according to so-called SAE J300 classification, the lubricant formulations that particularly meets the grading of SAE " xW-y " viscosity, wherein x=0,5,10 or 15 and wherein=10,20,30 or 40 and wherein (y-x) be less than or equal to 25.SAE represents the Society of Automotive Engineers of the U.S.." x " numerical value in this title requires relevant with the described composition peak viscosity of measuring by the cold start-up analog machine (VdCCS) under high-shear usually at low temperatures.Second numerical value " y " is relevant with the kinematic viscosity requirement under 100 ℃.
Aspect other, the invention provides the method for the ring bonding trend of improving piston cleanliness and reducing compression-ignition engine, comprise to engine and add lubricant compositions of the present invention.Another other aspect, the invention provides the crankcase that comprises compression-ignition engine (preferably have 25kW/ rises or bigger specific power output) and the combination of lubricant compositions of the present invention.Another other aspect, the invention provides the method for lubricated compression-ignition engine (preferred diesel motor, petrol engine or gaseous propellant engine), comprise with lubricant compositions of the present invention and operate engine and lubricating engine.Another other aspect, the present invention also relates to described lubricant compositions improves Engine Cleanliness Level in diesel engine, geseous fuel or petrol engine are used purposes.
To further describe the present invention by following non-limiting examples below:
Embodiment 1
By the base oil under every kind of situation of balance suitably to every kind of situation under viscosity modifier handle, two kinds of SAE 5W-40 of blend lubricant compositions is at-30 ℃ of suitable VdCCS (cold start-up viscosity) and suitable Vk100C down.
Use has two kinds of Fisher-Tropsch derived base oils (called after GTL base oil) of disclosed character in the table 1 and prepares lubricant compositions of the present invention.
Be used for contrast, based on preparing lubricant formulations from two kinds of commercially available mineral oil derived III class base oils of SK Corporation (Yubase is the registered trademark of SK Corporation) with Yubase 4 and Yubase 6." III class base oil " is the base oil according to American PetroleumInstitute (API) definition kind I and II.API Publication 1509, the 15 editions, appendix E has defined these API kinds in 2002 4 months.According to aforementioned ASTM method, III class base oil contains more than or equal to 90% saturates and the sulphur and the viscosity index that has greater than 120 of being less than or equal to 0.03%.Having used following additive: VISCOPLEX6-054, is to comprise the commercial dispersants of the compound with general formula I and viscosity index improver (VISCOPLEX is
GmbH ﹠amp; The registered trademark of Co.KG does not contain sulfate ash and phosphorus and is alkylmethacrylate/N-vinylpyrrolidone copolymer); Commercially available heavy duty diesel engine oil smoke ash dispersion agent; Infineum SV200 and Infineum SV150, the two all is that (" Infineum " is the trade mark of Infineum InternationalLtd. to commercially available viscosity index improver; SV is the abbreviation of Shell Vis, and the latter is the trade mark of Shell Chemical Company); With commercially available high alkaline detergent (Infineum C9371).By the base oil under every kind of situation of balance suitably to every kind of situation under viscosity modifier handle, the blend lubricant compositions is at-30 ℃ of suitable VdCCS (cold start-up viscosity) and suitable Vk100C down.
Table 1: the blend that is used for the test of Nissan TD25 piston cleanliness
| Component [%m/m] | Embodiment 1 | Comparative Examples |
| GTL base oil 1 (5mm 2/s(cSt)) | 63,60 | - |
| GTL base oil 2 (8mm 2/s(cSt)) | 7,50 | - |
| Yubase 4 | - | 62,00 |
| Yubase 6 | - | 6,36 |
| Ashless dispersant | 14,00 | 14,00 |
| High alkaline detergent | 2,40 | 2,40 |
| Viscosity modifier Viscoplex 6-054 | 1,50 | 1,50 |
| Viscosity modifier (Infineum SV151 ﹠ 201) | 11,00 (5.5+5.5) | 13,76 (5.76+8.00) |
| Defoamer [ppm] | 264 | 264 |
| Detect character | ||
| VK@100℃[mm 2/s(cSt)] | 15.47 | 15.69 |
| VK@40℃[mm 2/s(cSt)] | 93.25 | 94.59 |
| VdCCS@-30℃[mPas(cP)] | 6357 | 6583 |
| Noack vaporization losses ASTM D-5800[%m/m] | 7.9，8.0 | 12.3，12.5 |
In the simulation of the motorway of diesel powered passenger vehicle or light truck operation, the Nissan TD25 detergency of the detergency of implementation evaluation motor vehicle diesel under high temperature and high loading test (Japanese Automobile Standards Organization (JASO) M336:1998)).The JASO standard: Nissan TD25 detergency procedure is the part of JASO standard JASODH-1 and JASO DL-1.
Test engine is the 2.5L four-in-line formula TD25 diesel motor of being made by Nissan Diesel (Nissan Diesel is Nissan DieselMotor CO., the registered trademark of LTD.).Engine is placed in the engine power meter test board.Use by 2 class lightweight gas oil of JIS K 2202 regulation as test fuel.
Engine Block Test is included under full load and the peak torque with 4, and the speed of 300rpm was moved engine 200 hours continuously, removed changing oil fully under 100 hours.The engine oil temperature is 120 ℃, and refrigerant is 90 ℃ of temperature.
After the test, the mud of assessment piston mode and formation.The same abrasion loss of measuring piston ring and metal bearing, oil ring, camshaft and steam jacket.In addition, used oil is analyzed.Estimate lacquer deposits, wearing and tearing and the ring bonding of piston and ring.The obstruction of assessment oil ring.
Estimate the settling and the wearing and tearing of steam jacket.The combustion chamber deposit of assessment cylinder head.The mud of oily surface in contact forms in the assessment engine.Estimate kinematic viscosity, dust content, sulfate ash, total acid value, total basicnumber, insoluble substance, water, fuel dilution and the wear metal of used lubricant.The result that piston ring settling and inverted draw cut are filled has been described in the table 2:
Table 2:Nissan TD25 test result
| Component | Embodiment 1 | Comparative Examples |
| The piston detergency | ||
| Carbon residue [wt%] | 4.75 | 4.94 |
| Inverted draw cut is filled | ||
| [vol％] | 37.0 | 57.1 |
Therefore, described test is clear has described the piston cleanliness of obvious increase and the inverted draw cut of reduction is filled.
Claims (16)
1. lubricant compositions, described lubricant compositions has the sulfate ash content in the phosphorus content of the sulphur content of lubricant compositions gross weight 0.01-0.3wt%, 0.01-0.1wt% and 0.1-1.2wt%, described lubricant compositions comprises base oil or base oil blend, and the kinematic viscosity of wherein said lubricant compositions under 100 ℃ is greater than 5.0mm
2/ s (cSt), be lower than 9500mPas (cP) and be lower than 60000mPas in the cold start-up under-15 ℃ simulation dynamic viscosity according to the miniature rotary viscosity test value of ASTM D 4684 under-20 ℃ according to ASTM D 5293, comprise with wherein said base oil or base oil blend have n, the continuous sequence isoparaffin of n+1, n+2, n+3 and n+4 carbon atom, wherein n is 15-35.
2. the lubricant compositions of claim 1, wherein said base oil or base oil blend have the pour point that is lower than-39 ℃ and at 100 ℃ of following 3.8-8.5mm
2The kinematic viscosity of/s (cSt) and wherein said lubricant compositions have at 100 ℃ of following 9.3-16.3mm
2The kinematic viscosity of/s (cSt).
3. claim 1 or 2 lubricant compositions, wherein said base oil or base oil blend comprise the saturates of 98wt% and the naphthenic hydrocarbon that wherein said saturates cut comprises 10-40wt% at least.
4. the lubricant compositions of claim 3, wherein said saturates cut comprises the naphthenic hydrocarbon greater than 12wt%.
5. each lubricant compositions of claim 1-4, wherein said base oil or base oil blend can be obtained by the method that may further comprise the steps:
(a) hydrocracking/hydroisomerization fischer-tropsch product, described fischer-tropsch product have at least 60 or the compound of more a plurality of carbon atoms be at least 0.2 with weight ratio with compound of at least 30 carbon atoms, wherein in the fischer-tropsch product at least the compound of 30wt% have at least 30 carbon atoms
(b) be separated into the product of step (a) at least a or pluralities of fuel cut and base oil precursor fraction and
(c) base oil precursor fraction that obtains in the step (b) is implemented catalytic dewaxing step and randomly
(d) product that obtains in the step (c) is separated at least a or multiple base oil fraction and than low boiler cut.
6. each lubricant compositions of claim 1-5, wherein the fischer-tropsch product that uses in the step (a) contains at least 50wt% and the more preferably compound with at least 30 carbon atoms of 55wt% at least, wherein the fischer-tropsch product have at least 60 or the compound of more a plurality of carbon atoms and weight ratio with compound of at least 30 carbon atoms be at least 0.4 and wherein the fischer-tropsch product comprise C with ASF-α value (the Anderson-Schulz-Flory chainpropagation factor) of at least 0.925
20+ cut.
7. each lubricant compositions of claim 1-6, wherein said composition also comprises one or more zinc dithiophosphates, preferred zinc dialkyl dithiophosphate.
8. each lubricant compositions of claim 1-7, wherein said composition also comprises one or more salicylate purification agents, preferred bases earth metals salicylate.
9. each lubricant compositions of claim 1-8, wherein said lubricant compositions has the sulfate ash content in lubricant compositions gross weight 0.6-1.0wt%.
10. each lubricant compositions of claim 1-9, it has the sulphur content in lubricant compositions gross weight 0.12-0.20wt%.
11. each lubricant compositions of claim 1-10, it has the TBN value of the 5.0-12.0mg.KOH/g that measures by ASTMD2896.
12. each lubricant compositions of claim 1-11, it has the inverted draw cut that is lower than 50vol% according to NissanTD25 detergency test (Japanese Automobile Standards Organization (JASO) M336:1998) and fills.
13. each lubricant compositions of claim 1-10, it has the carbon residue content that is lower than 4.8wt% according to NissanTD25 detergency test (Japanese Automobile Standards Organization (JASO) M336:1998).
14. with each the method for the lubricated oil engine of lubricant compositions of claim 1-13, the preferred diesel motor of wherein said oil engine, petrol engine or gaseous propellant engine, wherein said lubricant compositions produce the inverted draw cut filling that is lower than 50vol% according to Nissan TD25 detergency test (JapaneseAutomobile Standards Organization (JASO) M336:1998).
15. each lubricant compositions of claim 1-13 improves the purposes of Engine Cleanliness Level in diesel engine, geseous fuel or petrol engine are used, wherein said lubricant compositions produces the carbon residue content that is lower than 4.8wt% according to Nissan TD25 detergency test (Japanese Automobile StandardsOrganization (JASO) M336:1998).
16. improve the piston cleanliness of compression-ignition engine and reduce the method for encircling bonding trend according to Nissan TD25 detergency test (Japanese AutomobileStandards Organization (JASO) M336:1998), comprise the lubricant compositions that adds claim 1-13 to engine.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP06123805.1 | 2006-11-10 | ||
| EP06123805 | 2006-11-10 |
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|---|---|---|---|
| CNA2007800466334A Pending CN101563441A (en) | 2006-11-10 | 2007-11-09 | Low sulphur, low sulphated ash, low phosphorus and highly paraffinic lubricant composition |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20100004148A1 (en) |
| EP (1) | EP2087079A1 (en) |
| JP (1) | JP2010509422A (en) |
| CN (1) | CN101563441A (en) |
| BR (1) | BRPI0718760A2 (en) |
| RU (1) | RU2009122225A (en) |
| WO (1) | WO2008055975A1 (en) |
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| CN112384599A (en) * | 2018-07-13 | 2021-02-19 | 国际壳牌研究有限公司 | Lubricating composition |
| CN115340894A (en) * | 2021-10-22 | 2022-11-15 | 福斯润滑油(中国)有限公司 | Low-viscosity lubricating oil for engine |
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| US8747650B2 (en) | 2006-12-21 | 2014-06-10 | Chevron Oronite Technology B.V. | Engine lubricant with enhanced thermal stability |
| EP2186872A1 (en) | 2009-12-16 | 2010-05-19 | Shell Internationale Research Maatschappij B.V. | Lubricating composition |
| WO2016123548A1 (en) * | 2015-01-30 | 2016-08-04 | Basf Corporation | Combination of low/no ash oil and emission control catalysts for improved emission control durability and performance |
| EP4317379A1 (en) * | 2021-03-29 | 2024-02-07 | Idemitsu Kosan Co.,Ltd. | Lubricant composition |
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| US4943672A (en) * | 1987-12-18 | 1990-07-24 | Exxon Research And Engineering Company | Process for the hydroisomerization of Fischer-Tropsch wax to produce lubricating oil (OP-3403) |
| US5059299A (en) * | 1987-12-18 | 1991-10-22 | Exxon Research And Engineering Company | Method for isomerizing wax to lube base oils |
| US7067049B1 (en) * | 2000-02-04 | 2006-06-27 | Exxonmobil Oil Corporation | Formulated lubricant oils containing high-performance base oils derived from highly paraffinic hydrocarbons |
| ES2248538T3 (en) * | 2001-02-13 | 2006-03-16 | Shell Internationale Research Maatschappij B.V. | LUBRICATING COMPOSITION. |
| US20030191032A1 (en) * | 2002-01-31 | 2003-10-09 | Deckman Douglas E. | Mixed TBN detergents and lubricating oil compositions containing such detergents |
| ATE310066T1 (en) * | 2002-07-18 | 2005-12-15 | Shell Int Research | METHOD FOR PRODUCING A MICROCRYSTALLINE WAX AND A MIDDLE DISTILLATE FUEL OR FUEL |
| US7704379B2 (en) * | 2002-10-08 | 2010-04-27 | Exxonmobil Research And Engineering Company | Dual catalyst system for hydroisomerization of Fischer-Tropsch wax and waxy raffinate |
| US20040154957A1 (en) * | 2002-12-11 | 2004-08-12 | Keeney Angela J. | High viscosity index wide-temperature functional fluid compositions and methods for their making and use |
| JP4477337B2 (en) * | 2003-10-16 | 2010-06-09 | 新日本石油株式会社 | Lubricating oil additive, lubricating oil additive composition and lubricating oil composition |
| CA2570514A1 (en) * | 2004-06-18 | 2005-12-29 | Shell Internationale Research Maatschappij B.V. | Lubricating oil composition |
| US20060089272A1 (en) * | 2004-10-25 | 2006-04-27 | The Lubrizol Corporation | Ashless consumable engine oil |
| JP5114006B2 (en) * | 2005-02-02 | 2013-01-09 | Ｊｘ日鉱日石エネルギー株式会社 | Lubricating oil composition for internal combustion engines |
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2007
- 2007-11-09 RU RU2009122225/04A patent/RU2009122225A/en not_active Application Discontinuation
- 2007-11-09 BR BRPI0718760-2A patent/BRPI0718760A2/en not_active IP Right Cessation
- 2007-11-09 WO PCT/EP2007/062138 patent/WO2008055975A1/en active Application Filing
- 2007-11-09 JP JP2009535741A patent/JP2010509422A/en active Pending
- 2007-11-09 EP EP07822427A patent/EP2087079A1/en not_active Withdrawn
- 2007-11-09 US US12/513,912 patent/US20100004148A1/en not_active Abandoned
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112384599A (en) * | 2018-07-13 | 2021-02-19 | 国际壳牌研究有限公司 | Lubricating composition |
| CN115340894A (en) * | 2021-10-22 | 2022-11-15 | 福斯润滑油(中国)有限公司 | Low-viscosity lubricating oil for engine |
Also Published As
| Publication number | Publication date |
|---|---|
| BRPI0718760A2 (en) | 2013-12-03 |
| WO2008055975A1 (en) | 2008-05-15 |
| JP2010509422A (en) | 2010-03-25 |
| RU2009122225A (en) | 2010-12-20 |
| EP2087079A1 (en) | 2009-08-12 |
| US20100004148A1 (en) | 2010-01-07 |
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Application publication date: 20091021 |