CN107406784A - Marine diesel lubricant oil composite - Google Patents

Marine diesel lubricant oil composite Download PDF

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Publication number
CN107406784A
CN107406784A CN201680007190.7A CN201680007190A CN107406784A CN 107406784 A CN107406784 A CN 107406784A CN 201680007190 A CN201680007190 A CN 201680007190A CN 107406784 A CN107406784 A CN 107406784A
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CN
China
Prior art keywords
detersive
parlkaline
oil
isomerization
lubricant
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CN201680007190.7A
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Chinese (zh)
Inventor
R·T·F·朱克斯
W·P·A·梵豪登
G·P·辛根
T·布鲁克哈特
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Chevron Oronite SAS
Chevron Oronite Technology BV
Chevron Oronite Co LLC
Original Assignee
Chevron Oronite SAS
Chevron Oronite Technology BV
Chevron Oronite Co LLC
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Application filed by Chevron Oronite SAS, Chevron Oronite Technology BV, Chevron Oronite Co LLC filed Critical Chevron Oronite SAS
Publication of CN107406784A publication Critical patent/CN107406784A/en
Pending legal-status Critical Current

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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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
    • C10M135/10—Sulfonic acids or derivatives thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02—Petroleum fractions
    • 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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/02—Sulfurised compounds
    • 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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • 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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
    • 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
    • C10M169/042—Mixtures of base-materials and additives the additives being compounds of unknown or incompletely defined constitution only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/0406—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides used as base material
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089—Overbased salts
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • 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
    • 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
    • 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
    • C10N2030/08—Resistance to extreme temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • 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
    • C10N2030/26—Waterproofing or water resistance
    • 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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  • 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)
  • Lubricants (AREA)
  • Lubrication Of Internal Combustion Engines (AREA)

Abstract

A kind of marine diesel lubricant oil composite of the TBN with about 5 to about 120, it contains the base oil of lubricant viscosity, parlkaline alkylaryl C10‑40Sulfonate detergent and parlkaline isomerization C10‑40Positive alhpa olefin base phenate detergents, wherein the weight of the overbased sulfonates detersive and the positive alhpa olefin base phenate detergents of the parlkaline isomerization than scope from 1：9 to 9：1.

Description

Marine diesel lubricant oil composite
Technical field
The present invention relates to marine lubricant composition, the bavin peculiar to vessel particularly as engine with outside guide and trunk-piston engine Oil machine lubricant.The lubricant oil composite shows improved oxidation stability, viscosity increase control, detergency and water-fast Property.
Background technology
Diesel engine be used as marine ship operation internal combustion engine, and be generally classified as at a slow speed, middling speed or at a high speed send out Motivation.
Slow-speed diesel engines are unique in size and operating method.Engine speed per minute 60 arrives about 200 turns Under the conditions of the output of these engines may be up to 100000 brake horsepowers.They are generally crosshead design and with two-stroke cycles Operation.The design and structure of these engines are attributed to, wherein crosshead separates igniting cylinder with crankcase, and stuffing box Sealing, cylinder and crankcase is completed to be lubricated respectively by oil vat for vessel oil and ship lubricant oil.
The major function of ship cylinder lubricant is that strong oil film is provided between cylinder jacket and piston ring.Run in engine Period consumes ship cylinder lubricant, therefore cylinder is lubricated on the basis of total losses.Although the fresh lubricating oil of regular replenishment With the part of compensation consumption, but it is exposed to the hot sulfur oxide that can cause incrementss with other stress (such as using residual fuel) Compound and residue of combustion increase and retained in lubricating oil.Therefore, engine long Time Continuous operating after, lubricating oil by Increase in the oxidation of sediment pollution and oil by deterioration and viscosity.
The crankcase of maritime applications system oil lubrication cross head marine diesel engine, and the part of engine can be cooled down, Particularly piston top.In some engines, system oil also has the function of oilgear and petrolift.System oil is generally important Performance be oxidation stability, viscosity increase control and oil detergency.
On the other hand, medium-speed engine is typically run in the range of about 250 to about 1100rpm, and is typically based on Four-stroke cycle is run.These engines are typically plunger design.Compared with slow speed engines, connecting rod is directly connected to piston On.Therefore, it is used for crankcase and cylinder lubrication using single lubricant in trunk-piston engine.Therefore, these oil needs have Formed between moving surface protective layer, in and acid and keep pollutant to be suspended in the ability in oil, these characteristics may be by Cause the loss of viscosity increase, neutralising capacity and detergency to the adverse effect of oily oxidation reaction.
Need to show improved oxidation stability, viscosity increase control, clear in the art in various marine vessel applications The lubricant oil composite of net property and water resistance.Use detersive of the parlkaline containing metal such as alkaline earth metal sulfonate, phenates and water Poplar hydrochlorate is known in the art to be used to neutralize adding for as caused by fuel combustion sulfur oxide and dispersion fuel deposit such as sludge Add agent.
Chain prepares a large amount of additives and surfactant to long chain alkyl aromatics in use.This kind of compound Example is the alkyl aromatic phenates for lubricant additive.Phenates is obtained extensively due to their detergency and antioxygenic property General use.
Low molecular weight alkyl phenol such as tetrapropylene benzene phenol (TPP) is used as the original of the parlkaline phenates of vulcanization by manufacturer Material.Generally when preparing the parlkaline phenates of vulcanization, unreacted alkylphenol be present in final reacting product.Americanized scientific principle Thing meeting petroleum additive is specialized in the genotoxicity research recently in rats that group subsidizes and shown, the unreacted of high concentration TPP can be adversely affected in male and female reproductive organ.
In order to reduce any health risk to user and avoid potential supervision problem, it is necessary to reduce parlkaline And vulcanization alkylating hydroxyaromatic compounds salt in unreacted low molecular weight alkyl hydroxy aromatic compound amount.Linearly Alkene is the possibility substitute for the genotoxicity for avoiding derivative alkyl phenol；However, the linearity of the alkene can cause containing The poor cryogenic property of the lubricating oil of derivative vulcanization parlkaline phenates.
It is contemplated that realize that marine diesel moistens by using the overbased detergent of the particular combination of optimal proportion The improvement of lubrication prescription performance.
Summary of the invention
The first aspect of the present invention is a kind of marine diesel lubricant compositions of the TBN with about 5 to about 120, bag Include：
(a) base oil of major amount of lubricant viscosity；
(b) the first detersive, it is parlkaline C10-40The alkali salt detersive of alkyl aryl sulphonic acid；With
(c) the second detersive, it is parlkaline isomerization C10-40The alkali salt detersive of positive alhpa olefin base phenol red；
The weight ratio of wherein described first detersive and second detersive is 1:9 to 9:1.
The second aspect of the present invention is a kind of marine diesel lubricating oil additive concentrate, contains compatible organic dilution Agent；First detersive, it is parlkaline C10-40The alkali salt detersive of alkyl aryl sulphonic acid；With second of detersive, its For parlkaline isomerization C10-40The alkali salt detersive of positive alhpa olefin base phenol red；Wherein described first detersive with it is described The weight ratio of second detersive is 1:9 to 9:1.
The third aspect of the present invention is related to by the way that the mixture of the component of lubricant oil composite to be mixed together to produce The method of the marine diesel lubricant oil composite of the present invention.The lubricant oil composite of gained shows the oxidation-stabilized of improvement Property, viscosity increase control, detergency and water resistance.
The fourth aspect of the present invention is a kind of method for operating marine diesel engine, including with about 5 to about 120 TBN lubricant oil composite lubricates the engine, and the lubricant oil composite includes：
(a) base oil of major amount of lubricant viscosity；
(b) the first detersive, it is parlkaline C10-40The alkali salt detersive of alkyl aryl sulphonic acid；With
(c) the second detersive, it is parlkaline isomerization C10-40The alkali salt detersive of positive alhpa olefin base phenol red；
Wherein the weight of the first detersive and the second detersive ratio is 1:9 to 9:1.
The fifth aspect of the present invention be it is a kind of lubricate marine diesel engine cylinder method, including with about 5 to About 120 TBN lubricant oil composite lubricates the cylinder, and the lubricant oil composite includes：
(a) base oil of major amount of lubricant viscosity；
(b) the first detersive, it is parlkaline C10-40The alkali salt detersive of alkyl aryl sulphonic acid；With
(c) the second detersive, it is parlkaline isomerization C10-40The alkali salt detersive of positive alhpa olefin base phenol red；
Wherein the weight of the first detersive and the second detersive ratio is 1:9 to 9:1.
In one embodiment, the over-based alkaline erath metal alkylaryl sulfonates detersive and the parlkaline alkali Alkaline-earth metal in the positive alpha-olefin vulcanization phenate detergents of earth metal isomerization is calcium.
In one embodiment, by making C14-C24The mixture isomerization of positive alpha-olefin prepares parlkaline isomerization The alkyl substituent of positive alhpa olefin base phenate detergents.
In one embodiment, over-based alkaline erath metal alkylaryl sulfonates detersive and over-based alkaline erath metal are different The weight of structureization positive alpha-olefin vulcanization phenate detergents is than scope from 1:9 to 9:1.
Embodiment
At its widest aspect, the present invention relates to the lubricant oil composite for ship.
Definition：
For the ease of the understanding to subject matter disclosed herein, be defined below multiple terms used herein, abbreviation or It is other to write a Chinese character in simplified form.Any undefined term, abridge or write a Chinese character in simplified form should be understood during with submission with the application with ability Its ordinary meaning of field technique librarian use.
Term " primary amount " used herein refers to that the concentration in lubricant oil composite is at least about 40 weight %.At one In embodiment, term " primary amount " refers to that the concentration in lubricant oil composite is at least about 50 weight %.In another implementation In scheme, term " primary amount " refers to that the concentration in lubricant oil composite is at least about 60 weight %.In another embodiment In, term " primary amount " refers to that the concentration in lubricant oil composite is at least about 70 weight %.In another embodiment, art Language " primary amount " refers to that the concentration in lubricant oil composite is at least about 80 weight %.In another embodiment, term is " main Measure " refer to concentration or at least about 90 weight % in lubricant oil composite.
Term " alkaline-earth metal " refers to calcium, barium, magnesium and strontium.
Term " alkali metal " refers to lithium, sodium, potassium, rubidium and caesium.
Term " alkene " refers to a kind of aliphatic unsaturated hydrocarbon with one or more carbon-to-carbon double bonds.Contain a double bond Those be referred to as monoolefine, have two double bonds those be referred to as diene, alkyl diene or alkadienes.Alpha-olefin is especially active, Because double bond is located between the first and second carbon atoms of hydrocarbon chain.The example of alpha-olefin includes 1- octenes and 1- vaccenic acids, its Starting point as medium biodegradable surfactant.Linear and branched-chain alkene is also included within the definition of alkene.
Term " positive alkene ", including " positive alhpa olefin ", the straight chain for referring to have at least one carbon-to-carbon double bond in chain, non-branch The alkene of chain hydrocarbon.
Term " isomerizing olefins " refers to the alkene by obtaining isomerisation of olefin.The alkene of usual isomerization with it Derivative starting olefin there is double bond in different positions, and can also have different characteristics.
Term " lime " refers to calcium hydroxide, also referred to as white lime or calcium hydroxide.
Term " phenates " refers to the salt of phenol.
Term " parlkaline " is used to describe metal detergent, wherein the equivalents of the equivalents of metal part and acid moieties it Than more than 1.Phrase " high parlkaline " refers to about 250 or bigger TBN.
Term " the parlkaline calcium salt of detersive " refers to that the metal cation of metal salt is substantially the alkali excessively of calcium cation Property detersive.A small amount of other cations may reside in metal salt, but the cation in metal salt is usually calcium ion, lead to Often it is at least 80, more typically at least 90, is for example, at least 95 moles of %.
Term " total base number " or " TBN " or " BN " refer to the equivalents milligram for neutralizing the KOH needed for 1 gram of product.Therefore, it is high TBN reflects strong parlkaline product, and therefore, antacid alkaline reserve is higher.The TBN of product can pass through ASTM standard D2896 Or equivalent programs determine.
Term " molar ratio of material " or " CMR ", it is the alkyl used in alkalinization is crossed when being related to phenate detergents The ratio between the molal quantity of phenol detersive/lime molal quantity.
Unless otherwise indicated, all substances concentration and ratio disclosed herein, are based on " active material " benchmark；I.e. Additive materials rather than diluent or solvent.
The base oil of lubricant viscosity：
Base oil (also referred to as base oil) for the lubricant viscosity of lubricant oil composite of the present invention is generally deposited with primary amount 50 weight %, preferably greater than about 70 weight % are being greater than, the weight % of more preferably from about 80- about 99.5, most preferably from about 80- is about 98 weight %, the gross weight based on composition." base oil " one word used herein should be understood that basestocks or basestocks mix Compound, it is produced in (independent of feed source or the place of manufacturer) by single manufacturer according to same size；Meet identical The specification of manufacturer；And by unique formula, product ID or both identified.Base oil for this paper can be The lubricant viscosity for being used to be formulated for the lubricant oil composite of marine diesel engine of any being currently known or later discovery Oil.
In one embodiment, the kinematic viscosity of lubricating base oil is 22 to 300mm at 40 DEG C2/ s, preferably 40 It is 22 to 140mm at DEG C2/ s, kinematic viscosity are 2 to 40mm at 100 DEG C2/ s, it is 3 to 15mm preferably at 100 DEG C2/s。
Basestocks can use including but not limited to distillation, solvent refining, hydrogen handle, be oligomeric, being esterified and re-refine each Kind distinct methods are manufactured.Refined material should be substantially free of by manufacturing, polluting or the material of previously used introducing.This hair The base oil of bright lubricant oil composite can be any natural or synthetic lubricating base oil.
Base oil can be derived from Natural lubricating oils, synthetic lubricant fluid or their mixture.Suitable base oil includes The basestocks obtained by synthetic wax and slack wax (slack wax) isomerization, and by making the aromatics and polarity group of crude product Divide and be hydrocracked hydrocracked base material caused by (rather than solvent extraction).Suitable base oil is included such as in API publications 1509, the 14th edition, all API categories defined in Addendum I, December 1998 are that in I, II, III, IV and V A little base oils.IV class base oils are poly alpha olefin (PAO).V class base oils be included in beyond I, II, III or IV class it is all its Its base oil.In one embodiment, the base oil of lubricant viscosity is I classes and/or II class base oils.
Useful natural oil includes mineral lubricating oil, for example, liquid petroleum；Solvent processing or acid treatment alkane category, The mineral lubricating oil of cycloalkanes category or mixing alkane category-cycloalkanes genotype；Oil derived from coal or shale；Animal oil；With vegetable oil (example Such as rapeseed oil, castor oil and lard).
Useful synthetic lubricant fluid includes but is not limited to hydrocarbon ils and the hydrocarbon ils of halogen substitution, such as the alkene of polymerization and copolymerization Such as polybutene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutylenes, poly- (1- hexenes), poly- (1- octenes), poly- (1- decene) And their mixture；Alkylbenzene such as detergent alkylate, Tetradecylbenzene, dinonyl benzene, two (2- ethylhexyls)-benzene etc., Polyphenyl such as biphenyl, terphenyl and the polyphenyl of alkylation, the diphenyl ether of alkylation and the diphenyl sulfide of alkylation and spreading out for they Biology, analog and homologue etc..These useful synthetic lubricant fluids include but is not limited to the alkene by making to be less than 5 carbon atoms Hydrocarbon such as ethene, propylene, butylene, isobutene, amylene and their mixture carry out the oil for polymerizeing preparation.Prepare this Type of Collective The method of thing oil is known to those skilled in the art.
Suitable hydrocarbon artificial oil include but is not limited to by vinyl polymerization or by 1- olefinic polymerizations with provide such as polyalphaolefin or Oil prepared by the polymer of PAO oil, or it is made for example by Fischer-Tropsch process by the hydrocarbon synthesis process using carbon monoxide and hydrogen Standby oil.
Other useful synthetic hydrocarbon oil includes the alhpa olefin liquid polymers with proper viscosity.Particularly useful synthesis hydrocarbon Oil is C6-C12The hydrogenated liquid oligomers of alhpa olefin, such as 1- decene tripolymers.
Another kind of useful synthetic lubricant fluid includes but is not limited to wherein terminal hydroxyl and is subject to for example, by being esterified or being etherified Modified alkylene oxide polymer, i.e. its homopolymer, copolymer and derivative.These oil are illustrated as by oxirane or epoxy third Oil prepared by the polymerization of alkane, alkyl and phenyl ether (such as the methyl with 1,000 mean molecule quantity of polyoxyalkylene polymers Polypropylene glycol ether, there is the diphenyl ether of the polyethylene glycol of 500-1000 molecular weight, and it is poly- with 1,000-1,500 molecular weight The Anaesthetie Ether of propane diols) or their list-and polycarboxylate such as acetic acid esters, the C of mixing3-C8Fatty acid ester is four sweet The C of alcohol13Oxygen-containing acid diesters.
The useful synthetic lubricant fluid of another class includes but is not limited to the ester of dicarboxylic acids and various alcohol, and the dicarboxylic acids is for example adjacent Phthalic acid, butanedioic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, decanedioic acid, fumaric acid, oneself two Acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic, the alcohol for example butanol, hexanol, dodecyl alcohol, 2-Ethylhexyl Alcohol, ethylene glycol, diethylene glycol monoether, propane diols.The instantiation of these esters includes dibutyl adipate, decanedioic acid Two (2- ethylhexyls) esters, fumaric acid di-n-hexyl ester, decanedioic acid dioctyl ester, azelaic acid diisooctyl ester, azelaic acid two are different The double eicosane base esters of decyl ester, phthalic acid dioctyl ester, phthalic acid didecyl base ester, decanedioic acid, linoleic acid dimer 2- ethylhexyls diester, compound by reacting 1 mole of decanedioic acid and 2 moles of tetraethylene glycols and 2 moles of 2 ethyl hexanoic acids to be formed Ester.
Ester as artificial oil also includes but is not limited to by the carboxylic acid with about 5 to about 12 carbon atoms and alcohol such as methanol With ethanol, polyalcohol and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythrite, dipentaerythritol, three seasons penta 4 Those esters prepared by alcohol.
For example poly- alkyl of silicon-based oil-, poly- aryl-, poly-alkoxyl-or poly- aryloxy group-silicone oil and silicic acid ester oil, form Another kind of useful synthetic lubricant fluid.These instantiation includes but is not limited to tetraethyl orthosilicate, the isopropyl ester of silicic acid four, silicic acid Four (2- ethylhexyls) esters, silicic acid four-(4- Methyl-hexyls) ester, silicic acid four (to tert-butyl-phenyl) ester, hexyl-(4- methyl- 2- amoxys) disiloxane, poly- (methyl) siloxanes and poly- (aminomethyl phenyl) siloxanes.Also other useful synthetic lubricant fluids The diethylester of including but not limited to phosphorous sour liquid ester, such as tricresyl phosphate, trioctyl phosphate and decane phosphonic acids and The tetrahydrofuran of polymerization.
Lubricating oil can be derived from unrefined oil, refined oil and rerefined oils, can be natural, synthesis or above-disclosed Any mixture of two or more in these types.Unrefined oil is directly by natural or synthetic source (such as coal, shale Or tar sand bitumen) without be further purified or handle acquisition those.The example of unrefined oil include but is not limited to directly by Retorting operation obtain shale oil, directly by distillation obtain oil or directly by esterification technique obtain ester oil, then they In each not further handle in the case of use.Refined oil except they in one or more purification steps further Processing is similar with unrefined oil outside one or more performances to improve.These purification techniques are known to those skilled in the art , including take such as solvent extraction, second distillation, acid or alkali carries, filter, be percolated, hydrotreating, dewaxing.Rerefined oils are led to Cross and handled used oil to obtain by similar to those methods for obtaining refined oil.This kind of rerefined oils also claim The technology made reclaimed oil or reprocessed oils and remove useless additive and oil decomposition product frequently by being related to is handled in addition.
Lube basestocks derived from wax hydroisomerization can also be used alone or with it is above-mentioned natural and/or synthesis Basestocks are applied in combination.This wax isomery oil by by natural or synthetic wax their mixture in hydroisomerisation catalysts Upper hydroisomerization produces.
The slack wax that native paraffin reclaims typically by the solvent dewaxing of mineral oil；Synthetic wax is typically by Fischer-Tropsch Wax caused by method.
Parlkaline alkylaryl sulfonates detersive：
Parlkaline alkylaryl sulfonates detersive is the alkaline-earth metal alkylaryl sulfonates with least 250 BN, Wherein aryl is not phenol, and alkyl is the straight chain containing 14 to 40 carbon atoms.Parlkaline alkylaryl sulfonates is peace and quiet Agent can be mixed in lubricant oil composite with 0.2-20.0 weight % amount, preferably 2.5-10.0 weight %, based on lubricating oil group The total amount of compound.
Parlkaline alkylaryl sulfonates detersive is preferably high overbased detergent, and has at least 250, preferably greatly In 350, more preferably greater than 450 total base number (TBN, in terms of mg KOH/g, being defined by ASTM 2896).
Aryl in parlkaline alkylaryl sulfonates detersive can be a kind of aromatic compounds or aromatic compounds Mixture.Suitable aromatic compounds or mixture of aromatic compounds include monocyclic aromatics, such as benzene, toluene, diformazan At least one of benzene, cumene or its mixture.In a preferred embodiment, the alkyl aromatic sulfonic acid or At least one aromatic fractions of salt not hydroxyl.In a preferred embodiment, the alkyl aromatic sulfonic acid or salt chemical combination At least one aromatic fractions of thing are not phenol.In one embodiment, at least one aromatic compounds or aromatics Polymer mixtures are toluene.
Linear alkyl chain in parlkaline alkylaryl sulfonates detersive contains 14 to 40 carbon atoms, preferably 14 to 24 Individual carbon atom, preferably 20 to 24 carbon atoms.Preferably, alkaline earth alkylaryl sulfonates is derived from C14-C40Positive alpha-olefin, more It is preferably derived from C20-C24Positive alpha-olefin.
Parlkaline alkylaryl sulfonates detersive can use any method known in the art to prepare.Generally, alkyl Arylsulphonate detersive can be prepared by using following steps：
A. use alkali in and alkyl aryl sulphonic acid；
B. alkali and CO are used2The alkyl aryl sulphonic acid of neutralization is carbonated to produce parlkaline alkylaryl sulfonates；
C. any sediment and solvent are removed.
In one embodiment, parlkaline alkylaryl sulfonates detersive can by U.S. Patent number 6,479, Prepared by the method described in 440 embodiments 1, its content is incorporated herein by reference.
The source of alkali can be alkaline earth metal alkali.Available for carry out the step suitable alkaline earth metal alkali include calcium, magnesium, The oxide or hydroxide of barium or strontium, particularly calcium oxide, calcium hydroxide, magnesia and its mixture.In an embodiment party In case, alkaline earth metal alkali is white lime (calcium hydroxide).
The positive alhpa olefin base phenate detergents of parlkaline isomerization：
The positive alhpa olefin base phenate detergents of parlkaline isomerization are the alkane of alkylate hydroxyl compound, wherein hydroxy compounds Base substituent is the residue of at least one alkene branched with about 15 to about 99 weight %.Isomerizing olefins can be C10-C40 Alkene.In one embodiment, the alkene of isomerization is C14-C24Alkene.In another embodiment, the alkene of isomerization Hydrocarbon is C20-C24Alkene.
Parlkaline isomerization can prepared just by the method described in U.S. Patent number 8,580,717 (embodiment 1-13) Alhpa olefin base phenate detergents, its content are incorporated herein by reference.The positive alhpa olefin base phenate detergents of parlkaline isomerization can be with It is prepared by the following method：
A) by least one hydroxy aromatic compound with least one with the branched isomery alkene of about 15 to about 99 weight % To provide at least one alkylating hydroxyaromatic compounds, the isomeric olefine has alkylating hydrocarbons by isomerization at least one The positive alpha-olefin of about 10 to about 40 carbon atoms obtains；
(b) with random order neutralize and alkyl monosulfide hydroxy aromatic compound with provide at least one neutralization, vulcanization Alkylating hydroxyaromatic compounds；With
(c) alkylating hydroxyaromatic compounds that make at least one neutralization, vulcanization cross alkalization；Wherein described hydroxyl Aromatic compounds is phenol, cresols, xylenols or its mixture.
Include the oxide or hydroxide of calcium, magnesium, barium or strontium available for the alkaline earth metal alkali for carrying out parlkaline processing, it is special It is not calcium oxide, calcium hydroxide, magnesia and its mixture.In one embodiment, alkaline earth metal alkali is white lime (hydrogen-oxygen Change calcium).
The positive alhpa olefin base phenate detergents of parlkaline isomerization have the total base number more than 200, preferably greater than 250 (TBN, being represented with mg KOH/g, defined by ASTM 2896).
Amount of the positive alhpa olefin base phenate detergents of parlkaline isomerization in lubricant oil composite be 0.1 weight % extremely About 20 weight %, the gross weight based on lubricant oil composite.In one embodiment, parlkaline in the lubricant oil composite The amount of the positive alhpa olefin base phenate detergents of isomerization be about 0.1 weight % to about 5 weight %, the gross weight based on lubricant oil composite Amount.
The weight of parlkaline alkylaryl sulfonates detersive and the positive alhpa olefin base phenate detergents of parlkaline isomerization compares model Enclose from 1:9 to 9:1, preferably 1:1.5 to 9:1, preferably 1:5 to 8:1, more preferably 1：2 to 6：1.
Other additives
The lubricant oil composite of the present invention, which can also contain to assign or improve these additives, is dispersed or dissolved in it In lubricant oil composite it is any needed for property other conventional additives.It is known to persons of ordinary skill in the art any to add Agent is added to can be used for lubricant oil composite disclosed herein.For example, lubricant oil composite can be with antioxidant, antiwear additive, clear Net agent such as metal detergent, antirust agent, defogger, demulsifier, matal deactivator, friction modifiers, pour point depressant, defoaming Agent, cosolvent, packaging compatilizer, corrosion inhibitor, ashless dispersant, dyestuff, extreme pressure agent and the blending of its mixture.It is a variety of to add It is known and commercially available to add agent.These additives, or their similar compound, it can be used to prepare this by common blending program The lubricant oil composite of invention.
The example of antioxidant includes but is not limited to amine, such as diphenylamines, phenyl-α-naphthylamine, the N, (alkylbenzenes of N- bis- Base) amine and alkylated phenylene-diamines；Phenols such as BHT, steric hindrance alkyl phenol, such as 2,6- DI-tert-butylphenol compounds, the uncles of 2,6- bis- Butyl paracresol and 2,6- di-t-butyls -4- (2- octyl group -3- propionic acid) phenol；The amount of antioxidant can be about 0.01 weight % To about 5 weight %.
The example of antiwear additive includes but is not limited to zinc dialkyl dithiophosphate and zinc diaryl dithiophosphates, such as It is published in Lubrication Science4-2, the Born in January, 1992 et al. entitled " Relationship between Chemical Structure and Effectiveness of some Metallic Dialkyl-and Diaryl- Those described in dithiophosphates in Different Lubricated Mechanisms " paper, referring to Such as the 97-100 pages；Aryl phosphate ester and phosphite ester；Containing thioesters；Phosphorus sulphur compound；Metal or ashless dithiocarbamates first Hydrochlorate, xanthates, alkyl sulfur compounds and its mixture.The amount of antiwear additive can be about 0.01 to about 5 weight %.
The example of antirust agent includes but is not limited to nonionic polyoxyalkylene reagent, such as polyoxyethylene lauryl ether, poly- It is the advanced alcohol ether of oxygen ethene, ethylene nonyl phenyl ether, NONIN HS 240, polyoxyethylene octyl stearyl base ether, poly- Oxygen ethene oil ether, polyoxyethylene sorbitol monostearate, octadecanoic acid ester of polyethylene glycol and polyethyleneglycol oleic acid Ester；Stearic acid and other aliphatic acid；Dicarboxylic acids；Metal soap；Aliphatic acid amine salt；The metal salt of heavy sulfonic acid；The carboxylic of polyalcohol Acid partial esters；Phosphate；(short chain) alkenyl succinic acid, its partial ester and its nitrogen containing derivative；The alkylaryl sulfonate of synthesis, such as gold Belong to dinonylnaphthalene sulfonic acid salt；And its mixture.The amount of antirust agent can be about 0.01 weight % to about 10 weight %.
The example of friction modifiers includes but is not limited to alkoxylated fats amine；Borated fatty epoxides；It is fatty sub- Phosphate；Fat epoxide；Fatty amine；Borated alkoxylated fatty amine；The metal salt of aliphatic acid；Fatty acid amide；With And such as U.S. Patent number 6, the fatty imidazolines disclosed in 372,696, its content is incorporated herein by this reference；Obtained from C4To C75、 It is preferred that C6To C24Most preferably C6To C20Fatty acid ester and nitrogen-containing compound selected from ammonia and alkanolamine and its mixture it is anti- Answer the friction modifiers of product.The amount of friction improver can be about 0.01 weight % to about 10 weight %.
The example of defoamer includes but is not limited to the polymer of alkyl methacrylate；The polymerization of dimethyl siloxane Thing, and its mixture.The amount of defoamer can be about 0.01 to about 1 weight %.
The example of pour point depressant includes but is not limited to polymethacrylates/salt, acrylate polymers, methyl Acrylate polymers, two (four-alkane phenol) phthalic acid esters/salt, the condensation product of four-alkane phenol, chlorination chain The condensation product of alkane and naphthalene, with and combinations thereof.In one embodiment, pour point depressant is total to including ethane-acetic acid ethyenyl ester Polymers, the condensation product of chlorinated paraffin and phenol, alkyl styrenes, with and combinations thereof.The amount of pour point depressant can be big About 0.01 weight % to about 10 weight %.
The example of demulsifier includes but is not limited to anion surfactant (for example, alkylnaphthalene sulfonate and benzene sulfonamide Hydrochlorate), Nonionic alkoxylated alkyl phenol resin, polymer (such as PEO, PPOX, the epoxy of oxyalkylene The block copolymer of ethane epoxy propane), the ester of oil-soluble acid, polyoxyethylene sorbitan esters, with and combinations thereof.Demulsification The amount of agent can be about 0.01 weight % to about 10 weight %.
The example of corrosion inhibitor includes but is not limited to the half ester or acid amides, phosphate, thio phosphorus of dodecyl succinate Hydrochlorate, alkyl imidazoline, methyl amimoacetic acid, with and combinations thereof.The amount of corrosion inhibitor can be about 0.01 weight % to about 5 weights Measure %.
The example of extreme pressure agent includes but is not limited to, fatty or oily, vulcanization the animal or plant of the animal or plant of vulcanization Fatty acid ester, phosphorus trivalent or the ester of complete or partial esterification of pentahydric acid, olefine sulfide, dihydrocarbyl polysulfide, vulcanization Diels-Alder adduct, vulcanization bicyclopentadiene, fatty acid ester and single unsaturated olefin vulcanization or co-vulcanization Mixture, aliphatic acid, the co-vulcanization blend of fatty acid ester and alpha-olefin, the dihydrocarbyl polysulfide of function substitution, thia aldehyde, Thia ketone, episulfide compounds, the acetal derivatives of sulfur-bearing, co-vulcanization blend, the polysulfide of terpenes and non-ring type alkene Olefin product, phosphate or thiophosphate amine salt, with and combinations thereof.The amount of extreme pressure agent can be about 0.01 weight % extremely About 5 weight %.
The present invention lubricant oil composite can by routine techniques by appropriate the first detersive and the second detersive with Any optional additive is mixed with the base oil of lubricant viscosity to prepare.
The TBN of the lubricant oil composite of the present invention is 5 to 120, and preferably 5-100, preferably 10-100, preferably 15-100 are excellent 20-100, preferably 5 to 70, more preferably 15 to 40, more preferably 5 to 40, more preferably 20 to 70, more preferably 20 to 50 are selected, more preferably For 15 to 70mgKOH/g.
The viscosity grade of the lubricant oil composite of the present invention is SAE 20-50.In one embodiment, lubricating oil has SAE 20 viscosity grade.In one embodiment, lubricating oil has SAE 30 viscosity grade.In an embodiment In, lubricating oil has SAE 40 viscosity grade.In one embodiment, lubricating oil has SAE 50 viscosity grade.
Kinematic viscosity of the lube base oil at 100 DEG C is 5.6 to 21.9mm2/ s, preferably 9.3 to 21.9mm2/ s, Preferably 9.3 to 16.3mm2/ s, preferably 9.3 to 12.5mm2/ s, preferably 12.5 to 16.3mm2/ s, preferably 16.3 to 21.9mm2/s。
Embodiment
Following non-limiting example is the explanation of the present invention.
Lubricant oil composite is prepared by the component shown in mixture table 1-3.
Resulting composition is tested using following test method：
Little Song heat pipes (KHT) are tested:Make glass tube one of the lubricant oil composite by the appropriate air stream temperature control of a use The fixed time.Then glass tube is cooled down and washed, any paint-like sediment of glass pipe internal surface is stayed in chromascope measure Color, rate range (0=is black, 10=cleaning) from 0 to 10.In the case where glass tube is deposited thing blocking completely, test As a result it is recorded as " blocking ".Excellent detergency is represented by maintaining higher KHT values in high temperature range.
Differential scanning calorimetry：The experiment is used to evaluate the film oxidation stability by formation testing according to ASTM D-6186. During experiment, by enter or in specimen cup by formation testing hot-fluid compared with reference cup.Oxidation starting temperature is Temperature when starting is aoxidized by formation testing.Oxidation induction time is that time when starting is aoxidized by formation testing.Oxidation reaction causes to put Thermal response, it is shown by hot-fluid.Oxidation induction time is calculated to evaluate the film oxidation stability by formation testing.The method of testing Copy can be from ASTM International at 100Barr Harbor Drive, PO Box0700, West Conshohocken, Pa.19428-2959 are obtained, and are incorporated herein by reference for all purposes.Generally oxidation lures Lead that the time is higher, and film oxidation stability is better.
Improved institute of Petroleum 48 (MIP-48) experiment, viscosity increase：Two lubricant oil composite samples are heated one section Time.When air is by another sample, nitrogen passes through a test sample.Then two samples are cooled down, it is determined that each The viscosity of sample.Kinematic viscosity is simultaneously at 100 DEG C by the way that kinematic viscosity at drum 100 DEG C of air sample to be subtracted to bulging nitrogen sample By kinematic viscosity at 100 DEG C that subtract each other result divided by drum nitrogen sample, oxidation is based on to calculate each maritime applications system fluid composition Rate of viscosity increase.It can prove preferably to resist the increased stability of viscosity based on oxidation by relatively low viscosity increase.
Improved institute of Petroleum 48 (MIP-48) experiment, BN losses：When two lubricant oil composite samples are heated into one section Between.When air is by another sample, nitrogen passes through a test sample.Then two samples are cooled down, it is determined that each sample The TBN of product.By the way that the TBN of drum air sample to be subtracted to the TBN of bulging nitrogen sample and result divided by drum nitrogen sample will be subtracted each other TBN, and result is multiplied by 100 and obtains the MIP-48TBN losses %, to calculate the MIP-48TBN losses.Relatively low BN damages It is desired to consume percentage.
Centrifuge water resistance：Centrifuge containing 5100g oil is constantly recycled at 80 DEG C with 50L/h.The 3 of centrifugation During hour, fresh water is continuously supplied with 1L/h speed.The final weight of deposit on measure centrifuge basket, distributor and rotating cylinder Amount.Calcium, phosphorus, zinc and water content before and after measure test in oil.Pass through higher calcium in lubricating oil, phosphorus or zinc Reservation shows more preferable water resistance.
Following component used below prepares the marine diesel lubricant compositions of embodiment.
Detersive A：The oil concentrate of parlkaline alkyl toluene sulfonic acids calcium detersive；Wherein alkyl derivative is from C20To C24Directly Chain alpha-olefin.The multifunctional additive for lubricating oils contains 16.1 weight %Ca, about 38.7 weight % flux oil, TBN 420.Based on work Property material, the TBN (being free of flux oil) of the additive is 685.
Detersive B：The oil concentrate of the parlkaline sulfurized calcium phenate of the derived from propylene tetramer.The additive contains 9.6 weights Measure %Ca, about 31.4 weight % flux oils, TBN 260.
Detersive C：Derived from degree of isomerization not less than the C that 85% and CMR is 0.4414The parlkaline phenol red of positive alpha-olefin The oil concentrate of calcium.The additive contains 9.8 weight %Ca, and about 31.4 weight % flux oils, TBN is about 260.
Detersive D：Derived from degree of isomerization not less than the C that 85% and CMR is 0.5714The parlkaline phenol red of positive alpha-olefin The oil concentrate of calcium.The additive contains about 10.2 weight %Ca, and about 31.4 weight % flux oils, TBN is about 260.
Detersive E：The C that derived from degree of isomerization be 65% and CMR is 0.3220-24The parlkaline sulfurized calcium phenate of positive alpha-olefin Oil concentrate.The additive contains about 9.45 weight %Ca, and about 31.4 weight % flux oils, TBN is about 260.
Detersive F：The C that derived from degree of isomerization be 65% and CMR is 0.4620-24The parlkaline sulfurized calcium phenate of positive alpha-olefin Oil concentrate.The additive contains 9.9 weight %Ca, and about 31.4 weight % flux oils, TBN is about 260.
Wear inhibitor：The C obtained from Chevron Oronite Company (San Ramon, CA)4And C6Alcohol mixture Secondary zinc dithiophosphate (ZnDTP).
I class base oils are the ExxonMobil obtained from ExxonMobil (Irving, TX.)600N basestocks.
Chevron RLOP 600N:II class base oils be from Chevron Products Company (San Ramon, CA.) the Chevron RLOP 600N basestocks obtained.
Example 1：Pass through the lubricant oil composite of the component formulation example 1 shown in mixture table 1.
Example 2：Pass through the lubricant oil composite of the component formulation example 2 shown in mixture table 2.
Example 3：Pass through the lubricant oil composite of the component formulation example 3 shown in mixture table 3.
Example 4：Pass through the lubricant oil composite of the component formulation example 4 shown in mixture table 4.
Table 1-4 show be related to the embodiment of the phenates from isomerizing olefins little Song heat pipes and MIP experiments show with Suitable performance in comparative example.Compared with comparative example, testing example also shows water resistance that is comparable or improving.
Example 5：Pass through the lubricant oil composite of the component formulation example 5 shown in mixture table 5.
Table 5 shows, under high BN, the embodiment for being related to the phenates derived from isomerizing olefins is tried in little Song heat pipes and MIP The performance suitable with comparative example is shown in testing.
It should be understood that various modifications can be carried out to embodiment disclosed herein.Therefore, foregoing description is not necessarily to be construed as Restricted, and the only example of preferred embodiment.For example, the work(of the optimal mode as the operation present invention of above-mentioned realization The purpose that can be merely to illustrate.Without departing from the scope and spirit of the present invention, those skilled in the art can realize Other arrangements and method.It is in addition, it may occur to persons skilled in the art that other in scope of the following claims and spirit Modification.

Claims (10)

1. a kind of marine diesel lubricant compositions of the TBN with about 5 to about 120, including：
(a) base oil of major amount of lubricant viscosity；
(b) the first detersive, it is parlkaline C10-40The alkali salt detersive of alkyl aryl sulphonic acid；With
(c) the second detersive, it is parlkaline isomerization C10-40The alkali salt detersive of positive alhpa olefin base phenol red
The weight of wherein described first detersive and second detersive is than scope from 1:9 to 9:1.
2. the composition of claim 1, wherein the parlkaline alkylsulfonate detersive and the positive α of parlkaline isomerization- Alkylene phenate detergents are all parlkaline calcium salts.
3. the composition of claim 1, wherein the alkyl substituent of the positive alpha-olefin phenate detergents of the parlkaline isomerization By making C14-C24It is prepared by positive alpha-olefin isomerization.
4. the composition of claim 1, wherein the base oil of the lubricant viscosity is I class base oils.
5. the composition of claim 1, wherein the base oil of the lubricant viscosity is I I class base oils.
6. the composition of claim 1, wherein the composition is free of glyceride or borated glycerol esters.
7. the positive alpha-olefin phenate detergents of the composition of claim 1, wherein parlkaline isomerization are alkylate hydroxyl chemical combination Thing, wherein the alkyl substituent of the hydroxy compounds is the residual of at least one alkene branched with about 15 to about 99 weight % Base.
8. the composition of claim 1, wherein the positive alpha-olefin phenate detergents of the parlkaline isomerization are alkylate hydroxyls Compound, wherein the alkyl substituent of the hydroxy compounds is at least one alkene branched with about 15 to about 99 weight % Residue.
9. a kind of method for operating marine diesel engine, including moistened with the lubricant oil composite of the TBN with about 5 to about 120 The sliding engine, the lubricant oil composite include：
(a) base oil of major amount of lubricant viscosity；
(b) the first detersive, it is parlkaline C10-40The alkali salt detersive of alkyl aryl sulphonic acid；With
(c) the second detersive, it is parlkaline isomerization C10-40The alkali salt detersive of positive alhpa olefin base phenol red；
Wherein the weight of the first detersive and the second detersive than scope from 1:9 to 9:1.
10. a kind of method for the cylinder for lubricating marine diesel engine, including the lubricating oil group with the TBN with about 5 to about 120 Compound lubricates the cylinder, and the lubricant oil composite includes：
(a) base oil of major amount of lubricant viscosity；
(b) the first detersive, it is parlkaline C10-40The alkali salt detersive of alkyl aryl sulphonic acid；With
(c) the second detersive, it is parlkaline isomerization C10-40The alkali salt detersive of positive alhpa olefin base phenol red；
Wherein the weight of the first detersive and the second detersive ratio is 1:9 to 9:1.
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CN112292441A (en) * 2018-06-22 2021-01-29 雪佛龙奥伦耐有限责任公司 Lubricating oil composition
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