CN102325866A - Prevent the method for exhaust valve seat shrinkage depression - Google Patents

Prevent the method for exhaust valve seat shrinkage depression Download PDF

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Publication number
CN102325866A
CN102325866A CN2010800081583A CN201080008158A CN102325866A CN 102325866 A CN102325866 A CN 102325866A CN 2010800081583 A CN2010800081583 A CN 2010800081583A CN 201080008158 A CN201080008158 A CN 201080008158A CN 102325866 A CN102325866 A CN 102325866A
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CN
China
Prior art keywords
natural gas
lubricating oil
weight
oil composition
gas engine
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CN2010800081583A
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Chinese (zh)
Inventor
M·F·托拜厄斯
J·F·冯斯塔登
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Chevron Oronite Co LLC
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Chevron Oronite Co LLC
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Publication of CN102325866A publication Critical patent/CN102325866A/en
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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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
    • 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
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L1/00—Valve-gear or valve arrangements, e.g. lift-valve gear
    • F01L1/12—Transmitting gear between valve drive and valve
    • F01L1/14—Tappets; Push rods
    • F01L1/16—Silencing impact; Reducing wear
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L1/00—Valve-gear or valve arrangements, e.g. lift-valve gear
    • F01L1/46—Component parts, details, or accessories, not provided for in preceding subgroups
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L3/00—Lift-valve, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces; Parts or accessories thereof
    • F01L3/22—Valve-seats not provided for in preceding subgroups of this group; Fixing of valve-seats
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L3/00—Lift-valve, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces; Parts or accessories thereof
    • F01L3/24—Safety means or accessories, not provided for in preceding sub- groups of this group
    • 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
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • 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
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • 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
    • 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
    • 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
    • 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
    • C10N2030/52—Base number [TBN]
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
    • F01L2810/00—Arrangements solving specific problems in relation with valve gears
    • F01L2810/02—Lubrication
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01M—LUBRICATING OF MACHINES OR ENGINES IN GENERAL; LUBRICATING INTERNAL COMBUSTION ENGINES; CRANKCASE VENTILATING
    • F01M9/00—Lubrication means having pertinent characteristics not provided for in, or of interest apart from, groups F01M1/00 - F01M7/00
    • F01M9/02—Lubrication means having pertinent characteristics not provided for in, or of interest apart from, groups F01M1/00 - F01M7/00 having means for introducing additives to lubricant

Abstract

Disclose and a kind ofly prevented or suppressed to be the method for exhaust valve seat shrinkage depression in the oil engine of fuel with the Sweet natural gas.This method relates to the lubrication viscosity oil of using lubricating oil composition lubricating engine, said lubricating oil composition to comprise (a) main amount; (b) the natural gas engine oil additive bag of minor amount, wherein said lubricating oil composition is substantially free of the alkaline earth salt of the condensation product of any various zn cpds and alkylene polyamine, aldehyde and substituted phenol.

Description

Prevent the method for exhaust valve seat shrinkage depression
Background of invention
1. technical field
Present invention relates in general to prevent or suppressing with the Sweet natural gas is the method for exhaust valve seat shrinkage depression in the oil engine of fuel.
2. Description of Related Art
Be that the mover of fuel is to use the act as a fuel mover in source of Sweet natural gas with the Sweet natural gas.To being used for the lubricating oil of natural gas engine, preferably has the lubricating oil that high anti-oxidation, nitrated property and viscosity increase usually owing to the related condition of this type of engine.
Sweet natural gas has higher ratio heat content than liquid hydrocarbon fuel, so it will be than the liquid hydrocarbon fuel De Gengre that burns under typical condition.In addition, because Sweet natural gas has been gas, it is not compared with the hydrocarbon fuel drop can make the inhaled air cooling through evaporation.And many is that the mover of fuel all is being in or is turning round near under the stoichiometric condition with the Sweet natural gas, and this moment, less excessive air can be used to dilution and cooling combusting gas.Consequently, with the Sweet natural gas be the mover burning gas temperature higher of fuel than the engine producing of combustion of liquid hydrocarbon fuel.In most of the cases, be mover use continuously under the 70-100% load of fuel with the Sweet natural gas, and the mover that turns round with vehicles is to be in full load in its time of 50% only.
This condition near full load operation has applied strict demand to lubricant continuously.For example, suffer continuous high temperature environment, the life-span of lubricant limited by oily oxidising process owing to making to lubricate.Equally, because nitrogen (NO x) form speed with temperature by exponential increase, be that the mover of fuel can produce and is enough to cause the serious nitrated high NO of lubricating oil with the Sweet natural gas xConcentration.
It also is important that good valve wear control reduces for the process cost that makes mover, and can assign to reach through the ash that appropriate amount and composition are provided.In addition, considered minimizes combustion chamber deposit and plug fouling in setting these oily ash oontent.The ash oontent of lubricating oil is limited, therefore must select purification agent carefully so that piston deposit and ring bonding minimize.
The valve abrasion resistance is to being that the weather resistance of the mover of fuel is important with the Sweet natural gas.Generally speaking, the vent valve shrinkage depression is the wearing and tearing that take place at the interface at valve and valve seat and is the most significant valve wear form in the mover that is fuel with the Sweet natural gas.When valve received obstruction and can not suitably be located, this can cause, and mover was coarse, the fuel economy of difference and excessively discharging.In order to correct excessive valve wearing and tearing, need the maintenance cylinder head usually.Though the mover that with the Sweet natural gas is fuel typically uses adamantine corrosion resistant material so that the cylinder head life-span of prolongation to be provided for valve surface and valve seat mating surface, this can't eliminate the valve shrinkage depression fully.
With the Sweet natural gas is that the mover of fuel and the lubricating oil that adds the mover of liquid hydrocarbon fuel have required difference.The liquid hydrocarbon fuel for example burning of diesel oil fuel produces a small amount of incomplete combustion thing (for example exhaust gas particle thing) usually.In the mover with liquid hydrocarbon fuel, these noncombustibleses are that vent valve/valve seat interface provides the lubricated of little but significance level, thereby guarantee the two wearing quality of cylinder head and valve.
With the Sweet natural gas engine combustion of fuel is incorporated into the combustion chamber with gas phase fuel.In fact the burning of gas fuel does not have unburned material normally very completely.Because for being that the lubricant as drop or soot that does not have fuel to produce for the vent valve/seat interface in the mover of fuel helps lubricate with the Sweet natural gas, so this has great influence to sniff valve and vent valve.Therefore, the weather resistance of cylinder head and valve receives ash oontent and other performance of lubricating oil and cooperates the control that the wear rate of lubricant is provided between the valve seat at thermal valve face and its.The very few ash content or the ash content of improper type can quicken the valve and the prooving of valve seat, and too much ash content can cause valve to produce groove and with the late gate scaling loss.Too much ash content also can cause the compression forfeiture or make the combustion chamber deposit detonation.Therefore, gas engine manufacturers usually stipulates the narrower ash content range that optimum performance is provided that they are known.Because most of combustion gas all have low sulfur content, so in order to solve alkaline requirement, do not need excessive ash content usually, the requirement that centers on valve makes ash oontent obtain very big optimization.Under the situation of using sulfurous gas or landfill gas maybe except.
Zinc dialkyl dithiophosphate is to be used to resistance to wear very effective additive with the natural gas engine oil additive bag of oxidation protection, and for example shows to impel and on vent valve, form ash content.Yet, think that in fact zinc dialkyl dithiophosphate can chemical reaction take place or can be easy to the compound removed from valve surface with the formation in other ash content source with the surface.
In addition, be the catalyst component of their p and s verivate murder by poisoning catalytic converter with using the relevant problem of zinc dialkyl dithiophosphate.This is kind main misgivings, because need effective catalytic converter to reduce to pollute and satisfy to reducing the for example set government regulations of hydrocarbon, carbon monoxide and oxynitride in the engine exhaust gas discharging of toxic gas.This type catalytic converter usually uses the for example combination of platinum and MOX of multiple catalytic metal, and be installed in exhaust flow for example in the automobile tail gas pipe so that toxic gas is converted into nontoxic gas.Therefore, the amount of zinc dialkyl dithiophosphate in the lubricating oil is eliminated in expectation, reduced catalyst deactivation thus and therefore improve the life-span and the validity of catalytic converter, and also satisfy the content of p and s in the engine oil that the futurity industry standard proposed simultaneously.Yet the amount that simply reduces zinc dialkyl dithiophosphate has problems, because this must reduce the wear resistance and the oxidation-inhibitive ability of lubricating oil.Therefore, be necessary to find a kind of method with oxidation susceptibility of resistance to wearing that keeps engine oil.
United States Patent(USP) No. 3,798,163 (" ' 163 patents ") disclose that a kind of to control or suppress with the Sweet natural gas through the lubricating oil composition that on the engine parts of oil engine, keeps lubricated amount be the method for vent valve shrinkage depression in the oil engine of fuel.' 163 also disclose a kind of lubricating oil composition; This lubricating oil composition contains the lubrication viscosity oil of (a) main amount; (b) be enough to improve at least a alkaline earth metal sulfonate and (c) at least a alkaline earth salt of the amount of said composition detergency, this alkaline earth salt is (i) alkylene polyamine; (ii) aldehyde and the (iii) condensation product of substituted phenol, wherein the alkaline earth salt of this condensation product exists with the amount that is enough to suppress engine exhaust valve and is depressed in the engine cylinder cover.
United States Patent(USP) No. 5; 726; 133 (" ' 133 patents ") disclose a kind of low grey gas engine oil; This engine oil comprises the lubricant viscosity base oil of main amount and is enough to provide the additive agent mixture for the minor amount of the sulfate ash content of about 0.1-0.6% according to ASTM D 874; This additive agent mixture comprises the purification agent mixture, this purification agent mixture comprise at least a have about 250 or first an alkali metal salt of littler low alkali value (TBN) or alkaline earth salt or their mixture and at least a ratio first low TBN salt have more neutral second an alkali metal salt or alkaline earth salt or their mixture.' 133 patents further disclose full formula gas engine oil also can typically contain other standard additive well known by persons skilled in the art, comprises that for example zinc dithiophosphate, dispersion agent, phenols or amine belong to (aminic) inhibitor, metal passivator, pour point depressor, skimmer and viscosity index improver to antiwear additive.
United States Patent(USP) No. 6; 174,842 (" ' 842 patents ") disclose a kind of lubricating composition, and said composition contains the lubricating oil of (a) main amount; (b) be substantially free of the soluble molybdenum compounds of reactive sulphur, (c) oil soluble diarylamine and (d) earth alkali metal phenates.' 842 patents also disclose said composition also can comprise the dialkyl zinc dithiophosphate as antiwear agents.Disclosed oily concoction 18 contains antiwear agents and in natural gas engine test, estimates with regard to the vent valve shrinkage depression among the embodiment 2 of patent in addition, ' 842.
Needing exploitation to prevent or suppressing with the Sweet natural gas is the improving one's methods of vent valve shrinkage depression in the oil engine of fuel, and this method is used the lubricating oil composition that does not contain any zn cpds at least and use the component of minimum quantity.
Summary of the invention
According to one embodiment of the invention; Provide and prevented or suppressed to be the method for exhaust valve seat shrinkage depression in the mover of fuel with the Sweet natural gas; This method comprises that said lubricating oil composition comprises the lubrication viscosity oil of (a) main amount with the lubricated said mover of lubricating oil composition; (b) the natural gas engine oil additive bag of minor amount, wherein said lubricating oil composition is substantially free of the alkaline earth salt of the condensation product of any various zn cpds and alkylene polyamine, aldehyde and substituted phenol.
According to second embodiment of the present invention; As being proved by the exhaust valve seat shrinkage depression in the mover of fuel with the Sweet natural gas through protection or inhibition; A kind of method of life that is used for improving with the Sweet natural gas mover vent valve that is fuel is provided; This method comprises that said lubricating oil composition comprises the lubrication viscosity oil of (a) main amount with the lubricated said mover of lubricating oil composition; (b) the natural gas engine oil additive bag of minor amount, wherein said lubricating oil composition is substantially free of the alkaline earth salt of the condensation product of any various zn cpds and alkylene polyamine, aldehyde and substituted phenol.
According to the 3rd embodiment of the present invention, providing lubricating oil composition to be used for preventing or having suppressed with the Sweet natural gas is the purposes of mover exhaust valve seat shrinkage depression of fuel, and said lubricating oil composition comprises lubrication viscosity oil of (a) main amount; (b) the natural gas engine oil additive bag of minor amount, wherein said lubricating oil composition is substantially free of the alkaline earth salt of the condensation product of any various zn cpds and alkylene polyamine, aldehyde and substituted phenol.
According to the 4th embodiment of the present invention; The natural gas engine oil compsn is provided; This lubricating oil composition comprises the lubrication viscosity oil of (a) main amount, (b) one or more ashless dispersants, (c) one or more containing metal purification agents; (d) one or more inhibitors, wherein said lubricating oil composition are substantially free of the alkaline earth salt of the condensation product of any various zn cpds and alkylene polyamine, aldehyde and substituted phenol.
According to the 5th embodiment of the present invention; The natural gas engine oil compsn is provided; This lubricating oil composition comprises the lubrication viscosity oil of (a) main amount; (b) one or more ashless dispersants, (c) one or more containing metal purification agents and (d) one or more inhibitors; Wherein said lubricating oil composition is substantially free of the alkaline earth salt of the condensation product of any various zn cpds and alkylene polyamine, aldehyde and substituted phenol, and wherein said in addition lubricating oil composition is compared the performance with bigger reduction exhaust valve seat shrinkage depression with the associated lubrication oil compsns that wherein has zn cpds.
According to the 6th embodiment of the present invention; The natural gas engine oil compsn is provided; This lubricating oil composition is basically by (a) the main lubrication viscosity oil of measuring, (b) one or more ashless dispersants, (c) one or more containing metal purification agents; (d) one or more inhibitors constitute, and wherein said lubricating oil composition is substantially free of any various zn cpds.
According to the 7th embodiment of the present invention, provide use lubricating oil composition lubricated with the mover of Sweet natural gas as fuel, said natural gas engine oil compsn comprises lubrication viscosity oil of (a) main amount; (b) the natural gas engine oil additive bag of minor amount, wherein said lubricating oil composition is substantially free of the alkaline earth salt of the condensation product of any various zn cpds and alkylene polyamine, aldehyde and substituted phenol.
Through using lubricating oil composition lubricated with the oil engine of Sweet natural gas as fuel; This lubricating oil composition comprises the lubrication viscosity oil of (a) main amount; (b) the natural gas engine oil additive bag of minor amount; Wherein said lubricating oil composition is substantially free of the alkaline earth salt of the condensation product of any various zn cpds and alkylene polyamine, aldehyde and substituted phenol; With wherein exist zn cpds for example the associated lubrication oil compsns of dialkyl phosphorodithioic acid zn cpds compare, advantageously preventing or suppressing with the Sweet natural gas is the exhaust valve seat shrinkage depression in the mover of fuel.This is beyond thought, because the dialkyl zinc dithiophosphate is to impel the known antiwear agents that on vent valve, forms ash content and typically be used for the natural gas engine oil compsn.
Description of Preferred Embodiments
The present invention relates to be used for to prevent or suppressing with the Sweet natural gas is the method for exhaust valve seat shrinkage depression of mover of fuel.Generally, said method relates to uses lubricating oil composition lubricated with the mover of Sweet natural gas as fuel, and said lubricating oil composition contains the lubrication viscosity oil of (a) main amount at least; (b) the natural gas engine oil additive bag of minor amount, wherein said lubricating oil composition is substantially free of the alkaline earth salt of the condensation product of any various zn cpds and alkylene polyamine, aldehyde and substituted phenol.As used herein term " be substantially free of " be construed as expression if any then in lubricating oil composition only trace, typically based on this lubricating oil composition gross weight meter, each all is lower than 0.001 weight % the alkaline earth salt of zn cpds and said condensation product.
Be used for the Sweet natural gas be fuel mover can have the sulfate ash content of measuring according to ASTM D 874 that is not more than about 1.5 weight % according to lubricating oil composition of the present invention; The sulfate ash content of preferably measuring that is not more than about 0.95 weight % according to ASTM D 874, the sulfate ash content of most preferably measuring that is not more than about 0.5 weight % according to ASTM D 874.In one embodiment; Be used for the Sweet natural gas according to the present invention being that the lubricating oil composition of the mover of fuel has the about 1.5 weight % of about 0.1 weight %-that measure according to ASTM D 874; The about 0.95 weight % of about 0.12 weight %-that preferably measures according to ASTM D 874, the sulfate ash content of the about 0.5 weight % of about 0.15 weight %-that most preferably measures according to ASTM D 874.The lubricant ash content advantageously serves as the solid lubricant at protection valve/valve seat interface, and having substituted is spontaneous exhaust gas particle in the mover of fuel with the hydrocarbon.
In one embodiment, natural gas engine oil compsn of the present invention is substantially free of any phosphorus, and for example phosphorus content is no more than 0.08 weight %, more preferably no more than 0.05 weight %.In another embodiment, lubricating oil composition of the present invention contains the low-level relatively 0.7 weight % that promptly is no more than, and preferably is no more than 0.5 weight %, more preferably no more than the sulphur of 0.3 weight %.
The present invention oil engine applicatory can show as rely on Sweet natural gas promptly be with the Sweet natural gas fuel operate those and comprise interior combustion gas.The instance of this type mover comprises Otto cycle engine etc.In preferred embodiments, oil engine is to be used for for example well head Sweet natural gas collection, compression and other natural gas line service; Generating (comprising cogeneration (co-generation)); And the stationary engine of irrigating.
The lubrication viscosity oil (being also referred to as base oil) that is used for lubricating oil composition of the present invention is typically with main amount; For example based on the said composition gross weight greater than 50wt.%; Be preferably greater than about 70wt.%, the about 99.5wt.% of 80-more preferably from about, most preferably from about the amount of the about 98wt.% of 85-exists.The employed statement of this paper " base oil " is construed as basestocks or the basestocks concoction that is meant as lubricant composition, its by single manufacturers according to same size production (not relying on the place of charging source or manufacturers); Satisfy the specification of same manufacturer; And discern by unique prescription (formula), product ID or the two.The base oil that is used for this paper can be any at present known or being used for regard to lubricant viscosity base oils any and all this type application preparation lubricating oil compositions of finding afterwards; Said application examples such as engine oil; Marine cylinder oil, functional liquid such as hydraulicefficiency oil, gear oil, transmission wet goods.In addition, the base oil that is used for this paper can be chosen wantonly and contain viscosity index improver, for example the polymerization alkyl methacrylate; Ethylenic copolymer such as ethylene-propylene copolymer or styrene-butadiene copolymer; And their analogue and mixture.
Can recognize easily that like those skilled in the art basic oil viscosity depends on application.Therefore, the basic oil viscosity that is used for this paper can be generally 100 degrees centigrade (℃) about 2000 centistokes(cst)s of about 2-(cSt) down.Normally; Base oil as machine oil can have the about 30cSt of about 2cSt-under 100 ℃ individually; The preferred about 16cSt of about 3cSt-; The kinematic viscosity range of the about 12cSt of 4cSt-most preferably from about; And can be depending in required end-use and the processed oil additive that produces required machine oil grade and select or concoct, said grade for example SAE viscosity grade is 0W, 0W-20,0W-30,0W-40,0W-50,0W-60,5W, 5W-20,5W-30,5W-40,5W-50,5W-60,10W, 10W-20,10W-30,10W-40,10W-50,15W, 15W-20,15W-30,15W-40,30,40 lubricating oil composition.
Basestocks can use and include but not limited to distill, solvent treatment, hydrogen are handled, oligomeric, esterification and the various different methods re-refined are made.Refining material should be substantially free of through making, pollute or the previous material of introducing that uses.The base oil of lubricating oil composition of the present invention can be any natural or synthetic lubricating base oil.Suitable hydrocarbon synthetic oil include but not limited to by vinyl polymerization or by the 1-olefinic polymerization so that the oil of polyalphaolefin for example or PAO oil bodying thing preparation to be provided, perhaps for example press the prepared oil of Fischer-Tropsch process by the hydrocarbon synthesis process that uses carbon monoxide and hydrogen.For example, suitable base oil is the last running that comprises seldom (if any); (if any) for example seldom at 100 ℃ of following viscosity base oil that is the lubricating oil distillate more than the 20cSt.
Base oil can be derived from natural lubricating oil, ucon oil or their mixture.Suitable base oil comprises the basestocks that obtains through synthetic wax and slack wax (slack wax) isomerizing, and the aromatics through making crude product and the hydrogen cracking basestocks of polar compound hydrogen cracking (rather than solvent extraction) generation.Suitable base oil comprises as API publication 1509, the 14 editions, Addendum I, and defined all the API classifications of Dec.1998 are those base oils among I, II, III, IV and the V.IV class base oil is poly-alpha olefins (PAO).V class base oil is included in all other base oils beyond I, II, III or the IV class.Though II, III and IV class base oil are preferred for the present invention, these base oils can be through preparing one or more merging in I, II, III, IV and V class basestocks or the base oil.
Useful natural oil comprises for example liquid petroleum of mineral lubricating oils; Paraffinic solvent treatment or acid-treated, cycloalkanes belong to or mix the mineral lubricating oils of paraffinic-cycloalkanes genotype; Derived from the oil of coal or shale, animal oil, vegetables oil (for example rapeseed oil, Viscotrol C and prepared lard) etc.
Useful ucon oil includes but not limited to hydrocarbon ils and the substituted hydrocarbon ils of halogen, for example polymerization and the alkene that gathers mutually such as polybutylenes, Vestolen PP 7052, propylene-isobutylene copolymers, chlorinated polybutylenes, gather (1-hexene), gather (1-octene), gather (1-decene) and their analogue and mixture; Korenyl such as dodecylbenzene, tetradecyl benzene, dinonyl benzene, two (2-ethylhexyl)-benzene etc.; Polyphenyl such as biphenyl, terphenyl, alkylating polyphenyl etc.; Alkylating phenyl ether and alkylating diphenyl sulfide and their verivate, analogue and homologue etc.
Other useful ucon oil includes but not limited to through making less than the alkene of 5 carbon atoms ethene, propylene, butylene, iso-butylene, amylene and their the mixture oil that carries out the polymerization preparation for example.The method for preparing this base polymer oil is known to those skilled in the art.
Useful synthetic hydrocarbon oil in addition comprises the alhpa olefin liquid polymers with proper viscosity.Useful especially synthetic hydrocarbon oil is C 6-C 12The hydrogenated liq oligopolymer of alhpa olefin, for example 1-decene tripolymer.
Another kind of useful ucon oil includes but not limited to that terminal hydroxyl wherein is through for example esterification or the etherificate in addition alkylene oxide polymer of modification, i.e. its homopolymer, multipolymer and verivate.These oil are illustrated as the oil through the polymerization preparation of oxyethane or propylene oxide; The alkyl of polyoxyalkylene polymers and phenyl ether (the methyl polypropylene glycol ether that for example has 1,000 molecular-weight average, diphenyl ether with 500-1000 molecular weight polyethylene glycol; Have 1; 000-1, the Anaesthetie Ether of the W 166 of 500 molecular weight, or the like) or they list-with polycarboxylate for example acetic ester, blended C 3-C 8The C of fatty ester or Tetraglycol 99 13The oxygen acid diester.
Another type of useful ucon oil includes but not limited to the ester of dicarboxylicacid and various alcohol; Said dicarboxylicacid is phthalic acid, succsinic acid, alkyl succinic acid, alkenyl succinic acid, toxilic acid, nonane diacid, suberic acid, sebacic acid, fumaric acid, hexanodioic acid, linoleic acid dimer, propanedioic acid, alkyl propanedioic acid, thiazolinyl propanedioic acid etc. for example, and said alcohol is butanols, hexanol, dodecyl alcohol, 2-Ethylhexyl Alcohol, terepthaloyl moietie, Diethylene Glycol monoether, Ucar 35 etc. for example.The specific examples of these esters comprises the 2-ethylhexyl diester of the two eicosyl esters of Polycizer W 260, sebacic acid two (2-ethylhexyl) ester, fumaric acid di-n-hexyl ester, sebacic acid dioctyl ester, nonane diacid diisooctyl ester, nonane diacid diiso decyl ester, phthalic acid dioctyl ester, phthalic acid didecyl ester, sebacic acid, linoleic acid dimer, by the complex ester that 1 mole of sebacic acid and 2 moles of Tetraglycol 99s and 2 moles of 2 ethyl hexanoic acids is reacted form etc.
Include but not limited to also by the carboxylic acid with about 12 carbon atoms of about 5-and alcohol for example methyl alcohol, ethanol etc. that as the ester of synthetic oil polyvalent alcohol and polyol ethers be those esters of preparing such as NSC 6366, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol, tripentaerythritol for example.
Silicon-based oil for example gather alkyl-, gather aryl-, gather alkoxyl group-or gather aryloxy-silicone oil and silicic acid ester oil, constitute another kind of useful ucon oil.These specific examples includes but not limited to tetraethyl orthosilicate, silicic acid four isopropyl esters, silicic acid four (2-ethylhexyl) ester, silicic acid four-(4-methyl-hexyl) ester, silicic acid four (to tert-butyl-phenyl) ester, hexyl-(4-methyl-2-pentyloxy) sily oxide, gathers (methyl) siloxanes, gathers (aminomethyl phenyl) siloxanes etc.Also in addition other useful ucon oil includes but not limited to contain the liquid ester diethyl ester etc. of Tritolyl Phosphate, trioctyl phosphate, decane phosphonic acids (phosphionic acid) for example of the acid of phosphorus, polymerizing tetrahydrofuran or the like.
Lubricating oil can be any two kinds or more kinds of mixtures in natural, synthetic or disclosed these types of preceding text derived from unrefined oil, treated oil and rerefined oils.Unrefined oil is directly not to be further purified or to be handled those of acquisition by natural or synthetic source (for example coal, shale or tar sand bitumen).The instance of unrefined oil includes but not limited to directly operate the shale oil that obtains by destructive distillation, the oil or the direct ester oil that obtains by esterification technique that directly obtain by distillation, and each is not using under situation about further not handling in them then.Treated oil is further handled to improve one or more performances similar with unrefined oil in one or more purification steps except them.These purification techniques are known to those skilled in the art, comprise for example solvent extraction, second distillation, acid or alkaline extraction, filtration, diafiltration, hydrotreatment, dewaxing etc.Rerefined oils is through handling used oil to obtain by being similar to those methods that are used to obtain treated oil.This type rerefined oils also is called recovered oil or reprocessed oils and often handles in addition through relating to the technology of removing useless additive and oil decomposition (breakdown) product.
Can also use separately or use derived from the lube basestocks of wax hydroisomerization with above-mentioned natural and/or synthetic basestocks combination.This wax isomer passes through natural or synthetic wax or the hydroisomerization generation on hydroisomerisation catalysts of their mixture.
Natural wax typically is the slack wax that reclaims through the solvent dewaxing of MO; Synthetic wax typically is the wax that produces through Fischer-Tropsch process.The instance of useful lubrication viscosity oil comprises HVI and XHVI basestocks, isomerized wax base oil of this type and UCBO (non-conventional base oil) base oil.
The lubricating oil composition that is used for the inventive method also can contain the natural gas engine oil additive bag of minor amount.Typically, additive-package can contain one or more binder components, and optional have one or more thinning oils, so that their easy handlings between transportation and shelf lives.The suitable diluents that is used for additive-package comprises any inert diluent, and preferred lubrication viscosity oil makes additive-package can easily mix with lubricating oil with the preparation lubricating oil composition.Can under 100 ° of F (38 ℃), can have the about 500Saybolt Universal of about 35-Seconds (Saybolt seconds universal) viscosity (SUS) as the proper lubrication oil of thinner, although can use any lubrication viscosity oil.If exist, one or more thinning oils will exist in the amount based on the about 90 weight % of the about 10 weight %-of additive-package gross weight.It is that the excellence of exhaust valve seat shrinkage depression prevents or suppresses in the mover of fuel with the Sweet natural gas that additive-package has advantageously provided in bringing lubricating oil composition into the time.
Usually, additive-package is in based on the about 15 weight % of the about 5 weight %-of lubricating oil composition gross weight in the natural gas engine oil compsn, and the amount of the preferred about 9 weight % of about 6 weight %-exists.In one embodiment; Additive-package contains (i) one or more ashless dispersants at least; (ii) one or more containing metal purification agents; (iii) one or more inhibitors, wherein said lubricating oil composition are substantially free of the for example alkaline earth salt of the condensation product of zinc dialkyl dithiophosphate compound and alkylene polyamine, aldehyde and substituted phenol of any various zn cpds.
One or more ashless dispersant compounds that use in the lubricating oil composition of the present invention are generally used for keeping the suspension of the insoluble substance that oxidation between the usage period produces, and therefore prevent greasy filth flocculation and deposition or are deposited on the metalwork.Nitrogenous ashless (not containing metal) dispersion agent is alkalescence, and helps the base number or the BN (can measure according to ASTM D 2896) of the lubricating oil composition that they join, and does not introduce other sulfated ash.As used herein term " base number " or " BN " are meant the alkali number that is equivalent to KOH milligram number in the 1 gram sample.Therefore, the high more product that reflects of BN number is alkalescence more, thereby basicity is big more.BN uses ASTM D 2896 tests to measure.Ashless dispersant comprise usually have can with the oil soluble polymeric hydrocarbon skeleton of treating the associating functional group of dispersed particles.The ashless dispersant of many types is well known in the art.
The representative example of ashless dispersant includes but not limited to be connected to through bridged group amine, alcohol, acid amides or the ester polarity part of polymer backbone.Ashless dispersant of the present invention can for example be selected from oil soluble salt, ester, amino ester, acid amides, imide He the oxazoline compound of the substituted list of long chain hydrocarbon and dicarboxylicacid or their acid anhydrides; Long chain hydrocarbon, has the thio carboxy acid ester derivative of the long chain aliphatic hydrocarbon of direct connected polyamines; And Mannich condensation product through long-chain substituted phenol and formaldehyde and polyalkylenepolyamines condensation are formed.
Carboxylic dispersion agent is to comprise at least about 34; Preferably at least about carboxylic acid acylating agent's (acid, acid anhydrides, ester etc.) of 54 carbon atoms and nitrogenous compound (for example amine); Organic hydroxy compounds (the aliphatic cpd that for example comprise monohydroxy and polyhydroxy-alcohol; Or comprise the aromatic substance of phenol and naphthols), and/or the reaction product of alkaline inorganic material.These reaction product comprise imide, acid amides and ester.
Succinimide dispersants is a type of carboxylic dispersion agent.They are through making hydrocarbyl substituted succinic acylating agent and organic hydroxy compounds, perhaps with comprise the amine that at least one is connected to the Wasserstoffatoms of nitrogen-atoms, perhaps the mixture reaction with oxy-compound and amine prepares.Term " succinic acylating agent " is meant the substituted succsinic acid of hydrocarbon or produces the compound of succsinic acid that the latter comprises acid itself.These materials typically comprise hydrocarbyl substituted succinic, acid anhydrides, ester (comprising half ester) and halogenide.
Amber acidic group dispersion agent has many chemical structures.One succinic acid base dispersion agent can be expressed from the next:
Figure BDA0000084138520000121
Each R wherein 1Be alkyl independently, the group of polyolefin derivative for example.Typically, alkyl is an alkyl, for example gathers isobutyl-.Perhaps with other expression mode, R 1Group can contain about 500 carbon atoms of the 40-that has an appointment, and these atoms can exist by aliphatic form.R 2Be alkylidene group, ethylidene (C normally 2H 4).The instance of succinimide dispersants comprises and is described in those that describe in the United States Patent(USP) No. 3,172,892,4.234,435 and 6,165,235 for example.
Derive said substituent polyolefine and generally be about 16 carbon atoms of 2-and the normally monomeric homopolymer of polymerizable olefins and the multipolymer of 2-6 carbon atom.The amine that generates said carboxylic disperser composition with said amber acylation agent reaction can be monoamine or polyamines.
Why like this succinimide dispersants appellation is because they contain usually mostly and are the nitrogen of imide functionality form, although amide functional group can be the form of amine salt, acid amides, tetrahydroglyoxaline and their mixture.In order to prepare succinimide dispersants, randomly in the presence of inert organic liquid solvents/diluents basically, heat one or more compounds that produce succsinic acids with one or more amine and typically remove and anhydrate.Temperature of reaction be generally about 80 ℃ to up to the decomposition temperature of said mixture or said product, this decomposition temperature typically is about 300 ℃ of about 100-.Other details and the instance for preparing the method for succinimide dispersants of the present invention comprises and is described in the United States Patent(USP) No. 3,172,892,3,219,666,3,272,746,4,234,435,6,165,235 and 6,440,905 for example those.
Suitable ashless dispersant can also comprise the amine dispersion agent, and it is relative high-molecular weight aliphatic halide and amine, the preferred reaction product of polyalkylenepolyamines.The instance of amine dispersion agent comprises and is described in the United States Patent(USP) No. 3,275,554,3,438,757,3,454,555 and 3,565,804 for example those like this.
Suitable ashless dispersant can also comprise " Mannich dispersion agent ", and it is that wherein alkyl contains the reaction product at least about induced by alkyl hydroxybenzene and the aldehyde (especially formaldehyde) and the amine (especially polyalkylenepolyamines) of 30 carbon atoms.The instance of amine dispersion agent comprises and is described in the United States Patent(USP) No. 3,036,003,3,586,629,3,591,598 and 3,980.569 for example those like this.
Suitable ashless dispersant can also be the ashless dispersant succinimide of aftertreatment for example of aftertreatment; For example relate to borate or ethylene carbonate post-treating method (for example United States Patent(USP) No. 4,612,132 and 4; 746,446 etc. disclosed) and other post-treating method.The alkenyl succinimide of processes of carbonate treatment is to be about 450-about 3000 derived from molecular weight; Preferred about 900-about 2500; More preferably from about 1300-is about 2400, and most preferably from about 2000-is about 2400, and the polybutylene succinimide of the polybutylenes of these molecular weight mixtures.Preferably; It is through for example United States Patent(USP) No. 5; 716; Disclosed in 912 (incorporating its content into this paper by reference), the unsaturated acid reactant copolymer of polybutylenes succinic acid derivative, unsaturated acid reactant (reagent) and alkene and the mixture reaction of polyamine are prepared.
Suitable ashless dispersant can be a polymeric, and they are for example decyl-octyl methacrylate, vinyl decyl ethers and high-molecular weight alkene and the monomeric interpretation that contains polar substituent of oil-soluble monomer.The instance of polymeric dispersion agent comprises and being described at for example United States Patent(USP) No. 3,329,658,3,449,250,3,666, those of 730 grades.
In a preferred embodiment of the invention, the ashless dispersant that is used for lubricating oil composition is the double amber imide derived from the polyisobutylene group with about 2300 number-average molecular weights of about 700-.The dispersion agent that is used for lubricating oil composition of the present invention preferably is non-polymeric (for example list or a double amber imide).
Usually, one or more ashless dispersants are in based on the about 8 weight % of the about 1-of lubricating oil composition gross weight, and the amount of the about 6 weight % of preferably about 1.5-is present in the lubricating oil composition.
The metallic purification agent compound of one or more that use in the lubricating oil composition of the present invention plays as reducing or remove sedimental purification agent and as two kinds of effects of acid neutralizing agent or rust-preventive agent, thereby reduces wearing and tearing and corrosion and prolong engine life.Purification agent comprises the polar head with long hydrophobicity afterbody usually, and this polar head comprises the metal-salt of acidic organic compound.
Can contain one or more purification agents according to lubricating oil composition of the present invention, it is salt normally, particularly overbased salt.Overbased salt or super-alkaline substance are even newton's system of single phase, it is characterized in that metal content surpassed according to metal and with the stoichiometry of the specific acidic organic compound of this metal reaction the metal content that should exist.In the reaction medium that comprises at least a inert organic solvents (for example MO, petroleum naphtha, toluene, YLENE), in the presence of the excessive metal base and promotor of stoichiometry, prepare super-alkaline substance through making acidic substance (typically being for example carbonic acid gas of mineral acid or low-grade carboxylic acid) and the mixture reaction that comprises acidic organic compound.
The effective acidic organic compound that is used to prepare the parlkaline compsn comprises carboxylic acid, sulfonic acid, phosphorated acid, phenol and their mixture.Preferably, acidic organic compound is the Whitfield's ointment of carboxylic acid or sulfonic acid and hydrocarbyl substituted.
For example salicylate can for example oxide compound or oxyhydroxide reaction prepare the carboxylate salt purification agent through making aromatic carboxylic acid and suitable metallic compound.Can obtain neutrality or parlkaline product by means commonly known in the art then.Aromatic carboxylic acid's aromatics part can contain one or more heteroatomss for example nitrogen and oxygen.Preferably, said part only contains carbon atom.More preferably, said part contains 6 or more a plurality of carbon atom, for example benzene part.The aromatic carboxylic acid can be contained the optional one or more aromatics parts that condense together or otherwise connect through alkylidene bridge, for example one or more phenyl ring.Aromatic carboxylic acid's representative example comprises Whitfield's ointment and sulphurated derivatives thereof the for example Whitfield's ointment and the verivate thereof of hydrocarbyl substituted.For example being used to vulcanize, the salicylic method of hydrocarbyl substituted is well known to a person skilled in the art.Whitfield's ointment typically for example prepares through the Kolbe-Schmitt method through the carboxylation of phenates.In this situation, Whitfield's ointment is pressed in thinner and the not mixture acquisition of the phenol of carboxylation usually.
The metal-salt of phenols and sulfurized phenols are through for example oxide compound or oxyhydroxide reaction prepare with suitable metallic compound.Neutrality or parlkaline product can obtain by means commonly known in the art.For example, sulfurized phenol can through make phenol and sulphur or sulfocompound for example hydrogen sulfide, a halogenation sulphur or dihalide reaction of Salmon-Saxl prepare, thereby form product, this product is the mixture of the compound of phenols through containing the sulphur bridge bridge joint more than 2 kinds wherein.
The metallic compound that is used for preparing overbased salt is periodic table of elements I family or II family metallic compound arbitrarily normally.Preferably, said metallic compound is II family metal and comprises IIa family earth alkali metal (for example magnesium, calcium, strontium, barium) and IIb family metal for example zinc or cadmium.Preferably, II family metal is magnesium, calcium, barium or zinc, more preferably magnesium or calcium, most preferably calcium.
The instance of overbased detergent includes but not limited to calcium sulphonate, phenol calcium, SAP 002, calcium stearate and their mixture.The overbased detergent that is suitable for lubricating oil composition of the present invention can be low parlkaline, and for example BN is lower than about 100 overbased detergent.The BN of this low overbased detergent can be about 50 for about 5-, or about 10-is about 30, or about 15-about 20.Perhaps, the overbased detergent that is suitable for being used for lubricating oil composition of the present invention can be a height parlkaline (for example BN is higher than about 100 overbased detergent).The BN of this height overbased detergent can be about 450 for about 100-, or about 200-is about 350, or about 250-about 280.BN is that about 17 low overbased calcium sulfonate detergents and BN are that about 120 height parlkaline sulfurized calcium phenate is two kinds of exemplary overbased detergent that are used for lubricating oil composition of the present invention.
Can contain more than a kind of overbased detergent according to lubricating oil composition of the present invention, this purification agent can all be low BN purification agent, all be high BN purification agent or their mixture.For example, lubricating oil composition of the present invention can contain first containing metal purification agent (it is that BN is over-based alkaline erath metal sulphonate or the phenates purification agent of about 100-about 450) and the second containing metal purification agent (it is that BN is over-based alkaline erath metal sulphonate or the phenates purification agent of about 10-about 50).
The suitable purification agent that is used for lubricating oil composition also comprises " mix (hybrid) " purification agent, for example phenates/salicylate, sulphonate/phenates, sulphonate/salicylate, sulphonate/phenates/salicylate, or the like.The instance that mixes purification agent comprises and is described in the United States Patent(USP) No. 6,153,565,6,281,179,6,429,178 and 6,429,179 for example those.
Usually, one or more containing metal purification agents are in based on the about 8.5 weight % of the about 0.5-of lubricating oil composition gross weight, and the amount of the about 6 weight % of preferably about 1-is present in the lubricating oil composition.When using two kinds of containing metal purification agents; Based on lubricating oil composition gross weight meter; The first containing metal purification agent is with the about 5 weight % of about 0.5-; The amount of the preferred about 3 weight % of about 1-is present in the lubricating oil composition, and the second containing metal purification agent is with the about 1.0 weight % of about 0.1-, and the amount of the about 0.5 weight % of preferably about 0.2-is present in lubricating oil composition.
One or more anti-oxidant compounds that are used for lubricating oil composition of the present invention have reduced the tendency that deterioration in use takes place basestocks, this deterioration can by the oxidation products on the metallic surface for example greasy filth and varnish deposit and oil viscosity increase prove.This type oxidation retarder comprises hindered phenol, ashless oil soluble phenates and sulfuration phenates, pentanoic, substituted aniline of alkyl and naphthylamines and their analogue and mixture.Pentanoic type oxidation retarder includes but not limited to alkylated diphenylamine, PA and alkylation-alpha-naphthylamine.
Usually, one or more anti-oxidant compounds are in based on the about 3 weight % of the about 0.1-of lubricating oil composition gross weight, and the amount of the about 2.5 weight % of preferably about 0.2-is present in the lubricating oil composition.
Lubricating oil composition of the present invention can be through with additive-package, randomly with other additive, concocts simply or mixes to come expediently with lubrication viscosity oil and prepare.Additive-package can also be closed the blending that contains the lubricating composition of desired concn additive with promotion as enriched material with suitable ratio preset.The concentration that the blending of additive-package and base oil is used is that they dissolve in the said oil and can be compatible with other additive in the required finished lube under this concentration.The compound (best (as well as) can be dissolved in the oil by the processing rate that is suitable for) that consistency in this case typically refers to existence does not cause other additive deposition under normal operation yet.Suitable oil dissolubility/consistency the scope of the given compound of lubricant formula can use conventional solvability testing method to confirm by those skilled in the art.For example, deposition taking place in the lubricating oil composition of envrionment conditions (about 20 ℃-25 ℃) preparation actual deposition takes place or makes " muddy (cloudy) " solution (it has proved the formation of insoluble Wax particles) to measure in can be through oil compsns.
Of preamble, lubricating oil composition described herein is substantially free of the alkaline earth salt of the condensation product of any zn cpds and alkylene polyamine, aldehyde and substituted phenol.In one embodiment, said lubricating oil composition also is substantially free of any molybdate compound.The alkylene polyamine of said condensation product can be following structure NH 2[R (R)-NH] nH, wherein R is the alkylidene group that contains about 6 carbon atoms of the 2-that has an appointment, n is the integer of 1-about 10.Typical alkylene polyamine comprises NSC 446, Triethylenetetramine (TETA), tetren etc.Aldehyde normally per molecule contains about 3 the carbon atom aliphatic aldehyde of 1-.Substituted phenol is to have the alkylation mono-hydroxy phenol that at least one length is enough to give the oil-soluble alkyl of condensation product.Representational alkylphenol is that wherein alkyl contains those alkylphenols of about 24 carbon atoms of the 4-that has an appointment (those alkyl that preferably have about 24 carbon atoms of about 8-), for example n-pentyl phenol, diamyl phenol, octyl phenol, NP, to the mixture of uncle's octyl phenol, phenols, the alkylating phenols of wax etc.
The lubricating oil composition that is used for the inventive method can also contain and is useful on other conventional additives that subsidiary function is provided and is dispersed or dissolved in finished lube compsn wherein to produce these additives.For example, can be with the blending of lubricating oil composition and following material: except that contain the zinc antiwear agents for example antiwear agents, the rust-preventive agent the zinc dialkyl dithiophosphate, remove clouding agent, emulsion splitter, metal passivator, friction modifiers, pour point depressor, skimmer, cosolvent, bag compatilizer (package compatibiliser), corrosion inhibitor, dyestuff, extreme pressure agent and their analogue and mixture.Various additives are known and commercially available.Can use these additives or their similar compound to prepare lubricating oil composition of the present invention through general blending method.
The instance of rust-preventive agent includes but not limited to non-ionic polyoxyethylene reagent, for example Brij30, the senior alcohol ether of T 46155, T 46155 nonylplenyl ether, polyoxyethylene octyl phenyl ether, the hard ester group ether of T 46155 octyl group, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol monoleate and polyethylene glycol monooleate; Triple Pressed Stearic Acid and other lipid acid; Dicarboxylicacid; Metallic soap; The lipid acid amine salt; The metal-salt of heavy sulfonic acid; The inclined to one side carboxylicesters of polyhydroxy-alcohol; SULPHOSUCCINIC ACID ESTER; (short chain) alkenyl succinic acid; Its partial ester and nitrogen containing derivative thereof; The synthetic alkylaryl sulfonate is the dinonylnaphthalene sulfonic acid metal-salt for example; And their analogue and mixture.
The instance of friction modifiers includes but not limited to oxyalkylated aliphatic amide; The fat epoxide of borated; The fat phosphorous acid ester, fat epoxide, aliphatic amide, the alkoxylated fats amine of borated, the metal-salt of lipid acid, fatty acid amide, glyceryl ester, the glyceryl ester of borated; And at United States Patent(USP) No. 6,372, disclosed fatty tetrahydroglyoxaline in 696 (incorporating its content into this paper by reference); Friction modifiers is by C 4-C 75, preferred C 6-C 24, C most preferably 6-C 20Fatty ester obtains with the reaction product of the nitrogenous compound that is selected from ammonia, alkanolamine and their analogue and mixture.
The instance of skimmer includes but not limited to the polymkeric substance of alkyl methacrylate; The polymkeric substance of dimethyl siloxane and analogue thereof and mixture.
Every kind of aforementioned additive is to use to give the lubricant desired properties with the function significant quantity in use.Therefore, for example, if additive is a friction modifiers, then the function significant quantity of this friction modifiers will be the amount that is enough to give the required friction modified characteristic of lubricant.Usually, these additives in use separately concentration count the about 20 weight % of about 0.001 weight %-based on the lubricating oil composition gross weight and in one embodiment for the about 10 weight % of about 0.01 weight %-.
Following non-limiting example explanation the present invention.
Embodiment 1
Form lubricating oil composition; This lubricating oil composition contains the mixture of 3.3 weight % double amber imides (derived from 1300MW polyisobutylene succinic anhydride (PIBSA)) and heavy polyamines and NSC 446; 0.43 weight % calcium sulphonate (17BN), 3.0 weight % sulfurized calcium phenates (114BN), 0.9 weight % hindered phenol antioxidant; 5ppm froth suppressor, surplus are II class base oil.Lubricating oil composition has the sulfate ash content of the about 0.46 weight % that measures according to ASTM D874.
The comparative example A
Lubricating oil composition prepares through the lubricating oil composition of accomplishing processing (top treat) embodiment 1 at last derived from the zinc dialkyl dithiophosphate of primary alconol with 0.38 weight %.Lubricating oil composition has the sulfate ash content of the about 0.50 weight % that measures according to ASTM D874.
Test
In Waukesha F11GSID mover, embodiment 1 and comparative example A's lubricating composition is estimated with regard to exhaust valve seat shrinkage depression protection effectiveness.In this test, equipment (instrument) 6-cylinder 250BHP Waukesha F11GSID mover is measured (for example pressing United States Patent(USP) No. 4,672, described in 843) to obtain dynamic electric voltage by 12 valves-6 suction valve and 6 vent valves.Each test is operated under 1800rpm with 90% load and was carried out 400 hours.At intake air temperature is that the duration of test of 110-150 ° of F is kept stoichiometric condition.Through based on test from each last 300 hours data carry out linear fit calculate embodiment 1 and comparative example A lubricating composition average valve shrinkage depression wear rate and report with per 1000 hours wear rates.In table 1, provide vent valve shrinkage depression result.In this table, the protection of the low more expression exhaust valve seat of valve wearing and tearing shrinkage depression speed shrinkage depression is renderd a service big more.
Table 1
Waukesha F11 vent valve shrinkage depression result
Figure BDA0000084138520000191
Shown in data, the lubricating oil composition of embodiment 1 shows the protection of better vent valve wearing and tearing shrinkage depression than the comparative example A's of containing the zinc dialkyl dithiophosphate wear inhibitor lubricating oil composition.
Be to be understood that and make various modifications to this paper disclosed embodiment.Therefore the foregoing description content should not be interpreted as and have restrictedly, and only is interpreted as the example of preferred embodiment.For example, mentioned above and only for purpose of explanation as the function of the optimal mode of embodiment of the present invention.Those skilled in the art take other configuration and method and do not depart from the scope of the present invention and spirit.In addition, those skilled in the art can be contemplated in the scope of its accompanying claims and other modification in the spirit.

Claims (15)

1. one kind prevents or suppresses with the Sweet natural gas to be the method for exhaust valve seat shrinkage depression in the mover of fuel, and this method comprises that said lubricating oil composition comprises lubrication viscosity oil of (a) main amount with the lubricated said mover of lubricating oil composition; (b) the natural gas engine oil additive bag of minor amount, wherein said lubricating oil composition is substantially free of the alkaline earth salt of the condensation product of any various zn cpds and alkylene polyamine, aldehyde and substituted phenol.
2. the process of claim 1 wherein that said lubrication viscosity oil is a natural gas engine oil.
3. the process of claim 1 wherein that said natural gas engine oil additive bag comprises (i) one or more ashless dispersants, (ii) one or more containing metal purification agents and (iii) one or more inhibitors.
4. the method for claim 3, wherein said one or more ashless dispersants are double amber imides.
5. the method for claim 3, wherein said one or more containing metal purification agents are that base number (BN) is the over-based alkaline erath metal salt purification agent of about 10-about 450.
6. the method for claim 3, wherein said one or more inhibitors are hindered phenol compound.
7. the process of claim 1 wherein that said lubricating oil composition has the sulfate ash content of the about 1.5 weight % of about 0.1 weight %-that measure according to ASTM D874.
8. the process of claim 1 wherein that this lubricating oil composition comprises based on lubricating oil composition gross weight meter:
About 8 one or more ashless dispersants of weight % of about 1-,
About one or more containing metal purification agents of 8.5 weight % of about 0.5-and
About 3 one or more inhibitors of weight % of about 0.1-.
9. natural gas engine oil compsn; This lubricating oil composition comprises the lubrication viscosity oil of (a) main amount; (b) one or more ashless dispersants; (c) one or more containing metal purification agents and (d) one or more inhibitors, wherein said lubricating oil composition are substantially free of the alkaline earth salt of the condensation product of any various zn cpds and alkylene polyamine, aldehyde and substituted phenol.
10. the natural gas engine oil compsn of claim 9, wherein said one or more ashless dispersants are double amber imides.
11. the natural gas engine oil compsn of claim 9, wherein said one or more containing metal purification agents are BN is the over-based alkaline erath metal salt purification agent of about 10-about 450.
12. the natural gas engine oil compsn of claim 9, wherein said one or more inhibitors are hindered phenol compound.
13. the natural gas engine oil compsn of claim 9, it has the sulfate ash content of the about 1.5 weight % of about 0.1 weight %-that measure according to ASTMD874.
14. the natural gas engine oil compsn of claim 9, based on this lubricating oil composition gross weight meter, it comprises:
About 8 one or more ashless dispersants of weight % of about 1-,
About one or more containing metal purification agents of 8.5 weight % of about 0.5-and
About 3 one or more inhibitors of weight % of about 0.1-.
15. the natural gas engine oil compsn of claim 9, it compares the performance with bigger reduction exhaust valve seat shrinkage depression with the corresponding natural gas engine oil compsn that wherein has zn cpds.
CN2010800081583A 2009-02-18 2010-02-17 Prevent the method for exhaust valve seat shrinkage depression Pending CN102325866A (en)

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US12/378,678 US20100206260A1 (en) 2009-02-18 2009-02-18 Method for preventing exhaust valve seat recession
PCT/US2010/024460 WO2010096472A2 (en) 2009-02-18 2010-02-17 Method for preventing exhaust valve seat recession

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