WO1994024237A1 - Procede de reduction des precurseurs de boue et de gomme dans des huiles lubrifiantes - Google Patents

Procede de reduction des precurseurs de boue et de gomme dans des huiles lubrifiantes Download PDF

Info

Publication number
WO1994024237A1
WO1994024237A1 PCT/US1994/004262 US9404262W WO9424237A1 WO 1994024237 A1 WO1994024237 A1 WO 1994024237A1 US 9404262 W US9404262 W US 9404262W WO 9424237 A1 WO9424237 A1 WO 9424237A1
Authority
WO
WIPO (PCT)
Prior art keywords
oil
lubricating oil
sludge
filter media
particles
Prior art date
Application number
PCT/US1994/004262
Other languages
English (en)
Inventor
Darrell W. Brownawell
Warren A. Thaler
Cruise K. Jones
Jacob Emert
Abhimanyu O. Patil
Original Assignee
Exxon Chemical Patents Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Exxon Chemical Patents Inc. filed Critical Exxon Chemical Patents Inc.
Priority to CA002160778A priority Critical patent/CA2160778C/fr
Priority to DE69431560T priority patent/DE69431560T2/de
Priority to JP6522526A priority patent/JPH08508773A/ja
Priority to EP94914211A priority patent/EP0703959B1/fr
Publication of WO1994024237A1 publication Critical patent/WO1994024237A1/fr

Links

Classifications

    • 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
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/12—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/14—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds a condensation reaction being involved
    • C10M149/22—Polyamines
    • 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
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/06—Particles of special shape or size
    • 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
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/0091—Treatment of oils in a continuous lubricating circuit (e.g. motor oil system)
    • 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
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • 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
    • C10M2215/26—Amines
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • 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
    • 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
    • C10N2040/251—Alcohol fueled engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/28—Rotary engines

Definitions

  • the present invention pertains to a method, apparatus and compositions for removing sludge and varnish precursors from a lubricating oil disposed within an internal combustion engine and for improving the oxidative stability of the lubricating oil. More particularly, the invention pertains to a method, apparatus and compositions for achieving this purpose by contacting the oil with an insoluble compound having a dispersant functional group and in some cases also an antioxidant functional group.
  • the compound may be in the form of a porous slab, a thin film, or in the form of discrete particles which are within a circulating oil system but do not have a core substrate. These discrete particles may be "encaged", i.e. held inside of some large structural member by means of filter paper, wire mesh or by some other suitable means.
  • polar hydrocarbon contaminants are formed due to incomplete combustion of the f el.
  • Typical contaminants include low molecular weight polar alkyl compounds such as alcohols, aldehydes, ketones, carboxylic acids, and the like.
  • These contaminants are sludge and varnish precursors which pass into the lubricating oil with combustion blow-by gases where they contact water in the oil and agglomerate to form an emulsion which is commonly referred to as sludge. Sludge and varnish precursors can also arise from oil oxidation.
  • the dispersant functional group is a crosslinked polyethylene amine which is in the form of discrete particles encaged within a conventional oil filter.
  • the invention provides a method of reducing the presence of sludge or varnish precursors in a lubricating oil which comprises contacting a lubricating oil containing sludge or varnish precursors with an oil insoluble, oil wettable compound having a dispersant functional group and in some cases an antioxidant functional group, which compound is capable of complexing with sludge or varnish precursors and which compound is in the form of a plurality of discrete solid particles which are not deposited on a substrate, thereby causing at least a portion of the sludge or varnish precursors to become immobilized on said particles.
  • the invention also provides a method for reducing the presence of sludge or varnish precursors in a lubricating oil by providing a plurality of oil insoluble, oil wettable, solid particles comprising one or more compounds having a dispersant functional group and in some cases an antioxidant functional group, which particles are capable of complexing with sludge or varnish precursors; and encaging said particles in the path of a lubricating oil circulating within an internal combustion engine without adhering said particles to a substrate, which encaging prevents the transmigration of said particles to said internal combustion engine by the lubricating oil.
  • the invention also provides compounds having a dispersant functional group and in some cases an antioxidant functional group, which are capable of complexing with sludge or varnish precursors and of reducing the presence of sludge in a lubricating oil, which compounds comprise polyamine polymers having a molecular weight in the range of from about 100 to about 60,000 which are crosslinked with a crosslinking agent selected from the group consisting of metal alkoxides, silanes, silicates, epoxides, quinones, and phenol-formaldehyde compounds.
  • a crosslinking agent selected from the group consisting of metal alkoxides, silanes, silicates, epoxides, quinones, and phenol-formaldehyde compounds.
  • Other suitable chain extending, cross-linking and insolubilizing agents may be utilized as are known to those skilled in the art.
  • the invention further provides an article of manufacture for reducing the presence of sludge or varnish precursors in a lubricating oil including a plurality of oil insoluble, oil wettable, solid particles comprising one or more compounds having a dispersant functional group and in some cases an antioxidant functional group, which particles are capable of complexing with sludge or varnish precursors; and means for encaging said particles in the path of a lubricating oil circulating within an internal combustion engine without adhering said particles to a substrate, which encaging means prevents the transmigration of said particles to said internal combustion engine by the lubricating oil.
  • the invention still further provides an oil filter which comprises, a hollow, oil impermeable housing having oil ingress and oil egress means; and a plurality of oil insoluble, oil wettable, solid particles in said housing, said particles comprising one or more compounds having a dispersant functional group and in some cases an antioxidant functional group, which particles are capable of complexing with sludge or varnish precursors; and means for encaging said particles between said oil ingress and oil egress means, such particles not having been deposited on a substrate, which encaging means prevents the removal of said particles from said housing by a lubricating oil when such oil is within said housing; and at least one filtering media selected from the group consisting of chemically active filter media, physically active filter media and inactive filter media.
  • dispersants are typically blended within a motor oil and comprise a solubilizing group such as polybutene and a functional group that complexes, reacts or interacts with sludge, sludge presursors and varnish precursors (hereinafter referred to as dispersant functional group) .
  • antioxidants are typically blended within a motor oil and may comprise a solubilizing group and an active antioxidant functional group.
  • An antioxidant functional group is a chemical group that protects a lubricating oil from oxidation without the need for a solubilizing group, although one may be present.
  • sludge and varnish precursors can be removed from a lubricating oil and antioxidation protection provided without the need for a solubilizing group by incorporating an antioxidant functional group and/or a dispersant functional group in the form of discrete particles positioned in the path of circulating engine oil.
  • an antioxidant functional group and/or a dispersant functional group in the form of discrete particles positioned in the path of circulating engine oil.
  • the compounds containing a dispersant functional group or antioxidant functional group useful within the context of the present invention are those which are oil insoluble but oil wettable. Essentially any such dispersant functional group which will complex with sludge or varnish precursors can be used.
  • suitable dispersant functional groups are, separately or in combination, amines, polyamines.
  • dispersant functional groups include polyethylene amines, other substituted amines (e.g. polypropylene amines), pentaerythritol, aminopropyl morpholine, their derivatives, or mixtures thereof.
  • derivatives include, but are not limited to, salts of these dispersant functional groups; reaction products of these functional groups with sultones, cyclic anhydrides, or their neutralized derivatives (e.g.
  • polyethylene amines are a particularly effective functional group.
  • the useful compounds are crosslinked amines having ethylene amine functionality.
  • One preferred class of polyethylene amines are those commercially available from the Virginia Chemical group of Hoechst Celanese Corporation as Corcat R grades P-12, P-18, P-150 and JP- 600.
  • amines include 2- methylpentamethylene diamine, diethylene triamine, triethylene tetraamine.
  • the most preferred class of amines includes Polyamine H, a bottoms product formed in the manufacture of polyethylene amine which contains approximately 6-8 ethylene groups and is commercially available from Union Carbide.
  • These amines are preferably crosslinked by a crosslinking agent, for example those selected from the group consisting of metal alkoxides, silanes, silicates, quinones, and phenol- formaldehyde compounds.
  • the most preferred crosslinking agent is benzoquinone.
  • the most preferred antioxidant functional group is benzoquinone.
  • the amount of dispersant functional group containing compound used can vary broadly depending upon the amount of sludge or sludge and varnish precursors in the oil. However, although only an amount effective to reduce the sludge and varnish precursor content of the lubricating oil need be used, the amount will typically range from about 0.1 to about 10 wt.%, preferably from about 0.2 to about 2.0 wt.%, based on weight of the lubricating oil, provided the dispersant functional group particles are the only dispersant functional group in the system.
  • the dispersant functional group containing compound is in the form of discrete particles which may have a particle size ranging from about 0.001 mm to about 50 mm, preferably from about 0.01 mm to about 10 mm and most preferably from about 0.1 mm to about 5 mm.
  • the discrete particles are positioned in the path of a lubricating oil circulating within an internal combustion engine without adhering or having deposited the particles on a substrate. This is preferably done by encaging them within a filter media to prevent the transmigration of the particles to said internal combustion engine by the lubricating oil.
  • One method of encaging such particles is to dispose them with or without a small amount of binder polymer between sheets of conventional paper or filter media in a typical oil filter.
  • Another method may be by enclosing the particles within a netting or screen material. Any method of encaging is useful provided the particles remain discrete, to expose essentially their entire surface area to circulating oil, while preventing the migration of the particles to the combustion chamber of the engine.
  • the particles can be located within or external to the lubrication system of the internal combustion engine. Preferably, the particles will be located within the lubrication system such as on the engine block or near the sump.
  • Sludge and sludge precursors are present in essentially any lubricating oil used in the lubrication system of essentially any internal combustion engine, including automobile and truck engines, two-cycle engines, aviation piston engines, marine and railroad engines, gas-fired engines, alcohol (e.g. methanol) powered engines, stationary powered engines, turbines, and the like.
  • the sludge precursors are commonly produced as the result of reaction between combustion by-products, fuel and lubricant.
  • Another source of sludge precursors is oil or additive oxidation.
  • the lubricating oil will normally comprise a major amount of lubricating oil basestock or lubricating base oil, and a minor amount of one or more additives.
  • the lubricating oil basestock can be derived from natural lubricating oils, synthetic lubricating oils, or mixtures thereof.
  • the lubricating oil basestock will have a viscosity in the range of about 5 to about 10,000 cSt at 40" C. , although typical applications will require an oil having a viscosity ranging from about 10 to about 1,000 cSt at 40° C.
  • Natural lubricating oils include animal oils, vegetable oils (e.g. castor oil and lard oil) , petroleum oils, mineral oils, and oils derived from coal or shale.
  • Synthetic oils include hydrocarbon oils and halo- substituted hydrocarbon oils such as polymerized and interpolymerized olefine (e.g. polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(l-hexenes) , poly(l- octenes) , poly(1-decenes) , etc., and mixtures thereof); alkylbenzenes (e.g.
  • Synthetic lubricating oils also include alkylene oxide polymers, interpolymers, copolymers and derivatives thereof wherein the terminal hydroxyl groups have been modified by esterification, etherification, etc.
  • This class of synthetic oils is exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide; the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g. methyl-polyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polyethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-1500) ; and mono- and polycarboxylic esters thereof (e.g., the acetic acid esters, mixed C 3 -C 8 fatty acid esters, and C1 3 oxo acid diester of tetraethylene glycol) .
  • polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide
  • the alkyl and aryl ethers of these polyoxyalkylene polymers e.g. methyl-polyisopropylene
  • Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids, etc.) with a variety of alcohols (e.g. butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.).
  • dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid,
  • esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid, and the like.
  • Esters useful as synthetic oils also include those made from C 5 to C ⁇ 2 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, tri ethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, and the like.
  • Synthetic hydrocarbon oils are also obtained from hydrogenated oligomers of normal olefins.
  • Silicon-based oils (such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils) comprise another useful class of synthetic lubricating oils.
  • oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl- 2-ethylhexyl) silicate, tetra(p-tert-butylphenyl) silicate, hexa-(4-methyl-2-pentoxy)-disiloxane, poly(methyl)-siloxanes and poly(methylphenyl) siloxanes, and the like.
  • Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) , polymeric tetrahydrofurans, polyalphaolefins, and the like.
  • liquid esters of phosphorus-containing acids e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid
  • polymeric tetrahydrofurans e.g., polymeric tetrahydrofurans, polyalphaolefins, and the like.
  • the lubricating oil may be derived from unrefined, refined, rerefined oils, or mixtures thereof.
  • Unrefined oils are obtained directly from a natural source or synthetic source (e.g., coal, shale, or tar sands bitumen) without further purification or treatment.
  • Examples of unrefined oils include a shale oil obtained directly from a retorting operation, a petroleum oil obtained directly from distillation, or an ester oil obtained directly from an esterification process, each of which is then used without further treatment.
  • Refined oils are similar to the unrefined oils except that refined oils have been treated in one or more purification steps to improve one or more properties.
  • Suitable purification techniques include distillation, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration, and percolation, all of which are known to those skilled in the art.
  • Rerefined oils are obtained by treating refined oils in processes similar to those used to obtain the refined oils. These rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.
  • the lubricating base oil may contain one or more additives to form a fully formulated lubricating oil.
  • Such lubricating oil additives include antiwear agents, antioxidants, corrosion inhibitors, detergents, pour point depressants, extreme pressure additives, viscosity index improvers, friction modifiers, and the like.
  • This invention can also be combined with the removal of sludge or varnish precursors from a lubricating oil as described in U.S. Patent 5,042,617 and discussed earlier herein.
  • This method provides for the incorporation of a dispersant functional group immobilized by intimate association with a substrate.
  • Examples of basic organonitrogen compounds include, but are not limited to, pyridines; anilines; piperazines; morpholines; alkyl, dialkyl, and trialkyl amines; alkyl polyamines; and alkyl and aryl guanidines.
  • Alkyl, dialkyl, and trialkyl phosphines are examples of basic organophosphorus compounds.
  • Examples of particularly effective weak bases are the dialkyl amines (R2HN) , trialkyl amines (R 3 N) , dialkyl phosphines (R 2 HP) , and trialkyl phosphines (R 3 P) , where R is an alkyl group, H is hydrogen, N is nitrogen. and P is phosphorus.
  • dialkyl and trialkyl amines examples include tributyl amine (or phosphine) , dihexyl amine (or phosphine) , decylethyl amine (or phosphine) , trihexyl amine (or phosphine) ,
  • trioctyl amine or phosphine
  • trioctyldecyl amine or phosphine
  • tridecyl amine or phosphine
  • Preferred trialkyl phosphines are trihexyl phosphine, trioctyldecyl phosphine, or mixtures thereof, with trioctadecyl phosphine being particularly preferred.
  • a suitable weak base is a polyethyleneamine imide or amide of polybutenylsuccinic anhydride with more than 40 carbons in the polybutenyl group (see for example U.S. patent 5,164,101 which is incorporated herein by reference) .
  • the weak base must be strong enough to neutralize the combustion acids (i.e., form a salt) .
  • Suitable weak bases will typically have a PKa from about 4 to about 12.
  • strong organic bases such as organoguanidines
  • the molecular weight of the weak base should be such that the protonated nitrogen compound retains its oil solubility.
  • the weak base should have sufficient solubility so that the salt formed remains soluble in the oil and does not precipitate. Adding alkyl groups to the weak base is the preferred method to ensure its solubility.
  • the amount of weak base in the lubricating oil for contact at the piston ring zone will vary depending upon the amount of combustion acids present, the degree of neutralization desired, and the specific applications of the oil. In general, the amount need only be that which is effective or sufficient to neutralize at least a portion of the combustion acids present at the piston ring zone. Typically, the amount will range from about 0.01 to about 3 wt.
  • the neutral salts are passed or circulated from the piston ring zone with the lubricating oil and contacted with a heterogeneous strong base.
  • strong base is meant a base that will displace the weak base from the neutral salts and return the weak base to the oil for recirculation to the piston ring zone where the weak base is reused to neutralize combustion acids.
  • Suitable strong bases include, but are not limited to, barium oxide (BaO) , magnesium carbonate (MgC ⁇ 3 ) , magnesium hydroxide (Mg(0H)2) magnesium oxide (MgO) , sodium aluminate (NaA10 2 ) , sodium carbonate (Na 2 C0 3 ) , sodium hydroxide (NaOH) , zinc oxide (ZnO) , or their mixtures, with MgO being particularly preferred.
  • heterogeneous strong base is meant that the strong base is in a separate phase (or substantially in a separate phase) from the lubricating oil, i.e., the strong base is insoluble or substantially insoluble in the oil.
  • the strong base may be incorporated (e.g.
  • the strong base since the strong base is not being continuously regenerated for reuse as is the weak base (i.e., the alkyl amine) , the amount of strong base must be at least equal to (and preferably be a multiple of) the equivalent weight of the weak base in the oil. Therefore, the amount of strong base should be from 1 to about 15 times, preferably from 1 to about 5 times, the equivalent weight of the weak base in the oil.
  • the strong base/strong combustion acid salts thus formed will be immobilized as heterogeneous deposits with the strong base or with the strong base on a substrate if one is used. Thus, deposits which would normally be formed in the piston ring zone are not formed until the soluble salts contact the strong base.
  • the strong base will be located such that it can be easily removed from the lubrication system (e.g., included as part of the oil filter system) .
  • the presence of a strong base also serves to protect the crosslinked dispersant functional group containing composition of this invention from the acids generated by an internal combustion engine.
  • the crosslinked dispersant functional group containing compositions used by this invention are generally weakly basic. Thus when such engine acids are carried to the filter, the crosslinked dispersant functional group containing composition would be neutralized and lose its functionality.
  • the strong base would neutralize the engine acids before they could neutralize the dispersant functional group and hence protect them.
  • any of the foregoing embodiments of this invention can be combined with the removal of carcinogenic components from a lubricating oil.
  • polynuclear aromatic hydrocarbons especially PNA's with at least three aromatic rings
  • PNA's with at least three aromatic rings that are usually present in used lubricating oil can be substantially removed (i.e., reduced by from about 60 to about 90% or more) by passing the oil through a sorbent located within the lubrication system through which the oil must circulate after being used to lubricate the engine.
  • the sorbent may be immobilized with the substrate described above or immobilized separate therefrom.
  • the substrate and sorbent will be part of the engine filter system for filtering oil.
  • the sorbent can be conveniently located on the engine block or near the sump, preferably downstream of the oil as it circulates through the engine; i.e., after the oil has been heated. Most preferably, the sorbent is downstream of the substrate when a substrate is present.
  • Suitable sorbents include activated carbon, attapulgus clay, silica gel, molecular sieves, dolomite clay. alumina, zeolite, or mixtures thereof.
  • Activated carbon is preferred because it is at least partially selective to the removal of polynuclear aromatics containing more than 3 (and preferably 4, 5 and 6) aromatic rings; the PNA's removed are tightly bound to the carbon and will not be leached-out to become free PNA's after disposal; the PNA's removed will not be redissolved in the used lubricating oil; and heavy metals such as lead and chromium will be removed as well.
  • an oil filter could comprise the sorbent capable of combining with polynuclear aromatic hydrocarbons held in pockets of filter paper.
  • the sorbent could be in the form of a solid cylinder as in allowed co-pending patent application 720,968 filed June 25, 1991, which is incorporated herein by reference.
  • This invention may also be combined with any method for removing hydroperoxides from a lubricating oil by contacting the oil with a heterogeneous hydroperoxide decomposer for a period of time sufficient to cause a reduction in the amount of hydroperoxides present in the oil.
  • Hydroperoxides are produced when hydrocarbons in the lubricating oil contact the peroxides formed during the fuel combustion process.
  • hydroperoxides will be present in essentially any lubricating oil used in the lubrication system of essentially any internal combustion engine, including those mentioned above.
  • patents 4,997,546 and 5,112,482 which are incorporated herein by reference, disclose the use of compounds, especially certain molybdenum compounds which decompose hydroperoxides. These include compounds such as MoS 2 , M04S4(ROCS 2 )g and NaOH or mixtures thereof.
  • the compounds of U.S. 4,997,546 and U.S. 5,112,482 function by being placed in a suitable container, such as an oil filter where lubricating oil is pumped over them and in which they decompose hydroperoxides.
  • the hydroperoxide decomposer is immobilized when contacting the oil so as not to pass into the oil.
  • One preferred hydroperoxide decomposer embodiment uses sodium hydroxide as described in allowed U.S.
  • hydroperoxide decomposer when the hydroperoxide decomposer is heterogeneous NaOH, hydroperoxides can be effectively removed from used lubricating oil provided the oil also contains a metal thiophosphate.
  • the NaOH should be immobilized in some manner when contacting the oil, for example in crystalline form or incorporated on a substrate to avoid solids passing into the oil.
  • hydroperoxides are removed from lubricating oil circulating within the lubrication system of an internal combustion engine by contacting the oil with crystalline NaOH immobilized within the lubrication system.
  • the precise amount of hydroperoxide decomposer used can vary broadly, depending upon the amount of hydroperoxide present in the lubricating oil. However, although only an amount effective or sufficient to reduce the hydroperoxide content of the lubricating oil need be used, the amount of decomposer will typically range from about 0.01 to about 2.0 wt.%, although greater amounts could be used. Preferably, from about 0.05 to about 1.0 wt.% (based on weight of the lubricating oil) of the decomposer will be used.
  • the hydroperoxide decomposer should be immobilized in some manner when contacting the oil. For example, it could be immobilized on a substrate. However, a substrate would not be required if the decomposer were in crystalline form.
  • the substrate may (or may not) be within the lubrication system of an engine. Preferably, however, the substrate will be located within the lubrication system, for example on the engine block or near the sump. More preferably, the substrate will be part of the filter system for filtering the engine's lubricating oil, although it could be separate therefrom.
  • Suitable substrates include, but are not limited to, alumina, activated clay, cellulose, cement binder, silica- alumina, and activated carbon. Alumina, cement binder, and activated carbon are preferred substrates, with activated carbon being particularly preferred.
  • the substrate may (but need not) be inert and can be formed into various shapes such as pellets or spheres.
  • the decomposer may be incorporated on or with the substrate by methods known to those skilled in the art.
  • the decomposer can be deposited by using the following technique.
  • the decomposer is dissolved in a volatile solvent.
  • the carbon is then saturated with the decomposer containing solution and the solvent evaporated, leaving the decomposer on the carbon substrate.
  • the concentration of the metal thiophosphate will range from about 0.1 to about 2 wt.%, preferably from about 0.3 to about 1 wt.%, of the lubricating oil.
  • NaOH and metal thiophosphates are commercially available from a number of vendors. As such, their methods of manufacture are well known to those skilled in the art.
  • the chemically active filter media will be or will contain a chemically active ingredient or ingredients, which may be supported on a substrate or unsupported. If supported, suitable substrates include those listed above.
  • the substrate may but need not be inert.
  • a chemically active filter media is a filter media that is or contains an oil insoluble, or substantially oil insoluble, strong base.
  • active filter media is meant a filter media that is inert and does not interact with the lubricating oil except to remove particulates from the oil.
  • the physically active filter media includes the same substrates suitable for use with the chemically active filter media as well as other substrates such as attapulgus clay, dolomite clay, and molecular sieves.
  • a physically active filter media is a media such as activated carbon that can remove polynuclear aromatics (PNA) from used lubricating oil, especially PNA's with at least three aromatic rings.
  • PNA polynuclear aromatics
  • Another example of a physically active filter media is also disclosed in U.S. patent 4,977,871 wherein the filter media is mixed, coated, or impregnated with one or more additives normally present in lubricating oils. These additives are oil soluble such that they will be slowly released into the oil to replenish the additives in the oil as they are depleted during its use of the oil.
  • Suitable inactive filter media may be found in today's conventional engine oil filters and include porous paper (e.g. pleated paper) , glass fibers, spun polymer filament, and the like. The inactive filter media serves to retain and remove solid particles from the oil. The precise amount of active filter media used will vary with the particular function to be performed.
  • lubricating oil is defined to include industrial oils, hydraulic oils and fluids, automatic transmission oil, two cycle oils, gear oils, power transmission fluids, and heat transfer oils that contains polar hydrocarbon sludge or varnish precursors from which sludge is formed.
  • TGA thermal gravimetric analysis
  • test sample of known weight is placed in a DSC 30 Cell (Mettler TA 3000) and continuously heated with an inert reference at a programmed rate under an oxidizing air environment. If the test sample undergoes an exothermic or endothermic reaction or a phase change, the event and magnitude of the heat effects relative to the inert reference are monitored and recorded. More specifically, the temperature at which an exothermic reaction begins due to oxidation by atmospheric oxygen is considered as a measure of the oxidative stability of the test sample. The higher the DSC Break Temperature, the more oxidatively stable the test sample.
  • the oxidation onset temperature is the temperature at which the baseline (on the exothermal heat flow versus temperature plot) intersects with a line tangent to the curve at a point one heat energy threshold above the baseline. At times it is necessary to visually examine the plot to identify the true heat energy threshold for the start of oxidation.
  • a test oil is formed for the evaluation of filter attractants by running a fully formulated non-dispersant passenger car lubricant for 3000 miles is a Ford Taurus for 3,000 miles of commuter operation.
  • the test oil is circulated through a filter assembly in a laboratory rig and evaluated for the formation of sludge. In some cases the filter assembly contains a filter attractant and in some cases it does not.
  • two 10 gram samples of the oil are tested. The first sample is centrifuged prior to a test run at 210°C for 4 hours. The second sample is preheated to 138°C for 16 hours and then the test is run at 210°C for 4 hours.
  • centrifugation The purpose of centrifugation is to remove separated sludge but to leave sludge precursors.
  • the sludge precursors form additional sludge during the SIB test.
  • the supernatant after centrifugation is subjected to heat cycling from about 150°C to room temperature over a period of 4 hours at a frequency of about 2 cycles per minute.
  • a gas containing a mixture of about 0.7 volume percent of S0 2 , 1.4 volume % NO and the balance air is bubbled through the test samples.
  • water vapor is bubbled through the test samples.
  • the liquid is centrifuged in weighed centrifuge tubes and the amount of sludge separated from the supernatant is determined and reported as milligrams of sludge.
  • the polymers are evaluated for dispersant filter performance in a lab filtration rig. Three tests are used for measuring performance. Sludge Inhibition Bench (SIB) for measuring sludge performance. Thermal Gravimetric Analysis (TGA) for measuring soot/ash removal and Differential Scanning Calorimetry (DSC) for measuring antioxidant performance.
  • the test consists of circulating 100 ml of a non-dispersant but otherwise fully formulated lubricant which has been used for 3000 miles in a Ford Taurus test car through a filter containing 0.5 grams of the compound under test for 8 hours.
  • the resulting oils are evaluated in a dispersant SIB bench test and in DSC (oxidation stability) .
  • the oils are also evaluated for Soot/Ash by TGA.
  • the SIB data are obtained for the samples both when not preheated, and also where samples are preheated overnight. The following results are observed and compared to other filter attractants.
  • the reference oil is obtained from a Ford Taurus test car operated for 3,000 miles with the same non-dispersant oil as Polymers A, B and C but with no polymer in the filter. These data show that all of these compounds are effective to remove sludge and varnish precursors.
  • Polymer F Benzoquinone with TETA (triethylene tetramine) amine.
  • Polymer G is evaluated for dispersant filter performance in the lab filtration rig.
  • the test used for measuring performance was FT-IR, Fourier Transform Infrared spectroscopy.
  • a fresh oil fully formulated except that it did not contain dispersant is compared by FT-IR with the same oil after 3,000 miles service in a Ford Taurus in commuter use.
  • the increase in the integrated area of absorbance in the OH stretching region, 3700-3100 cm-1, 34.09 units, is used as a measure of oil oxidation and sludge formation during the 3,000 miles of commuter service.
  • 100 grs. of the 3,000 mile used oil is circulated for 8 hours through a filter containing 0.5 grs. of polymer G. At the end of 8 hours the test oil is compared to the fresh oil.
  • the integrated area of absorbance, 8 hour test oil vs. fresh oil is 10.95 units representing a 68% reduction in oxidation products and sludge in the used oil.
  • the 68% reduction in oxidation products and sludge measured by infrared is similar to the 59% reduction in sludge measured by the SIB test for a repeat preparation of Polymer G designated Polymer H.
  • the hydrochloride is suspended in aqueous NH4OH (approximately 100 ml of 0.1 M aqueous solution of NH 4 OH are used per gram of the hydrochloride) with stirring for 16 hours at room temperature.
  • the pH of the solution is periodically adjusted to ca. 10 (pH paper) by the addition of a small amount of 1 M NH4OH.
  • the suspension is then filtered and the precipitate is washed out with ca. 400 ml of 0.1 M a NH OH followed by five 50 ml of a 1:1 mixture of methanol and 0.2M NaOH.
  • the polymer base is dried under vacuum at room temperature for 48 hours.
  • Example 1 * The same reference oil is used as in Example 1. The lower the result, the better the performance. Under Prodecure 1, the samples are not preheated and the test is run at 210°C for 4 hours. Under Procedure 2, the samples are preheated to 138°C for 16 hours and then the test is run at 210°C for 4 hours. These data show that all of these compounds are effective to remove sludge and varnish precursors.
  • the recovered solid is added to the oven at 90° C and nitrogen purged for 2 hours.
  • the nitrogen purge is replaced with a vacuum line and the product dried overnight at 90° C/0.1 mm Hg overnight.
  • the product yield is 228 g (84 wt% of theoretical) .

Abstract

Procédé, composition et filtre destinés à réduire la présence de précurseurs de boue ou de gomme dans une huile lubrifiante circulant à l'intérieur d'un moteur à combustion interne. L'huile lubrifiante contenant des précurseurs de boue ou de gomme est mise en contact avec des particules discrètes d'un composé pouvant être mouillé par de l'huile et insoluble dans l'huile, présentant un groupe fonctionnel d'anti-oxydants et/ou un groupe fonctionnel de dispersants lesquels sont capables de former un complexe avec des précurseurs de boue ou de gomme. Les composés comprennent de préférence une amine réticulée présentant une fonctionnalité amine éthylenique.
PCT/US1994/004262 1993-04-19 1994-04-19 Procede de reduction des precurseurs de boue et de gomme dans des huiles lubrifiantes WO1994024237A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CA002160778A CA2160778C (fr) 1993-04-19 1994-04-19 Methode pour reduire les quantites de precurseurs de vernis et de boues dans les huiles lubrifiantes
DE69431560T DE69431560T2 (de) 1993-04-19 1994-04-19 Verfahren zur verminderung des gehaltes an vorlauferverbindungen von schlamm undlack in schmierolen
JP6522526A JPH08508773A (ja) 1993-04-19 1994-04-19 潤滑油中のスラッジ及びワニスの先駆体の低減法
EP94914211A EP0703959B1 (fr) 1993-04-19 1994-04-19 Procede de reduction des precurseurs de boue et de gomme dans des huiles lubrifiantes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US4921093A 1993-04-19 1993-04-19
US049,210 1993-04-19

Publications (1)

Publication Number Publication Date
WO1994024237A1 true WO1994024237A1 (fr) 1994-10-27

Family

ID=21958615

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1994/004262 WO1994024237A1 (fr) 1993-04-19 1994-04-19 Procede de reduction des precurseurs de boue et de gomme dans des huiles lubrifiantes

Country Status (5)

Country Link
EP (1) EP0703959B1 (fr)
JP (1) JPH08508773A (fr)
CA (1) CA2160778C (fr)
DE (1) DE69431560T2 (fr)
WO (1) WO1994024237A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6843916B2 (en) 2002-07-16 2005-01-18 The Lubrizol Corporation Slow release lubricant additives gel
US7384896B2 (en) 2002-07-16 2008-06-10 The Lubrizol Corporation Controlled release of additive gel(s) for functional fluids
BE1017381A3 (nl) * 2006-12-06 2008-07-01 Atlas Copco Airpower Nv Werkwijze voor het beschermen van olie tegen oxidatie.
US7510653B2 (en) 2006-08-31 2009-03-31 Cummins Filtration Ip, Inc. Filter assembly with a weak base slow release mechanism
US7534747B2 (en) 2003-06-25 2009-05-19 The Lubrizol Corporation Gels that reduce soot and/or emissions from engines
WO2009138872A1 (fr) * 2008-05-16 2009-11-19 Toyota Jidosha Kabushiki Kaisha Séparateur de brouillard d'huile pour moteur à combustion interne
US8022021B2 (en) 2007-02-05 2011-09-20 The Lubrizol Corporation Low ash controlled release gels
US8109287B2 (en) 2001-08-24 2012-02-07 Cummins Filtration Ip, Inc. Controlled release of additives in fluid systems
US8425772B2 (en) 2006-12-12 2013-04-23 Cummins Filtration Ip, Inc. Filtration device with releasable additive
CN115386417A (zh) * 2022-09-05 2022-11-25 茂名市鹰鹏机电设备有限公司 一种化学结晶脱除废润滑油灰分的方法

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7250126B2 (en) 2004-08-11 2007-07-31 Fleetguard, Inc. Acid-neutralizing filter media
DE102008044306A1 (de) 2008-12-03 2010-06-10 Robert Bosch Gmbh Vorrichtung zur Stabilisierung eines Betriebsfluides für Kraftfahrzeuge
JP2010196658A (ja) * 2009-02-26 2010-09-09 Toyota Motor Corp 内燃機関のオイル劣化抑制装置、オイル劣化抑制用フィルム及びその製造方法
JP5168664B2 (ja) * 2009-03-06 2013-03-21 トヨタ自動車株式会社 内燃機関の潤滑装置
JP5240575B2 (ja) * 2009-04-14 2013-07-17 トヨタ自動車株式会社 内燃機関の潤滑装置
JP5845091B2 (ja) 2010-01-28 2016-01-20 株式会社豊田中央研究所 捕捉対象物質捕捉材、捕捉対象物質捕捉用フィルタ、液状有機化合物収容容器およびエンジンオイル

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2303546A (en) * 1939-08-08 1942-12-01 Herbert H Greger Method of separating impurities from lubricating oils
US2343427A (en) * 1941-02-28 1944-03-07 Purolator Products Inc Filter
US2609931A (en) * 1948-04-17 1952-09-09 Fram Corp Method of filtering
US3305478A (en) * 1964-08-13 1967-02-21 Dow Chemical Co Process for re-refining used lubricating oils
US3523074A (en) * 1968-12-16 1970-08-04 Exxon Research Engineering Co Novel lubricating oil system and oil filter for internal combustion engines
US4636322A (en) * 1985-11-04 1987-01-13 Texaco Inc. Lubricating oil dispersant and viton seal additives
EP0371639A1 (fr) * 1988-11-09 1990-06-06 Exxon Research And Engineering Company Procédé pour réduire la réduction de dépôt sur les pistons dans des moteurs à combustion interne
EP0416908A2 (fr) * 1989-09-07 1991-03-13 Exxon Research And Engineering Company Système de filtre pour régénérer des huiles lubrifiantes
EP0416906A2 (fr) * 1989-09-07 1991-03-13 Exxon Research And Engineering Company Procédé d'enlèvement d'hydropéroxydes des huiles lubrifiantes
US5042617A (en) * 1989-09-07 1991-08-27 Exxon Research & Engineering Company Method of reducing the presence of sludge in lubricating oils
EP0529979A1 (fr) * 1991-08-30 1993-03-03 BP Chemicals Limited Procédé de préparation de polymères réticulés

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2303546A (en) * 1939-08-08 1942-12-01 Herbert H Greger Method of separating impurities from lubricating oils
US2343427A (en) * 1941-02-28 1944-03-07 Purolator Products Inc Filter
US2609931A (en) * 1948-04-17 1952-09-09 Fram Corp Method of filtering
US3305478A (en) * 1964-08-13 1967-02-21 Dow Chemical Co Process for re-refining used lubricating oils
US3523074A (en) * 1968-12-16 1970-08-04 Exxon Research Engineering Co Novel lubricating oil system and oil filter for internal combustion engines
US4636322A (en) * 1985-11-04 1987-01-13 Texaco Inc. Lubricating oil dispersant and viton seal additives
EP0371639A1 (fr) * 1988-11-09 1990-06-06 Exxon Research And Engineering Company Procédé pour réduire la réduction de dépôt sur les pistons dans des moteurs à combustion interne
EP0416908A2 (fr) * 1989-09-07 1991-03-13 Exxon Research And Engineering Company Système de filtre pour régénérer des huiles lubrifiantes
EP0416906A2 (fr) * 1989-09-07 1991-03-13 Exxon Research And Engineering Company Procédé d'enlèvement d'hydropéroxydes des huiles lubrifiantes
US5042617A (en) * 1989-09-07 1991-08-27 Exxon Research & Engineering Company Method of reducing the presence of sludge in lubricating oils
EP0529979A1 (fr) * 1991-08-30 1993-03-03 BP Chemicals Limited Procédé de préparation de polymères réticulés

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8109287B2 (en) 2001-08-24 2012-02-07 Cummins Filtration Ip, Inc. Controlled release of additives in fluid systems
US8076273B2 (en) 2002-07-16 2011-12-13 The Lubrizol Corportion Slow release lubricant additives gel
US7799745B2 (en) 2002-07-16 2010-09-21 The Lubrizol Corporation Slow release lubricant additives gel
US7417012B2 (en) 2002-07-16 2008-08-26 The Lubrizol Corporation Slow release lubricant additives gel
US8299000B2 (en) 2002-07-16 2012-10-30 The Lubrizol Corporation Slow release lubricant additives gel
US7384896B2 (en) 2002-07-16 2008-06-10 The Lubrizol Corporation Controlled release of additive gel(s) for functional fluids
US6843916B2 (en) 2002-07-16 2005-01-18 The Lubrizol Corporation Slow release lubricant additives gel
US7534747B2 (en) 2003-06-25 2009-05-19 The Lubrizol Corporation Gels that reduce soot and/or emissions from engines
US7510653B2 (en) 2006-08-31 2009-03-31 Cummins Filtration Ip, Inc. Filter assembly with a weak base slow release mechanism
BE1017381A3 (nl) * 2006-12-06 2008-07-01 Atlas Copco Airpower Nv Werkwijze voor het beschermen van olie tegen oxidatie.
US8425772B2 (en) 2006-12-12 2013-04-23 Cummins Filtration Ip, Inc. Filtration device with releasable additive
US8022021B2 (en) 2007-02-05 2011-09-20 The Lubrizol Corporation Low ash controlled release gels
WO2009138872A1 (fr) * 2008-05-16 2009-11-19 Toyota Jidosha Kabushiki Kaisha Séparateur de brouillard d'huile pour moteur à combustion interne
US8499750B2 (en) 2008-05-16 2013-08-06 Toyota Jidosha Kabushiki Kaisha Oil mist separator for internal combustion engine
CN115386417A (zh) * 2022-09-05 2022-11-25 茂名市鹰鹏机电设备有限公司 一种化学结晶脱除废润滑油灰分的方法

Also Published As

Publication number Publication date
DE69431560D1 (de) 2002-11-21
EP0703959B1 (fr) 2002-10-16
DE69431560T2 (de) 2003-08-14
CA2160778A1 (fr) 1994-10-27
CA2160778C (fr) 2007-04-17
EP0703959A1 (fr) 1996-04-03
JPH08508773A (ja) 1996-09-17

Similar Documents

Publication Publication Date Title
US5478463A (en) Method of reducing sludge and varnish precursors in lubricating oils
CA2024006C (fr) Methode permettant d'eliminer le cambouis des huiles de graissage
CA2160778C (fr) Methode pour reduire les quantites de precurseurs de vernis et de boues dans les huiles lubrifiantes
US20040266630A1 (en) Novel additive composition that reduces soot and/or emissions from engines
EP0673991A1 (fr) Matière lubrifiante sans cendre
JP4587565B2 (ja) ポリα−オレフィンポリマーを使用する分散剤による磨耗コントロール
EP0649459A1 (fr) Composition de lubrifiant contenant un melange d'agents modifiant le frottement
US7534747B2 (en) Gels that reduce soot and/or emissions from engines
US5112482A (en) Filter for removing hydroperoxides from lubricating oils
US4997546A (en) Method of removing hydroperoxides from lubricating oils
EP1070112A1 (fr) Concentres renfermant des dispersants de haut poids moleculaire et leur preparation
JP5388490B2 (ja) 摩擦安定性が改良されたホウ素含有潤滑油
CA2024005A1 (fr) Methode permettant d'eliminer la suie des huiles de graissage
US5164101A (en) Method for reducing piston deposits
CA2465606C (fr) Methode pour reduire les quantites de precurseurs de vernis et de boues dans les huiles lubrifiantes
EP1831337A1 (fr) Systemes de lubrification
US5209839A (en) Method of removing hydroperoxides from lubricating oils using sodium hydroxide and a metal thiophosphate
EP1068285A1 (fr) Concentres contenant des dispersants de masse moleculaire elevee et leur preparation
EP0550182B1 (fr) Huile lubrifiante contenant un additif anti-usure et anti-oxydant
WO2006022724A1 (fr) Gels réduisant les suies et/ou les émissions de moteurs

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA JP

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2160778

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 1994914211

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1994914211

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 1994914211

Country of ref document: EP