EP1403359A1 - Mélange d'une composition d'huile lubrifiante à faible teneur en cendres et d'un carburant à faible teneur en soufre - Google Patents

Mélange d'une composition d'huile lubrifiante à faible teneur en cendres et d'un carburant à faible teneur en soufre Download PDF

Info

Publication number
EP1403359A1
EP1403359A1 EP20030255015 EP03255015A EP1403359A1 EP 1403359 A1 EP1403359 A1 EP 1403359A1 EP 20030255015 EP20030255015 EP 20030255015 EP 03255015 A EP03255015 A EP 03255015A EP 1403359 A1 EP1403359 A1 EP 1403359A1
Authority
EP
European Patent Office
Prior art keywords
ppm
less
lubricating oil
oil composition
preferably less
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP20030255015
Other languages
German (de)
English (en)
Inventor
Stephen Arrowsmith Arrowsmith
Alisdair James Brown
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Infineum International Ltd
Original Assignee
Infineum International Ltd
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 Infineum International Ltd filed Critical Infineum International Ltd
Priority to EP20030255015 priority Critical patent/EP1403359A1/fr
Publication of EP1403359A1 publication Critical patent/EP1403359A1/fr
Withdrawn legal-status Critical Current

Links

Images

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
    • 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
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • C10M129/54—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring containing hydroxy 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
    • 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
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/103—Carboxylix acids; Neutral salts thereof 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
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy 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
    • 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
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • 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
    • C10N2030/43—Sulfur free or low sulfur 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
    • C10N2030/50—Emission or smoke controlling properties
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • the present invention relates to low-ash lubricating oil compositions for use in, or used in, engines operated by low-sulphur fuels, which oil compositions provide improved lubricant properties, particularly improved lead corrosion protection and improved compatibility with engines equipped with particulate traps.
  • particulate trap which is to be incorporated into all passenger car and heavy duty diesel vehicles designed to comply with the requirements of Euro IV emissions legislation.
  • ash derived from metal-containing additives in the lubricant primarily from metal-containing detergents and antiwear agents, accumulate in the particulate trap. This ash cannot be purged without removing the trap from the engine and cleaning either via washing or blowing the ash from the particulate trap with compressed air. Ash allowed to accumulate in the particulate trap may cause an increase in pressure behind the trap (back pressure).
  • WO 02/18521 The use of reduced amounts of ZDDP, in combination with low sulphur fuels is described in WO 02/18521.
  • the amount of metal-containing antiwear agent, particularly ZDDP can be reduced while maintaining adequate wear performance. While reducing the amount of added ZDDP will reduce the ash content of the lubricant, WO 02/18521 does not suggest the use of lubricants in which ash content is minimized by reducing the amount of other metal-containing additives, particularly metal-containing detergents.
  • Engine combustion generates nitrogen oxide gases (NO x ). Further, when sulphur-containing fuel is burned in the engine, the sulphur is converted to sulphur oxide gases (SO x ).
  • NO x nitrogen oxide gases
  • SO x sulphur oxide gases
  • one of the major by-products of the combustion of a hydrocarbon fuel is water vapor.
  • NO x and SO x gases react with the water vapor mineral acids are formed. A portion of the mineral acids becomes introduced into the lubricants via blow-by causing engine corrosion.
  • EGR exhaust gas recirculation
  • Acids, including mineral acids are neutralized by the action of detergents in the lubricant.
  • NO x gases were the major contributor to acids that cause corrosion in the engine because of the greater proportion of NO x gases compared to other mineral acid forming gases (see Figure 1).
  • the amount of SO x gases was considered a lesser concern since many typical fuels contain only about 400 ppm of sulphur, and reducing the sulphur content to, for example 50 ppm, does not result in a significant reduction in the overall amount of acid in the lubricant. Therefore, it was believed that a reduction in the amount of sulphur in the fuel would not have a significant impact in the amount of detergent needed to neutralize acid in the lubricant.
  • acids derived from fuel sulphur are a major contributor to engine corrosion and the amount of sulphur in the fuel has a greater than expected impact on engine corrosion. Therefore, unexpectedly, the amount of detergent needed to neutralize mineral acids generated during combustion and ameliorate engine corrosion can be reduced dramatically in engines operated by low sulphur fuels.
  • the use of reduced levels of metal-containing detergents allows for the formulation of low ash content lubricants that are more compatible with engines equipped with particulate traps.
  • a lubricating oil composition used in, or for use in, a compression ignited (diesel) internal combustion engine operated with diesel fuel having a sulphur content of less than 50 ppm, preferably less than 30 ppm, more preferably less than 15 ppm, such as less than 10 ppm, said lubricating oil composition comprising a major amount of oil of lubricating viscosity, and a minor amount of at least one metal-containing detergent, wherein said lubricating oil composition has a total ash content of less than 1.0 wt. %, preferably less than 0.8 wt. %, such as less than 0.7 wt. %, more preferably less than 0.6 wt. %, based on the total weight of the lubricating oil composition.
  • the total amount of ash contributed to said lubricating oil composition by said at least one metal-containing detergent is from 0 to less than 0.9 wt. %, preferably less than 0.8 wt. %, more preferably less than 0.7 wt. %, such as less than 0.6 wt. %, based on the total weight of the lubricating oil composition.
  • a lubricating oil composition used in, or for use in, a spark ignited (gasoline) internal combustion engine operated with gasoline having a sulphur content of less than 50 ppm, preferably less than 30 ppm, more preferably less than 15 ppm, such as less than 10 ppm, said lubricating oil composition comprising a major amount of oil of lubricating viscosity, and a minor amount of at least one metal-containing detergent, wherein said lubricating oil composition has a total ash content of less than 0.7 or less than 0.65 %, preferably less than 0.6 wt. %, more preferably less than 0.5 wt. %, such as less 0.4 wt. %, based on the total weight of the lubricating oil composition.
  • the total amount of ash contributed to said lubricating oil composition by said at least one metal-containing detergent is from 0 to less than 0.6 or less than 0.55 wt. %, preferably less than 0.5 wt. %, more preferably less than 0.4 wt. %, such as less than 0.3 wt. %, based on the total weight of the lubricating oil composition.
  • said at least one metal-containing detergent comprises, and preferably consists essentially of, at least one salicylate detergent.
  • a compression ignited (diesel) internal combustion engine operated with diesel fuel having a sulphur content of less than 50 ppm, preferably less than 30 ppm, more preferably less than 15 ppm, such as less than 10 ppm and lubricated with a lubricating oil composition as defined in the first aspect.
  • a spark ignited (gasoline) internal combustion engine operated with gasoline having a sulphur content of less than 50 ppm, preferably less than 30 ppm, more preferably less than 15 ppm, such as less than 10 ppm and lubricated with a lubricating oil composition as defined in the second aspect.
  • a method of operating a compression ignited (diesel) internal combustion engine comprises operating said engine with a fuel having a sulphur content of less than 50 ppm, preferably less than 30 ppm, more preferably less than 15 ppm, such as less than 10 ppm, and lubricating said engine with a lubricating oil composition as defined in the first aspect.
  • a method of operating a spark ignited (gasoline) internal combustion engine comprises operating said engine with a fuel having a sulphur content of less than 50 ppm, preferably less than 30 ppm, more preferably less than 15 ppm, such as less than 10 ppm, and lubricating said engine with a lubricating oil composition as defined in the second aspect.
  • a lubricating oil composition as defined in either the first or second aspect to reduce the amount of particulate ash generated by consumption of metal-containing lubricant additives during operation of a lubricated internal combustion engine operated with a fuel having a sulphur content of less than 50 ppm, preferably less than 30 ppm, more preferably less than 15 ppm, such as less than 10 ppm.
  • a lubricating oil composition as defined in either the first or second aspect to reduce corrosion in an internal combustion engine operated with a fuel having less than 50 ppm of sulphur, preferably less than 30 ppm, more preferably less than 15 ppm, such as less than 10 ppm.
  • a combination of (i) a fuel having less than 50 ppm of sulphur, preferably less than 30 ppm, more preferably less than 15 ppm, such as less than 10 ppm, and (ii) a lubricating oil composition as defined in the first or second aspect, in an internal combustion engine, such as a compression- or spark-ignited engine.
  • the invention is applicable to all internal combustion engines including both spark-ignited (gasoline fueled) and compressionignited (diesel fueled) internal combustion engines.
  • the present invention is particularly applicable to internal combustion engines provided with a particulate trap or an exhaust gas recirculation (EGR) system or both particulate trap and an exhaust gas recirculation (EGR) system.
  • EGR exhaust gas recirculation
  • the exhaust gases and/or combustion air is/are preferably cooled prior to introduction into the engine combustion chamber.
  • the internal combustion engine is a passenger car diesel engine (PCD) or heavy duty diesel (HDD) engine, more particularly a PCD or HDD engine provided with a particulate trap.
  • PCD passenger car diesel engine
  • HDD heavy duty diesel
  • Fuels, whether gasoline or diesel fuel, useful in the practice of the invention have a sulphur content below 50 ppm, preferably below 30 ppm, more preferably below 15 ppm, such as below 10 ppm.
  • the sulphur content of the fuel is at least 5 ppm.
  • the level of sulphur may be determined using various methods including X-ray (ASTM D2622-1) or UV (ASTM D5453-93).
  • Such fuels may comprise saturated, olefinic and aromatic hydrocarbons or mixtures thereof.
  • Such fuels can be derived from straight run streams, thermally or catalytically cracked hydrocarbon feedstocks, hydrocracked petroleum fractions, catalytically reformed hydrocarbons or synthetically produced hydrocarbon mixtures, such as those derived from methane.
  • the sulphur content of fuels containing sulphur can be reduced by known methods, such as, for example, catalytic hydrodesulphurization.
  • oils of lubricating viscosity useful in the practice of the invention may range in viscosity from light distillate mineral oils to heavy lubricating oils such as gasoline engine oils, mineral lubricating oils and heavy duty diesel oils.
  • the viscosity of the oil ranges from about 2 mm 2 /sec (centistokes) to about 40 mm 2 /sec, especially from about 3 mm 2 /sec to about 20 mm 2 /sec, most preferably from about 4 mm 2 /sec to about 10 mm 2 /sec, as measured at 100°C.
  • Natural oils include animal oils and vegetable oils (e.g. castor oil, lard oil); liquid petroleum oils and hydrorefined, solvent-treated or acid-treated mineral oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale also serve as useful base oils.
  • Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g. polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1-hexenes), poly(1-octenes), poly(1-decenes)); alkylbenzenes (e.g. dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes); polyphenyls ( e.g. biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides and derivative, analogs and homologs thereof.
  • polymerized and interpolymerized olefins
  • Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc. constitute another class of known synthetic lubricating oils. These are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, and the alkyl and aryl ethers of polyoxyalkylene polymers ( e.g.
  • 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) with a variety of alcohols (e.g. butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol).
  • 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 dim
  • esters includes 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.
  • Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol esters such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
  • Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysilicone oils and silicate oils comprise another useful class of synthetic lubricants; such oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexyl)silicate, tetra-(p-tert-butyl-phenyl) silicate, hexa-(4-methyl-2-ethylhexyl)disiloxane, poly(methyl)siloxanes and poly(methylphenyl)siloxanes.
  • oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexy
  • Other synthetic lubricating oils include liquid esters of phosphorous-containing acids (e.g. tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.
  • liquid esters of phosphorous-containing acids e.g. tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid
  • polymeric tetrahydrofurans e.g. tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid
  • Unrefined, refined and re-refined oils can be used in lubricants of the present invention.
  • Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
  • a shale oil obtained directly from retorting operations; petroleum oil obtained directly from distillation; or ester oil obtained directly from an esterification and used without further treatment would be an unrefined oil.
  • Refined oils are similar to unrefined oils except that the oil is further treated in one or more purification steps to improve one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration and percolation are known to those skilled in the art.
  • Rerefined oils are obtained by processes similar to those used to provide refined oils but begin with oil that has already been used in service. Such re-refined oils are also known as reclaimed or reprocessed oils and are often subjected to additionally processing using techniques for removing spent additives and oil breakdown products.
  • the oil of lubricating viscosity may comprise a Group I, Group II, Group III, Group IV or Group V base stocks or base oil blends of the aforementioned base stocks.
  • the oil of lubricating viscosity is a Group II, Group III, Group IV or Group V base stock, or a mixture thereof, or a mixture of a Group I base stock and one or more a Group II, Group III, Group IV or Group V base stock.
  • the base stock, or base stock blend preferably has a saturate content of at least 65%, more preferably at least 75%, such as at least 85%. Most preferably, the base stock, or base stock blend, has a saturate content of greater than 90%.
  • the oil or oil blend itself will have a sulphur content of less than 0.5%, preferably less than 0.05%, more preferably less than 0.03%, by weight.
  • the sulphur content of oil or oil blend is preferably zero, more preferably at least 0.005 weight %.
  • the volatility of the oil or oil blend is less than or equal to 30%, preferably less than or equal to 25%, more preferably less than or equal to 20%, most preferably less than or equal 16%.
  • the viscosity index (VI) of the oil or oil blend is at least 85, preferably at least 100, most preferably from about 105 to 140.
  • Base stocks and base oils in this invention are the same as those found in the American Petroleum Institute (API) publication "Engine Oil Licensing and Certification System", Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998. Said publication categorizes base stocks as follows: a) Group I base stocks contain less than 90 percent saturates and/or greater than 0.03 percent sulphur and have a viscosity index between 80 and 120; b) Group II base stocks contain at least 90 percent saturates and no more than 0.03% sulphur and have a viscosity index between 80 and 120; c) Group III base stocks contain at least 90 percent saturates no more than 0.03% sulphur and have a viscosity index between 80 and 120; d) Group IV base stocks are polyalphaolefins (PAO).
  • PAO polyalphaolefins
  • Group V base stocks include all other base stocks not included in Group I, II, III, or IV.
  • Table 1 - Analytical Methods for Base Stock Property Test Method Saturates ASTM D 2007 Viscosity Index ASTM D 2270 Sulphur ASTM D 2622 ASTM D 4294 ASTM D 4927 ASTM D 3120
  • Metal-containing or ash-forming detergents function as both detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life.
  • Detergents generally comprise a polar head with a long hydrophobic tail.
  • the polar head comprises a metal salt of an acidic organic compound.
  • the salts may contain a substantially stoichiometric amount of the metal in which case they are usually described as normal or neutral salts, and would typically have a total base number or TBN (as can be measured by ASTM D2896) of from 0 to 80.
  • TBN total base number
  • a large amount of a metal base may be incorporated by reacting excess metal compound (e.g. an oxide or hydroxide) with an acidic gas (e.g. carbon dioxide).
  • the resulting overbased detergent comprises neutralized detergent as the outer layer of a metal base (e.g. carbonate) micelle.
  • a metal base e.g. carbonate
  • Such overbased detergents may have a TBN of 150 or greater, and typically will have a TBN of from 250 to 450 or more.
  • Detergents that may be used include oil-soluble neutral and overbased sulfonates, phenates, sulphurized phenates, thiophosphonates, salicylates, and naphthenates and other oil-soluble carboxylates of a metal, particularly the alkali or alkaline earth metals, e.g. barium, sodium, potassium, lithium, calcium, and magnesium.
  • a metal particularly the alkali or alkaline earth metals, e.g. barium, sodium, potassium, lithium, calcium, and magnesium.
  • the most commonly used metals are calcium and magnesium, which may both be present in detergents used in a lubricant, and mixtures of calcium and/or magnesium with sodium.
  • Particularly convenient metal detergents are neutral and overbased calcium sulfonates having TBN of from 20 to 450, neutral and overbased calcium phenates and sulphurized phenates having TBN of from 50 to 450 and neutral and overbased magnesium or calcium salicylates having a TBN of from 20 to 450. Combinations of detergents, whether overbased or neutral or both, may be used.
  • Sulfonates may be prepared from sulfonic acids which are typically obtained by the sulfonation of alkyl substituted aromatic hydrocarbons such as those obtained from the fractionation of petroleum or by the alkylation of aromatic hydrocarbons. Examples included those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl or their halogen derivatives such as chlorobenzene, chlorotoluene and chloronaphthalene.
  • the alkylation may be carried out in the presence of a catalyst with alkylating agents having from about 3 to more than 70 carbon atoms.
  • the alkylaryl sulfonates usually contain from about 9 to about 80 or more carbon atoms, preferably from about 16 to about 60 carbon atoms per alkyl substituted aromatic moiety.
  • the oil soluble sulfonates or alkaryl sulfonic acids may be neutralized with oxides, hydroxides, alkoxides, carbonates, carboxylate, sulfides, hydrosulfides, nitrates, borates and ethers of the metal.
  • the amount of metal compound is chosen having regard to the desired TBN of the final product but typically ranges from about 100 to 220 wt. % (preferably at least 125 wt. %) of that stoichiometrically required.
  • Metal salts of phenols and sulphurized phenols are prepared by reaction with an appropriate metal compound such as an oxide or hydroxide and neutral or overbased products may be obtained by methods well known in the art.
  • Sulphurized phenols may be prepared by reacting a phenol with sulphur or a sulphur containing compound such as hydrogen sulfide, sulphur monohalide or sulphur dihalide, to form products which are generally mixtures of compounds in which 2 or more phenols are bridged by sulphur containing bridges.
  • Alkylene bridged phenols are also suitable for use as metal phenates.
  • Carboxylate detergents e.g. salicylates
  • an aromatic carboxylic acid can contain heteroatoms, such as nitrogen and oxygen.
  • the moiety contains only carbon atoms; more preferably the moiety contains six or more carbon atoms; for example benzene is a preferred moiety.
  • the aromatic carboxylic acid may contain one or more aromatic moieties, such as one or more benzene rings, either fused or connected via alkylene bridges.
  • the carboxylic moiety may be attached directly or indirectly to the aromatic moiety.
  • the carboxylic acid group is attached directly to a carbon atom on the aromatic moiety, such as a carbon atom on the benzene ring. More preferably, the aromatic moiety also contains a second functional group, such as a hydroxy group or a sulfonate group, which can be attached directly or indirectly to a carbon atom on the aromatic moiety.
  • a second functional group such as a hydroxy group or a sulfonate group
  • aromatic carboxylic acids are salicylic acids and sulphurized derivatives thereof, such as hydrocarbyl substituted salicylic acid and derivatives thereof.
  • Processes for sulphurizing, for example a hydrocarbylsubstituted salicylic acid are known to those skilled in the art.
  • Salicylic acids are typically prepared by carboxylation, for example, by the Kolbe - Schmitt process, of phenoxides, and in that case, will generally be obtained, normally in a diluent, in admixture with uncarboxylated phenol.
  • Preferred substituents in oil - soluble salicylic acids are alkyl substituents.
  • the alkyl groups advantageously contain 5 to 100, preferably 9 to 30, especially 14 to 20, carbon atoms. Where there is more than one alkyl group, the average number of carbon atoms in all of the alkyl groups is preferably at least 9 to ensure adequate oil solubility.
  • Detergents generally useful in the formulation of lubricating oil compositions also include "hybrid" detergents formed with mixed surfactant systems, e.g. phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, sulfonates/phenates/salicylates, as described, for example, in pending U.S. Patent Application Nos. 09/180,435 and 09/180,436 and U.S. Patent Nos. 6,153,565 and 6,281,179 and EP 0 750 659.
  • the metal-containing detergent present in the lubricating oil compositions of the invention, comprises, preferably consists essentially of, at least one salicylate detergent. It is preferred that the detergent consists essentially of a calcium salicylate having a TBN of less than 80 and another calcium salicylate having a TBN greater than 150.
  • an amount of detergent contributing from 0 to less than 0.9 wt. %, preferably less than 0.8 wt. %, more preferably less than 0.7 wt. %, such as less than 0.6 wt % of ash to the lubricating oil composition is preferably sufficient to provide detergency and acid neutralization; in an embodiment the amount is zero ash, i.e. no metal-containing detergents, preferably at least 0.1 wt% of ash is derived from the metal containing detergent(s).
  • an amount of detergent contributing from 0 to less than 0.6 or less than 0.55 wt. %, preferably less than 0.5 wt. %, more preferably less than 0.4 wt. %, such as less than 0.3 wt %, of ash to the lubricating oil composition is preferably sufficient to provide detergency and acid neutralization; in an embodiment the amount is zero ash, i.e. no metal-containing detergents, preferably at least 0.1 wt% of ash is derived from the metal containing detergent(s).
  • Ash content expressed as "sulfated ash" or "SASH" can be determined by the methods of ASTM D874.
  • a detergent or other additive to a lubricating oil, or additive concentrate, in a diluent, such that only a portion of the added weight represents an active ingredient (A.I.).
  • detergent may be added together with an equal weight of diluent in which case the "additive" is 50% A.I. detergent.
  • weight percent when applied to a detergent or other additive refers to the weight of active ingredient.
  • the use of reduced amounts of metal-containing detergents allows for the formulation of lower ash content lubricating oil compositions.
  • the total ash content of the lubricating oil composition of the present invention is less than 0.9 wt. %, preferably less than 0.8 wt. %, such as less than 0.7 wt. %, more preferably less than 0.6 wt. %, such as less than 0.5 wt. % for lubricating oil formulated for diesel engines.
  • the lubricating oil formulated for diesel engines has zero ash, i.e. no metal-containing additives, more preferably at least 0.1 weight t%, based on the weight of the lubricating oil composition.
  • the total ash content of the lubricating oil composition of the present invention is preferably less than 0.65 wt. %, preferably less than 0.6 wt. %, such as less than 0.5 wt. %, such as less than 0.4 wt. %, based on the total weight of the lubricating oil composition.
  • the lubricating oil formulated for gasoline engines has zero ash, i.e. no metal-containing additives, more preferably at least 0.1 weight t%, based on the weight of the lubricating oil composition.
  • Metal-containing antioxidant and/or antiwear agents such as dihydrocarbyl dithiophosphate metal salts.
  • the metal may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper.
  • the zinc salts are conventionally used in lubricating oil in amounts of 0.1 to 10, preferably 0.2 to 2 wt. %, based upon the total weight of the lubricating oil composition.
  • DDPA dihydrocarbyl dithiophosphoric acid
  • a dithiophosphoric acid can be made by reacting a mixture of primary and secondary alcohols.
  • multiple dithiophosphoric acids can be prepared where the hydrocarbyl groups on one are entirely secondary in character and the hydrocarbyl groups on the others are entirely primary in character.
  • any basic or neutral zinc compound could be used but the oxides, hydroxides and carbonates are most generally employed. Commercial additives frequently contain an excess of zinc due to the use of an excess of the basic zinc compound in the neutralization reaction.
  • the preferred zinc dihydrocarbyl dithiophosphates are oil soluble salts of dihydrocarbyl dithiophosphoric acids and may be represented by the following formula: wherein R and R' may be the same or different hydrocarbyl radicals containing from 1 to 18, preferably 2 to 12, carbon atoms and including radicals such as alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic radicals. Particularly preferred as R and R' groups are alkyl groups of 2 to 8 carbon atoms.
  • the radicals may, for example, be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl.
  • the total number of carbon atoms (i.e. R and R') in the dithiophosphoric acid will generally be about 5 or greater.
  • the zinc dihydrocarbyl dithiophosphate can therefore comprise zinc dialkyl dithiophosphates.
  • the amount of dihydrocarbyl dithiophosphate metal salt is reduced concurrent with the amount of metal-containing detergent such that the dihydrocarbyl dithiophosphate metal salt and other metal-containing additives introduces no more than 0.1 wt. % to about 0.15 wt. % of ash into the lubricating oil composition.
  • the present invention may be particularly useful when the lubricant phosphorus level is from 0 to about 0.12 wt. %, preferably from about 0.03 to about 0.10 wt. %. More preferably, the phosphorous level of the lubricating oil composition will be less than about 0.08 wt. %, such as from about 0.05 to about 0.08 wt. %, as determined by the method of ASTM D5185.
  • lubricating oil compositions of the present invention contain no more than 0.5 wt. %, preferably no more than 0.3 wt. %, most preferably no more than 0.2 wt. % of sulphur, based on the total weight of the lubricating oil composition.
  • the lubricating oil composition contains at least 0.05, such as at least 0.1, wt % of sulphur, as determined by the method of ASTM D5185.
  • Sulphur is contributed both by the base oil and certain lubricant additives.
  • the use of sulphur-containing additives should be minimized or avoided where possible.
  • a reduction in the amount of ZDDP to reduce phosphorus content will also reduce the sulphur content of the lubricating oil composition.
  • reduced sulphur requirements favors the use of salicylate detergents, which are sulphur-free, over phenate and sulfonate detergents.
  • Additional additives may be incorporated into the compositions of the invention to enable particular performance requirements to be met.
  • additives which may be included in the lubricating oil compositions of the present invention are ashless dispersants, metal rust inhibitors, viscosity index improvers, corrosion inhibitors, oxidation inhibitors, ashless friction modifiers, anti-foaming agents, ashless anti-wear agents and pour point depressants, some of which are described below. These additives, where ashless (metal-free) do not bear on the present invention. Where other metal-containing additives are used, e.g. organo-molybdenum antioxidant/antiwear agents, it is preferable to control the amount thereof and use, where possible, alternate, metal-free additives.
  • the ashless dispersant comprises an oil soluble polymeric hydrocarbon backbone having functional groups that are capable of associating with particles to be dispersed.
  • the dispersants comprise amine, alcohol, amide, or ester polar moieties attached to the polymer backbone often via a bridging group.
  • the ashless dispersant may be, for example, selected from oil soluble salts, esters, amino-esters, amides, imides, and oxazolines of long chain hydrocarbon substituted mono and dicarboxylic acids or their anhydrides; thiocarboxylate derivatives of long chain hydrocarbons; long chain aliphatic hydrocarbons having a polyamine attached directly thereto; and Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine.
  • Rust inhibitors selected from the group consisting of nonionic polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols, and anionic alkyl sulfonic acids may be used.
  • Copper and lead bearing corrosion inhibitors may be used, but are typically not required with the formulation of the present invention.
  • such compounds are the thiadiazole polysulfides containing from 5 to 50 carbon atoms, their derivatives and polymers thereof.
  • Derivatives of 1,3,4 thiadiazoles such as those described in U.S. Patent Nos. 2,719,125; 2,719,126; and 3,087,932; are typical.
  • Other similar materials are described in U.S. Patent Nos. 3,821,236; 3,904,537; 4,097,387; 4,107,059; 4,136,043; 4,188,299; and 4,193,882.
  • additives are the thio and polythio sulfenamides of thiadiazoles such as those described in UK Patent Specification No. 1,560,830. Benzotriazoles derivatives also fall within this class of additives. When these compounds are included in the lubricating composition, they are preferably present in an amount not exceeding 0.2 wt. % active ingredient.
  • Oxidation inhibitors or antioxidants reduce the tendency of base stocks to deteriorate in service which deterioration can be evidenced by the products of oxidation such as sludge and varnish-like deposits on the metal surfaces and by viscosity growth.
  • oxidation inhibitors include hindered phenols, alkaline earth metal salts of alkylphenolthioesters having preferably C 5 to C 12 alkyl side chains, calcium nonylphenol sulfide, ashless oil soluble phenates and sulphurized phenates, phosphosulphurized or sulphurized hydrocarbons, alkyl substituted diphenylamine, alkyl substituted phenyl and naphthylamines, phosphorus esters, metal thiocarbamates, ashless thiocarbamates and oil soluble copper compounds as described in U.S. 4,867,890. Most preferred are the alkyl-substituted diphenylamines.
  • pour point depressants otherwise known as lube oil flow improvers, lower the minimum temperature at which the fluid will flow or can be poured.
  • Such additives are well known.
  • Typical of additives that improve the low temperature fluidity of the fluid are C 8 to C 18 dialkyl fumarate/vinyl acetate copolymers, polyalkylmethacrylates and the like.
  • Foam control can be provided by many compounds including an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane.
  • a small amount of a demulsifying component may be used.
  • a particularly suitable demulsifying component is described in EP 330,522. It is obtained by reacting an alkylene oxide with an adduct obtained by reacting a bis-epoxide with a polyhydric alcohol.
  • the demulsifier should be used at a level not exceeding 0.1 mass % active ingredient.
  • a treat rate of 0.001 to 0.05 mass % active ingredient is conventional.
  • the viscosity modifier functions to impart high and low temperature operability to lubricating oil.
  • Suitable viscosity modifiers are polyisobutylene, copolymers of ethylene and propylene and higher alpha-olefins, polymethacrylates, polyalkylmethacrylates, methacrylate copolymers, copolymers of an unsaturated dicarboxylic acid and a vinyl compound, inter polymers of styrene and acrylic esters, and partially hydrogenated copolymers of styrene/isoprene, styrene/butadiene, and isoprene/butadiene, as well as the partially hydrogenated homopolymers of butadiene and isoprene and isoprene/divinylbenzene.
  • additives can provide a multiplicity of effects; thus for example, a single additive may act as a dispersant-oxidation inhibitor.
  • Multifunctional viscosity modifiers that also function as dispersants are also known. The use of multifunctional additives is well known and does not require further elaboration.
  • each additive is typically blended into the base oil in an amount that enables the additive to provide its desired function.
  • Representative effective amounts of such additives excluding metal detergents and metal dihydrocarbyl dithiophates, which are discussed above, when used in crankcase lubricants, are listed below. All the values listed are stated as mass percent active ingredient.
  • the Noack volatility of the fully formulated lubricating oil composition (oil of lubricating viscosity plus all additives) will be no greater than 15, such as no greater than 13, preferably no greater than 10, such as no greater than 8 wt. %, as measured by ASTM 5880.
  • the lubricating oil composition of the present invention is a multigrade lubricating oil composition in the form of an SAE 15W-X, SAE 10W-X, SAE 5W-X or 0W-X composition, wherein X represents any one of 20, 30 and 40.
  • the oil composition is in the form of an SAE 5W-X or 0W-X when used in a gasoline engine, and the oil composition is in the form of an SAE 15W-X or 10W-X when used in a diesel engine.
  • X represents either 30 or 40, especially 30.
  • the properties of multigrades are defined in the Society of Automotive Engineers document SAE J300.
  • additive concentrates comprising additives (concentrates sometimes being referred to as additive packages) whereby several additives can be added simultaneously to the oil to form the lubricating oil composition.
  • the final composition may employ 5 to 25 mass %, preferably 5 to 18 mass %, typically 10 to 15 mass % of the concentrate (based on active ingredient), the remainder being oil of lubricating viscosity.
  • hydrocarbyl as used means that the group concerned is primarily composed of hydrogen and carbon atoms and is bonded to the remainder of the molecule via a carbon atom, but does not exclude the presence of other atoms or groups in a proportion insufficient to detract from the substantially hydrocarbon characteristics of the group.
  • oil-soluble or “oil-dispersible” does not mean that the compounds are soluble, dissolvable, miscible or capable of being suspended in the oil in all proportions. They do mean, however, that the compounds are, for instance, soluble or stable dispersible in the oil to an extent sufficient to exert their intended effect in the environment in which the composition is employed. Moreover, the additional incorporation of other additives such as those described above may affect the solubility or dispersibility of the compounds.
  • major amount means in excess of 50 mass % of the composition.
  • minor amount means less than 50 mass % of the composition.
  • Lubricant comprising conventional additives, metal-containing detergents and a ZDDP component were prepared by methods known in the art.
  • Table 3 provides the characteristics of the lubricants used in the Mack T10 engine test. The lubricants in Table 3 were blended to SAE 15W-40 viscometric grade.
  • the Mack T10 engine test developed for the API CI-4 category was used to examine the bearing lead corrosion, ring and liner wear performance of reduced ash lubricants also containing reduced levels of phosphorus and sulphur.
  • the standard Mack T10 test method incorporating EGR was used, however the tests were run on a non-automated stand.
  • the fuel sulphur level was varied during the experiments from 400 ppm to 15 ppm. All rated parameters were reported in the normal manner with the exception that an overall merit was not established.
  • TBN depletion and TAN total acid number
  • Oils A and B are in fact back-to-back runs of the same lubricant tested using high (400 ppm) and low (15 ppm) sulphur fuel, respectively.
  • the TBN depletion profile when testing with 400 ppm sulphur fuel is typical of a PC-9 oil.
  • TBN and TAN commonly cross between 150-200 hours. Approximately fifty to seventy five hours after the cross-over point, lead corrosion begins to increase significantly. In contrast, when 15 ppm sulphur fuel is used, TBN and TAN do not cross for the entirety of the 300 hour test.
  • Oils C and D compare the performance of phenate/sulphonate detergents with salicylate based detergents in typical PC-9 lubricating oil formulations.
  • the oils were matched for ZDDP, TBN and soap content.
  • the sulphur content of the salicylate formulation (Oil D) is lower than that of the phenate/sulphonate formulation (Oil C) as the salicylate detergent is sulphur free.
  • Both chemistry types provide passing performance, however, the data suggest that lead corrosion performance is superior for the salicylate chemistry.
  • Figure 3 illustrates the lead corrosion profile with test duration for the two test oils. The technical justification for this performance difference can be found by comparing the TBN depletion and TAN increase profiles of the two lubricants. Such a comparison is made in Figure 4.
  • TBN depletion for the salicylate oil is markedly reduced in comparison to that of the phenate/sulphonate oil.
  • a possible explanation for this reduced TBN depletion is that the salicylate oil neutralises acid present less effectively. However, if this were the case, a more rapid increase in TAN would be expected together with inferior corrosion performance. In contrast, the TAN increase for the salicylate oil is comparable to that of the phenate/sulphonate oil.
  • the superior performance of salicylate detergent allows for the formulation of lower ash lubricating oil compositions.
  • the performance of the detergent in the low ash lubricating oil compositions of the present invention was determined in passenger car diesel engines operated with both high (400 and 3000 ppm) and low (10 ppm) sulphur fuels using an OM 602A engine test (CEC L-051-A-9A).
  • lubricating oil compositions of the present invention were evaluated in passenger car diesel engines operated with low (10 ppm) and high (400 ppm and 3000 ppm) sulphur diesel fuels. All the tested compositions (Oils F to G) were SAE 5W-30 grade and contained comparable additives including identical salicylate detergents. The characteristics of the lubricating oil compositions and fuels used, and the results obtained, are set forth in Table 5.
  • compositions described as "comprising" a plurality of defined components are to be construed as including compositions formed by admixing the defined plurality of defined components.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
EP20030255015 2002-09-13 2003-08-13 Mélange d'une composition d'huile lubrifiante à faible teneur en cendres et d'un carburant à faible teneur en soufre Withdrawn EP1403359A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP20030255015 EP1403359A1 (fr) 2002-09-13 2003-08-13 Mélange d'une composition d'huile lubrifiante à faible teneur en cendres et d'un carburant à faible teneur en soufre

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP02256354 2002-09-13
EP02256354 2002-09-13
EP20030255015 EP1403359A1 (fr) 2002-09-13 2003-08-13 Mélange d'une composition d'huile lubrifiante à faible teneur en cendres et d'un carburant à faible teneur en soufre

Publications (1)

Publication Number Publication Date
EP1403359A1 true EP1403359A1 (fr) 2004-03-31

Family

ID=31979851

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20030255015 Withdrawn EP1403359A1 (fr) 2002-09-13 2003-08-13 Mélange d'une composition d'huile lubrifiante à faible teneur en cendres et d'un carburant à faible teneur en soufre

Country Status (1)

Country Link
EP (1) EP1403359A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1884557A1 (fr) 2006-07-20 2008-02-06 Infineum International Limited Composition d'huile lubrifiante
EP2049631A2 (fr) * 2006-08-09 2009-04-22 Chevron Oronite Company LLC Composition d'huile lubrifiante de faible teneur en phosphore limitant la corrosion du plomb

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5672570A (en) * 1993-08-11 1997-09-30 Idemitsu Kosan Co., Ltd. Lubricating oil composition for diesel engine and method for lubrication of diesel engine using same
GB2350865A (en) * 1999-06-09 2000-12-13 Caterpillar Inc Exhaust gas recirculation (EGR) system for turbocharged i.c. engines, with cooling of EGR gases
WO2000079117A1 (fr) * 1999-06-23 2000-12-28 Caterpillar Inc. Systeme de recirculation de gaz d'echappement
EP1104800A2 (fr) * 1999-12-02 2001-06-06 Oronite Japan Limited Composition d'huile lubrificante pour moteurs à gaz
EP1167497A2 (fr) * 2000-06-02 2002-01-02 Chevron Oronite Japan Limited Composition d'huile lubrifiante pour moteurs diesel
WO2002018521A2 (fr) * 2000-08-29 2002-03-07 Exxonmobil Research And Engineering Company Composition d'huile de graissage a faible teneur en phosphore
WO2002048293A1 (fr) * 2000-12-12 2002-06-20 Ethyl Corporation Compositions combustibles a tres faible teneur en soufre contenant des additifs organometalliques
US20020098991A1 (en) * 2000-10-05 2002-07-25 Adrian Dunn Lubricating oil composition

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5672570A (en) * 1993-08-11 1997-09-30 Idemitsu Kosan Co., Ltd. Lubricating oil composition for diesel engine and method for lubrication of diesel engine using same
GB2350865A (en) * 1999-06-09 2000-12-13 Caterpillar Inc Exhaust gas recirculation (EGR) system for turbocharged i.c. engines, with cooling of EGR gases
WO2000079117A1 (fr) * 1999-06-23 2000-12-28 Caterpillar Inc. Systeme de recirculation de gaz d'echappement
EP1104800A2 (fr) * 1999-12-02 2001-06-06 Oronite Japan Limited Composition d'huile lubrificante pour moteurs à gaz
EP1167497A2 (fr) * 2000-06-02 2002-01-02 Chevron Oronite Japan Limited Composition d'huile lubrifiante pour moteurs diesel
WO2002018521A2 (fr) * 2000-08-29 2002-03-07 Exxonmobil Research And Engineering Company Composition d'huile de graissage a faible teneur en phosphore
US20020098991A1 (en) * 2000-10-05 2002-07-25 Adrian Dunn Lubricating oil composition
WO2002048293A1 (fr) * 2000-12-12 2002-06-20 Ethyl Corporation Compositions combustibles a tres faible teneur en soufre contenant des additifs organometalliques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Erläuterung zum Memorandum der BRD zur Fortschreibung der EU-Kraftstoffrichtlinie bzgl. des Schwefelgehaltes von Kraftstoffen", BMU, 22 August 2001 (2001-08-22), pages 1 - 4, XP002227732, Retrieved from the Internet <URL:www.bmu.de/sachthemen/luft/erklaerung-memorandum.htm> [retrieved on 20030116] *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1884557A1 (fr) 2006-07-20 2008-02-06 Infineum International Limited Composition d'huile lubrifiante
EP2049631A2 (fr) * 2006-08-09 2009-04-22 Chevron Oronite Company LLC Composition d'huile lubrifiante de faible teneur en phosphore limitant la corrosion du plomb
EP2049631A4 (fr) * 2006-08-09 2011-09-14 Chevron Oronite Co Composition d'huile lubrifiante de faible teneur en phosphore limitant la corrosion du plomb

Similar Documents

Publication Publication Date Title
US20040127371A1 (en) Combination of a low ash lubricating oil composition and low sulfur fuel
CA2551594C (fr) Compositions d&#39;huiles lubrifiantes pour moteurs diesels a recirculation des gaz d&#39;echappement
US9347019B2 (en) Lubricating oil composition
CA2572354C (fr) Condensats de phenol a utiliser comme inhibiteur de rouille dans les compositions d&#39;huiles lubrifiantes
EP1942177A2 (fr) Huile de lubrification destinée à améliorer la propreté de piston
JP5330641B2 (ja) 潤滑油組成物
JP5291284B2 (ja) 潤滑油組成物
JP6559974B2 (ja) 潤滑油組成物
US8759262B2 (en) Lubricating oil compositions
CA2749634C (fr) Moteurs diesel a recirculation des gaz d&#39;echappement et compositions d&#39;huiles lubrifiantes connexes
CA2799378A1 (fr) Methode de reduction du taux d&#39;alcanilite d&#39;une composition d&#39;huile lubrifiante dans un moteur
EP1724330A1 (fr) Utilisation de compositions d&#39;huile librifiante pour réduire l&#39;usure dans le moteur d&#39;automobiles equipés d&#39;une tringlerie tournante
EP2428550B1 (fr) Composition d&#39;huile lubrifiante
EP1403359A1 (fr) Mélange d&#39;une composition d&#39;huile lubrifiante à faible teneur en cendres et d&#39;un carburant à faible teneur en soufre
EP1798278A1 (fr) Composition d&#39;huile lubrifiante
EP1803793B1 (fr) Composiitons d&#39;huile lubrifiante
EP1724329B1 (fr) Combinaison de détergents métalliques dans des compositions d&#39;huiles lubrifiantes
EP2690165B1 (fr) Utilisation d&#39;un détergent de salicylate de magnésium dans une composition d&#39;huile lubrifiante
EP3470499B1 (fr) Utilisation des détergents dans les huiles lubrifiantes de moteur à combustion interne

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20030813

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

AKX Designation fees paid

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20060207