EP2735603B1 - Lubrification de moteur marin - Google Patents

Lubrification de moteur marin Download PDF

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Publication number
EP2735603B1
EP2735603B1 EP13188944.6A EP13188944A EP2735603B1 EP 2735603 B1 EP2735603 B1 EP 2735603B1 EP 13188944 A EP13188944 A EP 13188944A EP 2735603 B1 EP2735603 B1 EP 2735603B1
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EP
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Prior art keywords
oil
basestock
lubricating oil
composition
lubricating
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EP13188944.6A
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German (de)
English (en)
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EP2735603A1 (fr
Inventor
James Dodd
Joshua Bradley-Shaw
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Infineum International Ltd
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Infineum International Ltd
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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
    • 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
    • C10M129/68—Esters
    • C10M129/72—Esters of polycarboxylic acids
    • 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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/045—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/108—Residual fractions, e.g. bright stocks
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms 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
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/127—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids polycarboxylic
    • 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
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • 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
    • C10M2207/28—Esters
    • C10M2207/2805—Esters 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
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/78—Fuel contamination
    • 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

Definitions

  • This invention relates to a trunk piston marine engine lubricating composition for a medium-speed four-stroke compression-ignited (diesel) marine engine and lubrication of such an engine.
  • Heavy Fuel Oil is the heaviest fraction of petroleum distillate and comprises a complex mixture of molecules including up to 15% of asphaltenes, defined as the fraction of petroleum distillate that is insoluble in an excess of aliphatic hydrocarbon (e.g. heptane) but that is soluble in aromatic solvents (e.g. toluene). Asphaltenes can enter the engine lubricant as contaminants either via the cylinder or the fuel pumps and injectors, and asphaltene precipitation can then occur, manifested in 'black paint' or 'black sludge' in the engine.
  • asphaltenes can enter the engine lubricant as contaminants either via the cylinder or the fuel pumps and injectors, and asphaltene precipitation can then occur, manifested in 'black paint' or 'black sludge' in the engine.
  • trunk piston engine oils 'TPEO's
  • TPEO's using Group 1 basestocks may have the ability to solubilise asphaltenes.
  • TPEO's using high saturate basestocks e.g. Group II or III
  • WO 2010/115594 (“594") and WO 2010/115595 (“595") describe the use, in trunk piston marine engine lubricating oil compositions that contain 50 mass % or more of a Group II basestock, of respective minor amounts of a calcium salicylate detergent and of a polyalkenyl-substituted carboxylic and anhydride.
  • the data in “594" and "595" show that the combination gives rise to improved asphaltene dispersancy.
  • a problem in the art is to improve still further the asphaltene dispersancy performance of TPEO's that employ high saturate basestocks.
  • the invention meets the above problem by employing an anhydride and an ester in a TPEO: a synergistic effect is observed as demonstrated in the data herein.
  • a first aspect of the invention is a trunk piston marine engine lubricating oil composition for improving asphaltene handling in use thereof in operation of the engine when fuelled by a heavy fuel oil, which composition comprises or is made by admixing
  • a second aspect of the invention is a method of operating a trunk piston medium-speed compression-ignited marine engine comprising
  • a third aspect of the invention is a method of dispersing asphaltenes in a trunk piston marine lubricating oil composition during its lubrication of surfaces of the combustion chamber of a medium-speed compression-ignited marine engine and operation of the engine, which method comprises:
  • a fourth aspect of the invention is the use of detergent (B) in combination with component (C) as defined in and in the amounts stated in the first aspect of the invention in a trunk piston marine lubricating oil composition for a medium-speed compression-ignited marine engine, which composition comprises an oil of lubricating viscosity (A) in a major amount as defined in the first aspect of the invention, to provide comparable or improved asphaltene handling during operation of the engine, fuelled by a heavy fuel oil, and its lubrication by the composition, in comparison with that of a comparable oil where the basestock is a Group I basestock.
  • organic ester basestocks that include but are not limited to monoesters , diesters and polyolesters, and also polymer esters. They are generally considered to be Group V basestocks and are typically derived from animal or vegetable sources. Naturally-occurring organic esters can be found in animal fats or in vegetable oils. Organic esters can be synthesised by reacting organic acids with alcohols.
  • Monesters may be prepared by reacting monohydric alcohols with monobasic fatty acids to create a molecule with a single ester linkage and linear or branched alkyl groups.
  • Diesters may be prepared by reacting monohydric alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol) with dibasic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) to create a molecule which may be linear, branched or aromatic with two ester groups.
  • monohydric alcohols e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol
  • 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.
  • Polyol esters may be prepared by esterifying one or more polyols such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol with one or more organic acids such as C 5 to C 12 monocarboxylic acids. See, for example, US-A-6,462,001 .
  • polyol esters include trimethylolpropane (TMP) esters.
  • Tricarboxylic acid esters are also preferred.
  • the tricarboxylic acid ester is preferably a benzene tricarboxylic acid.
  • a preferred benzene tricarboxylic acid ester is 1,2,4-benzenetricarboxylic acid having alkyl chain lengths ranging from 5 to 10, preferably from 7 to 9.
  • a preferred 1,2,4-benzenetricarboxylic acid is trioctyl trimellitate.
  • ester basestocks for use in the present invention are those having a kinematic viscosity of 2 to 10 mm 2 s -1 at 100°C or those having a kinematic viscosity of greater than 10 to 100 mm 2 s -1 at 100°C.
  • suitable polyol ester is Priolube (Registered Trade Mark) 3970, which is an ester of a neopentyl polyol, suitably TMP, with at least one aliphatic, saturated monocarboxylic acid and having 6 to 12 carbon atoms and a kinematic viscosity of 4.4 mm 2 s -1 at 100°C.
  • the ester basestock may be present in an amount in the range of 2 to 85, preferably 5 to 50, more preferably 8 to 40 mass %.
  • viscosity may range in viscosity from light distillate mineral oil to heavy lubricating oil. Generally, the viscosity of the oil ranges from 2 to 40 mm 2 s -1 , 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)); alkybenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulphides and derivative, analogues and homologues thereof.
  • 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; and petroleum oil obtained directly from distillation are unrefined oils.
  • 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.
  • Re-refined 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 additional processing using techniques for removing spent additives and oil breakdown products.
  • the basestocks (A2) embraces Group II, Group III and Group IV basestocks and also basestocks derived from hydrocarbons synthesised by the Fischer-Tropsch process.
  • synthesis gas containing carbon monoxide and hydrogen or 'syngas'
  • hydrocarbons typically require further processing in order to be useful as a base oil.
  • they may, by methods known in the art, be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed.
  • the syngas may, for example, be made from gas such as natural gas or other gaseous hydrocarbons by steam reforming, when the basestock may be referred to as gas-to-liquid (“GTL”) base oil; or from gasification of biomass, when the basestock may be referred to as biomass-to-liquid (“BTL” or “BMTL”) base oil; or from gasification of coal, when the basestock may be referred to as coal-to-liquid (“CTL”) base oil.
  • GTL gas-to-liquid
  • BTL biomass-to-liquid
  • CTL coal-to-liquid
  • the basestock (A2) when used in this invention, contains 50 mass % or more of the defined basestock or a mixture thereof. Preferably, it contains 60, such as 70, 80 or 90, mass % or more of the defined basestock or a mixture thereof. (A2) may comprise substantially all the defined basestock or a mixture thereof.
  • a metal detergent is an additive based on so-called metal "soaps", that is metal salts of acidic organic compounds, sometimes referred to as surfactants. They generally comprise a polar head with a long hydrophobic tail.
  • Overbased metal detergents which comprise neutralized metal detergents as the outer layer of a metal base (e.g. carbonate) micelle, may be provided by including large amounts of metal base by reacting an excess of a metal base, such as an oxide or hydroxide, with an acidic gas such as carbon dioxide.
  • a metal base e.g. carbonate
  • detergents include metal salicylates, phenates and salicylates and combinations thereof.
  • the overbased metal hydrocarbyl-substituted hydroxybenzoate is preferably a hydrocarbyl-substituted salicylate detergent.
  • the metal may be an alkali metal (e.g. Li, Na, K) or an alkaline earth metal (e.g. Mg, Ca).
  • Hydrocarbyl means a group or radical that contains carbon and hydrogen atoms and that is bonded to the remainder of the molecule via a carbon atom. It may contain hetero atoms, i.e. atoms other than carbon and hydrogen, provided they do not alter the essentially hydrocarbon nature and characteristics of the group.
  • hydrocarbyl there may be mentioned alkyl and alkenyl.
  • a preferred overbased metal hydrocarbyl-substituted hydroxybenzoate is a calcium alkyl-substituted salicylate and has the structure shown: wherein R is a linear alkyl group. There may be more than one R group attached to the benzene ring.
  • the COO - group can be in the ortho, meta or para position with respect to the hydroxyl group; the ortho position is preferred.
  • the R group can be in the ortho, meta or para position with respect to the hydroxyl group.
  • Salicylic acids are typically prepared by the carboxylation, by the Kolbe-Schmitt process, of phenoxides, and in that case will generally be obtained (normally in a diluent) in admixture with uncarboxylated phenol. Salicylic acids may be non-sulphurized or sulphurized, and may be chemically modified and/or contain additional substituents. Processes for sulphurizing an alkyl salicylic acid are well known to those skilled in the art, and are described in, for example, US 2007/0027057 .
  • the alkyl groups advantageously contain 5 to 100, preferably 9 to 30, especially 14 to 24, carbon atoms.
  • overbased is generally used to describe metal detergents in which the ratio of the number of equivalents of the metal moiety to the number of equivalents of the acid moiety is greater than one.
  • 'low-based' is used to describe metal detergents in which the equivalent ratio of metal moiety to acid moiety is greater than 1, and up to about 2.
  • an “overbased calcium salt of surfactants” is meant an overbased detergent in which the metal cations of the oil-insoluble metal salt are essentially calcium cations. Small amounts of other cations may be present in the oil-insoluble metal salt, but typically at least 80, more typically at least 90, for example at least 95, mole % of the cations in the oil-insoluble metal salt, are calcium ions. Cations other than calcium may be derived, for example, from the use in the manufacture of the overbased detergent of a surfactant salt in which the cation is a metal other than calcium.
  • the metal salt of the surfactant is also calcium.
  • Carbonated overbased metal detergents typically comprise amorphous nanoparticles. Additionally, the art discloses nanoparticulate materials comprising carbonate in the crystalline calcite and vaterite forms.
  • the basicity of the detergents may be expressed as a total base number (TBN), sometimes referred to as base number (BN).
  • TBN total base number
  • BN base number
  • a total base number is the amount of acid needed to neutralize all of the basicity of the overbased material.
  • the TBN may be measured using ASTM standard D2896 or an equivalent procedure.
  • the detergent may have a low TBN (i.e. a TBN of less than 50), a medium TBN (i.e. a TBN of 50 to 150) or a high TBN (i.e. a TBN of greater than 150, such as 150-500).
  • the bascicity may also be expressed as basicity index (BI), which is the molar ratio of total base to total soap in the overbased detergent.
  • the anhydride may constitute at least 1 to 7, preferably 2 to 6 mass % of the lubricating oil composition. Preferably it constitutes 3 to 5, even more preferably 4 to 5, mass %.
  • the anhydride may be mono or polycarboxylic, preferably dicarboxylic.
  • the polyalkenyl group preferably has from 8 to 400, such as 8 to 100, carbon atoms.
  • R 1 represents a C 8 to C 100 branched or linear polyalkenyl group.
  • the polyalkenyl moiety may have a number average molecular weight of from 200 to 3000, preferably from 350 to 950.
  • Suitable hydrocarbons or polymers employed in the formation of the anhydrides used in the present invention to generate the polyalkenyl moieties include homopolymers, interpolymers or lower molecular weight hydrocarbons.
  • such polymers comprise interpolymers of ethylene and at least one alpha-olefin of the above formula, wherein R 1 is alkyl of from 1 to 18 carbon atoms, and more preferably is alkyl of from 1 to 8 carbon atoms, and more preferably still of from 1 to 2 carbon atoms.
  • useful alpha-olefin monomers and comonomers include, for example, propylene, butene-1, hexene-1, octene-1, 4-methylpentene-1, decene-1, dodecene-1, tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1, nonadecene-1, and mixtures thereof (e.g., mixtures of propylene and butene-1, and the like).
  • Exemplary of such polymers are propylene homopolymers, butene-1 homopolymers, ethylene-propylene copolymers, ethylene-butene-1 copolymers, propylene-butene copolymers and the like, wherein the polymer contains at least some terminal and/or internal unsaturation.
  • Preferred polymers are unsaturated copolymers of ethylene and propylene and ethylene and butene-1.
  • the interpolymers may contain a minor amount, e.g. 0.5 to 5 mole %, of a C 4 to C 18 nonconjugated diolefin comonomer.
  • the polymers comprise only alpha-olefin homopolymers, interpolymers of alpha-olefin comonomers and interpolymers of ethylene and alpha-olefin comonomers.
  • the molar ethylene content of the polymers employed is preferably in the range of 0 to 80 %, and more preferably 0 to 60 %.
  • the ethylene content of such copolymers is most preferably between 15 and 50 %, although higher or lower ethylene contents may be present.
  • These polymers may be prepared by polymerizing an alpha-olefin monomer, or mixtures of alpha-olefin monomers, or mixtures comprising ethylene and at least one C 3 to C 28 alpha-olefin monomer, in the presence of a catalyst system comprising at least one metallocene (e.g., a cyclopentadienyl-transition metal compound) and an alumoxane compound.
  • a catalyst system comprising at least one metallocene (e.g., a cyclopentadienyl-transition metal compound) and an alumoxane compound.
  • the percentage of polymer chains exhibiting terminal ethenylidene unsaturation may be determined by FTIR spectroscopic analysis, titration, or C 13 NMR.
  • the chain length of the R 1 alkyl group will vary depending on the comonomer(s) selected for use in the polymerization.
  • These terminally unsaturated interpolymers may be prepared by known metallocene chemistry and may also be prepared as described in U.S. Patent Nos. 5,498,809 ; 5,663,130 ; 5,705,577 ; 5,814,715 ; 6,022,929 and 6,030,930 .
  • Another useful class of polymers is that of polymers prepared by cationic polymerization of isobutene, styrene, and the like.
  • Common polymers from this class include polyisobutenes obtained by polymerization of a C 4 refinery stream having a butene content of 35 to 75 mass %, and an isobutene content of 30 to 60 mass %, in the presence of a Lewis acid catalyst, such as aluminum trichloride or boron trifluoride.
  • a preferred source of monomer for making poly-n-butenes is petroleum feedstreams such as Raffinate II. These feedstocks are disclosed in the art such as in U.S. Patent No. 4,952,739 .
  • Polyisobutylene is a most preferred backbone because it is readily available by cationic polymerization from butene streams (e.g., using AlCl 3 or BF 3 catalysts). Such polyisobutylenes generally contain residual unsaturation in amounts of one ethylenic double bond per polymer chain, positioned along the chain.
  • a preferred embodiment utilizes polyisobutylene prepared from a pure isobutylene stream or a Raffinate I stream to prepare reactive isobutylene polymers with terminal vinylidene olefins.
  • these polymers referred to as highly reactive polyisobutylene (HR-PIB)
  • HR-PIB highly reactive polyisobutylene
  • these polymers have a terminal vinylidene content of at least 65%, e.g., 70%, more preferably at least 80%, most preferably, at least 85%.
  • the preparation of such polymers is described, for example, in U.S. Patent No. 4,152,499 .
  • HR-PIB is known and HR-PIB is commercially available under the tradenames Glissopal TM (from BASF) and Ultravis TM (from BP-Amoco).
  • Polyisobutylene polymers that may be employed are generally based on a hydrocarbon chain of from 400 to 3000. Methods for making polyisobutylene are known. Polyisobutylene can be functionalized by halogenation (e.g. chlorination), the thermal "ene” reaction, or by free radical grafting using a catalyst (e.g. peroxide), as described below.
  • halogenation e.g. chlorination
  • the thermal "ene” reaction e.g. peroxide
  • a catalyst e.g. peroxide
  • the hydrocarbon or polymer backbone may be functionalized with carboxylic anhydride-producing moieties selectively at sites of carbon-to-carbon unsaturation on the polymer or hydrocarbon chains, or randomly along chains using any of the three processes mentioned above or combinations thereof, in any sequence.
  • the polymer or hydrocarbon may be functionalized, with carboxylic acid anhydride moieties by reacting the polymer or hydrocarbon under conditions that result in the addition of functional moieties or agents, i.e., acid anhydride, onto the polymer or hydrocarbon chains primarily at sites of carbon-to-carbon unsaturation (also referred to as ethylenic or olefinic unsaturation) using the halogen assisted functionalization (e.g. chlorination) process or the thermal "ene" reaction.
  • halogen assisted functionalization e.g. chlorination
  • Selective functionalization can be accomplished by halogenating, e.g., chlorinating or brominating, the unsaturated ⁇ -olefin polymer to 1 to 8, preferably 3 to 7, mass % chlorine, or bromine, based on the weight of polymer or hydrocarbon, by passing the chlorine or bromine through the polymer at a temperature of 60 to 250°C, preferably 110 to 160°C, e.g., 120 to 140°C, for 0.5 to 10, preferably 1 to 7 hours.
  • halogenating e.g., chlorinating or brominating
  • the halogenated polymer or hydrocarbon (hereinafter backbone) is then reacted with sufficient monounsaturated reactant capable of adding the required number of functional moieties to the backbone, e.g., monounsaturated carboxylic reactant, at 100 to 250°C, usually 180°C to 235°C, for 0.5 to 10, e.g., 3 to 8 hours, such that the product obtained will contain the desired number of moles of the monounsaturated carboxylic reactant per mole of the halogenated backbones.
  • the backbone and the monounsaturated carboxylic reactant are mixed and heated while adding chlorine to the hot material.
  • chlorination normally helps increase the reactivity of starting olefin polymers with monounsaturated functionalizing reactant, it is not necessary with some of the polymers or hydrocarbons contemplated for use in the present invention, particularly those preferred polymers or hydrocarbons which possess a high terminal bond content and reactivity.
  • the backbone and the monounsaturated functionality reactant, (carboxylic reactant) are contacted at elevated temperature to cause an initial thermal "ene" reaction to take place. Ene reactions are known.
  • the hydrocarbon or polymer backbone can be functionalized by random attachment of functional moieties along the polymer chains by a variety of methods.
  • the polymer in solution or in solid form, may be grafted with the monounsaturated carboxylic reactant, as described above, in the presence of a free-radical initiator.
  • the grafting takes place at an elevated temperature in the range of 100 to 260°C, preferably 120 to 240°C.
  • free-radical initiated grafting would be accomplished in a mineral lubricating oil solution containing, e.g., 1 to 50, preferably 5 to 30, mass % polymer based on the initial total oil solution.
  • the free-radical initiators that may be used are peroxides, hydroperoxides, and azo compounds, preferably those that have a boiling point greater than 100°C and decompose thermally within the grafting temperature range to provide free-radicals.
  • Representative of these free-radical initiators are azobutyronitrile, 2,5-dimethylhex-3-ene-2, 5-bis-tertiary-butyl peroxide and dicumene peroxide.
  • the initiator, when used, is typically in an amount of between 0.005% and 1% by weight based on the weight of the reaction mixture solution.
  • the aforesaid monounsaturated carboxylic reactant material and free-radical initiator are used in a weight ratio range of from 1.0:1 to 30:1, preferably 3:1 to 6:1.
  • the grafting is preferably carried out in an inert atmosphere, such as under nitrogen blanketing.
  • the resulting grafted polymer is characterized by having carboxylic acid (or derivative) moieties randomly attached along the polymer chains, it being understood, of course, that some of the polymer chains remain ungrafted.
  • the free radical grafting described above can be used for the other polymers and hydrocarbons used in the present invention.
  • Mixtures of monounsaturated carboxylic materials (i) - (iv) also may be used.
  • the monounsaturation of the monounsaturated carboxylic reactant becomes saturated.
  • maleic anhydride becomes backbone-substituted succinic anhydride
  • acrylic acid becomes backbone-substituted propionic acid.
  • Such monounsaturated carboxylic reactants are fumaric acid, itaconic acid, maleic acid, maleic anhydride, chloromaleic acid, chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and lower alkyl (e.g., C 1 to C 4 alkyl) acid esters of the foregoing, e.g., methyl maleate, ethyl fumarate, and methyl fumarate.
  • lower alkyl e.g., C 1 to C 4 alkyl
  • the monounsaturated carboxylic reactant typically will be used in an amount ranging from equimolar amount to 100 mass % excess, preferably 5 to 50 mass % excess, based on the moles of polymer or hydrocarbon. Unreacted excess monounsaturated carboxylic reactant can be removed from the final dispersant product by, for example, stripping, usually under vacuum, if required.
  • the lubricating oil composition of the invention may comprise further additives, different from and additional to (B) and (C).
  • additional additives may, for example include ashless dispersants, other metal detergents, anti-wear agents such as zinc dihydrocarbyl dithiophosphates, anti-oxidants and demulsifiers. In some cases, an ashless dispersant need not be provided.
  • additives (B) and (C) can be added simultaneously to the base oil to form the lubricating oil composition. Dissolution of the additive package(s) into the lubricating oil may be facilitated by solvents and by mixing accompanied with mild heating, but this is not essential.
  • the additive package(s) will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration, and/or to carry out the intended function in the final formulation when the additive package(s) is/are combined with a predetermined amount of base oil.
  • additives (B) and (C), in accordance with the present invention may be admixed with small amounts of base oil or other compatible solvents together with other desirable additives to form additive packages containing active ingredients in an amount, based on the additive package, of, for example, from 2.5 to 90, preferably from 5 to 75, most preferably from 8 to 60, mass % of additives in the appropriate proportions, the remainder being base oil.
  • the final formulation as a trunk piston engine oil may typically contain 30, preferably 10 to 28, more preferably 12 to 24, mass % of the additive package(s), the remainder being base oil.
  • the trunk piston engine oil may have a compositional TBN (using ASTM D2896) of 20 to 60, such as, 30 to 55. For example, it may be 40 to 55 or 35 to 50.
  • Test trunk piston marine engine lubricating oils were evaluated for asphaltene dispersancy using light scattering according to the Focused Beam Reflectance Method ("FBRM”), which predicts asphaltene agglomeration and hence 'black sludge' formation.
  • FBRM Focused Beam Reflectance Method
  • the FBRM probe contains fibre optic cables through which laser light travels to reach the probe tip. At the tip, an optic focuses the laser light to a small spot. The optic is rotated so that the focussed beam scans a circular path between the window of the probe and the sample. As particles flow past the window, they intersect the scanning path giving backscattered light from the individual particles.
  • the scanning laser beam travels much faster than the particles; this means that the particles are effectively stationary. As the focussed beam reaches one edge of the particle, the amount of backscattered light increases; the amount will decrease when the focussed beam reaches the other edge of the particle.
  • the instrument measures the time of the increased backscatter.
  • the time period of backscatter from one particle is multiplied by the scan speed and the result is a distance or chord length.
  • a chord length is a straight line between any two points on the edge of a particle. This is represented as a chord length distribution, a graph of numbers of chord lengths (particles) measured as a function of the chord length dimensions in microns.
  • FBRM typically measures tens of thousands of chords per second, resulting in a robust number-by-chord length distribution. The method gives an absolute measure of the particle size distribution of the asphaltene particles.
  • the Focused beam Reflectance Probe (FBRM), model Lasentec D600L, was supplied by Mettler Toledo, Leicester, UK. The instrument was used in a configuration to give a particle size resolution of 1 ⁇ m to 1mm. Data from FBRM can be presented in several ways. Studies have suggested that the average counts per second can be used as a quantitative determination of asphaltene dispersancy. This value is a function of both the average size and level of agglomerate. In this application, the average count rate (over the entire size range) was monitored using a measurement time of 1 second per sample.
  • test TPEO's were heated to 60°C and stirred at 400rpm; when the temperature reached 60°C the FBRM probe was inserted into the sample and measurements made for 15 minutes.
  • An aliquot of heavy fuel oil (10% w/w) was introduced into the TPEO under stirring using a four-blade stirrer (at 400 rpm). A value for the average counts per second was taken when the count rate had reached an equilibrium value (typically overnight).
  • Example PIBSA (C) (% active matter) Priolube 3970 (A1) (wt %) Group II Oil (A2) Group I Oil Lasentec Counts Ref 1 - - - Balance 2,032.43 Ref 2 - - Balance - 5,988.84 Ref 3 - 10.00 Balance - 9,613.23 Ref 4 - 30.00 Balance - 732.81 Ref 5 4.80 - Balance - 2,205.86 1 4.80 10.00 Balance - 786.41 2 4.80 30.00 Balance - 12.82 3 4.80 80.83 - - 13.89
  • Ref 3 and Ref 4 are illustrative of US Patent Application Publication No. 2011/0319304 A1 ('304).
  • Ref 5 (use of PIBSA alone) confirms the teaching of '594.
  • Examples 1-3 confirm the synergy of PIBSA and ester. TABLE 2 Each TPEO tested had a BN of 40, contained 0.75 mass % (in terms of calcium) of calcium salicylate of BI 8.0 and 0.68 mass % (in terms of calcium) of calcium salicylate of BI 3.0, and contained the same amount of Zn.
  • Example PIBSA (C) (% active matter) Priolube 3970 (A1) (wt %) Ketjenlube 115 (A1) (wt%) Group II (A2) Group I Group III (A2) Lasentec Counts Ref 6 - - - - Balance - 933.83 4 4.80 1.00 - Balance - - 391.79 5 4.80 3.00 - Balance - - 223.56 6 4.80 5.00 - Balance - - 251.08 7 4.80 7.00 - Balance - - 161.13 8 4.80 10.00 - Balance - - 48.38 9 0.80 10.00 - Balance - - 3,499.45 10 1.60 10.00 - Balance - - 1,333.98 11 2.40 10.00 - Balance - - 421.74 12 3.20 10.00 - Balance - - 268.40 13 4.00 10.00 - Balance - - 47.87 14 4.80 10.00 - - -
  • Example 14 shows the applicability of the invention to a Group III base oil eyond that of Ref 6 (a Group I oil) and Example 15 shows the applicability of the invention to esters other than Priolube 3970.
  • Each TPEO treated had a BN of 30, contained 0.56 mass % (in terms of calcium) of calcium salicylate of BI 8.0 and 0.51 mass % (in terms of calcium) of calcium salicylate of BI 3.0, and contained the same amount of Zn.
  • Example PIBSA (C) (% active matter) Priolube 3970 (A1) (wt %) Group II (A2) Group I Lasentec Counts Ref 7 - - - Balance 1,755.35 Ref 8 2.40 - Balance - 3,638.42 17 2.40 1.00 Balance - 1,622.23 18 2.40 3.00 Balance - 1,805.06 19 2.40 5.00 Balance - 1,626.40 20 2.40 7.00 Balance - 1,135.09 21 2.40 10.00 Balance - 899.70

Claims (19)

  1. Composition d'huile lubrifiante pour moteurs marins à piston-fourreau, pour améliorer la maîtrise des asphaltènes lors de son utilisation dans le fonctionnement du moteur lorsqu'il est alimenté avec un fuel-oil lourd, composition qui comprend ou est préparée en mélangeant :
    (A) 50 % en masse ou plus de la composition d'une huile de viscosité propre à la lubrification, qui est soit :
    - une huile lubrifiante de base du type ester (A1), soluble dans l'huile ; soit
    - comprend 0,1 à 90 % en masse d'une huile lubrifiante de base du type ester (A1), soluble dans l'huile et, en une proportion égale ou supérieure à 50 % en masse du reste de l'huile de viscosité propre à la lubrification, une huile lubrifiante de base contenant une proportion supérieure ou égale à 90 % de composés saturés et une proportion inférieure ou égale à 0,03 % de soufre ou un de leurs mélanges (A2) ;
    (B) un détergent du type hydroxybenzoate métallique à substituant hydrocarbyle surbasique, soluble dans l'huile, en une petite quantité ; et
    (C) un anhydride d'acide carboxylique à substituant polyalcényle, soluble dans l'huile, en une petite quantité de plus de 0,1 à moins 10 % en masse de la composition, de préférence de plus de 1 à moins de 8 % en masse, le, ou au moins un, groupe polyalcényle étant dérivé d'un polyalcène ayant une moyenne en nombre du poids moléculaire de 200 à 3000.
  2. Huile lubrifiante suivant la revendication 1, dans laquelle, dans l'huile de viscosité propre à la lubrification, l'huile lubrifiante de base (A2), lorsqu'elle est présente, contient une proportion supérieure à 60 % en masse de l'huile lubrifiante de base contenant une proportion supérieure ou égale à 90 % de composés saturés et une proportion inférieure ou égale à 0,03 % de soufre ou un de leurs mélanges.
  3. Huile lubrifiante suivant la revendication 1 ou 2, dans laquelle l'huile lubrifiante de base (A2), lorsqu'elle est présente, est une huile lubrifiante de base du Groupe II, du Groupe III ou du Groupe IV.
  4. Huile lubrifiante suivant la revendication 1, 2 ou 3 dans laquelle le détergent métallique (B) est un détergent à base d'alkylsalicylate de calcium.
  5. Huile lubrifiante suivant la revendication 4, dans laquelle le détergent métallique (B) est un détergent métallique à substituant alkyle en C9 à C30.
  6. Huile lubrifiante suivant la revendication 4 ou 5, dans laquelle le détergent métallique (B) est un détergent métallique à substituant alkyle en C20 ou plus de C20.
  7. Huile lubrifiante suivant l'une quelconque des revendications 1 à 6, dans laquelle le substituant polyalcényle dans l'anhydride (C) a 8 à 400 atomes de carbone.
  8. Huile lubrifiante suivant l'une quelconque des revendications 1 à 7, dans laquelle le substituant polyalcényle dans l'anhydride (C) a une moyenne en nombre du poids moléculaire de 350 à 1000.
  9. Huile lubrifiante suivant l'une quelconque des revendications 1 à 8, dans laquelle l'anhydride d'acide carboxylique à substituant polyalcényle (C) est un anhydride succinique.
  10. Huile lubrifiante suivant la revendication 9, dans laquelle l'anhydride succinique (C) est un anhydride polybutène-succinique.
  11. Huile lubrifiante suivant l'une quelconque des revendications 1 à 10, dans laquelle l'huile lubrifiante de base du type ester (A1) est présente en une quantité de 10 à 90 % en masse.
  12. Huile lubrifiante suivant l'une quelconque des revendications 1 à 11, dans laquelle l'huile lubrifiante de base du type ester (A1) a une viscosité cinématique de 2 à 10 mm2s-1 à 100°C.
  13. Huile lubrifiante suivant l'une quelconque des revendications 1 à 12, dans laquelle l'huile lubrifiante de base du type ester (A1) est une huile lubrifiante de base du type ester de polyol.
  14. Composition d'huile lubrifiante suivant l'une quelconque des revendications 1 à 13, comprenant en outre une quantité d'un fuel-oil lourd.
  15. Procédé pour faire fonctionner un moteur marin à allumage par compression à piston-fourreau à vitesse moyenne, comprenant :
    (i) l'alimentation du moteur avec un fuel-oil lourd ; et
    (iii) la lubrification du carter du moteur avec une composition suivant l'une quelconque des revendications 1 à 14.
  16. Procédé de dispersion des asphaltènes dans une composition d'huile lubrifiante pour moteurs marins à piston-fourreau au cours de la lubrification des surfaces de la chambre de combustion d'un moteur marin à allumage par compression à vitesse moyenne et du fonctionnement du moteur, procédé qui comprend :
    (i) la fourniture d'une composition suivant l'une quelconque des revendications 1 à 14 ;
    (ii) la fourniture de la composition dans la chambre de combustion ;
    (iii) la fourniture d'un fuel-oil lourd dans la chambre de combustion ; et
    (iv) la combustion du fuel-oil lourd dans la chambre de combustion.
  17. Procédé suivant la revendication 16, dans lequel la dispersion des asphaltènes est mesurée en utilisant le procédé de réflectance de faisceau focalisé ("FBRM").
  18. Utilisation d'un détergent (B) en association avec le constituant (C) de la manière définie et en les quantités indiquées dans l'une quelconque des revendications 1 à 14 dans une composition d'huile lubrifiante pour moteurs marins à piston-fourreau pour un moteur marin à allumage par compression à vitesse moyenne, composition qui comprend une huile de viscosité propre à la lubrification (A) en une quantité dominante de la manière définie dans la revendication 1, pour parvenir à une maîtrise comparable ou améliorée des asphaltènes au cours du fonctionnement du moteur, alimenté avec un fuel-oil lourd, et sa lubrification avec la composition, par comparaison avec les résultats obtenus avec une huile comparable dans laquelle l'huile lubrifiante de base est une huile lubrifiante de base du Groupe I.
  19. Utilisation suivant la revendication 18, dans laquelle la maîtrise des asphaltènes au cours du fonctionnement du moteur est mesurée en utilisant le procédé de réflectance de faisceau focalisé ("FBRM").
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