EP3956423B1 - Procede de reduction et/ou controle de la combustion anormale du gaz dans un moteur marin ou un moteur a allumage commande - Google Patents

Procede de reduction et/ou controle de la combustion anormale du gaz dans un moteur marin ou un moteur a allumage commande Download PDF

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EP3956423B1
EP3956423B1 EP20718332.8A EP20718332A EP3956423B1 EP 3956423 B1 EP3956423 B1 EP 3956423B1 EP 20718332 A EP20718332 A EP 20718332A EP 3956423 B1 EP3956423 B1 EP 3956423B1
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Prior art keywords
monomers
engine
alkyl methacrylate
weight
copolymer
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German (de)
English (en)
French (fr)
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EP3956423A1 (fr
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Valérie Doyen
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TotalEnergies Onetech SAS
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TotalEnergies Onetech SAS
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
    • C10M145/14—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • 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
    • C10N2040/255—Gasoline engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/26—Two-strokes or two-cycle engines

Definitions

  • the present invention relates to the reduction and/or control of abnormal gas combustion in a marine engine or spark ignition engine.
  • the present invention relates to the use of one or more polymers in a lubricating composition to reduce and/or control the abnormal combustion of gas in a marine engine or a spark ignition engine.
  • the present invention also relates to a method for reducing and/or controlling the abnormal combustion of gas in a marine engine or a spark ignition engine.
  • the present invention also relates to the use of a lubricating composition to reduce and/or control the abnormal combustion of gas in a marine engine or a spark ignition engine.
  • controlled ignition coming either from contact between an electric arc and the gas or from an injection liquid fuel pilot initiating a diffusion flame.
  • Controlled ignition can be carried out directly in the combustion chamber of the marine engine or in a pre-combustion chamber of the marine engine adjacent to the combustion chamber thereof.
  • Controlled combustion can also be called normal combustion.
  • the Applicant highlighted that the abnormal combustion of the gas can, among other things, result from the self-ignition of droplets (or particles) of lubricating composition which are found in the combustion chamber during the gas compression cycle and/or gas combustion during operation of a marine engine or spark ignition engine.
  • Abnormal combustion means combustion of the gas in the combustion chamber initiated by uncontrolled pre-ignition. Abnormal combustion results in uncontrolled expansion of the flame front through the combustion chamber. Abnormal combustion also results in a pressure level in the combustion chamber higher than the nominal pressure of the combustion chamber by at least 10%, preferably at least 20%, more preferably at least 30%. combustion of gas in a marine engine or spark-ignition engine. Abnormal combustion is notably due to the self-ignition of droplets (or particles) of lubricating composition carried into the combustion chamber by the intake air.
  • Nominal pressure means the maximum pressure supported by the parts of an engine during controlled combustion of the gas in the combustion chamber. combustion without risk of damage to all or part of the internal parts of the engine, such as cylinders, pistons, spark plugs and valves.
  • Gas means a mixed mixture of gas and air.
  • the mixed mixture of gas and air is produced upstream of the combustion chamber or in the combustion chamber before ignition of the marine engine or the spark ignition engine.
  • the step allowing the mixed mixture of gas and air to be obtained is called the pre-mixing step.
  • the terms "gas” and “mixed mixture of gas and air” have equivalent meanings and can be used to replace one another.
  • marine engine means a two-stroke or four-stroke marine engine operating solely on gas, also called a pure gas engine, or operating on gas and fuel oil, also called a dual fuel engine.
  • the engines according to the invention are in particular 2-stroke engines or 4-stroke engines in which the lubricant is not pre-mixed with the fuel before its admission.
  • spark ignition engine we mean gasoline engines which can for example be two-stroke or four-stroke gasoline engines, pure gas engines and low pressure dual fuel gas engines.
  • the spark ignition engines used in the present invention are Otto cycle engines, as opposed to Diesel cycle engines.
  • the use according to the invention makes it possible to limit the presence of droplets (or particles) of lubricating composition in the combustion chamber, thus allowing a reduction and/or control of the abnormal combustion of gas in an engine, said engine which may be a marine engine or a spark ignition engine.
  • monomers (A) are different from monomers (B).
  • the copolymer (C) is obtained from at least one monomer (A) and at least one monomer (B).
  • the copolymer (C) is obtained from two different monomers of the (C10) alkyl methacrylate type, then preferably, one of the two monomers will have a linear C10 alkyl chain (this will then be monomer B) and the other monomer will have a branched C10 alkyl chain (this will then be monomer A).
  • the monomers (B) comprise at least one (C12)alkyl methacrylate.
  • the monomers (A) and (B) can be linear or branched.
  • the copolymer (C) of the invention comprises at least two units derived from monomers: a monomer (A) and a monomer (B) which are different.
  • the monomers (B) comprise 50 to 80% by weight of (C12) alkyl methacrylate relative to the total weight of the monomers (B), and preferably 55 to 70% by weight.
  • the monomers (B) further comprise at least one (C14) alkyl methacrylate.
  • the monomers (B) comprise 15 to 40% by weight of (C14) alkyl methacrylate relative to the total weight of the monomers (B), and preferably 20 to 30% by weight.
  • the copolymer (C) according to the invention may also comprise repeating units corresponding to other monomers.
  • Said other monomers may be chosen from (C1-C5)alkyl methacrylates, (C19-C24)alkyl methacrylates, crosslinking monomers, (C1-C24)alkyl acrylates, styrene, etc.
  • the copolymer is substantially free of monomers other than monomers (A) and monomers (B) defined in the present invention, in particular free of (C1-C5) alkyl methacrylates, including by example of methyl methacrylates.
  • the copolymer used according to the invention is substantially free of methyl methacrylate.
  • Methyl methacrylate type monomers reduce the solubility of the copolymer in oil, so that this type of monomer is typically used in small quantities or is typically absent from the copolymer according to the invention.
  • copolymer substantially free of a monomer X means that the copolymer comprises less than 3.0% by weight of said monomer by weight of said monomer X, preferably less than 0.5% by weight of said monomer X, relative to the total weight of the copolymer.
  • the monomers (A) chosen from (C6-C10) alkyl methacrylate monomers and the monomers (B) chosen from (C10-C18) alkyl methacrylate monomers represent at least 75% by weight of the total weight of the monomers used.
  • used in the copolymer (C) preferably at least 90%, more preferably at least 95%, preferably at least 97%, or better still at least 99% by weight, preferably at least 99.5% by weight.
  • the weight ratio of monomers (B) and monomers (A) in the copolymer is between 99:1 and 10:90.
  • the monomers (A) comprise at least 50% by weight of (C8) alkyl methacrylate relative to the total weight of monomers (A), preferably at least 75%, more preferably at least 90% and even more preferably at least 99% by weight.
  • the monomers (A) are branched monomers (i.e. where the alkyl part of the alkyl methacrylate is branched) such as for example 2-ethyl-hexyl methacrylate or isodecylmethacrylate.
  • the monomers (B) may comprise a mixture of at least one (C10) alkyl methacrylate, (C12) alkyl methacrylate, (C14) alkyl methacrylate, (C16) alkyl methacrylate, (C18) alkyl methacrylate, it being understood that the C10 alkyl methacrylate preferably has a linear alkyl chain.
  • the monomers (B) are linear and are chosen in particular from n-(C10)-alkyl methacrylate, n-(C11)-alkyl methacrylate, lauryl methacrylate (n-(C12)-alkyl methacrylate), n-(C13)-alkyl methacrylate, myristyl methacrylate (n-(C14)-alkyl methacrylate), n-(C15)-alkyl methacrylate, n-(C16)-alkyl methacrylate, n-(C17)-alkyl methacrylate, n -(C18)-alkyl methacrylate.
  • the ratios of the different monomers can be adapted by those skilled in the art according to the desired characteristics of the copolymer (C).
  • the weight ratio of monomer (B): monomer (A) can be 10:90, 15:85, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95:5 or 99:1.
  • the monomers may be present in a (C10-C18)alkyl methacrylate/(C8)alkyl methacrylate weight ratio of 10:90, 15:85, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95:5, or 99 :1.
  • the alkyl group of the (C8)alkyl methacrylate is a linear or branched C8 alkyl.
  • the (C8)alkyl methacrylate is 2-ethylhexyl methacrylate.
  • the copolymer (C) is a copolymer of 2-ethylhexyl methacrylate and a mixture of monomers comprising (C10)alkyl methacrylate, (C12)alkyl methacrylate, (C14)alkyl methacrylate, (C16) )alkyl methacrylate and (C18)alkyl methacrylate.
  • the copolymer (C) of the invention is a copolymer of a mixture of monomers comprising (C10) alkyl methacrylate, (C12) alkyl methacrylate, (C14) alkyl methacrylate, (C16) alkyl methacrylate and (C18)alkyl methacrylate and a (C8)alkyl methacrylate monomer, wherein the weight ratio of the monomer mixture to the (C8)alkyl methacrylate is from about 99:1 to about 10:90.
  • the copolymers (C) according to the invention have a mean radius of gyration (Rg) measured by hydrodynamic chromatography coupled with the measurement of the diffusion of laser light typically in a tetrahydrofuran solvent (HCC-MALS, in English "Hydrodynamic Column”). Chromatography-Multi Angle Light Scattering”) between approximately 100 and approximately 200 (nm) Rg, preferably between approximately 120 and approximately 190 (nm), preferably between approximately 130 and approximately 180, preferably between approximately 140 and approximately 170 (nm). nm) Rg.
  • Rg mean radius of gyration
  • copolymer (C) of the invention can be synthesized by all conventional methods of vinyl addition polymerization, known to those skilled in the art, such as for example solution polymerization, precipitation polymerization, dispersion polymerization, including suspension and emulsion polymerization.
  • the polymer is formed by suspension polymerization, in which monomers that are not water soluble or poorly water soluble are suspended as droplets in water.
  • the suspended monomer droplets are maintained by mechanical agitation and addition of stabilizers.
  • Polymeric surfactants such as cellulose ethers, poly(vinyl alcohol-co-vinyl acetate), poly(vinyl pyrrolidone) and alkali metal salts of polymer including (meth)acrylic acid and colloids (insoluble in water) inorganic powders such as tricalcium phosphate, hydroxyapatite, barium sulfate, kaolin, and magnesium silicates can be used as a stabilizer.
  • surfactants such as sodium dodecylbenzene sulfonate can be used in combination with one or more stabilizers.
  • Polymerization is initiated using an oil-soluble initiator. Suitable initiators include peroxides such as benzoyl peroxide, peroxy esters such as tert-butylperoxy-2-ethylhexanoate, and azo compounds such as 2,2'-azobis(2-methylbutyronitrile).
  • the solid polymer product can be separated from the reaction medium by filtration and washed with water, acid, base or solvent to remove unreacted monomers or free stabilizers.
  • the polymer is formed by emulsion polymerization, one or more monomers are dispersed in an aqueous phase and the polymerization is initiated using a water-soluble initiator.
  • the monomers are typically water insoluble or minimally water soluble, and a surfactant or soap is used to stabilize the monomer droplets in the aqueous phase.
  • Polymerization takes place in swollen micelles and latex particles.
  • phase transfer agents such as mercaptans (e.g. dodecyl mercaptan) to control molecular weight, electrolytes for pH control, and small amounts of organic solvent.
  • a water-soluble organic solvent including, but not limited to, acetone, 2-butanone, methanol, ethanol, and isopropanol, to adjust the polarity of the aqueous phase.
  • Initiators that can be used include alkali metal or ammonium salts of persulfate such as ammonium persulfate, water-soluble azo compounds such as 2,2'-azobis(2-aminopropane)dihydrochloride, and redox systems such as Fe(ll) and cumene hydroperoxide, and tert-butyl hydroperoxide-Fe(II)-sodium ascorbate.
  • Usable surfactants include in particular anionic surfactants such as fatty acid soaps (for example sodium or potassium stearate), sulfates and sulfonates (for example sodium dodecyl benzene sulfonate), sulfosuccinates (for example dioctyl sodium sulfosuccinate); non-ionic surfactants such as for example octylphenol ethoxylates and linear or branched alcohol ethoxylates; cationic surfactants such as cetyl trimethyl ammonium chloride; and amphoteric surfactants.
  • anionic surfactants such as fatty acid soaps (for example sodium or potassium stearate), sulfates and sulfonates (for example sodium dodecyl benzene sulfonate), sulfosuccinates (for example dioctyl sodium sulfosuccinate); non-ionic surfactants such as for example
  • Polymeric stabilizers such as poly(vinyl alcohol-co-vinyl acetate) can also be used as surfactants.
  • the solid polymer product free from the aqueous medium can be obtained by different processes including destabilization/coagulation of the final emulsion followed by filtration, solvent precipitation of the polymer from the latex or atomization of the latex.
  • the polymer can be isolated by conventional methods known to those skilled in the art, such as for example solvent exchange, solvent evaporation, atomization and lyophilization.
  • An initiator system may be a single initiator compound (e.g. persulfate salt) or a mixture of two or more compounds (e.g. hydrogen peroxide and sodium ascorbate).
  • the initiator system may include an oxidant, a reductant and optionally a metal salt.
  • the oxidant may be a persulfate, such as for example ammonium persulfate, or a peroxide such as for example hydrogen peroxide (H 2 O 2 ) or tert-butyl hydroperoxide (TBHP).
  • the desired copolymer can be obtained, for example, when the polymerization medium comprises tert-butyl hydroperoxide in an amount of about 0.01 to about 0.06 weight percent based on the weight of all monomers in the mixture.
  • the mixture may include tert-butyl hydroperoxide in an amount of about 0.01 to about 0.03% by weight of the monomer mixture.
  • the mixture further comprises tert-butyl hydroperoxide in an amount of 0.013% by weight of the monomer mixture.
  • Typical initiators of the copolymers of the invention include conventional redox initiators.
  • the reductant of the redox initiator system may be ascorbic acid or one of its salts.
  • the polymerization mixture may include sodium ascorbate in an amount of about 0.04 to about 0.1% by weight of the monomer mixture.
  • sodium ascorbate may be present in an amount of about 0.08 to about 0.1% by weight of the monomer mixture.
  • the polymerization mixture comprises sodium ascorbate in an amount of about 0.098% by weight of the monomer mixture.
  • the initiator system may also include a metal salt.
  • the metal can be any transition metal, such as, for example, iron.
  • the metal salt of the initiator system may be iron sulfate (FeSO 4 ).
  • the metal salt is present in the polymerization mixture in an amount of about 0.0005 to about 0.1% by weight of the monomer mixture. In some examples, the metal salt is added to the polymerization mixture as a solution.
  • the copolymer can also be in the form of a mixture further comprising a surfactant.
  • the surfactant may include a sulfonate group.
  • the surfactant may include a dialkyl sulfosuccinate, such as example sodium salt of dioctyl sulfosuccinate.
  • the surfactant can for example be Aerosol ® OT.
  • the copolymer may be a random copolymer, a block copolymer or a mixture.
  • the copolymer is substantially a random copolymer (e.g. greater than 90, 95, 98, or 99% by weight).
  • the copolymer may also be a partially random and partially block copolymer. In this case, the weight ratio of random copolymer to block copolymer is generally 90:10, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 20:80 or 10:90.
  • the copolymer may also be a substantially block copolymer (e.g. greater than 90, 95, 98, or 99% by weight).
  • the copolymer (C) of the invention may comprise other monomers in addition to the monomers (A) chosen from (C6-C10) alkyl methacrylate, and the monomers (B) chosen from (C10 -C18)alkyl methacrylate.
  • additional monomers may be present in an amount of less than 25% by weight, preferably less than 10% by weight.
  • the additional monomers are present in an amount of about 0.5 to 10% by weight, or about 1 to 10% by weight, or about 1 to about 5% by weight, or about 5 to 10% by weight.
  • the monomers are present in an amount less than 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 or about 0.5% by weight.
  • Additional monomers may include, for example, (C1-C5) alkyl methacrylates and (C19-C24) alkyl methacrylates, crosslinkable monomers, (C1-C24) alkyl acrylates, styrene, and other similar monomers.
  • the copolymer (C) can also be crosslinked.
  • the copolymer can therefore comprise monomeric units which link one or more chains of the polymer backbone.
  • the copolymer contains cross-linked monomeric units present in an amount of up to about 5% by weight of the copolymer.
  • the copolymer according to the invention is not crosslinked, and is substantially free of monomers which have a crosslinking agent function.
  • the mixture of monomers to obtain the copolymer is substantially free of crosslinking agents.
  • the expression "copolymer substantially free of crosslinking agents” means that the copolymer comprises less than 1.0% by weight, preferably less than 0.5% by weight, of monomeric units which bind one or more chains of the polymer backbone, relative to the total weight of the copolymer.
  • the crosslinked copolymer can be obtained by adding a crosslinking agent when the mixture of monomers comprises such a crosslinking agent.
  • the crosslinking agent is a diacrylate or dimethacrylate crosslinking agent, such as for example, 1,6-hexanediol dimethacrylate.
  • the mixture may, for example, include a crosslinking agent in an amount up to about 0.005% by weight of the monomers in the mixture.
  • the method includes the polymerization of monomers (A) chosen from (C6-C10) alkyl methacrylate and of monomers (B) chosen from (C10-C18) alkyl methacrylate, advantageously the polymerization of a mixture of monomers comprising C10 alkyl methacrylate, C12 alkyl methacrylate, C14 alkyl methacrylate, C16 alkyl methacrylate and C18 alkyl methacrylate, and C8 alkyl methacrylate, wherein the weight ratio of monomers (B)/monomers (A) in the copolymer is about 99:1 to approximately 10:90 (e.g.
  • the method includes: the combination of monomers (A) chosen from (C6-C10) alkyl methacrylate and monomers (B) chosen from (C10-C18) alkyl methacrylate, advantageously the combination of a mixture of monomers comprising C10 alkyl methacrylate, C12 alkyl methacrylate, C14 alkyl methacrylate, C16 alkyl methacrylate and C18 alkyl methacrylate, and C8 alkyl methacrylate in a weight ratio (mixture/C8 alkyl methacrylate) of approximately 10:90, 15:85, 20:80 , 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85 :15, 90:10, 95:5 or 99:1 and initiating the polymerization of the monomers to provide the copolymer.
  • the monomer ratio and initiators, or initiator system can be selected as described above.
  • the method may include other compounds to provide a copolymer with the desired properties.
  • the method can also include a surfactant, such as for example Aerosol ® OT, or a crosslinker, such as for example 1,6-hexanediol dimethacrylate.
  • the polymerization can be carried out in an aqueous medium or a mixture which includes an aqueous solvent and an organic solvent.
  • the polymerization medium may include a mixture of water and acetone.
  • the polymerization medium may require an organic solvent. It may be advantageous to include an organic solvent when (C10-C18) alkyl methacrylate monomers are used.
  • Organic solvents which can be used for such a polymerization reaction are known and can be selected by those skilled in the art.
  • Organic solvents which can be used include acetone, 2-butanone, methanol, ethanol and isopropanol.
  • the copolymer (C) is preferably used in an amount of 50 to 10,000 ppm by weight, preferably 100 to 1000 ppm by weight of active material, relative to the total weight of the lubricating composition.
  • the lubricating composition of the invention may also comprise detergents, in particular detergents well known to those skilled in the art.
  • the detergents commonly used in the formulation of lubricating compositions are typically anionic compounds comprising a long lipophilic hydrocarbon chain and a hydrophilic head.
  • the associated cation is typically a metallic cation of an alkali or alkaline earth metal.
  • the detergents are preferably chosen from alkali or alkaline earth metal salts of carboxylic acids, sulfonates, salicylates, naphthenates, as well as phenate salts.
  • the alkali and alkaline earth metals are preferably calcium, magnesium, sodium or barium. These metal salts may contain the metal in approximately stoichiometric quantities.
  • neutral detergents typically have a BN, measured according to ASTM D2896, less than 200 mg KOH/g, or less than 190, or even less than 180 mg KOH/g.
  • This type of so-called neutral detergents can contribute in part to the BN of the lubricants according to the present invention.
  • neutral detergents of the carboxylate, sulfonate, salicylate, phenate, naphthenate type of alkali and alkaline earth metals, for example calcium, sodium, magnesium, barium, will be used.
  • overbased detergents When the metal is in excess (in quantities greater than the stoichiometric quantity), we are dealing with so-called overbased detergents.
  • Their BN is high, greater than 150 mg KOH/g, typically between 200 and 700 mg KOH/g, generally between 250 and 450 mg KOH/g.
  • the excess metal providing the overbased character to the detergent is in the form of metal salts insoluble in oil, for example carbonate, hydroxide, oxalate, acetate, glutamate, preferably carbonate.
  • the metals in these insoluble salts may be the same as those in oil-soluble detergents or may be different. They are preferably chosen from calcium, magnesium, sodium or barium.
  • the overbased detergents are thus in the form of micelles composed of insoluble metal salts held in suspension in the lubricating composition by the detergents in the form of metal salts soluble in the oil. These micelles may contain one or more types of insoluble metal salts, stabilized by one or more types of detergents.
  • Overbased detergents comprising a single type of detergent-soluble metal salt will generally be named after the nature of the hydrophobic chain of the latter detergent. Thus, they will be called carboxylate, phenate, salicylate, sulfonate, naphthenate type depending on whether this detergent is respectively a carboxylate, phenate, salicylate, sulfonate, or naphthenate.
  • Overbased detergents will be called mixed type if the micelles include several types of detergents, different from each other by the nature of their hydrophobic chain.
  • the oil-soluble metal salts will preferably be carboxylates, phenates, sulfonates, salicylates, and mixed phenate - sulfonate detergents and/or salicylates of calcium, magnesium, sodium or barium.
  • the insoluble metal salts providing the overbased character are carbonates of alkali and alkaline earth metals, preferably calcium carbonate or magnesium carbonate.
  • the overbased detergents used in the lubricating compositions according to the present invention will preferably be carboxylates, phenates, sulfonates, salicylates and mixed phenate - sulfonate - salicylate detergents, overbased on calcium carbonate or magnesium carbonate.
  • the lubricating composition comprises from 4 to 30% by weight of detergents relative to the total weight of the lubricating composition, preferably from 5 to 25%, for example from 6 to 25%.
  • the lubricating composition has a BN determined according to standard ASTM D-2896 less than or equal to 70 milligrams of potash per gram of lubricant, more preferably less than or equal to 60 milligrams.
  • the lubricating composition has a BN determined according to the ASTM D-2896 standard of between 3 and 50 milligrams of potash per gram of lubricant, preferably between 4 and 40 milligrams of potash per gram of lubricant.
  • the base oil included in the lubricating composition is chosen from oils of mineral, synthetic or vegetable origin as well as their mixtures.
  • Mineral or synthetic oils typically used in the application belong to one of the classes defined in the API classification as summarized in the table below.
  • Table 1 Saturates content Sulfur content Viscosity index Group 1 Mineral oils ⁇ 90% > 0.03% 80 ⁇ VI ⁇ 120 Group 2 Hydrocracked oils ⁇ 90% ⁇ 0.03% 80 ⁇ VI ⁇ 120 Group 3 Hydroisomerized oils > 90% ⁇ 0.03% ⁇ 120 Group 4 DTP Group 5 Other bases not included in bases groups 1 to 4
  • Group 1 mineral oils can be obtained by distillation of selected naphthenic or paraffinic crudes and then purification of these distillates by processes such as solvent extraction, solvent or catalytic dewaxing, hydrotreatment or hydrogenation.
  • Group 2 and 3 oils are obtained by more severe purification processes, for example a combination of hydrotreating, hydrocracking, hydrogenation and catalytic dewaxing.
  • Synthetic Group 4 and 5 base oils can be chosen from esters, silicones, glycols, polybutene, polyalphaolefins (PAO), alkylbenzene or alkylnaphthalene.
  • the polyalphaolefins used as base oils are for example obtained from monomers comprising from 4 to 32 carbon atoms, for example from octene or decene, and whose viscosity at 100°C is between 1.5 and 15 mm 2 .s -1 according to ASTM D445. Their average molecular mass is generally between 250 and 3000 according to the ASTM D5296 standard.
  • the base oils can also be oils of natural origin, for example esters of alcohols and carboxylic acids, which can be obtained from natural resources such as sunflower oil, rapeseed oil, palm oil, soy etc.
  • base oils can be used alone or in a mixture.
  • Mineral oil can be combined with synthetic oil.
  • Cylinder oils for 2-stroke marine diesel engines typically have a viscosimetric grade SAE-40 to SAE-60, generally SAE-50 equivalent to a kinematic viscosity at 100°C of between 16.3 and 21.9 mm 2 /s.
  • Grade 40 oils have a kinematic viscosity at 100°C of between 12.5 and 16.3 mm 2 /s.
  • Grade 50 oils have a kinematic viscosity at 100°C of between 16.3 and 21.9 mm 2 /s.
  • Grade 60 oils have a kinematic viscosity at 100°C of between 21.9 and 26.1 mm 2 /s.
  • cylinder oils for 2-stroke marine diesel engines can be formulated to have a kinematic viscosity at 100°C of between 18 and 21.5, preferably between 19 and 21.5 mm 2 /s.
  • This viscosity can be obtained by mixing additives and base oils, for example containing Group 1 mineral bases such as Neutral Solvent bases (for example 500NS or 600 NS) and Brightstock and/or Group 2 mineral bases. Any other combination of mineral, synthetic or plant-based bases having, when mixed with the additives, a viscosity compatible with the SAE-50 grade can be used.
  • Group 1 mineral bases such as Neutral Solvent bases (for example 500NS or 600 NS) and Brightstock and/or Group 2 mineral bases.
  • the lubricating composition comprises at least 40% by weight of base oil(s), preferably at least 50% by weight of base oil(s), more preferably at least 60% by weight of base oil(s), or even at least 70% by weight of base oil(s), relative to the total weight of the lubricating composition.
  • a classic formulation of cylinder lubricant for slow 2-stroke marine diesel engines is of grade SAE 40 to SAE 60, preferably SAE 50 (according to the SAE J300 classification) and comprises at least 50% by weight of one or more oils of lubricating base of mineral and/or synthetic origin, suitable for use in marine engines, for example, API class Group 1 and/or Group 2, that is to say obtained by distillation of selected crudes then purification of these distillates by processes such as solvent extraction, solvent or catalytic dewaxing, hydrotreatment or hydrogenation.
  • Viscosity Index (VI) is between 80 and 120; their sulfur content is greater than 0.03% and their saturated content less than 90%.
  • For Group 2 base oils their Viscosity Index (VI) is between 80 and 120; their sulfur content is less than or equal to 0.03% and their saturated content greater than or equal to 90%.
  • the lubricating composition may further comprise one or more thickening additives whose role is to increase the viscosity of the composition, both hot and cold, or additives improving the index of viscosity (VI).
  • thickening additives whose role is to increase the viscosity of the composition, both hot and cold, or additives improving the index of viscosity (VI).
  • these additives are most often polymers of low molecular weight, of the order of 2000 to 50,000 Dalton (Mn).
  • PIB around 2000 dalton
  • poly-Acrylate or Poly Methacrylates around 30000 dalton
  • Olefin-copolymers Olefin and Alpha Olefin copolymers
  • EPDM Polybutenes
  • High molecular weight poly-Alphaolefins viscosity 100°C > 150
  • Styrene-Olefin copolymers hydrogenated or not.
  • the base oil(s) included in the lubricating composition according to the invention can be partially or totally substituted by these additives.
  • the polymers used to partially or completely substitute one or more of the base oils are preferably the aforementioned thickeners of the PIB type (for example marketed under the name Indopol H2100).
  • the lubricating composition may also comprise at least one anti-wear additive.
  • the anti-wear additive is zinc dithiophosphate or DTPZn.
  • DTPZn dithiophosphate
  • anti-wear additives there is a wide variety of anti-wear additives, but the most used category is that of phospho-sulfur additives such as metal alkylthiophosphates, in particular Zinc alkylthiophosphates, and more specifically Zinc dialkyldithiophosphates or DTPZn.
  • phospho-sulfur additives such as metal alkylthiophosphates, in particular Zinc alkylthiophosphates, and more specifically Zinc dialkyldithiophosphates or DTPZn.
  • Amine phosphates and polysulphides, particularly sulfur olefins, are also commonly used anti-wear additives.
  • anti-wear and extreme pressure additives of the nitrogen and sulfur type such as for example metallic dithiocarbamates, in particular molybdenum dithiocarbamate.
  • Glycerol esters are also anti-wear additives. Examples include mono, di and trioleates, monopalmitates and monomyristates.
  • the lubricating composition may also comprise at least one dispersant.
  • Dispersants are well-known additives used in the formulation of lubricating compositions, particularly for application in the marine sector. Their primary role is to maintain in suspension the particles initially present or appearing in the lubricating composition during its use in the engine. They prevent their agglomeration by playing on steric hindrance. They may also have a synergistic effect on neutralization.
  • Dispersants used as lubricant additives typically contain a polar group, associated with a relatively long hydrocarbon chain, containing generally from 50 to 400 carbon atoms.
  • the polar group typically contains at least one nitrogen, oxygen or phosphorus element.
  • succinimides are used, obtained by condensation of succinic anhydrides and amines, succinic esters obtained by condensation of succinic anhydrides and alcohols or polyols.
  • These compounds can then be treated with various compounds including sulfur, oxygen, formaldehyde, carboxylic acids and compounds containing boron or zinc to produce, for example, borated succinimides or zinc-blocked succinimides.
  • Mannich bases obtained by polycondensation of phenols substituted with alkyl groups, formaldehyde and primary or secondary amines, are also compounds used as dispersants in lubricants.
  • the lubricating composition may further comprise all types of functional additives adapted to their use, for example anti-foam additives, which may for example be polar polymers such as polymethylsiloxanes, polyacrylates, anti-foam additives.
  • oxidants and/or anti-rust agents for example organometallic detergents or thiadiazoles. These are known to those skilled in the art.
  • compositions of the lubricants described refer to the compounds taken separately before mixing, it being understood that said compounds may or may not retain the same chemical form before and after mixing.
  • the lubricants according to the present invention obtained by mixing the compounds taken separately are not in the form of emulsion or microemulsion.
  • the lubricating composition used in the invention comprises at least one additive chosen from detergents, dispersants, and their mixture.
  • the lubricating composition used in the invention comprises one or more detergents and one or more dispersants.
  • the mass proportion of detergent(s) will preferably be greater than the mass proportion of dispersant(s) and if the lubricating composition is used in a marine engine. controlled ignition, then the mass proportion of detergent(s) will preferably be less than the mass proportion of dispersant(s).
  • copolymer (C) according to the invention makes it possible to reduce and/or control the entrainment of droplets (or particles) of lubricating composition with the intake air, thus limiting the presence of lubricating composition in the combustion chamber which reduces and/or controls abnormal combustion of gas in an engine, such as a marine engine or a spark ignition engine, particularly in a marine engine.
  • the engine is a marine engine, in particular a pure gas or dual fuel engine, two-stroke or four-stroke.
  • the use of the copolymer (C) according to the invention makes it possible to reduce and/or control the abnormal combustion of gas in an engine, preferably a marine engine, from the automobile -inflammation of the lubricating composition.
  • the use of the copolymer (C) according to the invention in a lubricating composition makes it possible to reduce and/or control the abnormal combustion of any type of gas, in particular gas having a number of low methane (NM), preferably a methane number less than 80, more preferably less than 60.
  • NM low methane
  • Another object of the invention covers a method for reducing the quantity of lubricating composition in the combustion chamber of an engine, the method comprising the use of a copolymer (C) in said lubricating composition.
  • the engine is as defined above, in particular it may be a marine engine or a spark-ignition engine, preferably the engine is a marine engine.
  • copolymer (C) and the lubricating composition are as defined above.
  • the present invention also relates to the use of the copolymer (C) or the lubricating composition according to the invention to reduce and/or control the abnormal combustion of gas in an engine, preferably a marine engine, in particular a pure gas marine engine. or dual fuel, two-stroke or four-stroke.
  • an engine preferably a marine engine, in particular a pure gas marine engine. or dual fuel, two-stroke or four-stroke.
  • the present invention also relates to the use of the copolymer (C) or the lubricating composition according to the invention to reduce and/or control the abnormal combustion of gas in an engine, preferably a marine engine, resulting from self-ignition of the lubricating composition.
  • the use according to the invention relates to any type of gas, in particular gas having a low methane number (NM), preferably a methane number less than 80, more advantageously less than 60.
  • NM low methane number
  • the present invention also relates to a method for reducing and/or controlling abnormal gas combustion in an engine comprising lubricating the engine with a lubricating composition according to the invention or a lubricating composition comprising at least one copolymer (C) according to the invention.
  • the engine being as defined above, preferably, the engine is a marine engine, in particular of the pure gas or dual fuel type, two-stroke or four-stroke.
  • the present invention also relates to a method for reducing and/or controlling the abnormal combustion of gas in an engine resulting from the self-ignition of the lubricating composition comprising the lubrication of the engine with a lubricating composition according to the invention or a lubricating composition comprising at least one copolymer (C) according to the invention.
  • the engine being as defined above, preferably, the engine is a marine engine, in particular of the pure gas or dual fuel type, two-stroke or four-stroke.
  • the methods according to the invention relate to any type of gas, in particular gas having a low methane number (NM), preferably a methane number less than 80, more advantageously less than 60.
  • NM low methane number
  • the test to measure the frequency of pre-ignitions of the gas mixture when using different lubricating compositions was carried out in a single-cylinder gas engine comprising a combustion chamber with a bore of 108 mm and a stroke of 115 mm respectively. with a compression ratio of 11.4, corresponding to a single-cylinder displacement of 1054 cm 3 .
  • the rotation speed of the single-cylinder gas engine is 1000 rpm.
  • the operating point retained is equivalent to an Average Indicated Pressure of 23 bar, corresponding to a representative application of high engine load.
  • the single-cylinder gas engine has a spark plug ignition system with “open chamber” technology in order to be able to repeat the ignition command precisely on each engine combustion cycle.
  • the single-cylinder gas engine also has a cylinder pressure sensor in order to measure the evolution of the pressure in the cylinder, determine the maximum cylinder pressure values at each engine cycle and calculate the energy release produced during the combustion cycle.
  • a mixture Prior to the test to measure the abnormal combustion of a gas in the combustion chamber, a mixture is prepared consisting of gas having a methane number equivalent to 70% and air comprising nitrogen and oxygen with a excess air ratio (air/gas) of 1.6 compared to the stoichiometric ratio used for gas combustion.
  • air/gas excess air ratio
  • the air/gas mixture is heated to a temperature of approximately 55°C then gradually increased, in particular up to a maximum temperature of 110°C, and admitted compressed to 3.6 bar in the single-cylinder gas engine.
  • the copolymer (C) is obtained according to the following protocol: In a quadricol equipped with a stirrer, a condenser, a thermocouple and a nitrogen purge, 645.5 g of water and 8.7 g of Aerosol ® OT are added. Agitation is set at 200 rpm (revolution per minute) and the nitrogen purge is started. To the reaction mixture are added 240 g of C10-C18 alkyl methacrylate, 60 g of 2-ethylhexyl methacrylate and 129.9 g of acetone. The reaction medium is heated to 43°C via a water bath set at 45°C.
  • reaction medium When the reaction medium has reached 43°C, 0.04 g of t-butyl hydroperoxide in 7.5 g of water are added. After 5 minutes, 0.29g of sodium ascorbate dissolved in 7.5g of water and 0.60g of a 0.25% solution of iron sulfate ion hexahydrate are added. The nitrogen purge is replaced by nitrogen inerting. The reaction continues for 5 hours, then the reaction mixture is allowed to cool to room temperature and isolated.
  • Example 1 Experimental protocol for measuring the frequency of pre-ignition initiations by the lubricant before the ignition command of the single-cylinder gas engine and the frequency of abnormal combustion generated by the pre-ignition of the lubricant
  • the heat release law is measured for each combustion cycle.
  • the ignition control is set repeatably at -4° crankshaft angle before top dead center.
  • each increase in energy release beginning before -6° crankshaft angle is counted as an abnormal pre-ignition generated by the lubricant before the main ignition command of the engine.
  • the test is started at an inlet temperature of the air-gas premix set at approximately 55°C. Throughout the test, the temperature is gradually increased until a pre-ignition event is observed. All of these abnormal events compared to all of the 15,000 combustion events recorded during the 30 minutes of each test gives the frequency of abnormal pre-ignition generated by the lubricant before the main ignition command of the engine.
  • the maximum pressure reached in the cylinder is measured for each cycle.
  • the test is started at an inlet temperature of the air-gas premix set at approximately 55°C. Throughout the test, the temperature is gradually increased until a pre-ignition event is observed.
  • the operating point of the single-cylinder gas engine is fixed, and generates a normal maximum cylinder pressure of 80 bar. In the event of abnormal combustion, it is considered that the maximum cylinder pressure of the combustion chamber must exceed the limit of 120 bar for the cycle to be counted as abnormal pre-ignition generated by the lubricant. All of these abnormal events compared to all of the 15,000 combustion events recorded during the 30 minutes of each test gives the frequency of abnormal pre-ignition generated by the lubricant.
  • This test makes it possible to highlight, among other things, the effect of the lubricant on the resistance to the phenomenon of pre-ignition of the air/gas mixture due to the self-ignition of the lubricant before the normal ignition command and the effect of the lubricant on the intensity of the maximum cylinder pressure peaks in the event of abnormal combustion, representing the energy released by the abnormal combustion.
  • the results shown in the figure 1 are generated from temperature conditions in which an abnormal combustion phenomenon is initiated and reflect the intensity of the abnormal combustion phenomenon.
  • the pre-ignition frequency is measured by the lubricating composition. It is observed that this percentage decreases for the composition according to the invention. Furthermore, we note that the pre-ignition by the lubricant starts at a higher temperature for the lubricating compositions according to the invention.
  • compositions according to the invention make it possible both to limit the appearance of abnormal combustion phenomena and at the same time to limit its intensity, unlike the comparative composition.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Lubrication Details And Ventilation Of Internal Combustion Engines (AREA)
  • Lubrication Of Internal Combustion Engines (AREA)
EP20718332.8A 2019-04-18 2020-04-17 Procede de reduction et/ou controle de la combustion anormale du gaz dans un moteur marin ou un moteur a allumage commande Active EP3956423B1 (fr)

Applications Claiming Priority (2)

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FR1904164A FR3095209B1 (fr) 2019-04-18 2019-04-18 Procede de reduction et/ou controle de la combustion anormale du gaz dans un moteur marin ou un moteur a allumage commande
PCT/EP2020/060835 WO2020212562A1 (fr) 2019-04-18 2020-04-17 Procede de reduction et/ou controle de la combustion anormale du gaz dans un moteur marin ou un moteur a allumage commande

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US7648950B2 (en) * 2005-04-22 2010-01-19 Rohmax Additives Gmbh Use of a polyalkylmethacrylate polymer
US20150322368A1 (en) 2014-05-09 2015-11-12 Exxonmobil Research And Engineering Company Method for preventing or reducing low speed pre-ignition
FR3039836B1 (fr) 2015-08-06 2017-09-15 Total Marketing Services Compositions lubrifiantes pour prevenir ou diminuer le pre-allumage dans un moteur
FR3043691A1 (fr) 2015-11-12 2017-05-19 Total Marketing Services Compositions lubrifiantes pour prevenir ou diminuer la combustion anormale dans un moteur de vehicule automobile
EP3680313B1 (en) * 2016-06-17 2022-03-23 Total Marketing Services Lubricant polymers
KR102059973B1 (ko) * 2016-06-17 2019-12-27 아크조 노벨 케미칼즈 인터내셔널 비.브이. 윤활제 스프레이 폴리머
EP3257920A1 (en) 2016-06-17 2017-12-20 Total Marketing Services Lubricant polymers
FR3065964B1 (fr) * 2017-05-04 2020-03-13 Total Marketing Services Utilisation d'une amine grasse pour reduire et/ou controler la combustion anormale du gaz dans un moteur marin

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CN113710781B (zh) 2022-10-11
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WO2020212562A1 (fr) 2020-10-22
DK3956423T3 (da) 2024-01-15
ES2967917T3 (es) 2024-05-06
US20220213402A1 (en) 2022-07-07
FR3095209A1 (fr) 2020-10-23
CN113710781A (zh) 2021-11-26
JP7558968B2 (ja) 2024-10-01
JP2022529279A (ja) 2022-06-20
SG11202111291PA (en) 2021-11-29
US12043815B2 (en) 2024-07-23

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