WO2021240117A1 - Use of a fuel composition comprising three additives for cleaning the internal parts of petrol engines - Google Patents

Use of a fuel composition comprising three additives for cleaning the internal parts of petrol engines Download PDF

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Publication number
WO2021240117A1
WO2021240117A1 PCT/FR2021/050971 FR2021050971W WO2021240117A1 WO 2021240117 A1 WO2021240117 A1 WO 2021240117A1 FR 2021050971 W FR2021050971 W FR 2021050971W WO 2021240117 A1 WO2021240117 A1 WO 2021240117A1
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Prior art keywords
fuel
group
additive
additives
use according
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PCT/FR2021/050971
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French (fr)
Inventor
Jérôme OBIOLS
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Totalenergies Marketing Services
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Application filed by Totalenergies Marketing Services filed Critical Totalenergies Marketing Services
Priority to EP21734411.8A priority Critical patent/EP4157972A1/en
Priority to US17/928,141 priority patent/US20230212473A1/en
Priority to CN202180038622.1A priority patent/CN115667467A/en
Publication of WO2021240117A1 publication Critical patent/WO2021240117A1/en

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • C10L1/2387—Polyoxyalkyleneamines (poly)oxyalkylene amines and derivatives thereof (substituted by a macromolecular group containing 30C)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0415—Light distillates, e.g. LPG, naphtha
    • C10L2200/0423—Gasoline
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/22—Function and purpose of a components of a fuel or the composition as a whole for improving fuel economy or fuel efficiency
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2250/00—Structural features of fuel components or fuel compositions, either in solid, liquid or gaseous state
    • C10L2250/04—Additive or component is a polymer
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines

Definitions

  • TITLE USE OF A FUEL COMPOSITION CONTAINING 3 ADDITIVES TO CLEAN THE INTERNAL PARTS OF ENGINES
  • the present invention relates to the use, for reducing and / or preventing deposits present in the internal parts of a spark ignition engine, of a fuel composition which comprises at least three additives: a quaternary ammonium salt, a non-quaternary polyisobutylene succinimide, and a Mannich base, different from the other two additives.
  • the composition is such that the mass ratio of the amount of the first additive to the amount of the second additive is in the range from 0.2: 1 to 2.5: 1.
  • the invention also relates to the use, for improving the detergency properties of gasoline fuel, of a fuel concentrate comprising at least said three additives, in admixture with an organic liquid inert to said additives.
  • the composition is also used to maintain cleanliness (keep-clean effect) and / or to clean (clean-up effect) deposits in the engine, as well as to reduce the fuel consumption of the engine (“Fuel Eco” action) and / or minimize the loss of power of said engine, and / or reduce the emissions of pollutants, in particular, the emissions of particles from the combustion engine, and / or to reduce the clogging of the pistons of the engine, preferably in direct gasoline injection ( or IDE).
  • IDE direct gasoline injection
  • Liquid internal combustion engine fuels contain components that can be degraded during engine operation.
  • the problem of deposits in the internal parts of combustion engines is well known to engine manufacturers. It has been shown that the formation of these deposits has consequences on engine performance and in particular has a negative impact on fuel consumption and particle emissions (Gueit, J. et al., "Injector Fouling in Direct Injection Spark Ignition Engines - A New Test Procedure for the Evaluation of Gasoline Additives, "SAE Technical Paper 2017-01-2294). Advances in fuel additive technology have made it possible to tackle this problem. So-called detergent additives used in fuels have already been proposed to keep the engine clean by limiting deposits (“keep-clean” effect) or by reducing deposits already present. in the internal parts of the combustion engine (“clean-up” effect in English). Mention may be made, by way of example, of document US Pat. No. 4,171959 which describes a detergent additive for gasoline fuel containing a quaternary ammonium function.
  • the new gasoline direct injection systems expose the injectors to more severe pressure and temperature conditions, which favors the formation of deposits.
  • these new injection systems have more complex geometries to optimize spraying, in particular, more holes having smaller diameters but which, on the other hand, induce a greater sensitivity to deposits.
  • the presence of deposits can alter combustion performance, in particular increase pollutant emissions and particulate emissions.
  • a first type of deposit consists of those which form at high temperature on the intake valves of spark-ignition engines with indirect injection when using a fuel which does not contain any carbonate additive. detergency. These deposits consist in particular of carbonaceous residues associated with the phenomenon of coking (“coking” in English) and can also include deposits of the soap and / or varnish type (in English “lacquering”). These deposits are generally treated by the use of a detergent additive added to the fuel (additive fuel).
  • a second type of deposit consists of the viscous deposits, mentioned previously, which form at low temperature and appear on the intake valves of spark ignition engines with indirect injection when using additive fuels, thus causing the valve sticking phenomenon described above.
  • WO2006135881 describes a detergent additive containing a quaternary ammonium salt used to reduce or clean deposits in particular on the intake valves.
  • a fuel composition comprising at least three additives, as described below, has remarkable and unexpected detergency properties for internal combustion engines, preferably gasoline, known under the name spark ignition engines.
  • This combination of additives guarantees and improves the detergent power of fuels intended for internal combustion engines. It also produces an unexpected synergistic effect.
  • a subject of the present invention is thus the use, for reducing and / or preventing deposits in the internal parts of a spark-ignition engine, of a fuel composition
  • a fuel composition comprising:
  • additive (3) at least a third additive, different from additives (1) and (2), consisting of a Mannich base, and in which the mass ratio of the amount of the first additive to the amount of the second additive is included in the range from 0.2: 1 to 2.5: 1.
  • the mass ratio of the amount of the first additive to the amount of the second additive in the composition is in the range ranging from 1: 1 to 2: 1, and preferably ranging from 1.25: 1 to 1.5. : 1.
  • a subject of the invention is also the use of the composition, to maintain cleanliness (keep-clean effect) and / or clean (clean-up effect) the deposits in the internal parts of a spark-ignition engine, chosen from among the following: the combustion chamber and the fuel injection system, and preferably the fuel injection system.
  • a further subject of the invention is the use, to improve the detergency properties of a gasoline fuel, of a fuel concentrate comprising at least the above three additives, mixed with an organic liquid, said organic liquid. being inert with respect to the first, second and third additives, and miscible with said fuel.
  • the invention also relates to a method of maintaining the cleanliness and / or cleaning of at least one of the internal parts of a spark ignition engine (or internal combustion gasoline engine), comprising at least the following steps:
  • CN compound or group denotes a compound or a group containing in its chemical structure N carbon atoms.
  • the first additive quaternary ammonium
  • the composition according to the invention comprises a first additive consisting of a quaternary ammonium salt, obtained, in a first embodiment, by reaction with a quaternization agent of a nitrogen compound comprising a tertiary amine function, this nitrogen compound. being the reaction product of an acylating agent substituted with a hydrocarbon group and of a compound comprising at least one tertiary amine group and at least one group chosen from primary amines, secondary amines and alcohols.
  • the quaternary ammonium salt is chosen from quaternized PIBA (polyisobutylene-amine) compounds, or from quaternized polyether-amines.
  • said nitrogenous compound is the product of the reaction of an acylating agent substituted with a hydrocarbon group and of a compound comprising both an oxygen atom or a d atom.
  • nitrogen capable of condensing with said acylating agent that is to say that this compound comprises at least one group chosen from primary amines, secondary amines and alcohols) and a tertiary amine group.
  • the acylating agent is advantageously chosen from mono-or poly-carboxylic acids and their derivatives, in particular their ester, amide or anhydride derivatives.
  • the acylating agent is preferably chosen from succinic, phthalic and propionic acids and the corresponding anhydrides.
  • the acylating agent is substituted by a hydrocarbon group.
  • hydrocarbon group is understood to mean any group having a carbon atom directly attached to the rest of the molecule (ie to the acylating agent) and having mainly an aliphatic hydrocarbon character.
  • Hydrocarbon groups according to the invention can also contain non-hydrocarbon groups. For example, they can contain up to one non-hydrocarbon group per ten carbon atoms provided that the non-hydrocarbon group does not significantly modify the predominantly hydrocarbon character of the group.
  • the hydrocarbon substituents do not contain such non-hydrocarbon groups and are purely aliphatic hydrocarbons.
  • the hydrocarbon substituent of the acylating agent preferably comprises at least 8, preferably at least 12 carbon atoms. Said hydrocarbon substituent may comprise up to about 200 carbon atoms.
  • the hydrocarbon substituent of the acylating agent preferably has a number average molecular weight (Mn) of between 160 to 2800, for example between 250 to 2000, more preferably between 500 to 1500 and, even more preferably between de 500 to 1300.
  • Mn number average molecular weight
  • a range of value of M n between 700 and 1300 is particularly preferred, for example from 700 to 1200.
  • hydrocarbon groups substituting the acylating agent mention may be made of n-octyl, n-decyl, n-dodecyl, tetrapropenyl, n-octadecyl, oleyl, octadecyl or triacontyl groups.
  • the hydrocarbon substituent of the acylating agent can also be obtained from homo- or inter-polymers (for example copolymers, terpolymers) of mono- and di-olefins having from 2 to 10 carbon atoms, for example from ethylene, propylene, 1 -butene, isobutene, butadiene, isoprene, 1-hexene or 1-octene.
  • these olefins are 1-mono-olefins.
  • the hydrocarbon substituent of the acylating agent can also be chosen from derivatives of halogenated analogues (for example chlorinated or brominated) of these homopolymers or inter-polymers.
  • the hydrocarbon substituent of the acylating agent can be obtained from other sources, for example from high molecular weight alkenes monomers (eg, 1 -tetracontene) and their chlorinated analogues or hydrochlorinated, aliphatic petroleum fractions, for example paraffin waxes, their cracked, chlorinated and / or analogues thereof hydrochlorides, white oils, synthetic alkenes, for example produced by the Ziegler-Natta process (for example polyethylene fats) and other sources known to those skilled in the art.
  • high molecular weight alkenes monomers eg, 1 -tetracontene
  • aliphatic petroleum fractions for example paraffin waxes, their cracked, chlorinated and / or analogues thereof hydrochlorides
  • white oils for example synthetic alkenes, for example produced by the Ziegler-Natta process (for example polyethylene fats) and other sources known to those skilled in the art.
  • Any unsaturation present in the hydrocarbon group of the acylating agent can optionally be reduced or eliminated by hydrogenation according to any known process.
  • the hydrocarbon substituent of the acylating agent is preferably substantially saturated, i.e., it does not contain more than one carbon-to-carbon unsaturated bond for each slice of ten carbon-to-carbon single bonds. present.
  • the hydrocarbon substituent of the acylating agent advantageously contains no more than one non-aromatic carbon-to-carbon unsaturated bond per every 50 carbon-to-carbon bonds present.
  • the hydrocarbon substituent of the acylating agent is a polyisobutene group also called polyisobutylene (PIB).
  • PIB polyisobutylene
  • PIB polyisobutylene
  • Highly reactive polyisobutenes (PIB) are understood to mean polyisobutenes (PIB) in which at least 50 mol%, preferably at least 70 mol% or more, of the terminal olefinic double bonds are of the vinylidene type as described in document EP0565285.
  • preferred PIBs are those having more than 80 mole% and up to 100 mole% of vinylidene end groups as described in EP 1344785.
  • the acylating agent substituted with a hydrocarbon group is a polyisobutenyl succinic anhydride (PIB SA).
  • polyisobutenyl succinic anhydride can be prepared by mixing a polyolefin with maleic anhydride and then passing chlorine through the mixture (GB949981).
  • hydrocarbon groups comprising an internal olefin, for example such as those described in application WO2007 / 015080, can also be used as a substituent for the acylating agent.
  • internal olefin any olefin containing predominantly one non-alpha double bond, which is a beta or higher position olefin.
  • these materials are essentially beta-olefins or higher position olefins, for example containing less than 10% by mass of alpha-olefin, advantageously less than 5% by mass or less than 2% by mass.
  • Internal olefins can be prepared by isomerization of alpha-olefins according to any known process.
  • the compound comprising both an oxygen atom or a nitrogen atom capable of condensing with the acylating agent and a tertiary amine group can, for example, be chosen from the group consisting of: dimethylaminopropylamine, N, N-diethylaminopropylamine, N, N- dimethylamino-ethylamine, N, N-dimethyl-amino ethylamine ethylenediamine, 1,2-propylenediamine, 1, 3-propylene diamine, butylenediamines (isomers), diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetetraamine, teraethylenepentaamine, pentaethylenehexaamine, hexamethylenetetramine, bis (hexametliylene) triamine, diaminobenzenes, and the pentanediamines, hexanediamines, Nyopamine, and preferably heptanediamine
  • Said compound can also be chosen from heterocyclic compounds substituted by alkylamines such as l - (3- aminopropyl) -imidazole, 4- (3-aminopropyl) morpholine, l- (2-aminoethyl) piperidine, 3 , 3-diamino-N-methyldipropylamine, diaminopyridines, and 3'3-bisamino (N, N-dimethylpropylamine).
  • alkylamines such as l - (3- aminopropyl) -imidazole, 4- (3-aminopropyl) morpholine, l- (2-aminoethyl) piperidine, 3 , 3-diamino-N-methyldipropylamine, diaminopyridines, and 3'3-bisamino (N, N-dimethylpropylamine).
  • the compound comprising both an oxygen atom or a nitrogen atom capable of condensing with the acylating agent and a tertiary amine group can also be selected from alkanolamines, including, but not limited to. , triethanolamine, trimethanolamine, N, N-dimethylaminopropanol, N, N-dimethylaminoethanol, N, N- diethylaminopropanol, N, N-diethylaminoethanol, N, N- diethylaminobutanol, N, N, N-tris (hydroxyethyl ) amine, N, N, N- tris (hydroxymethyl) amine, laN, N, N tris (aminoethyl) amine, N, N- dibutylaminopropylamine and N, N, N'-trimethyl-N'-hydroxyethyl- bisaminoethyl ether , N, N-bis (3-dimethylamino-propyl
  • R6 and R7 are the same or different and represent, independently of each other, an alkyl group having 1 to 22 carbon atoms, preferably having 1 to 5 carbon atoms;
  • X is an alkylene group having 1 to 20 carbon atoms, preferably 1 to 5 carbon atoms; m is an integer between 1 and 5; n is an integer between 0 and 20; and
  • R8 is a hydrogen atom or a C1 to C22 alkyl group.
  • Said compound is preferably chosen from amines of formula
  • R8 is preferably a hydrogen atom or an alkyl C l -C 16, preferably an alkyl group of Cl to CIO, more preferably an alkyl group C l to C6.
  • R8 can, for example, be selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl and their isomers.
  • R8 is a hydrogen atom.
  • n is preferably an integer between 0 to 15, more preferably between 0 to 10, even more preferably between 0 to 5.
  • n is 0.
  • said nitrogenous compound is the product of the reaction of the acylating agent substituted with a hydrocarbon group and of a diamine of formula (I).
  • R6 and R7 represent, independently of one another, a group C1 to C16 alkyl , preferably a C1 to C10 alkyl group;
  • R6 and R7 represent, independently of one another, a methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl group or their isomers.
  • R6 and R7 represent, independently of one another, a C1 to C4 group, preferably a methyl group;
  • - X represents an alkylene group having 1 to 16 carbon atoms, preferably from 1 to 12 carbon atoms, more preferably from 1 to 8 carbon atoms, for example from 2 to 6 carbon atoms or from 2 to 5 carbon atoms. carbon.
  • X particularly preferably represents an ethylene, propylene or butylene group, in particular a propylene group.
  • the nitrogenous compound is the reaction product of a succinic acid derivative substituted with a hydrocarbon group, preferably a polyisobutenyl succinic anhydride, and of an alcohol or of an amine also comprising a tertiary amine group, in particular a compound of formula (I) or (II) as described above and more preferably a compound of formula (I).
  • a succinic acid derivative substituted with a hydrocarbon group preferably a polyisobutenyl succinic anhydride
  • an alcohol or of an amine also comprising a tertiary amine group, in particular a compound of formula (I) or (II) as described above and more preferably a compound of formula (I).
  • the succinic acid derivative substituted with a hydrocarbon group reacts with the amine also comprising a tertiary amine group under certain conditions to form a succinimide (closed form).
  • the reaction of the succinic acid derivative and the amine can also result under certain conditions in a succinamide, that is to say, a compound comprising an amide group and a carboxylic acid group (open form).
  • an alcohol also comprising a tertiary amine group reacts with the succinic acid derivative to form an ester also comprising a free carboxyl group —CO2H (open form).
  • the nitrogenous compound may be the reaction product of a succinic acid derivative and an amine or an alcohol which is an ester or an amide and which further also comprises a carboxyl group -CO 2 H unreacted (open form).
  • the quaternary ammonium salt forming the first additive according to the present invention is obtained directly by reaction between the nitrogenous compound described above comprising a tertiary amine function and a quaternization agent.
  • the quaternization agent is chosen from the group constituting dialkyl sulphates, carboxylic acid esters, alkyl halides, benzyl halides, hydrocarbon carbonates, and hydrocarbon epoxides. optionally as a mixture with an acid, alone or as a mixture, preferably the carboxylic acid esters.
  • quaternizing agent containing such an element it may be advantageous to perform a subsequent reaction to exchange the counterion.
  • a quaternary ammonium salt formed by reaction with an alkyl halide can then be reacted with sodium hydroxide and the sodium halide salt removed by filtration.
  • the quaternizing agent can include halides such as chloride, iodide or bromide; hydroxides; sulfonates; bisulfites; alkyl sulphates such as dimethyl sulphate; sulfones; phosphates; C1-C12 alkylphosphates ; C1-C12 dialkylphosphates; borates; C 1-C12 alkylborates; nitrites; nitrates; carbonates; bicarbonates; alkanoates; C 1 -C 12 0,0-dialkyldithiophosphates , alone or as a mixture.
  • the quaternization agent can be chosen from derivatives of dialkylsulphates such as dimethyl sulphate, of N-oxides, of sulphones such as propane- and butanesulfone, of alkyl halides. , acyl or aralkyl such as methyl and ethyl chloride, benzyl bromide, iodide or chloride, and hydrocarbon carbonates (or alkylcarbonates).
  • the aromatic ring is optionally substituted by one or more alkyl or alkenyl groups.
  • the hydrocarbon (alkyl) groups of the hydrocarbon carbonates can contain from 1 to 50, from 1 to 20, from 1 to 10 or from 1 to 5 carbon atoms per group. According to one embodiment, the hydrocarbon carbonates contain two hydrocarbon groups which may be identical or different. By way of example of hydrocarbon carbonates, mention may be made of dimethyl or diethyl carbonate.
  • the quaternization agent is chosen from the hydrocarbon epoxides represented by the following formula (III): in which R9, R10, R11 and R12 may be the same or different and represent, independently of each other, a hydrogen atom or a C 1 -C 50 hydrocarbon group .
  • R9, R10, R11 and R12 may be the same or different and represent, independently of each other, a hydrogen atom or a C 1 -C 50 hydrocarbon group .
  • R9, R10, R11 and R12 may be the same or different and represent, independently of each other, a hydrogen atom or a C 1 -C 50 hydrocarbon group .
  • R9, R10, R11 and R12 may be the same or different and represent, independently of each other, a hydrogen atom or a C 1 -C 50 hydrocarbon group .
  • styrene oxide ethylene oxide
  • propylene oxide propylene oxide
  • butylene oxide stilbene oxide
  • hydrocarbon epoxides can be used as a quaternizing agent in combination with an acid, for example with acetic acid.
  • the hydrocarbon epoxides can also be used alone as a quaternization agent, in particular without additional acid.
  • a protic solvent is used for the preparation of the quaternary ammonium salt.
  • protic solvents such as water, alcohols (including polyhydric alcohols) can be used alone or as a mixture.
  • Preferred protic solvents have a dielectric constant greater than 9.
  • the quaternization agent is chosen from the compounds of formula (IV): wherein R13 is an optionally substituted alkyl, alkenyl, aryl and aralkyl group, and R14 is a C1 to C22 alkyl, aryl or alkylaryl group.
  • the compound of formula (IV) is a carboxylic acid ester capable of reacting with a tertiary amine to form a quaternary ammonium salt.
  • Compounds of formula (IV) are selected, for example, from esters of carboxylic acids having a pKa of 3.5 or less.
  • the compound of formula (IV) is preferably chosen from esters of substituted aromatic carboxylic acid, of alpha-hydroxycarboxylic acid and of polycarboxylic acid.
  • the ester is a substituted aromatic carboxylic acid ester of formula (IV) in which R13 is a substituted aryl group.
  • R13 is a substituted aryl group having 6 to 10 carbon atoms, preferably a phenyl or naphthyl group, more preferably a phenyl group.
  • R13 is advantageously substituted with one or more groups chosen from the carboalkoxy, nitro, cyano, hydroxy, SR15 and NR15R16 radicals.
  • Each of the groups R15 and Rm can be a hydrogen atom or an optionally substituted alkyl, alkenyl, aryl or carboalkoxy group.
  • Each of the groups R15 and Ri 6 represents, advantageously, the hydrogen atom or an optionally substituted C 1 to C22 alkyl group, preferably the hydrogen atom or a C 1 to C16 alkyl group , more preferably 1 hydrogen atom or a C1 to C4 alkyl group, even more preferably the hydrogen atom or a C1 to C4 alkyl group.
  • R15 is preferably a hydrogen atom and R 1 6 a hydrogen atom or a C1 to C4 group.
  • R15 and Ri 6 are both hydrogen.
  • R13 is an aryl group substituted by one or more groups chosen from hydroxyl, carboalkoxy, nitro, cyano and NH2 radicals.
  • R13 can be a polysubstituted aryl group, for example trihydroxyphenyl.
  • R13 is a monosubstituted aryl group, preferably ortho substituted.
  • R13 is, for example, substituted by a group chosen from the OH, NH2, NO2 or COOMe radicals, preferably OH or NH2.
  • R13 is preferably a hydroxy-aryl group, in particular 2-hydroxyphenyl.
  • R14 is an alkyl or alkylaryl group.
  • R14 can be a C 1 to C16 , preferably C 1 to C10, advantageously C 1 to C8 alkyl group.
  • R14 may be a C 1 to C16, preferably C 1 to Cio , advantageously C 1 to C8 alkylaryl group.
  • R14 can for example be chosen from methyl, ethyl, propyl, butyl, pentyl, benzyl or their isomers.
  • R14 is a benzyl or methyl group, more preferably methyl.
  • a particularly preferred compound is methyl salicylate.
  • the compound of formula (IV) is an ester of an alpha-hydroxycarboxylic acid corresponding to the formula (V) following: wherein R17 and R18 are the same or different and are independently selected from the group consisting of the hydrogen atom, alkyl, alkenyl, aryl or aralkyl groups.
  • R17 and R18 are the same or different and are independently selected from the group consisting of the hydrogen atom, alkyl, alkenyl, aryl or aralkyl groups.
  • Examples of compounds of formula (IV) in which R13COO is the residue of an alpha-hydroxycarboxylic acid include methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, phenyl-, benzyl- or allyl- 2-hydroxy-isobutyric acid esters; methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-, phenyl- or allyl-esters of 2-hydroxy-2-methylbutyric acid; 2-hydroxy-2-ethylbutyric acid methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-, phenyl- or allyl-esters; methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-,
  • the compound of formula (IV) is an ester of a polycarboxylic acid chosen from dicarboxylic acids and carboxylic acids having more than two acid functions.
  • the carboxylic functions are preferably all in esterified form.
  • Preferred esters are C 1-4 alkyl esters.
  • the compound of formula (IV) can be chosen from oxalic acid diesters, phthalic acid diesters, maleic acid diesters, malonic acid diesters or citric acid diesters.
  • the compound of formula (IV) is dimethyl oxalate.
  • the compound of formula (IV) is a carboxylic acid ester having a pKa of less than 3.5.
  • the compound comprises more than one acidic group, reference will be made to the first dissociation constant.
  • the compound of formula (IV) can be chosen from one or more carboxylic acid esters chosen from oxalic acid, phthalic acid, salicylic acid, maleic acid, malonic acid, citric acid. , nitrobenzoic acid, aminobenzoic acid and 2,4,6-acid trihydroxybenzoic acid.
  • Preferred compounds of formula (IV) are dimethyl oxalate, methyl 2-nitrobenzoate and methyl salicylate.
  • the quaternary ammonium salt used in the invention is formed by reaction of a hydrocarbon epoxide, preferably chosen from those of formula (III) above and more preferably propylene oxide. , with the reaction product of a polyisobutenyl succinic anhydride in which the polyisobutylene group (PIB) has a number-average molecular mass (Mn) of between 700 and 1000 and dimethyl-aminoprop y lamin.
  • PIB polyisobutenyl succinic anhydride in which the polyisobutylene group (PIB) has a number-average molecular mass (Mn) of between 700 and 1000 and dimethyl-aminoprop y lamin.
  • the additive (1) is chosen from polyisobutylene succinimides functionalized with a quaternary ammonium group.
  • the composition according to the invention comprises the first additive (s) as described above in a preferential content ranging from 5 to 10,000 ppm by weight, preferably from 5 to 1000 ppm by weight, more preferably from 10 to 500 ppm by weight , more preferably from 15 to 200 ppm by weight, and better still from 20 to 150 ppm by weight, relative to the total weight of the fuel composition.
  • the second additive polyisobutylene succinimide
  • composition according to the invention comprises a second additive (2) consisting of a non-quaternary polyisobutylene succinimide, that is to say that it does not contain a quaternary ammonium group.
  • said second additive results from the condensation: of a compound A consisting of a dicarboxylic acid substituted with a polyisobutylene group or of an anhydride of such a diacid, with a compound B consisting of a primary polyamine of general formula (VI) below:
  • RI and R2 identical or different, represent hydrogen or a hydrocarbon group comprising from 1 to 4 carbon atoms, n is an integer varying from 1 to 3, m is an integer varying from 1 to 10, preferably from 1 to 4; and p is an integer equal to 0 or 1.
  • said additive (2) is obtained by condensation of compound A with compound B, used in amounts such that the molar ratio A / B is in the range going from 1: 1 to 1: 3 .
  • the molar ratio A / B is included in the range going from 1: 1, 1 to 1: 2, even more preferably the molar ratio A / B is included in the range going from 1: 1, 1 to 1: 1, 5.
  • Said additive (2) can in particular be obtained by condensation of 60 to 90% by weight of compound A, and from 10 to 30% by weight of compound B.
  • the average molar mass of the compounds A according to the present invention varies from 200 to 3000, preferably from 200 to 2000 g / mol, preferably from 200 to 1500 g / mol, even more preferably from 900 to 1300 g / mol. These compounds are well known from the prior art.
  • the polyamines of the group consisting of diethylene triamine, dipropylene triamine, triethylene tetramine, tetraethylene pentamine and their substituted derivatives, or mixtures thereof, are preferred.
  • the compound B that is to say the primary polyamine of formula (VI) is added to the compound A, that is to say the acid (s) carboxylic hydrocarbon (s) ( s) or anhydride (s).
  • Polyamine B is gradually added in an organic solvent, then to the solution of the mixture of carboxylic hydrocarbons at room temperature, the mixture is then heated between 65 and 250 ° C, and preferably between 80 and 220 ° C, for from 5 to 30 hours.
  • the organic solvent necessary for the solubilization of the primary polyamine is chosen with a boiling point of between 65 and 250 ° C, and preferably between 80 and 220 ° C, and its capacity to eliminate the water formed by condensation of the polyamine on compound A by azeotropic distillation of the water / solvent mixture.
  • the solvent is chosen from the group consisting of benzene, toluene, xylenes, ethylbenzene and commercial cuts of hydrocarbons, for example those distilling at 190 to 209 ° C. and containing 99% by weight of aromatic compounds.
  • a mixture of solvents can be used and in particular a mixture of xylenes, or else a xylene / alcohol mixture, preferably the alcohol is ethyl-2-hexanol for a on the one hand, to facilitate the homogeneity of the medium and, on the other hand, to promote the kinetics of the reaction.
  • the composition according to the invention comprises the second additive (s) as described above in a preferential content ranging from 5 to 10,000 ppm by weight, preferably from 5 to 1000 ppm by weight, more preferably from 10 to 500 ppm by weight, more preferably from 15 to 200 ppm by weight, and better still from 20 to 150 ppm by weight, relative to the total weight of the fuel composition.
  • the fuel composition according to the invention comprises a third additive (3), different from additives (1) and (2), consisting of a Mannich base.
  • a third additive (3) different from additives (1) and (2), consisting of a Mannich base.
  • the preparation of Mannich bases is known per se, and for example described in documents US2008 / 0052985, or US8016898.
  • the third additive is advantageously prepared by reacting a phenol substituted with a hydrocarbon group, an aldehyde and an amine.
  • the hydrocarbon substituent of said phenol may contain from 6 to 400 carbon atoms, advantageously from 30 to 180 carbon atoms, preferably from 10 to 110, better still from 40 to 110 carbon atoms.
  • the hydrocarbon substituent of said phenol can be derived from an olefin or a polyolefin.
  • alpha-olefins such as n-1-decene.
  • the hydrocarbon substituent of said phenol is a polyisobutylene group.
  • the polyolefins forming the hydrocarbon substituent of the phenol can be prepared by polymerization of olefin monomers according to any known polymerization process.
  • the polyolefins are chosen from polyisobutylenes having a number-average molar mass (Mn) of between 400 to 3000, preferably between 400 to 2500, more preferably between 400 and 1500, between 500 to 1500 or between 500 and 1000.
  • Mn number-average molar mass
  • Polyisobutylene is preferably very reactive, which differs from poorly reactive polyisobutylenes by their small amount of terminal ethylene double bonds.
  • the reactive polyisobutylenes according to the invention are composed of at least 85% by weight, preferably at least 90% by weight, preferably at least 95% by weight of isobutene units.
  • the polyisobutylenes preferably very reactive, have a polydispersity of less than 1.9, preferably less than 1.7 and even more preferably less than 1.5, the polydispersity being the quotient the mass-average molar mass Mw and the number-average molar mass Mn.
  • the phenol substituted with a hydrocarbon group can be prepared by alkylation of phenol with an olefin or polyolefin described above, such as polyisobutylene or polypropylene, preferably polyisobutylene, using conventional alkylation methods.
  • an olefin or polyolefin described above such as polyisobutylene or polypropylene, preferably polyisobutylene, using conventional alkylation methods.
  • the phenol can be substituted by one or more low molecular weight alkyl groups, for example a phenol carrying one or more alkyl chains of less than 28 carbon atoms, preferably of less than 24 carbon atoms, more preferably of less than 20 carbon atoms, even more preferably less than 18 carbon atoms, even more preferably 16 carbon atoms and even more preferably 14 carbon atoms.
  • a monoalkylic phenol having from 4 to 20 carbon atoms, preferably from 6 to 18, more preferably from 8 to 16, even more preferably from 10 to 14 carbon atoms, for example a phenol substituted by an alkyl group in C 12.
  • the aldehyde used to form the product of the Mannich reaction can consist of 1 to 10 carbon atoms, and is generally formaldehyde or its reactive equivalents such as formalin (methyl alcohol and formaldehyde), trioxanes, or para. formaldehyde, and preferably para-formaldehyde.
  • the amine used to form the Mannich reaction product can be a monoamine or a polyamine.
  • ethylamine dimethylamine, diethylamine, di-n-propylamine, di-isopropylamine, n-butylamine, dibutylamine, allylamine, isobutylamine.
  • the polyamines are chosen from compounds comprising two or more amino groups.
  • polyamines of polyalkylene polyamines in which the alkylene group has, for example, from 1 to 6, preferably from 1 to 4, more preferably from 2 to 3 carbon atoms.
  • the preferred polyamines are polyethylene- polyamines.
  • the polyamine can comprise 2 to 15 nitrogen atoms, preferably 2 to 10 nitrogen atoms, preferably 2 to 8 nitrogen atoms.
  • polyamines examples include: 3- (dimethylamino) -n-propylamine, di [3- (dimethylamino) -n-propyl] amine, di [3- (diethylamino) -n-propyl] amine, di [ 2- (dimethylamino) ethyl] amine, N-methylpiperazine,
  • the amine used to form the Mannich reaction product comprises a diamine, preferably which comprises a primary or secondary amine function taking part in the Mannich reaction and a tertiary amine function.
  • the additive (3) can be obtained by a Mannich reaction and then subjected to a reaction making it possible to obtain a tertiary amine function; for example, a process using an intermediate compound comprising a secondary amine and obtained by Mannich reaction, which is then modified, for example by alkylation to produce a tertiary amine.
  • the content of the additive (3) ranges from 5 to 10,000 ppm by weight, preferably from 5 to 1000 ppm by weight, more preferably from 50 to 500 ppm by weight, more preferably from 100 to. 500 ppm by weight, and more preferably 150 to 450 ppm by weight, relative to the total weight of the fuel composition.
  • the present invention also relates to the use, to improve the detergency properties of a gasoline fuel, of a fuel concentrate comprising at least the additives (1), (2) and (3), as defined herein. above, mixed with an organic liquid, said organic liquid being inert with respect to the first, second and third additives, and miscible with said fuel.
  • the organic liquid is advantageously miscible with liquid fuels, in particular those obtained from one or more sources chosen from the group consisting of mineral, preferably petroleum, animal, vegetable and synthetic sources.
  • miscible is understood to mean the fact that the additives and the organic liquid form a solution or a dispersion so as to facilitate the mixing of the additives according to the invention into liquid fuels according to conventional fuel additivation processes.
  • the organic liquid is preferably chosen from aromatic hydrocarbon solvents such as the solvent sold under the name “SOLVESSO”, alcohols, ethers and other oxygenated compounds, and paraffinic solvents such as hexane, pentane or isoparaffins, alone or as a mixture.
  • aromatic hydrocarbon solvents such as the solvent sold under the name “SOLVESSO”
  • alcohols, ethers and other oxygenated compounds such as hexane, pentane or isoparaffins, alone or as a mixture.
  • paraffinic solvents such as hexane, pentane or isoparaffins
  • the fuel according to the present invention contains a base resulting from one or more sources chosen from the group consisting of mineral, animal, vegetable and synthetic sources, and is preferably chosen from hydrocarbon fuels, non-essentially hydrocarbon fuels and theirs. mixtures
  • Oil will preferably be chosen as the mineral source.
  • the fuel is advantageously chosen from hydrocarbon-based fuels and non-essentially hydrocarbon-based fuels, alone or as a mixture.
  • hydrocarbon fuel is understood to mean a fuel consisting of one or more compounds consisting solely of carbon and hydrogen.
  • Gasolines are hydrocarbon fuels.
  • non-essentially hydrocarbon-based fuel is understood to mean a fuel consisting of one or more compounds consisting not essentially of carbon and of hydrogen, that is to say which also contain other atoms, in particular oxygen atoms.
  • Hydrocarbon fuels include in particular light distillates having a boiling point in the gasoline range, preferably between 30 and 210 ° C.
  • These light distillates can, for example, be chosen from distillates obtained by direct distillation of crude hydrocarbons, vacuum distillates, hydrotreated distillates, distillates resulting from catalytic cracking and / or hydrocracking of vacuum distillates, distillates resulting from ARDS-type conversion processes (by desulphurization of atmospheric residue).
  • the hydrocarbon fuel is chosen from gasolines.
  • Gasolines include, in particular, any commercially available spark ignition engine fuel compositions.
  • the gasolines generally have sufficiently high octane numbers to avoid the knocking phenomenon.
  • gasoline-type fuels marketed in Europe which comply with standard NF EN 228, have an engine octane number (MON in English "Motor Octane Number") greater than 85 and a research octane number (RON in English "Research Octane Number”) of a minimum of 95.
  • Gasoline type fuels have, generally, a RON ranging from 90 to 100 and a MON ranging from 80 to 90, the RON and MON being measured according to the standard ASTM D 2699-86 or D 2700-86.
  • Non-essentially hydrocarbon-based fuels include in particular oxygenates, for example distillates resulting from the BTL (in English “biomass to liquid”) conversion of plant and / or animal biomass, taken alone or in combination; biofuels, for example oils and / or esters of vegetable and / or animal oils; and bioethanols.
  • oxygenates for example distillates resulting from the BTL (in English “biomass to liquid”) conversion of plant and / or animal biomass, taken alone or in combination
  • biofuels for example oils and / or esters of vegetable and / or animal oils
  • bioethanols for example oils and / or esters of vegetable and / or animal oils
  • Mixtures of hydrocarbon fuel and non-essentially hydrocarbon fuel are typically gasolines of the Ex type.
  • gasoline of type Ex for a spark ignition engine is meant a gasoline fuel which contains x% (v / v) of oxygenates, generally ethanol, bioethanol and / or ethyl-tertio-butyl-ether ( ETBE).
  • x% (v / v) of oxygenates generally ethanol, bioethanol and / or ethyl-tertio-butyl-ether ( ETBE).
  • the fuel composition may comprise only new sources of distillates or be composed of a mixture with conventional petroleum lighter distillates as the gasoline-type fuel base.
  • the content of each additive (1) and (2) in the fuel composition according to the invention ranges from 5 to 10,000 ppm by weight, preferably from 5 to 1000 ppm by weight, more preferably from 10 to 500 ppm by weight, more preferably from 15 to 200 ppm by weight, and better still from 20 to 150 ppm by weight, relative to the total weight of the fuel composition.
  • the content of additive (3) in the fuel composition according to the invention ranges from 5 to 10,000 ppm by weight, preferably from 5 to 1000 ppm by weight, more preferably from 50 to 500 ppm by weight. , more preferably from 100 to 500 ppm by weight, and better still from 150 to 450 ppm by weight, relative to the total weight of the fuel composition.
  • the sulfur content in the fuel composition is less than or equal to 1500 ppm by weight, preferably less than or equal to 1000 ppm by weight, preferably less than or equal to 500 ppm by weight and preferably less than or equal to 50 ppm by weight, even more preferably less than or equal to 10 ppm by weight, relative to the total weight of the composition, and advantageously without sulfur.
  • the fuel composition can also comprise one or more additional additive (s), different from said additives according to the invention.
  • additional additives can for example be chosen, in a nonlimiting manner, from: detergent additives, anti-corrosion agents, anti-oxidants, carrier oils, dispersants, demulsifiers, tracers or markers, reodorants, friction modifiers, lubricity additives or lubricity additives, combustion aids (catalytic combustion and soot promoters), anti-sedimentation agents, antiwear agents and agents modifying the conductivity.
  • This or these additional additives are more preferably chosen from: a) lubricating additives or anti-wear agents, in particular (but not limited to) chosen from the group consisting of fatty acids and their ester or amide derivatives, in particular glycerol monooleate, and derivatives of mono- and polycyclic carboxylic acids. Examples of such additives are given in the following documents: EP680506, EP860494,
  • Another object of the invention is the use of the fuel composition to maintain cleanliness (keep-clean effect) and / or clean (clean-up effect) the deposits in the internal parts of an engine chosen from the following : the combustion chamber and the fuel injection system, and preferably the fuel injection system.
  • composition according to the invention is effective in conventional engines; or more modern engines such as, IDE, BMW B48, Renault H5FT and HR13DDT, PSA EB2DTS, Volkswagen EA1 11 ...; and in IIE the Mercedes M102E and Ml 11E, PSA EW 10A and EB2 engines ...
  • Another object of the invention is the use of the fuel composition comprising at least a first additive, at least a second additive and at least a third additive defined above to prevent and / or reduce coking (i.e. i.e. coke deposits), particularly in direct petrol injection (IDE), and / or lacquering (i.e. soap and / or varnish deposits), particularly in indirect petrol injection (IIE), and in particular on the valves.
  • coking i.e. i.e. coke deposits
  • IDE direct petrol injection
  • lacquering i.e. soap and / or varnish deposits
  • IIE indirect petrol injection
  • the invention thus makes it possible to prevent and / or reduce deposits of coke and / or soap on the fuel inlet valves in a spark-ignition engine with indirect injection
  • Another object of the invention is the use of the fuel composition comprising at least a first additive, at least a second additive and at least a third additive defined above to prevent and / or reduce sticking (or valve- sticking) of the fuel inlet valves in an engine, in particular a spark ignition engine with indirect gasoline injection (IIE).
  • said composition advantageously further comprises a fourth additive which is a carrier oil.
  • the composition preferably further comprises a carrier oil.
  • the carrier oil can be chosen from oils of poly (oxyalkylene) type, for example poly-butene oxide or poly-propene oxide.
  • the weight ratio of the amount of carrier oil to the amount of detergent additives is in the range of 0.1 to 2.5, preferably 0.3 to 1.5, even more preferably from 0.5 to 1.
  • Another object of the invention is the use of said fuel composition for reducing the fuel consumption of the engine (“Fuel Eco” action) and / or minimizing the loss of power from said engine, and / or reducing pollutant emissions. , in particular, particulate emissions from the combustion engine.
  • Another object of the invention is the use of said composition of additives to reduce the fouling of the area of the pistons, segments, and liners of the engine, preferably of a gasoline direct injection engine (or IDE ).
  • the quaternary ammonium additive (1) as defined in the present invention, is particularly effective in combating piston fouling, especially in IDE.
  • additives (1) and (2) are also very effective in combating piston fouling, especially in IDE.
  • the fuel composition can be used in indirect gasoline injection (IIE) or in direct gasoline injection (IDE), preferably in IDE.
  • IIE indirect gasoline injection
  • IDE direct gasoline injection
  • the IDE is central, and in another embodiment, the IDE is lateral.
  • the present invention is therefore effective and used in central and / or lateral IDE.
  • the fuel composition can also be used to combat corrosion in the engine.
  • the polyisobutylene succinimide additive (2), as defined in the present invention, is particularly effective in combating corrosion.
  • the use according to the invention is applicable to engines used in light vehicles (light vehicles), heavy goods vehicles (PL), stationary vehicles, agricultural machinery, thermal vehicles or hybrid vehicles (rechargeable or not), engines dual-fuel gasoline / gas, for example gasoline / NGV (natural gas) or gasoline / LPG; gasoline / CNG or gasoline / LPG concomitant injection engines ...
  • the additive, fuel or concentrate composition can be used in "harsh” or "easier to process” gasolines.
  • "Harsh” gasolines are distinguished from easy-to-process gasolines in that a harsh gasoline requires a higher additive compound processing rate to be effective than "easy-to-process” gasoline.
  • "severe” species the species similar to the reference species CEC RL12-09 and CEC RL-83.
  • the fuel composition according to the invention can be prepared according to any known process, by adding a liquid hydrocarbon cut as described above with at least the three additives as described above, and optionally one or more other additives other than those described above. additives according to the invention, as described above.
  • the invention also relates to a method of maintaining the cleanliness and / or cleaning of at least one of the internal parts of a spark-ignition engine, comprising at least the following steps:
  • the above step of preparing a fuel composition is preceded by a preliminary step of determining the content of each of the three additives to be incorporated into said fuel composition in order to achieve a given specification relating to the properties. detergency of the fuel composition.
  • This preliminary step is common practice in the field of fuel additives and involves defining at least one characteristic representative of the detergency properties of the fuel composition as well as a target value.
  • Fuel compositions were prepared by adding the following additives Al, A2 and A3 to gasoline E:
  • Al quaternary ammonium salt, formed by reaction of propylene oxide with the condensation product of a polyisobutenyl succinic anhydride, the polyisobutylene group (PIB) of which has a number average molecular mass (Mn) of 1000 g / mol and dimethyl-aminopropylamine;
  • PIB polyisobutylene group
  • A2 polyisobutylene succinimide, obtained by condensation of a polyisobutenyl-succinic anhydride, the polyisobutylene group (PIB) of which has a number-average molecular mass (Mn) of 1000 g / mol and tetraethylenepentamine;
  • A3 Mannich base, obtained by reacting a phenol substituted with a polyisobutylene group (PIB) having a number average molecular mass (Mn) of 1000 g / mol, with formaldehyde and dimethyl-aminopropylamine.
  • PIB polyisobutylene group
  • composition El is in accordance with the invention.
  • the compositions E2, E3 and E4 are comparative.
  • the additivation rate is identical between the three compositions El, E2 and E3 (433 ppm).
  • the engine used is a motor EB2DTS PSA, which is a gas cylinder 3 1199 cm 3 turbocharged direct injection engine, with the injectors in a central position.
  • the flow rate of the injectors is determined by means of a bench for measuring the flow rates of the EFS IFR 600 type injectors, which makes it possible in a manner known per se to measure the mass fuel flow rate of the injectors.
  • the principle of the test consists in making the engine run for 5 hours at 4300 revolutions / minute and 11 bars of mean effective pressure (hereinafter referred to as PME), by supplying it with the gasoline tested at a pressure of injection of 70 bars, after a heating period of 20 minutes, and a stabilization period of 10 minutes.
  • PME mean effective pressure
  • the test determines the average flow loss, defined as corresponding to the average restriction of the flow of gasoline emitted by the engine injectors at the end of the test.
  • test steps are as follows:
  • test conditions are as follows:
  • the engine is subjected to a gradual increase in speed, for a period of 20 minutes, until reaching a speed of 4000 revolutions / minute and an PME of 8 bar.
  • the engine is maintained under the operating conditions of the test, at a speed of 4300 revolutions / minute, at a PME of 11 bar and a fuel injection pressure of 70 bar, for a period of 10 minutes.
  • the engine then runs for 5 hours at 4300 rpm and 11 bar PME with a fuel injection pressure of 70 bar.
  • the injectors are removed in order to be evaluated by means of the EFS IFR 600 injector flow rate measuring bench, which makes it possible to measure the mass fuel flow rate of the injectors at the end of the test. . By comparison with the value of the mass fuel flow of the injectors measured before the test, the average loss of flow of the injectors is calculated.
  • composition E1 according to the invention containing the combination of the three additives A1, A2 and A3 leads to very good results in terms of reducing the fouling of the injectors (“keep clean” effect).
  • these results are significantly better than those obtained with the comparative compositions E2 and E3 containing only two of the three additives.
  • the results obtained with composition E4 containing only one of the three additives, and with the reference fuel E, are even worse.

Abstract

The present invention relates to the use, for reducing deposits in the internal parts of a spark ignition engine, of a fuel composition comprising at least three additives: a quaternary ammonium salt, a non-quaternary polyisobutylene succinimide and a Mannich base which is different from the other additives. The composition is such that the mass ratio of the quantity of the first additive to the quantity of the second additive is in the range from 0.2: 1 to 2.5: 1.

Description

DESCRIPTION DESCRIPTION
TITRE : UTILISATION D'UNE COMPOSITION DE CARBURANT COMPRENANT 3 ADDITIFS POUR NETTOYER LES PARTIES INTERNES DES MOTEURSTITLE: USE OF A FUEL COMPOSITION CONTAINING 3 ADDITIVES TO CLEAN THE INTERNAL PARTS OF ENGINES
ESSENCE ESSENCE
La présente invention concerne l’utilisation, pour réduire et/ou empêcher les dépôts présents dans les parties internes d’un moteur à allumage commandé, d’une composition de carburant qui comprend au moins trois additifs : un sel d’ ammonium quaternaire, un polyisobutylène succinimide non quaternaire, et une base de Mannich, différente des deux autres additifs. La composition est telle que le ratio massique de la quantité du premier additif sur la quantité du second additif est compris dans la gamme allant de 0.2 : 1 à 2.5 : 1. The present invention relates to the use, for reducing and / or preventing deposits present in the internal parts of a spark ignition engine, of a fuel composition which comprises at least three additives: a quaternary ammonium salt, a non-quaternary polyisobutylene succinimide, and a Mannich base, different from the other two additives. The composition is such that the mass ratio of the amount of the first additive to the amount of the second additive is in the range from 0.2: 1 to 2.5: 1.
L’invention concerne également l’utilisation, pour améliorer les propriétés de détergence d’un carburant essence, d’un concentré pour carburant comprenant au moins lesdits trois additifs, en mélange avec un liquide organique inerte vis-à-vis desdits additifs. The invention also relates to the use, for improving the detergency properties of gasoline fuel, of a fuel concentrate comprising at least said three additives, in admixture with an organic liquid inert to said additives.
La composition est également utilisée pour maintenir la propreté (effet keep-clean) et/ou nettoyer (effet clean-up) les dépôts dans le moteur, ainsi que pour réduire la consommation de carburant du moteur (action « Fuel Eco ») et/ou minimiser la perte de puissance dudit moteur, et/ou réduire les émissions de polluants, en particulier, les émissions de particules du moteur à combustion, et/ou pour réduire l’encrassement des pistons du moteur, de préférence en injection directe essence (ou IDE). The composition is also used to maintain cleanliness (keep-clean effect) and / or to clean (clean-up effect) deposits in the engine, as well as to reduce the fuel consumption of the engine (“Fuel Eco” action) and / or minimize the loss of power of said engine, and / or reduce the emissions of pollutants, in particular, the emissions of particles from the combustion engine, and / or to reduce the clogging of the pistons of the engine, preferably in direct gasoline injection ( or IDE).
ETAT DE L'ART ANTERIEUR STATE OF THE PRIOR ART
Les carburants liquides de moteurs à combustion interne contiennent des composants pouvant se dégrader au cours du fonctionnement du moteur. La problématique des dépôts dans les parties internes des moteurs à combustion est bien connue des motoristes. Il a été montré que la formation de ces dépôts a des conséquences sur les performances du moteur et notamment a un impact négatif sur la consommation et les émissions de particules (Gueit, J. et al., "Injector Fouling in Direct Injection Spark Ignition Engines - A New Test Procedure for the Evaluation of Gasoline Additives," SAE Technical Paper 2017-01-2294). Les progrès de la technologie des additifs de carburant ont permis de faire face à cette problématique. Des additifs dits détergents utilisés dans les carburants ont déjà été proposés pour maintenir la propreté du moteur en limitant les dépôts (effet « keep-clean » en anglais) ou en réduisant les dépôts déjà présents dans les parties internes du moteur à combustion (effet « clean-up » en anglais). On peut citer à titre d’exemple le document US4171959 qui décrit un additif détergent pour carburant essence contenant une fonction ammonium quaternaire. Liquid internal combustion engine fuels contain components that can be degraded during engine operation. The problem of deposits in the internal parts of combustion engines is well known to engine manufacturers. It has been shown that the formation of these deposits has consequences on engine performance and in particular has a negative impact on fuel consumption and particle emissions (Gueit, J. et al., "Injector Fouling in Direct Injection Spark Ignition Engines - A New Test Procedure for the Evaluation of Gasoline Additives, "SAE Technical Paper 2017-01-2294). Advances in fuel additive technology have made it possible to tackle this problem. So-called detergent additives used in fuels have already been proposed to keep the engine clean by limiting deposits ("keep-clean" effect) or by reducing deposits already present. in the internal parts of the combustion engine (“clean-up” effect in English). Mention may be made, by way of example, of document US Pat. No. 4,171959 which describes a detergent additive for gasoline fuel containing a quaternary ammonium function.
Néanmoins, la technologie des moteurs évolue sans cesse et les exigences sur les carburants doivent évoluer pour faire face à ces avancées technologiques des moteurs à combustion. Nevertheless, engine technology is constantly evolving and fuel requirements must evolve to cope with these technological advances in combustion engines.
En particulier, les nouveaux systèmes d’injection directe essence exposent les injecteurs à des conditions plus sévères en pression et température ce qui favorise la formation de dépôts. In particular, the new gasoline direct injection systems expose the injectors to more severe pressure and temperature conditions, which favors the formation of deposits.
En outre, ces nouveaux systèmes d’injection présentent des géométries plus complexes pour optimiser la pulvérisation, notamment, des trous plus nombreux ayant des diamètres plus petits mais qui, en revanche, induisent une plus grande sensibilité aux dépôts. La présence de dépôts peut altérer les performances de la combustion notamment augmenter les émissions polluantes et les émissions de particules. In addition, these new injection systems have more complex geometries to optimize spraying, in particular, more holes having smaller diameters but which, on the other hand, induce a greater sensitivity to deposits. The presence of deposits can alter combustion performance, in particular increase pollutant emissions and particulate emissions.
D’ autres conséquences de la présence excessive de dépôts ont été rapportées dans la littérature, telles que l’ augmentation de la consommation de carburant, et donc des émissions de particules, et des problèmes d’ agrément de conduite (« driveability » en anglais). Other consequences of the excessive presence of deposits have been reported in the literature, such as increased fuel consumption, and therefore particulate emissions, and driveability problems. .
La prévention et la réduction des dépôts dans ces nouveaux moteurs sont essentielles pour un fonctionnement optimal des moteurs d'aujourd'hui. Il existe donc un besoin de proposer des additifs détergents pour carburant favorisant un fonctionnement optimal des moteurs à combustion, notamment, pour les nouvelles technologies moteur mais également les technologies de moteur plus anciennes/classiques. The prevention and reduction of deposits in these new engines is essential for the optimal functioning of today's engines. There is therefore a need to provide detergent fuel additives promoting optimal operation of combustion engines, in particular, for new engine technologies but also older / conventional engine technologies.
Dans le cas des moteurs à allumage commandé (ou moteurs à essence) à injection indirecte, un problème particulier se pose, lié à la formation de dépôts sur les parties externes du moteur et notamment sur les tiges des soupapes d’admission du mélange d’air et de carburant en amont de la chambre de combustion, qui se traduit par un phénomène de collage des soupapes. In the case of positive-ignition engines (or gasoline engines) with indirect injection, a particular problem arises, linked to the formation of deposits on the external parts of the engine and in particular on the stems of the intake valves of the fuel mixture. air and fuel upstream of the combustion chamber, which results in a valve sticking phenomenon.
Ce phénomène, bien connu des spécialistes sous le terme anglais de « valve sticking » (collage de soupapes), est décrit dans une publication de référence de Seppo Mikkonen, Reino Karlsson et Jouni Kivi intitulée « Intake Valve Stiking in Some Carburetor Engines », SAE Technical Paper Sériés n°881643, International Fuels and Lubricants Meeting and Exposition, Portland, Oregon, October 10- 13, 1988. Ce phénomène est provoqué, lors du fonctionnement du moteur à basse température (par temps froid par exemple), par une accumulation de dépôts ayant une viscosité élevée à l’interface entre la tige de la soupape admission et le guide de la soupape, dans les moteurs à allumage commandé à injection indirecte. L’ accumulation de tels dépôts sur les tiges des soupapes gêne les déplacements de ces dernières, les tiges collent aux guides des soupapes, ce qui provoque une mauvaise fermeture des soupapes, engendre des problèmes d’étanchéité dans la chambre de combustion, et peut affecter de manière importante le fonctionnement du moteur, et en particulier peut en empêcher le démarrage par temps froid. This phenomenon, well known to specialists under the English term of “valve sticking”, is described in a reference publication by Seppo Mikkonen, Reino Karlsson and Jouni Kivi entitled “Intake Valve Stiking in Some Carburetor Engines”, SAE Technical Paper Series no.881643, International Fuels and Lubricants Meeting and Exposition, Portland, Oregon, October 10-13, 1988. This phenomenon is caused, during operation of the engine at low temperature (in cold weather for example), by an accumulation of deposits with a high viscosity at the interface between the inlet valve stem and the valve guide, in the indirect injection positive-ignition engines. The accumulation of such deposits on the valve stems impedes movement of the latter, the stems stick to the valve guides, which causes improper valve closure, causes sealing problems in the combustion chamber, and may affect importantly the operation of the engine, and in particular can prevent it from starting in cold weather.
De manière générale, on distingue différents types de dépôts sur les soupapes d’ admissions des moteurs à allumage commandé à injection indirecte. Ces types de dépôts sont bien connus des motoristes, et l’apparition de certains est dépendante des solutions de traitement des autres. In general, there are different types of deposits on the intake valves of indirect injection spark ignition engines. These types of deposits are well known to engine manufacturers, and the occurrence of some is dependent on the treatment solutions of others.
D’une part, un premier type de dépôt est constitué de ceux qui se forment à haute température sur les soupapes d’ admission des moteurs à allumage commandé à injection indirecte lors de l’emploi d’un carburant ne contenant pas d’ additif de détergence. Ces dépôts sont notamment constitués de résidus carbonés liés au phénomène de cokage (« coking » en anglais) et peuvent également comprendre des dépôts de type savon et/ou vernis (en anglais « lacquering »). Ces dépôts sont généralement traités par l’utilisation d’ additif détergent ajouté au carburant (carburant additivé). On the one hand, a first type of deposit consists of those which form at high temperature on the intake valves of spark-ignition engines with indirect injection when using a fuel which does not contain any carbonate additive. detergency. These deposits consist in particular of carbonaceous residues associated with the phenomenon of coking (“coking” in English) and can also include deposits of the soap and / or varnish type (in English “lacquering”). These deposits are generally treated by the use of a detergent additive added to the fuel (additive fuel).
D’ autre part, un second type de dépôt est constitué des dépôts visqueux, cités précédemment, qui se forment à basse température et apparaissant sur les soupapes d’ admission des moteurs à allumage commandé à injection indirecte lors de l’utilisation de carburants additivés, provoquant ainsi le phénomène de collage des soupapes décrit ci-avant. On the other hand, a second type of deposit consists of the viscous deposits, mentioned previously, which form at low temperature and appear on the intake valves of spark ignition engines with indirect injection when using additive fuels, thus causing the valve sticking phenomenon described above.
Ainsi, l’additivation du carburant pour le traitement et la prévention des dépôts qui se forment à haute température peut provoquer l’ apparition de dépôts visqueux à basse température. Thus, fuel additivation for the treatment and prevention of deposits that form at high temperatures can cause viscous deposits to appear at low temperatures.
Comme exposé dans la publication précitée (SAE Technical Paper Sériés n°881643), la composition de l’essence et des additifs qu’elle contient ont une influence très importante sur les phénomènes de collage des soupapes. En particulier, les additifs de détergence classiquement incorporés dans les essences pour préserver la propreté des soupapes se sont paradoxalement avérés favoriser des phénomènes de collage de celles-ci. De manière connue en soi, le problème de collage des soupapes ne se produit pas ou très peu lorsque l’ on emploie un carburant dépourvu d’ additifs de détergence. De plus, la publication précitée montre que les additifs de type polymériques, susceptibles d’être employés dans les essences et/ou les huiles moteurs, sont connus comme étant des agents promoteurs du collage des soupapes. As explained in the aforementioned publication (SAE Technical Paper Series No. 881643), the composition of gasoline and the additives it contains have a very significant influence on the valve sticking phenomena. In particular, the detergency additives conventionally incorporated in gasolines to preserve the cleanliness of the valves have paradoxically been found to promote phenomena of sticking thereof. In a manner known per se, the problem of valve sticking does not occur or very little when using a fuel devoid of carbon additives. detergency. In addition, the aforementioned publication shows that additives of polymeric type, capable of being used in gasoline and / or engine oils, are known as being agents for promoting valve sticking.
WO2006135881 décrit un additif détergent contenant un sel d'ammonium quaternaire utilisé pour réduire ou nettoyer les dépôts notamment sur les soupapes d'admission. WO2006135881 describes a detergent additive containing a quaternary ammonium salt used to reduce or clean deposits in particular on the intake valves.
Les solutions proposées dans l’ art antérieur ne sont pas totalement satisfaisantes. Il existe donc un besoin de proposer des additifs pour carburant favorisant un fonctionnement optimal des moteurs à allumage commandé, et qui soient efficaces pour prévenir tous types de dépôts y compris sur les soupapes d’ admission. The solutions proposed in the prior art are not completely satisfactory. There is therefore a need to provide fuel additives which promote optimal operation of spark ignition engines, and which are effective in preventing all types of deposits, including on the intake valves.
Il existe également un besoin d’un additif détergent universel capable d’ agir sur les dépôts quelle que soit la technologie du moteur (injection directe ou indirecte) et/ou les propriétés du carburant, tout en minimisant le taux de traitement c’est à dire les quantités d’additif(s) employées. There is also a need for a universal detergent additive capable of acting on deposits whatever the technology of the engine (direct or indirect injection) and / or the properties of the fuel, while minimizing the rate of treatment. state the quantities of additive (s) used.
OBJET DE L’INVENTION OBJECT OF THE INVENTION
La demanderesse a découvert que l’utilisation d’une composition de carburant comprenant au moins trois additifs, telle que décrits ci-après, possède des propriétés remarquables et inattendues de détergence pour les moteurs à combustion interne, de préférence essence, connus sous le nom de moteurs à allumage commandé. Cette association d’ additifs permet de garantir et améliorer le pouvoir détergent des carburants destinés aux moteurs à combustion interne. Elle produit également un effet synergique inattendu. The Applicant has discovered that the use of a fuel composition comprising at least three additives, as described below, has remarkable and unexpected detergency properties for internal combustion engines, preferably gasoline, known under the name spark ignition engines. This combination of additives guarantees and improves the detergent power of fuels intended for internal combustion engines. It also produces an unexpected synergistic effect.
Les avantages additionnels de la composition d’ additifs pour carburants utilisée selon l’invention sont : The additional advantages of the fuel additive composition used according to the invention are:
- la protection des pompes, des systèmes d’injection, de la zone des pistons, des segments, des chemises et de toutes les parties en mouvement avec lesquels cet additif entre en contact dans un moteur, - protection of pumps, injection systems, the area of pistons, rings, liners and all moving parts with which this additive comes into contact in an engine,
- un fonctionnement optimal du moteur, - optimum engine operation,
- une réduction de la consommation de carburant, - reduced fuel consumption,
- une économie due à moins d'entretien du moteur et à une moindre consommation, - savings due to less engine maintenance and lower consumption,
- une réduction des émissions de particules, - a reduction in particulate emissions,
- une efficacité en injection directe et en injection indirecte essence. La présente invention a ainsi pour objet l’utilisation, pour réduire et/ou empêcher les dépôts dans les parties internes d’un moteur à allumage commandé, d’une composition de carburant comprenant : - efficiency in direct injection and indirect petrol injection. A subject of the present invention is thus the use, for reducing and / or preventing deposits in the internal parts of a spark-ignition engine, of a fuel composition comprising:
( 1) au moins un premier additif constitué d’un sel d’ ammonium quaternaire,(1) at least a first additive consisting of a quaternary ammonium salt,
(2) au moins un second additif constitué d’un polyisobutylène succinimide non quaternaire, (2) at least one second additive consisting of a non-quaternary polyisobutylene succinimide,
(3) au moins un troisième additif, différent des additifs ( 1) et (2), constitué d’une base de Mannich, et dans laquelle le ratio massique de la quantité du premier additif sur la quantité du second additif est compris dans la gamme allant de 0,2 : 1 à 2,5 : 1. (3) at least a third additive, different from additives (1) and (2), consisting of a Mannich base, and in which the mass ratio of the amount of the first additive to the amount of the second additive is included in the range from 0.2: 1 to 2.5: 1.
De préférence, le ratio massique de la quantité du premier additif sur la quantité du second additif dans la composition est compris dans la gamme allant de 1 : 1 à 2 : 1 , et de préférence allant de 1 ,25 : 1 à 1 ,5 : 1 . Preferably, the mass ratio of the amount of the first additive to the amount of the second additive in the composition is in the range ranging from 1: 1 to 2: 1, and preferably ranging from 1.25: 1 to 1.5. : 1.
L’invention a également pour objet l’utilisation de la composition, pour maintenir la propreté (effet keep-clean) et/ou nettoyer (effet clean-up) les dépôts dans les parties internes d’un moteur à allumage commandé, choisies parmi les suivantes : la chambre de combustion et le système d’injection de carburant, et de préférence le système d’injection de carburant. A subject of the invention is also the use of the composition, to maintain cleanliness (keep-clean effect) and / or clean (clean-up effect) the deposits in the internal parts of a spark-ignition engine, chosen from among the following: the combustion chamber and the fuel injection system, and preferably the fuel injection system.
L’invention a en outre pour objet l’utilisation, pour améliorer les propriétés de détergence d’un carburant essence, d’un concentré pour carburant comprenant au moins les trois additifs ci-avant, en mélange avec un liquide organique, ledit liquide organique étant inerte vis-à-vis des premier, second et troisième additif, et miscible audit carburant. A further subject of the invention is the use, to improve the detergency properties of a gasoline fuel, of a fuel concentrate comprising at least the above three additives, mixed with an organic liquid, said organic liquid. being inert with respect to the first, second and third additives, and miscible with said fuel.
L’invention concerne également un procédé de maintien de la propreté et/ou de nettoyage d’ au moins une des parties internes d’un moteur à allumage commandé (ou moteur essence à combustion interne), comprenant au moins les étapes suivantes : The invention also relates to a method of maintaining the cleanliness and / or cleaning of at least one of the internal parts of a spark ignition engine (or internal combustion gasoline engine), comprising at least the following steps:
- la préparation d’une composition de carburant par additivation d’un carburant avec au moins les trois additifs définis ci-avant, ou un concentré les comprenant, puis la combustion de ladite composition de carburant dans ledit moteur à allumage commandé. - the preparation of a fuel composition by additivation of a fuel with at least the three additives defined above, or a concentrate comprising them, then the combustion of said fuel composition in said spark ignition engine.
D’ autres objets, caractéristiques, aspects et avantages de l’invention apparaîtront encore plus clairement à la lecture de la description qui suit. Other objects, characteristics, aspects and advantages of the invention will emerge even more clearly on reading the description which follows.
Dans ce qui suit, et à moins d’une autre indication, les bornes d’un domaine de valeurs sont comprises dans ce domaine, notamment dans les expressions « compris entre » et « allant/va/s’étend de ... à ... ». Par ailleurs, les expressions « au moins un » et « au moins » utilisées dans la présente description sont respectivement équivalentes aux expressions « un ou plusieurs » et « supérieur ou égal ». In what follows, and unless otherwise indicated, the limits of a domain of values are included in this domain, in particular in the expressions “comprised between” and “ranging / goes / extends from ... to ... ”. Furthermore, the expressions “at least one” and “at least” used in the present description are respectively equivalent to the expressions “one or more” and “greater than or equal”.
Enfin, de manière connue en soi, on désigne par composé ou groupe en CN un composé ou un groupe contenant dans sa structure chimique N atomes de carbone. Finally, in a manner known per se, the term “CN compound or group” denotes a compound or a group containing in its chemical structure N carbon atoms.
DESCRIPTION DETAILLEE DETAILED DESCRIPTION
Le premier additif : ammonium quaternaire The first additive: quaternary ammonium
La composition selon l’invention comprend un premier additif constitué d’un sel d’ ammonium quaternaire, obtenu, dans un premier mode de réalisation, par réaction avec un agent de quaternisation d’un composé azoté comprenant une fonction amine tertiaire, ce composé azoté étant le produit de la réaction d’un agent d’acylation substitué par un groupement hydrocarboné et d’un composé comprenant au moins un groupement amine tertiaire et au moins un groupement choisi parmi les amines primaires, les amines secondaires et les alcools. The composition according to the invention comprises a first additive consisting of a quaternary ammonium salt, obtained, in a first embodiment, by reaction with a quaternization agent of a nitrogen compound comprising a tertiary amine function, this nitrogen compound. being the reaction product of an acylating agent substituted with a hydrocarbon group and of a compound comprising at least one tertiary amine group and at least one group chosen from primary amines, secondary amines and alcohols.
Dans un second mode de réalisation, le sel d’ ammonium quaternaire est choisi parmi les composés PIBA (polyisobutylène-amine) quaternisés, ou parmi les polyéthers-amines quaternisés. In a second embodiment, the quaternary ammonium salt is chosen from quaternized PIBA (polyisobutylene-amine) compounds, or from quaternized polyether-amines.
Selon le premier mode de réalisation, qui est préféré, ledit composé azoté est le produit de la réaction d'un agent d'acylation substitué par un groupement hydrocarboné et d'un composé comprenant à la fois un atome d'oxygène ou un atome d'azote capable de se condenser avec ledit agent d'acylation (c’est-à-dire que ce composé comprend au moins un groupement choisi parmi les amines primaires, les amines secondaires et les alcools) et un groupement amine tertiaire. According to the first embodiment, which is preferred, said nitrogenous compound is the product of the reaction of an acylating agent substituted with a hydrocarbon group and of a compound comprising both an oxygen atom or a d atom. nitrogen capable of condensing with said acylating agent (that is to say that this compound comprises at least one group chosen from primary amines, secondary amines and alcohols) and a tertiary amine group.
L'agent d'acylation est avantageusement choisi parmi les acides mono-ou poly-carboxyliques et leurs dérivés, notamment leurs dérivés ester, amides ou anhydrides. L'agent d'acylation est préférentiellement choisi parmi les acides succiniques, phtaliques et propioniques et les anhydrides correspondants. The acylating agent is advantageously chosen from mono-or poly-carboxylic acids and their derivatives, in particular their ester, amide or anhydride derivatives. The acylating agent is preferably chosen from succinic, phthalic and propionic acids and the corresponding anhydrides.
Dans ce mode de réalisation, l’ agent d’acylation est substitué par un groupement hydrocarboné. On entend par groupement "hydrocarboné" , tout groupement ayant un atome de carbone directement fixé au reste de la molécule (ie à l’ agent d’ acylation) et ayant principalement un caractère hydrocarboné aliphatique. Des groupements hydrocarbonés selon l’invention peuvent également contenir des groupements non hydrocarbonés. Par exemple, ils peuvent contenir jusqu'à un groupement non-hydrocarboné pour dix atomes de carbone à condition que le groupement non-hydrocarboné ne modifie pas de façon significative le caractère principalement hydrocarboné du groupement. On peut citer à titre d’exemple de tels groupements bien connus de l'homme de l'art, les groupements hydroxyle, les halogènes (en particulier les groupements chloro- et fluoro-), les groupements alcoxy, alkylmercapto, alkyle sulfoxy. In this embodiment, the acylating agent is substituted by a hydrocarbon group. The term "hydrocarbon" group is understood to mean any group having a carbon atom directly attached to the rest of the molecule (ie to the acylating agent) and having mainly an aliphatic hydrocarbon character. Hydrocarbon groups according to the invention can also contain non-hydrocarbon groups. For example, they can contain up to one non-hydrocarbon group per ten carbon atoms provided that the non-hydrocarbon group does not significantly modify the predominantly hydrocarbon character of the group. By way of example of such groups which are well known to those skilled in the art, mention may be made of hydroxyl groups, halogens (in particular chloro- and fluoro- groups), alkoxy, alkylmercapto and alkyl sulfoxy groups.
Dans un mode de réalisation, de préférence les substituants hydrocarbonés ne contiennent pas de tels groupements non-hydrocarbonés et sont purement des hydrocarbures aliphatiques. In one embodiment, preferably the hydrocarbon substituents do not contain such non-hydrocarbon groups and are purely aliphatic hydrocarbons.
Le substituant hydrocarboné de l’ agent d'acylation comprend, de préférence, au moins 8, de préférence, au moins 12 atomes de carbone. Ledit substituant hydrocarboné peut comprendre jusqu'à environ 200 atomes de carbone. The hydrocarbon substituent of the acylating agent preferably comprises at least 8, preferably at least 12 carbon atoms. Said hydrocarbon substituent may comprise up to about 200 carbon atoms.
Le substituant hydrocarboné de l'agent d'acylation a, de préférence, une masse moléculaire moyenne en nombre (Mn) comprise entre 160 à 2800, par exemple entre 250 à 2000, plus préférentiellement entre 500 à 1500 et, encore plus préférentiellement entre de 500 à 1300. Une gamme de valeur de Mn comprise entre 700 et 1300 est particulièrement préférée, par exemple de 700 à 1200. The hydrocarbon substituent of the acylating agent preferably has a number average molecular weight (Mn) of between 160 to 2800, for example between 250 to 2000, more preferably between 500 to 1500 and, even more preferably between de 500 to 1300. A range of value of M n between 700 and 1300 is particularly preferred, for example from 700 to 1200.
A titre d’exemple de groupements hydrocarbonés substituant l'agent d'acylation, on peut citer les groupements n-octyle, n-décyle, n-dodécyle, tétrapropényle, n-octadécyle, oléyle, octadécyle ou triacontyle. By way of example of hydrocarbon groups substituting the acylating agent, mention may be made of n-octyl, n-decyl, n-dodecyl, tetrapropenyl, n-octadecyl, oleyl, octadecyl or triacontyl groups.
Le substituant hydrocarboné de l'agent d'acylation peut également être obtenu à partir d'homo- ou d'inter-polymères (par exemple de copolymères, terpolymères) de mono-et di-oléfines ayant de 2 à 10 atomes de carbone, par exemple à partir d'éthylène, de propylène, de 1 -butène, d'isobutène, de butadiène, d'isoprène, de 1-hexène ou de 1-octène. De préférence, ces oléfines sont des 1 -mono-oléfines. The hydrocarbon substituent of the acylating agent can also be obtained from homo- or inter-polymers (for example copolymers, terpolymers) of mono- and di-olefins having from 2 to 10 carbon atoms, for example from ethylene, propylene, 1 -butene, isobutene, butadiene, isoprene, 1-hexene or 1-octene. Preferably, these olefins are 1-mono-olefins.
Le substituant hydrocarboné de l'agent d'acylation peut également être choisi parmi les dérivés d’ analogues halogénés (par exemple chlorés ou bromés) de ces homo-ou inter-polymères. The hydrocarbon substituent of the acylating agent can also be chosen from derivatives of halogenated analogues (for example chlorinated or brominated) of these homopolymers or inter-polymers.
Selon une variante, le substituant hydrocarboné de l'agent d'acylation peut être obtenu à partir d'autres sources, par exemple à partir de monomères d’ alcènes à haut poids moléculaire (par exemple, 1 -tétracontène) et leurs analogues chlorés ou hydrochlorés, de fractions de pétrole aliphatiques, par exemple les cires de paraffine, leurs analogues craqués, chlorés et/ou hydrochlorés, d’huiles blanches, d’ alcènes synthétiques, par exemple produits par procédé Ziegler-Natta (par exemple les graisses de polyéthylène) et d'autres sources connues de l'homme de l'art. Alternatively, the hydrocarbon substituent of the acylating agent can be obtained from other sources, for example from high molecular weight alkenes monomers (eg, 1 -tetracontene) and their chlorinated analogues or hydrochlorinated, aliphatic petroleum fractions, for example paraffin waxes, their cracked, chlorinated and / or analogues thereof hydrochlorides, white oils, synthetic alkenes, for example produced by the Ziegler-Natta process (for example polyethylene fats) and other sources known to those skilled in the art.
Toute insaturation présente dans le groupement hydrocarboné de l'agent d'acylation peut éventuellement être réduite ou éliminée par hydrogénation selon tout procédé connu. Any unsaturation present in the hydrocarbon group of the acylating agent can optionally be reduced or eliminated by hydrogenation according to any known process.
Le substituant hydrocarboné de l'agent d'acylation est, de préférence, essentiellement saturé, c'est-à-dire qu'il ne contient pas plus d'une liaison insaturée carbone-carbone pour chaque tranche de dix liaisons simples carbone-carbone présentes. The hydrocarbon substituent of the acylating agent is preferably substantially saturated, i.e., it does not contain more than one carbon-to-carbon unsaturated bond for each slice of ten carbon-to-carbon single bonds. present.
Le substituant hydrocarboné de l'agent d'acylation ne contient, avantageusement, pas plus d'une liaison insaturée carbone-carbone non- aromatique tous les 50 liaisons carbone-carbone présentes. The hydrocarbon substituent of the acylating agent advantageously contains no more than one non-aromatic carbon-to-carbon unsaturated bond per every 50 carbon-to-carbon bonds present.
Selon un mode de réalisation préféré, le substituant hydrocarboné de l'agent d'acylation est un groupement polyisobutène aussi appelé polyisobutylène (PIB). On préfère tout particulièrement les polyisobutènes (PIB) dits hautement réactifs. On entend par polyisobutènes (PIB) hautement réactifs des polyisobutènes (PIB) dans lesquels au moins 50% en moles, de préférence au moins 70% en moles ou plus, des doubles liaisons oléfiniques terminales sont du type vinylidène comme décrit dans le document EP0565285. En particulier, les PIB préférés sont ceux ayant plus de 80% en moles et jusqu’ à 100% en moles de groupements terminaux vinylidène tel que décrits dans le document EP 1344785. According to a preferred embodiment, the hydrocarbon substituent of the acylating agent is a polyisobutene group also called polyisobutylene (PIB). Very particularly preferred are the so-called highly reactive polyisobutenes (PIB). Highly reactive polyisobutenes (PIB) are understood to mean polyisobutenes (PIB) in which at least 50 mol%, preferably at least 70 mol% or more, of the terminal olefinic double bonds are of the vinylidene type as described in document EP0565285. In particular, preferred PIBs are those having more than 80 mole% and up to 100 mole% of vinylidene end groups as described in EP 1344785.
Selon un mode de réalisation particulièrement préféré, l’ agent d'acylation substitué par un groupement hydrocarboné est un anhydride polyisobutényl-succinique (PIB SA). According to a particularly preferred embodiment, the acylating agent substituted with a hydrocarbon group is a polyisobutenyl succinic anhydride (PIB SA).
La préparation d’ anhydrides polyisobutényl-succiniques est connue en soi, et largement décrite dans la littérature. On peut citer à titre d’exemple les procédés comprenant la réaction entre des polyisobutènes (PIB) et de l'anhydride maléique décrits dans les documents US3361673 et US3018250 ou le procédé comprenant la réaction d'un polyisobutène (PIB) halogéné, en particulier chloré, avec de l'anhydride maléique (US3172892). The preparation of polyisobutenyl succinic anhydrides is known per se, and widely described in the literature. Mention may be made, by way of example, of the processes comprising the reaction between polyisobutenes (PIB) and maleic anhydride described in documents US3361673 and US3018250 or the process comprising the reaction of a halogenated polyisobutene (PIB), in particular chlorinated , with maleic anhydride (US3172892).
Selon une variante, l'anhydride polyisobutényl-succinique peut être préparé en mélangeant une polyoléfine avec de l'anhydride maléique puis en passant du chlore à travers le mélange (GB949981 ). Alternatively, polyisobutenyl succinic anhydride can be prepared by mixing a polyolefin with maleic anhydride and then passing chlorine through the mixture (GB949981).
D'autres groupements hydrocarbonés comprenant une oléfine interne, par exemple tels que ceux décrits dans la demande W02007/015080, peuvent également être utilisés comme substituant de l'agent d'acylation. On entend par oléfine interne, toute oléfine contenant principalement une double liaison non-alpha, qui est une oléfine bêta ou de position supérieure. Other hydrocarbon groups comprising an internal olefin, for example such as those described in application WO2007 / 015080, can also be used as a substituent for the acylating agent. We hear By internal olefin, any olefin containing predominantly one non-alpha double bond, which is a beta or higher position olefin.
De préférence, ces matériaux sont essentiellement des bêta-oléfines ou des oléfines de position supérieure, par exemple contenant moins de 10% massique d'alpha-oléfine, de manière avantageuse moins de 5% massique ou moins de 2% massique. Preferably, these materials are essentially beta-olefins or higher position olefins, for example containing less than 10% by mass of alpha-olefin, advantageously less than 5% by mass or less than 2% by mass.
Les oléfines internes peuvent être préparées par isomérisation d’ alpha-oléfines selon tout procédé connu. Internal olefins can be prepared by isomerization of alpha-olefins according to any known process.
Le composé comprenant à la fois un atome d'oxygène ou un atome d'azote capable de se condenser avec l’ agent d'acylation et un groupement amine tertiaire peut, par exemple, être choisi parmi le groupe consistant en : la diméthylaminopropylamine, la N,N-diéthylaminopropylamine, la N, N- diméthylamino- éthylamine, la N,N-diméthyl-amino éthylamine éthylènediamine, la 1,2-propylènediamine, la 1 ,3-propylène diamine, les butylènediamines (isomères), la diéthylènetriamine, la dipropylènetriamine, la dibutylènetriamine, la triéthylènetétraamine, la téraethylènepentaamine, la pentaéthylènehexaamine, l’hexaméthylènetétramine, la bis(hexametliylène) triamine, les diaminobenzènes, et les pentanediamines, hexanediamines, heptanediamines, et de préférence la N,N- diméthylaminopropy lamine. The compound comprising both an oxygen atom or a nitrogen atom capable of condensing with the acylating agent and a tertiary amine group can, for example, be chosen from the group consisting of: dimethylaminopropylamine, N, N-diethylaminopropylamine, N, N- dimethylamino-ethylamine, N, N-dimethyl-amino ethylamine ethylenediamine, 1,2-propylenediamine, 1, 3-propylene diamine, butylenediamines (isomers), diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetetraamine, teraethylenepentaamine, pentaethylenehexaamine, hexamethylenetetramine, bis (hexametliylene) triamine, diaminobenzenes, and the pentanediamines, hexanediamines, Nyopamine, and preferably heptanediamines, Nyopanediamines, and heptanediamines, Nyopanediamines, and heptanediamines, Nyopamine, and heptanediamines.
Ledit composé peut en outre être choisi parmi les composés hétérocycliques substitués par des alkylamines tels que la l -(3- aminopropyl)-imidazole, la 4-(3-aminopropyl)morpholine, la l-(2- aminoéthyl)pipéridine, la 3,3- diamino-N-methyldipropylamine, les diaminopyridines, et la 3'3-bisamino(N,N-diméthylpropylamine). Said compound can also be chosen from heterocyclic compounds substituted by alkylamines such as l - (3- aminopropyl) -imidazole, 4- (3-aminopropyl) morpholine, l- (2-aminoethyl) piperidine, 3 , 3-diamino-N-methyldipropylamine, diaminopyridines, and 3'3-bisamino (N, N-dimethylpropylamine).
Le composé comprenant à la fois un atome d'oxygène ou un atome d'azote capable de se condenser avec l’ agent d'acylation et un groupement amine tertiaire peut également être choisi parmi les alcanolamines, y compris, mais sans s'y limiter, la triéthanolamine, la triméthanolamine, le N,N-diméthylaminopropanol, le N,N-diméthylaminoéthanol, N,N- diéthylaminopropanol, le N,N-diéthylaminoéthanol, N,N- diethylaminobutanol, la N,N,N-tris(hydroxyéthyl)amine, la N,N,N- tris(hydroxyméthyl)amine, laN,N,N tris(aminoéthyl)amine, la N,N- dibutylaminopropylamine et le N,N,N'-triméthyl-N'-hydroxyéthyl- bisaminoéthyléther, la N,N-bis(3-diméthylamino-propyl)-N- isopropanolamine, la N-(3-diméthylamino-propyl)-N,N- diisopropanol amine, la N'-(3-(Diméthylamino)propyl)-N,N-diméthyl- 1 ,3- propanediamine; le 2-(2-diméthylaminoéthoxy)éthanol et la N,N,N’ - triméthylaminoéthyléthanolamine, ou leurs mélanges. Selon un mode de réalisation préféré, ledit composé comprenant au moins un groupement amine tertiaire et au moins un groupement choisi parmi les amines primaires, les amines secondaires et les alcools est choisi parmi les amines de formule (I) ou (II) suivantes :
Figure imgf000011_0001
The compound comprising both an oxygen atom or a nitrogen atom capable of condensing with the acylating agent and a tertiary amine group can also be selected from alkanolamines, including, but not limited to. , triethanolamine, trimethanolamine, N, N-dimethylaminopropanol, N, N-dimethylaminoethanol, N, N- diethylaminopropanol, N, N-diethylaminoethanol, N, N- diethylaminobutanol, N, N, N-tris (hydroxyethyl ) amine, N, N, N- tris (hydroxymethyl) amine, laN, N, N tris (aminoethyl) amine, N, N- dibutylaminopropylamine and N, N, N'-trimethyl-N'-hydroxyethyl- bisaminoethyl ether , N, N-bis (3-dimethylamino-propyl) -N- isopropanolamine, N- (3-dimethylamino-propyl) -N, N- diisopropanol amine, N '- (3- (Dimethylamino) propyl) - N, N-dimethyl-1,3-propanediamine; 2- (2-dimethylaminoethoxy) ethanol and N, N, N '- trimethylaminoethylethanolamine, or mixtures thereof. According to a preferred embodiment, said compound comprising at least one tertiary amine group and at least one group chosen from primary amines, secondary amines and alcohols is chosen from the following amines of formula (I) or (II):
Figure imgf000011_0001
(II) dans lesquelles : (II) in which:
R6 et R7 sont identiques ou différents et représentent, indépendamment l’un de l’ autre, un groupement alkyle ayant de 1 à 22 atomes de carbone, de préférence ayant de 1 à 5 atomes de carbone ; R6 and R7 are the same or different and represent, independently of each other, an alkyl group having 1 to 22 carbon atoms, preferably having 1 to 5 carbon atoms;
X est un groupement alkylène ayant de 1 à 20 atomes de carbone, de préférence de 1 à 5 atomes de carbone ; m est un nombre entier compris entre 1 et 5 ; n est un nombre entier compris entre 0 et 20 ; et X is an alkylene group having 1 to 20 carbon atoms, preferably 1 to 5 carbon atoms; m is an integer between 1 and 5; n is an integer between 0 and 20; and
R8 est un atome d’hydrogène ou un groupement alkyle de C l à C22. R8 is a hydrogen atom or a C1 to C22 alkyl group.
Ledit composé est choisi de préférence parmi les amines de formuleSaid compound is preferably chosen from amines of formula
(I) . (I).
Lorsque le composé azoté comprend une amine de formule (I), R8 est avantageusement un atome d’hydrogène ou un groupement alkyle en C l à C 16, de préférence un groupement alkyle en Cl à CIO, encore plus préférentiellement un groupement alkyle en C l à C6. When the nitrogen compound comprises an amine of formula (I), R8 is preferably a hydrogen atom or an alkyl C l -C 16, preferably an alkyl group of Cl to CIO, more preferably an alkyl group C l to C6.
R8 peut, par exemple, être choisi parmi le groupe consistant en l’hydrogène, méthyle, éthyle, propyle, butyle and leurs isomères. De manière préférée R8 est un atome d'hydrogène. R8 can, for example, be selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl and their isomers. Preferably R8 is a hydrogen atom.
Lorsque le composé azoté comprend une amine de formule (II), m est de préférence égal à 2 ou 3, plus préférentiellement égal à 2 ; n est de préférence un entier compris entre 0 à 15, plus préférentiellement entre 0 à 10, encore plus préférentiellement entre 0 à 5. Avantageusement, n vaut 0. When the nitrogenous compound comprises an amine of formula (II), m is preferably equal to 2 or 3, more preferably equal to 2; n is preferably an integer between 0 to 15, more preferably between 0 to 10, even more preferably between 0 to 5. Advantageously, n is 0.
Selon un mode de réalisation préférentiel, ledit composé azoté est le produit de la réaction de l’ agent d'acylation substitué par un groupement hydrocarboné et d’une diamine de formule (I). According to a preferred embodiment, said nitrogenous compound is the product of the reaction of the acylating agent substituted with a hydrocarbon group and of a diamine of formula (I).
Dans ce mode de réalisation, de préférence : In this embodiment, preferably:
- R6 et R7 représentent, indépendamment l’un de l’ autre, un groupement alkyle en C l à C16, de préférence un groupement alkyle en C l à CIO ; - R6 and R7 represent, independently of one another, a group C1 to C16 alkyl , preferably a C1 to C10 alkyl group;
- R6 et R7 représentent, indépendamment l’un de l’ autre, un groupement méthyle, éthyle, propyle, butyle, pentyle, hexyle, heptyle, octyle ou leurs isomères. Avantageusement, R6 et R7 représentent indépendamment l’un de l’autre, un groupement en C l à C4, de préférence un groupement méthyle ;- R6 and R7 represent, independently of one another, a methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl group or their isomers. Advantageously, R6 and R7 represent, independently of one another, a C1 to C4 group, preferably a methyl group;
- X représente un groupement alkylène ayant 1 à 16 atomes de carbone, de préférence de 1 à 12 atomes de carbone, plus préférentiellement de 1 à 8 atomes de carbone, par exemple de 2 à 6 atomes de carbone ou de 2 à 5 atomes de carbone. X représente de manière particulièrement préférée un groupement éthylène, propylène ou butylène, en particulier un groupe propylène. - X represents an alkylene group having 1 to 16 carbon atoms, preferably from 1 to 12 carbon atoms, more preferably from 1 to 8 carbon atoms, for example from 2 to 6 carbon atoms or from 2 to 5 carbon atoms. carbon. X particularly preferably represents an ethylene, propylene or butylene group, in particular a propylene group.
Selon un mode de réalisation particulièrement préféré, le composé azoté est le produit de réaction d'un dérivé d'acide succinique substitué par un groupement hydrocarboné, de préférence un anhydride polyisobutényl- succinique, et d'un alcool ou d'une amine comportant également un groupe amine tertiaire, notamment un composé de formule (I) ou (II) telle que décrite ci-avant et plus préférentiellement un composé de formule (I). According to a particularly preferred embodiment, the nitrogenous compound is the reaction product of a succinic acid derivative substituted with a hydrocarbon group, preferably a polyisobutenyl succinic anhydride, and of an alcohol or of an amine also comprising a tertiary amine group, in particular a compound of formula (I) or (II) as described above and more preferably a compound of formula (I).
Selon une première variante, le dérivé d'acide succinique substitué par un groupement hydrocarboné réagit avec l’ amine comprenant également un groupement amine tertiaire sous certaines conditions pour former un succinimide (forme fermée). La réaction du dérivé d'acide succinique et de l'amine peut également aboutir sous certaines conditions à un succinamide c’est-à-dire, un composé comprenant un groupe amide et un groupe acide carboxylique (forme ouverte). According to a first variant, the succinic acid derivative substituted with a hydrocarbon group reacts with the amine also comprising a tertiary amine group under certain conditions to form a succinimide (closed form). The reaction of the succinic acid derivative and the amine can also result under certain conditions in a succinamide, that is to say, a compound comprising an amide group and a carboxylic acid group (open form).
Selon une seconde variante, un alcool comprenant également un groupement amine tertiaire réagit avec le dérivé de l'acide succinique pour former un ester comprenant également un groupement carboxyle -CO2H libre (forme ouverte). Ainsi, dans certains modes de réalisation le composé azoté peut être le produit de réaction d'un dérivé d'acide succinique et d'une amine ou un alcool qui est un ester ou un amide et qui comprend en outre également un groupement carboxyle -C02H n'ayant pas réagi (forme ouverte). According to a second variant, an alcohol also comprising a tertiary amine group reacts with the succinic acid derivative to form an ester also comprising a free carboxyl group —CO2H (open form). Thus, in certain embodiments the nitrogenous compound may be the reaction product of a succinic acid derivative and an amine or an alcohol which is an ester or an amide and which further also comprises a carboxyl group -CO 2 H unreacted (open form).
Le sel d'ammonium quaternaire formant le premier additif selon la présente invention est directement obtenu par réaction entre le composé azoté décrit ci-dessus comprenant une fonction amine tertiaire et un agent de quaternisation. The quaternary ammonium salt forming the first additive according to the present invention is obtained directly by reaction between the nitrogenous compound described above comprising a tertiary amine function and a quaternization agent.
Selon un mode de réalisation particulier, l'agent de quaternisation est choisi parmi le groupe constituant en les dialkyle sulfates, les esters d'acide carboxylique, les halogénures d'alkyle, les halogénures de benzyle, les carbonates hydrocarbonés, et les époxydes hydrocarbonés éventuellement en mélange avec un acide, seuls ou en mélange, de préférence les esters d'acide carboxylique. According to a particular embodiment, the quaternization agent is chosen from the group constituting dialkyl sulphates, carboxylic acid esters, alkyl halides, benzyl halides, hydrocarbon carbonates, and hydrocarbon epoxides. optionally as a mixture with an acid, alone or as a mixture, preferably the carboxylic acid esters.
Dans les compositions de carburant, il est souvent souhaitable de réduire la teneur en halogène, soufre et les composés contenant du phosphore. In fuel compositions, it is often desirable to reduce the content of halogen, sulfur and phosphorus-containing compounds.
Ainsi, si un agent de quaternisation contenant un tel élément est utilisé, il peut être avantageux d'effectuer une réaction ultérieure pour échanger le contre-ion. Par exemple, un sel d'ammonium quaternaire formé par réaction avec un halogénure d'alkyle peut ensuite être mis en réaction avec de l'hydroxyde de sodium et le sel d'halogénure de sodium éliminé par filtration. Thus, if a quaternizing agent containing such an element is used, it may be advantageous to perform a subsequent reaction to exchange the counterion. For example, a quaternary ammonium salt formed by reaction with an alkyl halide can then be reacted with sodium hydroxide and the sodium halide salt removed by filtration.
L'agent de quaternisation peut comprendre des halogénures tels que les chlorure, iodure ou bromure ; des hydroxydes ; des sulfonates ; des bisulfites; des alkylsulfates tels que le sulfate de diméthyle; des sulfones; des phosphates; des alkylphosphates en Cl -C12; des dialkylphosphates en C1 -C12; des borates; des alkylborates en C 1-C12; des nitrites; des nitrates; des carbonates; des bicarbonates; des alcanoates; les 0,0- dialkyldithiophosphates en C1 -C12, seuls ou en mélange. The quaternizing agent can include halides such as chloride, iodide or bromide; hydroxides; sulfonates; bisulfites; alkyl sulphates such as dimethyl sulphate; sulfones; phosphates; C1-C12 alkylphosphates ; C1-C12 dialkylphosphates; borates; C 1-C12 alkylborates; nitrites; nitrates; carbonates; bicarbonates; alkanoates; C 1 -C 12 0,0-dialkyldithiophosphates , alone or as a mixture.
Selon un mode de réalisation particulier, l'agent de quaternisation peut être choisi parmi les dérivés de dialkylsulfates tels que le sulfate de diméthyle, de N-oxydes, de sulfones tels que le propane- et butane- sulfone, d’halogénures d’ alkyle, d’acyle ou d’ aralkyle tels que le chlorure de méthyle et éthyle, le bromure, iodure ou chlorure de benzyle, et les carbonates hydrocarbonés (ou alkylcarbonates). According to a particular embodiment, the quaternization agent can be chosen from derivatives of dialkylsulphates such as dimethyl sulphate, of N-oxides, of sulphones such as propane- and butanesulfone, of alkyl halides. , acyl or aralkyl such as methyl and ethyl chloride, benzyl bromide, iodide or chloride, and hydrocarbon carbonates (or alkylcarbonates).
Si l'halogénure d'acyle est le chlorure de benzyle, le noyau aromatique est éventuellement substitué par un ou plusieurs groupements alkyle ou alcényle. If the acyl halide is benzyl chloride, the aromatic ring is optionally substituted by one or more alkyl or alkenyl groups.
Les groupements hydrocarbonés (alkyles) des carbonates hydrocarbonés peuvent contenir de 1 à 50, de 1 à 20, de 1 à 10 ou 1 à 5 atomes de carbone par groupement. Selon un mode de réalisation, les carbonates hydrocarbonés contiennent deux groupements hydrocarbonés qui peuvent être identiques ou différents. A titre d’exemple de carbonates hydrocarbonés, on peut citer le carbonate de diméthyle ou de diéthyle. The hydrocarbon (alkyl) groups of the hydrocarbon carbonates can contain from 1 to 50, from 1 to 20, from 1 to 10 or from 1 to 5 carbon atoms per group. According to one embodiment, the hydrocarbon carbonates contain two hydrocarbon groups which may be identical or different. By way of example of hydrocarbon carbonates, mention may be made of dimethyl or diethyl carbonate.
Selon un mode de réalisation préféré, l'agent de quaternisation est choisi parmi les époxydes hydrocarbonés représentés par la formule (III) suivante: dans laquelle R9, RIO, Rl l et R12 peuvent être identiques ou différentes et représentent indépendamment les uns des autres un atome d’hydrogène ou un groupement hydrocarboné en Ci à C50. A titre d’exemple non limitatif, on peut citer l'oxyde de styrène, l'oxyde d'éthylène, l’ oxyde de propylène, l’oxyde de butylène, l'oxyde de stilbène et les époxydes en en Ci à C50. L'oxyde de styrène et l’oxyde de propylène sont particulièrement préférés, et mieux encore l’ agent de quaternisation est l’ oxyde de propylène. According to a preferred embodiment, the quaternization agent is chosen from the hydrocarbon epoxides represented by the following formula (III): in which R9, R10, R11 and R12 may be the same or different and represent, independently of each other, a hydrogen atom or a C 1 -C 50 hydrocarbon group . By way of nonlimiting example, mention may be made of styrene oxide, ethylene oxide, propylene oxide, butylene oxide, stilbene oxide and C 1 to C 50 epoxides . Styrene oxide and propylene oxide are particularly preferred, and more preferably the quaternizing agent is propylene oxide.
De tels époxydes hydrocarbonés peuvent être utilisés comme agent de quaternisation en combinaison avec un acide, par exemple avec l'acide acétique. Les époxydes hydrocarbonés peuvent également être utilisés seuls comme agent de quaternisation, notamment sans acide supplémentaire. Such hydrocarbon epoxides can be used as a quaternizing agent in combination with an acid, for example with acetic acid. The hydrocarbon epoxides can also be used alone as a quaternization agent, in particular without additional acid.
Sans être lié par cette hypothèse, il semblerait que la présence de la fonction acide carboxylique dans la molécule favorise la formation du sel d'ammonium quaternaire. Dans un tel mode de réalisation n’utilisant pas acide supplémentaire, un solvant protique est utilisé pour la préparation du sel d'ammonium quaternaire. A titre d’exemple, les solvants protiques comme l'eau, les alcools (y compris les alcools polyhydriques) peuvent être utilisés seul ou en mélange. Les solvants protiques préférés ont une constante diélectrique supérieure à 9. Without being bound by this hypothesis, it would seem that the presence of the carboxylic acid function in the molecule promotes the formation of the quaternary ammonium salt. In such an embodiment not using additional acid, a protic solvent is used for the preparation of the quaternary ammonium salt. For example, protic solvents such as water, alcohols (including polyhydric alcohols) can be used alone or as a mixture. Preferred protic solvents have a dielectric constant greater than 9.
Des sels d'ammonium quaternaire correspondants préparés à partir d'amides ou esters et des dérivés d'acide succinique sont décrits dans WO2010/132259 ou dans EP1896555. Corresponding quaternary ammonium salts prepared from amides or esters and derivatives of succinic acid are described in WO2010 / 132259 or in EP1896555.
Selon un autre mode de réalisation, l'agent de quaternisation est choisi parmi les composés de formule (IV) :
Figure imgf000014_0001
dans laquelle R13 est un groupement alkyle, alcényle, aryle et aralkyle éventuellement substitué, et R14 est un groupement alkyle, aryle ou alkylaryle en Ci à C22. According to another embodiment, the quaternization agent is chosen from the compounds of formula (IV):
Figure imgf000014_0001
wherein R13 is an optionally substituted alkyl, alkenyl, aryl and aralkyl group, and R14 is a C1 to C22 alkyl, aryl or alkylaryl group.
Le composé de formule (IV) est un ester d'acide carboxylique apte à réagir avec une amine tertiaire pour former un sel d'ammonium quaternaire. Des composés de formule (IV) sont choisis, par exemple parmi les esters d'acides carboxyliques ayant un pKa de 3,5 ou moins. Le composé de formule (IV) est, de préférence, choisi parmi les esters d'acide carboxylique aromatique substitué, d’ acide alpha-hydroxycarboxylique et d’ acide p oly carboxylique. The compound of formula (IV) is a carboxylic acid ester capable of reacting with a tertiary amine to form a quaternary ammonium salt. Compounds of formula (IV) are selected, for example, from esters of carboxylic acids having a pKa of 3.5 or less. The compound of formula (IV) is preferably chosen from esters of substituted aromatic carboxylic acid, of alpha-hydroxycarboxylic acid and of polycarboxylic acid.
Selon un mode de réalisation, l’ester est un ester d'acide carboxylique aromatique substitué de formule (IV) dans laquelle R13 est un groupement aryle substitué. De préférence, R13 est un groupement aryle substitué ayant 6 à 10 atomes de carbone, de préférence un groupement phényle ou naphtyle, plus préférentiellement un groupement phényle. R13 est avantageusement substitué par un ou plusieurs groupements choisis parmi les radicaux carboalcoxy, nitro, cyano, hydroxy, SR15 et NR15R16. Chacun des groupements R15 et Rm peut être un atome d’hydrogène ou un groupement alkyle, alcényle, aryle ou carboalcoxy éventuellement substitué. Chacun des groupements R15 et Ri6 représente, avantageusement, l'atome d’hydrogène ou un groupement alkyle en C l à C22 éventuellement substitué, de préférence l'atome d’hydrogène ou un groupement alkyle en C l à C16, plus préférentiellement l'atome d’hydrogène ou un groupement alkyle en Cl à CI O, encore plus préférentiellement l'atome d’hydrogène ou un groupement alkyle en Cl à C4. R15 est de préférence un atome d’hydrogène et R 16 un atome d’hydrogène ou un groupement en Cl à C4. Avantageusement, R15 et Ri6 sont tous les deux un atome d’hydrogène. According to one embodiment, the ester is a substituted aromatic carboxylic acid ester of formula (IV) in which R13 is a substituted aryl group. Preferably, R13 is a substituted aryl group having 6 to 10 carbon atoms, preferably a phenyl or naphthyl group, more preferably a phenyl group. R13 is advantageously substituted with one or more groups chosen from the carboalkoxy, nitro, cyano, hydroxy, SR15 and NR15R16 radicals. Each of the groups R15 and Rm can be a hydrogen atom or an optionally substituted alkyl, alkenyl, aryl or carboalkoxy group. Each of the groups R15 and Ri 6 represents, advantageously, the hydrogen atom or an optionally substituted C 1 to C22 alkyl group, preferably the hydrogen atom or a C 1 to C16 alkyl group , more preferably 1 hydrogen atom or a C1 to C4 alkyl group, even more preferably the hydrogen atom or a C1 to C4 alkyl group. R15 is preferably a hydrogen atom and R 1 6 a hydrogen atom or a C1 to C4 group. Advantageously, R15 and Ri 6 are both hydrogen.
Selon un mode de réalisation, R13 est un groupe aryle substitué par un ou plusieurs groupements choisis parmi les radicaux hydroxyle, carboalcoxy, nitro, cyano et NH2. R13 peut être un groupement aryle polysubstitué, par exemple trihydroxyphényle. Avantageusement, R13 est un groupement aryle monosubstitué, de préférence substitué en ortho. R13 est, par exemple, substitué par un groupement choisi parmi les radicaux OH, NH2, NO2 ou COOMe, de préférence OH ou NH2. R13 est, de préférence, un groupement hydroxy-aryle, en particulier le 2-hydroxyphényle. According to one embodiment, R13 is an aryl group substituted by one or more groups chosen from hydroxyl, carboalkoxy, nitro, cyano and NH2 radicals. R13 can be a polysubstituted aryl group, for example trihydroxyphenyl. Advantageously, R13 is a monosubstituted aryl group, preferably ortho substituted. R13 is, for example, substituted by a group chosen from the OH, NH2, NO2 or COOMe radicals, preferably OH or NH2. R13 is preferably a hydroxy-aryl group, in particular 2-hydroxyphenyl.
Selon un mode de réalisation particulier, R14 est un groupement alkyle ou alkylaryle. R14 peut être un groupement alkyle en C l à C16, de préférence en C l à CIO, avantageusement en C l à C8. R14 peut être un groupement alkylaryle en C l à C16, de préférence en C l à cio, avantageusement en C l à C8. R14 peut par exemple être choisi parmi les groupements méthyle, éthyle, propyle, butyle, pentyle, benzyle ou leurs isomères. De préférence, R14 est un groupement benzyle ou méthyle, plus préférentiellement méthyle. According to a particular embodiment, R14 is an alkyl or alkylaryl group. R14 can be a C 1 to C16 , preferably C 1 to C10, advantageously C 1 to C8 alkyl group. R14 may be a C 1 to C16, preferably C 1 to Cio , advantageously C 1 to C8 alkylaryl group. R14 can for example be chosen from methyl, ethyl, propyl, butyl, pentyl, benzyl or their isomers. Preferably, R14 is a benzyl or methyl group, more preferably methyl.
Un composé particulièrement préféré est le salicylate de méthyle.A particularly preferred compound is methyl salicylate.
Selon un mode de réalisation particulier, le composé de formule (IV) est un ester d'un acide alpha-hydroxycarboxylique répondant à la formule (V) suivante :
Figure imgf000016_0001
dans laquelle R17 et R18 sont identiques ou différents et sont indépendamment choisis parmi le groupe consistant en l’ atome d'hydrogène, les groupements alkyle, alcényle, aryle ou aralkyle. De tels composés sont par exemple décrits dans le document EP 1254889. According to a particular embodiment, the compound of formula (IV) is an ester of an alpha-hydroxycarboxylic acid corresponding to the formula (V) following:
Figure imgf000016_0001
wherein R17 and R18 are the same or different and are independently selected from the group consisting of the hydrogen atom, alkyl, alkenyl, aryl or aralkyl groups. Such compounds are for example described in document EP 1254889.
Des exemples de composés de formule (IV) dans laquelle R13COO est le résidu d'un acide alpha-hydroxycarboxylique comprennent les méthyl- , éthyl-, propyl-, butyl-,pentyl-, hexyl-, phényl-, benzyl- ou allyl-esters d’ acide 2-hydroxy-isobutyrique; les méthyl-, éthyl-, propyl-, butyl-, pentyl- , hexyl-, benzyl-, phényl- ou allyl-esters d’ acide 2-hydroxy-2- méthylbutyrique; les méthyl-, éthyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-, phényl- ou allyl-esters d’ acide 2-hydroxy-2-éthylbutyrique; les méthyl-, éthyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-, phényl- ou allyl- esters d’ acide lactique et les méthyl-, éthyl-, propyl-, butyl-, pentyl-, hexyl- , allyl-, benzyl-ou phényl-esters d’ acide glycolique. De ce qui précède, le composé préféré est le méthyl-2-hydroxyisobutyrate. Examples of compounds of formula (IV) in which R13COO is the residue of an alpha-hydroxycarboxylic acid include methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, phenyl-, benzyl- or allyl- 2-hydroxy-isobutyric acid esters; methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-, phenyl- or allyl-esters of 2-hydroxy-2-methylbutyric acid; 2-hydroxy-2-ethylbutyric acid methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-, phenyl- or allyl-esters; methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-, phenyl- or allyl- esters of lactic acid and methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl -, allyl-, benzyl- or phenyl-esters of glycolic acid. From the above, the preferred compound is methyl-2-hydroxyisobutyrate.
Selon un mode de réalisation particulier, le composé de formule (IV) est un ester d'un acide polycarboxylique choisi parmi les acides dicarboxyliques et les acides carboxyliques ayant plus de deux fonctions acides. Les fonctions carboxyliques sont de préférence toutes sous forme estérifiée. Les esters préférés sont les esters d’ alkyle en C l à C4. According to a particular embodiment, the compound of formula (IV) is an ester of a polycarboxylic acid chosen from dicarboxylic acids and carboxylic acids having more than two acid functions. The carboxylic functions are preferably all in esterified form. Preferred esters are C 1-4 alkyl esters.
Le composé de formule (IV) peut être choisi parmi les diesters d’ acide oxalique, les diesters d'acide phtalique, les diesters d'acide maléique, les diesters d'acide malonique ou les diesters d'acide citrique. De préférence, le composé de formule (IV) est l'oxalate de diméthyle. The compound of formula (IV) can be chosen from oxalic acid diesters, phthalic acid diesters, maleic acid diesters, malonic acid diesters or citric acid diesters. Preferably, the compound of formula (IV) is dimethyl oxalate.
Selon une variante préférée, le composé de formule (IV) est un ester d'acide carboxylique ayant un pKa inférieur à 3,5. Pour les cas où le composé comprend plus d'un groupe acide, on se référera à la première constante de dissociation. According to a preferred variant, the compound of formula (IV) is a carboxylic acid ester having a pKa of less than 3.5. For cases where the compound comprises more than one acidic group, reference will be made to the first dissociation constant.
Le composé de formule (IV) peut être choisi parmi un ou plusieurs esters d'acide carboxylique choisi parmi l'acide oxalique, l'acide phtalique, l'acide salicylique, l'acide maléique, l'acide malonique, l'acide citrique, l'acide nitrobenzoïque, l'acide aminobenzoïque et le 2,4,6-acide trihydroxybenzoïque. Les composés préférés de formule (IV) sont l'oxalate de diméthyle, le 2-nitrobenzoate de méthyle et le salicylate de méthyle. The compound of formula (IV) can be chosen from one or more carboxylic acid esters chosen from oxalic acid, phthalic acid, salicylic acid, maleic acid, malonic acid, citric acid. , nitrobenzoic acid, aminobenzoic acid and 2,4,6-acid trihydroxybenzoic acid. Preferred compounds of formula (IV) are dimethyl oxalate, methyl 2-nitrobenzoate and methyl salicylate.
Selon un mode de réalisation particulièrement préféré, le sel d'ammonium quaternaire employé dans l’invention est formé par réaction d’un époxyde hydrocarboné, de préférence choisi parmi ceux de formule (III) ci-avant et plus préférentiellement l’ oxyde de propylène, avec le produit de la réaction d'un anhydride polyisobutényl-succinique dont le groupement polyisobutylène (PIB) a une masse moléculaire moyenne en nombre (Mn) comprise entre 700 et 1000 et de la diméthyl- aminoprop y lamine. According to a particularly preferred embodiment, the quaternary ammonium salt used in the invention is formed by reaction of a hydrocarbon epoxide, preferably chosen from those of formula (III) above and more preferably propylene oxide. , with the reaction product of a polyisobutenyl succinic anhydride in which the polyisobutylene group (PIB) has a number-average molecular mass (Mn) of between 700 and 1000 and dimethyl-aminoprop y lamin.
Selon un mode de réalisation particulièrement préféré l’ additif (1 ) est choisi parmi les polyisobutylènes succinimides fonctionnalisés par un groupement ammonium quaternaire. According to a particularly preferred embodiment, the additive (1) is chosen from polyisobutylene succinimides functionalized with a quaternary ammonium group.
La composition selon l’invention comprend le ou les premiers additifs tels que décrits ci-avant à une teneur préférentielle allant 5 à 10 000 ppm en poids, de préférence de 5 à 1000 ppm en poids, plus préférentiellement de 10 à 500 ppm en poids, plus préférentiellement de 15 à 200 ppm en poids, et mieux encore de 20 à 150 ppm en poids, par rapport au poids total de la composition de carburant. The composition according to the invention comprises the first additive (s) as described above in a preferential content ranging from 5 to 10,000 ppm by weight, preferably from 5 to 1000 ppm by weight, more preferably from 10 to 500 ppm by weight , more preferably from 15 to 200 ppm by weight, and better still from 20 to 150 ppm by weight, relative to the total weight of the fuel composition.
Le second additif : polyisobutylène succinimide The second additive: polyisobutylene succinimide
La composition selon l’invention comprend un second additif (2) constitué d’un polyisobutylène succinimide non quaternaire, c’est-à-dire qu’il ne contient pas de groupement ammonium quaternaire. The composition according to the invention comprises a second additive (2) consisting of a non-quaternary polyisobutylene succinimide, that is to say that it does not contain a quaternary ammonium group.
Selon un mode de réalisation préféré, ledit second additif résulte de la condensation : d’un composé A constitué d’un diacide carboxylique substitué par un groupe polyisobutylène ou d’un anhydride d’un tel diacide, avec un composé B constitué d'une polyamine primaire de formule générale (VI) ci-après : According to a preferred embodiment, said second additive results from the condensation: of a compound A consisting of a dicarboxylic acid substituted with a polyisobutylene group or of an anhydride of such a diacid, with a compound B consisting of a primary polyamine of general formula (VI) below:
H2N-[-(CHRl -(CH2)p-CHR2)n-NH]m-H (VI) dans laquelle RI et R2, identiques ou différents, représentent l'hydrogène ou un groupement hydrocarboné comprenant de 1 à 4 atomes de carbone, n est un nombre entier variant de 1 à 3, m est un nombre entier variant de 1 à 10, de préférence de 1 à 4 ; et p est un nombre entier égal à 0 ou 1. H 2 N - [- (CHRl - (CH 2 ) p -CHR2) n -NH] m -H (VI) in which RI and R2, identical or different, represent hydrogen or a hydrocarbon group comprising from 1 to 4 carbon atoms, n is an integer varying from 1 to 3, m is an integer varying from 1 to 10, preferably from 1 to 4; and p is an integer equal to 0 or 1.
Dans un mode de réalisation préféré, ledit additif (2) est obtenu par condensation du composé A avec le composé B, utilisés dans des quantités telles que le rapport molaire A/B est compris dans la gamme allant de 1 : 1 à 1 : 3. De préférence, le rapport molaire A/B est compris dans la gamme allant de 1 : 1 , 1 à 1 : 2, encore plus préférentiellement le rapport molaire A/B est compris dans la gamme allant de 1 : 1 , 1 à 1 : 1 ,5. In a preferred embodiment, said additive (2) is obtained by condensation of compound A with compound B, used in amounts such that the molar ratio A / B is in the range going from 1: 1 to 1: 3 . Preferably, the molar ratio A / B is included in the range going from 1: 1, 1 to 1: 2, even more preferably the molar ratio A / B is included in the range going from 1: 1, 1 to 1: 1, 5.
Ledit additif (2) peut notamment être obtenu par condensation de 60 à 90% en poids du composé A, et de 10 à 30 % en poids du composé B. Said additive (2) can in particular be obtained by condensation of 60 to 90% by weight of compound A, and from 10 to 30% by weight of compound B.
La masse molaire moyenne des composés A selon la présente invention varie de 200 à 3000, de préférence de 200 à 2000 g/mol, de préférence de 200 à 1500 g/mol, encore plus préférentiellement de 900 à 1300 g/mol. Ces composés sont bien connus de l'art antérieur. The average molar mass of the compounds A according to the present invention varies from 200 to 3000, preferably from 200 to 2000 g / mol, preferably from 200 to 1500 g / mol, even more preferably from 900 to 1300 g / mol. These compounds are well known from the prior art.
Parmi les polyamines primaires selon la formule (VI), les polyamines du groupe constitué par la diéthylène triamine, la dipropylène triamine, la triéthylène tétramine, la tétraéthylène pentamine et leurs dérivés substitués, ou leurs mélanges, sont préférées. Among the primary polyamines according to formula (VI), the polyamines of the group consisting of diethylene triamine, dipropylene triamine, triethylene tetramine, tetraethylene pentamine and their substituted derivatives, or mixtures thereof, are preferred.
Le mélange de ces composés A et B peut se faire indifféremment dans l’ordre détaillé ci-après, ou dans un ordre différent. The mixing of these compounds A and B can be done either in the order detailed below, or in a different order.
Dans un mode préféré, le composé B, c'est-à-dire la polyamine primaire de formule (VI) est ajoutée au composé A, c'est-à-dire le ou les hydrocarbure(s) carboxylique(s) acide(s) ou anhydride(s). In a preferred mode, the compound B, that is to say the primary polyamine of formula (VI) is added to the compound A, that is to say the acid (s) carboxylic hydrocarbon (s) ( s) or anhydride (s).
La polyamine B est ajoutée de façon progressive dans un solvant organique, puis à la solution du mélange d'hydrocarbures carboxyliques à température ambiante, le mélange est ensuite chauffé entre 65 et 250°C, et de préférence entre 80 et 220°C, pendant de 5 à 30 heures. Polyamine B is gradually added in an organic solvent, then to the solution of the mixture of carboxylic hydrocarbons at room temperature, the mixture is then heated between 65 and 250 ° C, and preferably between 80 and 220 ° C, for from 5 to 30 hours.
Le solvant organique nécessaire à la solubilisation de la polyamine primaire est choisi avec un point d'ébullition compris entre 65 et 250°C, et de préférence entre 80 et 220°C, et sa capacité à éliminer l'eau formée par condensation de la polyamine sur le composé A par distillation azéotropique du mélange eau/solvant. Le solvant est choisi dans le groupe constitué par le benzène, le toluène, les xylènes, l 'éthylbenzène et les coupes commerciales d'hydrocarbures, par exemple ceux distillant de 190 à 209°C et contenant 99% en poids de composés aromatiques. The organic solvent necessary for the solubilization of the primary polyamine is chosen with a boiling point of between 65 and 250 ° C, and preferably between 80 and 220 ° C, and its capacity to eliminate the water formed by condensation of the polyamine on compound A by azeotropic distillation of the water / solvent mixture. The solvent is chosen from the group consisting of benzene, toluene, xylenes, ethylbenzene and commercial cuts of hydrocarbons, for example those distilling at 190 to 209 ° C. and containing 99% by weight of aromatic compounds.
Selon un autre mode de réalisation de l'invention, un mélange de solvants peut être utilisé et notamment un mélange de xylènes, ou encore un mélange xylène/alcool, de préférence l’ alcool est l'éthyl-2-hexanol pour d'une part, faciliter l'homogénéité du milieu et, d'autre part, favoriser la cinétique de la réaction. According to another embodiment of the invention, a mixture of solvents can be used and in particular a mixture of xylenes, or else a xylene / alcohol mixture, preferably the alcohol is ethyl-2-hexanol for a on the one hand, to facilitate the homogeneity of the medium and, on the other hand, to promote the kinetics of the reaction.
Après la fin de l'addition de la polyamine primaire B, le chauffage est maintenu sous reflux jusqu'à l'élimination complète de l'eau, pendant de 0,5 à 7 heures, de préférence de 1 à 5 heures. Dans un mode de réalisation, la composition selon l’invention comprend le ou les seconds additifs tels que décrits ci-avant à une teneur préférentielle allant 5 à 10 000 ppm en poids, de préférence de 5 à 1000 ppm en poids, plus préférentiellement de 10 à 500 ppm en poids, plus préférentiellement de 15 à 200 ppm en poids, et mieux encore de 20 à 150 ppm en poids, par rapport au poids total de la composition de carburant. After the end of the addition of the primary polyamine B, the heating is maintained under reflux until the complete elimination of the water, for 0.5 to 7 hours, preferably 1 to 5 hours. In one embodiment, the composition according to the invention comprises the second additive (s) as described above in a preferential content ranging from 5 to 10,000 ppm by weight, preferably from 5 to 1000 ppm by weight, more preferably from 10 to 500 ppm by weight, more preferably from 15 to 200 ppm by weight, and better still from 20 to 150 ppm by weight, relative to the total weight of the fuel composition.
Le troisième additif : base de Mannich The third additive: Mannich base
La composition de carburant selon l'invention comprend un troisième additif (3), différent des additifs ( 1) et (2), constitué d’une base de Mannich. La préparation des bases de Mannich est connue en soi, et par exemple décrite dans les documents US2008/0052985, ou US8016898. The fuel composition according to the invention comprises a third additive (3), different from additives (1) and (2), consisting of a Mannich base. The preparation of Mannich bases is known per se, and for example described in documents US2008 / 0052985, or US8016898.
Le troisième additif est avantageusement préparé par réaction d'un phénol substitué par un groupement hydrocarboné, d'un aldéhyde et d'une amine. The third additive is advantageously prepared by reacting a phenol substituted with a hydrocarbon group, an aldehyde and an amine.
Le substituant hydrocarboné dudit phénol peut contenir de 6 à 400 atomes de carbone, avantageusement de 30 à 180 atomes de carbone, de préférence de 10 à 110, mieux de 40 à 110 atomes de carbone. The hydrocarbon substituent of said phenol may contain from 6 to 400 carbon atoms, advantageously from 30 to 180 carbon atoms, preferably from 10 to 110, better still from 40 to 110 carbon atoms.
Le substituant hydrocarboné dudit phénol peut être dérivé d'une oléfine ou une polyoléfine. A titre d'exemple, on peut citer les alpha-oléfines tel que le n- l-décène. De préférence, le substituant hydrocarboné dudit phénol est un groupement polyisobutylène. The hydrocarbon substituent of said phenol can be derived from an olefin or a polyolefin. By way of example, mention may be made of alpha-olefins such as n-1-decene. Preferably, the hydrocarbon substituent of said phenol is a polyisobutylene group.
Les polyoléfines formant le substituant hydrocarboné du phénol peuvent être préparées par polymérisation de monomères d'oléfines selon tout procédé de polymérisation connu. The polyolefins forming the hydrocarbon substituent of the phenol can be prepared by polymerization of olefin monomers according to any known polymerization process.
Avantageusement, les polyoléfines sont choisies parmi les polyisobutylènes présentant une masse molaire moyenne en nombre (Mn) comprise entre 400 à 3000, de préférence entre 400 à 2500, plus préférentiellement entre 400 et 1500, entre 500 à 1500 ou entre 500 et 1000. Advantageously, the polyolefins are chosen from polyisobutylenes having a number-average molar mass (Mn) of between 400 to 3000, preferably between 400 to 2500, more preferably between 400 and 1500, between 500 to 1500 or between 500 and 1000.
Le polyisobutylène est de préférence très réactif, ce qui diffère des polyisobutylènes peu réactifs par leur faible quantité de double liaisons éthylèniques terminales. Les polyisobutylènes réactifs selon l’invention, sont composés d’au moins 85% en poids, de préférence d’ au moins 90% en poids, de préférence d’ au moins 95% en poids d’unités isobutène. Polyisobutylene is preferably very reactive, which differs from poorly reactive polyisobutylenes by their small amount of terminal ethylene double bonds. The reactive polyisobutylenes according to the invention are composed of at least 85% by weight, preferably at least 90% by weight, preferably at least 95% by weight of isobutene units.
De préférence, les polyisobutylènes, de préférence très réactifs, ont une polydispersité de moins de 1 ,9, de préférence moins de 1 ,7 et encore plus préférentiellement de moins de 1 ,5, la polydispersité étant le quotient de la masse molaire moyenne en masse Mw et de la masse molaire moyenne en nombre Mn. Preferably, the polyisobutylenes, preferably very reactive, have a polydispersity of less than 1.9, preferably less than 1.7 and even more preferably less than 1.5, the polydispersity being the quotient the mass-average molar mass Mw and the number-average molar mass Mn.
Le phénol substitué par un groupement hydrocarboné peut être préparé par alkylation de phénol avec une oléfine ou polyoléfine décrite ci- dessus, tel qu'un polyisobutylène ou polypropylène, de préférence un polyisobutylène, en utilisant des méthodes d'alkylation conventionnelles. The phenol substituted with a hydrocarbon group can be prepared by alkylation of phenol with an olefin or polyolefin described above, such as polyisobutylene or polypropylene, preferably polyisobutylene, using conventional alkylation methods.
Selon une variante, le phénol peut être substitué par un ou plusieurs groupements alkyle à bas poids moléculaire par exemple un phénol portant une ou plusieurs chaînes alkyle de moins de 28 atomes de carbone, de préférence de moins de 24 atomes de carbone, plus préférentiellement de moins de 20 atomes de carbone, encore plus préférentiellement de moins de 18 atomes de carbone, encore plus préférentiellement de 16 atomes de carbone et encore plus préférentiellement de 14 atomes de carbone. According to one variant, the phenol can be substituted by one or more low molecular weight alkyl groups, for example a phenol carrying one or more alkyl chains of less than 28 carbon atoms, preferably of less than 24 carbon atoms, more preferably of less than 20 carbon atoms, even more preferably less than 18 carbon atoms, even more preferably 16 carbon atoms and even more preferably 14 carbon atoms.
On préférera un phénol monoalkylique ayant de 4 à 20 atomes de carbone, de préférence de 6 à 18, plus préférentiellement de 8 à 16, encore plus préférentiellement de 10 à 14 atomes de carbone, par exemple un phénol substitué par un groupement alkyle en C 12. Preference will be given to a monoalkylic phenol having from 4 to 20 carbon atoms, preferably from 6 to 18, more preferably from 8 to 16, even more preferably from 10 to 14 carbon atoms, for example a phenol substituted by an alkyl group in C 12.
L'aldéhyde utilisé pour former le produit de la réaction de Mannich peut comprendre de 1 à 10 atomes de carbone, et est généralement du formaldéhyde ou ses équivalents réactifs tel que la formaline (alcool méthylique et formaldéhyde), des trioxanes, ou le para-formaldéhyde, et de préférence, le para-formaldéhyde. The aldehyde used to form the product of the Mannich reaction can consist of 1 to 10 carbon atoms, and is generally formaldehyde or its reactive equivalents such as formalin (methyl alcohol and formaldehyde), trioxanes, or para. formaldehyde, and preferably para-formaldehyde.
L'amine utilisée pour former le produit de la réaction de Mannich peut être une monoamine ou une polyamine. The amine used to form the Mannich reaction product can be a monoamine or a polyamine.
A titre d'exemples non limitatifs, on peut citer comme monoamines, l'éthylamine, la diméthylamine, la diéthylamine, la di-n-propylamine, la di- isopropylamine la n-butylamine, la dibutylamine, l'allylamine, l'isobutylamine, la cocoamine, la stéarylamine, la laurylamine, la méthyllaurylamine, l'oléylamine, la N-méthyl-octylamine, la dodécylamine, la diéthanolamine, la morpholine, la diméthylmorpholine, la dicyclohexylamine, la pyrrolidine, la pipéridine, la diéthylènetriamine, triéthylènetetramine, la N,N-diéthyléthylènediamine, la N,N,N',N'- tétraméthyldiéthylènetriamine, les polyéthylèneimines et l'octadécylamine. Les polyamines sont choisies parmi les composés comprenant deux ou plusieurs groupes aminé. By way of nonlimiting examples, mention may be made, as monoamines, of ethylamine, dimethylamine, diethylamine, di-n-propylamine, di-isopropylamine, n-butylamine, dibutylamine, allylamine, isobutylamine. , cocoamine, stearylamine, laurylamine, methyllaurylamine, oleylamine, N-methyl-octylamine, dodecylamine, diethanolamine, morpholine, dimethylmorpholine, dicyclohexylamine, pyrrolidine, piperidine, diethylenetriamine, triethyl N, N-diethylethylenediamine, N, N, N ', N'-tetramethyldiethylenetriamine, polyethyleneimines and octadecylamine. The polyamines are chosen from compounds comprising two or more amino groups.
A titre d'exemples non limitatifs, on peut citer comme polyamines, les polyalkylène polyamines dans lesquelles le groupement alkylène a par exemple de 1 à 6, de préférence de 1 à 4, plus préférentiellement de 2 à 3 atomes de carbone. Les polyamines préférées sont les polyéthylène- polyamines. La polyamine peut comprendre de 2 à 15 atomes d'azote, de préférence de 2 à 10 atomes d'azote, de préférence 2 à 8 atomes d'azote. Des exemples de polyamines sont : la 3-(diméthylamino)-n-propylamine, la di[3- (diméthylamino)-n-propyl]amine, la di[3-(diéthylamino)-n-propyl]amine, la di[2-(diméthylamino)éthyl]amine, la N-méthylpipérazine, By way of nonlimiting examples, mention may be made, as polyamines, of polyalkylene polyamines in which the alkylene group has, for example, from 1 to 6, preferably from 1 to 4, more preferably from 2 to 3 carbon atoms. The preferred polyamines are polyethylene- polyamines. The polyamine can comprise 2 to 15 nitrogen atoms, preferably 2 to 10 nitrogen atoms, preferably 2 to 8 nitrogen atoms. Examples of polyamines are: 3- (dimethylamino) -n-propylamine, di [3- (dimethylamino) -n-propyl] amine, di [3- (diethylamino) -n-propyl] amine, di [ 2- (dimethylamino) ethyl] amine, N-methylpiperazine,
Selon une variante, l'amine utilisée pour former le produit de réaction de Mannich comprend une diamine, de préférence qui comprend une fonction amine primaire ou secondaire prenant part à la réaction de Mannich et une fonction amine tertiaire. According to one variant, the amine used to form the Mannich reaction product comprises a diamine, preferably which comprises a primary or secondary amine function taking part in the Mannich reaction and a tertiary amine function.
Selon une autre variante, l’ additif (3) peut être obtenu par une réaction de Mannich puis soumis à une réaction permettant d'obtenir une fonction amine tertiaire ; par exemple, un procédé mettant en œuvre un composé intermédiaire comprenant une amine secondaire et obtenu par réaction de Mannich, qui est ensuite modifié par exemple par alkylation pour conduire à une amine tertiaire. According to another variant, the additive (3) can be obtained by a Mannich reaction and then subjected to a reaction making it possible to obtain a tertiary amine function; for example, a process using an intermediate compound comprising a secondary amine and obtained by Mannich reaction, which is then modified, for example by alkylation to produce a tertiary amine.
Selon un mode de réalisation, la teneur de l’ additif (3) va de 5 à 10 000 ppm en poids, de préférence de 5 à 1000 ppm en poids, plus préférentiellement de 50 à 500 ppm en poids, plus préférentiellement de 100 à 500 ppm en poids, et mieux encore de 150 à 450 ppm en poids, par rapport au poids total de la composition de carburant. According to one embodiment, the content of the additive (3) ranges from 5 to 10,000 ppm by weight, preferably from 5 to 1000 ppm by weight, more preferably from 50 to 500 ppm by weight, more preferably from 100 to. 500 ppm by weight, and more preferably 150 to 450 ppm by weight, relative to the total weight of the fuel composition.
Concentré pour carburant Fuel concentrate
La présente invention a également pour objet l’utilisation, pour améliorer les propriétés de détergence d’un carburant essence, d’un concentré pour carburant comprenant au moins les additifs ( 1), (2) et (3), tels que définis ci-dessus, en mélange avec un liquide organique, ledit liquide organique étant inerte vis-à-vis des premier, second et troisième additif, et miscible audit carburant. The present invention also relates to the use, to improve the detergency properties of a gasoline fuel, of a fuel concentrate comprising at least the additives (1), (2) and (3), as defined herein. above, mixed with an organic liquid, said organic liquid being inert with respect to the first, second and third additives, and miscible with said fuel.
Le liquide organique est avantageusement miscible aux carburants liquides, notamment ceux issus d’une ou de plusieurs sources choisies parmi le groupe consistant en les sources minérale, de préférence le pétrole, animale, végétale et synthétique. On entend par miscible, le fait que les additifs et le liquide organique forment une solution ou une dispersion de manière à faciliter le mélange des additifs selon l’invention dans les carburants liquides selon les procédés classiques d’ additivation des carburants. The organic liquid is advantageously miscible with liquid fuels, in particular those obtained from one or more sources chosen from the group consisting of mineral, preferably petroleum, animal, vegetable and synthetic sources. The term “miscible” is understood to mean the fact that the additives and the organic liquid form a solution or a dispersion so as to facilitate the mixing of the additives according to the invention into liquid fuels according to conventional fuel additivation processes.
Le liquide organique est de préférence choisi parmi les solvants hydrocarbonés aromatiques tels que le solvant commercialisé sous le nom « SOLVESSO », les alcools, les éthers et autres composés oxygénés, et les solvants paraffiniques tels que l’hexane, pentane ou les isoparaffines, seuls ou en mélange. The organic liquid is preferably chosen from aromatic hydrocarbon solvents such as the solvent sold under the name “SOLVESSO”, alcohols, ethers and other oxygenated compounds, and paraffinic solvents such as hexane, pentane or isoparaffins, alone or as a mixture.
Le carburant Fuel
Le carburant selon la présente invention contient une base issue d’une ou de plusieurs sources choisies parmi le groupe consistant en les sources minérales, animales, végétales et synthétiques, et est de préférence choisi parmi les carburants hydrocarbonés, les carburants non essentiellement hydrocarbonés et leurs mélanges The fuel according to the present invention contains a base resulting from one or more sources chosen from the group consisting of mineral, animal, vegetable and synthetic sources, and is preferably chosen from hydrocarbon fuels, non-essentially hydrocarbon fuels and theirs. mixtures
On choisira, de préférence, le pétrole comme source minérale. Oil will preferably be chosen as the mineral source.
Le carburant est avantageusement choisi parmi les carburants hydrocarbonés et les carburants non essentiellement hydrocarbonés, seuls ou en mélange. The fuel is advantageously chosen from hydrocarbon-based fuels and non-essentially hydrocarbon-based fuels, alone or as a mixture.
On entend par carburant hydrocarboné, un carburant constitué d'un ou de plusieurs composés constitués uniquement de carbone et d'hydrogène. Les essences sont des carburants hydrocarbonés. The term “hydrocarbon fuel” is understood to mean a fuel consisting of one or more compounds consisting solely of carbon and hydrogen. Gasolines are hydrocarbon fuels.
On entend par carburant non essentiellement hydrocarboné, un carburant constitué d'un ou de plusieurs composés constitués non essentiellement de carbone et d'hydrogène c'est-à-dire qui contiennent également d'autres atomes, en particulier des atomes d'oxygène. The term “non-essentially hydrocarbon-based fuel” is understood to mean a fuel consisting of one or more compounds consisting not essentially of carbon and of hydrogen, that is to say which also contain other atoms, in particular oxygen atoms.
Les carburants hydrocarbonés comprennent notamment des distillais légers ayant une température d’ébullition dans la gamme des essences, de préférence comprise entre 30 et 210°C. Hydrocarbon fuels include in particular light distillates having a boiling point in the gasoline range, preferably between 30 and 210 ° C.
Ces distillais légers peuvent, par exemple, être choisis parmi les distillais obtenus par distillation directe d’hydrocarbures bruts, les distillais sous vide, les distillais hydrotraités, des distillais issus du craquage catalytique et/ou de l’hydrocraquage de distillais sous vide, les distillais résultant de procédés de conversion type ARDS (par désulfuration de résidu atmosphérique). These light distillates can, for example, be chosen from distillates obtained by direct distillation of crude hydrocarbons, vacuum distillates, hydrotreated distillates, distillates resulting from catalytic cracking and / or hydrocracking of vacuum distillates, distillates resulting from ARDS-type conversion processes (by desulphurization of atmospheric residue).
En d’ autres termes, le carburant hydrocarboné est choisi parmi les essences. In other words, the hydrocarbon fuel is chosen from gasolines.
Les essences comprennent, en particulier, toutes compositions de carburant pour moteur par allumage commandé disponibles dans le commerce. On peut citer à titre d’exemple représentatif, les essences répondant à la norme NF EN 228. Les essences ont généralement des indices d’ octane suffisamment élevés pour éviter le phénomène de cliquetis. Typiquement, les carburants de type essence commercialisés en Europe, conformes à la norme NF EN 228 ont un indice d’ octane moteur (MON en anglais « Motor Octane Number ») supérieur à 85 et un indice d’octane recherche (RON en anglais « Research Octane Number ») d’un minimum de 95. Les carburants de type essence ont, généralement, un RON allant de 90 à 100 et un MON allant de 80 à 90, les RON et MON étant mesurés selon la norme ASTM D 2699-86 ou D 2700-86. Gasolines include, in particular, any commercially available spark ignition engine fuel compositions. By way of representative example, mention may be made of the gasolines meeting standard NF EN 228. The gasolines generally have sufficiently high octane numbers to avoid the knocking phenomenon. Typically, gasoline-type fuels marketed in Europe, which comply with standard NF EN 228, have an engine octane number (MON in English "Motor Octane Number") greater than 85 and a research octane number (RON in English "Research Octane Number") of a minimum of 95. Gasoline type fuels have, generally, a RON ranging from 90 to 100 and a MON ranging from 80 to 90, the RON and MON being measured according to the standard ASTM D 2699-86 or D 2700-86.
Les carburants non essentiellement hydrocarbonés comprennent notamment les oxygénés, par exemple les distillais résultant de la conversion BTL (en anglais « biomass to liquid ») de la biomasse végétale et/ou animale, pris seuls ou en combinaison ; les biocarburants, par exemple les huiles et/ou esters d'huiles végétales et/ou animales ; et les bioéthanols. Non-essentially hydrocarbon-based fuels include in particular oxygenates, for example distillates resulting from the BTL (in English “biomass to liquid”) conversion of plant and / or animal biomass, taken alone or in combination; biofuels, for example oils and / or esters of vegetable and / or animal oils; and bioethanols.
Les mélanges de carburant hydrocarboné et de carburant non essentiellement hydrocarboné sont typiquement les essences de type Ex. Mixtures of hydrocarbon fuel and non-essentially hydrocarbon fuel are typically gasolines of the Ex type.
On entend par essence de type Ex pour moteur par allumage commandé, un carburant essence qui contient x% (v/v) d’oxygénés, généralement de l’éthanol, du bioéthanol et/ou l’éthyl-tertio-butyl-éther (ETBE). By gasoline of type Ex for a spark ignition engine is meant a gasoline fuel which contains x% (v / v) of oxygenates, generally ethanol, bioethanol and / or ethyl-tertio-butyl-ether ( ETBE).
La composition de carburant peut comprendre uniquement des nouvelles sources de distillais ou être composée d’un mélange avec des distillais plus légers pétroliers classiques comme base carburant type essence. The fuel composition may comprise only new sources of distillates or be composed of a mixture with conventional petroleum lighter distillates as the gasoline-type fuel base.
De préférence, la teneur de chaque additif ( 1) et (2) dans la composition de carburant selon l’invention va de 5 à 10 000 ppm en poids, de préférence de 5 à 1000 ppm en poids, plus préférentiellement de 10 à 500 ppm en poids, plus préférentiellement de 15 à 200 ppm en poids, et mieux encore de 20 à 150 ppm en poids, par rapport au poids total de la composition de carburant. Preferably, the content of each additive (1) and (2) in the fuel composition according to the invention ranges from 5 to 10,000 ppm by weight, preferably from 5 to 1000 ppm by weight, more preferably from 10 to 500 ppm by weight, more preferably from 15 to 200 ppm by weight, and better still from 20 to 150 ppm by weight, relative to the total weight of the fuel composition.
De préférence, la teneur de l’ additif (3) dans la composition de carburant selon l’invention va de 5 à 10 000 ppm en poids, de préférence de 5 à 1000 ppm en poids, plus préférentiellement de 50 à 500 ppm en poids, plus préférentiellement de 100 à 500 ppm en poids, et mieux encore de 150 à 450 ppm en poids, par rapport au poids total de la composition de carburant. Preferably, the content of additive (3) in the fuel composition according to the invention ranges from 5 to 10,000 ppm by weight, preferably from 5 to 1000 ppm by weight, more preferably from 50 to 500 ppm by weight. , more preferably from 100 to 500 ppm by weight, and better still from 150 to 450 ppm by weight, relative to the total weight of the fuel composition.
De préférence, la teneur en soufre dans la composition de carburant est inférieure ou égale à 1500 ppm en poids, de préférence inférieure ou égale à 1000 ppm en poids, de préférence inférieure ou égale à 500 ppm en poids et préférentiellement inférieure ou égale à 50 ppm en poids, encore plus préférentiellement inférieure ou égale à 10 ppm en poids, par rapport au poids total de la composition, et avantageusement sans soufre. Preferably, the sulfur content in the fuel composition is less than or equal to 1500 ppm by weight, preferably less than or equal to 1000 ppm by weight, preferably less than or equal to 500 ppm by weight and preferably less than or equal to 50 ppm by weight, even more preferably less than or equal to 10 ppm by weight, relative to the total weight of the composition, and advantageously without sulfur.
Autres Additifs de la composition de carburant Other additives in the fuel composition
La composition de carburant peut également comprendre un ou plusieurs additif(s) additionnel(s), différent(s) desdits additifs selon l’invention. Ce ou ces additifs additionnel(s) peuvent par exemple être choisis, de manière non limitative, parmi : les additifs détergents, les agents anti corrosion, les anti-oxydants, les huiles porteuses, les dispersants, les désémulsifiants, les traceurs ou marqueurs, les réodorants, les modificateurs de friction, les additifs de lubrifiance ou additifs d'onctuosité, les agents d'aide à la combustion (promoteurs catalytiques de combustion et de suie), les agents anti-sédimentation, les agents anti-usure et les agents modifiant la conductivité. The fuel composition can also comprise one or more additional additive (s), different from said additives according to the invention. This or these additional additives can for example be chosen, in a nonlimiting manner, from: detergent additives, anti-corrosion agents, anti-oxidants, carrier oils, dispersants, demulsifiers, tracers or markers, reodorants, friction modifiers, lubricity additives or lubricity additives, combustion aids (catalytic combustion and soot promoters), anti-sedimentation agents, antiwear agents and agents modifying the conductivity.
Ce ou ces additifs additionnel(s) sont plus préférentiellement choisis parmi : a) les additifs de lubrifiance ou agents anti-usure, notamment (mais non limitativement) choisis dans le groupe constitué par les acides gras et leurs dérivés ester ou amide, notamment le monooléate de glycérol, et les dérivés d'acides carboxyliques mono- et polycycliques. Des exemples de tels additifs sont donnés dans les documents suivants : EP680506, EP860494,This or these additional additives are more preferably chosen from: a) lubricating additives or anti-wear agents, in particular (but not limited to) chosen from the group consisting of fatty acids and their ester or amide derivatives, in particular glycerol monooleate, and derivatives of mono- and polycyclic carboxylic acids. Examples of such additives are given in the following documents: EP680506, EP860494,
WO98/04656, EP915944, FR2772783, FR2772784 ; b) les additifs détergents notamment (mais non limitativement) choisis parmi les polyétheramines; c) les modificateurs de friction ou de frottements notamment (mais non limitativement) choisis dans le groupe constitué par les acides ou esters d’ acides gras ou mélanges d’ acides ou d’esters d’ acides gras, par exemple les acides oléique, linoléique, résiniques, palmitique ; ou parmi les dimères d’ acides gras, ou les esters mono ou di-propoxylés ; les esters de sorbitan ; les stéarates de sucrose ; ou parmi le glycérol et ses dérivés ; ou les esters de pentaérythritol ; ou les amines ; et de préférence choisis parmi les esters de glycérol ou polyglycérol, ou les acides ou esters d’ acides gras, ou leurs mélanges ; d) les additifs anticorrosion notamment (mais non limitativement) choisis dans le groupe constitué par les acides ou esters d’ acides gras ou mélanges d’ acides ou d’esters d’ acides gras, ou parmi les dimères d’ acides gras ; e) les anti-oxydants notamment (mais non limitativement) choisis dans le groupe constitué par le 2,6-di-t-butyl-4- méthyl phénol, la t-butyl hydroquinone, le 2,6 et le 2,4 di-t-butyl phénol, le 2,4-diméthyl-6-t-butyl phénol, le pyrogallol, le tocophérol, le 4,4'- méthylène bis (2,6-di-t-butyl phénol), seuls ou en mélange ; f) les huiles porteuses notamment (mais non limitativement) choisies dans le groupe constitué par les poly-oxyalkylènes comme par exemple le poly-oxyde de 1-butène ou le poly-oxyde de propène. Ces additifs additionnels peuvent être présents en quantité allant de 3 à 1 000 ppm (chacun) en poids, par rapport au poids total de la composition de carburant, de préférence de 5 à 500 ppm. WO98 / 04656, EP915944, FR2772783, FR2772784; b) detergent additives, in particular (but not limited to) chosen from polyetheramines; c) friction or friction modifiers in particular (but not limited to) chosen from the group consisting of acids or esters of fatty acids or mixtures of acids or esters of fatty acids, for example oleic and linoleic acids , resin, palmitic; or from fatty acid dimers, or mono or di-propoxylated esters; sorbitan esters; sucrose stearates; or from glycerol and its derivatives; or esters of pentaerythritol; or amines; and preferably chosen from esters of glycerol or polyglycerol, or acids or esters of fatty acids, or mixtures thereof; d) anticorrosion additives in particular (but not limited to) chosen from the group consisting of acids or esters of fatty acids or mixtures of acids or esters of fatty acids, or from dimers of fatty acids; e) antioxidants, in particular (but not limited to) chosen from the group consisting of 2,6-di-t-butyl-4-methyl phenol, t-butyl hydroquinone, 2,6 and 2,4 di -t-butyl phenol, 2,4-dimethyl-6-t-butyl phenol, pyrogallol, tocopherol, 4,4'-methylene bis (2,6-di-t-butyl phenol), alone or in mixed ; f) carrier oils in particular (but not limited to) chosen from the group consisting of poly-oxyalkylenes, such as, for example, poly-butene-oxide or poly-propene-oxide. These additional additives can be present in an amount ranging from 3 to 1000 ppm (each) by weight, relative to the total weight of the fuel composition, preferably from 5 to 500 ppm.
Les utilisations Uses
Un autre objet de l’invention est l’utilisation de la composition de carburant pour maintenir la propreté (effet keep-clean) et/ou nettoyer (effet clean-up) les dépôts dans les parties internes d’un moteur choisies parmi les suivantes : la chambre de combustion et le système d’injection de carburant, et de préférence le système d’injection de carburant. Another object of the invention is the use of the fuel composition to maintain cleanliness (keep-clean effect) and / or clean (clean-up effect) the deposits in the internal parts of an engine chosen from the following : the combustion chamber and the fuel injection system, and preferably the fuel injection system.
La composition selon l’invention est efficace dans les moteurs classiques ; ou moteurs plus modernes comme, IDE, les moteurs BMW B48, Renault H5FT et HR13DDT, PSA EB2DTS, Volkswagen EA1 11... ; et en IIE les moteurs Mercedes M102E et Ml 11E, PSA EW 10A et EB2 ... The composition according to the invention is effective in conventional engines; or more modern engines such as, IDE, BMW B48, Renault H5FT and HR13DDT, PSA EB2DTS, Volkswagen EA1 11 ...; and in IIE the Mercedes M102E and Ml 11E, PSA EW 10A and EB2 engines ...
Un autre objet de l’invention est l’utilisation de la composition de carburant comprenant au moins un premier additif, au moins un second additif et au moins un troisième additif définis ci-dessus pour empêcher et/ou réduire le coking (c’est-à-dire les dépôts de coke), notamment en injection directe essence (IDE), et/ou le lacquering (c’est-à-dire les dépôts de savons et/ou vernis) notamment en injection indirecte essence (IIE), et notamment sur les soupapes. Another object of the invention is the use of the fuel composition comprising at least a first additive, at least a second additive and at least a third additive defined above to prevent and / or reduce coking (i.e. i.e. coke deposits), particularly in direct petrol injection (IDE), and / or lacquering (i.e. soap and / or varnish deposits), particularly in indirect petrol injection (IIE), and in particular on the valves.
L’invention permet ainsi d’empêcher et/ou de réduire les dépôts de coke et/ou de savon sur les soupapes d’admission de carburant dans un moteur à allumage commandé à injection indirecte The invention thus makes it possible to prevent and / or reduce deposits of coke and / or soap on the fuel inlet valves in a spark-ignition engine with indirect injection
Un autre objet de l’invention est l’utilisation de la composition de carburant comprenant au moins un premier additif, au moins un second additif et au moins un troisième additif définis ci-dessus pour empêcher et/ou réduire le collage (ou valve-sticking) des soupapes d’ admission de carburant dans un moteur, notamment un moteur à allumage commandé à injection indirecte essence (IIE). Dans ce mode de réalisation, ladite composition comprend avantageusement en outre un quatrième additif qui est une huile porteuse. Another object of the invention is the use of the fuel composition comprising at least a first additive, at least a second additive and at least a third additive defined above to prevent and / or reduce sticking (or valve- sticking) of the fuel inlet valves in an engine, in particular a spark ignition engine with indirect gasoline injection (IIE). In this embodiment, said composition advantageously further comprises a fourth additive which is a carrier oil.
Dans le cas de l’utilisation pour lutter contre le valve-sticking, la composition comprend de préférence en outre une huile porteuse. L’huile porteuse peut être choisie parmi les huiles de type poly(oxyalkylène), par exemple le poly-oxyde de 1 -butène ou le poly-oxyde de propène. Dans un mode de réalisation, le ratio pondéral de la quantité d’huile porteuse sur la quantité d’ additifs détergents est compris dans la gamme allant de 0, 1 à 2,5, de préférence de 0,3 à 1 ,5, de manière encore plus préférée de 0,5 à 1. Un autre objet de l’invention est l’utilisation de ladite composition de carburant pour réduire la consommation de carburant du moteur (action « Fuel Eco ») et/ou minimiser la perte de puissance dudit moteur, et/ou réduire les émissions de polluants, en particulier, les émissions de particules du moteur à combustion. In the case of use for combating valve-sticking, the composition preferably further comprises a carrier oil. The carrier oil can be chosen from oils of poly (oxyalkylene) type, for example poly-butene oxide or poly-propene oxide. In one embodiment, the weight ratio of the amount of carrier oil to the amount of detergent additives is in the range of 0.1 to 2.5, preferably 0.3 to 1.5, even more preferably from 0.5 to 1. Another object of the invention is the use of said fuel composition for reducing the fuel consumption of the engine (“Fuel Eco” action) and / or minimizing the loss of power from said engine, and / or reducing pollutant emissions. , in particular, particulate emissions from the combustion engine.
Un autre objet de l’invention est l’utilisation de ladite composition d’ additifs pour réduire l’encrassement de la zone des pistons, des segments, et des chemises du moteur, de préférence d’un moteur à injection directe essence (ou IDE). Another object of the invention is the use of said composition of additives to reduce the fouling of the area of the pistons, segments, and liners of the engine, preferably of a gasoline direct injection engine (or IDE ).
L’ additif ( 1) ammonium quaternaire, tel que défini dans la présente invention, est particulièrement efficace pour lutter contre l’encrassement piston, notamment en IDE. The quaternary ammonium additive (1), as defined in the present invention, is particularly effective in combating piston fouling, especially in IDE.
L’ association des additifs (1 ) et (2) est également très efficace pour lutter contre l’encrassement piston, notamment en IDE. The combination of additives (1) and (2) is also very effective in combating piston fouling, especially in IDE.
La composition de carburant peut être utilisée en injection indirecte essence (IIE) ou en injection directe essence (IDE), de préférence en IDE. The fuel composition can be used in indirect gasoline injection (IIE) or in direct gasoline injection (IDE), preferably in IDE.
Dans un mode de réalisation, l’IDE est centrale, et dans une autre mode de réalisation, l’IDE est latérale. La présente invention est donc efficace et utilisée en IDE centrale et/ou latérale. In one embodiment, the IDE is central, and in another embodiment, the IDE is lateral. The present invention is therefore effective and used in central and / or lateral IDE.
La composition de carburant peut également être utilisée pour lutter contre la corrosion dans le moteur. L’ additif (2) polyisobutylène-succinimide, tel que défini dans la présente invention, est particulièrement efficace pour lutter contre la corrosion. The fuel composition can also be used to combat corrosion in the engine. The polyisobutylene succinimide additive (2), as defined in the present invention, is particularly effective in combating corrosion.
L’utilisation selon l’invention est applicable aux moteurs employés dans les véhicules légers (VL), les poids-lourds (PL), les engins stationnaires, les engins agricoles, les véhicules thermiques ou véhicules hybrides (rechargeables ou non), les moteurs à bicarburation essence/gaz par exemple essence/GNV (gaz naturel) ou essence/GPL ; les moteurs à injection concomitante essence/GNV ou essence/GPL... The use according to the invention is applicable to engines used in light vehicles (light vehicles), heavy goods vehicles (PL), stationary vehicles, agricultural machinery, thermal vehicles or hybrid vehicles (rechargeable or not), engines dual-fuel gasoline / gas, for example gasoline / NGV (natural gas) or gasoline / LPG; gasoline / CNG or gasoline / LPG concomitant injection engines ...
La composition d’ additifs, de carburant ou le concentré peut être utilisé dans des essences « sévères » ou « plus faciles à traiter ». Les essences « sévères » se distinguent des essences faciles à traiter en ce qu’une essence sévère nécessite une taux de traitement en composition d’additifs plus élevé pour être efficace qu’une essence « facile à traiter ». On peut mentionner comme essences « sévères » les essences similaires aux essences de référence CEC RL12-09 et CEC RL-83. The additive, fuel or concentrate composition can be used in "harsh" or "easier to process" gasolines. "Harsh" gasolines are distinguished from easy-to-process gasolines in that a harsh gasoline requires a higher additive compound processing rate to be effective than "easy-to-process" gasoline. One can mention as "severe" species the species similar to the reference species CEC RL12-09 and CEC RL-83.
Procédé (ou méthode) de préparation de la composition de carburant La composition de carburant selon l’invention peut être préparée selon tout procédé connu, en additivant une coupe d’hydrocarbures liquide telle que décrite précédemment avec au moins les trois additifs tels que décrits ci-dessus, et éventuellement un ou plusieurs autres additifs différents des additifs selon l’invention, tels que décrits précédemment. Process (or method) for preparing the fuel composition The fuel composition according to the invention can be prepared according to any known process, by adding a liquid hydrocarbon cut as described above with at least the three additives as described above, and optionally one or more other additives other than those described above. additives according to the invention, as described above.
Procédé pour améliorer la propreté du moteur Process to improve engine cleanliness
L’invention concerne également un procédé de maintien de la propreté et/ou de nettoyage d’ au moins une des parties internes d’un moteur à allumage commandé, comprenant au moins les étapes suivantes : The invention also relates to a method of maintaining the cleanliness and / or cleaning of at least one of the internal parts of a spark-ignition engine, comprising at least the following steps:
- la préparation d’une composition de carburant par additivation d’un carburant avec au moins les trois additifs tels que décrits ci-avant ou avec un concentré les comprenant, puis - the preparation of a fuel composition by additivation of a fuel with at least the three additives as described above or with a concentrate comprising them, then
- la combustion de ladite composition de carburant dans ledit moteur à allumage commandé. the combustion of said fuel composition in said spark ignition engine.
Toutes les caractéristiques des additifs, du carburant ou de l’utilisation sont applicables au procédé. All characteristics of additives, fuel or use are applicable to the process.
Selon une variante, l’étape de préparation d’une composition de carburant ci-avant est précédée d’une étape préalable de détermination de la teneur en chacun des trois additifs à incorporer à ladite composition de carburant pour atteindre une spécification donnée relative aux propriétés de détergence de la composition de carburant. According to one variant, the above step of preparing a fuel composition is preceded by a preliminary step of determining the content of each of the three additives to be incorporated into said fuel composition in order to achieve a given specification relating to the properties. detergency of the fuel composition.
Cette étape préalable relève de la pratique courante dans le domaine de l’ additivation des carburants et implique de définir au moins une caractéristique représentative des propriétés de détergence de la composition de carburant ainsi qu’une valeur cible. This preliminary step is common practice in the field of fuel additives and involves defining at least one characteristic representative of the detergency properties of the fuel composition as well as a target value.
Des méthodes d’évaluation des propriétés détergentes des carburants ont largement été décrites dans la littérature et relèvent des connaissances générales de l’homme du métier. On citera, à titre d’exemple non limitatif, les essais normalisés ou reconnus par la profession ou les méthodes décrites dans la littérature suivants, pour les moteurs par allumage commandé à injection indirecte : Methods for evaluating the detergent properties of fuels have been widely described in the literature and are within the general knowledge of those skilled in the art. Mention will be made, by way of nonlimiting example, of the tests standardized or recognized by the profession or the methods described in the following literature, for engines by positive ignition with indirect injection:
- la méthode Mercedes Benz M102E, méthode d’essai normée CEC F-05-A-93, et - the Mercedes Benz M102E method, CEC F-05-A-93 standardized test method, and
- la méthode Mercedes Benz M11 1E, méthode d’essai normée CEC F-20-A-98. - the Mercedes Benz M11 1E method, CEC F-20-A-98 standardized test method.
Ces méthodes permettent de mesurer les dépôts sur les soupapes d’ admission (IVD), les tests étant généralement réalisés sur une essence Eurosuper répondant à la norme EN228. Pour les moteurs par allumage commandé à injection directe : These methods make it possible to measure deposits on the intake valves (IVD), the tests generally being carried out on Eurosuper gasoline meeting the EN228 standard. For direct injection positive-ignition engines:
- la méthode décrite par la demanderesse dans l’ article « Evaluating Injector Fouling in Direct Injection Spark Ignition Engines», Mathieu Arondel, Philippe China, Julien Gueit ; Conventional and future energy for automobiles ; 10th international colloquium ; January 20-22, 2015, p.375-386 (Technische Akademie Esslingen par Techn. Akad. Esslingen, Ostfildern), pour l’évaluation des dépôts de type coking sur l’injecteur, - the method described by the applicant in the article "Evaluating Injector Fouling in Direct Injection Spark Ignition Engines", Mathieu Arondel, Philippe China, Julien Gueit; Conventional and future energy for automobiles; 10th international colloquium; January 20-22, 2015, p.375-386 (Technische Akademie Esslingen by Techn. Akad. Esslingen, Ostfildern), for the evaluation of coking type deposits on the injector,
- la méthode décrite dans le document US20130104826, pour l’évaluation des dépôts de type coking sur l’injecteur, - the method described in document US20130104826, for the evaluation of coking type deposits on the injector,
- la méthode VW EA 111 en cours de développement dans le cadre du CEC TDG- F- 113 sur base du moteur VW EA 111 (Glawar, A., et al., "Development of a Fuel System Cleanliness Test Method in a Euro 4 Direct-Injection Gasoline Engine (VW 1.4 L TSI 90 kW)," SAE Int. J. Fuels Lubr. 10(3):2017, doi: 10.4271/2017-01 -2296). - the VW EA 111 method under development within the framework of the CEC TDG- F- 113 based on the VW EA 111 engine (Glawar, A., et al., "Development of a Fuel System Cleanliness Test Method in a Euro 4 Direct-Injection Gasoline Engine (VW 1.4 L TSI 90 kW), "SAE Int. J. Fuels Lubr. 10 (3): 2017, doi: 10.4271 / 2017-01 -2296).
On peut également citer la méthode CEC Ll l 1 - 16 qui permet d’évaluer l’encrassement de la zone des pistons, des segments, et des chemises d’un moteur à injection directe essence. Mention may also be made of the CEC Ll l 1 - 16 method which makes it possible to assess the fouling of the area of the pistons, rings and liners of a gasoline direct injection engine.
Les exemples ci-après sont donnés à titre d’illustration de l’invention, et ne sauraient être interprétés de manière à en limiter la portée. The examples below are given by way of illustration of the invention, and should not be interpreted in such a way as to limit its scope.
EXEMPLES EXAMPLES
Les exemples ci-après ont été réalisés à partir d’une essence E, dont les caractéristiques sont détaillées dans le tableau 1 ci-dessous. The examples below were produced from an E gasoline, the characteristics of which are detailed in Table 1 below.
Tableau 1 : caractéristiques de l’essence E
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Table 1: characteristics of gasoline E
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Des compositions de carburant ont été préparées, en ajoutant à l’essence E les additifs Al , A2 et A3 suivants : Fuel compositions were prepared by adding the following additives Al, A2 and A3 to gasoline E:
Al : sel d’ ammonium quaternaire, formé par réaction de l’ oxyde de propylène avec le produit de condensation d'un anhydride polyisobutényl-succinique dont le groupement polyisobutylène (PIB) a une masse moléculaire moyenne en nombre (Mn) de 1000 g/mol et de la diméthyl-aminopropylamine ; Al: quaternary ammonium salt, formed by reaction of propylene oxide with the condensation product of a polyisobutenyl succinic anhydride, the polyisobutylene group (PIB) of which has a number average molecular mass (Mn) of 1000 g / mol and dimethyl-aminopropylamine;
A2 : polyisobutylène succinimide, obtenu par condensation d'un anhydride polyisobutényl-succinique dont le groupement polyisobutylène (PIB) a une masse moléculaire moyenne en nombre (Mn) de 1000 g/mol et de la tétraéthylènepentamine ; A2: polyisobutylene succinimide, obtained by condensation of a polyisobutenyl-succinic anhydride, the polyisobutylene group (PIB) of which has a number-average molecular mass (Mn) of 1000 g / mol and tetraethylenepentamine;
A3 : base de Mannich, obtenue par réaction d'un phénol substitué par un groupement polyisobutylène (PIB) ayant une masse moléculaire moyenne en nombre (Mn) de 1000 g/mol, avec le formaldéhyde et la diméthyl-aminopropylamine. A3: Mannich base, obtained by reacting a phenol substituted with a polyisobutylene group (PIB) having a number average molecular mass (Mn) of 1000 g / mol, with formaldehyde and dimethyl-aminopropylamine.
La quantité d’ additif ajoutée à chaque composition est détaillée dans le tableau 2 ci-dessous, dans lequel la teneur de chaque additif est indiquée en ppm en poids par rapport au poids total de la composition finale : The amount of additive added to each composition is detailed in Table 2 below, in which the content of each additive is indicated in ppm by weight relative to the total weight of the final composition:
Tableau 2 : compositions de carburant à partir de l’essence E
Figure imgf000030_0002
Table 2: Fuel compositions from gasoline E
Figure imgf000030_0002
La composition El est conforme à l’invention. Les compositions E2, E3 et E4 sont comparatives. Le taux d’ additivation est identique entre les trois compositions El , E2 et E3 (433 ppm). Composition El is in accordance with the invention. The compositions E2, E3 and E4 are comparative. The additivation rate is identical between the three compositions El, E2 and E3 (433 ppm).
Les performances en termes de détergence de chacune des compositions de carburant El à E4 ci-dessus ainsi que du carburant de référence E non additivé ont été évaluées en utilisant un test permettant de déterminer le niveau d’encrassement des injecteurs d’un moteur à injection directe essence (IDE). The performance in terms of detergency of each of the Fuel compositions E1 to E4 above as well as the reference fuel E without additives were evaluated using a test making it possible to determine the level of fouling of the injectors of a gasoline direct injection engine (IDE).
Le moteur utilisé est un moteur PSA EB2DTS, qui est un moteur essence 3 cylindres 1199 cm3 turbocompressé à injection directe, avec injecteurs en position centrale. The engine used is a motor EB2DTS PSA, which is a gas cylinder 3 1199 cm 3 turbocharged direct injection engine, with the injectors in a central position.
Avant la réalisation de l’essai, le débit des injecteurs est déterminé au moyen d’un banc de mesure des débits des injecteurs de type EFS IFR 600, qui permet de manière connue en soi de mesurer le débit de carburant massique des injecteurs. Before carrying out the test, the flow rate of the injectors is determined by means of a bench for measuring the flow rates of the EFS IFR 600 type injectors, which makes it possible in a manner known per se to measure the mass fuel flow rate of the injectors.
Le principe de l’essai consiste à faire tourner le moteur pendant 5 heures à 4300 tours/minute et 1 1 bars de pression moyenne effective (ci- après désignée par PME), en l’ alimentant avec l’essence testée à une pression d’injection de 70 bars, après une période de chauffe de 20 minutes, et une période de stabilisation de 10 minutes. The principle of the test consists in making the engine run for 5 hours at 4300 revolutions / minute and 11 bars of mean effective pressure (hereinafter referred to as PME), by supplying it with the gasoline tested at a pressure of injection of 70 bars, after a heating period of 20 minutes, and a stabilization period of 10 minutes.
Le test permet de déterminer la perte de débit moyenne, définie comme correspondant à la restriction moyenne du flux d’essence émis par les injecteurs du moteur à l’issue du test. Plus la perte de débit moyenne est élevée, plus le carburant a un effet encrassant sur les injecteurs du moteur, et moins ses performances détergentes sont bonnes. The test determines the average flow loss, defined as corresponding to the average restriction of the flow of gasoline emitted by the engine injectors at the end of the test. The higher the average flow loss, the more the fuel has a clogging effect on the engine's injectors, and the lower its detergent performance.
Les étapes de l’essai sont les suivantes : The test steps are as follows:
- Une étape de chauffe ; - A heating step;
- Une étape de stabilisation ; - A stabilization stage;
- Une étape d’encrassement ; - A fouling step;
- Une étape de détermination de la perte de débit des injecteurs. - A step of determining the flow loss of the injectors.
Les conditions de test sont les suivantes : The test conditions are as follows:
Températures : Temperatures:
- Eau en sortie moteur : 90 ± 2°C - Water at motor outlet: 90 ± 2 ° C
- Huile : 110 ± 5°C - Oil: 110 ± 5 ° C
- Air dans le collecteur d’ admission : 40 ± 2°C - Air in the intake manifold: 40 ± 2 ° C
- Carburant en boucle basse pression : 50 ± 2°C Pression d’injection du carburant : 70 bars - Low pressure loop fuel: 50 ± 2 ° C Fuel injection pressure: 70 bars
Pour la phase de chauffe, le moteur est soumis à une augmentation progressive de régime, pendant une durée de 20 minutes, jusqu’à atteindre un régime de 4000 tours/minute et une PME de 8 bar. For the heating phase, the engine is subjected to a gradual increase in speed, for a period of 20 minutes, until reaching a speed of 4000 revolutions / minute and an PME of 8 bar.
Pour la phase de stabilisation, le moteur est maintenu aux conditions opératoires de l’essai, à un régime de 4300 tours/minute, à une PME de 11 bar et une pression d’injection du carburant de 70 bar, pendant une durée de 10 minutes. For the stabilization phase, the engine is maintained under the operating conditions of the test, at a speed of 4300 revolutions / minute, at a PME of 11 bar and a fuel injection pressure of 70 bar, for a period of 10 minutes.
Pour la phase d’encrassement, le moteur tourne ensuite pendant 5 heures à 4300 tours/minute et 11 bars de PME avec une pression d’injection du carburant de 70 bars. For the fouling phase, the engine then runs for 5 hours at 4300 rpm and 11 bar PME with a fuel injection pressure of 70 bar.
A la fin de l’essai, les injecteurs sont déposés afin d’être évalués au moyen du banc de mesure des débits des injecteurs EFS IFR 600, qui permet de mesurer le débit de carburant massique des injecteurs à l’issue de l’essai. Par comparaison à la valeur du débit de carburant massique des injecteurs mesurée avant l’essai, la perte de débit moyenne des injecteurs est calculée. At the end of the test, the injectors are removed in order to be evaluated by means of the EFS IFR 600 injector flow rate measuring bench, which makes it possible to measure the mass fuel flow rate of the injectors at the end of the test. . By comparison with the value of the mass fuel flow of the injectors measured before the test, the average loss of flow of the injectors is calculated.
Les résultats obtenus sont détaillés dans le tableau 3 ci-dessous. The results obtained are detailed in Table 3 below.
Tableau 3: résultats
Figure imgf000032_0001
Table 3: results
Figure imgf000032_0001
Les résultats ci-dessus montrent que la composition El selon l’invention contenant l’ association des trois additifs A l , A2 et A3 conduit à de très bons résultats en termes de réduction de l’encrassement des injecteurs (effet « keep clean »). A teneur totale en additifs identique par ailleurs (433 ppm), ces résultats sont significativement meilleurs que ceux obtenus avec les compositions comparatives E2 et E3 contenant seulement deux des trois additifs. Les résultats obtenus avec la composition E4 contenant un seul des trois additifs, et avec le carburant de référence E, sont encore moins bons. The above results show that the composition E1 according to the invention containing the combination of the three additives A1, A2 and A3 leads to very good results in terms of reducing the fouling of the injectors (“keep clean” effect). . For a total additive content which is otherwise identical (433 ppm), these results are significantly better than those obtained with the comparative compositions E2 and E3 containing only two of the three additives. The results obtained with composition E4 containing only one of the three additives, and with the reference fuel E, are even worse.
Ces résultats illustrent les effets synergiques procurés par l’ association des deux additifs selon la présente invention. These results illustrate the synergistic effects provided by the combination of the two additives according to the present invention.

Claims

REVENDICATIONS
1. Utilisation, pour réduire et/ou empêcher les dépôts dans les parties internes d’un moteur à allumage commandé, d’une composition de carburant comprenant : 1. Use, to reduce and / or prevent deposits in the internal parts of a spark-ignition engine, of a fuel composition comprising:
(1 ) au moins un premier additif constitué d’un sel d’ ammonium quaternaire,(1) at least a first additive consisting of a quaternary ammonium salt,
(2) au moins un second additif constitué d’un polyisobutylène succinimide non quaternaire, (2) at least one second additive consisting of a non-quaternary polyisobutylene succinimide,
(3) au moins un troisième additif différent des additifs ( 1) et (2), constitué d’une base de Mannich, et dans laquelle le ratio massique de la quantité du premier additif sur la quantité du second additif est compris dans la gamme allant de 0,2 : 1 à 2,5 : 1. (3) at least a third additive different from additives (1) and (2), consisting of a Mannich base, and in which the mass ratio of the amount of the first additive to the amount of the second additive is within the range ranging from 0.2: 1 to 2.5: 1.
2. Utilisation selon la revendication 1 , dans laquelle le ratio massique de la quantité du premier additif sur la quantité du second additif est compris dans la gamme allant de 1 : 1 à 2 : 1, et de préférence de 1 ,25 : 1 à 1 ,5 : 1 . 2. Use according to claim 1, wherein the mass ratio of the amount of the first additive to the amount of the second additive is in the range from 1: 1 to 2: 1, and preferably from 1.25: 1 to 1, 5: 1.
3. Utilisation selon la revendication 1 ou 2, dans laquelle le premier additif ( 1) constitué de sel d’ ammonium quaternaire est obtenu par réaction avec un agent de quaternisation d’un composé azoté comprenant une fonction amine tertiaire, ce composé étant le produit de la réaction d’un agent d’ acylation substitué par un groupement hydrocarboné et d’un composé comprenant au moins un groupement amine tertiaire et au moins un groupement choisi parmi les amines primaires, les amines secondaires et les alcools. 3. Use according to claim 1 or 2, wherein the first additive (1) consisting of quaternary ammonium salt is obtained by reaction with a quaternization agent of a nitrogen compound comprising a tertiary amine function, this compound being the product. of the reaction of an acylating agent substituted with a hydrocarbon group and of a compound comprising at least one tertiary amine group and at least one group chosen from primary amines, secondary amines and alcohols.
4. Utilisation selon la revendication 3, dans laquelle l’ agent d’ acylation substitué par un groupement hydrocarboné est choisi parmi les acides mono-ou poly-carboxyliques et leurs dérivés, notamment leurs dérivés ester, amides ou anhydrides, et de préférence l'agent d'acylation est choisi parmi les acides succiniques, phtaliques et propioniques et les anhydrides correspondants. 4. Use according to claim 3, in which the acylating agent substituted with a hydrocarbon group is chosen from mono-or poly-carboxylic acids and their derivatives, in particular their ester, amide or anhydride derivatives, and preferably the. acylating agent is chosen from succinic, phthalic and propionic acids and the corresponding anhydrides.
5. Utilisation selon la revendication 3 ou 4, dans laquelle l’agent d’ acylation substitué par un groupement hydrocarboné est un anhydride polyisobutényl-succinique. 5. Use according to claim 3 or 4, wherein the acylating agent substituted with a hydrocarbon group is polyisobutenyl succinic anhydride.
6. Utilisation selon l’une quelconque des revendications 3 à 5, dans laquelle le composé comprenant au moins un groupement amine tertiaire et au moins un groupement choisi parmi les amines primaires, les amines secondaires et les alcools est choisi parmi les amines de formule (I) ou (II) suivantes :
Figure imgf000034_0001
6. Use according to any one of claims 3 to 5, in which the compound comprising at least one tertiary amine group and at least one group chosen from primary amines, secondary amines and alcohols is chosen from amines of formula ( I) or (II) following:
Figure imgf000034_0001
(II) dans lesquelles : (II) in which:
R6 et R7 sont identiques ou différents et représentent, indépendamment l’un de l’ autre, un groupement alkyle ayant de 1 à 22 atomes de carbone, de préférence ayant de 1 à 5 atomes de carbone ; R6 and R7 are the same or different and represent, independently of each other, an alkyl group having 1 to 22 carbon atoms, preferably having 1 to 5 carbon atoms;
X est un groupement alkylène ayant de 1 à 20 atomes de carbone, de préférence de 1 à 5 atomes de carbone ; m est un nombre entier compris entre 1 et 5 ; n est un nombre entier compris entre 0 et 20 ; et X is an alkylene group having 1 to 20 carbon atoms, preferably 1 to 5 carbon atoms; m is an integer between 1 and 5; n is an integer between 0 and 20; and
R8 est un atome d’hydrogène ou un groupement alkyle de C l à C22 ; et de préférence ledit composé est choisi parmi les amines de formule (I). R8 is a hydrogen atom or a C1 to C22 alkyl group; and preferably said compound is chosen from the amines of formula (I).
7. Utilisation selon l’une quelconque des revendications 3 à 6, dans laquelle l'agent de quaternisation est choisi parmi le groupe constituant en les dialkyl sulfates, les esters d'acide carboxylique; les halogénures d'alkyle, les halogénures de benzyle, les carbonates hydrocarbonés, et les époxydes hydrocarbonés éventuellement en mélange avec un acide, seuls ou en mélange, de préférence parmi les époxydes hydrocarbonés ou les esters d’ acide carboxylique, plus préférentiellement parmi l'oxyde de styrène et l’oxyde de propylène et mieux encore l’ agent de quaternisation est l’ oxyde de propylène. 7. Use according to any one of claims 3 to 6, wherein the quaternizing agent is selected from the group consisting of dialkyl sulfates, carboxylic acid esters; alkyl halides, benzyl halides, hydrocarbon carbonates, and hydrocarbon epoxides optionally mixed with an acid, alone or as a mixture, preferably from hydrocarbon epoxides or carboxylic acid esters, more preferably from carboxylic acid esters. styrene oxide and propylene oxide and more preferably the quaternizing agent is propylene oxide.
8. Utilisation selon l’une quelconque des revendications précédentes, dans laquelle l’ additif ( 1) est choisi parmi les polyisobutylènes succinimides fonctionnalisés par un groupement ammonium quaternaire. 8. Use according to any one of the preceding claims, in which the additive (1) is chosen from polyisobutylene succinimides functionalized with a quaternary ammonium group.
9. Utilisation selon l’une quelconque des revendications précédentes, dans laquelle l’ additif (2) constitué d’un polyisobutylène succinimide non quaternaire résulte de la condensation : 9. Use according to any one of the preceding claims, in which the additive (2) consisting of a non-quaternary polyisobutylene succinimide results from the condensation:
- d'un composé A constitué d’un diacide carboxylique substitué par un groupe polyisobutylène ou d’un anhydride d’un tel diacide, ; - of a compound A consisting of a dicarboxylic acid substituted with a polyisobutylene group or of an anhydride of such a dicacid,;
- avec un composé B constitué d'une polyamine primaire de formule générale (VI) ci-après : - with a compound B consisting of a primary polyamine of general formula (VI) below:
H2N-[-(CHRl -(CH2)p-CHR2)n-NH]m-H (VI) dans laquelle RI et R2, identiques ou différents, représentent l'hydrogène ou un groupement hydrocarboné comprenant de 1 à 4 atomes de carbone, n est un nombre entier variant de 1 à 3, m est un nombre entier variant de 1 à 10, de préférence de 1 à 4 ; et p est un nombre entier égal à 0 ou 1 . H 2 N - [- (CHRl - (CH 2 ) p -CHR2) n -NH] m -H (VI) in which R1 and R2, identical or different, represent hydrogen or a hydrocarbon group comprising from 1 to 4 carbon atoms, n is an integer varying from 1 to 3, m is an integer varying from 1 to 10, from preferably 1 to 4; and p is an integer equal to 0 or 1.
10. Utilisation selon la revendication 9, dans laquelle ledit additif (2) est obtenu par condensation du composé A avec le composé B utilisés dans des quantités telles que le rapport molaire A/B est compris dans la gamme allant de 1 : 1 à 1 : 3, de préférence de 1 : 1 , 1 à 1 : 2, encore plus préférentiellement de 1 : 1 , 1 à 1 : 1 ,5. 10. Use according to claim 9, wherein said additive (2) is obtained by condensation of compound A with compound B used in amounts such that the molar ratio A / B is in the range from 1: 1 to 1. : 3, preferably from 1: 1, 1 to 1: 2, even more preferably from 1: 1, 1 to 1: 1, 5.
11. Utilisation selon l’une quelconque des revendications précédentes, dans laquelle l’additif (3) constitué d’une base de Mannich est obtenu par réaction d'un phénol substitué par un groupement hydrocarboné, d'un aldéhyde et d'une amine, le substituant hydrocarboné dudit phénol comprenant de 6 à 400 atomes de carbone, avantageusement de 30 à 180 atomes de carbone, de préférence de 10 à 110, mieux de 40 à 1 10 atomes de carbone, et étant de préférence un groupement polyisobutylène. 11. Use according to any one of the preceding claims, in which the additive (3) consisting of a Mannich base is obtained by reaction of a phenol substituted with a hydrocarbon group, of an aldehyde and of an amine. , the hydrocarbon substituent of said phenol comprising from 6 to 400 carbon atoms, advantageously from 30 to 180 carbon atoms, preferably from 10 to 110, better still from 40 to 1 10 carbon atoms, and preferably being a polyisobutylene group.
12. Utilisation selon l’une quelconque des revendications précédentes, dans laquelle le carburant contient une base issue d’une ou de plusieurs sources choisies parmi le groupe consistant en les sources minérales, animales, végétales et synthétiques, et est de préférence choisi parmi les carburants hydrocarbonés, les carburants non essentiellement hydrocarbonés et leurs mélanges. 12. Use according to any one of the preceding claims, in which the fuel contains a base obtained from one or more sources chosen from the group consisting of mineral, animal, plant and synthetic sources, and is preferably chosen from among hydrocarbon fuels, non-essentially hydrocarbon fuels and mixtures thereof.
13. Utilisation selon l’une quelconque des revendications précédentes, dans laquelle la teneur de chaque additif (1) et (2) va de 5 à 1013. Use according to any one of the preceding claims, in which the content of each additive (1) and (2) ranges from 5 to 10
000 ppm en poids, de préférence de 5 à 1000 ppm en poids, plus préférentiellement de 10 à 500 ppm en poids, plus préférentiellement de 15 à 200 ppm en poids, et mieux encore de 20 à 150 ppm en poids, par rapport au poids total de la composition de carburant. 000 ppm by weight, preferably from 5 to 1000 ppm by weight, more preferably from 10 to 500 ppm by weight, more preferably from 15 to 200 ppm by weight, and better still from 20 to 150 ppm by weight, relative to the weight total fuel composition.
14. Utilisation selon l’une des revendications précédentes, dans laquelle la teneur de l’ additif (3) va de 5 à 10 000 ppm en poids, de préférence de 5 à 1000 ppm en poids, plus préférentiellement de 50 à 500 ppm en poids, plus préférentiellement de 100 à 500 ppm en poids, et mieux encore de 150 à 450 ppm en poids, par rapport au poids total de la composition de carburant. 14. Use according to one of the preceding claims, in which the content of the additive (3) ranges from 5 to 10,000 ppm by weight, preferably from 5 to 1000 ppm by weight, more preferably from 50 to 500 ppm by weight. weight, more preferably from 100 to 500 ppm by weight, and better still from 150 to 450 ppm by weight, relative to the total weight of the fuel composition.
15. Utilisation selon l’une des revendications précédentes, dans laquelle le carburant comprend en outre un ou plusieurs additifs additionnels, différents des premier, second et troisième additifs, choisis parmi les additifs détergents, les agents anti-corrosion, les antioxydants, les huiles porteuses, les dispersants, les désémulsifiants, les traceurs ou marqueurs, les réodorants, les modificateurs de friction, les additifs de lubrifiance ou additifs d'onctuosité, les agents d'aide à la combustion (promoteurs catalytiques de combustion et de suie), les agents anti-usure et les agents modifiant la conductivité. 15. Use according to one of the preceding claims, wherein the fuel further comprises one or more additional additives, other than the first, second and third additives, chosen from detergent additives, anti-corrosion agents, antioxidants, oils. carriers, dispersants, demulsifiers, tracers or markers, reodorants, friction modifiers, lubricity additives or lubricity additives, combustion aids (catalytic combustion and soot promoters), antiwear agents and conductivity modifiers.
16. Utilisation selon l’une quelconque des revendications 1 à 15, pour maintenir la propreté (effet keep-clean) et/ou nettoyer (effet clean- up) les dépôts dans les parties internes d’un moteur à allumage commandé choisies parmi les suivantes : la chambre de combustion, et le système d’injection de carburant, et de préférence le système d’injection de carburant. 16. Use according to any one of claims 1 to 15, for maintaining cleanliness (keep-clean effect) and / or clean (clean-up effect) the deposits in the internal parts of a spark-ignition engine chosen from among the following. following: the combustion chamber, and the fuel injection system, and preferably the fuel injection system.
17. Utilisation selon l’une quelconque des revendications 1 à 15, pour empêcher et/ou réduire les dépôts de coke et/ou de savon sur les soupapes d’ admission de carburant dans un moteur à allumage commandé à injection indirecte. 17. Use according to any one of claims 1 to 15, for preventing and / or reducing deposits of coke and / or soap on the fuel inlet valves in an indirect injection spark ignition engine.
18. Utilisation selon l’une quelconque des revendications 1 à 15, pour empêcher et/ou réduire le collage (ou valve-sticking) des soupapes d’ admission de carburant dans un moteur à allumage commandé à injection indirecte. 18. Use according to any one of claims 1 to 15, for preventing and / or reducing the sticking (or valve-sticking) of the fuel inlet valves in an indirect injection spark ignition engine.
19. Utilisation selon l’une quelconque des revendications 1 à 15, dans laquelle la composition d’ additifs est utilisée dans le carburant pour réduire la consommation de carburant du moteur (action « Fuel Eco ») et/ou minimiser la perte de puissance dudit moteur, et/ou réduire les émissions de polluants, en particulier, les émissions de particules du moteur à combustion. 19. Use according to any one of claims 1 to 15, in which the composition of additives is used in the fuel to reduce the fuel consumption of the engine (“Fuel Eco” action) and / or to minimize the loss of power of said engine. engine, and / or reduce pollutant emissions, in particular, particulate emissions from the combustion engine.
20. Utilisation selon l’une quelconque des revendications 1 à 15, pour réduire l’encrassement de la zone des pistons, des segments et des chemises du moteur, de préférence d’un moteur à injection directe essence (ou IDE). 20. Use according to any one of claims 1 to 15, for reducing the fouling of the area of the pistons, rings and liners of the engine, preferably of a gasoline direct injection (or IDE) engine.
21. Utilisation, pour améliorer les propriétés de détergence d’un carburant essence, d’un concentré pour carburant comprenant au moins les additifs (1), (2) et (3), tels que définis dans l’une quelconque des revendications 1 à 11 , 13 et 14, en mélange avec un liquide organique, ledit liquide organique étant inerte vis-à-vis des premier, second et troisième additif, et miscible audit carburant. 21. Use, to improve the detergency properties of a gasoline fuel, of a fuel concentrate comprising at least the additives (1), (2) and (3), as defined in any one of claims 1. to 11, 13 and 14, mixed with an organic liquid, said organic liquid being inert with respect to the first, second and third additives, and miscible with said fuel.
22. Procédé de maintien de la propreté et/ou de nettoyage d’ au moins une des parties internes d’un moteur à allumage commandé (ou moteur essence à combustion interne), comprenant au moins les étapes suivantes : 22. A method of maintaining the cleanliness and / or cleaning of at least one of the internal parts of a spark ignition engine (or internal combustion gasoline engine), comprising at least the following steps:
- la préparation d’une composition de carburant par additivation d’un carburant avec au moins les additifs (1 ), (2) et (3), tels que définis dans l’une quelconque des revendications 1 à 11 , 13 et 14 ou avec un concentré tel que défini dans la revendication 21 , puis - the preparation of a fuel composition by additivation of a fuel with at least the additives (1), (2) and (3), as defined in any one of claims 1 to 11, 13 and 14 or with a concentrate as defined in claim 21, then
- la combustion de ladite composition de carburant dans ledit moteur à allumage commandé. the combustion of said fuel composition in said spark ignition engine.
PCT/FR2021/050971 2020-05-29 2021-05-28 Use of a fuel composition comprising three additives for cleaning the internal parts of petrol engines WO2021240117A1 (en)

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EP21734411.8A EP4157972A1 (en) 2020-05-29 2021-05-28 Use of a fuel composition comprising three additives for cleaning the internal parts of petrol engines
US17/928,141 US20230212473A1 (en) 2020-05-29 2021-05-28 Use of a fuel composition comprising three additives for cleaning the internal parts of petrol engines
CN202180038622.1A CN115667467A (en) 2020-05-29 2021-05-28 Use of a fuel composition comprising three additives for cleaning internal parts of a gasoline engine

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FRFR2005699 2020-05-29
FR2005699A FR3110914A1 (en) 2020-05-29 2020-05-29 Use of a fuel composition to clean the internal parts of gasoline engines

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