EP4157971B1 - Additive composition for motor fuel - Google Patents

Description

The present invention relates to a fuel additive composition comprising at least one first additive chosen from quaternary ammonium salts other than betaines, and at least one second additive chosen from amido alkyl betaines. The composition is such that the mass ratio of the quantity of the first additive to the quantity of the second additive is included in the range from 1:4 to 4:1.

The invention also relates to a concentrate for fuel, comprising said composition of additives, mixed with an organic liquid inert with respect to the first and second additives and miscible with said fuel.

The invention further relates to a fuel composition comprising a fuel derived from one or more sources selected from the group consisting of mineral, animal, plant and synthetic sources, and mixtures thereof; and said fuel additive composition.

The invention also relates to the use of the additive composition, or the fuel composition, or the fuel concentrate, for maintaining cleanliness (keep-clean effect) and/or cleaning (clean-up effect) deposits. in at least one of the internal parts of an engine, gasoline or Diesel, preferably Diesel, chosen from the following: the combustion chamber and the fuel injection system.

In a preferred embodiment, the invention aims to prevent and/or reduce deposits of coke, and/or soaps and/or varnishes on injectors or injector needles, as well as reducing the consumption of fuel of an engine, preferably Diesel, (“Fuel Eco” action) and/or minimizing the loss of power of said engine, and/or reducing pollutant emissions.

STATE OF PRIOR ART

Liquid fuels for internal combustion engines contain components that can degrade 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 consumption and particle emissions. Advances in fuel additive technology have made it possible to address this problem. So-called detergent additives used in fuels have already been proposed to maintain the cleanliness of the engine by limiting deposits (“keep-clean” effect) or by reducing the deposits already present in the internal parts of the combustion engine (“keep-clean” effect). clean-up” in English). As an example, we can cite the document US4171959 which describes a detergent additive for gasoline fuel containing a quaternary ammonium function. The document WO2006135881 describes a detergent additive containing a quaternary ammonium salt used to reduce or clean deposits particularly on intake valves.

However, engine technology is continually evolving and fuel requirements must evolve to accommodate these technological advances in combustion engines.

In particular, new gasoline direct injection systems expose the injectors to more severe pressure and temperature conditions, which encourages the formation of deposits.

In addition, these new injection systems have more complex geometries to optimize spraying, in particular, more numerous holes with smaller diameters but which, on the other hand, induce greater sensitivity to deposits. The presence of deposits can alter combustion performance, in particular increasing polluting emissions and particle emissions.

In addition, the new Diesel direct injection systems expose the injectors to more severe pressure and pressure conditions. temperature which promotes the formation of deposits. In addition, these new injection systems have more complex geometries to optimize spraying, in particular, more numerous holes having smaller diameters but which, on the other hand, induce greater sensitivity to deposits.

In the case of indirect injection Diesel engines, the combustion of the fuel does not take place directly in the combustion chamber as with direct injection engines. As described for example in the document US4604102 , there is a prechamber before the combustion chamber in which the fuel injection takes place. The pressure and temperature in a prechamber are lower than in a combustion chamber of direct injection engines. Under these conditions, the pyrolysis of the fuel produces carbon which is deposited on the surface of the injector nozzles (“throttling nozzle or “fouling” in English) and blocks the nozzle orifices: this phenomenon is coking. Only the nozzle surfaces exposed to combustion gases present a risk of carbon deposits (coking/coking/coking). Coking is a phenomenon that only appears downstream of a Diesel injection system. In terms of performance, the coking phenomenon induces a loss of engine power and therefore in particular excess fuel consumption. This phenomenon is measured using the XUD9 engine which makes it possible to determine the injector flow rates and therefore the presence of coking or not.

Coking should be distinguished from “lacquering” (soap and/or varnish) which occurs in Diesel direct injection engines, on the injector needles. Lacquering does not concern deposits which are present outside the injection system and which are linked to coking, causing clogging and partial or total blockage of the injection nozzles. Lacquering and coking are therefore two very distinct phenomena in terms of the causes of these deposits, the conditions of appearance of these deposits and the place where these deposits occur.

The presence of these deposits, lacquering and coking, in engines, can alter combustion performance, and in particular increase polluting emissions and particle emissions. Other consequences of the excessive presence of deposits have been reported in the literature, such as an increase in fuel consumption.

Preventing and reducing deposits in these (new) engines is essential for optimal operation of today's engines. There is therefore a need to offer detergent additives for fuels promoting optimal operation of combustion engines, in particular but not limited to new engine technologies but also older/conventional engine technologies.

There also remains a need for universal detergency solutions, which make it possible to prevent or reduce all kinds of deposits on the internal parts of internal combustion engines, whatever the engine technology (Diesel or gasoline, direct or indirect injection) and /or the properties/nature of the fuel.

OBJECT OF THE INVENTION

The Applicant has discovered that a particular combination of additives, as defined below, have remarkable and unexpected detergency properties for internal combustion engines, gasoline or Diesel, and preferably in compression ignition engines or Diesel engines. This combination of additives makes it possible to guarantee and improve the detergent power of fuels intended for compression ignition engines. It also produces an unexpected synergistic effect, compared to each of the two additives considered separately.

• la protection des pompes, des systèmes d'injection et de toutes les parties en mouvement avec lesquels cet additif entre en contact dans un moteur,
• un fonctionnement optimal du moteur,
• une réduction de la consommation de carburant,
• une économie due à moins d'entretien du moteur et à une moindre consommation,
• une réduction des émissions de particules.

The additional advantages of the fuel additive composition according to the invention are:

• the protection of pumps, injection systems and all moving parts with which this additive comes into contact in an engine,
• optimal engine operation,
• a reduction in fuel consumption,
• a saving due to less engine maintenance and less consumption,
• a reduction in particle emissions.

1. (1) au moins un premier additif choisi parmi les sels d'ammonium quaternaire différents des bétaïnes, et
2. (2) au moins un second additif choisi parmi les amido alkyl bétaïnes, de formule (I) suivante :
   
   dans laquelle
   • R1 est une chaîne hydrocarbonée en C₁ à C₃₄, linéaire ou ramifiée,
   • R2 est un atome d'hydrogène ou une chaîne hydrocarbonée en C₁ à C₁₅,
   • R3 est une chaîne hydrocarbonée en C₁ à C₁₅, et
   • R4 et R5 sont identiques ou différents et choisis indépendamment l'un de l'autre parmi un atome d'hydrogène et une chaîne hydrocarbonée en C₁ à C₁₀, de préférence en C₁ à C₆, étant entendu que les groupements R₄ et R₅ peuvent contenir un ou plusieurs groupements azotés et/ou peuvent être reliés ensemble pour former un ou plusieurs cycles ; 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 1 : 4 à 4 : 1.

The subject of the present invention is therefore a composition of fuel additives comprising:

1. (1) at least one first additive chosen from quaternary ammonium salts other than betaines, and
2. (2) at least one second additive chosen from amido alkyl betaines, of formula (I) below:
   
   in which
   • R1 is a C ₁ to C ₃₄ hydrocarbon chain, linear or branched,
   • R2 is a hydrogen atom or a C ₁ to C ₁₅ hydrocarbon chain,
   • R3 is a C ₁ to C ₁₅ hydrocarbon chain, and
   • R4 and R5 are identical or different and chosen independently of one another from a hydrogen atom and a C ₁ to C ₁₀ hydrocarbon chain, preferably C ₁ to C ₆ , it being understood that the R ₄ groups and R ₅ may contain one or more nitrogen groups and/or may be linked together to form one or more rings; And
   • in which the mass ratio of the quantity of the first additive to the quantity of the second additive is included in the range from 1: 4 to 4: 1.

Preferably, the mass ratio of the quantity of the first additive to the quantity of the second additive is in the range going from 1:1 to 2.5:1, preferably from 1.5:1 to 2.1:1 .

The invention also relates to a concentrate for fuel comprising the composition of additives, mixed with an organic liquid, said organic liquid being inert with respect to the first and second additives, and miscible with said fuel.

1. (1) une base carburant issue d'une ou de plusieurs sources choisies parmi le groupe consistant en les sources minérales, animales, végétales et synthétiques, et de préférence choisie parmi les carburants hydrocarbonés, les carburants non essentiellement hydrocarbonés et leurs mélanges ; et
2. (2) une composition d'additifs pour carburant telle que définie dans la présente demande.

The invention also relates to a fuel composition comprising:

1. (1) a fuel base from one or more sources chosen from the group consisting of mineral, animal, vegetable and synthetic sources, and preferably chosen from hydrocarbon fuels, non-essentially hydrocarbon fuels and mixtures thereof; And
2. (2) a fuel additive composition as defined herein.

Preferably, the liquid fuel composition is chosen from hydrocarbon fuels, non-essentially hydrocarbon fuels, and mixtures thereof, for example gasoline or gas oils. Advantageously, the fuel (hydrocarbon) is chosen from gas oils, also called gas oil fuel, and which corresponds to the fuels used in diesel engines.

According to a preferred embodiment, the additive composition, the fuel composition or the concentrate, according to the invention, is used to prevent (keep-clean effect) and/or eliminate (clean-up effect) deposits in the internal parts of an engine selected from the following: the combustion chamber, the engine intake system and the fuel injection system, and preferably the fuel injection system. In particular, said composition is used in the liquid fuel to limit or avoid the formation of deposits in at least one of the internal parts of said engine and/or reduce the deposits existing in at least one of the internal parts of said engine.

In particular, the composition according to the invention is used to prevent, reduce or eliminate deposits chosen from coke, and/or soaps and/or varnishes on injectors or fuel injector needles, and/or coke, soap and/or valve-sticking of the fuel inlet valves in the combustion chamber.

The composition according to the invention also makes it possible to reduce the fuel consumption of an engine, preferably Diesel, (“Fuel Eco” action) and/or minimize the loss of power of said engine, and/or reduce emissions of pollutants, in particular, particulate emissions from the combustion engine.

In one embodiment, the engine is a gasoline engine. In another more preferred mode, the internal combustion engine is an engine compression ignition, also known as a Diesel engine.

• la préparation d'une composition de carburant par additivation d'un carburant avec au moins les deux additifs (1) et (2) tels que décrits ci-après , ou avec un concentré les comprenant, puis
• la combustion de ladite composition de carburant dans ledit moteur.

The present invention also relates to a method for maintaining the cleanliness and/or cleaning at least one of the internal parts of an engine, preferably a compression ignition engine or diesel engine, comprising at least the following steps :

• the preparation of a fuel composition by addition of a fuel with at least the two additives (1) and (2) as described below, or with a concentrate comprising them, then
• burning said fuel composition in said engine.

Other objects, characteristics, aspects and advantages of the invention will appear even more clearly on reading the description and examples which follow.

In what follows, and unless otherwise indicated, the limits of a domain of values are included in this domain, in particular in the expressions "between" and "ranging from ... to ...". Furthermore, the expressions “at least one” and “at least” used in this description are respectively equivalent to the expressions “one or more” and “greater or equal”.

Finally, in a manner known per se, the term C _N or CN compound or group denotes a compound or group containing N carbon atoms in its chemical structure.

DETAILED DESCRIPTION The first additive: quaternary ammonium

The composition according to the invention comprises a first additive consisting of a quaternary ammonium salt, different from betaines.

In a first embodiment, said first additive is obtained by reaction with a quaternization agent of a nitrogen compound comprising a tertiary amine function, this nitrogen compound being the product of the reaction of an acylating agent substituted by a group hydrocarbon and a compound comprising at least one group tertiary amine and at least one group chosen from primary amines, secondary amines and alcohols.

In a second embodiment, the quaternary ammonium salt is chosen from quaternized PIBA (polyisobutylene-amine) compounds, or from quaternized polyether-amines.

According to the first embodiment, which is preferred, said nitrogen compound is the product of the reaction of an acylating agent substituted by a hydrocarbon group and a compound comprising both an oxygen atom or an atom of nitrogen capable of condensing with said acylating agent (that is to say 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.

In this embodiment, the acylating agent is substituted by a hydrocarbon group. The term "hydrocarbon" group means any group having a carbon atom directly attached to the rest of the molecule (ie to the acylating agent) and mainly having 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 for every ten carbon atoms provided that the non-hydrocarbon group does not significantly modify the mainly hydrocarbon character of the group. Mention may be made, by way of example, of such groups, well known to those skilled in the art, of hydroxyl groups, halogens (in particular chloro- and fluoro- groups), alkoxy, alkylmercapto and alkyl sulfoxy groups.

In one embodiment, preferably 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 approximately 200 carbon atoms.

The hydrocarbon substituent of the acylating agent preferably has a number average molecular mass (Mn) of between 160 to 2800, for example between 250 to 1500, more preferably between 500 to 1500 and, even more preferably between 500 to 1300. A range of values of M _n between 700 and 1300 is particularly preferred, for example from 700 to 1200.

As an 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.

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 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.

The hydrocarbon substituent of the acylating agent can also be chosen from derivatives of halogenated analogues (for example chlorinated or brominated) of these homo-or inter-polymers.

Alternatively, the hydrocarbon substituent of the acylating agent may be obtained from other sources, for example from high molecular weight alkene monomers (e.g., 1-tetracontene) and their chlorinated analogues or hydrochlorinated, aliphatic petroleum fractions, e.g. paraffin waxes, their cracked, chlorinated and/or hydrochlorinated analogues, white oils, synthetic alkenes, e.g. produced by Ziegler-Natta process (e.g. polyethylene greases ) 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 essentially saturated, that is, it contains no more than one unsaturated carbon-carbon bond for every ten carbon-carbon single bonds. present.

The hydrocarbon substituent of the acylating agent advantageously contains no more than one non-aromatic carbon-carbon unsaturated bond for every 50 carbon-carbon bonds present.

According to a preferred embodiment, the hydrocarbon substituent of the acylating agent is a polyisobutene group also called polyisobutylene (PIB). We particularly prefer the so-called highly reactive polyisobutenes (PIB). By highly reactive polyisobutenes (PIB) is meant 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 the document EP0565285 . In particular, the preferred PIBs are those having more than 80 mol% and up to 100 mol% of vinylidene terminal groups as described in the document EP1344785 .

According to a particularly preferred embodiment, the acylating agent substituted with a hydrocarbon group is a polyisobutenyl-succinic anhydride (PIBSA).

The preparation of polyisobutenyl-succinic anhydrides is known per se, and widely described in the literature. We can cite by way of example the processes comprising the reaction between polyisobutenes (PIB) and maleic anhydride described in the documents US3361673 And US3018250 or the process comprising the reaction of a halogenated polyisobutene (PIB), in particular chlorinated, with maleic anhydride ( US3172892 ).

Alternatively, polyisobutenyl succinic anhydride can be prepared by mixing a polyolefin with maleic anhydride then passing chlorine through the mixture ( GB949981 ).

Other hydrocarbon groups comprising an internal olefin, for example such as those described in the application WO2007/015080 , can also be used as a substitute for the acylating agent. By internal olefin is meant any olefin containing mainly a non-alpha double bond, which is a beta or higher position olefin.

Preferably, these materials are essentially beta-olefins or higher position olefins, for example containing less than 10% by weight of alpha-olefin, advantageously less than 5% by weight or less than 2% by weight.

The 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-aminoethylamine ethylenediamine, 1,2-propylenediamine, 1,3-propylene diamine, butylenediamines (isomers), diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetetraamine, teraethylenepentaamine, pentaethylenehexaamine, hexamethylenetetramine, bis(hexametlylene)triamine, diaminobenzenes, and pentanediamines, hexanediamines, heptanediamines, and preferably N,N-dimethylaminopropylamine.

Said compound may also be chosen from heterocyclic compounds substituted with alkylamines such as 1-(3-aminopropyl)-imidazole, 4-(3-aminopropyl)morpholine, 1-(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 may also be chosen 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, N,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 -diisopropanolamine, N'-(3-(Dimethylamino)propyl)-N,N-dimethyl-1,3-propanediamine; 2-(2-dimethylaminoethoxy)ethanol and N,N,N'-trimethylaminoethylethanolamine, or mixtures thereof.

dans lesquelles :

• 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 ;
• 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
• R8 est un atome d'hydrogène ou un groupement alkyle de C1 à C22.

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):

in which :

• R6 and R7 are identical or different and represent, independently of each other, an alkyl group having from 1 to 22 carbon atoms, preferably having from 1 to 5 carbon atoms;
• X is an alkylene group having from 1 to 20 carbon atoms, preferably from 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 the amines of formula (I).

When the nitrogen compound comprises an amine of formula (I), R8 is advantageously a hydrogen atom or a C1 to C16 alkyl group, preferably a C1 to C10 alkyl group, even more preferably a C1 to C6 alkyl group .

R8 may, for example, be chosen from the group consisting of hydrogen, methyl, ethyl, propyl, butyl and their isomers. Preferably R8 is a hydrogen atom.

When the nitrogen 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.

According to a preferred embodiment, said nitrogen compound is the product of the reaction of the acylating agent substituted by a hydrocarbon group and a diamine of formula (I).

• R6 et R7 peuvent représenter, indépendamment l'un de l'autre, un groupement alkyle en C1 à C16, de préférence un groupement alkyle en C1 à C10 ;
• R6 et R7 peuvent représenter, 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 C1 à C4, de préférence un groupement méthyle ;
• 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.

In this embodiment:

• R6 and R7 may represent, independently of each other, a C1 to C16 alkyl group, preferably a C1 to C10 alkyl group;
• R6 and R7 may 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 each other, a C1 to C4 group, preferably a methyl group;
• * . X particularly preferably represents an ethylene, propylene or butylene group, in particular a propylene group.

According to a particularly preferred embodiment, the nitrogen compound is the reaction product of a succinic acid derivative substituted by a hydrocarbon group, preferably a polyisobutenyl-succinic anhydride, and of an alcohol or 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).

According to a first variant, the succinic acid derivative substituted by 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).

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 carboxyl group - free CO ₂ H (open form). Thus, in certain embodiments the nitrogen 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 also also comprises a carboxyl group -CO2H not having reacted (open form).

The quaternary ammonium salt forming the first additive according to the present invention is directly obtained by reaction between the nitrogen compound described above comprising a tertiary amine function and a quaternization agent.

According to a particular embodiment, the quaternization agent is chosen from the group constituting dialkyl sulfates, carboxylic acid esters; alkyl halides, benzyl halides, hydrocarbon carbonates, and hydrocarbon epoxides optionally mixed with an acid, alone or in mixture, preferably carboxylic acid esters.

For fuel applications, it is often desirable to reduce the content of halogen, sulfur and phosphorus-containing compounds.

Thus, if a quaternization 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 put into reaction with sodium hydroxide and the sodium halide salt removed by filtration.

The quaternizing agent may include halides such as chloride, iodide or bromide; hydroxides; sulfonates; bisulfites; alkyl sulfates such as dimethyl sulfate; sulfones; phosphates; C1-C12 alkylphosphates _; C1-C12 dialkylphosphates; borates; C1-C12 alkylborates; nitrites; nitrates; carbonates; bicarbonates; alkanoates; C1-C12 O,O-dialkyldithiophosphates, alone or in a mixture.

According to a particular embodiment, the quaternization agent can be chosen from derivatives of dialkyl sulfates such as dimethyl sulfate, N-oxides, sulfones such as propane- and butanesulfone, alkyl halides, acyl or aralkyl such as methyl and ethyl chloride, benzyl bromide, iodide or chloride, and hydrocarbon carbonates (or alkylcarbonates).

If the acyl halide is benzyl chloride, the aromatic ring is optionally substituted by one or more alkyl or alkenyl groups.

The hydrocarbon groups (alkyls) of hydrocarbon carbonates can contain from 1 to 50, from 1 to 20, from 1 to 10 or 1 to 5 carbon atoms per group. According to one embodiment, the hydrocarbon carbonates contain two hydrocarbon groups which may be identical or different. As an example of hydrocarbon carbonates, mention may be made of dimethyl or diethyl carbonate.

dans laquelle R9, R10, R11 et R12 peuvent être identiques ou différentes et représentent indépendamment les uns des autres un atome d'hydrogène ou un groupement hydrocarboné en C₁ 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 C₁ 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 hydrocarbon epoxides represented by the following formula (III):

in which R9, R10, R11 and R12 may be identical or different and independently represent a hydrogen atom or a C ₁ to C ₅₀ hydrocarbon group. As an example no limiting, we can cite 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.

Such hydrocarbon epoxides can be used as a quaternizing agent in combination with an acid, for example with acetic acid. Hydrocarbon epoxies can also be used alone as a quaternizing agent, especially without additional acid.

Without being bound by this hypothesis, it would seem that the presence of the carboxylic acid function in the molecule favors 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 and alcohols (including polyhydric alcohols) can be used alone or in a mixture. Preferred protic solvents have a dielectric constant greater than 9.

Corresponding quaternary ammonium salts prepared from amides or esters and succinic acid derivatives are described in WO2010/132259 or in EP1896555 .

dans laquelle R13 est un groupement alkyle, alcényle, aryle et aralkyle éventuellement substitué, et R14 est un groupement alkyle, aryle ou alkylaryle en C₁ à C₂₂.According to another embodiment, the quaternization agent is chosen from the compounds of formula (IV):

in which R13 is an optionally substituted alkyl, alkenyl, aryl and aralkyl group, and R14 is a C ₁ to C ₂₂ 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 chosen, for example from carboxylic acid esters having a pKa of 3.5 or less. The compound of formula (IV) is preferably chosen from esters substituted aromatic carboxylic acid, alpha-hydroxycarboxylic acid and polycarboxylic acid.

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 by one or more groups chosen from the carboalkoxy, nitro, cyano, hydroxy, SR ₁₅ and NR ₁₅ R ₁₆ radicals. Each of the R ₁₅ and R ₁₆ groups can be a hydrogen atom or an alkyl or alkenyl group. , aryl or optionally substituted carboalkoxy. Each of the groups R ₁₅ and R ₁₆ advantageously represents the hydrogen atom or an optionally substituted C1 to C22 alkyl group, preferably the hydrogen atom or a C1 to C16 alkyl group, more preferably the hydrogen atom or a C1 to C10 alkyl group, even more preferably the hydrogen atom or a C1 to C4 alkyl group. R ₁₅ is preferably a hydrogen atom and R ₁₆ a hydrogen atom or a C1 to C4 group. Advantageously, R ₁₅ and R ₁₆ are both a hydrogen atom.

According to one embodiment, R13 is an aryl group substituted by one or more groups chosen from hydroxyl, carboalkoxy, nitro, cyano and NH ₂ radicals. R13 may 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 radicals OH, NH ₂ , NO ₂ or COOMe, preferably OH or NH ₂ . R13 is preferably a hydroxyaryl group, in particular 2-hydroxyphenyl.

According to a particular embodiment, R14 is an alkyl or alkylaryl group. R14 may be a C1 to C16 alkyl group, preferably C1 to C10, advantageously C1 to C8. R14 may be a C1 to C16 alkylaryl group, preferably C1 to C10, advantageously C1 to C8. R14 can for example be chosen from among the methyl, ethyl, propyl, butyl, pentyl, benzyl groups or their isomers. Preferably, R14 is a benzyl or methyl group, more preferably methyl.

A particularly preferred compound is methyl salicylate.

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 following formula (V):

in which R17 and R18 are identical or different and are independently chosen from the group consisting of the hydrogen atom, alkyl, alkenyl, aryl or aralkyl groups. Such compounds are for example described in the document EP 1254889 .

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; methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-, phenyl- or allyl esters of 2-hydroxy-2-ethylbutyric acid; 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.

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. The preferred esters are C1 to C4 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. Preferably, the compound of formula (IV) is dimethyl oxalate.

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 includes more than one acid group, we will refer to the first dissociation constant.

The compound of formula (IV) may 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-trihydroxybenzoic acid. Preferred compounds of formula (IV) are dimethyl oxalate, methyl 2-nitrobenzoate and methyl salicylate.

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 whose polyisobutylene group (PIB) has a number average molecular mass (Mn) of between 700 and 1000 and dimethylaminopropylamine.

According to a particularly preferred embodiment, the additive (1) is chosen from polyisobutylenes succinimides functionalized with a quaternary ammonium group.

The composition according to the invention comprises the first additive(s) as described above at 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: betaine

dans laquelle :

• R1 est une chaîne hydrocarbonée en C₁ à C₃₄, linéaire ou ramifiée,
• R2 est un atome d'hydrogène ou une chaîne hydrocarbonée en C₁ à C₁₅
• R3 est une chaîne hydrocarbonée en C₁ à C₁₅, et
• R4 et R5 sont identiques ou différents et choisis indépendamment l'un de l'autre parmi un atome d'hydrogène et une chaîne hydrocarbonée en C₁ à C₁₀, de préférence en C₁ à C₆, étant entendu que les groupements R₄ et R₅ peuvent contenir un ou plusieurs groupements azotés et/ou peuvent être reliés ensemble pour former un ou plusieurs cycles.

The composition according to the invention comprises a second additive (2) chosen from amido alkyl betaines, of formula (I) below:

in which :

• R1 is a C ₁ to C ₃₄ hydrocarbon chain, linear or branched,
• R2 is a hydrogen atom or a C ₁ to C ₁₅ hydrocarbon chain
• R3 is a C ₁ to C ₁₅ hydrocarbon chain, and
• R4 and R5 are identical or different and chosen independently of each other from a hydrogen atom and a C ₁ to C ₁₀ hydrocarbon chain, preferably C ₁ to C ₆ , it being understood that the R ₄ groups and R ₅ may contain one or more nitrogen groups and/or may be linked together to form one or more rings.

Preferably, in formula (I), R1 is a C ₈ to C ₃₀ hydrocarbon chain, linear or branched, preferably C ₁₂ to C ₂₄ , more preferably C ₁₆ to C ₂₀ .

Preferably, in formula (I), R2 is a hydrogen atom or a C ₁ to C ₈ hydrocarbon chain, preferably a hydrogen atom. Preferably, in formula (I), R3 is a C ₁ to C ₈ hydrocarbon chain, preferably C ₂ to C ₄ .

Preferably, in formula (I), R4 and R5 are identical or different and chosen independently of each other from a hydrogen atom and a C ₁ to C ₆ hydrocarbon chain, it being understood that the R groups ₄ and R ₅ may contain one or more nitrogen groups and/or may be linked together to form a ring; more preferably R4 and R5 are identical and represent a methyl group or an ethyl group and even more preferably a methyl group.

1. (i) une amine tertiaire de formule R₄R₅R'₃N :
   • où R₄, R₅ sont tels que définis ci-avant pour la formule (I), les significations préférées de ces groupements pour la formule (I) étant également préférés pour ladite amine tertiaire;
   • où R'₃ désigne un groupement de formule -R₃-N(R₂)-CO-R₁, où R₁, R₂ et R₃ sont tels que définis ci-avant pour la formule (I), les significations préférées de ces groupements pour la formule (I) étant également préférés pour ladite amine tertiaire ; avec
2. (ii) l'acide acétique substitué par au moins un halogène, ou un de ses sels, ou un de ses dérivés ester ou amide.

In one embodiment, the second additive can be obtained by reacting:

1. (i) a tertiary amine of formula R ₄ R ₅ R' ₃ N:
   • where R ₄ , R ₅ are as defined above for formula (I), the preferred meanings of these groups for formula (I) also being preferred for said tertiary amine;
   • where R' ₃ designates a group of formula -R ₃ -N(R ₂ )-CO-R ₁ , where R ₁ , R ₂ and R ₃ are as defined above for formula (I), the preferred meanings of these groups for formula (I) also being preferred for said tertiary amine; with
2. (ii) acetic acid substituted by at least one halogen, or one of its salts, or one of its ester or amide derivatives.

According to a preferred embodiment, the reaction product is substantially free of non-covalent anionic species.

Preferably, compound (ii) is halogen-substituted acetic acid, or a salt of such an acid.

The salts may include alkali or alkaline earth metals, or ammoniums, including but not limited to sodium, lithium, calcium, potassium, magnesium, triethyl ammonium or triethanol ammonium salts.

In a preferred embodiment, chloroacetic acid or sodium or potassium chloroacetate salts are used.

The molar ratio of the quantity of carboxylic acid/ester/amide or one of their salts (ii) to the quantity of tertiary amine (i) is advantageously included in the range going from 1:0.1 to 0.1:1.0.

1. (i) d'une amine tertiaire substituée par un groupe hydrocarboné choisie parmi les (alkyle en C₈-C₃₀) amidopropyldi(alkyle en C₁-C₄)amines et les (alcényle en C₈-C₃₀) amidopropyldi(alkyle en C₁-C₄)amines; de préférence parmi les (alkyle en C₈-C₃₀) amidopropyldiméthylamines et les (alcényle en C₈-C₃₀) amidopropyldiméthylamines; avec
2. (ii) l'acide acétique substitué par un halogène, ou un de ses sels, ou un de ses dérivés ester ou amide;

ledit produit de réaction étant de préférence dépourvu d'espèces anioniques non covalentes.In a particularly preferred embodiment, the additive (2) is the reaction product:

1. (i) a tertiary amine substituted with a hydrocarbon group chosen from (C ₈ -C ₃₀ alkyl) amidopropyldi(C ₁ -C ₄ alkyl)amines and (C ₈ -C ₃₀ alkenyl) amidopropyldi(alkyl C ₁ -C ₄ )amines; preferably from (C ₈ -C ₃₀ alkyl) amidopropyldimethylamines and (C ₈ -C ₃₀ alkenyl) amidopropyldimethylamines; with
2. (ii) acetic acid substituted by a halogen, or one of its salts, or one of its ester or amide derivatives;

said reaction product preferably being free of non-covalent anionic species.

Preferably, compound (i) is oleylamido propyl dimethylamine and compound (ii) is sodium chloroacetate.

The composition of additives

The composition according to the invention is such that the mass ratio of the quantity of the first additive to the quantity of the second additive is included in the range going from 1:4 to 4:1.

Preferably, the mass ratio of the quantity of the first additive to the quantity of the second additive is in the range going from 1:1 to 2.5:1, preferably from 1.5:1 to 2.1:1.

According to an alternative embodiment, the mass ratio of the quantity of the first additive to the quantity of the second additive is included in the range going from 1:3 to 3:1, preferably from 1:2 to 2:1.

According to another alternative embodiment, the mass ratio of the quantity of the first additive to the quantity of the second additive is included in the range going from 1: 3 to 1.5: 1, preferably from 1: 2.5 to 1 : 1.

Other additives in the additive composition

The additive composition may also comprise one or more additional additive(s), different from said additives (1) and (2) described above.

This or these other additives can for example be chosen, in a non-limiting manner, from detergent additives, anti-corrosion agents, dispersants, demulsifiers, anti-foam agents, biocides, tracers or markers, reodorants, additives procetane, friction modifiers, lubricating additives or lubricity additives, combustion aiding agents (catalytic combustion and soot promoters), cold resistance additives and in particular agents improving the cloud point , pour point, TLF (“Filterability limit temperature”), anti-sedimentation agents, anti-wear agents and conductivity modifying agents.

1. a) les additifs procétane, notamment (mais non limitativement) choisis parmi les nitrates d'alkyle, de préférence le nitrate de 2-éthyl hexyle, les peroxydes d'aryle, de préférence le peroxyde de benzyle, et les peroxydes d'alkyle, de préférence le peroxyde de ter-butyle ;
2. b) les additifs anti-mousse, notamment (mais non limitativement) choisis parmi les polysiloxanes, les polysiloxanes oxyalkylés, et les amides d'acides gras issus d'huiles végétales ou animales. Des exemples de tels additifs sont donnés dans EP861882 , EP663000 , EP736590 ;
3. c) Les additifs fluidifiants à froid (CFI en anglais « Cold Flow Improver ») choisis parmi les copolymères d'éthylène et d'ester insaturé, tels que copolymères éthylène/acétate de vinyle (EVA), éthylène/propionate de vinyle (EVP), éthylène/éthanoate de vinyle (EVE), éthylène/méthacrylate de méthyle (EMMA), et éthylène/fumarate d'alkyle décrits, par exemple, dans les documents US3048479 , US3627838 , US3790359 , US3961961 et EP261957 ;
4. d) les additifs de point de trouble, notamment (mais non limitativement) choisis dans le groupe constitué par les terpolymères oléfine à chaîne longue/ester (méth)acrylique /maléimide, et les polymères d'esters d'acides fumarique /maléique. Des exemples de tels additifs sont donnés dans FR2528051 , FR2528051 , FR2528423 , EP112195 , EP172758 , EP271385 , EP291367 ;
5. e) les additifs polyfonctionnels d'opérabilité à froid choisis dans le groupe constitué par les polymères à base d'oléfine et de nitrate d'alkényle tels que décrits dans EP573490 ;
6. f) 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 , WO98/04656 , EP915944 , FR2772783 , FR2772784 ;
7. g) 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 ;
8. h) les additifs détergents différents des additifs (1) et (2), notamment (mais non limitativement) choisis dans le groupe constitué par les succinimides et les polyétheramines.

Among these additives, we can cite in particular:

1. a) procetane additives, in particular (but not limited to) chosen from alkyl nitrates, preferably 2-ethyl hexyl nitrate, aryl peroxides, preferably benzyl peroxide, and alkyl peroxides, preferably tert-butyl peroxide;
2. b) anti-foam additives, in particular (but not limited to) chosen from polysiloxanes, oxyalkylated polysiloxanes, and fatty acid amides derived from vegetable or animal oils. Examples of such additives are given in EP861882 , EP663000 , EP736590 ;
3. c) Cold flow improver additives (CFI) chosen from ethylene and unsaturated ester copolymers, such as ethylene/vinyl acetate (EVA), ethylene/vinyl propionate (EVP) copolymers. , ethylene/vinyl ethanoate (EVE), ethylene/methyl methacrylate (EMMA), and ethylene/alkyl fumarate described, for example, in the documents US3048479 , US3627838 , US3790359 , US3961961 And EP261957 ;
4. d) cloud point additives, in particular (but not limited to) chosen from the group consisting of long-chain olefin/(meth)acrylic ester/maleimide terpolymers, and fumaric/maleic acid ester polymers. Examples of such additives are given in FR2528051 , FR2528051 , FR2528423 , EP112195 , EP172758 , EP271385 , EP291367 ;
5. e) polyfunctional cold operability additives chosen from the group consisting of polymers based on olefin and alkenyl nitrate as described in EP573490 ;
6. f) 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 carboxylic acids. polycyclic. Examples of such additives are given in the following documents: EP680506 , EP860494 , WO98/04656 , EP915944 , FR2772783 , FR2772784 ;
7. g) friction or friction modifiers in particular (but not limited to) chosen from the group consisting of acids or esters fatty acids or mixtures of acids or esters of fatty acids, for example oleic, linoleic, resin, palmitic acids; or among fatty acid dimers, or mono- or di-propoxylated esters; sorbitan esters; sucrose stearates; or among glycerol and its derivatives; or pentaerythritol esters; or amines; and preferably chosen from glycerol or polyglycerol esters, or fatty acids or esters, or mixtures thereof;
8. h) detergent additives other than additives (1) and (2), in particular (but not limited to) chosen from the group consisting of succinimides and polyetheramines.

Fuel concentrate

The present invention also relates to a concentrate for fuel comprising a composition of additives as defined above, in mixture with an organic liquid, said organic liquid being inert with respect to the first and second additives, and miscible with said fuel.

The organic liquid is advantageously inert with respect to the constituents of the additive composition, and miscible with liquid fuels, in particular those coming from one or more sources chosen from the group consisting of mineral sources, preferably petroleum. , animal, vegetable and synthetic. By miscible is meant 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 in liquid fuels according to conventional fuel additive processes.

The organic liquid is preferably chosen from aromatic hydrocarbon solvents such as the solvent marketed under the name “SOLVESSO”, alcohols, ethers and other oxygenated compounds, and paraffinic solvents such as hexane, pentane or isoparaffins, alone. or mixed.

The concentrate may also comprise one or more additional additive(s), different from said additives according to the invention, as defined above.

Fuel composition

1. (1) une base carburant issue d'une ou de plusieurs sources choisies parmi le groupe consistant en les sources minérales, animales, végétales et synthétiques, de préférence choisie parmi les carburants hydrocarbonés, les carburants non essentiellement hydrocarbonés et leurs mélanges ; et
2. (2) la composition d'additifs pour carburant définie ci-dessus.

The present invention also relates to a fuel composition comprising:

1. (1) a fuel base from one or more sources chosen from the group consisting of mineral, animal, vegetable and synthetic sources, preferably chosen from hydrocarbon fuels, non-essentially hydrocarbon fuels and mixtures thereof; And
2. (2) the fuel additive composition defined above.

The fuel according to the present invention contains a base 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 their mixtures.

We will preferably choose petroleum as the mineral source.

The fuel is advantageously chosen from hydrocarbon fuels and non-essentially hydrocarbon fuels, alone or as a mixture.

Hydrocarbon fuel means a fuel consisting of one or more compounds consisting solely of carbon and hydrogen. Gasoline and diesel are hydrocarbon fuels.

By non-essentially hydrocarbon fuel is meant a fuel consisting of one or more compounds consisting not essentially of carbon and hydrogen, that is to say which also contain other atoms, in particular oxygen atoms.

According to a particular embodiment, the fuel composition may comprise at least one hydrocarbon fuel chosen from middle distillates with a boiling temperature of between 100 and 500°C, preferably 150 to 450°C, preferably 150 to 400°C. C, of preferably 150 to 370°C, or lighter distillates having a boiling temperature between 50 and 260°C.

These 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 distillates under vacuum, distillates resulting from ARDS type conversion processes (in English “atmospheric residue desulfurization”) and/or visbreaking, the distillates resulting from the valorization of Fischer Tropsch cuts. Hydrocarbon fuels are typically gasoline and diesel fuel (also called diesel fuel).

Advantageously, the fuel composition is chosen from gas oils or gasolines, preferably from gas oils.

Gasolines include, in particular, all commercially available spark ignition engine fuel compositions. As a representative example, we can cite gasolines meeting the NF EN 228 standard. Gasolines generally have sufficiently high octane indices to avoid the knocking phenomenon. Typically, gasoline-type fuels marketed in Europe, complying with the NF EN 228 standard, have a motor 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 generally have a RON ranging from 90 to 100 and a MON ranging from 80 to 90, the RON and MON being measured according to ASTM D 2699- 86 or D 2700-86.

Gas oils (diesel engine fuels) include, in particular, all commercially available diesel engine fuel compositions. We can cite, as a representative example, diesel fuels meeting the NF EN 590 standard.

Non-essentially hydrocarbon fuels include in particular oxygenated ones, for example distillates resulting from the BTL (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; THE biodiesels of animal and/or plant origin and bioethanols.

Mixtures of hydrocarbon fuel and non-essentially hydrocarbon fuel are typically type B _x diesels or type E _x gasolines.

By type B _x diesel fuel for Diesel engines, we mean a diesel fuel which contains x% (v/v) of esters of vegetable or animal oils (including used cooking oils) transformed by a chemical process called transesterification, obtained by reacting this oil with an alcohol to obtain fatty acid esters (FAE). With methanol and ethanol, fatty acid methyl esters (FAME) and fatty acid ethyl esters (FAFA) are obtained, respectively. The letter "B" followed by a number indicates the percentage of EAG contained in the diesel. Thus, a B99 contains 99% of EAG and 1% of middle distillates of fossil origin (mineral source), B20, 20% of EAG and 80% of middle distillates of fossil origin etc.... We therefore distinguish between type B ₀ gas oils which do not contain oxygenated compounds, type Bx gas oils which contain x% (v/v) of esters of vegetable oils or fatty acids, most often methyl esters (EMHV or FAME) , x denoting a number ranging from 0 to 100. When EAG is used alone in engines, the fuel is designated by the term B ₁₀₀ .

By type E _x gasoline for spark ignition engines, we mean a gasoline fuel which contains x% (v/v) of oxygenates, generally ethanol, bioethanol, methyl-tertio-butyl-ether (MTBE) and/or ethyl-tertio-butyl-ether (ETBE), x designating a number ranging from 0 to 100.

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.

In one embodiment, additional additives may be present in said fuel composition, such as those defined above.

In one embodiment, the content of each of said first and second additives (1) and (2) 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. weight, more preferably from 12 to 400 ppm by weight, and even better from 15 to 350 ppm by weight relative to the total weight of the fuel composition.

Use

Another object of the invention is the use of the additive composition, or the fuel composition, or the fuel concentrate, to maintain cleanliness (keep-clean effect) and/or clean (clean-up effect). ) deposits in at least one of the internal parts of an engine, preferably Diesel, chosen from the following: the air intake system, and the air and fuel intake system of the engine, the combustion chamber combustion and the fuel injection system, and preferably the fuel injection system.

Another object of the invention is the use of the additive composition, or the fuel composition, or the fuel concentrate to prevent and/or reduce coke deposits, and/or soaps and/or varnish on the injectors or injector needles; and/or soap and/or sticking (or valve-sticking) of gasoline engine valves, preferably to prevent and/or reduce soap and coking deposits and varnishes on injectors or injector needles in Diesel engines.

Deposits are distinguished depending on the type of internal combustion engine and the location of the deposits in the internal parts of said engine.

According to a preferred embodiment, the internal combustion engine is a compression ignition engine or Diesel engine, in particular a Diesel engine with direct injection or a Diesel engine with indirect injection, in particular a Diesel engine with a Common injection system. -Rail (CRDI in English “Common Rail Direct Injection”). The targeted deposits are located in at least one of the internal parts of said Diesel engine.

Advantageously, the targeted deposits are located in the injection system of the Diesel engine, preferably located on an external part of an injector of said injection system, for example the nose of the injector and/or on an internal part of an injector of said injection system (IDID in English “Internal Diesel Injector Deposits”), for example on the surface of an injector needle.

The deposits may consist of deposits linked to the phenomenon of coking (“coking” in English) and/or deposits of soap and/or varnish type (“lacquering”).

In one embodiment, the fuel composition according to the invention is used to reduce the fuel consumption of an engine, preferably Diesel (“Fuel Eco” action) and/or minimize the loss of power of said gasoline engine or Diesel, and/or reduce pollutant emissions, in particular, particulate emissions from the combustion engine.

Another object of the invention is the use of said additive composition to reduce fouling (i.e. prevent and/or eliminate deposits) in the area of the rings and/or pistons and/or or engine liners.

In said uses, the engine is preferably Diesel, with direct injection, said power loss being able to be determined according to the standardized engine test method CEC F-98-08, but can also be a Diesel engine with indirect injection.

Said compound(s) according to the invention can, advantageously, be used in fuel to reduce and/or avoid restriction of the flow of fuel emitted by the injector of a Diesel engine.

In another embodiment, in said uses, the engine is preferably Diesel, with indirect injection, said flow restriction being able to be determined according to the standardized engine test method CEC F-23-01.

The fuel composition according to the invention can be used to power engines used in all types of applications, for example in light vehicles (VL), heavy goods vehicles (PL), stationary vehicles, off-road vehicles. (mining, construction, works public...), agricultural machinery, thermal vehicles or hybrid vehicles (rechargeable or not)...

The additive composition or the concentrate according to the invention can be used in “severe” or “easier to process” gas oils. “Severe” gas oils are distinguished from “easy-to-treat” gas oils in that they require a higher rate of treatment in additive composition to be effective than an “easy-to-treat” gas oil.

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 fuel base as described above with at least the two additives as described above, and optionally one or more other additives different from the additives according to the invention, as described previously.

Process for improving engine cleanliness

• la préparation d'une composition de carburant par additivation d'un carburant avec au moins les deux additifs (1) et (2) tels que décrits ci-avant, ou avec un concentré les comprenant, puis
• la combustion de ladite composition de carburant dans ledit moteur.

The invention also relates to a method for maintaining the cleanliness and/or cleaning at least one of the internal parts, preferably of a Diesel engine, comprising at least the following steps:

• the preparation of a fuel composition by addition of a fuel with at least the two additives (1) and (2) as described above, or with a concentrate comprising them, then
• burning said fuel composition in said engine.

All characteristics of the additives, fuel or use are applicable to the process.

According to a first embodiment, the engine is a spark ignition engine, or gasoline engine, with direct or indirect injection.

The internal part kept clean and/or cleaned of the spark ignition engine is preferably chosen from the intake system of the engine, in particular the intake valves (IVD), the combustion chamber (CCD or TCD) and the injection system fuel, in particular the injectors of an indirect injection system (PFI) or the injectors of a direct injection system (DISI).

According to a second embodiment, the internal combustion engine is a compression ignition or Diesel engine, preferably a Diesel engine with direct injection, in particular a Diesel engine with a Common-Rail injection system (CRDI).

The internal part kept clean (keep-clean) and/or cleaned (clean-up) of the Diesel engine is, preferably, the injection system of the Diesel engine, preferably an external part of an injector of said injection system , for example the nose of the injector and/or one of the internal parts of an injector of said injection system, for example the surface of an injector needle.

According to a preferred variant, the step of preparing a fuel composition above is preceded by a preliminary step of determining the content of hydrocarbon compound(s) to be incorporated into said fuel composition to achieve a given specification relating to the detergency properties of the fuel composition.

This preliminary step is part of current 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.

The characteristic representative of the detergency properties of the fuel will depend on the type of internal combustion engine, for example Diesel or spark ignition, the direct or indirect injection system and the location in the engine of the deposits targeted for cleaning and/or maintaining cleanliness.

For direct injection Diesel engines, the characteristic representative of the detergency properties of the fuel can, for example, correspond to the loss of power due to the formation of deposits in the injectors or the restriction of the flow of fuel emitted by the injector at during operation of said engine.

The characteristic representative of the detergency properties can also correspond to the appearance of lacquering type deposits at the level of the injector needle (IDID).

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.

• la méthode DW10, méthode d'essai moteur normée CEC F-98-08, pour mesurer la perte de puissance des moteurs Diesel à injection directe ;
• la méthode XUD9, méthode d'essai moteur normée CEC F-23-01, pour mesurer la restriction de flux de carburant émise par l'injecteur ;
• la méthode décrite par la demanderesse dans la demande WO2014/029770 page 17 à 20, pour l'évaluation des dépôts lacquering (IDID).

We will cite, by way of non-limiting example, the following tests standardized or recognized by the profession or the methods described in the literature, for Diesel engines:

• the DW10 method, CEC F-98-08 standardized engine test method, to measure the power loss of direct injection Diesel engines;
• the XUD9 method, CEC F-23-01 standardized engine test method, to measure the fuel flow restriction emitted by the injector;
• the method described by the applicant in the application WO2014/029770 page 17 to 20, for the evaluation of lacquering deposits (IDID).

The examples below are given by way of illustration of the invention, and cannot be interpreted in such a way as to limit its scope.

EXAMPLES

The examples below were made using two diesel-type fuels:
- a so-called B7 diesel containing 6.8% by volume of methyl ester of fatty acids, representative of the fuels for diesel engines used in Europe, and whose characteristics are detailed in Table 1 below;
- a so-called B0 diesel fuel not containing oxygenated compounds, representative of fuels for diesel engines used outside Europe, and whose characteristics are detailed in table 2 below. <u>Table 1:</u>characteristics of B7 diesel Characteristic Method Value Lower calorific value measured ASTM D240 42.685 MJ/kg Carbon content ASTM D5291 83.8% by weight Hydrogen content ASTM D5291 13.2% by weight Total oxygen content ASTM D5291 adapted 0.5% by weight Oxidation stability ISO 12205 1g/ ^m3 Density at 15°C ISO 12185 835.7 kg/m ³ Viscosity at 40°C ISO 3104 2.25mm ² /s Cloud point (PTR)° ISO 3015 -6°C Filterability limit temperature (TLF) EN 116 -24°C Distillation profile ISO 3405 Initial point 158.6°C Point at 5% vol. 174.9°C Point at 10% vol. 181.2°C Point at 20% vol. 194.9°C Point at 30% vol. 212.7°C Point at 40% vol. 232.4°C Point at 50% vol. 252.9°C Point at 60% vol. 274.6°C Point at 70% vol. 296.1°C Point at 80% vol. 317.8°C Point at 90% vol. 338.4°C Point at 95% vol. 352.4°C Period 365.9°C E250 (% distilled at 250°C) 48.5% by volume E350 (% distilled at 350°C) 94.4% by volume Flash point ISO 2719 58.0°C Sulfur content ASTM D5453 8.8 mg/kg Water content ISO 12937 70 mg/kg Cetane number measured ISO 5165 54.1 Aromatic compound content EN12916 20% by weight Characteristic Method Value Lower calorific value measured ASTM D240 42.670 MJ/kg Carbon content ASTM D5291 86.5% by weight Hydrogen content ASTM D5291 13.4% by weight Total oxygen content ASTM D5291 adapted <0.5% by weight Oxidation stability ISO 12205 <1g/ ^m3 Density at 15°C ISO 12185 856.9 kg/ ^m3 Viscosity at 40°C ISO 3104 3.46mm ² /s Cloud point (PTR)° ISO 3015 9°C Filterability limit temperature (TLF) EN 116 4°C Distillation profile ISO 3405 Initial point 169.9°C Point at 5% vol. 190.2°C Point at 10% vol. 206.2°C Point at 20% vol. 225.9°C Point at 30% vol. 242.6°C Point at 40% vol. 257.5°C Point at 50% vol. 273.0°C Point at 60% vol. 289.1°C Point at 70% vol. 307.6°C Point at 80% vol. 330.7°C Point at 90% vol. 363.3°C Point at 95% vol. 389.7°C Period 403.7°C E250 (% distilled at 250°C) 35.0% by volume E350 (% distilled at 350°C) 86.4% by volume Flash point ISO 2719 57.5°C Sulfur content ASTM D5453 1566 mg/kg Water content ISO 12937 100 mg/kg Cetane number measured ISO 5165 46.6 Aromatic compound content EN12916 25.9% by weight

• A1: 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 ;
• A2 : amido alkyl bétaïne, obtenue par réaction de l'oléylamidopropyle diméthylamine, avec le chloroacétate de sodium.

Fuel compositions were prepared, by adding the following additives A1 and A2 to each of the B0 and B7 diesels:

• A1: quaternary ammonium salt, formed by reaction of propylene oxide with the condensation product of a polyisobutenyl-succinic anhydride whose polyisobutylene group (PIB) has a number average molecular mass (Mn) of 1000 g/ mol and dimethyl-aminopropylamine;
• A2: amido alkyl betaine, obtained by reaction of oleylamidopropyl dimethylamine with sodium chloroacetate.

The quantity of additive added to each composition is detailed in Tables 3 and 4 below, in which the content of each additive is indicated in ppm by weight relative to the total weight of the final composition: <u>Table 3:</u>fuel compositions from B7 diesel Additives added Composition B7-1 Composition B7-2 Composition B7-3 A1 250 0 125 A2 0 250 125 Additives added Composition B0-1 Composition B0-2 Composition B0-3 A1 250 0 125 A2 0 250 125

The performance in terms of detergency of each of the fuel compositions above was evaluated using the XUD9 engine test, consisting of determining the flow loss defined as corresponding to the restriction of the flow of a diesel fuel emitted by the injector d a pre-chamber Diesel engine during operation, according to the standardized engine test method CEC F-23-1-01. The objective of this test is to evaluate the ability of the composition of additives tested to reduce deposits on the injectors of a Peugeot XUD9 A/L four-cylinder engine with pre-chamber Diesel injection.

The tests were carried out with a Peugeot XUD9 A/L four-cylinder diesel pre-chamber injection engine equipped with clean injectors whose flow rate was determined beforehand.

• Débit du liquide de refroidissement (étape 2 uniquement): 85 ± 5 1/min Températures :
  • Sortie liquide de refroidissement : 95 ± 2°C
  • Huile : 100 ± 5°C
  • Entrée d'air : 32 ± 2°C
  • Carburant (à la pompe) : 31 ± 2°C
• Pressions :
  • A l'entrée de la pompe de carburant : -50 à + 100 mbar
  • A la sortie de la pompe de carburant : -100 à + 100 mbar
  • Pression de refoulement d'échappement (étape 2 uniquement) : 50 ± 10 mbar
  • entrée d'air : 950 ± 10 mbar.

The engine follows the test cycle detailed in the following table 5 repeated 134 times for a total duration of 10 hours and 3 minutes: <u>Table 5:</u> Stage Duration(s) Speed (rpm) Torque (Nm) 1 30 1200 ± 30 10 ± 2 2 60 3000 ± 30 50 ±2 3 60 1300 ± 30 35 ± 2 4 120 1850 ± 30 50 ± 2 The test conditions are as follows:

• Coolant flow (stage 2 only): 85 ± 5 1/min Temperatures:
  • Coolant outlet: 95 ± 2°C
  • Oil: 100 ± 5°C
  • Air inlet: 32 ± 2°C
  • Fuel (at the pump): 31 ± 2°C
• Pressures:
  • At the fuel pump inlet: -50 to + 100 mbar
  • At the fuel pump outlet: -100 to +100 mbar
  • Exhaust discharge pressure (stage 2 only): 50 ± 10 mbar
  • air inlet: 950 ± 10 mbar.

• Phase 1 d'encrassement (ou « dirty up ») avec le gazole de référence non additivé (B7 ou B0) La perte de débit évaluée après cette première phase est de 80% en moyenne.
• Phase 2 de nettoyage (ou « clean up ») avec le carburant candidat.

The following two consecutive phases were carried out, with the same test method for each phase:

• Phase 1 of clogging (or “dirty up”) with the non-additive reference diesel (B7 or B0) The flow loss evaluated after this first phase is 80% on average.
• Phase 2 of cleaning (or “clean up”) with the candidate fuel.

At the end of the test, the flow rate of the injectors is evaluated again. The flow loss is measured on the four injectors. Results are expressed as percentage flow loss for different needle lifts. Usually we compare the clogging values at 0.1 mm of needle lift because they are more discriminating and more precise and repeatable (repeatability < 5%). The evolution of the flow loss before/after test makes it possible to deduce the flow loss as a percentage. Taking into account the repeatability of the test, a significant detergent effect can be affirmed for a reduction in flow loss, i.e. a flow gain greater than 10 points (>10%).

At the end of the test at the end of the cleaning phase, the loss of flow rate from the injectors is again evaluated, and the percentage of injector cleaning is deduced.

The results obtained are detailed in tables 6 and 7 below. <u>Table 6:</u> results with additive type B7 fuels Composition B7-1 B7-2 B7-3 Cleaning 64% 55% 79% Composition B0-1 B0-2 B0-3 Cleaning 43% 44% 59%

The above results show that the compositions according to the invention (B7-3 and B0-3) containing the combination of additives A1 and A2 lead to very good results in terms of cleaning clogged injectors (“clean-up” effect). "). At an otherwise identical total additive content (250 ppm), these results are significantly higher than those obtained with the comparative compositions containing only one of the two additives (compositions B7-1, B7-2, B0-1 and B0-2).

These results illustrate the synergistic effects provided by the combination of the two additives according to the present invention.

Claims (15)

1. A fuel additive composition comprising:

   (1) at least one first additive selected from quaternary ammonium salts different from betaines, and

   (2) at least one second additive selected from amido alkyl betaines, of following formula (I):

   

   wherein

   R1 is a linear or branched C₁ to C₃₄ hydrocarbon chain,

   R2 is a hydrogen atom or a C₁ to C₁₅ hydrocarbon chain,

   R3 is a C₁ to C₁₅ hydrocarbon chain, and

   R4 and R5 are identical or different and selected independently of each other from a hydrogen atom and a C₁ to C₁₀ hydrocarbon chain, wherein the groups R4 and R5 can contain one or more nitrogen groups and/or can be bound together to form one or more rings; and

   wherein the weight ratio of the amount of the first additive to the amount of the second additive is within the range of from 1:4 to 4:1.
2. The composition according to claim 1, characterised in that in formula (I), R1 is a linear or branched C₈ to C₃₀, preferably C₁₂ to C₂₄, more preferably C₁₆ to C₂₀, hydrocarbon chain.
3. The composition according to any one of the preceding claims, characterised in that in formula (I), R2 is a hydrogen atom or a C₁ to C₈ hydrocarbon chain, preferably a hydrogen atom.
4. The composition according to any one of the preceding claims, characterised in that in formula (I), R3 is a C₁ to C₈, preferably C₂ to C₄, hydrocarbon chain.
5. The composition according to any one of the preceding claims, characterised in that in formula (I), R4 and R5 are identical or different and selected independently of each other from a hydrogen atom and a C₁ to C₆ hydrocarbon chain, wherein the groups R₄ and R₅ can contain one or more nitrogen groups and/or can be bound together to form a ring; preferably R4 and R5 are identical and represent a methyl group or an ethyl group and more preferably a methyl group.
6. The composition according to any one of the preceding claims, characterised in that the weight ratio of the amount of the first additive to the amount of the second additive is within the range of from 1:1 to 2.5:1, preferably from 1.5:1 to 2.1:1.
7. The composition according to any one of the preceding claims, characterised in that said first additive (1) is obtained by reaction with a quaternising agent of a nitrogen compound comprising a tertiary amine function, this compound being the product of the reaction of an acylating agent substituted by a hydrocarbon group and of a compound comprising at least one tertiary amine group and at least one group selected from primary amines, secondary amines and alcohols.
8. The composition according to the preceding claim, wherein the acylating agent substituted by a hydrocarbon group is selected from mono- or poly-carboxylic acids and the derivatives thereof, in particular the ester, amide or anhydride derivatives thereof, and preferably the acylating agent is selected from succinic, phthalic and propionic acids and the corresponding anhydrides, and more preferably the acylating agent substituted by a hydrocarbon group is a polyisobutenyl succinic anhydride.
9. The composition according to any one of claims 7 and 8, wherein the compound comprising at least one tertiary amine group and at least one group selected from primary amines, secondary amines and alcohols is selected from amines of the following formulas (II) or (III):

   

   

   wherein:

   R6 and R7 are identical 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 comprised between 1 and 5;

   n is an integer comprised between 0 and 20; and

   R8 is a hydrogen atom or a C1 to C22 alkyl group;

   and preferably said compound is selected from the amines of formula (II).
10. The composition according to any one of the preceding claims, characterised in that the additive (2) is the product of reaction:

    (i) of a tertiary amine substituted by a hydrocarbon group selected from the (C₈-C₃₀ alkyl) amidopropyldi (C₁-C₄ alkyl) amines and the (C₈-C₃₀ alkenyl) amidopropyldi (C₁-C₄ alkyl)amines; preferably from the (C₈-C₃₀ alkyl) amidopropyldimethylamines and (C₈-C₃₀ alkenyl) amidopropyldimethylamines; preferably oleylamidopropyl dimethylamine; with

    (ii) acetic acid substituted by a halogen, or one of the salts thereof, or one of the ester or amide derivatives thereof; preferably sodium chloroacetate;

    said reaction product preferably being devoid of noncovalent anionic species.
11. A fuel concentrate, comprising an additive composition according to any one of claims 1 to 10, in a mixture with an organic liquid, said organic liquid being inert relative to the first and second additives, and miscible with said fuel.
12. A fuel composition comprising:

    (1) a fuel base derived from one or more sources selected from the group consisting of mineral, animal, plant and synthetic sources, and preferably selected from hydrocarbon fuels, non-essentially hydrocarbon fuels and mixtures thereof; and

    (2) an additive composition as defined in any one of claims 1 to 10.
13. Use of the additive composition as defined in any one of claims 1 to 10, of the concentrate as defined in claim 11, or of the fuel composition as defined in claim 12, to prevent (keep-clean effect) and/or to eliminate (clean-up effect) the deposits in at least one of the internal parts of an engine, preferably a Diesel engine, selected from the following ones: the combustion chamber, the engine intake system and the fuel injection system, and preferably the fuel injection system.
14. Use of the fuel composition as defined in claim 12, to reduce the fuel consumption of a Diesel engine ("Fuel Eco" action) and/or lower the power loss of said engine, and/or reduce the pollutant emissions, in particular the particulate emissions from the combustion engine.
15. A method for maintaining the cleanliness and/or cleaning of at least one of the internal parts of an engine, preferably a compression ignition engine or Diesel engine, comprising at least the following steps:

    - the preparation of a fuel composition by additivating a fuel with at least the two additives (1) and (2) as defined in any one of claims 1 to 10, or with a concentrate as defined in claim 11, then

    - the combustion of said fuel composition in said engine.