Paraffin-based fuel composition
阅读说明：本技术 基于链烷烃的燃料组合物 (Paraffin-based fuel composition ) 是由 G.德洛姆 R.道芬 于 2020-01-24 设计创作，主要内容包括：本发明的主题为燃料组合物,其包括-至少85重量％的具有在从100℃延伸到400℃的范围内的馏程并且具有大于或等于90重量％的链烷含量的一种或多种烃级分；-至少一种由特定季铵盐构成的第一添加剂；和-至少一种由酚类抗氧化剂构成的第二添加剂。本发明的主题还为包括所述第一和第二添加剂的组合物用于改善富含链烷的燃料组合物的至少一种性质的用途。(Subject of the present invention is a fuel composition comprising-at least 85% by weight of one or more hydrocarbon fractions having a distillation range extending from 100 ℃ to 400 ℃ and having a paraffin content greater than or equal to 90% by weight; -at least one first additive consisting of a specific quaternary ammonium salt; and-at least one second additive consisting of a phenolic antioxidant. The subject of the present invention is also the use of a composition comprising said first and second additives for improving at least one property of a paraffin-rich fuel composition.)
1. A fuel composition comprising:
-at least 85% by weight of one or more paraffin fractions having a distillation range falling within the range of 100-400 ℃ and having a paraffin content of greater than or equal to 90% by weight;
-at least one first additive constituted by a quaternary ammonium salt obtained by reaction of a nitrogen-containing compound comprising a tertiary amine function with a quaternizing agent, the compound being the reaction product of polyisobutenylsuccinic anhydride with a compound comprising at least one tertiary amine group and at least one group chosen from primary amines, secondary amines and alcohols; and
-at least one second additive consisting of an antioxidant selected from compounds comprising phenolic groups.
2. Composition according to the preceding claim, characterized in that the distillation range of the paraffinic hydrocarbon fraction falls within the range of 130-350 ℃, preferably 150-320 ℃.
3. Composition according to any one of the preceding claims, characterized in that the paraffinic fraction has a paraffin content greater than or equal to 95% by weight, preferably greater than or equal to 99% by weight, more preferentially greater than or equal to 99.5% by weight, still better greater than or equal to 99.9% by weight, with respect to the total weight of the fraction.
4. Composition according to any one of the preceding claims, characterized in that the paraffinic fraction comprises at least 50% by weight of iso-paraffins, preferably at least 70% by weight and even better at least 90% by weight of iso-paraffins, relative to the weight of the fraction.
5. The composition according to any one of the preceding claims, wherein the one or more paraffinic fractions is a hydrotreated vegetable oil.
6. Composition according to any one of the preceding claims, characterized in that it comprises at least 90% by weight, preferably at least 93% by weight, more preferentially at least 95% by weight, even more preferentially at least 99% by weight, and even better at least 99.5% by weight of said one or more paraffinic fractions.
7. Composition according to any one of the preceding claims, characterized in that 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) and preferably from amines of formula (I):
wherein:
r6 and R7 are the same or different and independently of one another represent an alkyl group having 1 to 22 carbon atoms;
x is an alkylene group having 1 to 20 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-C22 alkyl group.
8. Composition according to any one of the preceding claims, characterized in that it comprises one or more first additives in a proportion ranging from 5 to 1000ppm, preferably from 10 to 500ppm, and more preferentially from 50 to 200ppm by weight, relative to the total weight of the composition.
9. Composition according to any one of the preceding claims, characterized in that the second additive is chosen from alkylphenols, and preferably the second additive is 2, 6-di-tert-butyl-4-methylphenol.
10. Composition according to any one of the preceding claims, characterized in that it comprises one or more second additives in a proportion ranging from 2 to 500ppm, preferably from 5 to 250ppm, and more preferentially from 10 to 150ppm by weight, relative to the total weight of the composition.
11. Composition according to any one of the preceding claims, characterized in that it further comprises one or more aminating antioxidants chosen from aliphatic, cycloaliphatic or aromatic amines, and preferably dicyclohexylamine, present in a proportion ranging from 0.2 to 50ppm, preferably from 0.2 to 25ppm and more preferentially from 1 to 20ppm by weight relative to the total weight of the composition.
12. Composition according to any one of the preceding claims, characterized in that it further comprises one or more metal deactivators selected from amines substituted by triazole groups, and more preferentially N, N-bis (2-ethylhexyl) - [ (1,2, 4-triazol-1-yl) methyl ] amine and N, N' -bis- (2-ethylhexyl) -4-methyl-1H-benzotriazolamide, alone or in a mixture, present in a proportion ranging from 0.2 to 50ppm, preferably from 0.5 to 25ppm, and more preferentially from 1 to 15ppm by weight relative to the total weight of the composition.
13. The composition as claimed in any one of the preceding claims, characterized in that it further comprises one or more chelating agents, preferably selected from amines substituted by Ν, Ν '-bissalicylidene groups, and more preferentially Ν, Ν' -bissalicylidene 1, 2-diaminopropane, present in a proportion ranging from 0.1 to 100ppm, preferably from 0.2 to 50ppm, more preferentially from 0.5 to 20ppm by weight, and even more preferentially from 0.5 to 10ppm by weight, relative to the total weight of the composition.
14. Use of an additive composition comprising at least one first additive and at least one second additive as defined in any one of claims 1, 7 and 9 for improving at least one property selected from the group consisting of electrical conductivity, corrosion resistance, oxidation stability and detergency of a fuel composition, preferably a diesel fuel composition, comprising at least 85 wt% of one or more hydrocarbon fractions having a distillation range falling within the range of 100-400 ℃ and having a paraffin content of greater than or equal to 90 wt%.
15. Use according to the preceding claim, wherein the additive composition further comprises:
-one or more aminating antioxidants selected from aliphatic, cycloaliphatic and aromatic amines, and preferably dicyclohexylamine;
-one or more metal deactivators selected from amines substituted by triazole groups, and more preferentially N, N-bis (2-ethylhexyl) - [ (1,2, 4-triazol-1-yl) methyl ] amine and N, N' -bis- (2-ethylhexyl) -4-methyl-1H-benzotriazolamine, alone or in a mixture; and
-one or more chelating agents, preferably selected from amines substituted by Ν, Ν '-disalicylidene groups, and more preferentially Ν, Ν' -disalicylidene 1, 2-diaminopropane.
Technical Field
The present invention relates to a fuel composition based on one or more paraffin-rich fractions, said fuel composition comprising: at least one first additive consisting of a quaternary ammonium salt, in combination with at least one second additive chosen from phenolic antioxidants.
The invention also relates to the use of an additive composition comprising a combination of said first and second additives for improving the properties of a fuel composition comprising a high paraffin content.
The invention also relates to the use of such a fuel composition for supplying a diesel engine.
Background
The use of particularly paraffinic hydrocarbon-rich fractions is becoming increasingly common in formulating fuels and in particular fuels for engines using compression ignition (or diesel engines). Hydrotreated vegetable oils, known by the person skilled in the art under the term HVO, constitute a classic example of a very paraffinic rich fraction, which can be introduced in greater or lesser proportions into the following fuels: intended for road vehicles (in particular cars and lorries such as lorries, dump trucks, buses and coaches) and off-road vehicles (in particular machines intended for construction site and/or municipal work operations, such as bulldozers, off-road trucks; handling machines; tractors and agricultural machines; ships; locomotives (locomotives), etc.).
The trend is that the proportion of such hydrocarbon fractions is increasing more and more than conventional fractions resulting from oil distillation, or even that it is sought to formulate fuel compositions from such fractions only. In particular, regulations in many countries encourage the introduction of increasing amounts of products of renewable origin, for example HVO-type fractions, for environmental reasons and/or for reasons of resource accessibility. This is because HVO does not have the deleterious effects that can be caused by ester-type biodiesel, such as increased NOx emissions, deposit formation, and the like.
However, formulating fuel compositions that include very high paraffin content poses a number of difficulties.
In particular, these fuels have proven to have insufficient corrosion resistance, which is clearly inferior to that of petroleum-derived fuels. Its use can lead to the phenomenon of rusting and corrosion of the materials in contact with these fuels, especially during the logistic (logistic) phase of the distribution (transport, storage, system for supplying the fuel to the vehicle) of these fuels.
In addition, such fuels cause metal extraction phenomena: they have a tendency to extract certain metals, in particular copper and zinc, from the materials with which they come into contact (for example the materials of transport and storage devices, systems for supplying fuels to vehicles, etc.).
They also have low electrical conductivity associated with their paraffinic nature. However, fuels with low electrical conductivity cause problems during fuel transfer (in particular when filling vehicle tanks): by friction or potential difference, if the fuel is not sufficiently conductive, an electrical discharge can occur, which leads to a fire risk.
Finally, these fuels pose specific stability problems in storage and use: in the case of long-term storage or in the case of use under high pressure or temperature conditions, the products have a tendency to oxidize and degrade (deteriorate). This phenomenon is catalyzed by any metals present in the fuel composition. This instability of the fuel can lead to fouling phenomena of the filters and fuel injection systems in the vehicle.
Patent application WO 2015/193463(Shell) describes the use of a combination of detergent (i), lubricity improver and conductivity improver (ii) in a diesel fuel composition comprising a high amount of paraffinic content, in particular normal paraffins resulting from fischer-tropsch synthesis, and an antioxidant.
The antioxidant is in particular chosen from phenolic compounds and amines. The synergistic combination of an antioxidant with compounds (i) and (ii) in diesel fuels having a high n-paraffin content is described as significantly increasing the stability of the fuel with respect to oxidation.
Disclosure of Invention
The applicant has now found that the use of a particular combination of two additives as defined below makes it possible to effectively remedy the aforementioned problems and allows the formulation of paraffin-rich fuel compositions with improved properties.
Accordingly, the present invention is directed to a fuel composition comprising:
-at least 85% by weight of one or more hydrocarbon fractions having a distillation range in the range of 100-400 ℃ and having a paraffin content of greater than or equal to 90% by weight;
-at least one first additive constituted by a quaternary ammonium salt obtained by reaction of a nitrogen-containing compound comprising a tertiary amine function with a quaternizing agent, the compound being the product of reaction of polyisobutenylsuccinic anhydride with a compound comprising at least one tertiary amine group and at least one group chosen from primary amines, secondary amines and alcohols; and
-at least one second additive consisting of an antioxidant selected from compounds comprising phenolic groups.
Such fuel compositions have excellent corrosion resistance properties and make it possible to avoid corrosion phenomena in the presence of both fresh water and salt water.
It also improves the stability of the fuel in the presence of metals very significantly and has very good electrical conductivity.
The compositions have an excellent level of stability and in particular good storage stability, good thermal stability and more generally good oxidation resistance.
Finally, it has also been demonstrated that the composition has good detergent properties and its use makes it possible to maintain the cleanliness of the engine, not only by limiting or preventing the formation of deposits ("keep-clean" effect), but also by reducing the deposits already present in the internal parts of the engine ("clean-up" effect).
It should be noted that these properties are improved without any deterioration of other intrinsic properties of the composition based on the paraffin-rich fraction, such as in particular its low foaming and demulsification (demulsification) level, its density, its cetane number, its good cold resistance (filterability limit temperature and pour point) in the case of the isoparaffin-rich fraction.
Its superior properties enable the fuel to be used in modern motor vehicles, particularly vehicles including diesel engines, including the most advanced engines such as ultra high pressure direct injection diesel engines.
Other objects, features, aspects and advantages of the present invention will become even more apparent upon reading the following specification and examples.
Hereinafter and unless otherwise indicated, the limits of the numerical ranges fall within the range, in particular in the expressions "comprised between … …" and "ranging from … … to (to) … …".
Also, the expressions "at least one" and "at least" used in the present specification are equal to the expressions "one or more" and "greater than or equal to", respectively.
Finally, as is known per se, CNBy a compound or group is meant a compound or group that contains N carbon atoms in its chemical structure.
Detailed Description
Paraffinic fraction
The composition according to the invention comprises one or more hydrocarbon fractions having a distillation range falling within the range of 100-400 ℃ and having a paraffin content of greater than or equal to 90% by weight, hereinafter referred to as "paraffin fractions".
The distillation range of the paraffinic fraction was determined according to NF EN ISO 3405. Preferably, it falls within the range of 130-.
The fraction has a paraffin content greater than or equal to 90% by weight, preferably greater than or equal to 95% by weight, still more preferentially greater than or equal to 99% by weight, even still better greater than or equal to 99.5% by weight, and even better greater than or equal to 99.9% by weight, relative to the total weight of the fraction.
By "alkane" is meant, as known per se, branched alkanes (also known as isoalkanes or isoalkanes) and unbranched alkanes (also known as normal alkanes or normal alkanes).
The paraffins present in the one or more paraffin fractions according to the invention advantageously comprise from 10 to 20 carbon atoms. It preferably comprises at least 60% by weight, more preferentially at least 80% by weight and even better still at least 90% by weight of alkanes containing from 12 to 18 carbon atoms, preferably from 14 to 18 carbon atoms and even more preferentially from 15 to 18 carbon atoms.
According to a preferred embodiment, the one or more paraffinic fractions used in the composition according to the invention comprise at least 50 wt.%, preferably at least 70 wt.%, of iso-paraffins relative to their total weight. According to a particularly preferred embodiment, they comprise at least 90% by weight of isoalkanes.
The paraffinic fraction or fractions have an aromatic content preferably less than or equal to 10,000ppm by weight, more preferentially less than or equal to 1500ppm by weight, even more preferentially less than or equal to 1000ppm by weight.
The naphthenic compound content is preferably less than or equal to 20,000ppm by weight, more preferably less than or equal to 10,000ppm by weight, and even better less than or equal to 1500ppm by weight.
The sulfur content is advantageously less than or equal to 10ppm by weight, and even better less than or equal to 5ppm by weight. Particularly preferably, this fraction is completely free of sulphur.
According to a particularly preferred embodiment, the one or more paraffinic fractions are hydrotreated vegetable oils, which are also known under the term HVO. These are oils of vegetable origin which have undergone successive treatments comprising hydrotreatment and then optionally isomerization.
Examples of suitable plant raw materials include rapeseed oil, canola oil, sunflower oil, soybean oil, hemp oil, olive oil, linseed oil, mustard oil, palm oil, castor oil and coconut oil.
Patent applications WO2016/185046 and WO2016/185047 describe hydrotreated vegetable oils and their preparation, which constitute examples of isoparaffinic fractions particularly suitable for the composition object of the present invention.
The composition according to the invention comprises at least 85% by weight of one or more paraffin fractions as described above. Preferably, it comprises at least 90 wt.%, more preferably at least 93 wt.% of one or more paraffin fractions.
According to one embodiment, the composition according to the invention comprises at least 95% by weight, preferably at least 99% by weight and even better at least 99.5% by weight of one or more paraffin fractions as described above.
First additive (Quaternary ammonium salt)：
The composition according to the invention comprises a first additive consisting of a quaternary ammonium salt obtained by reacting a nitrogen-containing compound comprising a tertiary amine function with a quaternizing agent, the nitrogen-containing compound being the reaction product of a polyisobutenylsuccinic anhydride and a compound comprising at least one tertiary amine group and at least one group selected from primary amines, secondary amines and alcohols.
The nitrogen-containing compound is a reaction product of polyisobutenyl succinic anhydride (PIBSA) and a compound including a tertiary amine group and both an oxygen atom and a nitrogen atom capable of condensing with the polyisobutenyl succinic anhydride.
The Polyisobutylene (PIB) group preferably has a number average molecular mass (Mn) of between 170 and 2800, for example between 250 and 1500, more preferably between 500 and 1500 and even more preferably between 500 and 1100. M between 700 and 1300, e.g. 700-1000nValue ranges are particularly preferred.
So-called highly reactive Polyisobutenes (PIBs) are particularly preferred. Highly reactive Polyisobutene (PIB) means a Polyisobutene (PIB) such that: wherein 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 EP 0565285. In particular, preferred PIBs are those having more than 80 mol% and up to 100% of vinylidene-type end groups, as described in document EP 1344785.
The preparation of polyisobutenyl succinic anhydrides is known per se and is widely described in the literature. Mention may be made, for example, of the processes described in documents US3361673 and US3018250 comprising a reaction between Polyisobutylene (PIB) and maleic anhydride, or else processes comprising a reaction of halogenated, in particular chlorinated, Polyisobutylene (PIB) with maleic anhydride (US 3172892).
According to one variant, polyisobutenyl succinic anhydrides can be prepared by mixing a polyolefin with maleic anhydride and then passing chlorine through the mixture (GB 949981).
The compound comprising at least one tertiary amine group and at least one group selected from primary amines, secondary amines and alcohols may for example be selected from: n, N-dimethylaminopropylamine, N-diethylaminopropylamine and N, N-dimethylaminoethylamine. Furthermore, the compound may be selected from heterocyclic compounds substituted with alkylamine such as 1- (3-aminopropyl) imidazole and 4- (3-aminopropyl) morpholine, 1- (2-aminoethyl) piperidine, 3-diamino-N-methyldipropylamine, and 3' 3-diamino (N, N-dimethylpropylamine).
The compound comprising at least one tertiary amine group and at least one group selected from primary amines, secondary amines and alcohols may 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, 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, N-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.
According to a preferred embodiment, the compound comprising at least one tertiary amine and at least one group selected from primary amines, secondary amines and alcohols is selected from amines of formula (I) or (II):
wherein:
r6 and R7 are the same or different and independently of one another represent an alkyl group having 1 to 22 carbon atoms;
x is an alkylene group having 1 to 20 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-C22 alkyl group.
When the nitrogen-containing compound comprises an amine of formula (I), R8 is advantageously a hydrogen atom or a C1-C16 alkyl group, preferably a C1-C10 alkyl group, even more preferentially a C1-C6 alkyl group. R8 can be selected, for example, from hydrogen, methyl, ethyl, propyl, butyl and isomers thereof. Preferably R8 is a hydrogen atom.
When the nitrogen-containing compound comprises an amine of formula (II), m is preferably equal to 2 to 3, more preferentially equal to 2; n is preferably an integer between 0 and 15, more preferably between 0 and 10, even more preferably between 0 and 5. Advantageously n is equal to 0.
According to a preferred embodiment, the nitrogen-containing compound is the reaction product of a polyisobutenyl succinic anhydride and a diamine of formula (I).
In this embodiment:
-R6 and R7 may represent, independently of each other, a C1-C16 alkyl group, preferably a C1-C10 alkyl group;
r6 and R7 may, independently of one another, represent a methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl group or isomers thereof. Advantageously R6 and R7 represent, independently of each other, a C1-C4 group, preferably a methyl group;
-X represents an alkyl group having from 1 to 16 carbon atoms, preferably from 1 to 12 carbon atoms, more preferentially from 1 to 8 carbon atoms, for example from 2 to 6 carbon atoms or from 2 to 5 carbon atoms. X particularly preferably represents an ethylene, propylene or butylene group, in particular a propylene group.
According to a particularly preferred embodiment, the nitrogen-containing compound is the reaction product of polyisobutenyl succinic anhydride with an alcohol or amine which also comprises a tertiary amine group, in particular a compound of formula (I) or (II) as described above, and more preferentially a compound of formula (I).
According to a preferred variant, polyisobutenyl succinic anhydride is reacted with an amine which also comprises a tertiary amine group under certain conditions to form a succinimide (closed form). The reaction of polyisobutenyl succinic anhydride with the amine also produces succinamide, a compound (open form) that includes an amide group and a carboxylic acid group, under certain conditions.
According to a second variant, an alcohol further comprising a tertiary amine group is reacted with polyisobutenyl succinic anhydride to form a polymer further comprising free carboxyl groups-CO2Esters of H groups (open form). Thus, in certain embodiments, the nitrogen-containing compound can be the following reaction product of polyisobutenyl succinic anhydride and an amine or alcohol: which is an ester or amide and which further comprises carboxyl groups-CO which have not yet been reacted2H group (open form).
The quaternary ammonium salts forming the second additive according to the invention are obtained directly by reaction between the nitrogen-containing compound comprising a tertiary amine function described above and the quaternizing agent.
According to one embodiment, the quaternizing agent is selected from dialkyl sulfates, carboxylic esters, alone or in a mixture; alkyl halides, benzyl halides, hydrocarbon carbonates, and hydrocarbon epoxides optionally mixed with acids.
For fuel applications, it is generally desirable to reduce the halogen and sulfur content and the proportion of phosphorus-containing compounds.
Thus, if a reagent for quaternization comprising such an element is used, it may be advantageous to carry out a subsequent reaction to exchange the counter ion. For example, the quaternary ammonium salt formed by reaction with the alkyl halide can then be reacted with sodium hydroxide and the sodium halide salt removed by filtration.
The quaternizing agents may include the following, either alone or in mixtures: halides, such as chloride, iodide or bromide; a hydroxide; a sulfonate salt or ester; a bisulfite salt or ester; alkyl sulfates such as dimethyl sulfate; a sulfone; a phosphate salt; phosphoric acid C1-C12 alkyl esters; C1-C12 dialkyl phosphate; a borate; boric acid C1-C12 alkyl esters; a nitrite salt or ester; a nitrate or ester; a carbonate salt or ester; a bicarbonate salt or ester; an alkanoic acid salt or ester; C1-C12O, O-dialkyldithiophosphate.
According to one embodiment, the quaternizing agent may be selected from: dialkyl sulfate derivatives such as dimethyl sulfate, N-oxides, sulfones such as propyl sulfone and butyl sulfone, alkyl, acyl or aralkyl halides such as methyl chloride and ethyl chloride, benzyl bromide, benzyl iodide or benzyl chloride, and hydrocarbon carbonates (or alkyl carbonates).
If the acid halide is benzyl chloride, the aromatic nucleus is optionally substituted with one or more alkyl or alkenyl groups.
The hydrocarbon (alkyl) group of the hydrocarbon carbonate may contain 1 to 50, 1 to 20, 1 to 10, or 1 to 5 carbon atoms per group. According to one embodiment, the hydrocarbon carbonate comprises two hydrocarbon groups, which may be the same or different. As examples of the hydrocarbon carbonate, dimethyl carbonate or diethyl carbonate may be mentioned.
According to a preferred embodiment, the quaternizing agent is selected from hydrocarbon epoxides represented by the following formula (III):
wherein R9, R10, R11 and R12 may be the same or different and represent independently of each other a hydrogen atom or C1-C50A hydrocarbon group. By way of non-limiting example, mention may be made of phenyloxirane (styrene oxide), ethylene oxide, propylene oxide, butylene oxide, 1, 2-diphenyloxirane and C1-C50An epoxide. Phenyl ethylene oxide and propylene oxide are particularly preferred.
Such hydrocarbon epoxides can be used as quaternizing agents in combination with an acid, for example with acetic acid. The hydrocarbon epoxides may also be used alone as quaternizing agents, particularly in the absence of additional acids. Without being bound by this hypothesis, it appears that the presence of a carboxylic acid functionality in the molecule favors the formation of quaternary ammonium salts. In such embodiments without any additional acid, a protic solvent is used to prepare the quaternary amine. As an example, protic solvents such as water and alcohols (including polyhydric alcohols) may be used alone or in mixtures. Preferred protic solvents have a dielectric constant of more than 9.
The corresponding quaternary ammonium salts prepared from amides or esters and succinic acid derivatives are described in WO 2010/132259.
According to another embodiment, the quaternizing agent is selected from compounds of formula (IV):
wherein R13 is an optionally substituted alkyl, alkenyl, aryl and aralkyl group and R14 is C1-C22Alkyl, aryl or alkylaryl groups.
The compound of formula (IV) is a carboxylic acid ester capable of reacting with a tertiary amine to form a quaternary ammonium salt. The compound of formula (IV) is selected from, for example, carboxylic acid esters having a pKa of 3.5 or less. The compound of formula (IV) is preferably selected from esters of substituted aromatic carboxylic acids, esters of alpha-hydroxycarboxylic acids and esters of polycarboxylic acids.
According to one embodiment, the ester is a substituted aromatic carboxylic acid ester of formula (IV) wherein R13 is a substituted aryl group. R13 is preferably a substituted aryl group having 6 to 10 carbon atoms, preferably a phenyl or naphthyl group, more preferably a phenyl group. R13 is advantageously chosen from alkoxycarbonyl, nitro, cyano, hydroxy, SR15And NR15R16One or more of the groups substituted. R15And R16Each of the groups may be a hydrogen atom, or an optionally substituted alkyl, alkenyl, aryl or alkoxycarbonyl group. R15And R16Each of the radicals advantageously represents a hydrogen atom or an optionally substituted C1-C22 alkyl group, preferably a hydrogen atom or a C1-C16 alkyl group, more preferentially a hydrogen atom or a C1-C10 alkyl group, even more preferentially a hydrogen atom or a C1-C4 alkyl group. R15Preferably a hydrogen atom and R16Is a hydrogen atom or a C1-C4 group. Advantageously, R15And R16Are all hydrogen atoms.
According to one embodiment, R13 is substituted with one or more groups selected from hydroxy, alkylOxycarbonyl, nitro, cyano and NH2Aryl groups substituted with groups of groups. R13 can be a polysubstituted aryl group, such as trihydroxyphenyl. Advantageously, R13 is a monosubstituted aryl group, which is preferably ortho-substituted. R13 is selected from OH, NH, for example2、NO2Or a COOMe group, preferably OH or NH2Substituted with a group of (a). R13 is preferably a hydroxyaryl group, in particular 2-hydroxyphenyl.
According to a specific embodiment, R14 is an alkyl or alkylaryl group. R14 may be a C1-C16, preferably C1-C10, advantageously C1-C8 alkyl group. R14 may be a C1-C16, preferably C1-C10, advantageously C1-C8 alkylaryl group. R14 may for example be selected from methyl, ethyl, propyl, butyl, pentyl or benzyl groups or isomers thereof. R14 is preferably a benzyl or methyl group, more preferably methyl.
A particularly preferred compound is methyl salicylate.
According to one embodiment, the compound of formula (IV) is an α -hydroxycarboxylic ester corresponding to the following formula (V):
wherein R17 and R18 are the same or different and are independently selected from a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or an aralkyl group. Such compounds are described, for example, in document EP 1254889.
Examples of compounds of formula (IV) wherein R13COO is a residue of an α -hydroxycarboxylic acid include: methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, benzyl or allyl esters of 2-hydroxyisobutyric acid; 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-ethylbutanoic acid; the methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl or allyl esters of lactic acid, and the methyl, ethyl, propyl, butyl, pentyl, hexyl, allyl, benzyl or phenyl esters of glycolic acid. Among the above, the preferred compound is methyl 2-hydroxyisobutyrate.
According to one embodiment, the compound of formula (IV) is an ester of a polycarboxylic acid selected from dicarboxylic acids and carboxylic acids having more than two acid functions. The carboxylic acid functions are preferably all in esterified form. Preferred esters are C1-C4 alkyl esters.
The compound of formula (IV) may be selected from oxalic acid diester, phthalic acid diester, maleic acid diester, malonic acid diester or citric acid diester. The compound of formula (IV) is preferably dimethyl oxalate.
According to a preferred variant, the compound of formula (IV) is a carboxylic ester having a pKa of less than 3.5. For the case where the compound includes more than one acid group, this will refer to the first order dissociation constant.
The compound of formula (IV) may be selected from one or more carboxylic acid esters as follows: selected from the group consisting of 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 salts used in the present invention are formed by reacting a hydrocarbon epoxide, preferably selected from those of formula (III) above, and more preferably propylene oxide, with the reaction product of polyisobutenyl succinic anhydride, the Polyisobutenyl (PIB) group of which has a number average molecular mass (Mn) of between 700 and 1000, and dimethylaminopropylamine.
The composition according to the invention comprises one or more first additives as described above, in a preferential content ranging from 5 to 1000ppm, preferably from 10 to 500ppm, and more preferentially from 50 to 200ppm by weight, with respect to the total weight of the composition.
Second additive (phenolic antioxidant):
the composition according to the invention comprises a second additive consisting of an antioxidant chosen from compounds comprising a phenolic group in their structure.
Suitable antioxidants are selected from 2, 6-di-tert-butyl-4-methylphenol (BHT), tert-butylhydroquinone (TBHQ), 2, 6-and 2, 4-di-tert-butylphenol, 2, 4-dimethyl-6-tert-butylphenol, pyrogallol, tocopherol, 4' -methylenebis (2, 6-di-tert-butylphenol) (CAS No.118-82-1), alone or in mixtures.
Particularly preferred antioxidants are selected from alkylphenols such as, in particular, 2, 6-di-tert-butyl-4-methylphenol (BHT).
The composition according to the invention comprises one or more second additives as described above, in a preferred content ranging from 2 to 500ppm, preferably from 5 to 250ppm and more preferentially from 10 to 150ppm by weight, relative to the total weight of the composition.
Other additives:
the composition according to the invention may also comprise one or more further additives different from the first and second additives as described above.
According to a preferred embodiment, the composition further comprises one or more aminating antioxidants, which may be chosen in particular from aliphatic, cycloaliphatic and aromatic amines. Dicyclohexylamine is particularly preferred.
The aminating antioxidant or antioxidants may be present in a proportion ranging from 0.2 to 50ppm, preferably from 0.5 to 25ppm, and more preferentially from 1 to 20ppm by weight relative to the total weight of the composition.
According to another preferred embodiment, the composition further comprises one or more metal deactivators selected from triazole derivatives, alone or in a mixture.
"triazole derivatives" means all compounds comprising a triazole unit, i.e. a five-membered aromatic cyclic unit comprising two double bonds and three nitrogen atoms. Depending on the position of the nitrogen atom, there are 1,2, 3-triazole units (known as V-triazole) and 1,2, 4-triazole units (known as S-triazole). As examples of triazole units, benzotriazole or tolyltriazole may be cited.
The one or more metal deactivators are preferably selected from amines substituted with triazole groups, alone or in a mixture. By "triazole group" is meant any substituent comprising a triazole unit as defined above.
The metal deactivator or metal deactivators are more preferably selected from N, N-bis (2-ethylhexyl) - [ (1,2, 4-triazol-1-yl) methyl ] amine (CAS 91273-04-0) and N, N' -bis- (2-ethylhexyl) -4-methyl-1H-benzotriazolamide (CAS 80584-90-3), alone or in a mixture.
Mention may also be made of the deactivators described on page 5 of application US 2006/0272597.
The one or more metal deactivators may be present in a proportion ranging from 0.2 to 50ppm, preferably from 0.5 to 25ppm and more preferentially from 1 to 15ppm by weight, with respect to the total weight of the composition.
According to another preferred embodiment, the composition further comprises one or more chelating agents (or metal masking agents), which may be chosen in particular from amines substituted by Ν, Ν '-disalicylidene groups, such as Ν, Ν' -disalicylidene 1, 2-diaminopropane (DMD).
The one or more chelating agents may be present in a proportion ranging from 0.1 to 100ppm, preferably from 0.2 to 50ppm, and more preferentially from 0.5 to 20ppm by weight, even more preferentially from 0.5 to 10ppm by weight, relative to the total weight of the composition.
The composition according to the invention may also comprise one or more other additives commonly used in fuels other than the aforementioned additives.
The composition may typically include one or more other additives selected from the group consisting of: detergents, anti-corrosion agents, dispersants, demulsifiers, tracers, biocides, deodorants, cetane additives, friction modifiers, lubricity or oiliness additives, combustion agents (promoters of the combustion of soot), anti-wear agents and/or agents for modifying electrical conductivity.
Among these additives, mention may be made in particular of:
a) cetane additive, which is chosen in particular (but not exclusively) from: alkyl nitrates, preferably 2-ethylhexyl nitrate, aryl peroxides, preferably benzyl peroxide, and alkyl peroxides, preferably tert-butyl peroxide;
b) a lubricating or antiwear additive, which is selected in particular (but not exclusively) from: 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,
c) demulsifying additives selected, for example and without limitation, from alkoxylated phenolic alkyl resins (such as compound CAS 63428-92-2),
d) a detergent.
According to a preferred embodiment, the composition comprises at least one detergent additive selected from triazole derivatives having the following formula (VI):
wherein
-R14 is selected from a hydrogen atom, a linear or branched aliphatic hydrocarbon group of C1-C8, preferably C1-C4, more preferentially C1-C2, and a carboxyl group (-CO 2H). Preferably, R14 is a hydrogen atom;
-R16 and R17 are the same or different and represent, independently of each other, a group selected from: a hydrogen atom, and a linear or branched, saturated or unsaturated, cyclic or acyclic aliphatic hydrocarbon group having from 2 to 200 carbon atoms, preferably from 14 to 200 carbon atoms, but more preferably from 50 to 170 carbon atoms, even more preferably between 60 and 120 carbon atoms.
It should be noted that we use the convention notation (bonds in dotted lines and labile bonds) to indicate that the positions of the hydrogen atoms and double bonds in the triazole rings can vary, and that the formula thus encompasses two possible positions.
According to a particular embodiment, the triazole derivative has formula (VI), wherein R16 and R17 are the same or different and represent, independently of each other, a group selected from: a hydrogen atom and an aliphatic hydrocarbon group having a number average molecular mass (Mn) of between 200 and 3000, preferably between 400 and 3000, more preferentially between 400 and 2500, even more preferentially between 400 and 1500 or between 500 and 1500. The aliphatic hydrocarbon radical is preferably a polyisobutene radical (also called polyisobutene, noted PIB) having a number-average molecular mass (Mn) of between 200 and 3000, preferably between 5400 and 3000, more preferably between 400 and 2500, even more preferably between 400 and 1500 or between 500 and 1500. According to a particularly preferred embodiment, R16 and R17 represent, respectively, a hydrogen atom and a PIB group as described above, or vice versa.
According to a preferred embodiment, the composition of the invention does not comprise an anti-foaming additive. This is because the good inherent properties of the composition according to the invention make the addition of such additives unnecessary. Examples of antifoam additives are, for record, in particular, but without limitation, polysiloxanes, alkoxylated polysiloxanes and fatty acid amides from vegetable or animal oils. Examples of such additives are given in EP861882, EP663000, EP 736590.
The application is as follows:
the invention also relates to the use of an additive composition comprising at least one first additive and at least one second additive as described above, for improving at least one property of a fuel composition comprising at least 85 wt% of one or more hydrocarbon fractions having a distillation range falling within the range of 100-400 ℃ and having a paraffin content of greater than or equal to 90 wt%.
The one or more improved properties are advantageously selected from the following: conductivity, corrosion resistance, oxidation stability and detergency.
The first and second additives are as described above. Such additive composition may further comprise one or more additional additives as described above, and in particular:
-one or more aminating antioxidants as described above;
-one or more metal passivators selected from triazole derivatives as described above;
-one or more chelating agents as described above.
Particularly preferred additive compositions include the following compounds:
-a quaternary ammonium salt formed by reacting propylene oxide with the reaction product of polyisobutenyl succinic anhydride and dimethylaminopropylamine, the Polyisobutenyl (PIB) group of the polyisobutenyl succinic anhydride having a number average molecular mass (Mn) of between 700 and 10000;
-2, 6-di-tert-butyl-4-methylphenol;
-dicyclohexylamine;
-N, N-bis (2-ethylhexyl) - [ (1,2, 4-triazol-1-yl) methyl ] amine; and
- Ν, Ν' -disalicylidene 1, 2-diaminopropane.
Finally, the invention is directed to the use of a composition as described above as a fuel for a diesel engine, in particular in a stationary engine or a vehicle equipped with a diesel engine, and more particularly in a diesel automobile. The composition according to the invention can be used in particular in the following vehicles: light vehicles, heavy goods vehicles (large trucks, domestic waste trucks, buses, coaches, etc. with different loads, called "medium load" and "heavy load"), and off-road vehicles (construction sites or municipal engineering machinery, tractors, trains, ships).
The following examples are given by way of illustration of the present invention and should not be construed to limit the scope thereof.
Examples
The following examples were carried out using a paraffin fraction (hereinafter fraction C1) consisting of Hydrotreated Vegetable Oil (HVO) whose properties are detailed in table I below:
[ Table I ]
Characteristics of
Method
Value of
Density at 15 deg.C
ISO 12185
779.9kg/m3
Viscosity at 40 deg.C
ISO 3104
2.9mm2/s
Cloud Point (CP) °
ASTM D7346
-36℃
Filterability Limit Temperature (LTF)
EN 116
-39℃
Distillation profile
ISO 3405
Initial point
216.0℃
Point at 5 vol%
252.4℃
Point at 10 vol%
262.1℃
Point at 20 vol%
269.8℃
Point at 30 vol%
273.4℃
Point at 40 vol%
275.7℃
Point at 50 vol%
277.8℃
Point at 60 vol%
279.7℃
Point at 70 vol%
282.1℃
Point at 80% by volume
285.0℃
Point at 90 vol%
289.2℃
Point at 95 vol%
293.0℃
Final point of termination
304.3℃
Distillation volume
98.6ml
Residue of
1.3ml
Loss of power
0.1ml
Aromatic content
EN12916
0% by weight
The hydrocarbon fraction included 99.9 wt.% paraffins, which included 92.6 wt.% iso-paraffins (hereinafter iso-paraffins) and 7.3 wt.% normal paraffins.
The exact composition is detailed in table II below:
[ Table II ]
The fuel composition was prepared by adding to the above C1 fraction the additive mixture detailed in table III below, wherein the proportions of the respective additives are expressed in ppm weight relative to the total weight of the final composition.
[ Table III ]
Additive agent
Mixture 1(MIX1)
Mixture 2(MIX2)
Quaternary ammonium salt 1
100
137
Composition 2
150
164
Anti-corrosive additive 3
0
5
(1) Formed by reacting propylene oxide with the reaction product of polyisobutenyl succinic anhydride and dimethylaminopropylamine, the Polyisobutenyl (PIB) group of the polyisobutenyl succinic anhydride having a number average molecular mass (Mn) of 1000 g/mol.
(2) An additive composition consisting of: 2, 6-di-tert-butyl-4-methylphenol; dicyclohexylamine; n, N-bis (2-ethylhexyl) - [ (1,2, 4-triazol-1-yl) methyl ] amine; and Ν, Ν' -disalicylidene 1, 2-diaminopropane.
(3) Tetrapropenyl succinic acid.
The properties of hydrocarbon fraction C1 were evaluated before and after the addition of each of the above additive mixtures.
Corrosion resistance
The method for evaluating corrosion resistance is that described in ASTM D665A (a standard described for lubricants but applicable to fuels). The rule is as follows: the steel samples were immersed in a beaker filled to 90% by volume with the fuel to be evaluated and to 10% by volume with fresh water. The solution was continuously stirred and the beaker was heated to 60 ℃. After 24 hours, the test specimens were observed to evaluate the presence of corrosion on the surface of the test specimens.
Corrosion is symbolized by a scale in the form of letters ranging from a to E, a denoting the absence of corrosion and E corresponding to the maximum degree of oxidation.
The results obtained are detailed in table IV below:
[ Table IV ]
These results show that: fraction C1 has very insufficient anti-corrosion properties, and the compositions according to the invention (C1+ MIX1 and C1+ MIX2) improve this property very significantly, including in the absence of any anti-corrosion additives (C1+ MIX 1).
Conductivity of electricity：
The conductivity test was carried out according to the method described in ISO 6297. The results obtained are detailed in table V below:
[ Table V ]
These results show that fraction C1 has very insufficient conductivity and that the compositions according to the invention (C1+ MEL1 and C1+ MEL2) improve this property quite appreciably.
Stability to oxidation：
The method for evaluating the oxidation stability is the so-called Rancimat method as described in EN 15751.
The test involves accelerating the aging process of the sample by exposing it to heat and passing a large volume of air. It measures the time required for the product to oxidize and is defined as the oxidation stability time. The results obtained are in hours. The longer the time, the more stable the fuel is under oxidation.
The results obtained are detailed in table VI below:
[ Table VI ]
These results show that: fraction C1 had very insufficient stability (which oxidized rapidly) and the compositions according to the invention (C1+ MIX1 and C1+ MIX2) improved this property very significantly.
Detergency：
Performance in terms of detergency was evaluated using the XUD9 engine test, which consists of determining the flow loss according to CEC standardized engine test method F-23-1-01, defined as the limit corresponding to the flow of diesel injected by a prechamber diesel engine injector during its operation. The purpose of this test was to evaluate the suitability of the tested additive composition for reducing deposits on the injectors of a four cylinder Peugeot XUD9 a/L engine using diesel pre-chamber injection.
The test was carried out by a Peugeot XUD9 a/L four cylinder engine using diesel pre-chamber injection equipped with a cleaning injector whose flow rate was pre-determined.
The engine followed the test cycle detailed in table VII below, repeated 134 times for a total duration of 10 hours and 3 minutes:
[ Table VII ]
The test conditions were as follows:
coolant flow rate (step 2 only): 85 +/-5 l/min
Temperature:
-a cooling liquid outlet: 95 +/-2 DEG C
-an oil: 100 +/-5 DEG C
-an air inlet: 32 + -2 deg.C
Fuel (at pump): 31 +/-2 DEG C
Pressure:
-inlet of the fuel pump: -50 to +100 mbar
-at the outlet of the fuel pump: -100 to +100 mbar
Exhaust gas discharge pressure (step 2 only): 50. + -.10 mbar
-an air inlet: 950. + -.10 mbar.
The following two successive stages were carried out, with the test method being the same for each stage:
stage 1 of fouling (or "fouling") with conventional B7 diesel fuel conforming to EN 590. The flow loss evaluated in this first stage case was 80%.
Phase 2 of cleaning (or "purging") with candidate fuel.
At the end of the test, the flow rate of the injector was evaluated again. The flow loss was measured for four injectors. The results are expressed as a percentage loss of flow for different needle lifts. Typical fouling values are compared at 0.1mm needle lift because they are more discriminative and more accurate and repeatable (repeatability < 5%). The change in flow loss before/after the test allows the flow loss to be deduced as a percentage. Due to the reproducibility of this test, significant detergent effects could be confirmed for a reduction in flux loss, i.e., flux gain, of more than 10 points (> 10%).
The results obtained are detailed in table VIII below:
[ Table VIII ]
Composition comprising a metal oxide and a metal oxide
C1
C1+MIX2
Flow loss (%)
59
0
The above results show that the compositions according to the invention bring very good detergency results in terms of cleaning ("scavenging" effect) of the fouled injectors.