FUEL COMPOSITION UNDERSTANDING QUATERNARY AMMONIUM SALT, METHOD OF IMPROVING ENGINE PERFORMANCE, ADD

专利摘要:
the invention relates to the quaternary ammonium salt of formula: where each of r1, r2, r3 and r4 is independently selected from an optionally substituted alkyl, alkenyl or aryl group, with less than 8 carbon atoms and r5 is hydrogen or an optionally substituted hydrocarbyl group.
公开号:BR112017001599B1
申请号:R112017001599-4
申请日:2015-07-28
公开日:2020-10-06
发明作者:Jacqueline Reid；Stephen Leonard Cook
申请人:Innospec Limited；
IPC主号:

专利说明:

[001] The present invention relates to the new quaternary ammonium compounds, to a composition comprising these compounds and to the methods and uses related to them.
[002] In particular, the present invention relates to the use of quaternary ammonium compounds as additives for fuel or lubricant, especially as additives for fuel and, preferably, as additives for diesel fuel.
[003] It is common to include detergent compounds containing nitrogen in the lubricating oil and fuel oil compositions to improve the performance of engines using such compositions. The inclusion of detergent additives prevents clogging of the moving parts of the engine. Without such additives, clogging would cause a decrease in engine performance or it could eventually stop working.
[004] Many different types of quaternary ammonium salts are known in the art for use as detergent additives in fuel and lubricating oil compositions. Examples of such compounds are described in US4171959 and US7951211. A commonly used class of quaternary ammonium additives is prepared by reacting a tertiary amine with an epoxide and an acid. These compounds typically include a quaternized nitrogen atom including at least one hydrophobic group. The hydrophobic group is usually a hydrocarbyl chain with at least 8 carbon atoms. The most commonly used quaternary ammonium salt additives are based on compounds with a hydrocarbyl substitute with a molecular weight of at least 200 and usually equal to at least 500. In fact, many of these compounds include a polyisobutenyl substituent having a weight average molecular weight of 1000 and sometimes higher.
[005] The present inventors have surprisingly found that good deposit control can be achieved by using quaternary ammonium salt additives prepared from low molecular weight amines.
[006] In accordance with a first aspect of the present invention, a quaternary ammonium salt of the formula is provided:
wherein each of R1, R2, R3 and R4 is independently selected from an optionally substituted alkyl, alkenyl or aryl group with less than 8 carbon atoms and R5 is hydrogen or an optionally substituted hydrocarbyl group.
[007] The quaternary ammonium salts of the present invention include the cations of the formula R1R2R3R 4N +, wherein each of R1, R2 R3 and R4 is independently an alkyl, alkenyl or aryl group optionally substituted with less than 8 carbon atoms.
[008] In this specification, unless otherwise stated, reference to optionally substituted alkyl groups may include aryl-substituted alkyl groups, and references to optionally substituted aryl groups may include alkyl-substituted or alkenyl-substituted aryl groups.
[009] R1, R2 R3 and R4 can be the same or different. In some preferred embodiments, R1 and R2 are the same, R3 is different and R4 is different.
Preferably, each of R1 and R2 is independently an optionally substituted alkyl, alkenyl or aryl group, with from 1 to 7 carbon atoms, preferably from 1 to 5 carbon atoms, and more preferably, from 1 to 7 4 carbon atoms.
[0011] Each of R1 and R2 can be optionally substituted with one or more selected groups of halogen (especially chlorine and fluorine), hydroxyl, alkoxy, keto, acyl, cyano, mercapto, alkylimerto, dialkylamino, nitro, nitrous and sulfoxy. The alkyl groups of these substituents can be further substituted.
[0012] Preferably, each of R1 and R2 is, independently, an optionally substituted alkyl or alkenyl group. Preferably, each of R1 and R2 is, independently, an optionally substituted alkyl group. Preferably, each of R1 and R2 is independently an alkyl or alkenyl group optionally substituted with from 1 to 7 carbon atoms, preferably from 1 to 6 carbon atoms, more preferably, from 1 to 5 carbon atoms, suitably, from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms and, more preferably, from 1 to 2 carbon atoms.
[0013] Preferably, R1 is an optionally substituted alkyl or alkenyl group having, preferably, from 1 to 6, preferably from 1 to 4 carbon atoms. Preferably, R1 is an alkyl group. It can be a substituted alkyl group, for example, a hydroxyl substituted alkyl group. Preferably, R1 is an unsubstituted alkyl group or a hydroxyalkyl group. More preferably, R1 is an unsubstituted alkyl group. The alkyl chain can be straight or branched. Preferably, R1 is selected from methyl, ethyl, propyl and butyl, including their isomers. Most preferably, R1 is methyl.
[0014] Preferably, R2 is an optionally substituted alkyl or alkenyl group having, preferably, from 1 to 6, preferably from 1 to 4 carbon atoms. Preferably, R2 is an alkyl group. It can be a substituted alkyl group, for example, a hydroxyl substituted alkyl group. Preferably, R2 is an unsubstituted alkyl group or a hydroxyalkyl group. More preferably, R2 is an unsubstituted alkyl group. The alkyl chain can be straight or branched. Preferably, R2 is selected from methyl, ethyl, propyl and butyl, including their isomers. Most preferably, R2 is methyl.
[0015] In some embodiments, R3 is an alkyl or alkenyl group optionally substituted with 1 to 7 carbon atoms, preferably 1 to 6 carbon atoms, more preferably, 1 to 5 carbon atoms, suitably, 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms and, more preferably, 1 to 2 carbon atoms. Suitable substituents include halogen (especially chlorine and fluorine), hydroxyl, alkoxy, keto, acyl, cyano, mercapto alkylmercapto, amino, alkyl, alkenyl, aryl, dialkylamino, alkylamino, nitro, nitrous, sulfoxy, starch, alkylamido, imido and alkylimido. The alkyl, alkenyl and aryl groups of these substituents can be further substituted.
[0016] Suitably, R3 is an optionally substituted alkyl group. Preferably, R3 is a substituted alkyl group. Preferred substituents include the alkoxy and hydroxyl groups.
[0017] R3 can be selected from an unsubstituted alkyl group and a hydroxyalkyl group. In some preferred embodiments, R3 is an alkyl group substituted with hydroxyl. The alkyl chain can be straight or branched. More preferably, R3 is a hydroxyethyl group.
[0018] Preferably, R4 is an optionally substituted alkyl, alkenyl or aryl group having, preferably, from 1 to 6, and preferably, from 1 to 4 carbon atoms. Preferably, R4 is an optionally substituted alkyl group. More preferably, R4 is a hydroxyl substituted alkyl group. More preferably, R4 is a 2-hydroxyalkyl group. Suitably, R4 is selected from 2-hydroxyethyl, 2-hydroxypropyl and 2-hydroxybutyl. In an especially preferred embodiment, R4 is 2-hydroxybutyl.
[0019] The anion of the quaternary ammonium salts of the present invention is the carboxylate group of formula R5COO-. It is suitably the residue of an acid of formula R5COOH. R5 can comprise one or more additional acid or ester groups. It can be a monoacid, a diacid or a polyacid. It can be a monoester of a diacid or a partial ester of a polyacid. Thus, R5 can be -R’H, -R’COO; - R'COOH, - R'COOR ”or R '(COOR”) n, where each R' is independently an optionally substituted hydrocarbyl group, each R ”can be independently H or an optionally substituted hydrocarbyl group, and n is at least 1.
[0020] R5 can be hydrogen or an optionally substituted hydrocarbyl group.
[0021] As used in the present invention, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its common sense, which is well known to those skilled in the art. Specifically, it refers to a group with a carbon atom directly attached to the rest of the molecule and of a predominantly hydrocarbon character. Examples of hydrocarbyl groups include: (i) hydrocarbon groups, that is, aliphatic substituents (which can be saturated or unsaturated, linear or branched, for example, alkyl or achenyl), alicyclics (for example, cycloalkyl, cycloalkenyl) and aromatic substituents, substituted aliphatics and alicyclics, as well as cyclic substituents, in which the ring is completed by means of another portion of the molecule (for example, two substituents together form a ring); (ii) substituted hydrocarbon groups, that is, substituents containing groups that are not hydrocarbons that, in the context of the present invention, do not alter the predominant hydrocarbon nature of the substituent (eg, halogen (especially chlorine and fluorine), hydroxyl, alkoxy, keto, acyl, cyano, mercapto, alkylmercapto, amino, alkylamino, nitro, nitrous and sulfoxy); (iii) heterosubstitutes, that is, substituents that, despite having a predominantly hydrocarbon character, in the context of the present invention, contain a different carbon atom in a ring or chain composed, in addition, by carbon atoms. Heteroatoms include sulfur, oxygen, nitrogen and include substituents such as pyridyl, furyl, thienyl and imidazolyl. In general, no more than two, and preferably no more than a different hydrocarbon substituent will be present for all ten carbon atoms in the hydrocarbyl group; typically, there will be no substituents other than hydrocarbons in the hydrocarbyl group.
[0022] R5 is preferably selected from hydrogen and an optionally substituted alkyl, alkenyl or aryl group.
[0023] In some embodiments, R5 is an optionally substituted phenol residue. For example, R5 can be a 2-hydroxyphenyl group.
[0024] In one embodiment, R5 is COOR0, where R ° is a C1 to C4 alkyl group. In one embodiment, R5 is a 2- (methylcarboxy) -phenyl group.
[0025] Thus, the R5COO- anion of the quaternary ammonium salt may be the residue of an ester of salicylic acid, oxalic acid or phthalic acid.
[0026] R5 can be hydrogen and the anion is a residue of formic acid. In some embodiments, R5 is a low molecular weight alkyl or alkenyl group, from 1 to 8, preferably from 1 to 6, preferably from 1 to 4, such as 1 or 2 carbon atoms. The alkyl or alkenyl group can be straight or branched.
[0027] The present inventors were very surprised to find that the modalities of the present invention, in which R5 has less than 8 carbon atoms, for example, less than 5 carbon atoms, provided excellent deposit control in modern diesel engines , since common sense would lead the person skilled in the art to believe that a deposit control additive should include a long-chain hydrocarbyl group.
[0028] The R5COO- anion can be the residue of a monoacid, a diacid or a polyacid. It can be the residue of a monoester of a diacid or a partial ester of a polyacid.
[0029] In some embodiments, R5 is an alkyl or alkenyl group Ce to C50 optionally substituted, preferably an alkyl or alkenyl group Ce to C40, more preferably, an alkyl or alkenyl group Cs to C36, preferably an alkyl or alkenyl group Cs to C30, suitably, a C10 to C24 alkyl or alkenyl group. for example, a C10 to C20 alkyl or alkenyl group. The alkyl or alkenyl group can be straight or branched.
[0030] In some embodiments, R5COO- may be the residue of a diacid or a monoester of a diacid, for example, the residue of an optionally substituted phthalic acid or succinic acid derivative. Some preferred species are derived from phthalic acid or succinic acid substituted with hydrocarbyl, where the hydrocarbyl substituent has a molecular weight of 100 to 5000, preferably from 300 to 4000, suitably, from 450 to 2500, for example, from 500 to 2000 or 600 to 1500.
[0031] In some embodiments, R5COO- may be the residue of a polyacid, or a partial ester of a polyacid, for example, the residue of an optionally substituted pyromelitic acid derivative. Some preferred species are derived from hydrocarbyl-substituted pyromelitic acid, where the hydrocarbyl substituent has a molecular weight of 100 to 5000, preferably 300 to 4000, suitably 450 to 2500, for example, 500 to 2000 or 600 to 1500.
[0032] In some embodiments, R5 is CHR11CHR12COOR13, where each of R11, R12 and R13 is hydrogen or an optionally substituted hydrocarbyl group. Preferably, one of R11 and R12 is hydrogen and the other is an optionally substituted hydrocarbyl group. The optionally substituted hydrocarbyl group is preferably a polyisobutenyl group, preferably with a molecular weight of 100 to 5000, preferably from 300 to 4000, suitably, from 450 to 2500, for example, from 500 to 2000 or from 600 to 1500.
[0033] In some modalities, R13 is hydrogen. In some embodiments, R13 is an optionally substituted alkyl group, preferably having from 1 to 20 carbon atoms. Suitably, R13 is an unsubstituted alkyl group, preferably having from 1 to 12 carbon atoms. In one embodiment, R13 is a 2-ethylhexyl group. In another modality, R13 is methyl.
[0034] In an especially preferred embodiment, R5 is methyl. In another especially preferred embodiment, R5 is a C17 alkenyl group.
[0035] The quaternary ammonium compounds of the present invention can be prepared by any suitable method. Such methods are well known to the person skilled in the art.
[0036] Suitably, the quaternary ammonium salts of the present invention are prepared by reacting a tertiary amine of formula R1R2R3N with a quaternizing agent.
[0037] The quaternary ammonium salts of the present invention can be prepared by reacting a tertiary amine with a quaternizing agent selected from dialkyl sulfates, benzyl halides, substituted hydrocarbyl carbonates, alkyl halides, alkyl sulfonates, sultones, substituted hydrocarbyl phosphates, substituted hydrocarbyl borates, alkyl nitrites, alkyl nitrates, hydroxides, N-oxides or mixtures thereof, followed by an anion exchange reaction.
[0038] In the preferred embodiments, the quaternary ammonium salts of the present invention are prepared by reacting a tertiary amine of formula R1R2R3N with a quaternizing agent selected from: (i) an ester of formula R5COOR4; (ii) a carbonate compound of formula R ° OCOOR4 and then a carboxylic acid of formula R5COOH; and (iii) an epoxide with less than 8 carbon atoms and a carboxylic acid of the formula R5COOH; wherein R ° is an optionally substituted hydrocarbyl group.
The present invention, therefore, can provide a method of preparing a quaternary ammonium salt of the first aspect, the method comprising reacting a tertiary amine of formula R1R2R3N with a quaternizing agent selected from: (i) an ester of formula R5COOR4; (ii) a carbonate compound of formula R ° OCOOR4 and then a carboxylic acid of formula R5COOH; and (iii) an epoxide with less than 8 carbon atoms and a carboxylic acid of the formula R5COOH; wherein R ° is an optionally substituted hydrocarbyl group.
[0040] The tertiary amine compounds of formula R1R2R3N preferably do not include any primary or secondary amine groups. In some embodiments, they can be derived from compounds, including these groups, but preferably these later reacted to form additional tertiary amine species. The tertiary amine compound used as component (a) can contain more than one tertiary amine group. Tertiary amine compounds, including primary or secondary amine groups, are within the scope of the invention so long as these groups do not prevent the quaternization of tertiary amine species.
[0041] Preferably, the tertiary amine is an alkylamino and / or hydroxyalkylamino compound of formula R1R2R3N, wherein each of R1, R2 and R3 is an alkyl group or a hydroxyalkyl group. Each of R1, R2 and R3 can be the same or different. Suitably, each of R1, R2 and R3 is independently selected from an alkyl or hydroxyalkyl group having 1 to 6 carbon atoms, for example, 1 to 4 carbon atoms. Each of R1, R2 and R3 can be independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl and hydroxyhexyl. The tertiary amine can be a trialkylamine, a dialkylhydroxyalkylamine, a dihydroxyalkylalkylamine or a trihydroxyalkylamine. There are many different compounds of this type, and these will be known to those skilled in the art.
[0042] Some preferred tertiary amine compounds for use in this document include trimethylamine, N, N-dimethylethylamine, N, N-dimethylpropylamine, N, N-dimethylbutylamine, triethylamine, N, N <liethylmethylamine, N, N-diethylpropylamine, N, N-diethylbutylamine, tripropylamine, N, N-dipropylmethylamine, N, N-dipropylethylamine, N, N-dipropylbutylamine, tributylamine, N, N-dibutylmethylamine, N, N-dibutylethylamine, N, N-dibutylpropylamine, N, N-dimethylmethanolamine , methyldimethanolamine, N, N-dimethylethanolamine, N, N-dimethylpropanolamine, N, N-dimethylpropanolamine, N, N-dimethylbutanolamine, methyldibutanolamine, N, N-diethylmethanolamine, ethyldimethanolamine, N, N-diethylethanolamine, ethyldiethanolamine, N, N-diethylamine , N, N-diethylbutanolamine, ethyldibutanolamine, N, N-dipropylmethanolamine, propyldimethanolamine, N, N-dipropylethanolamine, propyldiethanolamine, N, N-dipropylpropanolamine, propyldipropanolamine, N, N-dipropyl butanol, propyldethanolamine, N, N-dibutylmethanol, N, n-dibutylmethanol anolamine, N, N-dibutylethanolamine, butyldiethanolamine, N, N-dibutylpropanolamine, butyldipropanolamine, N, N-dibutylbutanolamine, butyldibutanolamine, trimethanolamine, triethanolamine, tripropanolamine, tributanolamine and mixtures and isomers thereof.
[0043] Tertiary amine compounds especially preferred for use in this document include N, N-dimethylethanolamine and N, N-dimethylbutylamine.
[0044] In one embodiment, the quaternizing agent is (i) an ester of formula R5COOR4.
[0045] In such embodiments, R4 is a C1-6 alkyl group and R5 is the residue of a carboxylic acid selected from a substituted aromatic carboxylic acid, a-hydroxycarboxylic acid and a polycarboxylic acid.
[0046] Preferred ester quaternization agents are the compounds of formula (X):
where R5 and R4 are as previously defined in this document. The compound of formula (X) is suitably an ester of a carboxylic acid capable of reacting with a tertiary amine to form a quaternary ammonium salt.
Suitable quaternizing agents include esters of carboxylic acids with a pKa of 3.5 or less.
[0048] The compound of formula (X) is preferably an ester of a carboxylic acid selected from a substituted aromatic carboxylic acid, a-hydroxycarboxylic acid and a polycarboxylic acid.
[0049] In some preferred embodiments, the compound of formula (X) is an ester of a substituted aromatic carboxylic acid and therefore R5 is a substituted aryl group.
[0050] Especially preferred compounds of formula (X) are lower alkyl esters of salicylic acid, such as methyl salicylate, ethyl salicylate, n and i-propyl salicylate and butyl salicylate, preferably methyl salicylate.
[0051] In some embodiments, the compound of formula (X) is an ester of a-hydroxycarboxylic acid. In such modalities, the compound has the structure:
where Rx and Ry are the same or different, and each is selected from hydrogen, alkyl, alkenyl or aryl. Compounds of this type suitable for use in that document are described in EP 1254889.
[0052] A preferred compound of this type is methyl 2-hydroxy-isobutyrate.
[0053] In some embodiments, the compound of formula (X) is an ester of a polycarboxylic acid. In this definition, we intend to include dicarboxylic acids and carboxylic acids with more than 2 acidic portions.
[0054] An especially preferred compound of formula (X) is dimethyl oxalate.
[0055] The ester quaternizing agent can be selected from an ester of a carboxylic acid selected from one or more oxalic acid, phthalic acid, tartaric acid, salicylic acid, maleic acid, malonic acid, citric acid, nitrobenzoic acid , aminobenzoic acid and 2,4,6-trihydroxybenzoic acid.
Preferred ester quaternizing agents include dimethyl oxalate, methyl 2-nitrobenzoate, dimethyl phthalate, dimethyl tartrate and methyl salicylate.
[0057] In some embodiments, the quaternary ammonium salts are prepared by reacting a tertiary amine of formula R1R2R3N with (ii) a carbonate of formula RθOCOOR4 and then with a carboxylic acid of formula R5COOH. R4 is as defined above. R ° is preferably an alkyl, alkenyl or aryl group optionally substituted with up to 30 carbon atoms. Preferably, R4 is an optionally substituted alkyl group. Preferably, R ° is an alkyl group with up to 24 carbon atoms, preferably with up to 20 carbon atoms, suitably with up to 16 carbon atoms, preferably up to 12 carbon atoms, suitably up to 8, for example, up to 4 or even 6 carbon atoms.
[0058] Preferably, R ° is an unsubstituted alkyl group. In one embodiment, R ° can be the same or different from R4 Preferably, R ° is equal to R4. Preferred carbonates are dimethyl carbonate and diethyl carbonate. Dimethyl carbonate is especially preferred. Once the tertiary amine reacted with a quaternizing carbonate group, the resulting salt then reacts with a carboxylic acid of formula R5COOH to provide a compound of the first aspect.
[0059] Suitably, the quaternary ammonium salts of the present invention are prepared by reacting a tertiary amine of formula R1R2R3N with an acid-activated alkylating agent and R4 is the residue of the alkylating agent. Suitably, R4 is the residue of an epoxide.
[0060] The present invention suitably provides a quaternary ammonium compound, which is the product of the reaction of: (a) a tertiary amine of formula R1R2R3N; (b) an acid-activated alkylating agent; and (c) a carboxylic acid of the formula R5COOH.
[0061] Component (b) used to prepare the quaternary ammonium compound of the present invention is an acid-activated alkylating agent. The preferred acid-activated alkylating agents are epoxide compounds.
[0062] The present invention suitably provides a quaternary ammonium compound, which is the product of the reaction of: (a) a tertiary amine of formula R1R2R3N; (b) an epoxide; and (c) a carboxylic acid of the formula R5COOH.
[0063] According to a second aspect of the present invention, there is provided a method of preparing a quaternary ammonium salt, the method comprising reacting (a) a tertiary amine of formula R1R2R3N with (b) an acid-activated alkylating agent in presence of (c) a carboxylic acid of formula R5COOH.
[0064] Preferred features of the second aspect of the invention are as defined in relation to the first aspect. Other preferred features of the invention will now be described that apply to the first and second aspects.
[0065] Component (a) is a tertiary amine of formula R1R2R3N, wherein R1, R2 and R3 are as previously defined in the present invention. Thus, in especially preferred embodiments, component (a) is selected from N, N-dimethylethanolamine and N, N-dimethylbutylamine.
[0066] Any suitable epoxy compound with less than 8 carbon atoms can be used as component (b). Suitable epoxide compounds are those of the formula:
where each of R6, R7, R8 and R9 is independently selected from hydrogen or an optionally substituted alkyl, alkenyl or aryl group. At least one of R6, R7, R8 and R9 is hydrogen. Preferably, at least two of R6, R7, R8 and R9 are hydrogen. More preferably, three of R6, R7, R8, and R9 are hydrogen. Most preferably, R6, R7, R8, and R9 can all be hydrogen.
[0067] In the structure above and in the definitions that follow, R6 and R7 are interchangeable and, therefore, when these groups are different, any enantiomer or diastereoisomer can be used as component (b).
[0068] In the structure above and in the definitions that follow, R8 and R9 are interchangeable and, therefore, when these groups are different, any enantiomer or diastereoisomer can be used as component (b).
[0069] Preferably, R6 is hydrogen or an optionally substituted alkyl, alkenyl or aryl group. Most preferably, R6 is hydrogen.
[0070] Preferably, R7 is hydrogen or an optionally substituted alkyl, alkenyl or aryl group. Most preferably, R7 is hydrogen.
[0071] Preferably, R8 is hydrogen or an optionally substituted alkyl, alkenyl or aryl group. Most preferably, R8 is hydrogen.
[0072] Preferably, R9 is hydrogen or an optionally substituted alkyl, alkenyl or aryl group. Preferably, R9 is an alkyl group having 1 to 5 carbon atoms. In some embodiments, R9 may include an oxygen atom in the carbon chain, that is, R9 may include a functional ether group.
[0073] Preferred epoxide compounds for use as component (b) include ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, hexylene oxide and heptylene oxide. These can be supplied as appropriate in any isomeric form or as a mixture of isomers. Glycidyl ether compounds, for example, isopropylglycidyl ether, are also useful.
[0074] Component (c) used to prepare the quaternary ammonium salts of the present invention is a carboxylic acid of formula R5COOH.
[0075] Component (c) includes a carboxylic acid functional group. It can be a very small simple molecule. In some embodiments, component (c) may be a simple fatty acid compound. However, component (c) can also be a more complex molecule, including additional functional acid groups.
[0076] For the avoidance of doubt, component (c) is an acid that activates the alkylating agent (b) and forms the anionic counterion of the quaternary ammonium salt.
[0077] Example of small simple acids suitable for use as component (c) include formic acid, acetic acid, propionic acid and butyric acid.
[0078] Fatty acids suitable for use as component (c) include caprylic acid, capris acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, undecylenic acid and docosahexenoic acid.
[0079] Complex acids suitable for use as component (c) can be optionally substituted phthalic acid and succinic acid.
[0080] In embodiments where component (c) includes more than one functional acid group, additional groups may be present such as the free acid or the ester. Where there is more than one free acid group, there are suitably an equivalent number of cations.
[0081] For example, in the case of diacid components (a), (b) and (c) preferably react at a molar ratio of 2 ± 0.5: 2 ± 0.5: 1; preferably, 2 ± 0.2: 2 ± 0.2: 1, and more preferably, 2 ± 0.1: 2 ± 0.1: 1.
[0082] The quaternary ammonium compounds of the present invention have been found to be effective as deposit control additives for use in fuel or lubricant additives.
[0083] Thus, the present invention provides the use of a quaternary ammonium compound of the first aspect as an additive for fuel or lubricating oil compositions.
[0084] The present invention can provide the use of a quaternary ammonium compound of the first aspect as a deposit control additive for fuel or lubricating oil compositions.
[0085] The present invention can provide the use of a quaternary ammonium compound of the first aspect as a deposit control additive for lubricating oil compositions.
[0086] The present invention can provide the use of a quaternary ammonium compound of the first aspect as a deposit control additive for fuel compositions.
[0087] The present invention can provide the use of a quaternary ammonium compound of the first aspect as a deposit control additive for gasoline or diesel fuel compositions.
[0088] The present invention can provide the use of a quaternary ammonium compound of the first aspect as a deposit control additive for gasoline fuel compositions.
[0089] The present invention can provide the use of a quaternary ammonium compound of the first aspect as a deposit control additive for diesel fuel compositions.
[0090] According to a third aspect of the present invention, an additive composition is provided, comprising a quaternary ammonium salt of the first aspect and a diluent or carrier.
[0091] The additive composition of the third aspect can be an additive composition for lubricating oil.
[0092] The additive composition of the third aspect can be an additive composition for gasoline.
[0093] Preferably, the additive composition of the third aspect is an additive composition for diesel fuel.
[0094] The quaternary ammonium compound is suitably present in the additive composition in an amount of 1 to 99% by weight, for example, from 1 to 75% by weight.
[0095] The additive composition may comprise a mixture of two or more quaternary ammonium compounds of the present invention. In such embodiments, the above amounts suitably refer to the total amount of all these compounds present in the composition.
[0096] The additive composition may include one or more additional additives. These can be selected from antioxidants, dispersants, detergents, metal deactivating compounds, anti-wax sedimentation agents, cold flow improvers, cetane index improvers, water removers, stabilizers, demulsifiers, defoamers, corrosion inhibitors, improvers lubricants, dyes, markers, combustion enhancers, metal deactivators, deodorants, drag reducers and conductivity enhancers.
[0097] In some preferred embodiments, the additive composition includes one or more additional nitrogen-containing detergents.
[0098] The present invention can provide a fuel or lubricating oil composition comprising a quaternary ammonium salt of the first aspect.
[0099] According to a fourth aspect of the present invention, a lubricating composition is provided which comprises a lubricating viscosity oil and, as an additive, a quaternary ammonium salt of the first aspect.
[00100] Preferred characteristics of the quaternary ammonium compound are as defined in relation to the first and second aspects.
[00101] The additive composition of the third aspect appropriately after dilution provides a lubricating composition of the fourth aspect.
[00102] According to a fifth aspect of the present invention, a fuel composition is provided which comprises, as an additive, a quaternary ammonium salt of the first aspect.
[00103] Preferred characteristics of the quaternary ammonium compound are as defined in relation to the first and second aspects.
[00104] The additive composition of the third aspect appropriately after dilution provides a combustible composition of the fifth aspect.
[00105] The additives of the invention can be added to diesel fuel at any convenient location in the supply chain. For example, additives can be added to the fuel at the refinery, at a distribution terminal or after the fuel leaves the distribution terminal. If the additive is added to the fuel after leaving the distribution terminal, this is called an after-sales application. After-sales applications include such circumstances as adding fuel additive to the distribution tank, directly to the customer’s bulk storage tank or directly to the end user’s vehicle reservoir. After-sales applications may include providing the fuel additive in small bottles suitable for direct addition to fuel storage tanks or vehicle tanks.
[00106] The present invention can further provide a method of preparing a combustible composition, the method comprising preparing a quaternary ammonium salt, according to the method of the second aspect, and mixing the quaternary ammonium salt in the fuel.
[00107] The composition of the present invention can be a gasoline composition or a diesel fuel composition. Preferably, it is a diesel fuel composition.
[00108] For diesel fuel we include any fuel suitable for use in a diesel engine, for use on the road or not. This includes, but is not limited to, fuels described as diesel, marine diesel, heavy fuel oil, industrial fuel oil, etc.
[00109] The diesel fuel composition of the present invention can comprise a petroleum-based fuel oil, especially a medium distilled fuel oil. Such distilled fuel oils generally boil in the temperature range of 110 ° C to 500 ° C, for example, from 150 ° C to 400 ° C. Diesel fuel may comprise atmospheric distillate or vacuum distillate, cracked diesel or a mixture, in any proportion, of direct and refinery distillation flows, such as thermally and / or catalytically cracked and hydrocracked distillates.
[00110] The diesel fuel composition of the present invention can comprise non-renewable Fischer-Tropsch fuels, such as those described as GTL (gas-to-liquid), CLT (coal-to-liquid) and OTL (asphalt-to-sand) fuels -liquid).
[00111] The diesel fuel composition of the present invention can comprise a renewable fuel, such as a biofuel composition or biodiesel composition.
[00112] The diesel fuel composition can comprise 1st generation biodiesel. First generation biodiesel contains esters, for example, of vegetable oils, animal fats and used cooking fats. This form of biodiesel can be obtained by transesterifying oils, for example, rapeseed oil, soy oil, safflower oil, palm oil, corn oil, peanut oil, cottonseed oil, tallow, coconut oil, jatropha oil, sunflower seed oil, used cooking oils, hydrogenated vegetable oils or any mixture thereof, with an alcohol, usually a mono-alcohol, and usually in the presence of a catalyst.
[00113] The diesel fuel composition can comprise second generation biodiesel. Second generation biodiesel is derived from renewable sources, such as vegetable oils and animal fats, and processed, often at the refinery, often using hydroprocessing as the H-Bio process developed by Petrobras. Second-generation biodiesel can be similar in properties and quality to petroleum-based fuel oil streams, for example, renewable diesel produced from vegetable oils, animal fats, etc. and marketed by ConocoPhillips as renewable diesel and Neste as NExBTL.
[00114] The diesel fuel composition of the present invention may comprise third generation biodiesel. Third generation biodiesel uses gasification and Fischer-Tropsch technology, including those described as BTL fuels (biomass for liquid). Third generation biodiesel does not differ much from some second generation biodiesels, but aims to explore the entire plant (biomass) and, therefore, expands the base of raw material.
[00115] The diesel fuel composition may contain combinations of any or all of the above diesel fuel compositions.
[00116] In some embodiments, the diesel fuel composition of the present invention may be a blended diesel fuel comprising biodiesel. In such mixtures, biodiesel can be present in an amount, for example, up to 0.5%, up to 1%, up to 2%, up to 3%, up to 4%, up to 5%, up to 10%, up to 20% , up to 30%, up to 40%, up to 50%, up to 60%, up to 70%, up to 80%, up to 90%, up to 95% or up to 99%.
[00117] In some embodiments, the fuel composition may comprise pure biodiesel.
[00118] In some embodiments, the fuel composition may comprise a pure GTL fuel.
[00119] In some embodiments, the diesel fuel composition may comprise a secondary fuel, for example, ethanol. Preferably, however, the diesel fuel composition does not contain ethanol.
[00120] The diesel fuel composition of the present invention may contain a relatively high sulfur content, for example, greater than 0.05% by weight, such as 0.1% or 0.2%.
[00121] However, in preferred embodiments, diesel fuel has a sulfur content of a maximum of 0.05% by weight, more preferably, a maximum of 0.035% by weight, and especially, a maximum of 0.015%. Fuels with even lower levels of sulfur are also suitable, such as fuels with less than 50 ppm of sulfur by weight, preferably with less than 20 ppm, for example, 10 ppm or less.
[00122] Suitably, the quaternary ammonium salt additive is present in the diesel fuel composition in an amount of at least 0.1 ppm, preferably at least 1 ppm, more preferably, at least 5 ppm, suitably at least 10 ppm, for example, at least 20 ppm or at least 25 ppm.
[00123] Suitably, the quaternary ammonium salt additive is present in the diesel fuel composition in an amount less than 10,000 ppm, preferably less than 1000 ppm, preferably less than 500 ppm, preferably less than 250 ppm, suitably less than 200 ppm, for example, less than 150 ppm or less than 100 ppm.
[00124] The diesel fuel composition of the fifth aspect of the present invention may comprise a mixture of two or more quaternary ammonium salts of the first aspect. In such embodiments, the above amounts refer to the total amounts of all of these additives present in the composition.
[00125] The diesel fuel composition of the present invention can include one or more additional additives, such as those that are commonly found in diesel fuels. These include, for example, antioxidants, dispersants, detergents, metal deactivating compounds, anti-wax sedimentation agents, cold flow improvers, cetane index improvers, water removers, stabilizers, demulsifiers, defoamers, corrosion inhibitors, lubrication, dyes, markers, combustion improvers, metal deactivators, deodorants, drag reducers and conductivity enhancers. Examples of suitable amounts of each of these types of additives will be known to the person skilled in the art.
[00126] In some preferred embodiments, the diesel fuel composition of the present invention comprises one or more additional detergents. Nitrogen-containing detergents are preferred.
[00127] The one or more additional detergents can be selected from: (i) an additional quaternary ammonium salt additive that is not a quaternary ammonium compound of the first aspect; (ii) the product of a Mannich reaction between an aldehyde, an amine and an optionally substituted phenol; (iii) the reaction product of an acylating agent derived from carboxylic acid and an amine; (iv) the reaction product of an acylating agent derived from carboxylic acid and hydrazine; (v) a salt formed by the reaction of a carboxylic acid with di-n-butylamine or tri-n-butylamine; (vi) the reaction product of a hydrocarbyl or anhydride substituted dicarboxylic acid and an amine or salt compound, the product of which comprises at least one aminotriazole group; and (vii) a substituted polyaromatic detergent additive.
[00128] In some embodiments, the diesel fuel composition comprises an additional quaternary ammonium salt that is not a quaternary ammonium compound of the first aspect.
[00129] The additional quaternary ammonium salt additive is suitably the product of the reaction of a nitrogen-containing species with at least one tertiary amine group and a quaternizing agent.
[00130] Nitrogen-containing species can be selected from: (x) the reaction product of a hydrocarbyl-substituted acylating agent and a compound comprising at least one tertiary amine group and a primary amine, a secondary amine or an alcohol group ; (y) a product of the Mannich reaction which comprises a tertiary amine group; and (z) a polyalkylene amine substituted with at least one tertiary amine group.
[00131] Examples of quaternary ammonium salt and methods for preparing them are described in the following patents, which are incorporated in that document by reference, US2008 / 0307698, US2008 / 0052985, US2008 / 0113890 and US2013 / 031827.
[00132] Component (x) can be considered as the reaction product of a hydrocarbyl-substituted acylating agent and a compound that has an oxygen or nitrogen atom capable of condensing with said acylating agent, and also having an amine group tertiary. The preferred characteristics of these compounds are as described above with respect to the tertiary amine component (a) used to prepare the quaternary ammonium salt additives of the present invention.
[00133] The preparation of some suitable quaternary ammonium salt additives, in which nitrogen-containing species include component (x), is described in WO 2006/135881 and WO2011 / 095819.
[00134] The component (y) is a product of the Mannich reaction with a tertiary amine. The preparation of quaternary ammonium salts formed from nitrogen-containing species, including component (y), is described in US 2008/0052985. The preferred characteristics of these compounds are as described above with respect to the tertiary amine component (a) used to prepare the quaternary ammonium salt additives of the present invention.
[00135] The preparation of quaternary ammonium salt additives, in which nitrogen-containing species include component (z), is described, for example in US 2008/0113890. The preferred characteristics of these compounds are as described above with respect to the tertiary amine component (a) used to prepare the quaternary ammonium salt additives of the present invention.
[00136] To form the additional quaternary ammonium salt additives (I), nitrogen-containing species with a tertiary amine group react with a quaternizing agent.
[00137] The quaternizing agent can be suitably selected from esters and non-esters.
[00138] In some preferred embodiments, the quaternizing agents used to form the quaternary ammonium salt additives of the present invention are esters.
[00139] Preferred ester quaternizing agents are the compounds of formula (III):
wherein R is an optionally substituted alkyl, alkenyl, aryl or alkylaryl group, and R1 is a C1 to C22 alkyl, aryl or alkylaryl group. The compound of formula (III) is suitably an ester of a carboxylic acid capable of reacting with a tertiary amine to form a quaternary ammonium salt.
Suitable quaternizing agents include esters of carboxylic acids with a pKa equal to 3.5 or less.
[00141] The compound of formula (III) is preferably an ester of a carboxylic acid selected from a substituted aromatic carboxylic acid, a-hydroxycarboxylic acid and a polycarboxylic acid.
[00142] In some preferred embodiments, the compound of formula (III) is an ester of a substituted aromatic carboxylic acid and, therefore, R is a substituted aryl group.
[00143] Especially preferred compounds of formula (III) are lower alkyl esters of salicylic acid, such as methyl salicylate, ethyl salicylate, n and i-propyl salicylate and butyl salicylate, preferably methyl salicylate.
[00144] In some embodiments, the compound of formula (III) is an ester of a-hydroxycarboxylic acid. In such modalities, the compound has the structure:
where R7 and R8 are the same or different, and each is selected from hydrogen, alkyl, alkenyl, aralkyl or aryl. Compounds of this type suitable for use in that document are described in EP 1254889.
[00145] A preferred compound of this type is methyl 2-hydroxy-isobutyrate.
[00146] In some embodiments, the compound of formula (III) is an ester of a polycarboxylic acid. In this definition, it is intended to include dicarboxylic acids and carboxylic acids with more than 2 acidic portions.
[00147] An especially preferred compound of formula (III) is dimethyl oxalate.
[00148] The ester quaternizing agent can be selected from an ester of a carboxylic acid selected from one or more oxalic acid, phthalic acid, tartaric acid, salicylic acid, maleic acid, malonic acid, citric acid, nitrobenzoic acid , aminobenzoic acid and 2,4,6-trihydroxybenzoic acid.
Preferred ester quaternizing agents include dimethyl oxalate, methyl 2-nitrobenzoate, dimethyl phthalate, dimethyl tartrate and methyl salicylate.
[00150] Quaternizing agents that are not suitable esters include dialkyl sulfates, benzyl halides, hydrocarbyl substituted carbonates, hydrocarbyl substituted epoxides in combination with an acid, alkyl halides, alkyl sulfonates, sultones, hydrocarbyl substituted phosphates, borates replaced with hydrocarbyl, alkyl nitrites, alkyl nitrates, hydroxides, N-oxides or mixtures thereof.
[00151] In some embodiments, the quaternary ammonium salt can be prepared from, for example, an alkyl or benzyl halide (especially a chloride) and then subjected to an ion exchange reaction to provide an anion different, as part of the quaternary ammonium salt. Such a method may be suitable for preparing quaternary ammonium hydroxides, alkoxides, nitrites or nitrates.
[00152] Quaternizing agents that are not preferred esters include dialkyl sulfates, benzyl halides, hydrocarbyl substituted carbonates, hydrocarbyl substituted epoxides in combination with an acid, alkyl halides, alkyl sulfonates, sultones, hydrocarbyl substituted phosphates, borates replaced with hydrocarbyl, N-oxides or mixtures thereof.
[00153] Dialkyl sulfates suitable for use in this document, as quaternizing agents, include those including alkyl groups having 1 to 10 carbon atoms in the alkyl chain. A preferred compound is dimethyl sulfate.
[00154] Suitable benzyl halides include chlorides, bromides and iodides. A preferred compound is benzyl bromide.
Suitable hydrocarbyl-substituted carbonates can include two hydrocarbyl groups, which can be the same or different. Preferred compounds of this type include diethyl carbonate and dimethyl carbonate.
[00156] Suitable substituted hydrocarbyl epoxides have the formula:
wherein each of R1, R2, R3 and R4 is, independently, hydrogen or a hydrocarbyl group having from 1 to 50 carbon atoms. Examples of suitable epoxides include ethylene oxide, propylene oxide, butylene oxide, styrene oxide and stilbene oxide. Hydrocarbyl epoxides are used as quaternizing agents in combination with an acid. In such embodiments, the acid is not an acid of the type defined with respect to component (c) used to prepare the quaternary ammonium salts of the present invention.
[00157] In embodiments where the hydrocarbyl-substituted acylating agent has more than one acyl group, and it reacts with the compound of formula (I) or of formula (II) which is a dicarboxylic acylating agent, no separate acid needs to be added. However, in other embodiments, an acid, such as acetic acid, can be used.
[00158] Especially preferred quaternizing epoxide agents are propylene oxide and styrene oxide.
[00159] Suitable sultones include propane sultone and butane sultone.
Suitable hydrocarbyl substituted phosphates include dialkyl phosphates, trialkyl phosphates and O, O-dialkyldithiophosphates.
Suitable hydrocarbyl substituted borate groups include alkyl borates having 1 to 12 carbon atoms.
[00162] Preferred alkyl nitrites and alkyl nitrates have 1 to 12 carbon atoms.
[00163] Preferably, the non-ester quaternizing agent is selected from dialkyl sulfates, benzyl halides, hydrocarbyl substituted carbonates, hydrocarbyl substituted epoxides in combination with an acid and mixtures thereof.
[00164] Quaternizing agents that are not especially preferred esters for use in this document are epoxides substituted with hydrocarbyl, in combination with an acid. These can include modalities in which a separate acid is supplied, or modalities in which the acid is supplied by the tertiary amine compound being quaternized. Preferably, the acid is supplied by the tertiary amine molecule being quaternized.
Preferred quaternizing agents for use in this document include dimethyl oxalate, methyl 2-nitrobenzoate, methyl salicylate and styrene oxide or propylene oxide, optionally, along with an additional acid.
[00166] An additional especially preferred quaternary ammonium salt for use in this document is formed by the reaction of methyl salicylate or dimethyl oxalate with the reaction product of a succinic anhydride substituted with polyisobutylene, having a molecular weight PIB of 700 to 1300 and dimethylaminopropylamine.
[00167] Other suitable additional quaternary ammonium salts include quaternized terpolymers, for example, as described in US2011 / 0258917; quaternized copolymers, for example, as described in US2011 / 0315107; and the acid-free quaternized nitrogen compounds disclosed in US2012 / 0010112.
[00168] In addition, additional quaternary ammonium compounds suitable for use in the present invention include the quaternary ammonium compounds described in the applicant's copending application WO2013 / 017889.
[00169] In some embodiments, the diesel fuel composition comprises the product of a Mannich reaction between an aldehyde, an amine and an optionally substituted phenol. This product of the Mannich reaction is not suitably a quaternary ammonium salt.
[00170] Preferably, the aldehyde component used to prepare the Mannich additive is an aliphatic aldehyde. Preferably, the aldehyde has 1 to 10 carbon atoms. Most preferably, the aldehyde is formaldehyde.
[00171] The amine used to prepare the Mannich additive is preferably a polyamine. It can be selected from any compound, including two or more amino groups. Preferably, the polyamine is a polyalkylene polyamine, preferably a polyethylene polyamine. More preferably, the polyamine comprises tetraethylenepentamine or ethylenediamine.
[00172] The optionally substituted phenol component used to prepare the Mannich additive can be substituted with 0 to 4 groups in the aromatic ring (in addition to the OH phenol). For example, it can be a cresol substituted with hydrocarbyl. More preferably, the phenol component is a monosubstituted phenol. Preferably, it is a hydrocarbyl-substituted phenol. Preferred hydrocarbyl substituents are alkyl substituents with 4 to 28 carbon atoms, especially 10 to 14 carbon atoms. Other preferred hydrocarbyl substituents are polyalkenyl substituents, such as polyisobutenyl substituents with an average molecular weight of 400 to 2500, for example, from 500 to 1500.
[00173] In some embodiments, the diesel fuel composition comprises the reaction product of an acylating agent derived from carboxylic acid and an amine.
[00174] These can also be referred to in this document, in general, as compounds containing acylated nitrogen.
[00175] Suitable acylated nitrogen-containing compounds can be made by reacting a carboxylic acid acylating agent with an amine, and are known to those skilled in the art.
[00176] Preferred acylated nitrogen-containing compounds are replaced with hydrocarbyl. The hydrocarbyl substituent can be in the portion derived from the molecule's carboxylic acid acylating agent or in the amine derived portion of the molecule, or both. Preferably, however, it is in the acylating agent portion. A preferred class of acylated nitrogen-containing compounds suitable for use in the present invention are those formed by reacting an acylating agent with a hydrocarbyl substituent of at least 8 carbon atoms and a compound comprising at least one primary or secondary amine group.
[00177] The acylating agent can be a mono- or polycarboxylic acid (or reactive equivalent thereof), for example, a substituted succinic, phthalic or propionic acid or anhydride.
[00178] The term "hydrocarbyl" is as previously defined in this document. The hydrocarbyl substituent, in such acylating agents, preferably comprises at least 10, more preferably at least 12, for example, at least 30 or at least 40 carbon atoms. It can comprise up to about 200 carbon atoms. Preferably, the hydrocarbyl substituent of the acylating agent has a number of average molecular weight (Mn) between 170 and 2800, for example, from 250 to 1500, preferably from 500 to 1500 and, more preferably, from 500 to 1100. One Mn 700 to 1300 is especially preferred. In a particularly preferred embodiment, the hydrocarbyl substituent has an average molecular weight number of 700 to 850, for example, equal to 750.
[00179] Preferred hydrocarbyl-based substitutes are polyisobutenes. Such compounds are known to the person skilled in the art.
Preferred hydrocarbyl-substituted acylating agents are polyisobutenylsuccinic anhydrides. These compounds are commonly referred to as "PIBSAs" and are known to the person skilled in the art.
[00181] Conventional polyisobutenes and so-called "highly reactive" polyisobutenes are suitable for use in the invention.
Especially preferred PIBSAs are those that have a molecular weight PIB (Mn) of 300 to 2800, preferably from 450 to 2300, and more preferably from 500 to 1300.
[00183] To prepare these additives, the acylating agent derived from carboxylic acid reacts with an amine. Suitably, it reacts with a primary or secondary amine. Examples of suitable amines are known to the person skilled in the art and include polyalkylene polyamines, substituted heterocyclic polyamines and aromatic polyamines.
Preferred amines are polyethylene-polyamines, including ethylenediamine, diethylene triamine, triethylene tetramine, tetraethylenepentamine, pentaethylene-hexamine, hexaethylene-heptamine and mixtures and isomers thereof.
[00185] In preferred embodiments, the reaction product of the acylating agent derived from carboxylic acid and an amine includes at least one primary or secondary amine group.
[00186] A compound containing preferred acylated nitrogen for use in this document is prepared by reacting an acylating agent derived from succinic acid substituted with (poly) isobutene (eg anhydride, acid, ester, etc.) in which the substituent ( poly) isobutene has an average molecular weight (Mn) number of between 170 to 2800 with a mixture of ethylene polyamines having from 2 to about 9 amino nitrogen atoms, preferably about 2 to about 8 nitrogen atoms per ethylene polyamine and about 1 to about 8 ethylene groups. These acylated nitrogen compounds are suitably formed by reacting an acylating agent: amino compound molar ratio from 10: 1 to 1:10, preferably from 5: 1 to 1: 5, more preferably, from 2: 1 to 1 : 2, and more preferably, from 2: 1 to 1: 1. In particularly preferred embodiments, the acylated nitrogen compounds are formed by reacting the acylating agent with the amino compound in a molar ratio of 1.8: 1 to 1: 1.2, preferably 1.6: 1 to 1 : 1.2, more preferably, from 1.4: 1 to 1: 1.1, and more preferably, from 1.2: 1 to 1: 1. Acylated amino compounds of this type and their preparation are well known to those skilled in the art and are described, for example, in EP0565285 and US5925151.
[00187] In some preferred embodiments, the composition comprises a detergent of the type formed by the reaction of an acylating agent derived from succinic acid substituted with polyisobutene and a polyethylene polyamine. Suitable compounds are, for example, described in document W02009 / 040583.
[00188] In some embodiments, the diesel fuel composition comprises the reaction product of an acylating agent derived from carboxylic acid and hydrazine.
[00189] Suitably, the additive comprises the product of the reaction between a hydrocarbyl-substituted succinic acid or anhydride and hydrazine.
Preferably, the hydrocarbyl group of the hydrocarbyl-substituted succinic acid or succinic anhydride comprises a Cs-Cse group, preferably a Cs-Cw group. Alternatively, the hydrocarbyl group can be a polyisobutylene group with an average molecular weight number between 200 and 2500, preferably between 800 and 1200.
[00191] Hydrazine has the formula NH2-NH2. Hydrazine can be hydrated or non-hydrated. Hydrazine monohydrate is preferred.
[00192] The reaction between hydrocarbyl-substituted succinic acid or anhydride and hydrazine produces a variety of products, as disclosed in US 2008/0060259.
[00193] In some embodiments, the diesel fuel composition comprises a salt formed by the reaction of a carboxylic acid with di-n-butylamine or tri-n-butylamine. Exemplary compounds of this type are described in US 2008/0060608.
[00194] Such additives may suitably be the di-n-butylamine or tri-n-butylamine salt of a fatty acid of the formula [R '(COOH) x] y, wherein each R' is, independently, a hydrocarbon group with between 2 and 45 carbon atoms, ex is an integer between 1 and 4.
[00195] In a preferred embodiment, the carboxylic acid comprises pine resin fatty acid (TOFA).
[00196] Other preferred characteristics of additives of this type are described in EP1900795.
[00197] In some embodiments, the diesel fuel composition comprises the reaction product of a hydrocarbyl-substituted dicarboxylic acid or anhydride and an amine or salt compound, the product of which comprises at least one aminotriazole group.
[00198] Additives of this type are suitably the product of the reaction of a dicarboxylic acid or anhydride substituted with hydrocarbyl and an amine compound with the formula:

[00199] where R is selected from the group consisting of a hydrogen and a hydrocarbyl group containing from about 1 to about 15 carbon atoms, and R1 is selected from the group consisting of hydrogen and a hydrocarbyl group containing from about 1 to about 20 carbon atomsThe additive suitably comprises the reaction product of an amine compound, having the formula:
and a hydrocarbilcarbonyl compound of the formula:
wherein R2 is a hydrocarbyl group with an average molecular weight number ranging from about 100 to about 5000, and preferably from 200 to 3000.
[00200] Without wishing to stick to the theory, it is believed that the reaction product of the amine and the hydrocarbilcarbonyl compound is an aminotriazole, as a bis-aminotriazole compound of the formula:
including tautomers with an average molecular weight number in the range of about 200 to about 3000 containing from about 40 to about 80 carbon atoms. The five-membered ring of the triazole is considered aromatic.
[00201] Other preferred characteristics of additive compounds of this type are as defined in document US2009 / 0282731.
[00202] In some embodiments, the diesel fuel composition comprises a substituted polyaromatic detergent additive.
[00203] A preferred compound of this type is the product of the reaction of an ethoxylated naphthol and paraformaldehyde, which then reacts with an acylating agent substituted with hydrocarbyl.
[00204] Other preferred characteristics of these detergents are described in EP1884556.
[00205] In some embodiments, the fuel composition may comprise a fuel composition of gasoline.
[00206] Suitably, the quaternary ammonium salt additive is present in the fuel composition of gasoline in an amount of at least 0.1 ppm, more preferably, at least 1 ppm, more preferably, at least 5 ppm and, suitably of at least 10 ppm, for example, at least 20 ppm or at least 25 ppm.
[00207] Suitably, the quaternary ammonium salt additive is present in the fuel composition of gasoline in an amount less than 10,000 ppm, preferably less than 1000 ppm, preferably less than 500 ppm, preferably less than 250 ppm, suitably less than 200 ppm, for example, less than 150 ppm or less than 100 ppm.
[00208] The gasoline fuel composition of the fifth aspect of the present invention may comprise a mixture of two or more quaternary ammonium salts of the first aspect. In such embodiments, the above amounts refer to the total amounts of all of these additives present in the composition.
[00209] In such embodiments, the composition may comprise one or more gasoline detergents selected from: (y) hydrocarbyl amines or polyoxyalkylene polyethylene substituted; (z) acylated nitrogen compounds which are the reaction product of an acylating agent derived from carboxylic acid and an amine; (aa) hydrocarbyl substituted amines, wherein the hydrocarbyl substituent is substantially aliphatic and contains at least 8 carbon atoms; (bb) Mannich-based additives comprising condensates containing nitrogen from a phenol, aldehyde and primary or secondary amine; (cc) aromatic esters of a polyalkylphenoxycanol; (dd) an additional quaternary ammonium salt additive that is not a quaternary ammonium compound of the first aspect; and (ee) tertiary hydrocarbyl amines with a maximum of 30 carbon atoms.
[00210] Suitable polyoxyalkylene amines substituted with suitable hydrocarbyl or polyetheramines (p) are described in US 6217624 and US 4288612. Other suitable polyetheramines are those taught in US 5089029 and US 5112364.
[00211] The gasoline composition of the present invention may comprise, as an additive, acylated nitrogen compounds (q) which are the reaction product of an acylating agent derived from carboxylic acid and an amine. Such compounds are preferably as previously defined in that document, in relation to component (iii) of the additives that can be added to the diesel fuel compositions of the invention.
[00212] Hydrocarbyl-substituted amines (r) suitable for use in the gasoline fuel compositions of the present invention are well known to those skilled in the art and are described in various patents. Among these are US Patent Nos. 3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,755,433 and 3,822,209. These patents describe hydrocarbyl amines suitable for use in the present invention, including their method of preparation.
[00213] Mannich additives comprise condensates containing nitrogen from a phenol, aldehyde and primary or secondary amine, and are suitably as defined in relation to component (ii) of additives suitable for use in diesel fuel compositions.
[00214] The gasoline compositions of the present invention may further comprise, as additives, (t) the aromatic esters of polyalkylphenoxycancanol.
[00215] The aromatic ester component that may be the additive composition employed is an aromatic ester of a polyalkylphenoxycancanol and has the following general formula:
or soluble / fuel-soluble salt / salts thereof, where R is hydroxyl, nitro or - (CH2) x-NR5R6, where Rs and Re are independently hydrogen or lower alkyl with 1 to 6 carbon atoms and x is 0 or 1;
[00216] Ri is hydrogen, hydroxyl, nitro or -NRzRs, where R and Rs are independently hydrogen or lower alkyl of 1 to 6 carbon atoms;
[00217] R2 θ Ra are independently hydrogen or lower alkyl having from 1 to 6 carbon atoms; and
[00218] R4 is a polyalkyl group with an average molecular weight in the range of about 450 to 5,000.
[00219] Preferred characteristics of these aromatic ester compounds are as described in WO2011141731.
[00220] Additional quaternary ammonium salt additives (u) are suitably as defined in relation to component (i) of additives suitable for use in diesel fuel compositions.
[00221] Tertiary hydrocarbilamines (v) suitable for use in the gasoline fuel compositions of the present invention are tertiary amines of formula R1R2R3N, wherein R1, R2 and R3 are the same or different C1-C20 hydrocarbyl residues, and the total number of carbon atoms is not greater than 30. Suitable examples are N, N-dimethyl-N-dodecylamine, 3- (N, N-dimethylamino) propanol and N, N-di (2-hydroxyethyl) -oleylamine. Preferred characteristics of these tertiary hydrocarbilamines are as described in US2014 / 0123547.
[00222] The gasoline composition may further comprise a base oil.
[00223] The base oil can have any suitable molecular weight. A preferred molecular weight is in the range of 500 to 5000.
[00224] In one embodiment, the carrier oil may comprise a lubricating viscosity oil, including natural or synthetic oils of lubricating viscosity, oil derived from hydrocracking, hydrogenation, hydro-finishing, unrefined, refined and refined oils, or mixtures thereof.
[00225] Natural oils include oils of animal origin, vegetable oils, mineral oils or mixtures thereof. Synthetic oils can include hydrocarbon oils, such as those produced by Fischer-Tropsch reactions, and can usually be hydroisomerized hydrocarbons or Fischer-Tropsch waxes.
[00226] In another embodiment, the base oil may comprise a polyether base oil. In a preferred embodiment, the polyether base oil is a monoprotected end polyalkylene glycol, especially a monoprotected end polypropylene glycol. Such oils and bases will be known to the person skilled in the art.
[00227] The gasoline fuel compositions of the invention may contain one or more additional additives conventionally added to gasoline, for example, other detergents, dispersants, antioxidants, antifreeze agents, metal deactivators, lubricity additives, friction modifiers, oil removers water, corrosion inhibitors, dyes, markers, octane improvers, anti-valve seat recession additives, stabilizers, demulsifiers, defoamers, deodorants, conductivity improvers and combustion enhancers.
[00228] The quaternary ammonium salts of the present invention are useful as deposit control additives for fuel and lubricating oil compositions. It was found that the inclusion of these additives in the fuel compositions reduces the deposits in the engines in which the fuel is burned. This can be achieved by preventing or reducing the formation of deposits, that is, keeping the engine clean, or it can be by removing existing deposits, that is, cleaning a clogged engine.
[00229] The quaternary ammonium compounds of the present invention have been found to be particularly effective in diesel engines, especially in modern diesel engines with a high pressure fuel system.
[00230] Due to consumer demand and legislation, diesel engines, in recent years, have become much more energy efficient, have an improved performance and have reduced emissions.
[00231] These improvements in performance and emissions were brought about by improvements in the combustion process. To achieve the fuel atomization required for this improved combustion, fuel injection equipment has been developed that uses higher injection pressures and reduced fuel injector nozzle diameters. The fuel pressure at the injection nozzle is currently greater than 1500 bar (1.5 x 108 Pa). To achieve these pressures, the work that must be done with the fuel also increases the temperature of the fuel. These high pressures and temperatures can cause fuel degradation. In addition, timing, quantity and control of fuel injection have become increasingly accurate. This accurate fuel measurement must be maintained to achieve optimal performance.
[00232] Diesel engines with high pressure fuel systems may include, but are not limited to, heavy-duty diesel engines and smaller passenger vehicle-type diesel engines. Heavy-duty diesel engines can include very powerful engines, such as the 4000 MTU diesel series with 20-cylinder variants, designed primarily for ships and power generation, with output power up to 4300 kW, or engines like the Renault dXi 7 , with 6 cylinders and output power of about 240 kW. A typical passenger car diesel engine is Peugeot's DW10, with 4 cylinders and output power of 100 kW or less, depending on the variant.
[00233] In preferred diesel engines related to this invention, a common feature is a high pressure fuel system. Typically, pressures greater than 1350 bar (1.35 x 108 Pa) are used, but often pressures of up to 2000 bar (2 x 108 Pa) or more may exist.
[00234] Two non-limiting examples of such high pressure fuel systems are: the common rail injection system, in which the fuel is compressed using a high pressure pump that supplies it to the fuel injection valves via a common rail; and the unit injection system, which integrates the high pressure pump and the fuel injection valve in one assembly, reaching the highest possible injection pressures in excess of 2000 bar (2 x 108 Pa). In both systems, when the fuel is pressurized, the fuel gets hotter, often at temperatures of around 100 ° C, or higher.
[00235] In common rail systems, fuel is stored under high pressure on the central accumulator rail or in separate accumulators, before being supplied to the injectors. Often, some of the heated fuel is returned to the low pressure side of the fuel system or back to the fuel tank. In unit injection systems, fuel is compressed within the injector to generate high injection pressures. This, in turn, increases the temperature of the fuel.
[00236] In both systems, fuel is present in the injector body before injection, where it is additionally heated due to the heat of the combustion chamber. The fuel temperature at the tip of the injector can be as high as 250 to 350 ° C.
[00237] Thus, the fuel is forced at pressures of 1350 bar (1.35 x 108 Pa) up to more than 2000 bar (2 x 108 Pa) and at temperatures of about 100 ° C to 350 ° C before injection, sometimes recirculating within the fuel system, thus increasing the time for the fuel to experience these conditions.
[00238] A common problem with diesel engines is the clogging of the injector, particularly the injector body and the nozzle. Clogging can also occur in the fuel filter. Nozzle clogging occurs when the nozzle is blocked with diesel fuel tanks. The clogging of the fuel filters may be related to the recirculation of the fuel back into the fuel tank. Deposits increase with fuel degradation. The deposits may take the form of coke-like carbonaceous residues, lacquers or sticky or gum-like residues. Diesel fuels become increasingly unstable the more they are heated, particularly if heated under pressure. Thus, diesel engines with high pressure fuel systems can cause increased fuel degradation. In recent years, the need to reduce emissions has led to the continuous redesign of injection systems to help meet lower targets. This has led to increasingly complex injectors and low deposit tolerance.
[00239] The injector clogging problem can occur when using any type of diesel fuel. However, some fuels may be particularly likely to cause clogging, or clogging may occur more quickly when these fuels are used. For example, fuels containing biodiesel and those containing metallic species can lead to increased deposits.
[00240] When the injectors are blocked or partially blocked, the fuel release is less efficient and there is a bad mixture of the fuel with the air. Over time, this leads to a loss of engine power, increased exhaust emissions and poor fuel economy.
[00241] It is known that deposits occur in the spray channels of the injector, leading to reduced flow and loss of power. As the injector nozzle hole size is reduced, the relative impact of deposit build-up becomes more significant. Deposits are also known to occur at the tip of the injector. Here, they affect the fuel spray pattern and cause less effective combustion and associated higher emissions, and higher fuel consumption.
[00242] In addition to these "external" injector deposits in the nozzle bore and in the injector tip, which lead to reduced flow and loss of power, deposits can occur inside the injector body, causing more problems. These deposits can be referred to as internal diesel injector deposits (or IDIDs). IDIDs occur within the gun at critical moving parts. They can make it difficult to move these parts that affect timing and the amount of fuel injection. As modern diesel engines operate under very precise conditions, these deposits can have a significant impact on performance.
[00243] IDIDs cause a number of problems, including loss of power and reduced fuel economy due to sub-optimal fuel measurement and combustion. Initially, the user may experience cold start problems and / or difficult engine operation. These deposits can lead to more serious adherence of the injector. This occurs when deposits prevent parts of the injector from moving and the injector stops working. When several or all of the injectors stick, the engine can fail completely.
[00244] The addition of detergents containing nitrogen to diesel fuel to reduce coking is known. Typical nitrogen-containing detergents include those formed by reacting a polyisobutylene-substituted succinic acid derivative with a polyalkylene polyamine. However, new engines including thinner nozzles are more sensitive and current diesel fuels may not be suitable for use with new engines incorporating these smaller nozzle holes.
[00245] As mentioned above, the injector clogging problem may be more likely to occur when fuel compositions comprising metal species are used. Several species of metal can be present in the fuel compositions. This may be due to contamination of the fuel during manufacture, storage, transportation or use, or due to contamination of the fuel additives. Metal species can also be added to fuels deliberately. For example, transition metals are sometimes added as fuel-operated catalysts, for example, to improve the performance of diesel particulate filters.
[00246] The present inventors believe that problems with adhesion to the injector occur when metal or ammonium species, particularly sodium species, react with carboxylic acid species in the fuel.
[00247] It is believed that the contamination with sodium of the diesel fuel and the resulting formation of carboxylate salts are one of the main causes of adhesion in the injector.
[00248] In preferred embodiments, the diesel fuel compositions used in the present invention comprise sodium and / or calcium. Preferably, they comprise sodium. Sodium and / or calcium is typically present in a total amount of 0.01 to 50 ppm, preferably from 0.05 to 5 ppm, preferably from 0.1 to 2 ppm, as from 0.1 to 1 ppm .
[00249] Other species containing metal may also be present as a contaminant, for example, through the corrosion of the metal and metal oxide surfaces by acidic species present in the fuel or lubricating oil. In use, fuels such as diesel fuels routinely come into contact with metal surfaces, for example, in vehicle filling systems, in fuel tanks, in means of transporting fuel, etc. Typically, metal-containing contamination may comprise transition metals, such as zinc, iron and copper; group I or group II metals and other metals, such as lead.
[00250] The presence of species containing metal can give rise to fuel filter deposits and / or external injector deposits, including injector tip deposits and / or nozzle deposits.
[00251] In addition to the metal-containing contamination, which may be present in diesel fuels, there are circumstances where species containing metal may be deliberately added to the fuel. For example, as is known in the art, fuel-operated catalyst species containing metal can be added to assist with the regeneration of particulate collectors. The presence of such catalysts can also give rise to deposits in the injector, when fuels are used in diesel engines with high pressure fuel systems.
[00252] The contamination containing metal, depending on its origin, can be in the form of insoluble particles or soluble compounds, or complexes. Fuel-operated catalysts containing metal are often soluble or complex compounds or colloidal species.
[00253] In some embodiments, diesel fuel may comprise metal-containing species comprising a fuel-operated catalyst. Preferably, the fuel operated catalyst comprises one or more metals selected from iron, cerium, platinum and manganese, and metals from group I and group II, for example, calcium and strontium. Most preferably, the fuel operated catalyst comprises a metal selected from iron and cerium.
[00254] In some embodiments, diesel fuel may comprise species containing metal including zinc. Zinc can be present in an amount of 0.01 to 50 ppm, preferably from 0.05 to 5 ppm, and more preferably, from 0.1 to 1.5 ppm.
[00255] Typically, the total amount of all species containing metal in diesel fuel, expressed in terms of the total weight of metal in the species, varies between 0.1 and 50 ppm by weight, for example, between 0.1 and 20 ppm , preferably between 0.1 and 10 ppm by weight, based on the weight of the diesel fuel.
[00256] It is advantageous to provide a diesel fuel composition that prevents or reduces the occurrence of deposits in a diesel engine. Such deposits may include "external" injector deposits, such as deposits in and around the nozzle bore and at the injector tip and "internal" injector deposits or IDIDs. Such combustible compositions can be considered to have a "keep clean" function, that is, they prevent or inhibit clogging. It is also desirable to provide a diesel fuel composition that could help to clean deposits of these types. Such fuel composition, when burned in a diesel engine, removes deposits from it, thus “cleaning” an already clogged engine.
[00257] As with the “keep clean” properties, the “cleaning” of a clogged engine can provide significant advantages. For example, superior cleaning can lead to an increase in power and / or an increase in fuel economy. In addition, the removal of deposits from an engine, in particular injectors, can lead to an increase in downtime before maintenance or injector replacement is required, thereby reducing maintenance costs.
[00258] Although for the reasons mentioned above injector deposits are a particular problem found in modern diesel engines, with high pressure fuel systems, it is desirable to provide a diesel fuel composition that also provides effective detergency in older traditional diesel engines , so that a single fuel supplied to the pumps can be used in engines of all types.
[00259] It is also desirable that the fuel compositions reduce the clogging of the vehicle's fuel filters. It is useful to provide compositions that prevent or inhibit the occurrence of fuel filter deposits, that is, that provide a “keep clean” function. It is useful to provide compositions that remove existing deposits from fuel filter deposits, that is, that provide a "cleaning" function. Compositions capable of providing both functions are especially useful.
[00260] In accordance with a sixth aspect of the present invention, there is provided a method of improving the performance of an engine, the method comprising burning, in said engine, a combustible composition comprising, as an additive, a quaternary ammonium salt of formula:
wherein each of R1, R2, R3 and R4 is independently selected from an optionally substituted alkyl, alkenyl or aryl group with less than 8 carbon atoms and R5 is hydrogen or an optionally substituted hydrocarbyl group.
[00261] Preferential characteristics of the sixth aspect of the invention are as defined in relation to the first, second, third and fifth aspects.
[00262] In the fifth aspect method, the engine can be a gasoline engine and the fuel composition can be a gasoline fuel.
[00263] Preferably, in the method of the fourth aspect, the engine is a diesel engine and the fuel composition is a diesel fuel composition.
[00264] The method of the fourth aspect of the present invention is particularly effective in improving the performance of a modern diesel engine, having a high pressure fuel system.
[00265] Such diesel engines can be characterized in different ways.
[00266] Such engines are typically equipped with fuel injection equipment, meeting or exceeding "emissions legislation 5" or equivalent legislation in the US or other countries.
[00267] These engines are usually equipped with fuel injectors having a plurality of openings, with each opening having an inlet and an outlet.
[00268] Such motors can be characterized by openings that are tapered, so that the diameter of the spray holes is larger than the diameter of the socket.
[00269] Such modern engines can be characterized by openings with an outlet diameter of less than 500 pm, preferably less than 200 pm, more preferably less than 150 pm, preferably less than 100 pm, and more preferably less than 80 pm or any less.
[00270] Such modern diesel engines can be characterized by openings where an inner edge of the inlet is rounded.
[00271] Such modern diesel engines can be characterized by the injector having more than one opening, suitably more than 2 openings, preferably more than 4 openings, for example, 6 or more openings.
[00272] Such modern diesel engines can be characterized by a maximum operating temperature above 250 ° C.
[00273] Such modern diesel engines can be characterized by a fuel injection system that provides a fuel pressure greater than 1350 bar, preferably greater than 1500, and more preferably, greater than 2000 bar. Preferably, the diesel engine has a fuel injection system that comprises a common rail injection system.
[00274] The method of the present invention preferably improves the performance of an engine with one or more of the characteristics described above.
[00275] The method of the present invention improves the performance of an engine. This performance improvement is achieved properly by reducing deposits on the engine.
[00276] The present invention, therefore, can provide a method of combating deposits in an engine which comprises combustion in said engine of a fuel composition of the fourth aspect.
[00277] The sixth aspect of the present invention relates to a method of combating deposits in an engine, preferably a diesel engine. Combating deposits may involve reducing or preventing the formation of deposits on an engine compared to operating the engine using unaddited fuel. This method can be considered to achieve "keep clean" performance.
[00278] Combating deposits may involve removing existing deposits on an engine. This can be considered as achieving "cleaning" performance.
[00279] In especially preferred embodiments, the method of the sixth aspect of the present invention can be used to provide "keep clean" and "clean" performance.
[00280] As explained above, deposits can occur in different locations within a diesel engine, for example, in a modern diesel engine.
[00281] The present invention is particularly useful in preventing, reducing or removing internal deposits in engine injectors operating at high pressures and temperatures, in which the fuel can be recirculated and which comprises a plurality of fine openings through which the fuel is released to the engine. The present invention finds utility in engines for heavy vehicles and passenger vehicles. Passenger vehicles that incorporate a high-speed direct injection engine (HSDI) can, for example, benefit from the present invention.
[00282] The present invention can also provide better performance in modern diesel engines having a high pressure fuel system, through the control of external injector deposits, for example, those that occur at the injector nozzle and / or at the injector tip . The ability to provide control of internal injector deposits and external injector deposits is a useful advantage of the present invention.
[00283] Suitably, the present invention can reduce or prevent the formation of external injector deposits. It can therefore provide "keep clean" performance against external injector deposits.
[00284] Suitably the present invention can reduce or remove deposits from external injector. It can therefore provide "cleaning" performance in relation to external injector deposits.
[00285] Properly, the present invention can reduce or prevent the formation of internal deposits from the diesel injector. It can therefore provide "keep clean" performance in relation to the diesel injector's internal deposits.
[00286] Suitably, the present invention can reduce or remove the existing deposits of the existing diesel injector. It can therefore provide "cleaning" performance in relation to the diesel injector's internal deposits.
[00287] The present invention can also combat deposits on vehicle fuel filters. This may include reducing or avoiding the formation of deposits ("keeping clean" performance) or reducing or removing existing deposits ("cleaning" performance).
[00288] The diesel fuel compositions of the present invention can also provide better performance when used with traditional diesel engines. Preferably, improved performance is achieved when using diesel fuel compositions in modern diesel engines with high pressure fuel systems and when using compositions in traditional diesel engines. This is important because it allows a single fuel to be supplied, which can be used in new engines and older vehicles.
[00289] The removal or reduction of IDIDs, according to the present invention, will lead to an improvement in the performance of the engine.
[00290] The improvement in the performance of the diesel engine system can be measured in several ways. Appropriate methods will depend on the type of engine and whether the performance of "keeping clean" and / or "cleaning" is measured.
[00291] An improvement in the performance of "keeping clean" can be measured by comparison with a base fuel. The "cleaning" performance can be seen by an improvement in the performance of an already clogged engine.
[00292] The effectiveness of fuel additives is often assessed using a controlled engine test.
[00293] In Europe, the European Coordinating Council for the development of performance tests for transport fuels, lubricants and other fluids (the body of the industry known as CEC), has developed a test for additives for modern diesel engines, such as HSDI engines. The CEC F-98-08 test is used to assess whether diesel fuel is suitable for use in engines that meet the new European Union emission regulations, known as the "Euro 5" regulations. The test is based on a Peugeot DW10 engine, using Euro 5 injectors, and is commonly referred to as the DW10 test. This test measures the loss of power in the engine due to deposits on the injectors, and is further described in example 7.
[00294] Preferably, the use of the fuel composition of the present invention leads to reduced deposits in the DW10 test. For the performance of "keeping clean" a reduction in the occurrence of deposits is preferably observed.
[00295] For the "cleaning" performance, the removal of deposits is preferably observed. The DW10 test is used to measure the power loss in modern diesel engines with a high pressure fuel system.
[00296] Suitably, the use of a fuel composition of the present invention can provide "keep clean" performance in modern diesel engines, that is, the formation of deposits on the injectors of these engines can be inhibited or prevented. Preferably, this performance is such that a power loss of less than less than 5%, preferably less than 2%, is observed after 32 hours, as measured by the DW10 test.
[00297] In some embodiments, the present invention can provide a power gain. Suitably, when burning a fuel composition according to the present invention, a power gain in the DW10 test is observed compared to the burning of a non-additive base fuel and with clean injectors. Suitably, a power gain of at least 0.5%, preferably at least 1%, is achieved within 4 hours, and preferably, within 2 hours. Details of the methods used to measure the power gain are described in example 8.
[00298] Suitably, the use of a fuel composition of the present invention can provide "cleaning" performance in modern diesel engines, that is, deposits on the injectors of an already clogged engine can be removed. Preferably, this performance is such that the power of a clogged engine can return to within 1% of the level achieved when using clean injectors within 16 hours, preferably 12 hours, and more preferably, 8 hours, as measured in the test DW10.
[00299] Preferably, a quick "cleaning" can be achieved in which the power returns to within 1% of the level observed using clean injectors within 4 hours, preferably within 2 hours.
[00300] In some preferred modes, cleaning can also provide an increase in power. Thus, a clogged engine can be treated to remove existing deposits and provide additional energy gain.
[00301] Clean injectors can include new injectors or injectors that have been removed and physically cleaned, for example, in an ultrasound bath.
[00302] According to a seventh aspect of the present invention, there is the use of an additive in a fuel composition to improve the performance of an engine that burns said fuel composition, in which the additive is a quaternary ammonium salt of the formula:
wherein each of R1, R2, R3 and R4 is independently selected from an optionally substituted alkyl, alkenyl or aryl group with less than 8 carbon atoms and R5 is hydrogen or an optionally substituted hydrocarbyl group.
[00303] Preferred features of the seventh aspect of the present invention are as defined in relation to the first, second, third and fifth aspects, and especially as defined in relation to the sixth aspect.
[00304] The invention will now be further described with reference to the following non-limiting examples. In the following examples, the values given in parts per million (ppm) to refer to the rates denote the amount of active agent, not the amount of a formulation as added, and containing an active agent. All parts per million are by weight. Example 1 Additive A1 was prepared as follows: 65 g of a polyisobutyl substituted succinic acid, with an average polyisobutene molecular weight of 1000 (PIBWOOSAcid), was dissolved in 50 ml of toluene in a reactor flask of 250 ml Radley. Six equivalents of water were added, followed by two equivalents of dimethylethanolamine and two equivalents of epoxybutane. The reaction was heated to 60 ° C. After 6 hours, an equivalent of more than epoxybutane was added. After another 6 hours, the volatile compounds were removed in a rotary evaporator and the product was swollen to form a 50% w / w solution of Shellsol A150. Example 2 Additive A2 was prepared as follows: 48 g of oleic acid was mixed with 50 ml of toluene in a 250 ml bottle of the Radley reactor. Six equivalents of water were added, followed by an equivalent of dimethylethanolamine and epoxybutane. The reaction was heated to 60 ° C. After 6 hours, an equivalent of more than epoxybutane was added. After another 6 hours, the volatile compounds were removed in a rotary evaporator and the product was swollen to form a 50% w / w solution of Shellsol A150. Example 3 Additive A3 was prepared as follows: 41 g of dodecenylsuccinic acid was dissolved in 50 ml of toluene in a 250 ml bottle of the Radley reactor. Six equivalents of water were added, followed by two equivalents of dimethylbutylamine and two equivalents of epoxybutane. The reaction was heated to 60 ° C. After 6 hours, an equivalent of more than epoxybutane was added. After another 6 hours, the volatile compounds were removed in a rotary evaporator and the product was swollen to form a 50% w / w solution of Shellsol A150. Example 4 Additive A4 was prepared as follows: 22 g of acetic acid was mixed with 50 ml of toluene in a 250 ml Radley reactor flask. Six equivalents of water were added, followed by an equivalent of dimethylethanolamine and an equivalent of epoxybutane. The reaction was heated to 60 ° C. After 6 hours, an equivalent of more than epoxybutane was added. After another 6 hours, the volatile compounds were removed in a rotary evaporator and the product was swollen to form a 50% w / w solution of 2-ethylhexanol. Example 5 Additive A5 was prepared as follows: With FTIR monitoring, a technical grade oleic acid sample (Fisher, 15.31 g) was mixed with isopropylglycidyl ether (6.36 g) by magnetic stirring before adding water (3.90 g) and, finally, with N, N-dimethylethanolamine (14.45 g). The addition of Amine was accompanied by an increase in temperature from 21 to 30 ° C, controlled by the increase of an oil bath to room temperature around the flask. After the initial exotherm subsided, the oil bath heater was turned on and adjusted to provide 100 ° C. After three hours at an internal temperature of 94 to 95 ° C, the reaction was considered, by FTIR, as completed. The reaction mass was transferred to an extraction funnel and extracted in a rotary evaporator at 100 ° C and 9 mBar. The mass balances were consistent with the formation of the desired 2-hydroxy-N- (2-hydroxyethyl) -3-isopropoxy-N, N-dimethylpropan-1-amine salt. A residual amount of ester was evident in the IR spectra. Example 6 Diesel fuel compositions were prepared comprising the additives listed in table 1, added in aliquots that were all taken from a common batch of base fuel RF06 and containing 1 ppm zinc (as zinc neodecanoate). Table 1

Table 2 below shows the specification for the RF06 base fuel. Table 2

Example 7 The fuel compositions 1 to 4 listed in table 1 were tested according to method CECF-98-08 DW 10. The injector clogging test engine is the PSA DW10BTED4. In summary, the engine features are: Design: Four cylinders in line, with overhead meat shaft, turbocharged with EGR Capacity: 1998 cm3 Combustion chamber: Four valves, bowl on the piston, direct injection guided by the wall Power: 100 kW a 4000 rpm Torque: 320 Nm at 2000 rpm Injection system: Common rail with 6 piezoelectronically controlled injectors. Maximum pressure: 1600 bar (1.6 x 108 Pa). Proprietary SIEMENS VDO design Emission control: In accordance with Euro IV limit values when combined with the exhaust gas after-treatment (DPF) system This engine was chosen as a representative design of the high-pressure direct injection diesel engine modern European speed capable of meeting current and future European emissions requirements. The common rail injection system uses a highly efficient nozzle design with rounded inlet edges and tapered spray holes for optimal hydraulic flow. This type of nozzle, when combined with high fuel pressure, has shown advances to be achieved in terms of combustion efficiency, noise reduction and reduced fuel consumption, but are sensitive to influences that can disrupt fuel flow, such as formation deposits in the spray holes. The presence of these deposits causes a significant loss of engine power and an increase in gross emissions. The test is performed with a future injector design representative of the anticipated Euro V injector technology. It is considered necessary to establish a reliable baseline of the injector condition before starting clogging tests, and thus, a sixteen hour operating schedule for the test injectors is specified, using non-fouling reference fuel. Additional details of the CEC F-98-08 test method can be obtained from the CEC. The coking cycle is summarized below. 1. A heating cycle (12 minutes), according to the following regime:
2. 8 hours of engine operation, consisting of 8 repetitions of the next cycle

for the expected range see method CEC CEC-F 98-08. 3. Cool until idle in 60 seconds and inactive for 10 seconds 4. immersion period of 4 h The standard test method CEC F-98-08 consists of 32 hours of engine operation corresponding to 4 repetitions of steps 1 to 3 above and 3 repetitions of step 4, that is, a total test time of 56 hours, excluding warming and cooling. Figure 1 shows the results of the DW10 test for compositions 1 and 3. Figure 2 shows the results of the DW10 test for compositions 2 and 4. Example 8 Due to the surprising apparent increase in the power observed when using the additives of the invention , an additional modified DW10 test was performed. An initial base fuel test in an independent laboratory, with the base fuel RF-06, comprising 1 ppm zinc, showed a power loss of 8.27% during the 32 hour test. When, in the same installation, additive A2 was tested at a treatment rate of 50 ppm of active compound in the same fuel, comprising 1 ppm of zinc, it showed an increase in power equal to 3.21%. The increase in power appeared shortly after the start of the test, with a 2.1% increase registered after one hour. This level of increased power in this test is surprising. The test of the reference fuel RF-06, without zinc or additive, does not provide any loss of energy, but also, does not provide any increase in power, during the entire 32 h test. To verify the increase in power found with the A2 additive, another test was configured on a different DW10 engine in a second independent laboratory. This test was performed only for 10 hours, but this was long enough to observe a 3.7% increase in power and, again, the increase in power was observed in the first few hours. In a subsequent test, in the second laboratory, the DW10 CEC F-098-08 engine test was performed on the base reference fuel RF-06-03 (ie, without added Zn) containing 50 ppm of additive A2 made according to example 2. Power increased in the first hour before leveling with a 1.8% gain. After 16 hours, the fuel was changed to non-additive base fuel RF-06. A power difference between the two otherwise identical fuels was immediately obvious, with the second fuel, after 16 hours of operation, providing an increase of just 0.9% and, compared to the initial pre-test checks. Finally, the injectors were removed and cleaned (as usual between tests), and when returning to the engine and during an 8-hour test, the output power was indistinguishable from that of the previous 16 hours. Example 9 The additive A6 was prepared as a 50% w / w solution in 2-ethylhexanol, as follows: 7.0 g of a polyisobutyl substituted succinic acid, with an average polyisobutene molecular weight of 1000 (PIBWOOSAcid), was dissolved in 10.82 ml of 2-ethylhexan-1-ol in a boiling tube. Two equivalents of dimethylethanolamine and two equivalents of 1,2-epoxybutane were added, and the reaction was heated to 95 ° C for 6 hours. The product was confirmed using FTIR spectra. Example 10 Additional compounds of the invention were prepared using a method analogous to example 9, except that the acid was replaced with an equivalent amount of:
Example 11 Additive A10 was prepared using a method analogous to example 1, except that the acid was replaced with an equivalent amount of a mixture of dimerized fatty acids. Example 12 Additional compounds of the invention were prepared using a method analogous to example 9, except that the acid was replaced with an equivalent amount of:
Example 13 The additive A20, Bis- (N, N, N-triethyl-N-methylammonium) octadecenyl succinate was prepared as follows: Triethylamine (2.779 g, 27.2 mMol), dimethyl carbonate (9.507 g, 106 mMol ) and methanol (12.5 cm3) were placed in a tube and heated, with stirring, for three hours at 130 ° C, under autogenous pressure. The formation of a methyl carbonate salt was confirmed by FTIR (characteristic absorbance at 1651 cm-1). The tube material was transferred to a round bottom flask and reacted with a single equivalent (acid number base, 0.5 molar equivalent) of octadecenylsuccinic acid, as set out above. Significant levels of foaming were observed in the removal of volatile compounds in the rotary evaporator. A product with the expected characteristic FTIR absorbances (1574 and cm-1) was obtained with a good mass balance and was resuspended in a 50% solution by weight of 2-ethylhexanol. Example 14 Additive A22, N, N, N-trimethyl-2-hydroxyethylammonium oleate, was prepared as follows N, N-dimethylethanolamine (2.456 g, 27.6 mMol), dimethyl carbonate (9.95 g, 110 mMol) and methanol (12 cm3) were placed in a tube and heated to 130 ° C for 75 minutes. The FTIR spectrum of the reaction mixture showed an absorbance at 1644 cm-1, characteristic of methyl carbonate salts. The reaction product additionally reacted with oleic acid (7.844 g, 27.8 mMol), releasing gases over a few minutes, while forming a clear solution. The absorbance attributed to methyl carbonate was almost completely removed and replaced by clear characteristics in 1575 and 1386 cm-1, specific to the carboxylate salts. The reaction mixture was extracted in the rotary evaporator, forming a viscous brown oil. The oil was dissolved in Shellsol A150 (50% by weight) Example 15 105 ppm of each of the compound additives listed in table A was added to the base fuel RF06. Each of the prepared fuel compositions was tested using jet fuel thermal oxidation test equipment (JFTOT). In this test, 800 mL of fuel flowed into an aluminum tube heated to 260 ° C at a pressure of approximately 540 psi (3.72 x106 Pa). The test duration is 2.5 hours. At the end of the test, the aluminum tube is removed and the thickness of the tank is compared to that of the base fuel. Table A
These results show that the additives of the present invention can lead to reduced deposits. Example 16 The effectiveness of the fuel compositions of the present invention on the old engine was assessed using an industry standard test - test method CEC No. CEC F-23-A-01. This test measures the nozzle coking using a Peugeot XUD9 A / L engine and provides a means of discriminating between fuels of different propensity to coking the nozzle. Nozzle coking is the result of carbon deposits that form between the injector nozzle and the needle fitting. The deposition of the carbon deposit occurs due to the exposure of the needle and the injector fitting to the combustion gases, potentially causing undesirable variations in engine performance. The Peugeot XUD9 A / L engine is a 4-cylinder indirect injection diesel engine with 1.9 liter expulsion volume, obtained from Peugeot Citroen Motors, specifically for the CEC method PF023. The test engine is equipped with clean injectors using unblocked injector needles. The air flow at different needle elevation positions was measured on a flow platform before the test. The engine is operated for a period of 10 hours under cyclical conditions.
The propensity of the fuel to promote the formation of deposit on the fuel injectors is determined by measuring the air flow from the nozzle again at the end of the test, and comparing these values with the values before the test. The results are expressed in terms of the percentage of airflow reduction at different needle elevation positions for all nozzles. The average value of the reduction of air flow in the elevation of the 0.1 mm needle of all four nozzles is considered as the injector coking level for a given fuel. A fuel additive formulation containing Additive A2 of Example 2, along with solvent, cetane number enhancer, corrosion inhibitor, demulsifier, defoamer and metal deactivator was added to the diesel fuel at a treatment rate to provide a rate of active treatment of 58 ppm of additive A2. A keep clean test was performed using this fuel, and the results are shown below. Keep XUD9 clean
A cleaning test was performed with the same formulation and at twice the treatment rate. In the cleaning test, a test cycle is performed on non-additive fuel (RF-06) to clog the injectors, followed by an operation with additive fuel to determine the additive's ability to clean the clogged injectors. Clean XUD9
Example 7 Combustible compositions similar to 11 and 12 (but with the addition of 1 ppm of zinc as zinc neodecanoate) were also tested in the DW10 test described in example 7. Fuel composition 13 was analyzed as a keep clean test. The fuel composition 14 was analyzed as a cleaning test. The results are shown in figures 3 and 4.

Example 18 In Europe, the European Coordinating Council for the development of performance tests for transport fuels, lubricants and other fluids (the industry body known as CEC) has developed a new test for additives for modern diesel engines, like HSDI engines. The CEC F-110-xx 1 test is used to assess whether diesel fuel is suitable for use in engines that meet the new European Union emission regulations, known as the "Euro 5" regulations. The test is based on a Peugeot DW10 engine, using Euro 5 injectors, and is commonly referred to as the DW10 test. This test measures the effects of deposits on specific injectors for IDIDs in relation to adherence to the injector. In this test, thermocouples are positioned on the engine to allow the exhaust temperature of each cylinder to be measured. This, together with other measured parameters, allows injector adherence to be tested. The engine of the injector clogging test is the PSA DW10CTED4 / E5. In summary, the characteristics of the engine are: Design: Four cylinders in line, with overhead meat axis, turbocharged with EGR Capacity: 1997 cm3 Combustion chamber: Four valves, piston bowl, direct injection guided by the wall Power: 120 kW a 3750 rpm Torque: 340 Nm at 2000 rpm Injection system: Common rail with 6 piezoelectronically controlled injectors. Maximum pressure: 1600 bar (1.6 x 108 Pa). Delphi's proprietary design Emission control: According to Euro V limit values when combined with the exhaust gas after-treatment (DPF) system This engine was chosen as a representative design of the high-speed direct injection diesel engine European system capable of meeting current and future European emissions requirements. The common rail injection system uses a highly efficient nozzle design with rounded inlet edges and tapered spray holes for optimal hydraulic flow. This type of nozzle, when combined with high fuel pressure, made it possible to achieve advances in combustion efficiency, noise reduction and reduced fuel consumption, but they are sensitive to the influences that can cause adherence to the injector. The test is carried out using the current injector design in accordance with Euro V injector technology. Full details of the CEC F-110 test method can be obtained from the CEC. The test cycle is summarized below. 1. Stages of heating:
2. Main operation
The test procedure consists of alternating sequences of immersion periods followed by cold starts preceding the main operating cycles of engine operation. There are 5 main operations and 6 cold starts. If the engine fails to start or stop during engine operation and is not restarted, the test is aborted. During the ECU test, parameters are recorded along with exhaust temperatures to assess any indication of adherence to the injector. These parameters contribute to an overall demerit assessment at the conclusion of the test. 1 Test procedure still in the provisional format and the final cec edition number is not yet available. The base fuel for the test was the CEC DF79 base fuel, containing 0.5 mg / kg of Na in the form of sodium naphthenate and 10 mg / kg dodecyl succinic acid (DDSA). The engine operated on a base fuel according to the current procedure. During the 30-hour test cycle, the increase in exhaust temperatures was observed after 18 hours, providing an indication of adherence to the injector. At this point, the engine was switched to the same base fuel (ie DF79 + 0.5 mg / Kg Na + 10 mg / Kg DDSA) + 120 mg / Kg (active) A2. After 24 hours (ie, 6 hours of cleaning), the engine showed improved exhaust temperatures and this continued for 30 hours, indicating normal engine operation, and no evidence of adhesion to the injector.

权利要求:
Claims (16)
[0001]
1. Fuel composition comprising, as an additive, one or more quaternary ammonium salts of the formula:
[0002]
2. Fuel composition according to claim 1, characterized by the fact that the product of the reaction of a tertiary amine of formula R1R2R3N with a quaternizing agent is selected from: (i) an ester of formula R5COOR4; (ii) a carbonate compound of formula R ° OCOOR4 and then a carboxylic acid of formula R5COOH; and (iii) an epoxide with less than 8 carbon atoms and a carboxylic acid of the formula R5COOH; wherein R ° is an optionally substituted hydrocarbyl group.
[0003]
Fuel composition according to claim 1 or 2, characterized in that the quaternary ammonium salt is the product of the reaction of: (a) a tertiary amine of formula R1R2R3N; (b) an epoxide with less than 8 carbon atoms; and (c) a carboxylic acid of the formula R5COOH.
[0004]
Fuel composition according to any one of the preceding claims, characterized in that R1 is an optionally substituted alkyl or alkenyl group having 1 to 6 carbon atoms, R2 is an optionally substituted alkyl or alkenyl group having 1 to 6 atoms carbon and R3 is an optionally substituted alkyl or alkenyl group having 1 to 6 carbon atoms.
[0005]
Fuel composition according to any one of the preceding claims, characterized in that R1 is an unsubstituted alkyl group or a hydroxyalkyl group, R2 is an unsubstituted alkyl group or a hydroxyalkyl group and R3 is an unsubstituted alkyl group or a hydroxyalkyl group.
[0006]
Fuel composition according to any one of the preceding claims, characterized in that R4 is a hydroxy substituted alkyl group.
[0007]
7. Fuel composition according to claim 6, characterized in that the fuel is a diesel fuel, and optionally comprises one or more additional detergents selected from: (i) an additional quaternary ammonium salt additive that does not is a quaternary ammonium compound as defined in claim 1; (ii) the product of a Mannich reaction between an aldehyde, an amine and an optionally substituted phenol; (iii) the reaction product of an acylating agent derived from carboxylic acid and an amine; (iv) the reaction product of an acylating agent derived from carboxylic acid and hydrazine; (v) a salt formed by the reaction of a carboxylic acid with di-n-butylamine or tri-n-butylamine; (vi) the reaction product of a hydrocarbyl-substituted dicarboxylic acid or anhydride and an amine or salt compound, the product of which comprises at least one aminotriazole group; and (vii) a substituted polyaromatic detergent additive.
[0008]
8. Fuel composition, according to claim 6, characterized in that the fuel is gasoline fuel, and optionally comprises one or more gasoline detergents selected from: (p) hydrocarbyl-substituted polyoxyalkylene amines or polyethylene; (q) acylated nitrogen compounds which are the reaction product of an acylating agent derived from carboxylic acid and an amine; (r) hydrocarbyl substituted amines, wherein the hydrocarbyl substituent is substantially aliphatic and contains at least 8 carbon atoms; (s) Mannich-based additives comprising condensates containing nitrogen from a phenol, aldehyde and primary or secondary amine; (t) aromatic esters of a polyalkylphenoxycanol; (u) an additional quaternary ammonium salt additive that is not a quaternary ammonium compound as defined in claim 1; and (v) tertiary hydrocarbyl amines with a maximum of 30 carbon atoms.
[0009]
9. Method of improving the performance of an engine, the method being characterized by the fact that it comprises the combustion, in said engine, of a fuel composition as defined in any of the previous claims.
[0010]
10. Method according to claim 9, characterized by the fact that the engine is a gasoline engine and the fuel is a gasoline fuel.
[0011]
11. Method according to claim 9, characterized by the fact that the engine is a diesel engine with a fuel injection system comprising a high pressure fuel injection system (HPFI) with fuel pressures greater than 135 mPa (1350 bar).
[0012]
12. Method, according to claim 9 or 11, characterized by the fact that the improvement in performance is achieved by fighting deposits on the engine.
[0013]
13. Method, according to claim 12, characterized by the fact that it combats the internal deposits of the diesel injector; and / or combating external diesel injector deposits, including injector nozzle deposits and injector tip deposits; and / or combat fuel filter deposits.
[0014]
14. Method, according to claim 9 or 11, characterized by the fact that the improvement in performance is a power gain compared to the combustion of a non-additive base fuel and with clean injectors.
[0015]
15. Use of an additive in a fuel composition to improve the performance of an engine that burns said fuel composition, characterized by the fact that the additive is a quaternary ammonium salt, comprised in the composition as defined in any one of claims 1 to 6.
[0016]
16. Method of preparing a combustible composition, as defined in any one of claims 1 to 6, characterized in that the method comprises adding the quaternary ammonium salt additive to the fuel after the fuel leaves the dispensing terminal.

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同族专利:

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公开号 | 公开日

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RU2017103487A3|2019-02-21|

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US10087384B2|2018-10-02|

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KR20170037639A|2017-04-04|

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SG11201610982RA|2017-02-27|

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EP3174847A1|2017-06-07|

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GB201513305D0|2015-09-09|

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CA2955599A1|2016-02-04|

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US20170218291A1|2017-08-03|

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GB201413355D0|2014-09-10|

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BR112017001599A2|2018-01-30|

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CN106795087A|2017-05-31|

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RU2713658C2|2020-02-06|

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GB2535253A|2016-08-17|

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GB2535253B|2019-04-17|

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CN106795087B|2020-07-14|

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AU2015295049B2|2019-07-11|

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RU2017103487A|2018-08-28|

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WO2016016641A1|2016-02-04|

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EP3174847B1|2019-11-13|

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AU2015295049A1|2017-02-02|

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AU2015295049C1|2020-10-01|

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法律状态:
2019-12-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-04-22| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-10-06| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 28/07/2015, OBSERVADAS AS CONDICOES LEGAIS. |

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