fuel composition and engine performance improvement method

专利摘要:
QUARTENARY AMMONIUM COMPOUNDS AND ADDITIVE FOR USE AS FUEL, COMPOSITIONS AND METHODS. The present invention relates to a quaternary ammonium compound which is the reaction product of: (a) a tertiary amine that has a molecular weight less than 1,000; (b) an acid-activated alkylating agent; and (c) a diacid that includes an optionally substituted chemical hydrocarbyl moiety that has at least 5 carbon atoms.
公开号:BR112016001099B1
申请号:R112016001099-0
申请日:2014-07-28
公开日:2021-01-05
发明作者:Jacqueline Reid；Stephen Leonard Cook
申请人:Innospec Limited；
IPC主号:

专利说明:

[1] The present invention relates to innovative quaternary ammonium compounds, to a composition comprising such compounds and to methods and uses in relation thereto.
[2] In particular, the present invention relates to the use of quaternary ammonium compounds as fuel additives or lubricants, specifically, as fuel additives and, preferably, as diesel fuel additives.
[3] It is common to include detergent compounds that contain nitrogen in lubricating oil and fuel oil compositions in order to improve the performance of engines using such compositions. The inclusion of detergent additives prevents the fouling of moving parts of the engine. Without such additives, fouling would cause the engine's performance to decrease and eventually cease.
[4] Many different types of quaternary ammonium salts are known in the art for use as detergent additives in fuel and lubricant 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. Various acids can be used, but they are typically small acid molecules, for example, acetic acid, and the quaternary ammonium cation counterion is not considered important.
[5] Detergent additive compounds typically include a polar group and a hydrophobic group. The hydrophobic group is typically a chemical moiety of long-chain hydrocarbyl. A common feature of existing quaternary ammonium salt detergent additives is that the hydrophobic group is included within the cationic portion of the compound. The present inventors have surprisingly concluded that quaternary ammonium salts that include a hydrophobic chemical portion in the anion can provide good performance as a detergent even when a lower molecular weight cation is used. In addition, the inventors have found that the use of diacid species such as the anion is particularly beneficial.
[6] According to a first aspect of the present invention, a quaternary ammonium compound is provided which is the reaction product of:
[7] (a) a tertiary amine having a molecular weight less than 1,000;
[8] (b) an acid-activated alkylating agent; and
[9] (c) a diacid that includes an optionally substituted chemical hydrocarbyl moiety that has at least 5 carbon atoms.
[10] Component (a) used to prepare the quaternary ammonium salts of the present invention is a tertiary amine that has a molecular weight less than 1,000. Any suitable tertiary amine can be used.
[11] The tertiary amine compounds of the present invention preferably do not include any primary or secondary amine groups. In some embodiments, they can be derived from compounds that include such groups, but, preferably, they have been reacted subsequently to form additional tertiary amine species. The tertiary amine compound used as component (a) can contain more than one tertiary amine group. However, tertiary amine compounds that include primary or secondary amine groups are within the scope of the invention, as long as these groups do not prevent the quaternization of tertiary amine species.
[12] The present inventors surprisingly concluded that quaternary ammonium salts provide good detergency even when the amines from which they are derived have a much lower molecular weight than the compounds typically used in the prior art. Suitably, the tertiary amine of component (a) has a molecular weight less than 900, preferably less than 800, more preferably less than 700, preferably less than 600, more preferably less than 500, for example less than 400 or less than 300. In some embodiments, the tertiary amine of component (a) has a molecular weight less than 250 or less than 200.
[13] The tertiary amines for use in the present invention are compounds of the formula R1R2R3N, wherein each of R1, R2 and R3 is, independently, an optionally substituted alkyl, alkenyl or aryl group.
[14] In this specification, unless otherwise specified, references 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. .
[15] R1, R2 and R3 can be the same or different. In some preferred embodiments, R1 and R2 are the same and R3 is different.
[16] Preferably, each of R1 and R2 is, independently, an optionally substituted alkyl, alkenyl or aryl group having from 1 to 50 carbon atoms, preferably from 1 to 40 carbon atoms, more preferably from 1 to 30 carbon atoms, suitably 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms.
[17] Each of R1 and R2 can be optionally substituted by one or more groups selected from halo (specifically, chlorine and fluoro), hydroxy, alkoxy, keto, acyl, cyano, mercapto, alkylmercapto, dialkylamino, nitro, nitrous, and sulfoxy. The alkyl groups of these substituents can be further substituted.
[18] 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 optionally substituted alkyl or alkenyl group having 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms. carbon, suitably from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, more preferably from 1 to 10 carbon atoms, suitably from 1 to 8 carbon atoms, for example, from 1 to 6 atoms of carbon.
[19] In some embodiments, R1 is an optionally substituted alkyl or alkenyl group, preferably having 1 to 10, preferably 1 to 4 carbon atoms. Preferably, R1 is an alkyl group. The same can be a substituted alkyl group, for example, a hydroxy substituted alkyl group. Suitably, R1 is an unsubstituted alkyl group or a hydroxy substituted alkyl group. Preferably, R1 is an unsubstituted alkyl group. The alkyl chain can be straight or branched. Preferably, R1 is selected from methyl, ethyl, propyl, butyl, hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl, including isomers thereof. More preferably, R1 is selected from methyl, ethyl, propyl and butyl, including some isomers thereof. Most preferably, R1 is methyl.
[20] In some embodiments, R2 is an optionally substituted alkyl or alkenyl group, preferably having 1 to 10, preferably 1 to 4 carbon atoms. Preferably, R2 is an alkyl group. The same can be a substituted alkyl group, for example, a hydroxy substituted alkyl group. Suitably, R2 is an unsubstituted alkyl group or a hydroxy substituted alkyl group, preferably R2 is an unsubstituted alkyl group. The alkyl chain can be straight or branched. Preferably, R2 is selected from methyl, ethyl, propyl, butyl, hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl, including some isomers thereof. More preferably, R2 is selected from methyl, ethyl, propyl and butyl, including some isomers thereof. Most preferably, R2 is methyl.
[21] In some embodiments, R3 is an optionally substituted alkyl or alkenyl group having 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms, more preferably, 1 to 30 carbon atoms, suitably 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, suitably 1 to 8 carbon atoms, for example, 1 to 6 carbon atoms. Suitable substituents include halo (specifically chlorine and fluoro), hydroxy, alkoxy, keto, acyl, cyano, mercapto, alkylmercapto, amino, alkylamino, nitro, nitrous, sulfoxy, starch, alkylamido, imido, alkylimido. The alkyl groups of these substituents can be further substituted.
[22] In some embodiments, R3 is an optionally substituted alkyl or alkenyl group, preferably having 1 to 10, preferably 1 to 4 carbon atoms. Suitably, R3 is an optionally substituted alkyl group. Preferably, R3 is a substituted alkyl group. Preferred substituents include alkoxy and hydroxyl groups. Preferably, R3 is selected from methyl, ethyl, propyl, butyl, hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl, including some isomers thereof.
[23] In some preferred embodiments, R3 is an alkyl group substituted by hydroxyl. The alkyl chain can be straight or branched. Preferably, R3 is selected from hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl, including some isomers thereof. Most preferably, R3 is a hydroxyethyl group.
[24] Preferably, component (a) is an alkylamino and / or hydroxyalkyl amino compound of the 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 10, preferably 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. Component (a) can be a trialkylamine, a dialkylhydroxyalkylamine, a dihydroxyalkylalkylamine or a trihydroxyalkylamine. There are many different compounds of this type and they will be known to the person skilled in the art.
[25] Some preferred compounds for use as component (a) include Trimethylamine, N, N-dimethylethylamine, N, N-dimethylpropylamine, N, N-dimethylbutylamine, triethylamine, N, N-diethylmethylamine, 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, propyldanolanol, N, N-di butylmethanolamine, butyldimethanolamine, N, N-dibutylethanolamine, butyldiethanolamine, N, N-dibutylpropanolamine, butyldipropanolamine, N, N-dibutylbutanolamine, butyldibutanolamine, trimethanolamine, triethanolamine, tripropanolamine, and tributanolamine.
[26] Tertiary amine compounds specifically preferred for use as component (a) include N, N-dimethyl ethanolamine and N, N-dimethylbutylamine.
[27] The present invention can adequately provide a quaternary ammonium compound which is the reaction product of:
[28] (a) a tertiary amine of formula R1R2R3N, wherein each of R1, R2 and R3 is independently selected from an alkyl or hydroxyalkyl group having 1 to 10 carbon atoms;
[29] (b) an acid-activated alkylating agent; and
[30] (c) a diacid that includes an optionally substituted chemical hydrocarbyl moiety that has at least 5 carbon atoms, preferably at least 6 carbon atoms.
[31] 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.
[32] Any suitable epoxide compound can be used. Suitable epoxide compounds are those of the formula:

[33] where each of R4, R5, R6, R7 is independently selected from hydrogen or an optionally substituted alkyl, alkenyl or aryl group.
[34] At least one of R4, R5, R6 and R7 is hydrogen. Preferably, at least two of R4, R5, R6 and R7 are hydrogen. Most preferably, three out of R4, R5, R6 and R7 are hydrogen. R4, R5, R6 and R7 can all be hydrogen.
[35] In the structure above and in the following definitions, R4 and R5 are interchangeable, and therefore, when these groups are different, both an enantiomer and a diastereomer can be used as the component (b).
[36] In the structure above and in the definitions below, R6 and R7 are interchangeable and therefore, when these groups are different, both an enantiomer and a diastereomer can be used as the component (b).
[37] Preferably, R4 is hydrogen or an optionally substituted alkyl, alkenyl or aryl group, preferably having 1 to 10, preferably 1 to 4 carbon atoms. Preferably, R4 is hydrogen or an alkyl group. Most preferably, R4 is hydrogen.
[38] Preferably, R5 is hydrogen or an optionally substituted alkyl, alkenyl or aryl group, preferably having 1 to 10 carbon atoms.
[39] In some preferred embodiments, R5 is an optionally substituted aryl group. For example, R5 can be phenyl.
[40] In some preferred embodiments, R5 is an optionally substituted alkyl or alkenyl group. Suitably, R5 is an alkyl group, for example, an unsubstituted alkyl group. R5 can be an alkyl group having 1 to 12, for example, 1 to 8 or 1 to 4 carbon atoms.
[41] Preferably, R5 is hydrogen or an alkyl group. Most preferably, R5 is hydrogen.
[42] Preferably, R6 is hydrogen or an optionally substituted alkyl, alkenyl or aryl group, preferably having 1 to 10, preferably 1 to 4 carbon atoms. Preferably, R6 is hydrogen or an alkyl group. Most preferably, R6 is hydrogen.
[43] Preferably, R7 is hydrogen or an optionally substituted alkyl, alkenyl or aryl group.
[44] In some preferred embodiments, R7 is an optionally substituted aryl group. For example, R7 can be phenyl.
[45] In some preferred embodiments, R7 is an optionally substituted alkyl or alkenyl group. R7 can be an alkyl group, for example, an unsubstituted alkyl group. R7 can be an alkyl group having 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms, suitably 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, for example, 1 to 8 or 1 to 4 carbon atoms.
[46] In some embodiments, R7 is hydrogen.
[47] In some preferred embodiments, R7 is the CH2OR8 or CH2OCOR9 chemical moiety where each of R8 and R9 can be an optionally substituted alkyl, alkenyl or aryl group.
[48] R8 is preferably an optionally substituted alkyl or aryl group, preferably having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, suitably 1 to 12 carbon atoms. When R8 is an alkyl group, it can be straight or branched. In some modalities, the same is branched. R8 can be an optionally substituted phenyl group.
[49] In one embodiment, R8 is a 2-methyl phenyl group. In another embodiment, R8 is CH2C (CH2CH3) CH2CH2CH2CH3.
[50] R9 can be an optionally substituted alkyl, alkenyl or aryl group.
[51] R9 is preferably an optionally substituted alkyl or aryl group, preferably having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, suitably 1 to 12 carbon atoms. When R9 is an alkyl group it can be straight or branched. In some preferred modalities, it is branched. R9 can be an optionally substituted phenyl group.
[52] In one embodiment, R9 is C (CH3) R2 where each R is an alkyl group.
[53] Component (b) is preferably an epoxide. The present invention therefore provides a quaternary ammonium compound which is the reaction product of:
[54] (a) a tertiary amine having a molecular weight less than 1,000;
[55] (b) an epoxide; and
[56] (c) a diacid which includes an optionally substituted alkyl or alkenyl chemical moiety that has at least 5 carbon atoms, preferably at least 6 carbon atoms.
[57] Preferred epoxide compounds for use as component (b) include styrene oxide, ethylene oxide, propylene oxide, butylene oxide, epoxyhexane, octene oxide, stilbene oxide and other alkylene and alkenyl epoxides that have 2 to 50 carbon atoms.
[58] Other suitable epoxide compounds include glycidyl ethers and glycidyl esters, for example, glycidyl 2 methyl phenyl ether and glycidyl ester of versatic acid.
[59] Component (c) used to prepare the quaternary ammonium salts of the present invention is a diacid that includes an optionally substituted chemical hydrocarbyl moiety that has at least 5 carbon atoms, preferably at least 6 carbon atoms.
[60] As used herein, the term "substituent, chemical moiety or group" hydrocarbyl "is used in its ordinary sense, which is well known to those of ordinary skill in the art. Specifically, it refers to a group that has a carbon atom attached directly to the rest of the molecule and which has a predominantly hydrocarbon character. Examples of hydrocarbyl groups include:
[61] (i) hydrocarbon groups, that is, aliphatic substituents (which can be saturated or unsaturated, linear or branched, for example, alkyl or alkenyl), alicyclic (for example, cycloalkyl, cycloalkenyl), and aromatic substituted aromatic substituents , aliphatic and alicyclic, as well as cyclic substituents in which the ring is terminated through another portion of the molecule (for example, two substituents together form a ring);
[62] (ii) substituted hydrocarbon groups, that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent (eg halo (specifically chlorine and fluoro), hydroxy, alkoxy , keto, acyl, cyano, mercapto, alkylmercapto, amino, alkylamino, nitro, nitrous, and sulfoxy);
[63] (iii) hetero substituents, that is, substituents that, while having a predominantly hydrocarbon character, in the context of this invention, contain a component other than carbon in a ring or chain, otherwise composed of carbon atoms. Heteroatoms include sulfur, oxygen, nitrogen, and include substituents such as pyridyl, furyl, thienyl and imidazolyl. In general, no more than two, preferably no more than one, non-hydrocarbon substituents will be present for every ten carbon atoms in the hydrocarbyl group; typically, there will be no non-hydrocarbon substituents on the hydrocarbyl group.
[64] Component (c) is a diacid and therefore includes two functional groups of carboxylic acid and an optionally substituted chemical hydrocarbyl moiety that has at least 5 carbon atoms, preferably at least 6 carbon atoms. In some embodiments, component (c) may be a simple fatty acid compound. However, component (c) can also be a more complex molecule that includes these functional groups.
[65] 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.
[66] Component (c) is a separate component from component (a). The quaternary ammonium salts of the present invention are prepared from the reaction of the three separate compounds.
[67] Component (c) is preferably an acid that includes an optionally substituted hydrocarbyl chemical moiety that has at least 8 carbon atoms, preferably at least 10 carbon atoms.
[68] Component (c) is a diacid that includes two functional groups of the COOH formula. Component (c) can also include additional functional groups, including additional acid-based groups. However, any such additional acid groups are preferably esterified.
[69] In some preferred embodiments, component (c) is an optionally substituted phthalic acid or succinic acid derivative. In some embodiments, (c) is a derivative of phthalic acid or succinic acid substituted by hydrocarbyl in which the hydrocarbyl substituent has a molecular weight of 100 to 5,000, preferably 200 to 3,000.
[70] In some preferred embodiments, the optionally substituted hydrocarbyl group is a polyisobutenyl group, preferably having a molecular weight of 100 to 5,000, more preferably, 200 to 3,000.
[71] In some preferred embodiments, component (c) is a derivative of phthalic acid or succinic acid which is substituted by a C6 to C30 alkyl or alkenyl group, suitably a substituted alkyl or alkenyl group, preferably an alkyl group or C8 to C26 alkenyl, more preferably, an C10 to C24 alkyl or alkenyl group. Most preferably, phthalic acid or succinic acid is replaced by an alkyl group.
[72] According to a second aspect of the present invention, a method of preparing a quaternary ammonium salt is provided, the method comprising reacting (a) a tertiary amine having a molecular weight less than 1,000 with (b) an acid-derived alkylating agent in the presence of (c) a diacid which includes an optionally substituted chemical hydrocarbyl moiety that has at least 5 carbon atoms, preferably at least 6 carbon atoms.
[73] The preferential aspects of the second aspect are as defined in relation to the first aspect.
[74] In the method of the second aspect, components (a), (b) and (c) are preferably reacted in a molar ratio between 2 ± 0.5: 2 ± 0.5: 1; preferably, 2 ± 0.2: 2 ± 0.2: 1, more preferably, 2 ± 0.1: 2 ± 0.1: 1.
[75] The conditions suitable for carrying out the method of the second aspect are well known to the person skilled in the art and can be as described in the examples.
[76] The present invention can suitably provide a quaternary ammonium salt of the formula:

[77] where R1, R2, R3 R4, R5, R6 and R7 are as defined herein and A includes an optionally substituted chemical hydrocarbyl moiety that has at least 5 carbon atoms, preferably at least 6 atoms carbon.
[78] Suitably, A is the residue of a derivative of phthalic acid or succinic acid that includes an optionally substituted hydrocarbyl group that has at least 5 carbon atoms, preferably at least 6 carbon atoms. In the preferred embodiments, A is CHRCH2 where R is an optionally substituted hydrocarbyl group having at least 5 carbon atoms, preferably at least 6 carbon atoms. In some embodiments, R is a polyisobutyl group as described earlier in this document. In some embodiments, R is a C6 to C30 alkyl or alkenyl group as described earlier in this document.
[79] The present invention relates mainly to quaternary ammonium salts of a diacid prepared by reacting a tertiary amine with an acid-activated alkylating agent in the presence of the diacid. However, it is contemplated that the same compounds formed by an alternative method are also within the scope of the invention. Therefore, the present invention can additionally provide a quaternary ammonium compound of formula (X):

[80] wherein each of R0, R1, R2 and R3 is independently an optionally substituted alkyl, alkenyl or aryl group and A includes an optionally substituted chemical hydrocarbyl moiety that has at least 5 carbon atoms, preferably at least 6 carbon atoms.
[81] Suitably, residues N, R1, R2 and R3 shown in formula (X) have a combined molecular weight less than 1,000.
[82] In formula (X), R1, R2 and R3 are suitably as defined earlier in this document, and -OOCACOO- is preferably the residue of a diacid as described earlier in this document.
[83] R0 may be a small alkyl group, for example, methyl. Preferably, it is a group of formula:

[84] where R4, R5, R6 and R7 are as defined in this document.
[85] The quaternary ammonium compounds of the present invention have been found to be effective as detergent additives for use in fuel or lubricant compositions.
[86] Therefore, the present invention provides the use of a quaternary ammonium compound of the first aspect as an additive for fuel or lubricant oil compositions.
[87] The present invention can provide the use of a quaternary ammonium compound of the first aspect as a detergent additive for fuel oil or lubricant compositions.
[88] The present invention can provide the use of a quaternary ammonium compound of the first aspect as a detergent additive for lubricating oil compositions.
[89] The present invention can provide the use of a quaternary ammonium compound of the first aspect as a detergent additive for fuel compositions.
[90] The present invention can provide the use of a quaternary ammonium compound of the first aspect as a detergent additive for gasoline or diesel fuel compositions.
[91] The present invention can provide the use of a quaternary ammonium compound of the first aspect as a detergent additive for gasoline fuel compositions.
[92] The present invention can provide the use of a quaternary ammonium compound of the first aspect as a detergent additive for diesel fuel compositions.
[93] According to a third aspect of the present invention, an additive composition is provided which comprises a quaternary ammonium salt of the first aspect and a diluent or carrier.
[94] The additive composition of the third aspect may be an additive composition for lubricating oil.
[95] The additive composition of the third aspect may be an additive composition for gasoline.
[96] Preferably, the additive composition of the third aspect is an additive composition for diesel fuel.
[97] 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.
[98] 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 such compounds present in the composition.
[99] The additive composition may include one or more additional additives. They can be selected from antioxidants, dispersants, detergents, metal deactivating compounds, anti-wax sedimentation agents, cold flow enhancers, cetane enhancers, turbidity reducers, stabilizers, demulsifier, antifoams, corrosion inhibitors, lubricity enhancers, dyes, markers, combustion enhancers, metal deactivators, odor masks, drag reducers and conductivity enhancers.
[100] In some preferred embodiments, the additive composition includes one or more detergents that contain additional nitrogen.
[101] The present invention can provide a fuel oil or lubricant composition that comprises a quaternary ammonium salt of the first aspect.
[102] According to a fourth aspect of the present invention, a lubricant composition is provided which comprises a lubricating viscosity oil and, as an additive, a quaternary ammonium compound which is the reaction product of:
[103] (a) a tertiary amine having a molecular weight less than 1,000;
[104] (b) an acid-activated alkylating agent; and
[105] (c) a diacid which includes an optionally substituted alkyl or alkenyl chemical moiety that has at least 5 carbon atoms, preferably at least 6 carbon atoms.
[106] The preferred features of the quaternary ammonium compound are as defined in relation to the first and second aspects.
[107] According to a fifth aspect of the present invention, a fuel composition is provided which comprises, as an additive, a quaternary ammonium compound which is the reaction product of:
[108] (a) tertiary amine having a molecular weight less than 1,000;
[109] (b) an acid-activated alkylating agent; and
[110] (c) a diacid which includes an optionally substituted alkyl or alkenyl chemical moiety that has at least 5 carbon atoms, preferably at least 6 carbon atoms.
[111] The preferred features of the quaternary ammonium compound are as defined in relation to the first and second aspects.
[112] The additive composition of the third aspect, suitably, upon dilution, provides a fuel composition of the fourth aspect.
[113] The present invention can additionally provide a method of preparing a fuel 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.
[114] Preferably, the present invention provides a fuel composition which comprises, as an additive, a quaternary ammonium compound which is the reaction product of:
[115] (a) a tertiary amine having a molecular weight less than 1,000;
[116] (b) an epoxide; and
[117] (c) a diacid which includes a chemical moiety of alkyl or optionally substituted alkenyl which has at least 5 carbon atoms, preferably at least 6 carbon atoms.
[118] The composition of the present invention can be a gasoline composition or a diesel fuel composition. Preferably, it is a diesel fuel composition.
[119] Diesel fuel includes any fuel suitable for use in a diesel engine for both road use and non-road use. This includes, but is not limited to, fuels described as diesel, marine diesel, heavy fuel oil, industrial fuel oil, etc.
[120] The diesel fuel composition of the present invention may comprise a petroleum-based fuel oil, specifically, an intermediate distillate fuel oil. Such distillate fuel oils generally boil within the range of 110 ° C to 500 ° C, for example, 150 ° C to 400 ° C. Diesel fuel can comprise atmospheric distillate or vacuum distillate, cracked diesel, or a blend in any proportion of straight run and refinery streams, such as thermally and / or catalytically cracked distillates and hydrocracked distillates.
[121] The diesel fuel composition of the present invention may comprise non-renewable Fischer-Tropsch fuels, such as those described as GTL (gas to liquid), CTL (coal to liquid) and OTL (sand and oil to liquid).
[122] The diesel fuel composition of the present invention can comprise a renewable fuel, such as a biofuel composition or biodiesel composition.
[123] The diesel fuel composition may comprise 1st generation biodiesel. First generation biodiesel contains esters of, for example, vegetable oils, animal fats and used cooking fats. This form of biodiesel can be obtained by transesterifying oils, for example, rapeseed oil, soybean oil, safflower oil, palm oil 25, corn oil, peanut oil, cottonseed oil, tallow, oil coconut oil, jatropha oil, sunflower seed oil, used cooking oils, hydrogenated vegetable oils or any mixture thereof, with an alcohol, usually a monoalcohol, usually in the presence of a catalyst.
[124] The diesel fuel composition may 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, such 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.
[125] The diesel fuel composition of the present invention can comprise third generation biodiesel. Third generation biodiesel uses gasification and Fischer-Tropsch technology, including those described as BTL fuels (liquid biomass). Third generation biodiesel does not differ widely from some second generation biodiesel, but aims to exploit the entire plant (biomass) and, therefore, expands the raw material base.
[126] The diesel fuel composition may contain mixtures of any or all of the diesel fuel compositions above.
[127] In some embodiments, the diesel fuel composition of the present invention may be a blended diesel fuel that comprises biodiesel. In such blends, biodiesel can be present in an amount of, 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%.
[128] In some embodiments, the fuel composition may comprise pure biodiesel.
[129] In some embodiments, the fuel composition may comprise a pure GTL fuel.
[130] 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.
[131] 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%.
[132] However, in preferred embodiments, diesel fuel has a sulfur content of a maximum of 0.05% by weight, more preferably, of a maximum of 0.035% by weight, specifically of a maximum of 0.015%. Fuels with even lower levels of sulfur are also suitable, such as fuels with less than 50 ppm sulfur by weight, preferably less than 20 ppm, for example, 10 ppm or less.
[133] 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.
[134] Suitably, the quaternary ammonium salt additive is present in the diesel fuel composition in an amount of less than 10,000 ppm, preferably less than 1,000 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.
[135] 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 such additives present in the composition.
[136] The diesel fuel composition of the present invention can include one or more additional additives, such as those that are commonly included in diesel fuels. These include, for example, antioxidants, dispersants, detergents, metal deactivating compounds, anti-wax waxing agents, cold flow enhancers, cetane enhancers, turbidity reducers, stabilizers, demulsifier, antifoams, corrosion inhibitors, lubricity enhancers, dyes, markers, combustion enhancers, metal deactivators, odor masks, 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.
[137] In some preferred embodiments, the diesel fuel composition of the present invention comprises one or more additional detergents. Nitrogen-containing detergents are preferred.
[138] One or more additional detergents can be selected from:
[139] (i) an additional quaternary ammonium salt additive that is not a quaternary ammonium compound of the first aspect;
[140] (ii) the product of a Mannich reaction between an aldehyde, an amine and an optionally substituted phenol;
[141] (iii) the reaction product of an acylating agent derived from carboxylic acid and an amine;
[142] (iv) the reaction product of an acylating agent derived from carboxylic acid and hydrazine;
[143] (v) a salt formed by the reaction of a carboxylic acid with di-n-butylamine or tri-n-butylamine;
[144] (vi) the reaction product of an optionally substituted hydrocarbyl-substituted dicarboxylic acid or anhydride and an amine or salt compound whose product comprises at least one amino triazole group; and
[145] (vii) a substituted polyaromatic detergent additive.
[146] In some embodiments, the diesel fuel composition comprises an additional quaternary ammonium salt additive that is not a quaternary ammonium compound of the first aspect.
[147] The additional quaternary ammonium salt additive is suitably the reaction product of a nitrogen-containing species that has at least one tertiary amine group and a quaternizing agent.
[148] The nitrogen-containing species can be selected from:
[149] (x) the reaction product of an optionally substituted hydrocarbyl-substituted acylating agent and a compound comprising at least one tertiary amine group and a primary amine group, secondary amine or alcohol;
[150] (y) a Mannich reaction product that comprises a tertiary amine group; and
[151] (z) a polyalkylene substituted amine that has at least one tertiary amine group.
[152] Examples of quaternary ammonium salt and methods for preparing it are described in the following patents, which are incorporated by reference, US2008 / 0307698, US2008 / 0052985, US2008 / 0113890 and US2013 / 031827.
[153] Component (x) can be interpreted as the reaction product of an optionally substituted hydrocarbyl-substituted acylating agent and a compound having an oxygen or nitrogen atom capable of condensing with said acylating agent and which additionally has an tertiary amino group. The preferred features 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.
[154] The preparation of some suitable quaternary ammonium salt additives in which the nitrogen-containing species includes component (x) is described in WO 2006/135881 and WO2011 / 095819.
[155] Component (y) is a Mannich reaction product that has a tertiary amine. The preparation of quaternary ammonium salts formed from the nitrogen-containing species that includes component (y) is described in US 2008/0052985. The preferred features 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.
[156] The preparation of quaternary ammonium salt additives in which the nitrogen-containing species includes component (z) is described, for example, in US 2008/0113890. The preferred features 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.
[157] To form the additional quaternary ammonium salt additives (i), the nitrogen-containing species that has a tertiary amine group is reacted with a quaternizing agent.
[158] The quaternizing agent can be selected appropriately from esters and non-esters.
[159] In some preferred embodiments, the quaternizing agents used to form the quaternary ammonium salt additives of the present invention are esters.
[160] Ester quaternizing agents are compounds of formula (III):

[161] where 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.
[162] Suitable quaternizing agents include esters of carboxylic acids that have a pKa of 3.5 or less.
[163] The compound of formula (III) is preferably an ester of a carboxylic acid selected from a substituted aromatic carboxylic acid, an α-hydroxycarboxylic acid and a polycarboxylic acid.
[164] 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.
[165] Specifically, the 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.
[166] In some embodiments, the compound of formula (III) is an ester of an α-hydroxycarboxylic acid. In such modalities the compound has the structure:

[167] where R7 and R8 are the same or different, and each is selected from hydrogen, alkyl, alkenyl, aralkyl or aryl. Such compounds suitable for use in the present invention are described in EP 1254889.
[168] A preferred compound of this type is methyl 2-hydroxy-isobutyrate.
[169] 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 that have more than 2 acidic chemical moieties.
[170] A specifically preferred compound of formula (III) is dimethyl oxalate.
[171] The ester quaternizing agent can be selected from an ester of a carboxylic acid selected from one or more of oxalic acid, phthalic acid, salicylic acid, maleic acid, malonic acid, citric acid, nitrobenzoic acid, aminobenzoic acid and 2,4,6-trihydroxybenzoic acid.
[172] Preferred ester quaternizing agents include dimethyl oxalate, methyl 2-nitrobenzoate and methyl salicylate.
[173] Suitable non-ester quaternizing agents 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 substituted by hydrocarbyl, alkyl nitrites, alkyl nitrates, hydroxides, N-oxides or mixtures thereof.
[174] In some embodiments, the quaternary ammonium salt can be prepared from, for example, an alkyl or benzyl halide (specifically a chloride) and then subjected to an ion exchange reaction to provide a different anion as part of the quaternary ammonium salt. Such a method may be suitable for preparing quaternary ammonium hydroxides, alkoxides, nitrites or nitrates.
[175] Preferred non-ester quaternizing agents 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 substituted by hydrocarbyl, N-oxides or mixtures thereof.
[176] Dialkyl sulfates suitable for use in the present invention as quaternizing agents include those that include alkyl groups that have 1 to 10 carbon atoms in the alkyl chain. A preferred compound is dimethyl sulfate.
[177] Suitable benzyl halides include chlorides, bromides and iodides. A preferred compound is benzyl bromide.
[178] Suitable hydrocarbyl-substituted carbonates may include two hydrocarbyl groups, which may be the same or different. Preferred compounds of this type include diethyl carbonate and dimethyl carbonate.
[179] Suitable hydrocarbyl-substituted epoxides have the formula:

[180] where each of R1, R2, R3 and R4 is independently hydrogen or an optionally substituted hydrocarbyl group having 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.
[181] In embodiments in which the hydrocarbyl-substituted acylating agent has more than one acyl group and is reacted with the compound of formula (I) or formula (II), it 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.
[182] Specifically preferred epoxide quaternizing agents are propylene oxide and styrene oxide.
[183] Suitable sultones include sultone prane and sultone butane.
[184] Suitable hydrocarbyl-substituted phosphates include dialkyl phosphates, trialkyl phosphates and O, O-dialkyl dithiophosphates.
[185] Suitable hydrocarbyl-substituted borate groups include borates that have 1 to 12 carbon atoms.
[186] Preferred alkyl nitrites and alkyl nitrates have 1 to 12 carbon atoms.
[187] Preferably, the non-ester quaternizing agent is selected from dialkyl sulfates, benzyl halides, hydrocarbyl substituted carbonates, hydrocarbyl substituted epoxies in combination with an acid, and mixtures thereof.
[188] Non-ester quaternizing agents specifically preferred for use in the present invention are hydrocarbyl-substituted epoxies 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 that is subjected to quaternization. Preferably, the acid is supplied by the tertiary amine molecule which is subjected to quaternization.
[189] Preferred quaternizing agents for use in the present invention include dimethyl oxalate, methyl 2-nitrobenzoate, methyl salicylate and styrene oxide or propylene oxide, optionally, in combination with an additional acid.
[190] For the avoidance of doubt, in such embodiments, the additional acid is not an acid that includes an optionally substituted chemical hydrocarbyl moiety that has at least 5 carbon atoms, as defined in relation to the first aspect of the present invention.
[191] An additional quaternary ammonium salt specifically preferred for use in the present invention is formed by reacting methyl salicylate or dimethyl oxalate with the reaction product of a polyisobutylene-substituted succinic anhydride that has a molecular weight of GDP of 700 to 1,300 and dimethylaminopropylamine.
[192] 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 o the acid-free quaternized nitrogen compounds disclosed in US2012 / 0010112.
[193] In addition, additional quaternary ammonium compounds suitable for use in the present invention include the quaternary ammonium compounds described in the applicants' copending patent application in WO2013 / 017889.
[194] 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 Mannich reaction product, appropriately, is not a quaternary ammonium salt.
[195] 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.
[196] The amine used to prepare the Mannich additive is preferably a polyamine. It can be selected from any compound that includes two or more amino groups. Preferably, the polyamine is a polyalkylene polyamine, preferably a polyethylene polyamine. Most preferably, the polyamine comprises tetraethylenepentamine or ethylenediamine.
[197] The substituted phenol component optionally used to prepare the Mannich additive can be substituted by 0 to 4 groups on the aromatic ring (in addition to the phenol OH). For example, it can be an optionally substituted hydrocarbyl-substituted cresol. Most preferably, the phenol component is a monosubstituted phenol. Preferably, it is a hydrocarbyl-substituted phenol. Preferred hydrocarbyl substituents are alkyl substituents that have 4 to 28 carbon atoms, specifically, 10 to 14 carbon atoms. Other preferred hydrocarbyl substituents are polyalkenyl substituents, such as polyisobutenyl substituents that have an average molecular weight of 400 to 2,500, for example, 500 to 1,500.
[198] In some embodiments, the diesel fuel composition comprises the reaction product of an acylating agent derived from carboxylic acid and an amine.
[199] These may also be called, in this document, in general, compounds containing acylated nitrogen.
[200] Suitable acylated nitrogen-containing compounds can be produced by reacting a carboxylic acid acylating agent with an amine and are known to those skilled in the art.
[201] Preferred acylated nitrogen-containing compounds are replaced with an optionally substituted hydrocarbyl group. The hydrocarbyl substituent can be either in the carboxylic acid-derived moiety of the molecule or in the amine-derived moiety of the molecule, or both. Preferably, however, it is found in the acylating agent portion. A preferred class of acylated nitrogen-containing compounds suitable for use in the present invention are those formed by the reaction of an acylating agent that has a hydrocarbyl substituent of at least 8 carbon atoms and a compound that comprises at least one primary amine group or secondary.
[202] The acylating agent may be a mono- or polycarboxylic acid (or reactive equivalent thereof), for example, a substituted succinic, phthalic or propionic acid or anhydride.
[203] The term “hydrocarbyl” was defined earlier 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 an average numerical molecular weight (Mn) between 170 to 2,800, for example, from 250 to 1,500, preferably from 500 to 1,500 and more preferably, 500 to 1,100. A 700 to 1,300 Mn is especially preferred. In a particularly preferred embodiment, the hydrocarbyl substituent has an average numerical molecular weight of 700 to 1,000, preferably 700 to 850, for example 750.
[204] The preferred hydrocarbyl-based substituents are polyisobutenes. Such compounds are well known to the person skilled in the art.
[205] The preferred hydrocarbyl-substituted acylating agents are polyisobutenyl succinic anhydrides. These compounds are commonly called "PIBSAs" and are known to the person skilled in the art.
[206] Conventional polyisobutenes and so-called "highly reactive" polyisobutenes are suitable for use in the invention.
[207] Specifically preferred PIBSAs are those that have a molecular weight of GDP (Mn) of 300 to 2,800, preferably 450 to 2,300, more preferably 500 to 1,300.
[208] To prepare these additives, the acylating agent derived from carboxylic acid is reacted with an amine. Suitably, it is reacted 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.
[209] Preferred amines are polyethylene polyamines that include ethylenediamine, diethylene triamine, triethylene tetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, and mixtures and isomers thereof.
[210] 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.
[211] A compound containing preferred acylated nitrogen for use in the present invention is prepared by reacting an acylating agent derived from succinic acid substituted by poly (isobutene) (e.g., anhydride, acid, ester, etc.) in which the substituent poly (isobutene) has an average numerical molecular weight (Mn) between 170 and 2,800 with a mixture of ethylene polyamines having 2 to about 9 amino nitrogen atoms, preferably about 2 to about 8 atoms nitrogen, per ethylene polyamine and about 1 to about 8 ethylene groups. These acylated nitrogen compounds are formed appropriately by reacting a molar ratio of acylating agent: amino compound from 10: 1 to 1:10, preferably from 5: 1 to 1: 5, more preferably, from 2: 1 to 1: 2 and, most preferably, from 2: 1 to 1: 1. In specifically preferred embodiments, the acylated nitrogen compounds are formed by reacting the acylating agent to the amino compound in a molar ratio between 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, most 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.
[212] 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 by polyisobutene and a polyethylene polyamine. Suitable compounds are described, for example, in WO2009 / 040583.
[213] In some embodiments, the diesel fuel composition comprises the reaction product of an acylating agent derived from carboxylic acid and hydrazine.
[214] Suitably, the additive comprises the reaction product between a hydrocarbyl-substituted succinic acid or anhydride and hydrazine.
[215] Preferably, the hydrocarbyl group of the hydrocarbyl-substituted succinic acid or succinic anhydride comprises a C8-C36 group, preferably a C8-C18 group. Alternatively, the hydrocarbyl group can be a polyisobutylene group with an average numerical molecular weight between 200 and 2,500, preferably between 800 and 1,200.
[216] Hydrazine has the formula NH2-NH2. Hydrazine can be hydrated or non-hydrated. Hydrazine monohydrate is preferred.
[217] The reaction between hydrocarbyl-substituted succinic acid or anhydride and hydrazine produces a variety of products, such as disclosed in US 2008/0060259.
[218] 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.
[219] 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', where each R 'is independently a group hydrocarbon of between 2 and 45 carbon atoms, ex is an integer between 1 and 4.
[220] In a preferred embodiment, the carboxylic acid comprises talanol fatty acid (TOFA).
[221] Additional preferred features of additives of this type are described in EP1900795.
[222] In some embodiments, the diesel fuel composition comprises the reaction product of a hydrocarbyl-substituted dicarboxylic acid or anhydride and an amine compound or salt whose product comprises at least one triazole amino group.
[223] Additives of this type are suitably the reaction product of a hydrocarbyl-substituted dicarboxylic acid or anhydride and an amine compound that has the formula:

[224] where R is selected from the group consisting of hydrogen and a hydrocarbyl group containing about 1 to about 15 carbon atoms, and R1 is selected from the group consisting of hydrogen and a hydrocarbyl group containing about from 1 to about 20 carbon atoms.
[225] The additive properly comprises the reaction product of an amine compound that has the formula:

[226] and a hydrocarbyl carbonyl compound of the formula:

[227] where R2 is a hydrocarbyl group having an average numerical molecular weight in the range of about 100 to about 5,000, preferably 200 to 3,000.
[228] Without sticking to the theory, the reaction product of the amine and the hydrocarbyl carbonyl compound is believed to be an aminotriazole, such as a bis-aminotriazole compound of the formula:

[229] including tautomers that have an average numerical molecular weight in the range of about 200 to about 3,000 containing about 40 to about 80 carbon atoms. The five-membered ring of the triazole is considered to be aromatic.
[230] The additional preferred features of additive compounds of this type are as defined in US2009 / 0282731.
[231] In some embodiments, the diesel fuel composition comprises a substituted polyaromatic detergent additive.
[232] A preferred compound of this type is the reaction product of an ethoxylated naphthol and paraformaldehyde, which is then reacted with a hydrocarbyl-substituted acylating agent.
[233] The additional preferred features of these detergents are described in EP1884556.
[234] In some embodiments, the fuel composition may be a fuel gasoline composition.
[235] Suitably, the quaternary ammonium salt additive is present in the gasoline 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.
[236] Suitably, the quaternary ammonium salt additive is present in the gasoline fuel composition in an amount of less than 10,000 ppm, preferably less than 1,000 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.
[237] 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 such additives present in the composition.
[238] In such modalities, the composition may comprise one or more gasoline detergents selected from:
[239] (p) polyoxyalkylene amines or polyetheramines substituted by hydrocarbyl;
[240] (q) acylated nitrogen compounds that are the reaction product of an acylating agent derived from carboxylic acid and an amine;
[241] (r) hydrocarbyl substituted amines in which the hydrocarbyl substituent is substantially aliphatic and contains at least 8 carbon atoms;
[242] (s) Mannich base additives comprising condensates containing nitrogen from a phenol, aldehyde and primary or secondary amine;
[243] (t) aromatic esters of a polyalkylphenoxycancanol;
[244] (u) an additional quaternary ammonium salt additive that is not a quaternary ammonium compound of the first aspect; and
[245] (v) hydrocarbyl tertiary amines of which have a maximum of 30 carbon atoms.
[246] Suitable polyoxyalkylene amines or hydrocarbyl-substituted polyetheramines (p) are described in US 6217624 and US 4288612. Other suitable polyetherines are those taught in US 5089029 and US 5112364.
[247] 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 this document in relation to the component (iii) of the additives that can be added to the diesel fuel compositions of the invention.
[248] 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 those patents are U.S. Patents 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.
[249] Mannich's additives (s) comprise condensates that contain 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 .
[250] The gasoline compositions of the present invention may further comprise as additives (t) aromatic esters of a polyalkylphenoxycanol.
[251] The aromatic ester component that can be used in the additive composition is an aromatic ester of a polyalkylphenoxycananol and has the following general formula:

[252] or a fuel-soluble salt (s) of the same where R is hydroxy, nitro or - (CH2) x-NR5R6, where R5 and R6 are, independently, hydrogen or lower alkyl having 1 to 6 carbon atoms ex is 0 or 1;
[253] R1 is hydrogen, hydroxy, nitro or -NR7R8 where R7 and R8 are, independently, hydrogen or lower alkyl having 1 to 6 carbon atoms;
[254] R2 and R3 are, independently, hydrogen or lower alkyl having 1 to 6 carbon atoms; and
[255] R4 is a polyalkyl group that has an average molecular weight in the range of about 450 to 5,000.
[256] The preferred features of these aromatic ester compounds are as described in WO2011141731.
[257] Additional quaternary ammonium salt additives (u) are suitably as defined in relation to component (i) of additives suitable for use in diesel fuel compositions.
[258] The tertiary hydrocarbyl amines (v) suitable for use in the gasoline fuel compositions of the present invention are tertiary amines of the formula R1R2R3N where R1, R2 and R3 are the same or different C1-C20 hydrocarbyl residues and the total number of carbon atoms is not more than 30. Suitable examples are N, N dimethyl n dodecylamine, 3- (N, N-dimethylamino) propanol and N, N-di (2-hydroxyethyl) -oleylamine. The preferred features of these tertiary hydrocarbyl amines are described in US2014 / 0123547.
[259] The gasoline composition may additionally comprise a carrier oil.
[260] Carrier oil can be any suitable molecular weight. A preferred molecular weight is in the range of 500 to 5,000.
[261] In one embodiment, the carrier oil may comprise an oil of lubricating viscosity, which includes natural or synthetic oils of lubricating viscosity, oil derived from hydrocracking, hydrogenation, hydro finishing, unrefined, refined and refined oils or mixtures thereof.
[262] Natural oils include animal oils, vegetable oils, mineral oils or mixtures thereof. Synthetic oils can include hydrocarbon oils, such as those produced by Fischer-Tropsch reactions, and, typically, can be hydroisomerized hydrocarbons or Fischer-Tropsch waxes.
[263] In another embodiment, the carrier oil may comprise a polyether carrier oil. In a preferred embodiment, the polyether carrier oil is a blocked chain terminal monopolyalkylene glycol, specifically a blocked chain terminal monopolypropylene glycol. Carrier oils of this type will be known to the person skilled in the art.
[264] The gasoline fuel compositions of the invention may contain one or more additional additives conventionally additional to gasoline, for example, other detergents, dispersants, antioxidants, antifreeze agents, metal deactivators, lubricity additives, friction modifiers, turbidity, corrosion inhibitors, dyes, markers, octane enhancers, valve seat anti-recession additives, stabilizers, demulsifier, antifoams, odor masks, conductivity enhancers and combustion enhancers.
[265] The quaternary ammonium salts of the present invention are useful as detergent additives for fuel oil and lubricant compositions. It has been found that the inclusion of these additives in the fuel compositions reduces deposits within the engines in which the fuel is subjected to combustion. This can be achieved by avoiding or reducing the formation of deposits, that is, keeping the engine clean, or it can be the removal of existing deposits, that is, cleaning a blocked engine.
[266] It has been found that the quaternary ammonium compounds of the present invention are particularly effective in diesel engines, specifically, in modern diesel engines that have a high pressure fuel system.
[267] Due to consumer demand and legislation, diesel engines have become much more energy efficient in recent years, have shown improved performance and have reduced emissions.
[268] These improvements in performance and emissions were produced 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 orifice diameters. The fuel pressure at the injection nozzle is now commonly in excess of 1,500 bar (1.5 x 108 Pa). To achieve these pressures, the work that needs to be done on the fuel also increases the temperature of the fuel. These high pressures and temperatures can cause fuel degradation. In addition, timing, quantity and fuel injection control have become increasingly accurate. Accurate fuel measurement needs to be maintained to achieve optimum performance.
[269] Diesel engines that have high pressure fuel systems may include, but are not limited to, heavy duty diesel engines and smaller passenger car type diesel engines. Heavy duty diesel engines can include very powerful engines, such as the MTU series 4000 diesel which has 20-cylinder variants designed primarily for ships and power generation with a power output of up to 4,300 kW or engines such as the Renault dXi 7 , which has 6 cylinders and a power output of around 240kW. A typical diesel engine for the passenger car is the Peugeot DW10 which has 4 cylinders and a power output of 100 kW or less depending on the variant.
[270] In diesel engines preferred by this invention, a common feature is a high pressure fuel system. Typically, pressures in excess of 1,350 bar (1.35 x 108 Pa) are used, but pressures of up to 2,000 bar (2 x 108 Pa) or more can often exist.
[271] 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 the same to the fuel injection valves via a common rail; and the unit injection system that integrates the high pressure pump and the fuel injection valve in one assembly, reaching the highest possible injection pressures, exceeding 2,000 bar (2 x 108 Pa). In both systems, when pressurizing the fuel, the fuel often becomes hot, to temperatures around 100 ° C or more.
[272] In common rail systems, fuel is stored at high pressure on the central accumulator rail or in separate accumulators before being delivered to the injectors. Often, a portion of the heated fuel is returned to the low pressure side of the fuel system or returned to the fuel tank. In unit injection systems, fuel is compressed inside the injector in order to generate the high injection pressures. This, in turn, increases the temperature of the fuel.
[273] In both systems, fuel is present in the injector body prior to injection where it is further heated due to the heat of the combustion chamber. The fuel temperature at the injection tip can be as high as 250 to 350 ° C.
[274] Therefore, the fuel is tensioned at pressures from 1,350 bar (1.35 x 108 Pa) to 2,000 bar (2 x 108 Pa) and temperatures of around 100 ° C to 350 ° C before injection, sometimes being recirculated back into the fuel system, thereby increasing the time for which the fuel experiences these conditions.
[275] A common problem with diesel engines is the injector fouling, particularly the injector body, and the injector nozzle. Fouling can also occur on the fuel filter. Injector nozzle encrustation occurs when the nozzle becomes blocked with deposits of diesel fuel. The fouling of fuel filters can be related to the recirculation of fuel back into the fuel tank. Deposits increase with fuel degradation. The deposits may take the form of residues similar to carbonaceous coke, lacquers or sticky or gum-like residues. Diesel fuels become more and more unstable the more they are heated, particularly if heated under pressure. Therefore, diesel engines that have 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 assist in reaching lower targets. This has led to increasingly complex injectors and a lower tolerance to deposits.
[276] The injector scale problem can occur when using any type of diesel fuel. However, some fuels may be particularly prone to scale, or scale may occur more quickly when these fuels are used. For example, fuels that contain biodiesel and those that contain metallic species can lead to increased deposits.
[277] When the injectors become blocked or partially blocked, the delivery of fuel is less efficient, and there is an insufficient mixture of the fuel with the air. Over time, this leads to a loss in engine power, increased exhaust emissions and low fuel economy.
[278] Deposits are known to occur in the sprinkler channels of the injector, leading to reduced flow and loss of power. As the size of the injector nozzle orifice is reduced, the relative impact of increasing the deposit becomes more significant. Deposits are known to occur at the injection tip. Here, they affect the fuel sprinkling pattern and cause less effective combustion and associated higher emissions and increased fuel consumption.
[279] In addition to these “external” injector deposits in the nozzle orifice and the injection tip, which lead to reduced flow and loss of power, deposits can occur within the injector body, causing additional problems. These deposits can be called internal diesel injector deposits (or IDIDs). IDIDs occur inside the injector in the fundamental moving parts. They can prevent the movement of these parts, affecting the timing and the amount of fuel injection. Since diesel engines operate under very precise conditions, these deposits can have a significant impact on performance.
[280] IDIDs cause several problems, including loss of power and reduced fuel economy due to suboptimal measurement and combustion. Initially, the user may experience problems with cold ignition and / or irregular engine running. These deposits can lead to more serious injector adhesion. This occurs when deposits interrupt the movement of parts of the injector and, thus, the injector stops working. When several or all of the injectors adhere, the engine may fail completely.
[281] Adding nitrogen-containing detergents to diesel fuel is known to reduce coke formation. Typical nitrogen-containing detergents include those formed by reacting a polyisobutylene-substituted succinic acid derivative with a polyalkylene polyamine. However, newer engines that include thinner injector nozzles are more sensitive, and current diesel fuels may not be suitable for use with new engines that incorporate these smaller nozzle orifices.
[282] As mentioned above, the injector fouling problem may be more likely to occur when using fuel compositions that comprise metal species. Various types of metal can be present in fuel compositions. This may be due to contamination of the fuel during manufacture, storage, transportation or use or due to contamination of fuel additives. Metal species can also be added to fuels intentionally. For example, transition metals are occasionally added as catalysts from fuel, for example, to improve the performance of diesel particulate filters.
[283] The present inventors believe that injector adherence problems occur when metal or ammonium species, particularly sodium species, react with the carboxylic acid species in the fuel.
[284] Sodium contamination of diesel fuel and the resulting formation of carboxylate salts is believed to be the major cause of injector adhesion.
[285] 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 are typically present in a total amount of 0.01 to 50 ppm, preferably 0.05 to 5 ppm, preferably 0.1 to 2 ppm, such as 0.1 to 1 ppm .
[286] Other species that contain metal may also be present as a contaminant, for example, through the corrosion of metal and metal oxide surfaces by acidic species present in the fuel or from the lubricating oil. In use, fuels such as diesel fuels routinely come into contact with metal surfaces, for example, in vehicle fueling systems, fuel tanks, means of transporting fuel, etc. Typically, metal-containing contamination may comprise metals transition, such as zinc, iron and copper; other metals of group I or group II and other metals such as lead.
[287] The presence of metal-containing species can lead to fuel filter deposits and / or external injector deposits that include injector tip deposits and / or nozzle deposits.
[288] In addition to the metal-containing contamination that may be present in diesel fuels, there are circumstances in which metal-containing species may be intentionally added to the fuel. For example, as is known in the art, catalyst species from fuel containing metal can be added to aid in the regeneration of particulate catches. The presence of such catalysts can also cause injector deposits when fuels are used in diesel engines that have high pressure fuel systems.
[289] Contamination containing metal, depending on its source, may be in the form of insoluble particles or soluble compounds or complexes. Metal-containing fuel catalysts are often soluble compounds or complexes or colloidal species.
[290] In some embodiments, diesel fuel may comprise metal-containing species that comprise a fuel-derived catalyst. Preferably, the fuel-derived catalyst comprises one or more metals selected from iron, cerium, platinum, manganese, group I and group II metals, for example, calcium and strontium. Most preferably, the fuel-derived catalyst comprises a metal selected from iron and cerium.
[291] In some embodiments, diesel fuel may comprise metal-containing species that comprise zinc. Zinc can be present in an amount of 0.01 to 50 ppm, preferably 0.05 to 5 ppm, more preferably 0.1 to 1.5 ppm.
[292] Typically, the total amount of all species that contain metal in diesel fuel, expressed in terms of the total weight of metal in the species, is 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.
[293] It is advantageous to provide a diesel fuel composition that prevents or reduces deposits on a diesel engine. Such deposits may include "external" injector deposits, such as deposits in and around the nozzle orifice and at the injection tip, and "internal" injector deposits or IDIDs. Such fuel compositions can be considered to perform a “keep clean” function, that is, they prevent or inhibit fouling. It is also desirable to provide a diesel fuel composition that can assist in cleaning deposits of these types. Such a fuel composition that, when subjected to combustion in a diesel engine, removes deposits from it, thus effecting the "cleaning" of an engine already encrusted.
[294] As well as the “keep clean” properties, “cleaning” an encrusted 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, removing deposits from an engine, in particular injectors, can lead to an increase in the time interval before maintenance, or replacement of the injector is necessary, thus reducing maintenance costs.
[295] Although, for the reasons mentioned above, injector deposits are a specific problem seen in modern diesel engines with high pressure fuel systems, it is desirable to provide a diesel fuel composition that also provides effective detergency in diesel engines older traditional engines, so that a single fuel supplied at the pumps can be used in engines of all types.
[296] It is also desirable for fuel compositions to reduce the fouling of vehicle fuel filters. It is useful to provide compositions that prevent or inhibit the occurrence of fuel filter deposits, that is, provide a "keep clean" function. It is useful to provide compositions that remove existing deposits from fuel filter deposits, that is, provide a “clean” function. Compositions capable of providing both of these functions are specifically useful.
[297] In accordance with a sixth aspect of the present invention, a method of improving the performance of an engine is provided, the method comprising combustion in said engine of a fuel composition comprising, as an additive, a compound of quaternary ammonium which is the reaction product of:
[298] (a) a tertiary amine having a molecular weight less than 1,000;
[299] (b) an acid-activated alkylating agent; and
[300] (c) a diacid which includes an optionally substituted alkyl or alkenyl chemical moiety that has at least 5 carbon atoms, preferably at least 6 carbon atoms.
[301] The preferred features of the sixth aspect of the present invention are as defined in relation to the first, second, third and fifth aspects.
[302] Preferably, the sixth aspect of the present invention comprises combustion, in an engine, a fuel composition comprising, as an additive, a quaternary ammonium compound which is the reaction product of:
[303] (a) a tertiary amine having a molecular weight less than 1,000;
[304] (b) an epoxide; and
[305] (c) a diacid which includes an optionally substituted alkyl or alkenyl chemical moiety that has at least 5 carbon atoms, preferably at least 6 carbon atoms.
[306] The sixth aspect of the present invention can adequately provide a method of improving the performance of an engine which comprises the steps of: preparing a quaternary additive, according to the method of the second aspect; adding the quaternary ammonium salt additive to a fuel composition; and subject the fuel composition added to the engine to combustion
[307] In the sixth aspect method, the engine can be a gasoline engine, and the fuel composition can be a gasoline fuel.
[308] Preferably, in the sixth aspect method, the engine is a diesel engine, and the fuel composition is a diesel fuel composition.
[309] The present inventors surprisingly concluded that, for the lower molecular weight cations of the present invention, quaternary ammonium salts formed from diacids show a significant improvement in performance, compared to quaternary ammonium salts formed from from monoesters of the same diacid.
[310] The sixth aspect method of the present invention is particularly effective in improving the performance of a modern diesel engine that has a high pressure fuel system.
[311] Such diesel engines can be characterized in several ways.
[312] Such engines are typically equipped with fuel injection equipment that meets or exceeds “Euro 5” emissions legislation, or equivalent legislation in the U.S. or other countries.
[313] Such engines are typically equipped with fuel injectors that have a plurality of openings, with each opening having an inlet and an outlet.
[314] Such motors can be characterized by openings that are tapered in such a way that the inlet diameter of the spray holes is larger than the outlet diameter.
[315] Such modern engines can be characterized by openings having an outlet diameter less than 500 μm, preferably less than 200 μm, more preferably less than 150 μm, preferably less than 100 μm, most preferably, less than 80 μm or less.
[316] Such modern diesel engines can be characterized by openings in which an inner edge of the inlet is rounded.
[317] Such modern diesel engines can be characterized by the fact that the injector has more than one opening, suitably, more than 2 openings, preferably more than 4 openings, for example, 6 or more openings.
[318] Such modern diesel engines can be characterized by a peak operating temperature in excess of 250 ° C.
[319] Such modern diesel engines can be characterized by a fuel injection system that provides a fuel pressure greater than 1,350 bar (135 MPa), preferably greater than 1,500 bar (150 MPa), more preferably, more than 2,000 bar (200 MPa). Preferably, the diesel engine has a fuel injection system that comprises a common rail injection system.
[320] The method of the present invention preferably improves the performance of an engine that has one or more of the characteristics described above.
[321] The method of the present invention improves the performance of an engine. This performance improvement is adequately achieved by reducing deposits on the engine.
[322] The present invention can therefore provide a method of combating deposits in an engine that comprises combustion, in said engine, of a fifth composition fuel composition.
[323] The sixth aspect of the present invention relates, preferably, 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 running the engine using unaddited fuel. It can be interpreted that this method achieves a “keep clean” performance.
[324] Combating deposits may involve removing existing deposits on an engine. It can be interpreted that this achieves a "clean" performance.
[325] In specifically preferred embodiments, the method of the sixth aspect of the present invention can be used to provide "keep clean" and "clean" performance.
[326] As explained above, deposits can occur at different locations within a diesel engine, for example, a modern diesel engine.
[327] The present invention is particularly useful for preventing or reducing or removing internal deposits in engine injectors that operate at high pressures and temperatures at which the fuel can be recirculated, and that comprise a plurality of fine openings through which the fuel is delivered to the engine. The present invention finds utility in engines for heavy duty vehicles and passenger vehicles. Passenger vehicles that incorporate a high-speed direct injection engine (or HSDI) can, for example, benefit from the present invention.
[328] The present invention can also provide improved performance in modern diesel engines that have a high pressure fuel system by controlling external injector deposits, for example, those that occur in the injector nozzle and / or the injector tip. . The ability to provide control of internal injector deposits and external injector deposits is a useful advantage of the present invention.
[329] 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.
[330] Suitably, the present invention can reduce or remove existing external injector deposits. It can provide “clean” performance against external injector deposits.
[331] Suitably, the present invention can reduce or prevent the formation of internal diesel injector deposits. It can, therefore, provide “keep clean” performance against internal diesel injector deposits.
[332] Suitably, the present invention can reduce or remove existing internal diesel injector deposits. It can, therefore, provide “clean” performance against internal diesel injector deposits.
[333] The present invention can also combat deposits on vehicle fuel filters. This may include reducing or preventing the formation of deposits ("keep clean" performance) or the reduction or removal of existing deposits ("clean" performance).
[334] The diesel fuel compositions of the present invention can also provide improved performance when used with traditional diesel engines. Preferably, improved performance is achieved by using diesel fuel compositions in modern diesel engines that have high pressure fuel systems and by using compositions in traditional diesel engines. This is important, as it allows the supply of a single fuel that can be used in new engines and older vehicles.
[335] The removal or reduction of IDIDs in accordance with the present invention will lead to an improvement in engine performance.
[336] 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 “keep clean” and / or “clean” performance is measured.
[337] An improvement in “keep clean” performance can be measured by comparison with a base fuel. The "clean" performance can be seen by an improvement in the performance of an already encrusted engine.
[338] The effectiveness of fuel additives is often assessed using a controlled engine test.
[339] In Europe, the coordinating European council for the development of performance tests for transport fuels, lubricants and other fluids (the industrial entity 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 European Union emissions regulations, known as the “Euro 5” regulations. The test is based on a Peugeot DW10 engine using Euro 5 injectors, and is commonly called the DW10 test. This test measures the power loss in the engine due to deposits on the injectors, and is further described in example 8.
[340] 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 subjects the said fuel composition to combustion in which the additive is a quaternary ammonium compound. which is the reaction product of:
[341] (a) a tertiary amine having a molecular weight less than 1,000;
[342] (b) an acid-activated alkylating agent; and
[343] (c) a diacid that includes an optionally substituted alkyl or alkenyl chemical moiety that has at least 5 carbon atoms, preferably at least 6 carbon atoms.
[344] The preferred features of the seventh aspect of the present invention are as defined with respect to the first, second, third and fifth aspects and, specifically, as defined with respect to the sixth aspect.
[345] The invention will now be described further with reference to the following non-limiting examples. In the examples that follow, the values determined in parts per million (ppm) for treatment rates indicate the amount of active agent, not the amount of a formulation as added, which contains an active agent. All parts per million are by weight. EXAMPLE 1
[346] Additive A1 was prepared as follows.
[347] A sample of polyisobutenyl succinic anhydride prepared from 1,000 MW of gdp (PIB1000SA) was hydrolyzed by reaction with a slight excess of water at 90 to 95 ° C. The acid value of the resulting PIB1000SAcid was determined to be 1.50 mmol / g by titration against 0.1N lithium methoxide in toluene.
[348] The PIB1000SAcid sample (50.10 g, 75 mmol of CO2H) was loaded into a 3-neck round bottom flask. The flask was fitted with an N2 discharge, reflux condenser, stir bar and thermocouple well. A thermostatically controlled oil bath to maintain 105 ° C was used to heat the contents of the flask with agitation. The flask was charged with Shellsol AB (70.73 g) and was heated with strong agitation to 95 ° C. Water (3.384 g, 188 mmol, 2.51 CO2H equivalents) was added, forming a cloudy solution.
[349] N, N-Dimethyl ethanolamine (6.76 g, 76 mmol, 1.0 equivalents) was then added. This significantly reduced, but did not remove, turbidity. FTIR confirmed the formation of an amine salt. After two hours, a second FTIR spectrum was essentially unchanged from the first.
[350] 2-ethylhexylglycidyl ether (14.06 g, 75.6 mmol, 1.01 equivalents) was added, lowering the temperature from 94 to 88 ° C. Heating continued and, after a further 90 minutes at a temperature of 95 ° C, an additional FTIR spectrum was acquired. The peak associated with the carboxylate salt was shifted slightly to 1,574 cm-1 and was approximately doubled in height in relation to CH2 absorbances at 1,463 and 1,455 cm-1. The additive A1, the quaternary ammonium di-salt of PIB1000SAcid, by opening the 2-ethylhexylglycidyl ether ring with N, N-dimethyl ethanolamine was formed as a 50% solution in aromatic solvent.
Additive A1 EXAMPLE 2
[351] Additional compounds of the invention and comparative compounds were prepared using a method analogous to example 1, except that the acid was replaced by an acid having the formula HOOCCHRCH2COOX, as follows:

[352] The skilled person will recognize that compounds, such as A8, will exist as a mixture of isomers that include molecules of the formula HOOCCH2CHRCOOX.
[353] In each case, the same amine and epoxide as in example 1 were used (A2 to A7), but for acids where X is H, two cation equivalents are present per acid equivalent. When X is methyl (A8), a cation equivalent is present. EXAMPLE 3
[354] The additive A9 of the invention was prepared using a method analogous to that described in example 1. In this case, 2 molar equivalents of dimethylethanolamine were reacted with 2 molar equivalents of dodecylene oxide and one equivalent of dodecenyl succinic acid. EXAMPLE 4 (COMPARATIVE)
[355] The additive A10 (not of the invention) was prepared from dimethylethanolamine, 2-ethylexyl glycidyl ether and acetic acid. EXAMPLE 5 (COMPARATIVE)
[356] Additive B is a 60% active ingredient solution (in aromatic solvent) of a polyisobutenyl succinimide obtained from the condensation reaction of a polyisobutenyl succinic anhydride derived from Mn polyisobutene approximately 750 with a mixture of polyethylene polyamine of medium composition approaching tetraethylene pentamine. The product was obtained by mixing PIBSA and polyethylene polyamine at 50 ° C under nitrogen and heating at 160 ° C for 5 hours with water removal. EXAMPLE 6 (COMPARATIVE) ADDITIVE C
[357] A reactor is loaded with 33.2 kg (26.5 mol) of PIBSA (produced from 1,000 MW of GDP and maleic anhydride) and heated to 90 ° C. DMAPA (2.71 kg, 26.5 mol) was loaded, and the mixture stirred for 1 hour at 90 to 100 ° C. The temperature was raised to 140 ° C for 3 hours and the water was removed. Methyl salicylate (4.04 kg, 26.5 mol) was loaded and the mixture kept at 140 ° C for 8 hours. Caromax 20 (26.6 kg) was added. EXAMPLE 7
[358] Diesel fuel compositions were prepared comprising the additives listed in Table 1, added to aliquots, all taken from a common batch of base fuel RF06, and containing 1 ppm zinc (as zinc neodecanoate). TABLE 1

[359] Table 2 below shows the specification for the RF06 base fuel. TABLE 2

EXAMPLE 8
[360] The fuel compositions 1 to 3 listed in Table 1 were tested according to method CECF-98-08 DW 10.
[361] The engine for the injection fouling test is the PSA DW10BTED4. Briefly, the characteristics of the engine are:
[362] Design: Four cylinders in line, camshaft control, turbocharger with EGR
[363] Capacity: 1,998 cm3
[364] Combustion chamber: Four valves, piston vessel, direct wall-guided injection
[365] Power: 100 kW at 4,000 rpm
[366] Torque: 320 Nm at 2,000 rpm
[367] Injection system: Common rail as electronically controlled 6-hole piezo injectors.
[368] Maximum pressure: 1,600 bar (1.6 x 108 Pa). Property project by SIEMENS VDO
[369] Emission control: Conforms to Euro IV limit values when combined with exhaust gas after treatment (DPF)
[370] This engine was chosen as a representative design of the European high speed direct injection diesel engine capable of meeting current and future European emissions requirements. The common direct 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, allowed advantages to be achieved in combustion efficiency, reduced noise and reduced fuel consumption, but it is sensitive to influences that can interrupt the flow of fuel, such as deposit formation in spray holes. The presence of these deposits causes a significant loss of engine power and increased gross emissions.
[371] The test is performed with an injector design of the future representative of the anticipated Euro V injector technology.
[372] It is considered necessary to establish a reliable injector condition baseline before starting fouling tests, so a sixteen hour run schedule for the test injectors is specified, using reference fuel without inlay.
[373] Full details of the CEC F-98-08 test method can be obtained from CEC. The coke formation cycle is summarized below. 1. A HEATING CYCLE (12 MINUTES) ACCORDING TO THE FOLLOWING REGIME:
2. 8 HOURS OF ENGINE OPERATION THAT CONSISTS OF 8 CYCLE REPEATS TO FOLLOW
for the expected range, consult the CEC method of CEC-F-98-08 3. COOL TO INACTIVITY IN 60 SECONDS AND INACTIVATE FOR 10 SECONDS 4. 4 HOURS OF EMBEDDING PERIOD
[374] The standard CEC F-98-08 test method consists of 32 hours of engine operation, which corresponds to 4 repetitions of steps 1 to 3 above, and 3 repetitions of step 4, that is, 56 hours of time. of full test excluding heating and cooling.
[375] The results of these tests are shown in figure 1. EXAMPLE 9
[376] The effectiveness of the additives detailed in Table 3 below in older types of engines was assessed using an industry standard test - CEC test method No CEC F-23-A-01.
[377] This test measures the formation of coke in the injector nozzle using a Peugeot XUD9 A / L engine and provides a means of distinguishing between fuels of different propensities for coke formation in the injector nozzle. The formation of coke in the nozzle is the result of carbon deposits that form between the injector needle and the needle seat. The deposition of carbon deposit occurs due to the exposure of the needle and the injector seat to combustion gases, potentially causing undesired variations in engine performance.
[378] The Peugeot XUD9 A / L engine is an indirect injection diesel engine with 4 cylinders of 1.9 liters of displaced volume, obtained from Peugeot Citroen Motors, specifically for the CEC method PF023.
[379] The test engine is fitted with clean injectors using flattened injector needles. Air flow at various needle lift positions was measured on a flow device prior to testing. The engine is operated for a period of 10 hours under cyclical conditions.


[380] The propensity of the fuel to promote deposit formation in the fuel injectors is determined by measuring the air flow from the injector nozzle again at the end of the test, and comparing these values to those before the test. The results are expressed in terms of the percentage of airflow reduction in various needle lift positions for all nozzles. The mean value of the 0.1 mm needle lift air flow reduction from all 4 nozzles is considered the level of coke formation in the injector for a given fuel.
[381] The results of this test using the specified additive combinations of the invention are shown in Table 3. In each case, the specified amount of additive was added to a base fuel RF06 that meets the specification determined in Table 2 (example 5) above. TABLE 3


[382] These results show that the quaternary ammonium salt additives of the present invention achieve an excellent reduction in the occurrence of deposits in traditional diesel engines.
[383] Additives of the invention that are formed from a diacid that includes an optionally substituted chemical hydrocarbyl moiety that has at least 5 carbon atoms perform better than equivalent compounds in which there is no chemical hydrocarbyl moiety that has at least 5 carbon atoms (compositions 11 and 14) or where the diacid monoester is used (composition 12).

权利要求:
Claims (15)
[0001]
1. Fuel composition comprising as an additive one or more quaternary ammonium compounds of formula (X):
[0002]
Fuel composition according to claim 1 which includes one or more compounds of formula:
[0003]
Fuel composition according to claim 2, characterized in that the quaternary ammonium compound is the reaction product of: (a) a tertiary amine R1R R3N that has a molecular weight less than 1,000; (b) an epoxide of formula
[0004]
Fuel composition according to any one of the preceding claims, characterized in that each of R1, R2 and R3 is independently selected from an alkyl or hydroxyalkyl group having 1 to 6 carbon atoms.
[0005]
5. Fuel composition according to any one of the preceding claims, characterized by the fact that the fuel is diesel fuel.
[0006]
6. Fuel composition according to claim 5, characterized by the fact that it optionally comprises one or more additional detergents selected from: (i) an additional quaternary ammonium salt additive that is not 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 an optionally substituted hydrocarbyl-substituted dicarboxylic acid or anhydride and an amine or salt compound whose product comprises at least one amino triazole group; and (vii) a substituted polyaromatic detergent additive.
[0007]
Fuel composition according to any one of claims 1 to 4, characterized by the fact that the fuel is gasoline fuel.
[0008]
8. Fuel composition according to claim 7, characterized by the fact that it optionally comprises one or more gasoline detergents selected from: (p) polyoxyalkylene amines or polyetheramines substituted by hydrocarbyl; (q) acylated nitrogen compounds that are the reaction product of an acylating agent derived from carboxylic acid and an amine; (r) hydrocarbyl-substituted amines in which 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; and (u) an additional quaternary ammonium salt additive that is not a quaternary ammonium compound, as defined in claim 1; and (v) tertiary hydrocarbon amines that have 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 preceding 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 that has a fuel injection system comprising a high pressure fuel injection system (HPFI) with higher fuel pressures than 135 mPa (1350 bar).
[0012]
12. Method, according to claim 11, characterized by the fact that the improvement in performance is achieved by combating deposits on the engine.
[0013]
13. Method, according to claim 12, characterized by the fact that it combats internal diesel injector deposits.
[0014]
14. Method according to claim 12 or 13, characterized by the fact that it combats external diesel injector deposits, including injector nozzle deposits and injector tip deposits.
[0015]
15. Method according to any one of claims 12 to 14, characterized in that it combats deposits on the fuel filter.

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法律状态:
2019-12-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-11-17| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-01-05| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 28/07/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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GBGB1313423.4A|GB201313423D0|2013-07-26|2013-07-26|Compositions and methods|

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GB1313423.4|2013-07-26|

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PCT/GB2014/052312|WO2015011507A1|2013-07-26|2014-07-28|Quaternary ammonium compounds as fuel or lubricant additives|

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