Method and use involving reduction of NOx emissions in diesel engines with nitrogenous detergents

Abstract

A method of reducing nitrogen monoxide and / or nitrogen dioxide emissions produced when a diesel engine combusts a diesel fuel composition, the method comprising metering at least one nitrogen-containing cleaning agent as an additive to the diesel fuel composition.

Description

Technical Field

[0001] This invention relates to diesel fuel compositions and related methods and uses. In particular, this invention relates to diesel fuel compositions that reduce nitrogen oxide emissions. Background Technology

[0002] The combustion of fossil fuels leads to the formation of nitrogen oxides (NOx). The formed nitrogen oxides (commonly known as NO) x This includes nitric oxide (NO) and nitrogen dioxide (NO2).

[0003] NO x It is known to cause serious health and environmental problems. For example, exposure to NO... x It can cause breathing difficulties, especially asthma.

[0004] Currently, reducing NO x Emissions mitigation efforts focus on treating exhaust gases after they leave the combustion chamber, achieved through devices including Selective Catalytic Reduction (SCR). SCR devices remove NO from the exhaust stream. x It converts other harmful gases into less harmful substances. SCR devices typically involve using urea as a reducing agent in the presence of a catalyst. Selective catalytic reduction devices consist of a porous ceramic support and a catalyst, which typically contains metals or zeolites. This device is part of the diesel engine's afterburner system, which usually includes a series of components that exhaust gases must pass through before exiting the vehicle.

[0005] SCR units require regular maintenance and may need to be treated with additives. Some vehicles include a device for metering the addition of a separate additive specifically for catalyst regeneration into the exhaust stream. This increases the cost and complexity of vehicle maintenance procedures.

[0006] Therefore, it is desirable to provide a solution that can reduce NO and NO2 during combustion. x The fuel composition of the emissions. Surprisingly, the inventors have discovered that including certain additives in diesel fuel can advantageously lead to NO and NO2 emissions. x Emissions reduction. Summary of the Invention

[0007] According to a first aspect of the invention, a method is provided for reducing nitrogen monoxide and / or nitrogen dioxide emissions generated when a diesel engine burns a diesel fuel composition, the method comprising metering in at least one nitrogen-containing cleaning agent as an additive to the diesel fuel composition.

[0008] According to a second aspect of the invention, at least one nitrogen-containing cleaning agent is provided as an additive for reducing nitrogen monoxide and / or nitrogen dioxide emissions generated when a diesel engine burns a diesel fuel composition.

[0009] This invention relates to the use of additives to reduce nitrogen monoxide and / or nitrogen dioxide emissions during the combustion of diesel fuel compositions.

[0010] This invention relates to the use of one or more nitrogen-containing cleaning agents as additives. Therefore, this invention can include using one nitrogen-containing cleaning agent as an additive, or using multiple nitrogen-containing cleaning agents as multiple additives.

[0011] For the avoidance of doubt, each additive used in this invention may comprise a mixture of compounds, and unless otherwise stated, references to an additive or such additive include mixtures. In particular, mixtures of isomers and mixtures of homologues are within the scope of this invention. Those skilled in the art will understand that commercial sources of some of the additive compounds described herein may comprise mixtures of isomers and / or mixtures of homologues.

[0012] This invention relates to the use of one or more nitrogen-containing cleaning agents. Any suitable nitrogen-containing cleaning agent can be used.

[0013] Preferably, the one or more nitrogen-containing cleaning agents are selected from: (a) Quaternary ammonium salt additives; (b) Reaction products of carboxylic acid-derived acylating agents and amines; (c) The products of the Mannich reaction between aldehydes, amines and optionally substituted phenols; (d) Reaction products of carboxylic acid derivatives with hydrazine; (e) Salts formed by the reaction of carboxylic acids with C1 to C10 alkylamines (such as di-n-butylamine or tri-n-butylamine); (f) The reaction product of a hydrocarbon-substituted dicarboxylic acid or anhydride with an amine compound or salt, the product comprising at least one aminotriazole group; and (g) Compounds of formula (I): (I) in: A is a nitrogen-containing group; L represents a bond or linker group; and R¹ is an optionally substituted hydrocarbon group; and the compound has a nitrogen content of at least 4% by mass.

[0014] The one or more nitrogen-containing cleaning agents are preferably selected from one or more of the following: (a) Quaternary ammonium salt additives; (b) Reaction products of carboxylic acid-derived acylating agents and amines; (c) The products of the Mannich reaction between aldehydes, amines, and optionally substituted phenols; and (g) Compounds of formula (I): (I) in: A is a nitrogen-containing group; L is a bond or linking group; and R¹ is an optionally substituted hydrocarbon group; The compound has a nitrogen content of at least 4% by mass.

[0015] In some embodiments, the one or more nitrogen-containing cleaning agents may contain (a) a quaternary ammonium salt additive.

[0016] In this article, the terms "quaternary ammonium compound" and "quaternary ammonium salt additive" and "quaternary ammonium salt" are used interchangeably.

[0017] Preferably, the quaternary ammonium salt additive is a reaction product of a compound containing a tertiary amine group and a quaternizing agent.

[0018] Any suitable quaternizing agent can be used. Quaternizing agents can be suitably selected from esters and non-esters.

[0019] Suitable quaternizing agents include carboxylic acid esters, dialkyl sulfates, benzyl halides, hydrocarbon-substituted carbonates, hydrocarbon-substituted epoxides (optionally combined with acids), alkyl halides, alkyl sulfonates, sulfonyl lactones, hydrocarbon-substituted phosphates, hydrocarbon-substituted borates, alkyl nitrites, alkyl nitrates, hydroxides, N-oxides, chloroacetic acid or their salts, or mixtures thereof.

[0020] In some preferred embodiments, the quaternizing agent used to form the quaternary ammonium salt additive of the present invention is an ester.

[0021] Preferred ester quaternizing agents are compounds of formula (II): (II) Where R 3 It is an optionally substituted alkyl, alkenyl, aryl, or alkylaryl group, and R 2 It is C1 to C22 alkyl, aryl, or alkylaryl. The compounds of formula (II) are suitably esters of carboxylic acids capable of reacting with tertiary amines to form quaternary ammonium salts.

[0022] Suitable quaternizing agents include esters of carboxylic acids with a pKa of 3.5 or less.

[0023] The compound of formula (II) is preferably an ester of a carboxylic acid selected from substituted aromatic carboxylic acids, α-hydroxycarboxylic acids and polycarboxylic acids.

[0024] In some preferred embodiments, the compound of formula (II) is an ester of a substituted aromatic carboxylic acid, therefore R 3 For the substituted aryl group.

[0025] Preferably, R 3 The substituted aryl group has 6 to 10 carbon atoms, preferably phenyl or naphthyl, with phenyl being the most preferred. 3 Suitablely composed of one or more groups selected from carboalkoxy, nitro, cyano, hydroxyl, SR x or NR x R y The group is substituted. R x and R y Each can be hydrogen or optionally substituted alkyl, alkenyl, aryl, or alkoxycarbonyl. Preferably, R x and R y Each is hydrogen or optionally substituted C1 to C22 alkyl, preferably hydrogen or C1 to C16 alkyl, more preferably hydrogen or C1 to C10 alkyl, and even more preferably hydrogen or C1 to C4 alkyl. Preferably, R x It is hydrogen and R y It is hydrogen or a C1 to C4 alkyl group. Most preferably, R x and R y All are hydrogen. Preferably, R 3 It is an aryl group substituted with one or more groups selected from hydroxyl, alkoxycarbonyl, nitro, cyano, and NH2. 3 It can be a polysubstituted aryl group, such as trihydroxyphenyl. In some embodiments, R 3 It can be a hydrocarbon group substituted with an aryl group, such as an alkyl group substituted with an aryl group. In some embodiments, R 3 It can be an aryl group substituted with a hydroxyl group and a hydrocarbon group (such as an alkyl group), as described in EP2631283.

[0026] Preferably, R 3 It is a monosubstituted aryl group. Preferably, R 3 For ortho-substituted aryl. Suitablely, R 3 It is substituted with a group selected from OH, NH2, NO2, or COOMe. Preferably, R 3 Replaced by an OH or NH2 group. Suitablely, R 3 The aryl group is hydroxylated. Most preferably, R... 3 It is 2-hydroxyphenyl.

[0027] Preferably, R 2 It is alkyl, arylalkyl, or alkylaryl. R 2 It can be a C1 to C16 alkyl group, preferably a C1 to C10 alkyl group, and suitably a C1 to C8 alkyl group. R 2 It can be C7 to C16 arylalkyl or alkylaryl, preferably C7 to C10 arylalkyl or alkylaryl. 2 It can be methyl, ethyl, propyl, butyl, pentyl, benzyl, or an isomer thereof. Preferably, R 2It is benzyl or methyl. Most preferably, R 2 It is a methyl group.

[0028] Particularly preferred compounds of formula (II) are lower alkyl esters of salicylic acid, such as methyl salicylate, ethyl salicylate, n-propyl and isopropyl salicylate, and butyl salicylate, with methyl salicylate being preferred.

[0029] In some embodiments, the compound of formula (II) is an ester of an α-hydroxycarboxylic acid. In such embodiments, the compound has the following structure: Where R 4 and R 5 They may be the same or different, and each is selected from hydrogen, alkyl, alkenyl, arylalkyl or aryl. Such compounds applicable to this document are described in EP1254889.

[0030] Where R 3 Examples of compounds of formula (II) with COO being an α-hydroxycarboxylic acid residue include methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl, and allyl esters of 2-hydroxyisobutyric acid; methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl, and allyl esters of 2-hydroxy-2-methylbutyric acid; methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl, and allyl esters of 2-hydroxy-2-ethylbutyric acid; methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl, and allyl esters of lactic acid; and methyl, ethyl, propyl, butyl, pentyl, hexyl, allyl, benzyl, and phenyl esters of glycolic acid. A preferred compound is methyl 2-hydroxyisobutyrate.

[0031] In some embodiments, the compound of formula (II) is an ester of a polycarboxylic acid. In this definition, we mean including dicarboxylic acids and carboxylic acids having more than two acidic groups. In such embodiments, R... 3 COO is preferably present in the form of an ester, i.e., R 3 One or more additional acid groups present in the group are in esterified form. However, embodiments in which not all acid groups are esterified are also within the scope of this invention. Mixed esters of polycarboxylic acids may also be used. Preferred esters are C1 to C4 alkyl esters.

[0032] The ester quaternizing agent may be selected from diester oxalate, diester phthalate, diester maleate, diester malonate, or diester citrate. A particularly preferred compound of formula (II) is dimethyl oxalate.

[0033] In a preferred embodiment, the compound of formula (II) is an ester of a carboxylic acid with a pKa less than 3.5. In embodiments where such compounds contain more than one acid group, we mean the first dissociation constant.

[0034] The ester quaternizing agent may be selected from esters of carboxylic acids, wherein the carboxylic acid is selected from one or more of the following: oxalic acid, phthalic acid, salicylic acid, maleic acid, malonic acid, citric acid, nitrobenzoic acid, aminobenzoic acid, 2,4,6-trihydroxybenzoic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, ethynyl dicarboxylic acid, pentenic acid, mucoconic acid, citraconic acid, mesocarboxylic acid, itaconic acid, hydroxymalonic acid, pyruvic acid, tartaric acid, oxaloacetic acid, dioxosuccinic acid, α-hydroxyglutaric acid, biphenyl acid, and 2,6-naphthalenedicarboxylic acid.

[0035] The ester quaternizing agent may be selected from esters of carboxylic acids, wherein the carboxylic acid is 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.

[0036] Preferred ester quaternizing agents include dimethyl oxalate, methyl 2-nitrobenzoate, and methyl salicylate.

[0037] In some preferred embodiments, the quaternizing agent used to form the quaternary ammonium salt additive of the present invention is an ester selected from dimethyl oxalate, methyl 2-nitrobenzoate and methyl salicylate, preferably dimethyl oxalate and methyl salicylate.

[0038] Suitable non-ester quaternizing agents include dialkyl sulfates, benzyl halides, hydrocarbon-substituted carbonates, hydrocarbon-substituted epoxides (optionally in combination with acids), alkyl halides, alkyl sulfonates, sulfonyl lactones, hydrocarbon-substituted phosphates, hydrocarbon-substituted borates, alkyl nitrites, alkyl nitrates, hydroxides, N-oxides, chloroacetic acid or their salts, or mixtures thereof.

[0039] Preferred non-ester quaternizing agents include dialkyl sulfates, benzyl halides, hydrocarbon-substituted carbonates, hydrocarbon-substituted epoxides in combination with acids, alkyl halides, alkyl sulfonates, sulfonyl lactones, hydrocarbon-substituted phosphates, hydrocarbon-substituted borates, N-oxides, chloroacetic acid or their salts, or mixtures thereof.

[0040] In some embodiments, the quaternary ammonium salt can be prepared, for example, from alkyl or benzyl halides (especially chlorides), followed by an ion exchange reaction to provide different anions as part of the quaternary ammonium salt. Such a method is applicable to the preparation of quaternary ammonium hydroxides, alkoxides, nitrites, or nitrates.

[0041] Alkyl halides applicable to this article include chlorides, bromides, and iodides.

[0042] Suitable benzyl halides include chlorides, bromides, and iodides. The phenyl group may be optionally substituted, for example, with one or more alkyl or alkenyl groups, especially when using chlorides. A preferred compound is benzyl bromide.

[0043] The dialkyl sulfates used herein as quaternizing agents include alkyl groups having 1 to 10, preferably 1 to 4, carbon atoms in the alkyl chain. A preferred compound is dimethyl sulfate.

[0044] Suitable hydrocarbon-substituted carbonates may comprise two hydrocarbon groups, which may be the same or different. Each hydrocarbon group may contain 1 to 50 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and suitably 1 to 5 carbon atoms. Preferably, the hydrocarbon group or each hydrocarbon group is an alkyl group. Such preferred compounds include diethyl carbonate and dimethyl carbonate.

[0045] Suitable hydrocarbon-substituted epoxides have the following formula: Where R 6 R 7 R 8 and R 9 Each epoxide is independently hydrogen or a hydrocarbon group having 1 to 50 carbon atoms. Examples of suitable epoxides include ethylene oxide, propylene oxide, butane oxide, styrene oxide, and stilbene oxide. Hydrocarbon epoxides are used in combination with acids as quaternizing agents.

[0046] In some embodiments, the compound containing the tertiary amine group also includes an acid functional group. In these embodiments, if an epoxide is used as the quaternizing agent, the addition of a separate acid is not required. However, in other embodiments, an acid, such as acetic acid, may be used.

[0047] Particularly preferred epoxide quaternizing agents are propylene oxide and styrene oxide, optionally in combination with additional acids.

[0048] Suitable alkyl sulfonates include those having 1 to 20, preferably 1 to 10, more preferably 1 to 4 carbon atoms.

[0049] Suitable sulfonyl lactones include propanesulfonyl lactone and butanesulfonyl lactone.

[0050] Suitable hydrocarbon-substituted phosphates include monoalkyl phosphates, dialkyl phosphates, trialkyl phosphates, and O,O-dialkyl dithiophosphates. Preferred alkyl groups have 1 to 12 carbon atoms.

[0051] Suitable hydrocarbon-substituted borate groups include alkyl borates having 1 to 12 carbon atoms.

[0052] Preferred alkyl nitrites and alkyl nitrites have 1 to 12 carbon atoms.

[0053] Preferably, the non-ester quaternizing agent is selected from dialkyl sulfates, benzyl halides, hydrocarbon-substituted carbonates, hydrocarbon-substituted epoxides (optionally combined with additional acids), chloroacetic acid or its salts, and mixtures thereof.

[0054] Particularly preferred non-ester quaternizing agents used herein are hydrocarbon-substituted epoxides in combination with an acid. This can include embodiments providing the acid alone, or embodiments where the acid is provided by a quaternized tertiary amine compound. Preferably, the acid is provided by a quaternized tertiary amine molecule.

[0055] Preferred quaternizing agents used herein include dimethyl oxalate, methyl 2-nitrobenzoate, methyl salicylate, chloroacetic acid or its salts, and styrene oxide or propylene oxide (optionally in combination with additional acids).

[0056] In some implementations, a mixture of two or more quaternizing agents may be used.

[0057] To form quaternary ammonium salt additives, the quaternizing agent is reacted with a compound containing a tertiary amine group.

[0058] Any suitable compound containing a tertiary amine group can be used.

[0059] Compounds containing at least one tertiary amine group may be selected from: (i) The reaction product of a hydrocarbon-substituted acylated agent and a compound comprising at least one tertiary amine group and a primary amine, secondary amine or alcohol group; (ii) Mannich reaction products containing tertiary amine groups; (iii) A polyalkylene-substituted amine having at least one tertiary amine group; and (iv) Simple alkylamines and alkanolamines.

[0060] For the avoidance of doubt, a compound containing at least one tertiary amine group and a primary amine, secondary amine or alcohol group is a compound whose molecular structure contains at least one tertiary amine group and additionally at least one group selected from primary amine groups, secondary amine groups or alcohol groups.

[0061] Examples of quaternary ammonium salts and their preparation methods are described in the following patents: US2008 / 0307698, US2008 / 0052985, US2008 / 0113890 and US2013 / 031827.

[0062] The preparation of some suitable quaternary ammonium salt additives (compounds containing at least one tertiary amine group including component (i)) is described in WO2006 / 135881, US2020 / 0024536 and WO2011 / 095819.

[0063] Component (ii) is a Mannich reaction product containing a tertiary amine. The preparation of compounds containing at least one tertiary amine group, including quaternary ammonium salts of component (ii), is described in US 2008 / 0052985.

[0064] The preparation of quaternary ammonium salt additives comprising component (iii) of compounds containing at least one tertiary amine group is described, for example, in US2008 / 0113890.

[0065] The preparation of some suitable quaternary ammonium salt additives (compounds containing at least one tertiary amine group including component (i)) is described, for example, in WO2016 / 016641.

[0066] Other suitable quaternary ammonium salts include quaternized terpolymers, such as those described in US2011 / 0258917; quaternized copolymers, such as those described in US2011 / 0315107; and acid-free quaternized nitrogen compounds disclosed in US2012 / 0010112.

[0067] In some embodiments, the present invention does not include acid-free quaternary ammonium compounds. In a preferred embodiment, the quaternary ammonium salt additive of the present invention comprises separate anions and separate cations.

[0068] Other suitable quaternary ammonium salt additives for use in this invention include those described in the applicant’s applications in WO2011 / 095819, WO2013 / 017889, WO2015 / 011506, WO2015 / 011507, WO2016 / 016641 and WO2017 / 017454.

[0069] In some embodiments, the compound containing at least one tertiary amine group is (i) a reaction product of a hydrocarbon-substituted acylating agent and a compound containing at least one tertiary amine group and a primary amine, secondary amine or alcohol group, wherein the hydrocarbon-substituted acylating agent may be provided by a hydrocarbon-substituted succinic acid-derived acylating agent.

[0070] In such embodiments, the quaternary ammonium salt additive (a) is a quaternization reaction product of a hydrocarbon-substituted succinic acid derivative acylating agent and a compound capable of reacting with said acylating agent and containing a tertiary amine group.

[0071] For the avoidance of doubt, references to quaternization reaction products are intended to refer to reaction products containing tertiary amines subsequently quaternized to form quaternary ammonium groups. Quaternary ammonium salt additives are formed by reacting a quaternizing agent with a hydrocarbon-substituted succinic acid-derived acylating agent and a compound capable of reacting with said acylating agent and containing a tertiary amine group.

[0072] As used herein, the term "hydrocarbon substituent" or "hydrocarbon group" is used in its common sense, as is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and possessing predominantly hydrocarbon properties. Examples of hydrocarbon groups include: (i) Hydrocarbon groups, namely aliphatic (which may be saturated or unsaturated, straight or branched, such as alkyl or alkenyl), alicyclic (such as cycloalkyl, cycloalkenyl) substituents, and aromatic (including aliphatic- and alicyclic-substituted aromatic) substituents, and cyclic substituents, wherein the ring is completed by another part of the molecule (e.g., two substituents together form a ring). (ii) Substituted hydrocarbon groups, i.e., substituents containing non-hydrocarbon groups, which do not alter the main hydrocarbon properties of the substituent in the context of this invention (e.g., halogen (such as chlorine, fluorine or bromine), hydroxyl, alkoxy (such as C1 to C4 alkoxy), ketone, acyl, cyano, mercapto, amino, amide, nitro, nitrosyl, sulfinyl, nitryl and carboxyl). (iii) Heteroatom substituents, which are substituents that, in the context of this invention, possess predominantly hydrocarbon properties while also containing atoms other than carbon in a ring or chain composed of carbon atoms. Heteroatoms include sulfur, oxygen, and nitrogen, and substituents such as pyridyl, furanyl, thiophene, and imidazolyl. Generally, no more than two, preferably no more than one, non-hydrocarbon substituents will be present for every ten carbon atoms in the hydrocarbon group; typically, the hydrocarbon group will not contain any non-hydrocarbon substituents.

[0073] Suitable hydrocarbon-substituted succinic acid derivatives and their preparation methods are well known in the art. For example, a common method for preparing hydrocarbon-substituted succinic acid derivatives is to react maleic anhydride with an olefin by using a chlorination route or a thermal route (the so-called "olefinification" reaction).

[0074] Illustrative examples of hydrocarbon substituents include n-octyl, n-decyl, n-dodecyl, tetrapropenyl, n-octadecyl, oleyl, chlorooctadecyl, triacontyl, etc. Hydrocarbon substituents can be prepared from homopolymers or interpolymers (e.g., copolymers, terpolymers) of mono- and di-olefins having 2 to 10 carbon atoms (e.g., ethylene, propylene, butane-1, isobutylene, butadiene, isoprene, 1-hexene, 1-octene, etc.). Preferably, these olefins are 1-monoolefins. Alternatively, substituents can be prepared from other sources, such as monomeric high molecular weight olefins (e.g., 1-tetradecene), aliphatic petroleum fractions, such as paraffin wax and its cracking analogues, white oil, synthetic olefins such as those produced by the Ziegler-Natta process (e.g., poly(ethylene) grease), and other sources known to those skilled in the art. If desired, any unsaturation in the substituents can be reduced or eliminated by hydrogenation according to methods known in the art.

[0075] Preferably, the hydrocarbon substituents are primarily saturated, meaning that for every ten carbon-carbon single bonds present, they contain no more than one carbon-carbon unsaturated bond. Most preferably, for every 50 carbon-carbon bonds present, they contain no more than one carbon-carbon non-aromatic unsaturated bond.

[0076] The succinic acid-derived acylating agent preferably contains at least 10, more preferably at least 12, for example at least 30 or at least 40 carbon atoms as hydrocarbon substituents. It may contain up to about 200 carbon atoms. Preferably, the number average molecular weight (Mn) of the hydrocarbon substituents of the acylating agent is 170 to 2800, for example 250 to 1500, preferably 500 to 1500, and more preferably 500 to 1100. Particularly preferred is an Mn of 700 to 1300.

[0077] Technicians are familiar with standard techniques for measuring number-average molecular weight, such as vapor pressure permeation, end-group titration, proton NMR, boiling point elevation, freezing point depression (freezing point depression determination), and GPC (gel permeation chromatography).

[0078] Hydrocarbon-substituted succinic acid derivatizing agents can comprise mixtures of compounds. For example, a mixture of compounds with different hydrocarbon substituents can be used.

[0079] Preferred hydrocarbon substituents are polyisobutylene. Such compounds are known to those skilled in the art.

[0080] Preferred hydrocarbon-substituted succinic acid derivatizing agents are polyisobutylene succinic anhydride. These compounds are commonly referred to as "PIBSA" and are known to those skilled in the art.

[0081] Both conventional polyisobutylene and so-called "highly reactive" polyisobutylene are applicable to this invention. Highly reactive polyisobutylene is defined in this context as polyisobutylene, as described in EP0565285, wherein at least 50%, preferably 70% or more, of the terminal olefinic double bonds are of the vinylidene type. Particularly preferred polyisobutylenes are those having more than 80 mol% and up to 100 mol% of terminal vinylides, as described in US7291758. Preferred polyisobutylenes have the preferred molecular weight (Mn) range generally described above for hydrocarbon substituents.

[0082] Other preferred hydrocarbon groups include those having an internal olefin, such as those described in the applicant’s published application WO2007 / 015080.

[0083] As used herein, internal olefins refer to any olefin that primarily contains non-α double bonds, i.e., β or higher olefins. Preferably, such materials are substantially entirely β or higher olefins, for example containing less than 10% by weight of α olefins, more preferably less than 5% by weight or less than 2% by weight. Typical internal olefins include Neodene 1518IO, available from Shell.

[0084] Internal alkenes are sometimes also called isomerized alkenes and can be prepared from α-olefins by isomerization methods known in the art, or obtained from other sources. The fact that they are also called internal alkenes reflects that they do not necessarily have to be prepared by isomerization.

[0085] The preferred hydrocarbon-substituted succinic acid derivatizing agent used to prepare the quaternary ammonium salt additive (a) of the present invention is polyisobutylene-substituted succinic anhydride or PIBSA. Particularly preferred PIBSAs are those having a PIB molecular weight (Mn) of 300 to 2800, preferably 450 to 2300, more preferably 500 to 1300.

[0086] Hydrocarbon-substituted succinic acid derivatizing acylates are suitably prepared by reacting maleic anhydride with an olefin (e.g., polyisobutylene). The resulting product (e.g., PIBSA) still contains a double bond. The maleic anhydride exists in the resulting molecule as the succinic acid moiety. The initial product is monomaleicated PIBSA.

[0087] Monomaleic acid-modified PIBSA may have structure (A) or (B): The double bond in the monomaleic acid product can react with another molecule of maleic anhydride to form dimaleic acid PIBSA with structure (C) or (D): Therefore, it is possible to provide hydrocarbon groups that are substituted by more than one succinic acid moiety.

[0088] Those skilled in the art will understand that the additives used in this invention typically comprise a mixture of compounds and will be prepared from a mixture of mono- and bis-maleic acidified PIBSA. The PIBSA can be defined according to its level of bis-maleic acidification.

[0089] One way to determine this level is by calculating the average amount of succinic acid per molecule of acylated agent.

[0090] Monomaleic acid-modified PIBSA has one succinic acid portion per module.

[0091] Dimaleated PIBSA has two succinic acid moieties per molecule.

[0092] A mixture containing monomaleic acid-modified PIBSA and bismaleic acid-modified PIBSA in a 1:1 molar ratio will contain an average of 1.5 succinic acid fractions per molecule of PIBSA.

[0093] The average amount of succinic acid moiety per molecule of acylating agent is sometimes referred to in the art as the "P-value".

[0094] Suitable, the quaternary ammonium salt additive is prepared from a succinic acid derivative acylating agent containing an average of 1 to 2 succinic acid moieties per molecule.

[0095] In some preferred embodiments, the invention may involve the use of quaternary ammonium salts derived from hydrocarbon-substituted acylating agents comprising an average of at least 1.2 succinic acid moieties per molecule.

[0096] As a technician will understand, a single molecule cannot have 1.2 succinic acid moieties. At least 1.2 succinic acid moieties means the average number of succinic acid moieties per molecule of acylating agent, obtained by dividing the sum of all succinic acid moieties present in the sample by the total number of acylating agent molecules in the sample that have one or more succinic acid moieties.

[0097] Preferably, the hydrocarbon-substituted succinic acid derivative acylated agent comprises an average of at least 1.21 succinic acid moieties per molecule, more preferably at least 1.22 succinic acid moieties per molecule.

[0098] In some embodiments, the hydrocarbon-substituted succinic acid derivative acylating agent may contain at least 1.23 or at least 1.24 succinic acid moieties per molecule.

[0099] In some embodiments, the hydrocarbon-substituted succinic acid derivative acylating agent may contain at least 1.25, at least 1.26, or at least 1.27 succinic acid moieties per molecule.

[0100] In some embodiments, the hydrocarbon-substituted succinic acid derivative acylating agent may contain at least 1.28, at least 1.29, or at least 1.30 succinic acid moieties per molecule.

[0101] By the succinic acid moiety, we mean succinic acid residues that exist in the form of diacids or anhydrides.

[0102] In some embodiments, the compound containing at least one tertiary amine group is a reaction product of (i) a hydrocarbon-substituted acylated agent and a compound containing at least one tertiary amine group and a primary amine, secondary amine, or alcohol group, wherein the hydrocarbon-substituted acylated agent may be provided by a fatty acid. A suitable fatty acid is of formula R. z Compounds of COOH, wherein R z It is an alkyl or alkenyl group having 6 to 36 carbon atoms, preferably 8 to 30 carbon atoms or 12 to 24 carbon atoms. A preferred fatty acid is oleic acid.

[0103] The hydrocarbon-substituted acylating agent is reacted with a compound that can react with the acylating agent and contains a tertiary amine group. The tertiary amine group is quaternized to provide a quaternary ammonium salt additive.

[0104] Examples of suitable compounds capable of reacting with alkyl-substituted acylating agents and containing a tertiary amine group include, but are not limited to, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, and N,N-dimethylaminoethylamine. Nitrogen- or oxygen-containing compounds capable of condensing with acylating agents and further having a tertiary amine group may also include aminoalkyl-substituted heterocyclic compounds, such as 1-(3-aminopropyl)imidazolium and 4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-diamino-N-methyldipropylamine, and 3,3-aminobis(N,N-dimethylpropylamine). Other types of nitrogen- or oxygen-containing compounds that can condense with acylating agents and have a tertiary amino group include alkanolamines, including but not limited to triethanolamine, trimethanolamine, N,N-dimethylaminopropanol, N,N-dimethylaminoethanol, N,N-diethylaminopropanol, N,N-diethylaminoethanol, N,N-diethylaminobutanol, N,N,N-tris(hydroxyethyl)amine, N,N,N-tris(hydroxymethyl)amine, N,N,N-tris(aminoethyl)amine, and N,N-dibutylamino Propylamine and N,N,N'-trimethyl-N'-hydroxyethyl-diaminoethyl ether; N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine; N-(3-dimethylaminopropyl)-N,N-diisopropanolamine; N'-(3-(dimethylamino)propyl)-N,N-dimethyl-1,3-propanediamine; 2-(2-dimethylaminoethoxy)ethanol, N,N,N'-trimethylaminoethylethanolamine and 3-(2-(dimethylamino)ethoxy)propylamine.

[0105] Preferably, the compound capable of reacting with a hydrocarbon-substituted acylation agent and containing a tertiary amine group is an amine of formula (III) or (IV): Where R 10 and R 11 X is an alkyl, alkenyl, aryl, alkylaryl, or arylalkyl group having 1 to 22 carbon atoms, whether identical or different; X is a bond or an optionally substituted alkylene group having 1 to 20 carbon atoms; n is 0 to 20; m is 1 to 5; and R 12 Hydrogen or C1 to C 22 alkyl.

[0106] When using compounds of formula (III), R 12 Preferably hydrogen or C1 to C 16 Alkyl groups, preferably C1 to C2 10 Alkyl, more preferably C1 to C6 alkyl. When R 12When it is alkyl, it can be linear or branched. It can be substituted with, for example, hydroxyl or alkoxy substituents. Preferably, R 12 Not a substituted alkyl group. More preferably, R 12 Selected from hydrogen, methyl, ethyl, propyl, butyl, and their isomers. Most preferably, R 12 It is hydrogen.

[0107] When using a compound of formula (IV), m is preferably 2 or 3, most preferably 2; n is preferably 0 to 15, more preferably 0 to 10, and even more preferably 0 to 5. Most preferably, n is 0 and the compound of formula (IV) is an alcohol.

[0108] Preferably, the hydrocarbon-substituted acylated agent reacts with the diamine compound of formula (III).

[0109] R 10 and R 11 These can be the same or different alkyl, alkenyl, aryl, alkylaryl, or arylalkyl groups having 1 to 22 carbon atoms. In some embodiments, R 10 and R 11 They can combine to form a ring structure, such as piperidine, imidazole, or morpholine moieties. Therefore, R 10 and R 11 They can together form aromatic and / or heterocyclic moieties. R 10 and R 11 It can be a branched alkyl or alkenyl group. Each can be substituted with, for example, a hydroxyl or alkoxy substituent.

[0110] Preferably, R 10 and R 11 Each independently is C1 to C 16 Alkyl groups, preferably C1 to C2 10 Alkyl group. R 10 and R 11 It can be independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or any isomer thereof. Preferably, R 10 and R 11 Each is independently a C1 to C4 alkyl group. Preferably, R 10 It is methyl. Preferably, R 11 It is a methyl group.

[0111] X is a bond or an optionally substituted alkylene group having 1 to 20 carbon atoms. In a preferred embodiment, when X is an alkylene group, the group can be straight-chain or branched. The alkylene group may contain a cyclic structure. It may be optionally substituted with, for example, hydroxyl or alkoxy substituents. In some embodiments, X may contain heteroatoms within the alkylene chain; for example, X may contain an ether functional group.

[0112] X is preferably an alkylene group having 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, such as 2 to 6 carbon atoms or 2 to 5 carbon atoms. In some preferred embodiments, X is an unsubstituted alkylene group. Most preferably, X is ethylene, propylene, or butylene, especially propylene.

[0113] Examples of compounds of formula (III) applicable to this document include 1-aminopiperidine, 1-(2-aminoethyl)piperidine, 1-(3-aminopropyl)-2-methylpiperidine, 1-methyl-(4-methylamino)piperidine, 4-(1-pyrrolyl)piperidine, 1-(2-aminoethyl)pyrrolidine, 2-(2-aminoethyl)-1-methylpyrrolidine, N,N-diethylethylenediamine, N,N-dimethylethylenediamine, N,N-dibutylethylenediamine, N,N-diethyl-1,3-diaminopropane, N,N-dimethyl-1,3-diaminopropane, N,N,N'-trimethylethylenediamine, N,N-dimethyl-N'-ethylethylenediamine, N,N-diethyl-N'-methylethylenediamine, N,N,N'-tri ... Ethylethylenediamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, 3-dibutylaminopropylamine, N,N,N'-trimethyl-1,3-propanediamine, N,N,2,2-tetramethyl-1,3-propanediamine, 2-amino-5-diethylaminopentane, N,N,N',N'-tetraethyldiethylenetriamine, 3,3'-diamino-N-methyldipropylamine, 3,3'-iminobis(N,N-dimethylpropylamine), 1-(3-aminopropyl)imidazolium and 4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-diamino-N-methyldipropylamine, 3,3-aminobis(N,N-dimethylpropylamine), 3-(2-(dimethylamino)ethoxy)propylamine, or combinations thereof.

[0114] In some preferred embodiments, the compound of formula (III) is selected from N,N-dimethyl-1,3-diaminopropane, N,N-diethyl-1,3-diaminopropane, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dibutylethylenediamine, 3-(2-(dimethylamino)ethoxy)propylamine, or combinations thereof.

[0115] Examples of compounds of formula (IV) applicable to this document include alkanolamines, including but not limited to triethanolamine, N,N-dimethylaminopropanol, N,N-diethylaminopropanol, N,N-diethylaminobutanol, triisopropanolamine, 1-[2-hydroxyethyl]piperidine, 2-[2-(dimethylamine)ethoxy]-ethanol, N-ethyldiethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, N,N-diethylaminoethanol, and N,N-dimethylaminoethanol. 2-Dimethylamino-2-methyl-1-propanol; N,N,N'-trimethyl-N'-hydroxyethyl-diaminoethyl ether; N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine; N-(3-dimethylaminopropyl)-N,N-diisopropanolamine; N'-(3-(dimethylamino)propyl)-N,N-dimethyl-1,3-propanediamine; 2-(2-dimethylaminoethoxy)ethanol and N,N,N'-trimethylaminoethylethanolamine.

[0116] In some preferred embodiments, the compound of formula (III) is selected from triisopropanolamine, 1-[2-hydroxyethyl]piperidine, 2-[2-(dimethylamine)ethoxy]-ethanol, N-ethyldiethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, N,N-diethylaminoethanol, N,N-dimethylaminoethanol, 2-dimethylamino-2-methyl-1-propanol, or combinations thereof.

[0117] The most preferred compound of formula (III) is N,N-dimethyl-1,3-diaminopropane (dimethylaminopropylamine).

[0118] In some embodiments, the quaternary ammonium salt additive is the product of a quaternization reaction of a fatty acid (e.g., formula RCOOH, where R is an alkyl or alkenyl group having 12 to 24 carbon atoms) with a compound of formula (II), suitably wherein R 10 and R 11 All are C1 to C4 alkyl groups, and X is an alkylene group having 2 to 5 carbon atoms.

[0119] In some preferred embodiments, the quaternary ammonium salt additive is the product of the quaternization reaction of oleic acid with dimethylaminopropylamine.

[0120] In such embodiments, suitable quaternizing agents for reacting with the above-described reaction products include dialkyl sulfates, benzyl halides, hydrocarbon-substituted carbonates, hydrocarbon-substituted epoxides in combination with acids, alkyl halides, alkyl sulfonates, sulfonyl lactones, hydrocarbon-substituted phosphates, hydrocarbon-substituted borates, N-oxides, chloroacetic acid or salts thereof, or mixtures thereof. Preferably, the quaternizing agent is chloroacetic acid or a salt thereof, such as sodium chloroacetate.

[0121] In such embodiments, the quaternary ammonium salt additive may have formula (V): Where R 14 It is an alkyl or alkenyl group having 7 to 22 carbon atoms; R 15 and R 16 Each is independently an alkyl, hydroxyalkyl, or carboxyl group having 1 to 6 carbon atoms; m is 2 to 4; n is 0 or 1; X is an alkylene group having 1 to 6 carbon atoms and optionally substituted with a hydroxyl group; and Y is -CO2 or -SO3.

[0122] Preferably, the quaternary ammonium salt additive is an amide betaine having the following formula: Where R 14 R 15 and R 16 As specified above, where m is 2 or 3.

[0123] Preferably, R 14 It has 16 to 22 carbon atoms. R 14 Preferably, it is an alkenyl group having 16 to 22 carbon atoms. For example, R 14 It can be a C derived from oleic acid 17 Alkenyl. R 15 and R 16 Methyl is preferred.

[0124] In a preferred embodiment, the quaternary ammonium salt additive is the product of the quaternization reaction of oleic acid with dimethylaminopropylamine, wherein the reaction product has been quaternized with chloroacetic acid or a salt thereof.

[0125] When the compound of formula (III) reacts with a succinic acid derivatizing acylinter, the product is a succinate. When the succinic acid derivatizing agent reacts with R... 12 When a compound of formula (II) containing hydrogen reacts, the product can be succinimide or succinamide. When the succinylating agent reacts with R... 12 When a compound of formula (III) that is not hydrogen reacts, the product obtained is an amide.

[0126] In some embodiments, the succinylating agent is combined with a compound containing a primary amine moiety (e.g., wherein R... 12 The reaction of a compound of formula (III) containing hydrogen can form an amide bond, an imide bond, or a mixture thereof. Therefore, the reaction product can be succinimid or succinamide, or a mixture thereof. Whether succinimid or succinamide is formed may depend on the reaction conditions used. Those skilled in the art will be able to select appropriate reaction conditions to predominantly form the succinimid form or predominantly form the succinamide form of the reaction product. Succinamide suitably comprises a free carboxylic acid moiety and an amide bond formed between the succinylating agent and the amine compound.

[0127] In some preferred embodiments, the reaction product (i) of the hydrocarbon-substituted succinic acid derivative acylating agent and a compound capable of reacting with the acylating agent and containing a tertiary amine group is a succinimide, preferably a polyisobutylene succinimide (referred to as "PIBSI").

[0128] In some preferred embodiments, the reaction product (i) of the hydrocarbon-substituted succinic acid derivative acylating agent and a compound capable of reacting with the acylating agent and containing a tertiary amine group is succinamide, preferably polyisobutylene succinamide.

[0129] In some embodiments, to form a quaternary ammonium salt additive, a hydrocarbon-substituted acylating agent is reacted with a compound containing a tertiary amine group that is capable of reacting with the acylating agent. The reaction product is then quaternized by reacting it with a quaternizing agent.

[0130] The reaction product of the acylating agent and the compound containing the tertiary amine group preferably reacts with at least one molar equivalent of the quaternizing agent for every mole of the tertiary amine group present in the reaction product.

[0131] In some embodiments, the reaction product of the acylating agent and the compound containing the tertiary amine group can react with more than 1 molar equivalent of the quaternizing agent present in the reaction product per mole of the tertiary amine group, preferably at least 1.2 molar equivalents of the quaternizing agent per mole of the tertiary amine group, more preferably at least 1.5 molar equivalents of the quaternizing agent, suitably at least 1.7 molar equivalents of the quaternizing agent, for example at least 1.9 molar equivalents of the quaternizing agent.

[0132] In some embodiments, the reaction product of the acylating agent and the compound containing the tertiary amine group can react with 2 or more molar equivalents of the quaternizing agent per mole of the tertiary amine group present in the reaction product, preferably at least 2.1 molar equivalents of the quaternizing agent.

[0133] In some embodiments, the reaction product of the acylating agent and the compound containing a tertiary amine group is reacted with a quaternizing agent present in the reaction product in an amount greater than 2.2 molar equivalents per mole of tertiary amine group, such as 2.3 to 4 molar equivalents, 2.3 to 3 molar equivalents, or 2.3 to 2.7 or 2.5 to 3 molar equivalents of quaternizing agent.

[0134] In order to form some of the preferred quaternary ammonium salt additives of the present invention, the compound of formula (II) is reacted with the compound formed by the reaction of a hydrocarbon-substituted acylating agent with an amine of formula (III) or (IV).

[0135] The compounds of formula (III) or (IV) are as described above.

[0136] Preferably, the amine of formula (III) or (IV) is reacted with a hydrocarbon-substituted succinic acid derivative acylating agent (such as succinic acid or succinic anhydride).

[0137] Suitable, approximately one equivalent of amine is added for each succinic acid moiety present in the acylating agent. Therefore, the proportion of amine used will generally depend on the average amount of succinic acid moiety present in each molecule of acylating agent.

[0138] The quaternary ammonium salts preferred for use herein can be formed by reacting methyl salicylate, dimethyl oxalate, or propylene oxide (optionally in combination with an acid) with the reaction product of polyisobutylene-substituted succinic anhydride (having a PIB molecular weight (Mn) of 700 to 1300) and dimethylaminopropylamine. Mixtures of two or more such quaternary ammonium salts may be used.

[0139] The quaternary ammonium salts used in this article are particularly preferred to be formed by reacting methyl salicylate or dimethyl oxalate with the reaction product of polyisobutylene-substituted succinic anhydride (having a PIB molecular weight (Mn) of 700 to 1300) and dimethylaminopropylamine.

[0140] In a preferred embodiment, the polyisobutylene-substituted succinic anhydride comprises an average of at least 1.2 succinic acid moieties per molecule.

[0141] In some preferred embodiments, the quaternary ammonium salt additive (a) is formed by reacting a quaternizing agent with the reaction product of polyisobutylene-substituted succinic anhydride (having a PIB molecular weight (Mn) of 700 to 1300) and dimethylaminopropylamine, wherein the reaction product of polyisobutylene-substituted succinic anhydride and dimethylaminopropylamine is primarily in the form of succinimide. Preferably, the quaternizing agent is an alkylene oxide (preferably propylene oxide) (optionally in combination with an acid), chloroacetic acid or a salt thereof, methyl salicylate, or dimethyl oxalate. In some preferred embodiments, the quaternizing agent is methyl salicylate.

[0142] In some preferred embodiments, the quaternary ammonium salt additive (a) is formed by reacting a quaternizing agent with the reaction product of polyisobutylene-substituted succinic anhydride (having a PIB molecular weight (Mn) of 700 to 1300) and dimethylaminopropylamine, wherein the reaction product of polyisobutylene-substituted succinic anhydride and dimethylaminopropylamine is primarily in the form of succinamide. Preferably, the quaternizing agent is an alkylene oxide (preferably propylene oxide) (optionally in combination with an acid), chloroacetic acid or a salt thereof, methyl salicylate, or dimethyl oxalate. In some preferred embodiments, the quaternizing agent is propylene oxide.

[0143] In some embodiments, the quaternary ammonium salt additive (a) is the reaction product of a quaternizing agent and a compound containing a tertiary amine group (selected from (iv) simple alkylamines and alkanolamines).

[0144] In such embodiments, the compound (iv) containing the tertiary amine group is of formula R. 13 R 14 R 15 N-tertiary amines, where R 13 R14 and R 15 Each can be independently substituted with an alkyl, alkenyl, aryl, alkylaryl, or arylalkyl group.

[0145] Formula R 13 R 14 R 15 Tertiary amines of N can be small compounds with low complexity and low molecular weight. In some embodiments, tertiary amines can be complex molecules and / or high molecular weight molecules containing tertiary amine groups.

[0146] Formula R 13 R 14 R 15 Tertiary amine compounds of N preferably do not contain any primary or secondary amine groups. In some embodiments, they may be derived from compounds containing such groups, but preferably these groups have subsequently been reacted to form additional tertiary amines. Formula R 13 R 14 R 15 Tertiary amine compounds of N may contain more than one tertiary amine group. However, tertiary amine compounds containing primary or secondary amine groups are also within the scope of this invention, provided that these groups do not impede the quaternization of the tertiary amine class.

[0147] In equation R 13 R 14 R 15 In some embodiments of the N compound, R 13 R 14 and R 15 Each can be independently substituted with an alkyl, alkenyl, aryl, arylalkyl, or alkylaryl group.

[0148] R 13 R 14 and R 15 They can be the same or different. In some preferred embodiments, R 13 and R 14 Same, and R 15 different.

[0149] Preferably, R 13 and R 15 Each of the above is independently an alkyl, alkenyl, aryl, arylalkyl or alkylaryl group having 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms.

[0150] R 13 and R 14 Each group may be optionally substituted with one or more groups selected from halogens (especially chlorine and fluorine), hydroxyl, alkoxy, ketone, acyl, cyano, mercapto, alkyl mercapto, dialkylamino, nitro, nitroso, and sulfinyl. The alkyl groups of these substituents may be further substituted.

[0151] Preferably, R 13 and R 14 Each is independently an optionally substituted alkyl or alkenyl group. Preferably, R 13 and R 14 Each is independently an optionally substituted alkyl group. In some embodiments, R 13 and R 14 Each is independently an 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.

[0152] In some preferred embodiments, R 13 The alkyl or alkenyl group is optionally substituted, and preferably has 1 to 10, more preferably 1 to 4, carbon atoms. Preferably, R 13 It is an alkyl group. It can be a substituted alkyl group, such as a hydroxylated alkyl group. Preferably, R... 13 It is an unsubstituted alkyl group. The alkyl chain can be straight or branched. Preferably, R 13 Selected from methyl, ethyl, propyl, and butyl, including their isomers. Most preferably, R 13 It is a methyl group.

[0153] In some preferred embodiments, R 14 The alkyl or alkenyl group is optionally substituted, and preferably has 1 to 10, more preferably 1 to 4, carbon atoms. Preferably, R 14 It is an alkyl group. It can be a substituted alkyl group, such as a hydroxylated alkyl group. Preferably, R... 14 It is an unsubstituted alkyl group. The alkyl chain can be straight or branched. Preferably, R 14 Selected from methyl, ethyl, propyl, and butyl, including their isomers. Most preferably, R 14 It is a methyl group.

[0154] In some implementation schemes, R 15 The substituents are optionally substituted alkyl or alkenyl groups 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 halogens (especially chlorine and fluorine), hydroxyl groups, alkoxy groups, ketone groups, acyl groups, cyano groups, mercapto groups, alkyl mercapto groups, amino groups, alkylamino groups, nitro groups, nitroso groups, sulfinyl groups, amide groups, alkylamide groups, imide groups, and alkylimide groups. The alkyl groups of these substituents may be further substituted.

[0155] In some implementation schemes, R15 The alkyl or alkenyl group is optionally substituted, preferably having 1 to 10, more preferably 1 to 4, carbon atoms. Suitably, R 15 The alkyl group is optionally substituted. Preferably, R 15 The alkyl group is substituted. Preferred substituents include alkoxy and hydroxyl groups.

[0156] In some preferred embodiments, R 15 The alkyl group is hydroxylated. The alkyl chain can be straight or branched. Most preferably, R 15 It is hydroxyethyl.

[0157] Suitable formula R 13 R 14 R 15 N-tertiary amine compounds include simple alkylamino and hydroxyalkylamino compounds; trialkylamino compounds with high molecular weight substituents; Mannich reaction products containing tertiary amines; and substituted acylated amines or alcohols containing tertiary amines.

[0158] Simple alkylamino and hydroxyalkylamino compounds are preferably of formula R 13 R 14 R 15 Compounds of N, where R 13 R 14 and R 15 Each is either alkyl or hydroxyalkyl. R 13 R 14 and R 15 They can be the same or different. In some implementations, R 13 R 14 and R 15 Each is independently selected from alkyl or hydroxyalkyl groups having 1 to 10, preferably 1 to 6, carbon atoms, for example 1 to 4 carbon atoms. R 13 R 14 and R 15 Each of these can be independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, and hydroxyhexyl. Formula R 13 R 14 R 15 The amine of N can be a trialkylamine, a dialkylhydroxyalkylamine, a dihydroxyalkylalkylamine, or a trihydroxyalkylamine. There are many different compounds of this type, and these will be known to those skilled in the art.

[0159] In some implementations, group R 13 R 14 and R 15 One or two of them are short-chain alkyl groups having 1 to 6, preferably 1 to 4 carbon atoms, and the other or two groups are long-chain alkyl groups or groups having 6 to 30, preferably 10 to 24 carbon atoms.

[0160] In some implementation schemes, R 13 and R 14 Each is a C1 to C4 alkyl group, preferably methyl, and R 15 It is an alkyl or alkenyl group having 6 to 36, preferably 10 to 30, for example 12 to 24 carbon atoms.

[0161] Such compounds include, for example, dimethyloctadecylamine and hexadecyldimethylamine.

[0162] To provide quaternary ammonium salt additives, hexadecyl dimethylamine can be quaternized by reacting it with propylene oxide (e.g., 1 to 3 molar equivalents of propylene oxide) and polyisobutylene succinic acid (e.g., 1 molar equivalent of polyisobutylene succinic acid).

[0163] For example, in some implementation schemes, R 13 It is a C1 to C4 alkyl group, preferably methyl, and R 14 and R 15 Each is an alkyl or alkenyl group having 6 to 36, preferably 8 to 30, for example 10 to 24 carbon atoms.

[0164] Such compounds include, for example, hexadecyl dimethylamine, N-methylNN-ditallowamine, and dicosyl methylamine.

[0165] Especially preferred formula R 13 R 14 R 15 N-tertiary amine compounds include N,N-dimethylethanolamine, dimethyloctadecylamine, and N-methylNN-ditallowamine, and mixtures thereof.

[0166] In some preferred embodiments, the quaternary ammonium salt additive (a) is the reaction product of a compound containing a tertiary amine group and a quaternizing agent, wherein the compound containing the tertiary amine group is selected from one or more of the following: (ia) Formula R z The fatty acids of COOH (of which R) z The product of the reaction of an alkyl or alkenyl group having 12 to 24 carbon atoms with a compound of formula (II), wherein R 10 and R 11 All are C1 to C4 alkyl groups, and X is an alkylene group having 2 to 5 carbon atoms; (ib) The reaction product of a hydrocarbon-substituted succinic acid derivative acylating agent with a compound of formula (II), wherein R 10 and R 11 All are C1 to C4 alkyl groups, and X is an alkylene group having 2 to 5 carbon atoms; and (iv-a) Equation R 13 R 14 R15 N-tertiary amines, where R 13 R 14 and R 15 Each is independently an alkyl or hydroxyalkyl group.

[0167] The quaternizing agent is preferably selected from alkyl oxidants (preferably propylene oxide) (optionally combined with an acid), chloroacetic acid or its salts, methyl salicylate or dimethyl oxalate.

[0168] In some preferred embodiments, the quaternary ammonium salt additive (a) is the reaction product of a compound containing a tertiary amine group and a quaternizing agent, wherein the compound containing the tertiary amine group is selected from one or more of the following: (ia) Formula R z The fatty acids of COOH (of which R) z The product of the reaction of an alkyl or alkenyl group having 12 to 24 carbon atoms with a compound selected from N,N-dimethyl-1,3-diaminopropane, N,N-diethyl-1,3-diaminopropane, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dibutylethylenediamine, 3-(2-(dimethylamino)ethoxy)propylamine, or combinations thereof; (ib) The reaction product of a hydrocarbon-substituted succinic acid derivatizing agent with a compound selected from N,N-dimethyl-1,3-diaminopropane, N,N-diethyl-1,3-diaminopropane, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dibutylethylenediamine, 3-(2-(dimethylamino)ethoxy)propylamine, or combinations thereof; and (iv-a) Equation R 13 R 14 R 15 N-tertiary amines, where R 13 R 14 and R 15 Each is independently an alkyl or hydroxyalkyl group.

[0169] In some preferred embodiments, the quaternary ammonium salt additive (a) is the reaction product of a compound containing a tertiary amine group and a quaternizing agent; The quaternizing agent is selected from alkyl oxides (preferably propylene oxide) (optionally combined with an acid), chloroacetic acid or its salt, methyl salicylate or dimethyl oxalate. Compounds containing tertiary amine groups are selected from one or more of the following: (ia) Formula R z The fatty acids of COOH (of which R) zThe product of the reaction of an alkyl or alkenyl group having 12 to 24 carbon atoms with a compound selected from N,N-dimethyl-1,3-diaminopropane, N,N-diethyl-1,3-diaminopropane, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dibutylethylenediamine, 3-(2-(dimethylamino)ethoxy)propylamine, or combinations thereof; (ib) The reaction product of a hydrocarbon-substituted succinic acid derivatizing agent with a compound selected from N,N-dimethyl-1,3-diaminopropane, N,N-diethyl-1,3-diaminopropane, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dibutylethylenediamine, 3-(2-(dimethylamino)ethoxy)propylamine, or combinations thereof; and (iv-a) Equation R 13 R 14 R 15 N-tertiary amines, where R 13 R 14 and R 15 Each is independently an alkyl or hydroxyalkyl group.

[0170] In some particularly preferred embodiments, the quaternary ammonium salt additive (a) is the reaction product of a compound containing a tertiary amine group and a quaternizing agent; The quaternizing agent is selected from alkyl oxides (preferably propylene oxide) (optionally combined with an acid), chloroacetic acid or its salt, methyl salicylate or dimethyl oxalate. Compounds containing tertiary amine groups are selected from one or more of the following: (ia) Formula R z The fatty acids of COOH (of which R) z The product of the reaction of an alkyl or alkenyl group having 12 to 24 carbon atoms with N,N-dimethyl-1,3-diaminopropane (DMAPA); (ib) The reaction product of polyisobutylene-substituted succinic anhydride with a PIB molecular weight (Mn) of 700 to 1300 and N,N-dimethyl-1,3-diaminopropane; and (iv-a) Equation R 13 R 14 R 15 N-tertiary amines, where R 13 and R 14 Each is a C1 to C4 alkyl group, preferably methyl, and R 15 It is an alkyl or alkenyl group having 12 to 24 carbon atoms.

[0171] In some embodiments, the present invention relates to the use of the reaction product of (b) carboxylic acid derivatives with amines as an additive.

[0172] These compounds may also be referred to in this paper as acylated nitrogen-containing compounds.

[0173] Suitable acylated nitrogen-containing compounds can be prepared by reacting a carboxylic acid acylating agent with an amine, as is known to those skilled in the art.

[0174] Preferred hydrocarbon-substituted acylation agents are polyisobutylene succinic anhydride. These compounds are commonly referred to as "PIBSA" and are known to those skilled in the art.

[0175] Both conventional polyisobutylene and so-called "highly reactive" polyisobutylene are suitable for this invention. These are suitable as described above regarding the preparation of some preferred quaternary ammonium detergents.

[0176] Particularly preferred PIBSAs are those with a PIB molecular weight (Mn) of 300 to 2800, preferably 450 to 2300, and more preferably 500 to 1300.

[0177] In a preferred embodiment, the reaction product of the carboxylic acid derivative acylated agent and the amine contains at least one primary or secondary amine group.

[0178] The acylated nitrogen compounds preferred for use herein are prepared by reacting a poly(isobutylene)-substituted succinic acid-derived acylinder (such as anhydride, acid, ester, etc., wherein the poly(isobutylene) substituent has a number average molecular weight (Mn) of 170 to 2800 with a mixture of ethylene polyamines having 2 to 9 amino nitrogen atoms, preferably about 2 to 8 nitrogen atoms, and about 1 to 8 ethylene groups per ethylene polyamine polyamine. These acylated nitrogen compounds are suitably formed by a reaction in which the acylinder:amino compound molar ratio is 10:1 to 1:10, preferably 5:1 to 1:5, more preferably 2:1 to 1:2, and most preferably 2:1 to 1:1. In a particularly preferred embodiment, the acylated nitrogen compounds are formed by a reaction in which the acylinder:amino compound molar ratio is 1.8:1 to 1:1.2, preferably 1.6:1 to 1:1.2, more preferably 1.4:1 to 1:1.1, and most preferably 1.2:1 to 1:1. Such acylated amino compounds and their preparation are well known to those skilled in the art and are described, for example, in EP0565285 and US5925151.

[0179] In some preferred embodiments, the composition comprises such a cleaning agent formed by reacting a polyisobutylene-substituted succinic acid-derived acylated agent with a polyethylene polyamine. Suitable compounds are described, for example, in WO2009 / 040583.

[0180] In a preferred embodiment, the reaction product (b) of the carboxylic acid derivative acylating agent with the amine comprises the reaction product of polyisobutylene-substituted succinic acid or succinic anhydride with a polyethylene polyamine selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexadecimaline, and mixtures and isomers thereof; wherein the polyisobutylene substituent has a number average molecular weight of 500 to 2000, preferably 600 to 1200.

[0181] In some embodiments, the invention may involve the use of the Mannich reaction product between (c) aldehydes, amines and optionally substituted phenols.

[0182] Preferably, component (c) comprises the Mannich reaction product between the following substances: (x) Aldehyde; (y) amines; and (z) Optional substituted phenols.

[0183] 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.

[0184] Suitable amines for preparing Mannich additives include monoamines and polyamines. A suitable monoamine is butylamine.

[0185] The amine used to prepare the Mannich additive is preferably a polyamine. This can be selected from any compound containing two or more amine groups. Preferably, the polyamine is a polyalkylene polyamine, more preferably a polyethylene polyamine. The polyamine can be, for example, selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexadecimaline heptamine, heptaethylene octamine, propane-1,2-diamine, 2(2-amino-ethylamino)ethanol, and N... 1 N 1 -Bis(2-aminoethyl)ethylenediamine (N(CH2CH2NH2)3). Most preferably, the polyamine comprises tetraethylenepentamine or, in particular, ethylenediamine.

[0186] The optional substituted phenolic component used in the preparation of Mannich additives may be substituted with 0 to 4 groups on the aromatic ring (except for the phenol OH). For example, it may be a hydrocarbon-substituted cresol. Most preferably, the phenolic component is a monosubstituted phenol. Preferably, it is a hydrocarbon-substituted phenol. Preferred hydrocarbon substituents are alkyl substituents having 4 to 28 carbon atoms, especially 10 to 14 carbon atoms. Other preferred hydrocarbon substituents are polyolefin substituents. Such polyisobutylene substituents have a number average molecular weight of 400 to 2500, for example 500 to 1500.

[0187] The Mannich reaction products preferred for use in the present invention are typically formed by reacting components (x), (y), and (z) in a molar ratio of 1.1 to 5 parts (x): 1 part (y): 1.1 to 2 parts (z).

[0188] Suitable Mannich reaction products and methods for preparing such additives will be known to those skilled in the art, including, for example, compounds described in applicant publications WO2009040582 and WO2013017887.

[0189] Preferred additives for the Mannich reaction product are the reaction products of formaldehyde, polyethylene polyamine, and para-substituted monoalkylphenols.

[0190] The Mannich reaction product additives used in this article are particularly preferred to be the reaction product of dodecylphenol, formaldehyde and ethylenediamine.

[0191] In some embodiments, the additives used in this invention comprise (g) compounds of formula (I): (I) in: A is a nitrogen-containing group; L represents a bond or linking group; R 1 The hydrocarbon group is optionally substituted; and the compound has a nitrogen content of at least 4% by mass.

[0192] Preferably, R 1 The substituted alkyl, alkenyl, or aminoalkyl groups are optional, and preferably have a molecular weight (Mn) of up to 1000.

[0193] Compounds of formula (I) contain at least 4% by mass of nitrogen atoms. Thus, we mean that at least 4% of the molecular weight of a nitrogen-containing compound is provided by nitrogen atoms, preferably on a number-average molecular weight basis. The mass amount of nitrogen in such compounds can be calculated using standard methods or determined by elemental analysis. Since additives may comprise mixtures of compounds of formula (I), such as isomers, homologues, and / or structurally similar compounds produced by reactions used to form nitrogen-containing compounds, the aforementioned mass percentage of nitrogen is suitably an average of such mixtures of nitrogen-containing compounds.

[0194] Preferably, the compound of formula (I) contains at least 5% by mass of nitrogen atoms, more preferably at least 7% by mass or at least 10% by mass.

[0195] Suitably, the compound of formula (I) contains up to 50% by mass or up to 40% by mass of nitrogen atoms. Suitably, the nitrogen-containing compound contains up to 35% by mass of nitrogen atoms, suitably up to 30% by mass.

[0196] Suitably, the compound of formula (I) contains 4% to 50% by mass of nitrogen atoms, suitably 4% to 40% by mass. In a preferred embodiment, the compound of formula (I) contains 4% to 35% by mass of nitrogen atoms, suitably 5% to 30% by mass or 10% to 30% by mass.

[0197] The inventors discovered that the relatively high proportion of nitrogen atoms present in the additive of formula (I) is very advantageous.

[0198] The useful compounds of formula (I) in this invention preferably contain no more than twelve NH bonds. NH bonds may be referred to as “free” NH bonds. Preferably, the nitrogen-containing compounds contain fewer than five, four, or three NH bonds. Preferably, the above-described limitation on the number of NH bonds applies only to the NH bonds on the amino group in the compounds of formula (I). For example, NH bonds in amide groups and / or NH bonds on nitrogen atoms in aromatic heterocyclic rings are not included in the NH bond limitations described herein.

[0199] The inventors have discovered that the relatively low number of free NH bonds in the additive (which contains a relatively high proportion of nitrogen) can help provide the beneficial effects described herein.

[0200] Suitable compounds of formula (I) are the reaction products of p) hydrocarbon-substituted reagent and q) nitrogen-containing reagent.

[0201] In some embodiments, the compound of formula (I) is a reaction product of the following substances: p) Hydrocarbon-substituted carboxylic acid acylating agents; and q) Nitrogen-containing reagents; As further described below.

[0202] In some embodiments, the compound of formula (I) is a reaction product of the following substances: p) Amines or polyamines containing hydrocarbon groups; q) Nitrogen-containing reagents; and r) Aldehyde; As further described below.

[0203] The additive compound of formula (I) can be a mixture of the reaction products of p) a hydrocarbon-substituted reagent and q) a nitrogen-containing reagent. For example, the additive compound of formula (I) can contain the reaction products of the following substances: p) Hydrocarbon-substituted carboxylic acid acylating agents; and q) Nitrogen-containing reagents; and the reaction products of the following substances: p) Amines or polyamines containing hydrocarbon groups; q) Nitrogen-containing reagents; and r) Aldehyde; As further described below.

[0204] When the compound of formula (I) is the reaction product of p) a hydrocarbon-substituted reagent and q) a nitrogen-containing reagent, the nitrogen-containing reagent q) suitably contains a nitrogen-containing group A. The hydrocarbon-substituted reagent p) suitably contains a hydrocarbon group R. 1 .

[0205] The A group appropriately provides a significant amount of the desired nitrogen content for the additive, and R 1 The group can be a solubilizing group, which provides the additive with sufficient solubility in diesel fuel to make the additive effective in use. Appropriate selection of A and R... 1 The group provides at least 4% by mass of the desired nitrogen content in the compound of formula (I).

[0206] In some embodiments, the nitrogen-containing reagent q) suitably comprises a nitrogen-containing heterocyclic group. The heterocyclic group suitably provides a significant amount of the desired nitrogen content for the additive. In such embodiments, the A group of the nitrogen-containing reagent q) is a nitrogen-containing heterocyclic group.

[0207] The nitrogen-containing heterocyclic group can be any heterocyclic group containing at least one nitrogen atom, aromatic or aliphatic. The nitrogen-containing heterocyclic group may contain other heteroatoms, such as at least one oxygen atom or at least one sulfur atom, preferably at least one oxygen atom. In some embodiments, the nitrogen-containing heterocyclic group contains no other heteroatoms besides nitrogen. The nitrogen-containing heterocyclic group of group A can be selected from optionally substituted piperazine, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, quinazoline, five-membered heterocyclic rings such as pyrazole or imidazole, or benzofused five-membered heterocyclic rings such as benzimidazole and their derivatives. The nitrogen-containing heterocyclic group is suitably selected to interact with R. 1 Any other nitrogen atoms present in the group together provide at least 4% by mass of the required nitrogen content.

[0208] Preferably, group A is selected from optionally substituted five-membered nitrogen-containing heterocycles or benzofused five-membered nitrogen-containing heterocycles and their derivatives. Preferably, group A is optionally substituted benzotriazole, indazole, triazole, tetraazole, imidazole, benzimidazole, or imidazoline or its derivatives. Suitably, group A is optionally substituted benzotriazole, benzimidazole, indazole, triazole, or tetraazole.

[0209] In some embodiments, group A is a non-cyclic nitrogen-containing group. In such embodiments, group A can be an amine or a polyamine. Suitable polyamines may have the following formula: Where n is from 1 to 10. The additive can be a mixture of compounds of formula (I) with different n numbers in the "A" group. Therefore, n is suitably the average of the different n numbers present in the mixture. Thus, n can be a non-integer value from 1 to 10, i.e., 1.0 to 10.0. Preferably, n is from 1 to 6, 1 to 4, or 1 to 3.

[0210] Therefore, the A group can be provided by ethylenediamine, diethylenetriamine (DETA), triethylenetetramine (TETA), or tetraethylenepentamine (TEPA). Preferably, the A group is provided by TETA or TEPA.

[0211] R of hydrocarbon-substituted reagent p) 1 The functional group preferably has a molecular weight (Mn) of up to 1000, up to 600, or up to 400. R 1 The group preferably has a molecular weight of at least 50, at least 100, or at least 150. R 1 The groups preferably have a molecular weight of 50 to 500, more preferably 100 to 400 or 150 to 350.

[0212] In some implementation schemes, R 1 The group is a hydrocarbon group.

[0213] The hydrocarbon group preferably contains at least 10 carbon atoms, more preferably at least 14 carbon atoms or at least 18 carbon atoms. Preferably, the hydrocarbon group contains up to 30 carbon atoms, more preferably up to 28 carbon atoms or up to 26 carbon atoms. The hydrocarbon group may contain 10 to 30 carbon atoms, 14 to 26 carbon atoms, 18 to 26 carbon atoms or more preferably 20 to 24 carbon atoms.

[0214] The hydrocarbon substituents can be mixtures of hydrocarbon groups having the above-mentioned range (average) of carbon atoms. Therefore, the molecular weight of the hydrocarbon group is suitably defined as the number average molecular weight (Mn). The hydrocarbon group preferably has an Mn of 50 to 500, more preferably 100 to 400 or 150 to 350.

[0215] Technicians are familiar with standard techniques used to measure number-average molecular weight, such as vapor pressure permeation, end-group titration, proton NMR, boiling point elevation, freezing point depression (freezing point depression determination), and gel permeation chromatography (GPC).

[0216] The hydrocarbon substituent can be an olefin having the above-mentioned number of carbons and / or Mn.

[0217] Hydrocarbon substituents can be prepared from homopolymers or interpolymers (e.g., copolymers, terpolymers) of mono- and di-olefins having 2 to 10 carbon atoms, such as ethylene, propylene, butene-1, isobutene, butadiene, isoprene, 1-hexene, 1-octene, etc. Preferably, these olefins are 1-monoolefins. Hydrocarbon substituents can also be derived from halogenated (e.g., chlorinated or brominated) analogs of such homopolymers or interpolymers. Alternatively, hydrocarbon substituents can be obtained from other sources, such as monomeric high molecular weight olefins (e.g., 1-tetradecene) and their chlorinated and hydrochlorinated analogs, aliphatic petroleum fractions, such as paraffin wax and its cracked and chlorinated and hydrochlorinated analogs, white oils, synthetic olefins such as those produced by the Ziegler-Natta process (e.g., poly(ethylene) grease), and other sources known to those skilled in the art. If desired, any unsaturation in the substituents can be reduced or eliminated by hydrogenation according to methods known in the art.

[0218] The hydrocarbon substituent can be polyisobutylene, preferably having the aforementioned number of carbons and / or Mn. Both conventional polyisobutylene and so-called "highly reactive" polyisobutylene are applicable to this invention. Highly reactive polyisobutylene is defined in this context as polyisobutylene in which at least 50%, preferably 70% or more of the terminal olefinic double bond is of the vinylidene type, as described in EP0565285. Particularly preferred polyisobutylenes are those having more than 80 mol% and up to 100 mol% of terminal vinylides, as described in EP1344785.

[0219] Other preferred hydrocarbon groups include those having an internal olefin, such as those described in the applicant’s published application WO2007 / 015080.

[0220] As used herein, internal olefins refer to any olefin that primarily contains non-α double bonds, i.e., β or higher olefins. Preferably, such materials are substantially entirely β or higher olefins, for example containing less than 10% by weight of α olefins, more preferably less than 5% by weight or less than 2% by weight. Typical internal olefins include Neodene 1518IO, available from Shell.

[0221] Internal alkenes are sometimes also called isomerized alkenes, and can be prepared from α-olefins by isomerization methods known in the art, or obtained from other sources. The fact that they are also called internal alkenes reflects that they do not necessarily have to be prepared by isomerization.

[0222] The reaction of a hydrocarbon-substituted reagent p) with a nitrogen-containing reagent q) preferably forms a nitrogen-containing group A and a hydrocarbon group R. 1 The linking group L. The L group can be a bond, amine, amide, succinimide, succinic acid, or an amide of succinic acid.

[0223] The compound that is the product of the reaction between the p) hydrocarbon-substituted reagent and the q) nitrogen-containing reagent has formula (I): (I) in: A is a nitrogen-containing group; L is a bond or linking group; and R 1 The substituted hydrocarbon group is preferred, preferably an substituted alkyl, alkenyl, or aminoalkyl group, and preferably has a molecular weight (Mn) of up to 1000. A, L, and R 1 The groups are as defined above.

[0224] In some embodiments, the nitrogen-containing compound is the reaction product of p) a hydrocarbon-substituted reagent and q) a nitrogen-containing reagent, wherein p) is a hydrocarbon-substituted carboxylic acid acylating agent.

[0225] In such embodiments, the compound of formula (I) is preferably a reaction product of the following substances: p) Hydrocarbon-substituted carboxylic acid acylating agents; and q) Nitrogen-containing reagents.

[0226] In such implementations, the hydrocarbon group R 1 The linking group L between the nitrogen-containing group A and the nitrogen-containing group A is provided by an amide of succinic acid or a succinic acid derivative, as further described below.

[0227] Suitablely, component p) contains R as defined above. 1 Groups. Suitably, component p) comprises hydrocarbon groups as defined above, preferably polyisobutylene or olefin groups as defined above.

[0228] Component p) suitably has formula (VI): (VI) Where R 1 It is an optionally substituted alkyl, alkenyl, or aminoalkyl group having a molecular weight (Mn) of up to 1000.

[0229] R 1 Preferably, the hydrocarbon group is as discussed above, and more preferably has 18 to 26 carbon atoms and / or 100 to 400 Mn.

[0230] R 1 It can be a polyisobutylene group or an internal olefin group having 18 to 26 carbon atoms and / or 100 to 400 Mn.

[0231] In some embodiments, component p) is polyisobutylene succinic anhydride. These compounds are commonly referred to as "PIBSA" and are known to those skilled in the art. Suitably, the polyisobutylene group of PIBSA is as defined above.

[0232] PIBSA can be prepared by reacting a suitable polyisobutylene with maleic anhydride.

[0233] The preparation of polyisobutylene-substituted succinic anhydride (PIBSA) is documented in the art. Suitable methods include thermally reacting polyisobutylene with maleic anhydride (see, for example, US-A-3,361,673 and US-A-3,018,250), and reacting halogenated, particularly chlorinated, polyisobutylene (PIB) with maleic anhydride (see, for example, US-A-3,172,892). Alternatively, polyisobutylene-substituted succinic anhydride can be prepared by mixing a polyolefin with maleic anhydride and passing chlorine gas through the mixture (see, for example, GB-A-949,981).

[0234] In some implementations, component p) is PIB having Mn of 250-270.

[0235] In some embodiments, component p) is an alkenyl succinic anhydride. These compounds are commonly referred to as "ASA" and are known to those skilled in the art. Suitably, the olefinic group of ASA is as defined above. Preferably, ASA is a C16 to C18 alkenyl succinic anhydride (ASA), such as Pentasize 68.

[0236] The reaction of component p) with component q) suitably forms amide bonds, imide bonds, or mixtures thereof.

[0237] Component q) preferably contains a reactive amino group or reactive nitrogen as part of a nitrogen-containing heterocyclic compound.

[0238] In some embodiments, component q) comprises a nitrogen-containing heterocycle, preferably selected from optionally substituted piperazine, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, quinazoline, 2-aminoimidazoline, 5-phenyl-2-aminoimidazoline, 5-methyl-2-aminoimidazolium, 5-amino-indazole, 6-aminoindazole, 2-aminobenzimidazole, a five-membered heterocyclic ring, or a benzo-fused five-membered heterocyclic ring. Preferably, component q) comprises a five-membered heterocyclic ring such as pyrazole or imidazole, a benzo-fused five-membered heterocyclic ring such as benzimidazole, an amino-substituted five-membered heterocyclic ring, or an amino-substituted benzo-fused five-membered heterocyclic ring. Preferably, component q) comprises benzotriazole, indazole, triazole, or tetraazole. Component q) may be selected from optionally substituted benzotriazole, amino-benzotriazole, indazole, amino-indazole, triazole, amino-triazole, tetraazole, or amino-tetraazole.

[0239] In some embodiments, component q) comprises an amine or polyamine compound. Suitably, component q) is a polyamine. Suitably, component q) has the formula: Where n is from 1 to 10. The nitrogen-containing compound can be a mixture of compounds having different n numbers in the "A" group. Therefore, n is suitably the average of the different n numbers present in the mixture. Thus, n can be a non-integer value from 1 to 10, i.e., 1.0 to 10.0. Preferably, n is from 1 to 6, 1 to 4, or 1 to 3.

[0240] Component q) may be selected from ethylenediamine, diethylenetriamine (DETA), triethylenetetramine (TETA), and tetraethylenepentamine (TEPA).

[0241] Preferably, the nitrogen-containing compound is a reaction product of the following substances: p) Polyisobutylene succinic anhydride or alkenyl succinic anhydride; and q) A polyamine selected from ethylenediamine, diethylenetriamine (DETA), triethylenetetramine (TETA), and tetraethylenepentamine (TEPA); or a nitrogen-containing heterocycle selected from optionally substituted benzotriazole, amino-benzotriazole, indazole, amino-indazole, triazole, amino-triazole, tetraazole, or amino-tetraazole.

[0242] In such embodiments, the nitrogen-containing compound formed by the p) and q) reactions may have the structure described below, for example, as a major component in the mixture of compounds produced by the reaction.

[0243] The L group of the nitrogen-containing compound of formula (I) may be provided by an amide of succinic acid or a succinic acid derivative. In such embodiments, the nitrogen-containing compound formed by the reactions p) and q) may have formula (VIA): (VIA) in: R 1 It is an optionally substituted alkyl, alkenyl, or aminoalkyl group having a molecular weight (Mn) of up to 1000; A is a nitrogen-containing group; and R 17 For OH, NH2, OR 24 OM, NHR 24 or NR 24 R 25 , or a bond connected to A, wherein M is a cation, preferably an alkali metal cation or an ammonium cation, and wherein R 24 and R 25 Independently selected from optionally substituted C1-6 alkyl or alkenyl groups. R 24 and R 25 It can independently contain quaternary ammonium groups.

[0244] Therefore, in some embodiments, the nitrogen-containing compound used in the first and second aspects of the present invention is preferably of formula (VIA).

[0245] In some preferred embodiments, R 17 It is an amide with OH radical, and therefore the L group is succinic acid.

[0246] R 1 The solubilizing group can be bonded to any carbon atom between the acid and the amide group. Nitrogen-containing compounds can be R... 1 A mixture of isomers with different group positions.

[0247] In such implementations, R 1 Preferably, the hydrocarbon group is as discussed above, and more preferably has 18 to 26 carbon atoms and / or 100 to 400 Mn.

[0248] In such implementations, R 1 It may be a polyisobutylene group or an internal olefin group having 18 to 26 carbon atoms and / or 100 to 400 Mn.

[0249] In some embodiments of the nitrogen-containing compound of formula (VIA), the nitrogen-containing group A may be selected from optionally substituted piperazine, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, quinazoline, five-membered heterocyclic rings such as pyrazole or imidazole, or benzo[a]fused five-membered heterocyclic rings such as benzimidazole and their derivatives. Preferably, group A is selected from optionally substituted five-membered heterocyclic rings or benzo[a]fused five-membered heterocyclic rings or their derivatives. Preferably, group A is optionally substituted benzo[a]triazole, indazole, triazole, or tetraazole.

[0250] In such embodiments, the A group is suitably tetrazolium. Therefore, the nitrogen-containing compound preferably has the formula (VII): (VII) Where R 1 and R 17 As specified above.

[0251] In such embodiments, the compound of formula (VII) may also exist in the imide form of formula (VIII): (VIII) In such embodiments, the nitrogen-containing compound may have formula (IX), which is an isomer of formula (VII): (IX) Where R 1 and R 17 As specified above.

[0252] In such embodiments, the nitrogen-containing compound may be a mixture of compounds of formulas (VII), (VIII) and (IX).

[0253] In such implementations, R 17 Preferably OH or O - X + , where X is a cation, such as a metal cation or an ammonium ion.

[0254] In such implementations, R 1 Preferably, it has a hydrocarbon group having 100 to 500, more preferably 150 to 350 or 200 to 300 Mn.

[0255] For example, R 1 It can be a polyisobutylene or olefin having Mn of 100 to 500, preferably 150 to 350 or 200 to 300.

[0256] In some implementation schemes, R 1 The nitrogen-containing compound has a polyisobutylene group, therefore it has the formula (X), (XI) or (XII), or a mixture thereof: Where n is from 1 to 3. The nitrogen-containing compound can be a mixture of compounds with different n numbers in the polyisobutylene group. Therefore, n is suitably the average of the different n numbers present in the mixture. Thus, n can be a non-integer value from 1 to 3, that is, n is from 1.0 to 3.0.

[0257] In some implementation schemes, R 1 The olefinic group is C10-24, preferably C12-22 or C16-18. In such embodiments, the nitrogen-containing compound may have formula (XIII), (XIV), or (XV), or a mixture thereof: Each R 18 The alkyl group is independently selected to provide R having 12 to 22 carbon atoms. 1 Group.

[0258] In some embodiments of the nitrogen-containing compound of formula (VIA), the A group is a non-cyclic nitrogen-containing group as described above, such as an amine or polyamine group. In such embodiments, the main component of the nitrogen-containing compound may be a cyclic imide, wherein R... 17 For bonds to be attached to the A group, a suitable bond is a bond attached to the amine group of the A group. Therefore, nitrogen-containing compounds can have formula (XVI): (XVI) Where R 1 As specified above.

[0259] In such embodiments, the A group can be polyethyleneimine. Therefore, the nitrogen-containing compound can have formula (XVII): (XVII) Where n is from 1 to 10. The nitrogen-containing compound can be a mixture of compounds having different n numbers in the "A" group. Therefore, n is suitably the average of the different n numbers present in the mixture. Thus, n can be a non-integer value from 1 to 10, i.e., 1.0 to 10.0. Preferably, n is from 1 to 6, 1 to 4, or 1 to 3.

[0260] In such embodiments, the nitrogen-containing compound may comprise some ring-opening analogs having formula (XVIII): (XVIII) Where R 17 Preferably OH or O - X + , where X is a cation, such as a metal cation or an ammonium ion.

[0261] In such embodiments of compounds of formula (XVII) and / or (XVIII), R 1 Preferably, it has a hydrocarbon group having 100 to 500, more preferably 150 to 350 or 200 to 300 Mn.

[0262] For example, R 1 It can be a polyisobutylene or olefin having Mn of 100 to 500, preferably 150 to 350 or 200 to 300.

[0263] In some implementation schemes, R 1 The nitrogen-containing compounds have the formula (XIX) and / or (XX) because they are polyisobutylene groups. Where n is 1 to 10; and m is 1 to 3. Preferably, n is 1 to 4 or 1 to 3. As mentioned above, n and m can be average values, where there are mixtures of compounds containing different numbers of n and m. Therefore, n and m can be non-integer values ​​representing average values, i.e., n is 1.0 to 10.0; and m is 1.0 to 3.0.

[0264] In some implementation schemes, R 1 The olefinic group is C10-24, preferably C12-22 or C16-18. Therefore, the nitrogen-containing compound has formula (XXI) and / or formula (XXII) or a mixture thereof: Where n is between 1 and 10 and can be the average of non-integer values; and Each R 18 The alkyl group is independently selected to provide R having 12 to 22 carbon atoms. 1 Group. Preferably, n is 1 to 4 or 1 to 3.

[0265] In some embodiments of the invention, the nitrogen-containing compound is the reaction product of a p) hydrocarbon-substituted reagent and a q) nitrogen-containing reagent, wherein p) is an amine or polyamine containing a hydrocarbon group. In such embodiments, the nitrogen-containing compound may be the product of a Mannich reaction involving an aldehyde. Therefore, the nitrogen-containing compound may be the reaction product of the following substances: p) Amines or polyamines containing hydrocarbon groups; q) Nitrogen-containing reagents; and r) Aldehyde.

[0266] In such implementations, the hydrocarbon group R 1 The linking group L between the nitrogen-containing group A and the nitrogen-containing group A is provided by a bond, as further described below.

[0267] Suitablely, component p) contains R as defined above. 1 Group. Suitably, component p) is an alkylamine as defined above, preferably having the formula NHR. 19 R 20 , where R 19 and R 20 Each component is independently selected from H, optionally substituted C1-20 alkyl groups, or optionally substituted C1-20 alkenyl groups. Therefore, component p) is preferably a dialkylamine. Preferably, R... 19 and R 20 Each component is independently selected from C1-20 alkyl groups, preferably C2-20 alkyl groups. The alkyl group can be branched, straight-chain, or cyclic. Branched or straight-chain alkyl groups are preferred. Preferably, R... 19 and R 20 The same and selected from C1-20 alkyl groups, preferably C2-20 alkyl groups.

[0268] Component p) may be selected from diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, bis(2-ethylhexyl)amine or dicosylamine.

[0269] Component q) is preferably a nitrogen-containing reagent comprising a nitrogen-containing heterocycle. Preferably, component q) is selected from optionally substituted five-membered nitrogen-containing heterocyclic compounds or benzo[a]-fused five-membered nitrogen-containing heterocyclic compounds. Preferably, component q) is selected from optionally substituted triazoles, tetraazoles, indole, indole, or benzo[a]triazoles. Preferably, component q) is selected from triazoles, tetraazoles, indole, indole, or benzo[a]triazoles, and more preferably triazoles, tetraazoles, or benzo[a]triazoles.

[0270] Component r) is suitably an aliphatic aldehyde. Preferably, the aldehyde has 1 to 10 carbon atoms. Most preferably, the aldehyde is formaldehyde or a formaldehyde source.

[0271] In a preferred embodiment, the nitrogen-containing compound is a reaction product of the following substances: p) Having the formula NHR 19 R 20 Alkylamines, wherein R 19 and R 20 Each is independently selected from H, optionally substituted C1-20 alkyl, or optionally substituted C1-20 alkenyl; q) A nitrogen-containing reagent selected from optionally substituted triazoles, tetraazoles, indole, indazoles, or benzotriazoles, and r) Formaldehyde or formaldehyde source.

[0272] In such embodiments, the nitrogen-containing compound formed by the reactions p), q), and r) can have the structure described below, for example, as a major component in the mixture of compounds produced by the reaction.

[0273] In some embodiments of the invention, L may be a bond in the nitrogen-containing compound of formula (I). In such embodiments, the nitrogen-containing compound may have formula (XXIII): (XXIII) in: R 1 It is an optionally substituted alkyl, alkenyl, or aminoalkyl group having a molecular weight (Mn) of up to 1000; W, X, Y, and Z are each independently selected from CH, C, N, NH, S, and SH, and they may be arbitrarily substituted where appropriate; and The compound may optionally contain a cycloalkyl or aryl ring connecting Y and Z.

[0274] Therefore, in some embodiments, the nitrogen-containing compounds used in the first and second aspects of the present invention preferably have the formula (XXIII).

[0275] R 1 The solubilizing group can be bonded to any suitable atom of the nitrogen-containing heterocyclic group. The nitrogen-containing compound can be R... 1 A mixture of isomers with different group positions. Preferably, R 1 It is bonded to the nitrogen of a nitrogen-containing heterocyclic group.

[0276] In such implementations, R 1 Preferably, it is an aminoalkyl group having a molecular weight (Mn) of up to 1000. The aminoalkyl group preferably has a molecular weight (Mn) of 50 to 500, more preferably 50 to 350 or 50 to 300.

[0277] R 1 It can have the formula -CH2NR 19 R 20 , where R 19 and R 20 Each is independently selected from H, optionally substituted C1-20 alkyl groups, or optionally substituted C1-20 alkenyl groups. Preferably, R 19 and R 20 Each component is independently selected from C1-20 alkyl groups, preferably C2-20 alkyl groups. The alkyl group can be branched or straight-chain alkyl. Preferably, R... 19 and R 20 The same and selected from C1-20 alkyl groups, preferably C2-20 alkyl groups. In some embodiments, R 19 and R 20 Each is independently selected from C1-12 alkyl groups, preferably C2-10 alkyl groups.

[0278] In some embodiments of nitrogen-containing compounds of formula (XXIII), the heterocyclic group is an optionally substituted five-membered nitrogen-containing heterocycle. In such embodiments, W, X, Y, and Z are each independently selected from CH, C, N, and NH. In such embodiments, the heterocyclic group is preferably selected from optionally substituted triazoles or tetraazoles. For example, the nitrogen-containing compound may have formula (XXIV): (XXIV) Where R 19 and R 20 Each is independently selected from optionally substituted C1-20 alkyl groups, preferably optionally substituted C2-20 alkyl groups. In some embodiments, R 19 and R 20 Each is independently selected from optionally substituted C1-12 alkyl groups, preferably optionally substituted C2-10 alkyl groups.

[0279] Nitrogen-containing compounds may have formulas (XXV) and / or (XXVI) or mixtures thereof: Where R 19 and R 20 Each compound is independently selected from C1-20 alkyl groups, preferably C2-20 alkyl groups. Nitrogen-containing compounds can be mixtures of such compounds. For example, nitrogen-containing compounds can be mixtures of compounds of formula (XXV) and (XXVI) in a ratio of 1:10 to 10:1, suitably 1:5 to 5:1.

[0280] In some embodiments of nitrogen-containing compounds of formula (XXIII), the heterocyclic group is an optionally substituted benzo[a]fused five-membered nitrogen-containing heterocycle. In such embodiments, the nitrogen-containing compound has formula (XXVII): (XXVII) in: R 1 It is an optionally substituted alkyl, alkenyl, or aminoalkyl group having a molecular weight (Mn) of up to 1000; W and X are each independently selected from C and N; and Each R 21 It is independently selected from H, C1-6 alkyl or C1-6 alkenyl.

[0281] Preferably, each R 21 For H.

[0282] In such implementations, R 1 Preferably, it is an aminoalkyl group having a molecular weight (Mn) of up to 1000. The aminoalkyl group preferably has a molecular weight (Mn) of 50 to 500, more preferably 50 to 350 or 50 to 300.

[0283] As mentioned above, R 1 Preferred formula -CH2NR 19 R 20 , where R 19 and R 20 Each is independently selected from H, optionally substituted C1-20 alkyl groups, or optionally substituted C1-20 alkenyl groups. Preferably, R 19 and R 20 Each component is independently selected from C1-20 alkyl groups, preferably C2-20 alkyl groups. The alkyl group can be branched, straight-chain, or cyclic. Branched or straight-chain alkyl groups are preferred. Preferably, R... 19 and R 20 The same and selected from C1-20 alkyl groups, preferably C2-20 alkyl groups.

[0284] Therefore, nitrogen-containing compounds can have the formula (XXVIII): (XXVIII) in: W and X are each independently selected from C and N; Each R 21 Independently selected from H, C1-6 alkyl, or C1-6 alkenyl; and R 19 and R 20 Each is independently selected from C1-20 alkyl groups, preferably C2-20 alkyl groups.

[0285] In some embodiments, the nitrogen-containing heterocycle is an optionally substituted benzotriazole, and the nitrogen-containing compound has the formula (XXIX): (XXIX) in: R 1 It is an optionally substituted alkyl, alkenyl, or aminoalkyl group having a molecular weight (Mn) of up to 1000; and Each R 21 It is independently selected from H, C1-6 alkyl or C1-6 alkenyl.

[0286] In a preferred embodiment, the compound of formula (I) has formula (XXX): (XXX) in: Each R 21 Independently selected from H, C1-6 alkyl, or C1-6 alkenyl; and R 19 and R 20 Each is independently selected from C1-20 alkyl groups, preferably C2-20 alkyl groups.

[0287] The appropriate treatment rate of one or more nitrogen-containing cleaning agents used in this invention may depend on the type of fuel used, and may require different levels of additives to achieve different levels of performance.

[0288] In a preferred embodiment, one or more nitrogen-containing cleaning agents are selected from: (a) Quaternary ammonium salt additives; (b) Reaction products of carboxylic acid-derived acylating agents and amines; (c) The products of the Mannich reaction between aldehydes, amines, and optionally substituted phenols; and (g) Compounds of formula (I): (I) in: A is a nitrogen-containing group; L represents a bond or linking group; R 1 The hydrocarbon group is optionally substituted; wherein the compound has a nitrogen content of at least 4% by mass.

[0289] Preferably, the diesel fuel composition used in this invention contains a total of 0.1 to 10,000 ppm, more preferably 1 to 1,000 ppm, more preferably 2 to 500 ppm, for example 5 to 250 ppm of a nitrogen-containing cleaning agent.

[0290] In some embodiments, the diesel fuel composition contains 0.1 to 10,000 ppm, preferably 1 to 1,000 ppm, preferably 5 to 250 ppm, for example 5 to 100 ppm of (a) a quaternary ammonium salt additive.

[0291] In some embodiments, the diesel fuel composition contains 0.1 to 10,000 ppm, preferably 1 to 1,000 ppm, preferably 5 to 500 ppm, for example 5 to 250 ppm of the reaction product of (b) a carboxylic acid-derived acylated agent and an amine.

[0292] In some embodiments, the diesel fuel composition comprises 0.1 to 10,000 ppm, preferably 1 to 1,000 ppm, preferably 5 to 500 ppm, for example 5 to 100 ppm, of the Mannich reaction product between (c) aldehydes, amines and optionally substituted phenols.

[0293] In some embodiments, the diesel fuel composition comprises 0.1 to 10,000 ppm, preferably 1 to 1,000 ppm, more preferably 5 to 500 ppm, for example 5 to 100 ppm of a compound of formula (I) (g): (I) in: A is a nitrogen-containing group; L represents a bond or linking group; R 1 The hydrocarbon group is optionally substituted; and the compound has a nitrogen content of at least 4% by mass.

[0294] Additives (a), (b), (c), and (g) may each be provided as a mixture of compounds. The amounts mentioned above refer to the total amount of all such compounds present in the composition.

[0295] For the avoidance of doubt, the above amounts refer to the amount of active additive compounds present in the composition, excluding any impurities, solvents or diluents that may be present.

[0296] Unless otherwise stated, ppm in this specification refers to parts per million by weight.

[0297] In some embodiments, the diesel fuel composition comprises (a) a quaternary ammonium salt additive and (b) a reaction product of a carboxylic acid derivative acylizer and an amine.

[0298] In some embodiments, the diesel fuel composition comprises (a) a quaternary ammonium salt additive and (c) a Mannich reaction product between an aldehyde, an amine, and an optionally substituted phenol.

[0299] In some embodiments, the diesel fuel composition comprises (b) the reaction product of a carboxylic acid-derived acylated agent and an amine and (c) the Mannich reaction product between an aldehyde, an amine and an optionally substituted phenol.

[0300] In some embodiments, the diesel fuel composition comprises (a) a quaternary ammonium salt additive, (b) a reaction product of a carboxylic acid derivative acylizer and an amine, and (c) a Mannich reaction product between an aldehyde, an amine, and an optionally substituted phenol.

[0301] In some embodiments, the diesel fuel composition comprises (b) a reaction product of a carboxylic acid-derived acylating agent and an amine, and (c) a Mannich reaction product of an aldehyde, an amine, and optionally a substituted phenol; wherein component (b) comprises a reaction product of polyisobutylene-substituted succinic acid or succinic anhydride and a polyethylene polyamine selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexadecimalylheptamine, and mixtures and isomers thereof; wherein the polyisobutylene substituent has a number average molecular weight of 500 to 2000, preferably 600 to 1000; and component (c) comprises a reaction product of formaldehyde, a polyethylene polyamine, and a para-substituted monoalkylphenol (preferably dodecylphenol).

[0302] In some embodiments, the diesel fuel composition comprises (a) a quaternary ammonium salt additive and (c) a Mannich reaction product between an aldehyde, an amine, and optionally a substituted phenol, suitably wherein (a) and (c) are present in a weight ratio of 1:2 to 1:4, preferably about 1:3; wherein component (a) comprises a quaternary ammonium salt formed by reacting methyl salicylate, dimethyl oxalate, or propylene oxide (optionally in combination with an acid) with a reaction product of polyisobutylene-substituted succinic anhydride (having a PIB molecular weight (Mn) of 700 to 1300) and dimethylaminopropylamine; and component (c) comprises a reaction product of formaldehyde, polyethylene polyamine, and para-substituted monoalkylphenol (preferably dodecylphenol).

[0303] In some embodiments, the diesel fuel composition comprises (a) a quaternary ammonium salt additive, (b) a reaction product of a carboxylic acid derivative acylating agent and an amine, and (c) a Mannich reaction product between an aldehyde, an amine, and optionally a substituted phenol; wherein component (a) comprises a quaternary ammonium salt formed by reacting methyl salicylate, dimethyl oxalate, or propylene oxide (optionally in combination with an acid) with a reaction product of polyisobutylene-substituted succinic anhydride (having a PIB molecular weight (Mn) of 700 to 1300) and dimethylaminopropylamine; component (b) comprises a reaction product of polyisobutylene-substituted succinic acid or succinic anhydride with a polyethylene polyamine selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexadecimalylheptamine, and mixtures and isomers thereof; wherein the polyisobutylene substituent has a number average molecular weight of 500 to 2000, preferably 600 to 1000; and component (c) comprises a reaction product of formaldehyde, a polyethylene polyamine, and a para-substituted monoalkylphenol (preferably dodecylphenol).

[0304] In the method of the first aspect and / or the use of the second aspect, the diesel fuel composition suitably comprises (a) a quaternary ammonium salt additive and (c) a Mannich reaction product between an aldehyde, an amine and an optionally substituted phenol, suitably wherein (a) and (c) are present in a weight ratio of 1:2 to 1:4, preferably about 1:3; wherein component (a) comprises a quaternary ammonium salt formed by reacting a compound containing a tertiary amine group with a quaternizing agent; The quaternizing agent is selected from alkyl oxides (preferably propylene oxide) (optionally combined with an acid), chloroacetic acid or its salt, methyl salicylate or dimethyl oxalate. Compounds containing tertiary amine groups are selected from one or more of the following: (ia) Formula R z The fatty acids of COOH (of which R) z The product of the reaction of alkyl or alkenyl groups having 12 to 24 carbon atoms with N,N-dimethyl-1,3-diaminopropane (DMAPA); (ib) The reaction product of polyisobutylene-substituted succinic anhydride with a PIB molecular weight (Mn) of 700 to 1300 and N,N-dimethyl-1,3-diaminopropane; and (iv-a) Equation R 13 R 14 R 15 N-tertiary amines, where R 13 and R 14 Each is a C1 to C4 alkyl group, preferably methyl, and R 15 It is an alkyl or alkenyl group having 12 to 24 carbon atoms; and Component (c) comprises the reaction product of formaldehyde, polyethylene polyamine and para-substituted monoalkylphenol (preferably dodecylphenol).

[0305] In some embodiments, the diesel fuel composition comprises (a) a quaternary ammonium salt additive, (b) a reaction product of a carboxylic acid-derived acylating agent and an amine, and (c) a Mannich reaction product between an aldehyde, an amine, and an optionally substituted phenol; wherein component (a) comprises a quaternary ammonium salt formed by reacting a compound containing a tertiary amine group with a quaternizing agent; The quaternizing agent is selected from alkyl oxides (preferably propylene oxide), and can be optionally combined with an acid, chloroacetic acid or its salt, methyl salicylate or dimethyl oxalate. Compounds containing tertiary amine groups are selected from one or more of the following: (ia) Formula R z The fatty acids of COOH (of which R) z The product of the reaction of alkyl or alkenyl groups having 12 to 24 carbon atoms with N,N-dimethyl-1,3-diaminopropane (DMAPA); (ib) The reaction product of polyisobutylene-substituted succinic anhydride with a PIB molecular weight (Mn) of 700 to 1300 and N,N-dimethyl-1,3-diaminopropane; and (iv-a) Equation R 13 R 14 R 15 N-tertiary amines, where R 13 and R 14 Each is a C1 to C4 alkyl group, preferably methyl, and R 15 It is an alkyl or alkenyl group having 12 to 24 carbon atoms; Component (b) comprises the reaction product of polyisobutylene-substituted succinic acid or succinic anhydride with a polyethylene polyamine selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexadecimalylheptamine, and mixtures and isomers thereof; wherein the polyisobutylene substituent has a number average molecular weight of 500 to 2000, preferably 600 to 1000; and Component (c) comprises the reaction product of formaldehyde, polyethylene polyamine and para-substituted monoalkylphenol (preferably dodecylphenol).

[0306] In some embodiments, the diesel fuel composition comprises (a) a quaternary ammonium salt additive and (c) a Mannich reaction product between an aldehyde, an amine and an optional substituted phenol, suitably wherein (a) and (c) are present in a weight ratio of 1:2 to 1:4, preferably about 1:3; wherein component (a) comprises a quaternary ammonium salt formed by reacting a compound containing a tertiary amine group with a quaternizing agent; The quaternizing agent is selected from alkyl oxides (preferably propylene oxide) (optionally combined with an acid), chloroacetic acid or its salt, methyl salicylate or dimethyl oxalate. Compounds containing tertiary amine groups are of formula (ia) R. z The fatty acids of COOH (of which R) z The product of the reaction of an alkyl or alkenyl group having 12 to 24 carbon atoms with N,N-dimethyl-1,3-diaminopropane (DMAPA); and Component (c) comprises the reaction product of formaldehyde, polyethylene polyamine and para-substituted monoalkylphenol (preferably dodecylphenol).

[0307] In some embodiments, the diesel fuel composition comprises (a) a quaternary ammonium salt additive, (b) a reaction product of a carboxylic acid-derived acylating agent and an amine, and (c) a Mannich reaction product between an aldehyde, an amine, and an optionally substituted phenol; wherein component (a) comprises a quaternary ammonium salt formed by reacting a compound containing a tertiary amine group with a quaternizing agent; The quaternizing agent is selected from alkyl oxides (preferably propylene oxide) (optionally combined with an acid), chloroacetic acid or its salt, methyl salicylate or dimethyl oxalate. Compounds containing tertiary amine groups are of formula (ia) R. z The fatty acids of COOH (of which R) z The product of the reaction of alkyl or alkenyl groups having 12 to 24 carbon atoms with N,N-dimethyl-1,3-diaminopropane (DMAPA); Component (b) comprises the reaction product of polyisobutylene-substituted succinic acid or succinic anhydride with a polyethylene polyamine selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexadecimalylheptamine, and mixtures and isomers thereof; wherein the polyisobutylene substituent has a number average molecular weight of 500 to 2000, preferably 600 to 1000; and Component (c) comprises the reaction product of formaldehyde, polyethylene polyamine and para-substituted monoalkylphenol (preferably dodecylphenol).

[0308] In some embodiments, the diesel fuel composition comprises (a) a quaternary ammonium salt additive and (c) a Mannich reaction product between an aldehyde, an amine and an optional substituted phenol, suitably wherein (a) and (c) are present in a weight ratio of 1:2 to 1:4, preferably about 1:3; wherein component (a) comprises a quaternary ammonium salt formed by reacting a compound containing a tertiary amine group with a quaternizing agent; The quaternizing agent is selected from alkyl oxides (preferably propylene oxide) (optionally combined with an acid), chloroacetic acid or its salt, methyl salicylate or dimethyl oxalate. Compounds containing tertiary amine groups are (iv-a) formula R 13 R 14 R 15 N-tertiary amines, where R 13 and R 14 Each is a C1 to C4 alkyl group, preferably methyl, and R 15 It is an alkyl or alkenyl group having 12 to 24 carbon atoms; and Component (c) comprises the reaction product of formaldehyde, polyethylene polyamine and para-substituted monoalkylphenol (preferably dodecylphenol).

[0309] In some embodiments, the diesel fuel composition comprises (a) a quaternary ammonium salt additive, (b) a reaction product of a carboxylic acid-derived acylating agent and an amine, and (c) a Mannich reaction product between an aldehyde, an amine, and an optionally substituted phenol; wherein component (a) comprises a quaternary ammonium salt formed by reacting a compound containing a tertiary amine group with a quaternizing agent; The quaternizing agent is selected from alkyl oxides (preferably propylene oxide) (optionally combined with an acid), chloroacetic acid or its salt, methyl salicylate or dimethyl oxalate. Compounds containing tertiary amine groups are (iv-a) formula R 13 R 14 R 15 N-tertiary amines, where R13 and R 14 Each is a C1 to C4 alkyl group, preferably methyl, and R 15 It is an alkyl or alkenyl group having 12 to 24 carbon atoms; Component (b) comprises the reaction product of polyisobutylene-substituted succinic acid or succinic anhydride with a polyethylene polyamine selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexadecimalylheptamine, and mixtures and isomers thereof; wherein the polyisobutylene substituent has a number average molecular weight of 500 to 2000, preferably 600 to 1000; and Component (c) comprises the reaction product of formaldehyde, polyethylene polyamine and para-substituted monoalkylphenol (preferably dodecylphenol).

[0310] In some embodiments, the diesel fuel composition comprises (a) a quaternary ammonium salt additive, (b) a reaction product of a carboxylic acid-derived acylating agent and an amine, (c) a Mannich reaction product between an aldehyde, an amine, and optionally a substituted phenol, and (g) a compound of formula (I); wherein component (a) comprises a quaternary ammonium salt formed by reacting methyl salicylate, dimethyl oxalate, or propylene oxide (optionally in combination with an acid) with a reaction product of polyisobutylene-substituted succinic anhydride (having a PIB molecular weight (Mn) of 700 to 1300) and dimethylaminopropylamine; component ( b) A reaction product comprising polyisobutylene-substituted succinic acid or succinic anhydride with a polyethylene polyamine selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentethylenehexamine, hexadecimalylheptamine, and mixtures and isomers thereof; wherein the polyisobutylene substituent has a number average molecular weight of 500 to 2000, preferably 600 to 1000; component (c) comprises a reaction product comprising formaldehyde, a polyethylene polyamine, and a para-substituted monoalkylphenol (preferably dodecylphenol); and component (g) comprises a compound of formula (XXX): (XXX) in: R 19 R 20 and R 21 As specified above, Compounds of formula (XXV) and / or (XXVI) or mixtures thereof: Where R 19 and R 20 As specified above, Or compounds of formula (VII): (VII) Where R 1 and R 17 As specified above, Or compounds of formula (VIII): (VIII) (VII) Where R 1 As specified above, Or compounds of formula (IX): (IX) Where R 1 and R 17 As specified above.

[0311] One or more nitrogen-containing additives can be added to diesel fuel at any convenient point in the supply chain. For example, additives can be added to fuel at the refinery, distribution terminal, or after the fuel has left the distribution terminal. If the additive is added to fuel after it has left the distribution terminal, this is called an aftermarket application. Aftermarket applications include scenarios such as adding additives to fuel in a delivery tanker, adding them directly to a customer's bulk storage tank, or adding them directly to the end user's vehicle fuel tank. Aftermarket applications may include supplying fuel additives in vials suitable for direct addition to fuel storage tanks or vehicle fuel tanks.

[0312] This invention relates to the metering addition of at least one nitrogen-containing detergent to a diesel fuel composition as an additive. The at least one nitrogen-containing detergent can be added directly as a pure additive. The at least one nitrogen-containing detergent can be added as part of an additive composition. The additive composition may contain one or more diluents or carriers and optionally one or more other fuel additives. Preferred diluents and carriers are organic compounds, preferably hydrocarbon solvents such as aromatic solvents. Suitable diluents and carriers will be known to those skilled in the art.

[0313] Preferably, the additive composition is not aqueous. Preferably, the additive composition is not provided as an emulsion. Preferably, the additive composition does not contain water. Trace amounts of water may be present due to the manufacturing process, but in the preferred embodiment, water is not intentionally added to the additive composition.

[0314] Suitablely, the additive composition contains less than 10% by weight of water, preferably less than 5% by weight, suitably less than 1% by weight, for example less than 0.1% by weight.

[0315] Therefore, in a preferred embodiment, the method and use of the present invention do not involve adding water to a diesel fuel composition.

[0316] By diesel fuel, we include any fuel suitable for use in diesel engines, whether for on-road or off-road use. This includes, but is not limited to, fuels described as diesel, marine diesel, heavy fuel oil, industrial fuel oil, etc.

[0317] The diesel fuel compositions used in this invention may comprise petroleum-based fuel oils, particularly middle distillate fuel oils. Such distillate fuel oils typically boil in the range of 110°C to 500°C (e.g., 150°C to 400°C). The diesel fuel may comprise atmospheric or vacuum distillates, cracked gas oils, or straight-run and refinery streams in any proportion, such as thermal cracking and / or catalytic cracking and hydrocracking fractions.

[0318] Diesel fuel compositions may contain non-renewable Fischer-Tropsch fuels, such as those described as GTL (gas-to-liquid) fuel, CTL (coal-to-liquid) fuel, and OTL (oil sands-to-liquid) fuel.

[0319] Diesel fuel compositions may contain renewable fuels, such as biofuel compositions or biodiesel compositions.

[0320] Diesel fuel compositions may contain first-generation biodiesel. First-generation biodiesel contains, for example, esters of vegetable oils, animal fats, and waste cooking fats or oils. This form of biodiesel can be obtained by reacting oils (such as rapeseed oil, soybean oil, canola oil, safflower oil, palm oil, corn oil, peanut oil, cottonseed oil, tallow, coconut oil, jatropha oil, sunflower oil, waste cooking oil, hydrogenated vegetable oil, or any mixture thereof) with alcohols (usually monools), typically in the presence of a catalyst.

[0321] Diesel fuel compositions may include second-generation biodiesel. Second-generation biodiesel is derived from renewable resources such as vegetable oils and animal fats, and is typically processed in refineries using methods such as hydrotreating (e.g., the H-Bio process developed by Petrobras). Second-generation biodiesel may be similar in properties and quality to petroleum-based fuel streams, such as renewable diesel produced from vegetable oils, animal fats, etc., and is marketed by ConocoPhillips as Renewable Diesel and Neste as NExBTL.

[0322] Diesel fuel compositions may include third-generation biodiesel. Third-generation biodiesel utilizes gasification and Fischer-Tropsch technologies, including those described as BTL (biomass-to-liquid) fuels. Third-generation biodiesel is not significantly different from some second-generation biodiesel, but it is designed to utilize whole plants (biomass), thereby expanding the feedstock base.

[0323] In some embodiments, the diesel fuel composition may contain pyrolysis oil, such as plastic pyrolysis oil or biomass (wood, vegetable oil, algae) pyrolysis oil.

[0324] The diesel fuel composition may comprise a mixture of any or all of the above-described diesel fuel compositions.

[0325] In some embodiments, the diesel fuel composition may be a blended diesel fuel containing biodiesel. In such a blend, biodiesel may be present, for example, in amounts 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%.

[0326] In some embodiments, the fuel composition may contain pure biodiesel.

[0327] In some preferred embodiments, the fuel composition contains at least 5% by weight of biodiesel.

[0328] In some embodiments, the fuel composition may contain GTL fuel or be pure GTL fuel.

[0329] In some embodiments, the diesel fuel composition may contain a secondary fuel, such as ethanol. However, preferably, the diesel fuel composition does not contain ethanol.

[0330] The diesel fuel composition used in this invention may contain a relatively high sulfur content, for example, greater than 0.05% by weight, such as 0.1% by weight or 0.2% by weight.

[0331] However, in a preferred embodiment, the sulfur content of the diesel fuel composition is at most 0.05% by weight, more preferably at most 0.035% by weight, and especially at most 0.015% by weight. Fuels with even lower sulfur content are also suitable, such as fuels having less than 50 ppm by weight, preferably less than 20 ppm by weight, for example, 10 ppm by weight or less of sulfur.

[0332] The diesel fuel composition used in this invention preferably contains at least 5% by weight of biodiesel and less than 50 ppm of sulfur.

[0333] Preferably, the diesel fuel composition is not an emulsion. Preferably, the diesel fuel composition does not contain water. Trace amounts of water may be present due to manufacturing processes or contamination (e.g., during storage), but in the preferred embodiment, water is not intentionally added to the diesel fuel composition.

[0334] Suitablely, the diesel fuel composition contains less than 10% by weight of water, preferably less than 5% by weight, suitably less than 1% by weight, for example less than 0.1% by weight.

[0335] In some implementations, the diesel fuel composition is pure renewable diesel.

[0336] Diesel fuel compositions may suitably be 100% derived from renewable resources. Such fuels are referred to herein as renewable diesel. Suitable renewable diesel is obtained through the hydrodeoxygenation of fats and oils (which are derived from renewable resources). For example, renewable diesel can be hydrotreated triglyceride oils, such as hydrogenated vegetable oils (HVO). HVO suitably conforms to EN 15940 Class A. Such HVO fuels are available from Coryton and Neste.

[0337] Such renewable diesel fuels are suitably produced from biologically derived raw materials. These can be suitably selected from vegetable oils, animal fats, fish oils, and mixtures thereof. Examples include rapeseed oil, canola oil, tallow oil, sunflower oil, soybean oil, hemp seed oil, olive oil, flaxseed oil, mustard oil, flaxseed oil, palm oil, palm kernel oil, peanut oil, castor oil, coconut oil, animal fats such as tallow or recycled food fats, genetically engineered raw materials, and biological raw materials produced by microorganisms such as algae and bacteria.

[0338] Preferably, renewable diesel oil is provided via a process involving hydrodeoxygenation (HDO) and optional isomerization steps. The hydrodeoxygenation (HDO) step results in the structural breakdown of the bio-ester or triglyceride components, the elimination of oxygen-, phosphorus-, and sulfur-containing compounds, and the hydrogenation of olefin bonds. The products of the hydrodeoxygenation reaction may subsequently be isomerized. Optional fractionation steps may be performed after the hydrodeoxygenation and isomerization steps.

[0339] Preferably, the renewable diesel fuel has a cetane number of 50 to 90, more preferably 55 to 90, and more preferably 60 to 85. The cetane number is suitably measured by the standard test method specified in IP 498.

[0340] Preferably, the renewable diesel fuel has a cloud point of less than 25°C, more preferably less than 10°C. Suitably, the alkane fuel has a cloud point of less than -5°C, for example less than -10°C. The cloud point can be suitably measured using the standard test methods described in IP 219.

[0341] Preferably, the kinematic viscosity of the renewable diesel oil at 40°C is 1 to 20 mm. 2 s -1 Preferably 2 to 15 mm 2 s -1 More preferably 2 to 10 mm 2 s -1 The optimal size is 2 to 4.5 mm. 2 s -1 Kinematic viscosity can be measured according to ASTM D445.

[0342] Preferably, the initial boiling point (IBP) and final boiling point (FBP) of the renewable diesel oil are in the range of 265 to 380°C, more preferably in the range of 275 to 380°C, and most preferably in the range of 290 to 375°C.

[0343] Preferably, the boiling range of the renewable diesel oil is less than 80°C, more preferably less than 70°C, suitably less than 60°C, for example, 30 to 60°C. Boiling range refers to the difference between the final boiling point and the initial boiling point.

[0344] The initial boiling point, final boiling point, and boiling range can be determined according to the methods specified in IP 123.

[0345] In a preferred embodiment, the renewable diesel fuel mainly comprises straight-chain alkanes and branched alkanes.

[0346] Preferably, the renewable diesel contains less than 20% by weight of cycloalkanes, preferably less than 10% by weight, suitably less than 5% by weight, preferably less than 1% by weight, for example less than 0.1% by weight.

[0347] For the avoidance of ambiguity, the terms cycloalkanes or cycloalkanes are used to refer to any saturated hydrocarbon compound containing a non-aromatic cyclic moiety.

[0348] Preferably, the weight ratio of n-alkanes to isoalkanes in the renewable diesel fuel is 99:1 to 1:99, more preferably 90:10 to 10:99, and most preferably 75:25 to 25:75. Techniques for determining the ratio of n-alkanes to isoalkanes are known to those skilled in the art and include gas chromatography.

[0349] The ratio of n-alkanes to isoalkanes present in fuels typically depends on the hydrotreating method used to prepare the fuel, which may also include an isomerization step.

[0350] Renewable diesel fuel may contain more than 4% by weight, preferably more than 5% by weight, of C14 to C16 n-alkanes.

[0351] Renewable diesel fuel may contain less than 8% by weight, preferably less than 6% by weight, of C14 to C16 n-alkanes.

[0352] Renewable diesel fuel may contain 4 to 8% by weight, preferably 5 to 6% by weight, of C14 to C16 n-alkanes.

[0353] Renewable diesel fuel may contain more than 5% by weight, preferably more than 7% by weight, and more preferably more than 10% by weight of C14 to C18 n-alkanes.

[0354] Renewable diesel fuel may contain less than 20% by weight, preferably less than 18% by weight, and more preferably less than 16% by weight of C14 to C18 n-alkanes.

[0355] Renewable diesel fuel may contain 5 to 20% by weight, preferably 7 to 18% by weight, and more preferably 10 to 16% by weight of C14 to C18 n-alkanes.

[0356] Renewable diesel fuel may contain 3 to 30% by weight of C6 to C24 n-alkanes (i.e., n-alkanes).

[0357] Renewable diesel fuel suitably has an oxygen content of less than 1% by weight, preferably less than 0.1% by weight, as measured according to EN 14078.

[0358] Renewable diesel fuel appropriately has an aromatic content of less than 5% by weight, preferably less than 1% by weight.

[0359] Preferably, the renewable diesel oil is a hydrotreated triglyceride oil having the above-mentioned content and properties, suitably HVO.

[0360] Appropriately, renewable diesel fuel conforms to the standard specifications specified in EN15940.

[0361] Preferably, the renewable diesel oil is a hydrotreated triglyceride oil having an aromatic content of less than 5% by weight, preferably less than 1% by weight, and suitably HVO.

[0362] Preferably, the renewable diesel fuel has a cetane number of 50 to 90, preferably 55 to 90, more preferably 60 to 85 (according to IP 498); a cloud point of less than 10°C, preferably less than -5°C (according to IP 219); and a thickness of 1 to 20 mm at 40°C. 2 s -1 Preferably 2 to 10 mm 2 s -1 Hydrogenated triglyceride oil with a kinematic viscosity (according to ASTM 445) suitable for HVO.

[0363] Preferably, the renewable diesel oil is a hydrotreated triglyceride oil having an initial boiling point and an ultimate boiling point in the range of 265 to 380°C, preferably 290 to 375°C, and a boiling range of less than 80°C, preferably 30 to 60°C, and suitably HVO.

[0364] The diesel fuel composition used in this invention suitably comprises at least 10% by volume of the renewable diesel fuel as defined above, suitably at least 25% by volume, at least 50% by volume, or at least 90% by volume of renewable diesel fuel, wherein the renewable diesel fuel is a hydrotreated triglyceride oil, preferably HVO.

[0365] Fuel containing 100% renewable diesel is designated R100; fuel containing 90% mineral diesel and 10% renewable diesel (by volume) is designated R10; fuel containing 50% mineral diesel and 50% renewable diesel (by volume) is designated R50; and so on.

[0366] In some preferred embodiments, the fuel composition of the present invention comprises renewable diesel oil and one or more other components selected from biodiesel, mineral diesel oil and mixtures thereof.

[0367] In some embodiments, the fuel composition comprises renewable diesel oil and at least 5% by volume biodiesel.

[0368] In some embodiments, the fuel composition comprises renewable diesel oil and at least 20% by volume biodiesel.

[0369] In a preferred embodiment, the diesel fuel composition is pure (i.e., 100% by volume) renewable diesel as defined above, preferably pure hydrotreated triglyceride oil, and more preferably pure HVO. Such fuel may be referred to as R100 diesel fuel.

[0370] Various metals can be present in diesel fuel compositions. This may be due to fuel contamination during manufacturing, storage, transportation, or use, or due to contamination from fuel additives. Metals can also be intentionally added to fuel. For example, transition metals are sometimes added as fuel-carrying catalysts, such as to improve the performance of diesel particulate filters.

[0371] Other metallic substances can also exist as contaminants, for example, through corrosion of metal and metal oxide surfaces by acidic substances present in the fuel or from lubricating oils. During use, fuels such as diesel fuel are typically in contact with metal surfaces, for example, in vehicle refueling systems, fuel tanks, and fuel transportation methods. Generally, metallic contaminants can include transition metals such as zinc, iron, and copper; Group I or II metals; and other metals such as lead.

[0372] Besides the potential presence of metal contaminants in diesel fuel, metal-containing substances can be intentionally added to fuel in certain situations. For example, as is known in the art, metal-containing fuel-carrying catalysts can be added to aid in the regeneration of particulate filters. The presence of such catalysts can also lead to injector deposits when the fuel is used in diesel engines with high-pressure fuel systems.

[0373] Depending on their source, metal contaminants can exist as insoluble particles, soluble compounds, or complexes. Metal-containing fuel-carrying catalysts are typically soluble compounds, complexes, or colloids.

[0374] In some embodiments, the diesel fuel may contain a metal-containing compound, which includes a fuel-carrying catalyst. Preferably, the fuel-carrying catalyst contains one or more metals selected from iron, cerium, platinum, manganese, and Group I and II metals (such as calcium and strontium). Most preferably, the fuel-carrying catalyst contains a metal selected from iron and cerium.

[0375] Typically, the total amount of all metals in diesel fuel, expressed as the total weight of the metals in the categories, is 0.1 to 50 ppm by weight, for example 0.1 to 20 ppm by weight, preferably 0.1 to 10 ppm by weight, based on the weight of the diesel fuel.

[0376] The diesel fuel compositions used in this invention may include one or more additional additives, such as those commonly found in diesel fuels. These include, for example, antioxidants, dispersants, detergents, metal passivating compounds, wax antisettling agents, cold flow improvers, cetane number improvers, demisters, stabilizers, demulsifiers, defoamers, corrosion inhibitors, lubricity improvers, dyes, markers, combustion improvers, metal passivators, odor masking agents, drag reducers, and conductivity improvers. Examples of suitable amounts of each of these classes of additives will be known to those skilled in the art.

[0377] Suitable cetane number improvers can be selected from C2-24 alkyl nitrates and dialkyl peroxides, preferably decyl nitrate, 2-ethylhexyl nitrate, and di-tert-butyl peroxide. Such cetane number improvers are suitably used at a concentration of 50-6,000 ppm, preferably 50-750 ppm, based on the diesel fuel composition.

[0378] The method and application of the present invention reduce nitrogen oxide emissions when a diesel engine burns a diesel fuel composition.

[0379] Diesel engines can be either direct injection diesel engines or indirect injection diesel engines.

[0380] In some implementations, the engine can be a non-road engine, such as a marine, rail, or stationary engine. Stationary engines include those used for power generation and pumping.

[0381] Preferably, the engine is a direct injection diesel engine.

[0382] The additives used in this invention have been found to be particularly effective in modern diesel engines with high-pressure fuel systems.

[0383] Suitablely, the present invention can be used to reduce nitrogen monoxide and / or nitrogen dioxide emissions from diesel engines with high-pressure fuel systems. Suitablely, the diesel engine has a fuel pressure exceeding 1350 bar (1.35 x 10⁻⁶ bar). 8 It can have up to 2000 bar (2 x 10). 8 (Pa) or higher pressure.

[0384] Such diesel engines can be characterized in a variety of ways.

[0385] These engines are typically equipped with fuel injection systems that meet or exceed Euro 5 emission standards or equivalent regulations in the United States or other countries.

[0386] Such engines are typically equipped with fuel injectors with multiple orifices, each having an inlet and an outlet.

[0387] Such engines can be characterized by orifices, which are conical, such that the inlet diameter of the nozzle is larger than the outlet diameter.

[0388] Such modern engines can be characterized by orifices with an outlet diameter of less than 500 μm, preferably less than 200 μm, more preferably less than 150 μm, more preferably less than 100 μm, and most preferably less than 80 μm or smaller.

[0389] Such modern diesel engines can be characterized by a hole with rounded inner edges at the inlet.

[0390] Such modern diesel engines can be characterized by injectors having more than one orifice, suitably more than two orifices, preferably more than four orifices, such as six or more orifices.

[0391] Such modern diesel engines can be characterized by operating tip temperatures exceeding 250°C.

[0392] Such modern diesel engines can be characterized by fuel injection systems that provide fuel pressures of more than 1,350 bar, preferably more than 1,500 bar, and more preferably more than 2,000 bar.

[0393] Two non-limiting examples of such high-pressure fuel systems are: a common rail injection system in which fuel is compressed using a high-pressure pump and supplied to the fuel injection valves via a common rail; and a unit injection system that integrates the high-pressure pump and fuel injection valves into a single component, achieving pressures exceeding 2000 bar (2 x 10⁻⁶). 8 The maximum feasible injection pressure (Pa). In both systems, the fuel heats up when pressurized, typically to a temperature of about 100°C or higher.

[0394] Preferably, the diesel engine has a fuel injection system that includes a common rail injection system.

[0395] In common rail systems, fuel is stored at high pressure in a central accumulator rail or a separate accumulator before being delivered to the injectors. Typically, some of the heated fuel is returned to the low-pressure side of the fuel system or back to the fuel tank. In unit injection systems, fuel is compressed within the injectors to generate high injection pressure. This, in turn, increases the fuel temperature.

[0396] In both systems, the fuel is present in the injector body before injection, where it is further heated by heat from the combustion chamber. The fuel temperature at the injector tip can reach as high as 250-350°C.

[0397] Therefore, the fuel at 1350 bar (1.35 x 10) 8 Pa) to over 2000 bar (2 x 10) 8 The fuel is subjected to stress before injection at pressures of 100 Pa and temperatures of approximately 100°C to 350°C, and sometimes recirculated within the fuel system, thus increasing the time the fuel spends under these conditions.

[0398] This invention can also be used to reduce nitrogen monoxide and / or nitrogen dioxide emissions from conventional diesel engines (such as indirect injection diesel engines).

[0399] The method and application of the present invention reduce the emission of nitric oxide and / or nitrogen dioxide during the combustion of diesel fuel compositions in diesel engines.

[0400] In some implementations, the method and its use reduce nitrogen monoxide emissions.

[0401] In some implementations, the method and its use reduce nitrogen dioxide emissions.

[0402] In some implementations, the method and its use reduce emissions of nitric oxide and nitrogen dioxide.

[0403] The term "NO" x "This term typically refers to the total emissions of nitric oxide (NO) and nitrogen dioxide (NO2). Therefore, this method and its applications can reduce NO." x Emissions.

[0404] In the context of this invention, by reducing nitric oxide and / or nitrogen dioxide emissions, we mean that when a diesel fuel composition containing at least one nitrogen-containing detergent as an additive is burned, the amount of nitric oxide and / or nitrogen dioxide emitted from the exhaust of a diesel engine is lower than when a diesel fuel composition of the same nature without additives is burned.

[0405] The amount of nitric oxide and / or nitrogen dioxide emitted from the engine can be measured by any suitable method. Such methods will be known to those skilled in the art. A suitable method is described in Example 9.

[0406] Emission reductions can be measured by comparing emissions per unit volume of fuel combustion and / or by comparing emissions per unit volume of exhaust gas.

[0407] By reducing the amount of nitric oxide and / or nitrogen dioxide emitted from the engine, we mean a reduction in the amount of nitric oxide and / or nitrogen dioxide emitted directly during combustion, rather than the total amount of nitric oxide and / or nitrogen dioxide emitted from the vehicle.

[0408] Therefore, the present invention suitably reduces the amount of nitric oxide and / or nitrogen dioxide emitted from the combustion chamber.

[0409] Other features of the combustion system, such as selective catalytic reduction (SCR) devices, can also affect the total amount of nitric oxide and / or nitrogen dioxide emitted from the engine. However, this invention specifically relates to reducing the amount of nitric oxide and / or nitrogen dioxide emitted from the combustion chamber.

[0410] Suitablely, the present invention reduces the emission of nitrogen monoxide and / or nitrogen dioxide in exhaust gases that are emitted directly from the engine before entering the afterburner system.

[0411] Preferably, the method and use of the present invention reduce nitric oxide emissions by at least 2%, preferably at least 5%.

[0412] Preferably, the method and use of the present invention reduce nitrogen dioxide emissions by at least 2%, preferably at least 5%.

[0413] Preferably, the method and use of the present invention reduce the total emissions of nitric oxide and nitrogen dioxide by at least 2%, preferably at least 5%.

[0414] Because this invention reduces the levels of nitric oxide and / or nitrogen dioxide emitted by diesel engines, less of these gases need to be treated by a selective catalytic reduction (SCR) unit. Therefore, the SCR unit may require less frequent maintenance, and / or the SCR additive may require less frequent replenishment.

[0415] Therefore, the method and application of the present invention advantageously increase the maintenance intervals of vehicles equipped with selective catalytic reduction (SCR) devices.

[0416] Furthermore, the methods and uses of the present invention can reduce the additive consumption of selective catalytic reduction (SCR) devices.

[0417] The present invention will now be further described with reference to the following non-limiting embodiments.

[0418] Example 1 Additive A, a quaternary ammonium salt additive, is prepared as follows: 700 g (0.7 mol) of polyisobutylene (Mn 1000) was charged into a nitrogen-purged jacketed reactor equipped with a top stirrer. The starting material was heated to 120 °C and stirred, with repeated nitrogen inertization. The reaction temperature was raised to 190 °C, and maleic anhydride (82.4 g, 0.84 mol, 1.2 equivalents) was added over 1 hour. After maintaining the temperature at 190 °C for another hour, the temperature was raised to 200–208 °C and maintained within this range for 8 hours. Then, a vacuum (<30 mbar) was applied for 2.5 hours while maintaining the reaction temperature, reducing the residual maleic anhydride content to ≤0.05% by weight. The reactants were cooled to ≤80 °C and then discharged from the reactor.

[0419] The material was then loaded into a nitrogen-purged jacketed reactor equipped with a top stirrer and heated to 120°C. 3-(dimethylamino)propylamine (DMAPA) was slowly added (1 equivalent relative to the anhydride group), maintaining the reaction temperature between 120-130°C. After stirring at 120°C for another hour, the reaction temperature was raised to 140°C and maintained for 3 hours, while water was distilled off. Methyl salicylate (2.1 equivalents relative to the anhydride group) was added in a single batch, and heating was continued at 140°C for 10 hours. The reactants were diluted with Aromatic 150 solvent to provide a total solids content of 60% by weight and then discharged from the reactor.

[0420] Example 2 Additive B, a Mannich reaction product additive, is prepared as follows: Dodecylphenol (170.6 g, 0.65 mol), ethylenediamine (30.1 g, 0.5 mol), and Caromax 20 (123.9 g) were charged into a 1 L reactor. The mixture was heated to 95 °C, and a 37 wt% formaldehyde solution (73.8 g, 0.9 mol) was added over 1 hour. The temperature was raised to 125 °C and held for 3 hours, and water was removed. In this example, the molar ratio of aldehyde (a):amine (b):phenol (c) was approximately 1.8:1:1.3.

[0421] Example 3 Additive C is a 60% by weight solution of the active ingredient (in an aromatic solvent) of polyisobutylene succinimide, which is obtained by the condensation reaction of polyisobutylene succinic anhydride (PIBSA) (derived from polyisobutylene with a Mn of approximately 750) with a mixture of polyethylene polyamines with an average composition approximately similar to tetraethylenepentamine. The product is obtained by mixing PIBSA and polyethylene polyamines under nitrogen at 50°C and heating to 160°C for 5 hours while simultaneously removing water.

[0422] Example 4 Additive D, an oleoylaminopropyl betaine additive, is prepared as follows: 183.5 g (0.5 mol) of oleoylaminopropyl dimethylamine (N-[3-(dimethylamino)propyl]oleamide), 68 ml of isopropanol, 25.5 g (1.42 mol) of water, and 56.5 g (0.48 mol) of sodium chloroacetate were charged into a Lenz jacketed reactor. The reaction mixture was heated to 80 °C, then heated to 80–85 °C for about 6 hours, then cooled and allowed to stand overnight under nitrogen. The reaction mixture was then reheated to 60 °C and 300 ml of isopropanol (IPA) and 67.5 g of 2-ethylhexanol were added. The heat was then further increased to 90 °C. This provided azeotropic removal of water and IPA and precipitation of NaCl. A vacuum of 100 mbar was applied to remove residual water and some solvent, and the resulting suspension was filtered through a glass microfiber filter at 75–80 °C. 275.6 g of additive D containing 53% by weight of active ingredient was collected.

[0423] Example 5 Additive E, a quaternary ammonium compound, was prepared by quaternizing succinamide with propylene oxide in the absence of an additional acid, using a procedure similar to that described in Preparation Example 1 of US9255236 B2. Succinamide was prepared by reacting polyisobutylene succinic anhydride (having a PIB number-average molecular weight of 1000) with dimethylaminopropylamine (DMAPA). The material obtained as a solution contained 50% by weight of the active ingredient.

[0424] Example 6 Additive F, a quaternary ammonium compound, was prepared by quaternizing hexadecyl dimethylamine with 2 equivalents of propylene oxide in the presence of polyisobutylene succinic acid having a PIB number-average molecular weight of 1000, as described in the general synthesis method of WO2014 / 195464 and Example 6. The material obtained as a solution contained 60% by weight of the active ingredient.

[0425] Example 7 Additive G, comprising the main components shown, is prepared as follows: Main components: In a 500 mL round-bottom flask, benzotriazole (26.0 g, 0.218 mol, 1.0 equivalent) and A150 solvent (116.0 g) were added and heated to 90 °C. Armeen 2C (87.4 g, 0.218 mol, 1 equivalent [equivalent weight 401 g / mol]) (dicoalkylamine, where cocoalkyl = a mixture of C6-18 alkyl groups) was added to the flask. Formalin (37% w / w, 0.218 mol, 1.0 equivalent) was then added over 5 minutes, and the reaction mixture was stirred at 90 °C for 2.5 hours. The temperature in the reaction flask was raised to 119 °C over a 3-hour period, and water was removed using a Dean and Stark trap. When no more aqueous phase was collected and the product was clear and bright, the temperature was cooled to ambient temperature. 222.5 g of clear, bright amber liquid was collected (as a 50% active ingredient solution).

[0426] Example 8 Prepare a diesel fuel composition comprising the following components: Table 1 .

[0427] The base fuel used is RF-06-03 diesel fuel (Haltermann Carless, UK), with the following specifications: .

[0428] Example 9 Engine tests were conducted as described below to evaluate the effect of the nitrogen-containing additive of the present invention in reducing NO and NO2 in diesel engine exhaust. x Performance in terms of emissions.

[0429] Engine Details A 2.0-liter HSDI engine conforming to Euro 6 standards was connected to an automated testing system and a test bench equipped with an engine dynamometer. The engine was controlled by an ECU provided by the engine manufacturer. The engine had been used for over 1100 hours prior to the first test. The engine oil was changed before the first test.

[0430] Modification / Test Setup 1. There is no SCR catalyst or related components in the exhaust system.

[0431] 2. The high-pressure EGR cooler was manually controlled to 40°C during testing.

[0432] 3. Connect the FTIR, and place the sampling point before the aftertreatment at the turbocharger exhaust outlet.

[0433] Diesel fuel compositions 1 to 8 of Example 9 were tested (Table 2).

[0434] Test program The injectors were not cleaned between each test run.

[0435] Engine start + warm-up • Passive DPF regeneration is performed by varying engine speed and load until regeneration is complete. The regeneration progress is monitored using the differential pressure across the DPF. Engine stopped • Replace test fuel • Restart and warm up the engine • 8-hour steady-state test cycle 1200 RPM ·60Nm • Engine stopped.

[0436] Emissions outputs were recorded as an average of 8 hours of testing, and the results are provided in Table 3. Emissions of nitric oxide (NO) and nitrogen dioxide (NO2) were measured. x Total emissions.

[0437] Table 2 .

Claims

1. A method for reducing nitrogen monoxide and / or nitrogen dioxide emissions generated when a diesel engine burns a diesel fuel composition, the method comprising metering in at least one nitrogen-containing cleaning agent as an additive to the diesel fuel composition.

2. The use of at least one nitrogen-containing cleaning agent as an additive for reducing nitrogen monoxide and / or nitrogen dioxide emissions generated when a diesel engine burns a diesel fuel composition.

3. The method or use according to claim 1 or claim 2, wherein one or more nitrogen-containing cleaning agents are selected from: (a) Quaternary ammonium salt additives; (b) Reaction products of carboxylic acid-derived acylating agents and amines; (c) The products of the Mannich reaction between aldehydes, amines and optionally substituted phenols; (d) Reaction products of carboxylic acid derivatives with hydrazine; (e) Salts formed by the reaction of carboxylic acids with di-n-butylamine or tri-n-butylamine; (f) The reaction product of a hydrocarbon-substituted dicarboxylic acid or anhydride with an amine compound or salt, said product comprising at least one aminotriazole group; and (g) Compounds of formula (I): (I) in: A is a nitrogen-containing group; L is a bond or linking group; and R 1 is an optionally substituted hydrocarbyl group; and wherein the compound has a nitrogen content of at least 4 mass %.

4. The method or use according to any one of the preceding claims, wherein one or more nitrogen-containing cleaning agents are selected from: (a) Quaternary ammonium salt additives; (b) Reaction products of carboxylic acid-derived acylating agents and amines; (c) The products of the Mannich reaction between aldehydes, amines, and optionally substituted phenols; and (g) Compounds of formula (I): (I) in: A is a nitrogen-containing group; L is a bond or linking group; and R 1 is an optionally substituted hydrocarbyl group; and wherein the compound has a nitrogen content of at least 4 mass %.

5. The method or use according to any one of the preceding claims, wherein the diesel fuel composition comprises (a) a quaternary ammonium salt additive, (b) a reaction product of a carboxylic acid-derived acylated agent and an amine, and (c) a Mannich reaction product between an aldehyde, an amine, and an optionally substituted phenol.

6. The method or use according to any one of the preceding claims, wherein the diesel fuel composition comprises a quaternary ammonium salt additive (a), which is a reaction product of a compound containing a tertiary amine group and a quaternizing agent; The quaternizing agent is selected from epoxides (preferably propylene oxide), chloroacetic acid or its salts, methyl salicylate or dimethyl oxalate, which are optionally combined with acids. Compounds containing tertiary amine groups are selected from one or more of the following: (i-a) a fatty acid of the formula R z a reaction product of a fatty acid of the formula R z is an alkyl or alkenyl group having 12 to 24 carbon atoms; (ib) The reaction product of a hydrocarbon-substituted succinic acid derivatizing agent with a compound selected from N,N-dimethyl-1,3-diaminopropane, N,N-diethyl-1,3-diaminopropane, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dibutylethylenediamine, 3-(2-(dimethylamino)ethoxy)propylamine, or combinations thereof; and (iv-a) Equation R 13 R 14 R 15 N-tertiary amines, where R 13 R 14 and R 15 Each is independently an alkyl or hydroxyalkyl group.

7. The method or use according to any one of the preceding claims, wherein the diesel fuel composition comprises a quaternary ammonium salt additive (a), which is a reaction product of a compound containing a tertiary amine group and a quaternizing agent; The quaternizing agent is selected from epoxides (preferably propylene oxide), chloroacetic acid or its salts, methyl salicylate or dimethyl oxalate, which are optionally combined with acids. Compounds containing tertiary amine groups are selected from one or more of the following: (ia) Formula R z The reaction products of fatty acids of COOH with N,N-dimethyl-1,3-diaminopropane (DMAPA), in which R z It is an alkyl or alkenyl group having 12 to 24 carbon atoms; (ib) The reaction product of polyisobutylene-substituted succinic anhydride with a PIB molecular weight (Mn) of 700 to 1300 and N,N-dimethyl-1,3-diaminopropane; and (iv-a) Equation R 13 R 14 R 15 N-tertiary amines, where R 13 and R 14 Each is a C1 to C4 alkyl group, preferably methyl, and R 15 It is an alkyl or alkenyl group having 12 to 24 carbon atoms.

8. The method or use according to any one of the preceding claims, wherein the diesel fuel composition comprises (b) a reaction product of a carboxylic acid derivative acylating agent and an amine, which is a reaction product of polyisobutylene-substituted succinic acid or succinic anhydride and a polyethylene polyamine selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexadecimalylheptamine, and mixtures and isomers thereof; wherein the polyisobutylene substituent has a number average molecular weight of 500 to 2000, preferably 600 to 1200.

9. The method or use according to any one of the preceding claims, wherein the diesel fuel composition comprises (c) the Mannich reaction product between formaldehyde, polyethylene polyamine and para-substituted monoalkylphenol.

10. The method or use according to any one of the preceding claims, wherein the diesel fuel composition comprises a reaction product of the following substances: p) Having the formula NHR 19 R 20 Alkylamines, wherein R 19 and R 20 Each is independently selected from H, optionally substituted C1-20 alkyl, or optionally substituted C1-20 alkenyl; q) A nitrogen-containing reagent selected from optionally substituted triazoles, tetraazoles, indole, indazoles, or benzotriazoles, and r) Formaldehyde or formaldehyde source.

11. The method or use according to any one of the preceding claims reduces nitrogen monoxide emissions.

12. The method or use according to any one of the preceding claims reduces nitrogen dioxide emissions.

13. The method or use according to any one of the preceding claims reduces emissions of nitric oxide and nitrogen dioxide.

14. The method or use according to any one of the preceding claims reduces emissions of nitric oxide and / or nitrogen dioxide by at least 5%.

15. The method or use according to any one of the preceding claims, which reduces nitrogen monoxide and / or nitrogen dioxide emissions from a direct injection diesel engine.

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