Fuel additive composition and method for controlling carbon deposits in internal combustion engines

Abstract

A method for controlling carbon deposits in an internal combustion engine using a nitrogen-containing surfactant is disclosed. The nitrogen-containing surfactant is 【Chemical 1】 JPEG2026511712000032.jpg1961 defined as or its acceptable salts, [wherein X 1 and X 2 are independently H, C, N, O, or S, and X 1 or X 2 independently contains one or more C2-C 20 alkyl groups or one or more aromatic rings, and each A, B, and D is selected from hydrogen, a monovalent organic group, and a monovalent heterocyclic organic group in the form of a group or moiety bonded through a carbon atom, and any two or more of A, B, and D may optionally be bonded together to form a cyclic structure, and X 1 and X 2 may optionally be bonded together to form a cyclic structure], or one or more nitrogen-containing surfactants selected from aliphatic hydrocarbyl-substituted amines or hydrocarbyl-substituted poly(oxyalkylene)amines. Fuel compositions and concentrate compositions containing the nitrogen-containing surfactant are also disclosed.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority rights to U.S. Provisional Application No. 63 / 455,285, filed on 29 March 2023, the disclosures of which are incorporated herein by reference.

[0002] This disclosure relates to fuel additives. More specifically, this disclosure describes compositions and methods for promoting deposit cleaning performance. [Background technology]

[0003] Modern engines can be susceptible to the accumulation of various types of deposits. For example, carbon buildup on intake valves can lead to a reduction in airflow to the cylinders. This can result in decreased performance, including reduced power and torque, reduced fuel economy, and increased emissions. Therefore, it is necessary to effectively clean the intake valve surfaces in a cost-effective and time-efficient manner. [Overview of the Initiative]

[0004] In one embodiment, a fuel composition comprising the following is provided: i) hydrocarbon fuels including gasoline and diesel fuel, ii) one or more carrier fluids containing alkyl polyethoxylate of formula 1: [ka] [In the formula, each R b and R c R is independently hydrogen, a C1-C4 hydrocarbyl group, or a C1-C3 alcohol. a C4-C 100 [A hydrocarbyl group, carboxyl group, ether group, thioether group, or aromatic group, where x is 1 to 20], and iii) One or more nitrogen-containing surfactants of formula 2 [ka] or an acceptable salt thereof [wherein, X 1 and X 2 are each independently H, C, N, O, or S, and X 1 or X 2 each independently contains one or more C2-C 20 alkyl groups or one or more aromatic rings, and each of A, B, and D is independently hydrogen, a monovalent organic group, and a monovalent heterocyclic organic group in the form of a group or moiety bonded through a carbon atom, and any two or more of A, B, and D can optionally be bonded together to form a cyclic structure, and X 1 and X 2 can optionally be bonded together to form a cyclic structure].

[0005] In another aspect, the fuel composition further comprises an aliphatic hydrocarbyl-substituted amine or a hydrocarbyl-substituted poly(oxyalkylene) amine.

[0006] In another aspect, the fuel composition further comprises iv) one or more amine surfactants of Formula 8: R 21 -O-(CH2) y -NHR 22 Formula 8 wherein, R 21 is a hydrocarbyl group having 8 to 20 carbons, R 22 is hydrogen or (CH2) z NH2 moiety, and y and z are each independently an integer having a value of 2 or more.

[0007] In another aspect, a method for controlling carbon deposits in an internal combustion engine, comprising providing a fuel to the internal combustion engine, the fuel comprising: i) a hydrocarbon fuel comprising gasoline or diesel oil, iii) one or more nitrogen-containing surfactants of Formula 2:

Chemical formula

[0008] In another embodiment, the fuel used in the present method further comprises: ii) one or more carrier fluids containing an alkyl polyethoxylate of formula 1: [ka] In the formula, each R b and R c R is independently hydrogen, a C1-C4 hydrocarbyl group, or a C1-C3 alcohol. a C4-C 100 The group is a hydrocarbyl group, carboxyl group, ether group, thioether group, or aromatic group, and x is between 1 and 20.

[0009] In another embodiment, the fuel used in the method further comprises an aliphatic hydrocarbyl-substituted amine or a hydrocarbyl-substituted poly(oxyalkylene)amine.

[0010] In another embodiment, the fuel used in the method further comprises iv) one or more amine surfactants of formula 8: R 21 -O-(CH2) y -NHR 22 formula 8 In the formula, R 21 R is a hydrocarbyl group having 8 to 20 carbon atoms. 22 is hydrogen or (CH2) zThis is the NH2 part, where y and z are independent integers with values ​​greater than or equal to 2.

[0011] In another embodiment, the provided concentrated composition comprises about 30 to 90% by weight of an organic solvent with a boiling point in the range of 65°C to 205°C, and about 10 to 70% by weight of a surfactant mixture comprising ii) one or more carrier fluids as described herein, and iii) one or more nitrogen-containing surfactants as described herein.

[0012] In another embodiment, the concentrated composition may further contain (iv) one or more amine surfactants described herein. [Modes for carrying out the invention]

[0013] This disclosure provides compositions and methods for improving engine performance, specifically, improving deposit cleaning performance and / or reducing particulate matter emissions. The present invention may be effective in controlling carbon deposits in internal combustion engines. In particular, significant improvements in deposit control can be achieved through the use of compositions comprising at least one or more nitrogen-containing surfactants as disclosed herein (iii).

[0014] fuel composition Generally, the fuel composition of the present invention comprises (i) a hydrocarbon fuel, (ii) a carrier fluid, and (iii) one or more nitrogen-containing surfactants. The fuel composition may further comprise (iv) an amine surfactant.

[0015] Hydrocarbon fuels Examples of hydrocarbon fuels include gasoline or diesel fuel. Hydrocarbon fuels may include ethanol. In some embodiments, ethanol is present at a concentration of about 50% by volume (vol%) or less, for example, 45% or less, 40% or less, 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, or 5% or less.

[0016] In certain embodiments, the hydrocarbon fuel comprises gasoline and ethanol. Suitable gasoline-ethanol blends for use in the present composition and method contain about 5% to about 35% by volume of ethanol, for example, about 10% to 20% by volume of ethanol, or about 15% to about 25% by volume of ethanol. In certain embodiments, the hydrocarbon fuel is an E20 fuel or a gasoline fuel containing 20% ​​by volume of ethanol. In certain embodiments, the hydrocarbon fuel is an E10 fuel or a gasoline fuel containing 10% by volume of ethanol.

[0017] Gasoline fuel is at least primarily C4-C 12 This refers to a composition containing hydrocarbons. In one embodiment, gasoline or gasoline boiling point range components are at least mainly C4-C 12 Further defined to mean a composition containing hydrocarbons and having a boiling point range of approximately 37.8°C (100°F) to approximately 204°C (400°F). In alternative embodiments, gasoline is defined as at least primarily C4-C 12 This term is defined to mean a composition that contains hydrocarbons, has a boiling point range of approximately 37.8°C (100°F) to approximately 204°C (400°F), and is further defined to satisfy ASTM D4814.

[0018] Diesel fuel is, at least, mainly C 10 -C 25 This refers to intermediate distillate fuels containing hydrocarbons. In one embodiment, diesel means at least primarily C 10 -C 25 It is further defined to mean a composition containing hydrocarbons and having a boiling point range of approximately 165.6°C (330°F) to approximately 371.1°C (700°F). In alternative embodiments, diesel is defined as at least primarily C as defined above. 10 -C 25 This refers to a composition containing hydrocarbons and having a boiling point range of approximately 165.6°C (330°F) to approximately 371.1°C (700°F), and is further defined as satisfying ASTM D975.

[0019] Hydrocarbon fuels are present in the majority by weight percent of the total fuel composition. In some embodiments, the hydrocarbon fuels are present in amounts of about 50% or more by weight, 55% or more by weight, 60% or more by weight, 65% or more by weight, 70% or more by weight, 75% or more by weight, 80% or more by weight, 85% or more by weight, 90% or more by weight, 95% or more by weight, or any range from about 50% to 100% by weight.

[0020] According to some embodiments, the gasoline used in the present invention may be clean combustion gasoline (CBG). CBG refers to a gasoline formulation containing small amounts of sulfur, aromatic compounds, and olefins. The exact formulation may vary depending on the definition of local regulations.

[0021] Carrier fluid The composition of the present invention comprises one or more carrier fluids. While not limited to theory, it is believed that carrier fluids can enhance the compatibility of nitrogen-containing surfactants in hydrocarbon fuels.

[0022] A carrier fluid is a chemically inert hydrocarbon-soluble liquid vehicle that contributes somewhat to increasing the required octane number but substantially increases the non-volatile residue (NVR), or solvent-free fluid fraction, of the fuel additive composition. Fuel-soluble non-volatile carrier fluids or oils may also be used with the compounds of this disclosure. In some embodiments, the carrier fluid is a surfactant.

[0023] The carrier fluid of the present invention comprises, or essentially consists of, an alkyl polyethoxylate compound represented by the following formula 1: [ka] In the formula, each R b and R c R is independently hydrogen, a C1-C4 hydrocarbyl group, or a C1-C3 alcohol. a C4-C 100The group is a hydrocarbyl group, carboxyl group, ether group, thioether group, or aromatic group, and x is between 1 and 20.

[0024] The term "hydrocarbyl" refers to a chemical group or part derived from hydrocarbons, including saturated and unsaturated hydrocarbons. Examples of hydrocarbyl groups include alkenyl, alkyl, polyalkenyl, polyalkyl, and phenyl groups. Specific examples of hydrocarbyl groups include butyl, isopropyl, and polyisobutenyl groups.

[0025] In certain embodiments, the alkyl polyethoxylated compound is a nonylphenol ethoxylate. In certain embodiments, the alkyl polyethoxylated compound is ethoxylated (C 12 -C 14 It is a secondary alcohol.

[0026] In certain embodiments, x is in the range of 1 to 15, for example, 2 to 11, 1 to 6, or 7 to 12.

[0027] In a particular embodiment, R a C4-C 100 Aromatic groups, for example, alkyl-substituted phenyl groups. In certain embodiments, R a C4-C 14 Hydrocarbyl groups, for example, C5-C 13 , C6-C 12 , or C7-C 11 It is a hydrocarbyl group.

[0028] The carrier fluid may be used in amounts ranging from about 35 to about 5000 ppm by weight (i.e., ppmw) of the hydrocarbon fuel (e.g., about 50 ppmw to about 4000 ppmw, about 100 ppmw to about 3000 ppmw, or about 1000 ppmw to about 3000 ppmw). When used in a fuel concentrate, the carrier fluid may be present in amounts ranging from 20 to 60% by weight (e.g., 30 to 50% by weight). In one embodiment, the fuel composition contains about 35 ppmw to about 5000 ppmw of carrier fluid.

[0029] Nitrogen-containing surfactants The composition of the present invention comprises one or more nitrogen-containing surfactants.

[0030] In one embodiment, the nitrogen-containing surfactant is a compound or an acceptable salt thereof given by the following formula 2: [ka] In the formula, X 1 and X 2 Independently, are H, C, N, O, or S, and X 1 Or X 2 It is independent of one or more C2-C 20 Each A, B, and D comprises an alkyl group (e.g., C1-C6 alkyl) or one or more aromatic rings, and each A, B, and D is selected from a monovalent heteroorganic group in the form of a group or part bonded via hydrogen, a monovalent organic group (e.g., an aromatic or aliphatic group) and a carbon atom (e.g., an aromatic or aliphatic group containing one or more N, O, S, or P), and any two or more of A, B, and D may optionally bond together to form a cyclic structure (e.g., a 5-membered ring, a 6-membered ring, or a 7-membered ring), X 1 and X 2 These can optionally bond together to form a cyclic structure (e.g., a 5-membered ring, a 6-membered ring, or a 7-membered ring). In some embodiments, A, B, and D do not contain acidic functionalities such as carboxylic acid or sulfonic acid moieties.

[0031] The cyclic structure may be aromatic or aromatic, and may also vary from fully saturated to fully unsaturated, including partially saturated and partially unsaturated structures.

[0032] In certain embodiments, the cyclic structure formed from two or more bonds among A, B, and D is aromatic. In certain embodiments, the cyclic structure formed from two or more bonds among A, B, and D is non-aromatic.

[0033] The cyclic structure formed from two or more bonds of A, B, and D can range from fully saturated to fully unsaturated. In certain embodiments, the cyclic structure formed from two or more bonds of A, B, and D is fully saturated. In certain embodiments, the cyclic structure formed from two or more bonds of A, B, and D is partially unsaturated. In certain embodiments, the cyclic structure formed from two or more bonds of A, B, and D is fully saturated.

[0034] In a particular embodiment, X 1 and X 2 The cyclic structure formed from the bond is aromatic. In certain embodiments, X 1 and X 2 The cyclic structure formed from these bonds is non-aromatic.

[0035] In certain embodiments, [A] is H. In certain embodiments, [B] is H. In certain embodiments, [D] is H.

[0036] In a particular embodiment, X 1 and X 2 One of them is not H. In a particular embodiment, X 1 and X 2 Neither of them is H.

[0037] In a particular embodiment, X 1 and X 2 One of them is N. In a particular embodiment, X 1 and X 2 Both are N. In a particular embodiment, X 1 This is one C2-C20 alkyl group (for example, C 1- It is N bonded to C6 alkyl and [B]. In certain embodiments, X 1 is N bonded to one aromatic ring and to [B]. In certain embodiments, X 1 is N bonded to H and bonded to [B]. In a particular embodiment, X 2 is one C2-C 20It is N bonded to an alkyl group (e.g., C1-C6 alkyl) and bonded to [D]. In certain embodiments, X 2 is N bonded to one aromatic ring and bonded to [D]. In certain embodiments, X 2 is N bonded to H and bonded to [D].

[0038] In certain embodiments, X 1 is N bonded to one aromatic ring and bonded to [B], and X 2 is N bonded to one aromatic ring and bonded to [D].

[0039] In certain embodiments, X 1 and X 2 one of which is C. In certain embodiments, X 1 and X 2 both are C. In certain embodiments, X 1 is C bonded to one C2-C 20 alkyl group (e.g., C1-C6 alkyl), bonded to H, and bonded to [B]. In certain embodiments, X 1 is C bonded to one aromatic ring, bonded to H, and bonded to [B]. In certain embodiments, X 1 is CH2 and is bonded to [B]. In certain embodiments, X 2 is C bonded to one C2-C 20 alkyl group (e.g., C1-C6 alkyl), bonded to H, and bonded to [D]. In certain embodiments, X 2 is C bonded to one aromatic ring, bonded to H, and bonded to [D]. In certain embodiments, X 2 is CH2 and is bonded to [D].

[0040] In certain embodiments, X 1 is O bonded to [B]. In certain embodiments, X 2 is O bonded to [D]. In certain embodiments, X 1 is S bonded to [B]. In certain embodiments, X 2 is S bonded to [D].

[0041] In certain embodiments, A, C, and D of the organic and heteroorganic groups may have 1 to 10 carbon atoms (for example, 1 to 6 carbon atoms).

[0042] Suitable examples of compounds of formula 2 include, but are not limited to, guanidine, aminoguanidine, amidine, benzamidine, imidazole, benzimidazole, aminobenzimidazole, and trizazole.

[0043] In certain embodiments, the nitrogen-containing surfactant is guanidine, substituted guanidine, its derivatives, or acceptable salts thereof. Useful guanidine compounds include those represented by the following formula 3: [ka] In the formula, R 1 , R 2 , R 3 , R 4 and R 5 Each is independently a hydrogen atom, a monovalent organic group (e.g., an aromatic or aliphatic group), or a monovalent heteroorganic group in the form of a group or part bonded via a carbon atom (e.g., an aromatic or aliphatic group containing one or more N, O, S, or P), and R 1 , R 2 , R 3 , R 4 and R 5 Any two or more of these can be optionally bonded together to form a cyclic structure (e.g., a 5-membered ring, a 6-membered ring, or a 7-membered ring). The cyclic structure may be aromatic or aromatic, and may vary from fully saturated to fully unsaturated. The organic and heteroorganic groups may have 1 to 10 carbon atoms (e.g., 1 to 6 carbon atoms). In some embodiments, A, B, and D do not contain acidic functionalities such as carboxylic acid or sulfonic acid moieties.

[0044] In a particular embodiment, R 1 , R 2 , R3 , R 4 and R 5 One or more of these are aromatic groups, such as phenyl or substituted phenyl. In certain embodiments, R 1 , R 2 , R 3 , R 4 and R 5 Two or more of these are aromatic groups. In certain embodiments, R 1 , R 2 , R 3 , R 4 and R 5 Three or more of these are aromatic groups. In certain embodiments, the compound is diphenylguanidine.

[0045] Representative examples of compounds of formula 3 include 1-phenylguanidine (formula 3A), 1,3-diphenylguanidine (formula 3B), 1,2,3-triphenylguanidine (formula 3C), N-phenyl-1H-benzo[d]imidazole-2-amine (formula 3D), N-phenyl-1H-imidazole-2-amine (formula 3E), 2-aminoimidazole (formula 3F), 2-aminobenzimidazole (formula 3G), 1-phenylbiguanide (formula 3H), 2-guanidinobenzimidazole (formula 3I), and 2-phenyl Examples include henyl-2-imidazoline (formula 3J), 1,1,3,3-tetramethylguanidine (TMG, formula 3K), 2-tert-butyl-1,1,3,3-tetramethylguanidine (BTMG, formula 3L), 1,5,7-triazabicyclo[4.4.0]deca-5-ene (TBD, formula 3M), 7-methyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene (MTBD, formula 3N), and (Z)-N,N'-dicyclohexylmorpholine-4-carboxymidoamide (formula 3O). Representative structures are shown below. [ka] [ka]

[0046] In certain embodiments, the nitrogen-containing surfactant is aminoguanidine, substituted aminoguanidine, its derivatives, or acceptable salts thereof. Useful aminoguanidine compounds include those that can be represented by the following formula 4: [ka] In the formula, R 1 , R 2 , R 3 , R 5 , R 6 and R 7 Each is independently selected from hydrogen, a monovalent organic group (e.g., an aromatic or aliphatic group), and a monovalent heteroorganic group in the form of a group or part bonded via a carbon atom (e.g., an aromatic or aliphatic group containing one or more N, O, S, or P), and R 1 , R 2 , R 3 , R 5 , R 6 and R 7 Any two or more of these can be optionally bonded together to form a cyclic structure (e.g., a 5-membered ring, a 6-membered ring, or a 7-membered ring). The cyclic structure may be aromatic or aromatic, and may vary from fully saturated to fully unsaturated. The organic and heteroorganic groups may have 1 to 10 carbon atoms (e.g., 1 to 6 carbon atoms). In some embodiments, A, B, and D do not contain acidic functionalities such as carboxylic acid or sulfonic acid moieties.

[0047] In a particular embodiment, R 1 , R 2 , R 3 , R 5 , R 6 and R 7 One or more of these are aromatic groups, such as phenyl or substituted phenyl. In certain embodiments, R 1 , R 2 , R 3 , R 5 , R 6 and R 7 Two or more of these are aromatic groups. In certain embodiments, R1 , R 2 , R 3 , R 5 , R 6 and R 7 Three or more of these are aromatic groups.

[0048] Representative examples of compounds of formula 4 include 2-benzylhydrazine-1-carboxymidoamide (formula 4A), N',2-dibenzylhydrazine-1-carboxymidohydrazide (formula 4B), and N',N”,2-tribenzylhydrazine-1-carbohydrazone hydrazide (formula 4C). Representative structures are shown below. [ka]

[0049] In certain embodiments, the nitrogen-containing surfactant is an amidine, a substituted amidine, a benzamidine, a substituted benzamidine, or an acceptable salt thereof. Useful amidines include those that can be represented by the following formula 5: [ka] In the formula, R 8 , R 9 , R 10 and R 11 Each is independently selected from hydrogen, a monovalent organic group, a monovalent heterovalent organic group (for example, in the form of groups and parts bonded via a carbon atom, containing nitrogen, oxygen, sulfur, or phosphorus, and combinations thereof), R 8 , R 9 , R 10 and R 11 Any two or more of these can be optionally bonded together to form a cyclic structure (e.g., a 5-membered ring, a 6-membered ring, or a 7-membered ring). The cyclic structure may be aromatic or aromatic, and may vary from fully saturated to fully unsaturated. The organic group and heteroorganic group may have 1 to 10 carbon atoms (e.g., 1 to 6 carbon atoms). In some embodiments, R 8 , R 9 , R10 , and R 11 It does not contain acidic functionalities such as carboxylic acid or sulfonic acid moieties.

[0050] In a particular embodiment, R 8 , R 9 , R 10 and R 11 One or more of these are aromatic groups, such as phenyl or substituted phenyl. In certain embodiments, R 8 , R 9 , R 10 and R 11 Two or more of these are aromatic groups. In certain embodiments, R 8 , R 9 , R 10 and R 11 Three or more of these are aromatic groups.

[0051] Representative examples of compounds of formula 5 include benzimidamide (or benzamidine, formula 5A), N-phenylbenzimidamide (formula 5B), benzimidazole (formula 5C), 2-phenyl-1H-benzo[d]imidazole (formula 5D), 2-phenylimidazole (formula 5E), and N-phenylpyridine-2-amine (formula 5F), 1,4,5,6-tetrahydropyrimidine (formula 5G), 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine (formula 5H), and 1,2-diethyl-1,4,5,6-tetrahydropyrimidine (formula 5A). Examples include 5I), 1,5-diazabicyclo[4.3.0]nona-5-ene (DBN, formula 5J), 1,8-diazabicyclo[5.4.0]-undeca-7-ene (DBU, formula 5K), benzimidazole (formula 5L), oxazole-2-amine (formula 5M), 4,5-dihydroxazole-2-amine (formula 5N), thiazole-2-amine (formula 5O), 4,5-dihydrothiazole-2-amine (formula 5P), benzo[d]thiazole-2-amine (formula 5Q), and 2-phenyl-1H-benzo[d]imidazole (formula 5R). Representative structures are shown below. [ka] [ka]

[0052] In certain embodiments, the nitrogen-containing surfactant is imidazole, substituted imidazole, benzamidazole, substituted benzamidazole, aminobenzimidazole, substituted aminobenzimidazole, or an acceptable salt thereof. Useful imidazoles, substituted imidazoles, benzamidazole, substituted benzamidazole, aminobenzimidazole, and substituted aminobenzimidazole include those that can be represented by the following formula 6: [ka] In the formula, Y is R 15 or NR 16 R 17 And R 12 , R 13 , R 14 , R 15 , R 16 and R 17 Each is independently selected from hydrogen, a monovalent organic group, a monovalent heterovalent organic group (for example, in the form of groups and parts bonded via a carbon atom, containing nitrogen, oxygen, sulfur, or phosphorus, and combinations thereof), R 12 , R 13 , R 14 , R 15 , R 16 and R 17 Any two or more of these can be optionally bonded together to form a cyclic structure (e.g., a 5-membered ring, a 6-membered ring, and a 7-membered ring). The cyclic structure may be aromatic or aromatic, and may vary from fully saturated to fully unsaturated. The organic and heteroorganic groups may have 1 to 10 carbon atoms (e.g., 1 to 6 carbon atoms). In some embodiments, A, B, and D do not contain acidic functionalities such as carboxylic acid or sulfonic acid moieties.

[0053] In a particular embodiment, R 12 , R 13 , R 14 , R 15 , R16 and R 17 One or more of these are aromatic groups, such as phenyl or substituted phenyl. In certain embodiments, R 12 , R 13 , R 14 , R 15 , R 16 and R 17 Two or more of these are aromatic groups. In certain embodiments, R 12 , R 13 , R 14 , R 15 , R 16 and R 17 Three or more of these are aromatic groups.

[0054] Representative examples of compounds of formula 6 include imidazole (formula 6A), 1-methylimidazole (formula 6B), 1-decylimidazole (formula 6C), 1-ethylimidazole (formula 6D), 1-propylimidazole (formula 6E), 1-n-butylimidazole (formula 6F), 2-methylimidazole (formula 6G), 2-isopropylimidazole (formula 6H), 4-methylimidazole (formula 6I), 1,2-dimethylimidazole (formula 6J), 2-ethyl-4(5)-methylimidazole (formula 6K), 1-vinylimidazole (formula 6L), 2-ethylimidazole (formula 6M), and 1-dodecylimidazole (formula 6N). Representative structures are shown below. [ka]

[0055] In certain embodiments, the nitrogen-containing surfactant is a triazole, a substituted triazole, or an acceptable salt thereof. Useful triazoles and substituted triazoles can be represented by the following formula 7: [ka] In the formula, R 18 , R 19 and R 20Each is independently selected from hydrogen, a monovalent organic group, a monovalent heterovalent organic group (for example, in the form of groups and parts bonded via a carbon atom, containing nitrogen, oxygen, sulfur, or phosphorus, and combinations thereof), R 18 , R 19 and R 20 Any two or more of these can be optionally bonded together to form a cyclic structure (e.g., a 5-membered ring, a 6-membered ring, or a 7-membered ring). The cyclic structure may be aromatic or aromatic, and may vary from fully saturated to fully unsaturated. The organic group and heteroorganic group may have 1 to 10 carbon atoms (e.g., 1 to 6 carbon atoms). In some embodiments, R 18 , R 19 and R 20 It does not contain acidic functionalities such as carboxylic acid or sulfonic acid moieties.

[0056] In a particular embodiment, R 18 , R 19 and R 20 One or more of these are aromatic groups, such as phenyl or substituted phenyl. In certain embodiments, R 18 , R 19 and R 20 Two or more of these are aromatic groups.

[0057] A typical example of a compound of formula 7 is 1,2,4-triazole (formula 7A), shown below. [ka]

[0058] Amine-based surfactants The composition of the present invention may contain one or more amine-based surfactants.

[0059] Each amine surfactant can be present in an exemplary composition in amounts ranging from about 10 ppm to about 3000 ppm, based on the total fuel composition, for example, about 1000 to about 2500, about 1250 to about 2250, 1500 to about 2000, and 10 ppm to about 750 ppm (for example, 20 to 700, 30 to 650, 50 to 600, 100 to 500, 200 to 400, 250 to 350, etc.).

[0060] In certain embodiments, the amine surfactant is an aliphatic hydrocarbyl-substituted amine compound or a hydrocarbyl-substituted poly(oxyalkylene)amine.

[0061] Specifically, the aliphatic hydrocarbyl-substituted amines used in the present invention may be linear or branched hydrocarbyl-substituted amines having at least one basic nitrogen, where the hydrocarbyl group has a number-average molecular weight of about 700 to 3,000. Specific examples of aliphatic hydrocarbyl-substituted amines include polyisobutenylamines and polyisobutylamines. These amines can be derived as monoamines or polyamines. The preparation of aliphatic amines is generally well known and is detailed in U.S. Patents 3,438,757, 3,565,804, 3,574,576, 3,848,056, 3,960,515, 4,832,702, and 6,203,584, all of which are incorporated herein by reference.

[0062] In certain embodiments, the amine surfactant is a hydrocarbyl-substituted poly(oxyalkylene)amine compound (also called a "polyetheramine"). Specifically, hydrocarbyl-substituted poly(oxyalkylene)amines used in the present invention include hydrocarbyl poly(oxyalkylene)amines (monoamines or polyamines), where the hydrocarbyl group contains about 1 to about 30 carbon atoms. The number of oxyalkylene units can range from about 5 to about 100. The amine moiety is derived from ammonia, a primary alkyl or secondary dialkyl monoamine, or a polyamine having a terminal amino nitrogen atom. The oxyalkylene moiety may be oxypropylene or oxybutylene, or a mixture thereof. Hydrocarbyl-substituted poly(oxyalkylene)amines are described in U.S. Patents 6,217,624 and 5,112,364, which are incorporated herein by reference. Specific examples of hydrocarbyl-substituted poly(oxyalkylene) monoamines include alkylphenyl poly(oxyalkylene) monoamines, where the poly(oxyalkylene) portion contains oxypropylene units, oxybutylene units, or a mixture of oxypropylene and oxypropylene units. The alkyl group on the alkylphenyl portion is a linear or branched alkyl group with approximately 1 to approximately 24 carbon atoms. A preferred alkylphenyl portion is tetrapropenylphenyl, where the alkyl group is a 12-carbon branched alkyl group derived from a propylene tetramer.

[0063] More specifically, additional hydrocarbyl-substituted poly(oxyalkylene)amines include the hydrocarbyl-substituted poly(oxyalkylene)aminocarbamates disclosed in U.S. Patents No. 4,288,612, 4,236,020, 4,160,648, 4,191,537, 4,270,930, 4,233,168, 4,197,409, 4,243,798, and 4,881,945, which are incorporated herein by reference. These hydrocarbyl-substituted poly(oxyalkylene)aminocarbamates contain at least one basic nitrogen atom and have an average molecular weight of about 500 to 10,000, preferably about 500 to 5,000, and more preferably about 1,000 to 3,000. A preferred aminocarbamate is an alkylphenylpoly(oxybutylene)aminocarbamate, where the amine moiety is derived from ethylenediamine or diethylenetriamine.

[0064] The amine-based surfactant of the present invention (more specifically, a linear / branched aliphatic etheramine) is represented by the following formula: R 21 -O-(CH2) y -NHR 22 formula 8 In the formula, R 21 R is a hydrocarbyl group having 8 to 20 carbon atoms. 22 is hydrogen or (CH2) z The NH2 portion is where y and z are independent integers with a value of 2 or greater. The hydrocarbyl group may be saturated or unsaturated. In some embodiments, the hydrocarbyl group may contain two or more unsaturated bonds.

[0065] One advantage is that the amine-based surfactants of the present invention can deliver more basic nitrogen at the same processing rate compared to conventional amine-based fuel surfactants (e.g., polyisobutylamine, polyetheramine, etc.). This property is important in measuring cleaning power. Another advantage is that the low molecular weight amine-based surfactants of the present invention, along with their low decomposition temperature and high volatility, prevent the formation of harmful deposits from amine-based surfactants.

[0066] Particularly exemplary aliphatic etheramines compatible with the present invention include isotridecyloxypropylamine and 2-ethylhexyloxypropylamine. In certain embodiments, the amine surfactant comprises or essentially consists of isotridecyloxypropylamine. These are examples not intended to be limiting.

[0067] Other additives Fuel compositions may include other commonly known fuel additives. Suitable examples include, but are not limited to, antioxidants, metal deactivators, emulsifiers, oxygen additives, anti-knock agents, dispersants, and other detergents. In diesel fuels, other well-known additives such as pour point depressants and fluidity improvers may be used.

[0068] Each of the aforementioned additives, when used, is used in a functionally effective amount to impart the desired properties to the fuel composition. Generally, the concentration of each of these additives, when used, may range from about 0.001 to about 20% by weight, for example, from about 0.01 to about 10% by weight, unless otherwise specified.

[0069] concentrate The compounds of this disclosure can be formulated as concentrates using inert, stable, lipophilic (i.e., soluble in hydrocarbon fuels) organic solvents that boil in the range of 65°C to 205°C. Aliphatic or aromatic hydrocarbon solvents such as benzene, toluene, xylene, or aromatic compounds or aromatic diluents with higher boiling points may be used. Aliphatic alcohols containing 2 to 8 carbon atoms, such as ethanol, isopropanol, methyl isobutylcarbinol, and n-butanol, in combination with hydrocarbon solvents are also suitable for use with the additive. In the concentrate, the amount of the additive may be in the range of 10 to 70% by weight (e.g., 20 to 40% by weight).

[0070] In one embodiment, the concentrated composition comprises about 30 to 90% by weight of an organic solvent with a boiling point in the range of 65°C to 205°C, and about 10 to 70% by weight of a surfactant mixture comprising one or more carrier fluids disclosed herein and one or more nitrogen-containing compounds disclosed herein.

[0071] In certain embodiments, the concentrated composition further comprises one or more amine surfactants selected from the compounds of formula 8: R 21 -O-(CH2) y -NHR 22 formula 8 In the formula, R 21 R is a hydrocarbyl group having 8 to 20 carbon atoms. 22 is hydrogen or (CH2) z This is the NH2 part, where y and z are independent integers with values ​​greater than or equal to 2.

[0072] How to use Nitrogen-containing surfactants can be advantageously used in compositions and methods for improving engine performance, specifically, they can improve deposit cleaning performance and / or reduce particulate matter emissions. In certain embodiments, exemplary nitrogen-containing surfactants can be applied to an internal combustion engine by any suitable means, either alone or in the form of a fuel composition or concentrate composition, for the purpose of controlling, preventing, or reducing carbon deposits. In particular, significant improvements in deposit control (e.g., intake valve deposit control) can be achieved through the use of compositions comprising at least one or more nitrogen-containing surfactants disclosed herein (iii).

[0073] In one embodiment, the method is a method for controlling carbon deposits in an internal combustion engine.

[0074] In one embodiment, the method comprises supplying fuel to an internal combustion engine, the fuel being i) a hydrocarbon fuel including gasoline, diesel fuel, or a blend of gasoline and ethanol, and ii) one or more nitrogen-containing surfactants disclosed herein, for example, a nitrogen-containing compound selected from the compounds of Formula 2 or any acceptable salts thereof: [ka] [In the formula, X 1 and X 2 Independently, are H, C, N, O, or S, and X 1 Or X 2 It is independent of one or more C2-C 20 It comprises an alkyl group or one or more aromatic rings, where each A, B, and D is selected from a monovalent heteroorganic group in the form of a group or part bonded via hydrogen, a monovalent organic group, and a carbon atom, and any two or more of A, B, and D can optionally bond together to form a cyclic structure, X 1 and X 2[Optionally, they can be bonded together to form a cyclic structure] or comprise one or more nitrogen-containing surfactants selected from aliphatic hydrocarbyl-substituted amines or hydrocarbyl-substituted poly(oxyalkylene)amines. In some embodiments, A, B, and D do not contain acidic functionalities such as carboxylic acid or sulfonic acid moieties.

[0075] In certain embodiments, the fuel used in the method further includes: ii) One or more carrier fluids containing an alkyl polyethoxylate selected from the compounds of Formula 1: [ka] In the formula, each R b and R c R is independently hydrogen, a C1-C4 hydrocarbyl group, or a C1-C3 alcohol. a C4-C 100 The group is a hydrocarbyl group, carboxyl group, ether group, thioether group, or aromatic group, and x is between 1 and 20.

[0076] In certain embodiments, the fuel used in the method further includes: iv) One or more amine-based surfactants selected from the compounds of formula 8: R 21 -O-(CH2) y -NHR 22 formula 8 In the formula, R 21 R is a hydrocarbyl group having 8 to 20 carbon atoms. 22 is hydrogen or (CH2) z This is the NH2 part, where y and z are independent integers with values ​​greater than or equal to 2.

[0077] In certain embodiments, the nitrogen-containing surfactant and carrier fluid can be optionally combined with an amine-containing surfactant and applied to an internal combustion engine in the form of a concentrated composition described herein.

[0078] The following examples are intended to be non-limiting. [Examples]

[0079] Examples 1-4: Deposition control performance of exemplary and comparative compositions The tests were performed on a 2006 3.5L Chevy Impala Flex Fuel engine, including a V6 naturally aspirated engine. The tests were Dirty-Up / Clean-Up (DU / CU) tests, in which the engine first completed a 100-hour DU segment to generate intake valve deposits, followed by a 1-tank (20-gallon) CU segment. The 100-hour DU segment was run using an E20 base fuel (base fuel containing 20 vol% ethanol) prepared by diluting 49-state specification PUL E10 unadditiveed fuel to E20 with additional ethanol. The 1-tank CU segment was run using the same E20 base fuel and test additive compositions or exemplary compositions. At the completion of the DU and CU segments, the intake valves were removed, weighed, and the IVD CU% value was calculated.

[0080] DU cycle: Steady state 2000 rpm / 100 Nm

[0081] 1-tank CU cycle: A five-stage cycle consisting of idle, low-speed and load segments, and medium-speed and load segments.

[0082] The tested composition contained an E20 base fuel and one or more of the following additives: 1,3-diphenylguanidine (DPG, an exemplary nitrogen-containing surfactant), nonylphenol ethoxylate (carrier fluid A), and ethoxylated (C). 12 -C 14 ) Secondary alcohol (carrier fluid B), and isotridecyloxypropylamine (a typical amine-based surfactant).

[0083] Table 1 shows the removal of intake valve deposits (IVD) caused by CU treatment with each test composition. [Table 1]

[0084] All documents described herein are incorporated herein by reference and, to the extent that they do not conflict with the foregoing, include any priority documents and / or test procedures. While multiple forms of this disclosure have been illustrated and described, as will be apparent from the general descriptions and specific embodiments above, various modifications can be made without departing from the spirit and scope of this disclosure. Therefore, this disclosure is not intended to be limited thereto.

[0085] For the sake of brevity, this specification explicitly discloses only certain ranges. However, ranges from any lower bound may be combined with any upper bound to enumerate ranges not explicitly described, and similarly, ranges from any lower bound may be combined with other arbitrary lower bounds to enumerate ranges not explicitly described, and similarly, ranges from any upper bound may be combined with other arbitrary upper bounds to enumerate ranges not explicitly described. Furthermore, ranges include all points or individual values ​​between their endpoints, even if not explicitly listed. Thus, all points or individual values, combined with other points or individual values, or with other lower or upper bounds, may function as their own lower or upper bounds, enumerating ranges not explicitly described.

[0086] Similarly, the term “comprising” is considered synonymous with the term “including.” Likewise, whenever there is a transitional phrase “comprising” before a composition, element, or group of elements, it is understood that the description of that composition, element, or group of elements also assumes the same composition or group of elements that is preceded by the transitional phrase “essentially consists of,” “consists of,” “selected from a group consisting of,” or “is,” and vice versa.

[0087] As used herein, the terms "a" and "the" are understood to include both singular and plural forms.

[0088] Various terms are defined above. To the extent that a term used in a claim is not defined above, the broadest definition given to that term by experts in the relevant art should be provided, as reflected in at least one printed publication or issued patent. Furthermore, all patents, test methods, and other documents cited in this application shall be fully incorporated by reference, to the extent that such disclosure does not conflict with this application and in all jurisdictions where such incorporation is permitted.

[0089] The above description of the Disclosure is illustrative and illustrative. Furthermore, while the Disclosure illustrates and describes only preferred embodiments, as stated above, the Disclosure is applicable in a variety of other combinations, modifications, and environments, and it should be understood that changes or modifications are possible within the scope of the concepts expressed herein to match the art or knowledge of the above teachings and / or related art. Although the above is directed toward embodiments of the Disclosure, other further embodiments of the Disclosure can be devised without departing from its basic scope, the scope of which will be determined by the claims that follow.

[0090] Where combinations, subsets, or groups of elements (for example, combinations of components in a composition or combinations of steps in a method) are disclosed, specific references to various individual and collective combinations and permutations of these elements may not be expressly disclosed, but each is understood to be specifically intended and described herein.

[0091] The embodiments described herein are intended to further illustrate the best known modes for carrying out the invention and to enable those skilled in the art to utilize the disclosure with various modifications necessary for a particular use or application in such or other embodiments. Therefore, the description is not intended to limit the embodiments disclosed herein. Furthermore, the appended claims are intended to be interpreted as encompassing alternative embodiments.

Claims

1. A fuel composition, i) Hydrocarbon fuels including gasoline, diesel fuel, or a blend of gasoline and ethanol, ii) Below: 【Chemistry 1】 In the formula, each R ｂ and R ｃ are independently hydrogen, C １ -C ４ hydrocarbyl group, or C １ -C ３ alcohol, R ａ is a C ４ -C １００ hydrocarbyl group, carboxyl group, ether group, thioether group, or aromatic group, x is 1 to 20, and one or more carrier fluids containing an alkyl polyethoxylate defined as such, and iii) Below: 【Chemistry 2】 In the formula, X １ and X ２ These are independently H, C, N, O, or S, and X １ Or X ２ Each is independently one or more C ２ -C ２０ Containing an alkyl group or one or more aromatic rings, Each of A, B, and D is independently selected from hydrogen, a monovalent organic group, and a monovalent heteroorganic group in the form of a group or part bonded via a carbon atom. Two or more of A, B, and D can be optionally combined to form a ring structure. X １ and X ２ One or more nitrogen-containing surfactants or their acceptable salts, which can optionally combine to form a cyclic structure, or The fuel composition comprising one or more nitrogen-containing surfactants selected from aliphatic hydrocarbyl-substituted amines or hydrocarbyl-substituted poly(oxyalkylene)amines.

2. The aforementioned composition further, iv) Below: R ２１ -O-(CH ２ ) ｙ -NHR ２２ In the formula, R ２１ R is a hydrocarbyl group having 8 to 20 carbon atoms. ２２ is hydrogen or (CH ２ ) ｚ NH ２ The fuel composition according to claim 1, comprising one or more amine-based surfactants, defined as a part, where y and z are independently integers having a value of 2 or more.

3. The fuel composition according to claim 1, wherein the one or more nitrogen-containing surfactants include guanidine, substituted guanidine, a derivative thereof, or an acceptable salt thereof.

4. The guanidine, substituted guanidine, its derivatives, or acceptable salts thereof have the following structure: 【Transformation 3】 In the formula, R １ , R ２ , R ３ , R ４ and R ５ Each is independently selected from hydrogen, a monovalent organic group, and a monovalent heteroorganic group in the form of a group or part bonded via carbon. R １ , R ２ , R ３ , R ４ and R ５ The fuel composition according to claim 3, wherein any two or more of the above can be optionally combined to form a cyclic structure.

5. The fuel composition according to claim 1, wherein the one or more nitrogen-containing surfactants include diphenylguanidine.

6. The fuel composition according to claim 1, wherein the one or more carrier fluids include a nonylphenol ethoxylate.

7. The one or more carrier fluids undergo ethoxylation (C １２ -C １４ The fuel composition according to claim 1, comprising a secondary alcohol.

8. The fuel composition according to claim 1, wherein the fuel composition comprises the carrier fluid in an amount of about 35 ppmW to about 5000 ppmW and one or more nitrogen-containing surfactants in an amount of about 500 ppmW to about 3000 ppmW.

9. The fuel composition according to claim 2, wherein the fuel composition comprises the carrier fluid in an amount of about 35 ppmW to about 5000 ppmW, one or more nitrogen-containing surfactants in an amount of about 500 ppmW to about 3000 ppmW, and one or more amine-based surfactants in an amount of about 100 ppmW to 750 ppmW.

10. A method for controlling carbon deposits in an internal combustion engine, This includes supplying fuel to the internal combustion engine, wherein the fuel is i) Hydrocarbon fuels including gasoline, diesel fuel, or a blend of gasoline and ethanol, and ii) Below: 【Chemistry 4】 In the formula, X １ and X ２ These are independently H, C, N, O, or S, and X １ Or X ２ Each is independently one or more C ２ -C ２０ Containing an alkyl group or one or more aromatic rings, Each of A, B, and D is selected from hydrogen, a monovalent organic group, and a monovalent heteroorganic group in the form of a group or part bonded via a carbon atom. Two or more of A, B, and D can be optionally combined to form a ring structure. X １ and X ２ One or more nitrogen-containing surfactants or their acceptable salts, which can optionally combine to form a cyclic structure, or The control method comprising one or more nitrogen-containing surfactants selected from aliphatic hydrocarbyl-substituted amines or hydrocarbyl-substituted poly(oxyalkylene)amines.

11. The aforementioned fuel further, iii) Below: 【Transformation 5】 In the formula, each R ｂ and R ｃ These are independently hydrogen and C １ -C ４ Hydrocarbyl group, or C １ -C ３ It is an alcohol, R ａ C ４ -C １００ The method according to claim 10, comprising one or more carrier fluids containing an alkyl polyethoxylate defined as a hydrocarbyl group, a carboxyl group, an ether group, a thioether group, or an aromatic group, where x is 1 to 20.

12. The aforementioned fuel further, below: R ２１ -O-(CH ２ ) ｙ -NHR ２２ In the formula, R ２１ R is a hydrocarbyl group having 8 to 20 carbon atoms. ２２ is hydrogen or (CH ２ ) ｚ NH ２ The method according to claim 10, comprising one or more amine-based surfactants defined as a part, where y and z are independently integers having a value of 2 or more.

13. The aforementioned fuel further, below: 【Transformation 6】 In the formula, each R ｂ and R ｃ These are independently hydrogen and C １ -C ４ Hydrocarbyl group, or C １ -C ３ It is an alcohol, R ａ C ４ -C １００ One or more carrier fluids comprising alkyl polyethoxylates defined as hydrocarbyl groups, carboxyl groups, ether groups, thioether groups, or aromatic groups, where x is 1 to 20, and below: R ２１ -O-(CH ２ ) ｙ -NHR ２２ In the formula, R ２１ R is a hydrocarbyl group having 8 to 20 carbon atoms. ２２ is hydrogen or (CH ２ ) ｚ NH ２ The method according to claim 10, comprising one or more amine-based surfactants defined as a part, where y and z are independently integers having a value of 2 or more.

14. The method according to claim 10, wherein the hydrocarbon fuel comprises a blend of gasoline and ethanol.

15. A solvent in an amount of approximately 30 to 90% by weight with a boiling point in the range of 65°C to 205°C, and A surfactant mixture containing approximately 10 to 70% by weight, below: 【Transformation 7】 In the formula, each R ｂ and R ｃ is independently hydrogen, C １ -C ４ hydrocarbyl group, or C １ -C ３ alcohol, R ａ is a C ４ -C １００ hydrocarbyl group, carboxyl group, ether group, thioether group, or aromatic group, x is 1 to 20, and one or more carrier fluids containing an alkyl polyethoxylate defined as such, and below: 【Transformation 8】 wherein, X １ and X ２ are independently H, C, N, O, or S, and X １ or X ２ independently includes one or more C ２ -C ２０ alkyl groups or one or more aromatic rings, Each of A, B, and D is selected from hydrogen, a monovalent organic group, and a monovalent heteroorganic group in the form of a group or part bonded via a carbon atom. Two or more of A, B, and D can be optionally combined to form a ring structure. X １ and X ２ One or more nitrogen-containing surfactants or their acceptable salts, which can optionally combine to form a cyclic structure, or A surfactant mixture comprising one or more nitrogen-containing surfactants selected from aliphatic hydrocarbyl-substituted amines or hydrocarbyl-substituted poly(oxyalkylene)amines, A concentrated composition containing the following:

16. The aforementioned composition, further, below: R ２１ -O-(CH ２ ) ｙ -NHR ２２ In the formula, R ２１ R is a hydrocarbyl group having 8 to 20 carbon atoms. ２２ is hydrogen or (CH ２ ) ｚ NH ２ The concentrated composition according to claim 15, comprising one or more amine-based surfactants defined as a part, where y and z are independently integers having a value of 2 or more.

17. The concentrated composition according to claim 15, wherein the one or more nitrogen-containing surfactants are guanidine, substituted guanidine, a derivative thereof, or an acceptable salt thereof.

18. The guanidine, substituted guanidine, its derivatives, or acceptable salts thereof are as follows: 【Chemistry 9】 In the formula, R １ , R ２ , R ３ , R ４ and R ５ Each is independently selected from hydrogen, a monovalent organic group, and a monovalent heteroorganic group in the form of a group or part bonded via a carbon atom. R １ , R ２ , R ３ , R ４ and R ５ The concentrated composition according to claim 15, which is structure-based, wherein any two or more of the elements can be optionally combined to form a cyclic structure.

19. The concentrated composition according to claim 15, wherein one or more nitrogen-containing surfactants include diphenylguanidine.

20. The concentrated composition according to claim 15, wherein one or more carrier fluids contain a nonylphenol ethoxylate.

21. The one or more carrier fluids undergo ethoxylation (C １２ -C １４ The concentrated composition according to claim 15, comprising a secondary alcohol.

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