Method for controlling fuel additive compositions and deposits

Abstract

A fuel composition is disclosed. The composition comprises a hydrocarbon fuel, including gasoline or diesel, and one or more guanidine-based or amidine-based surfactants, or acceptable salts thereof.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to U.S. Provisional Application No. 63 / 455,289, filed on 29 March 2023, the disclosure of which is incorporated herein by reference.

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

[0003] Conventional fuel additives developed for port fuel injection (PEI) gasoline engines are not optimized for controlling deposit formation in direct injection spark ignition (DISI) engines, also commonly known as direct injection gasoline (DIG) or direct gasoline injection (GDI) engines. Unlike PFI engines, DISI engines deliver fuel directly to the combustion chamber. When fuel is injected directly, it is immediately exposed to high temperature and pressure. In this environment, combustion products can accumulate on the external and / or internal surfaces of the injector and nozzle (known as injector fouling).

[0004] The formation of deposits both around the injector nozzle and within the combustion chamber can have a significant negative impact on one or more of the following: fuel flow rate, injection duration, and spray pattern. Furthermore, deposit formation in injectors can affect not only gasoline engines but also diesel engines. This can, in turn, lead to increased exhaust emissions, increased particulate matter (PM) formation, reduced fuel economy, loss of power / performance, increased wear, and / or reduced equipment lifespan. [Brief explanation of the drawing]

[0005] [Figure 1] A to C show photographs of the deposition control described in the Examples section. [Overview of the project]

[0006] In one embodiment, a fuel composition comprising the following is provided: i) a hydrocarbon fuel including gasoline or diesel, and ii) one or more guanidine or amidine-based surfactants.

[0007] In another embodiment, a method for controlling carbon deposits in an internal combustion engine is provided, comprising supplying fuel to the internal combustion engine, wherein the fuel comprises i) a hydrocarbon fuel including gasoline or diesel; and ii) one or more guanidine or amidine-based surfactants.

[0008] In another embodiment, a concentrated composition is provided comprising: ii) an organic solvent having a boiling point in the range of 65°C to 205°C in about 30 to 90% by weight; and ii) a surfactant mixture comprising about 10 to 70% by weight, including one or more nitrogen-containing surfactants as described herein. [Modes for carrying out the invention]

[0009] 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, a significant improvement in deposit control can be achieved through the use of compositions comprising at least one nitrogen-containing surfactant disclosed herein.

[0010] fuel composition Generally speaking, the fuel compositions of the present invention comprise (i) a hydrocarbon fuel and one or more nitrogen-containing surfactants.

[0011] Hydrocarbon fuels Examples of hydrocarbon fuels include gasoline and diesel. Gasoline fuel is at least primarily C4-C 12It means a composition containing hydrocarbons. In one embodiment, gasoline or gasoline boiling range components mainly consist of at least C4-C 12 It further means a composition that contains hydrocarbons and has a boiling point of about 37.8 °C (100 °F) to about 204 °C (400 °F). In an alternative embodiment, gasoline mainly consists of at least C4-C 12 It is defined to mean a composition that contains hydrocarbons, has a boiling point of about 37.8 °C (100 °F) to about 204 °C (400 °F), and further meets ASTM D4814.

[0012] In certain embodiments, the hydrocarbon fuel includes gasoline and ethanol. A blend of gasoline and ethanol suitable for use in the present composition and method contains about 5 to about 35 volume % ethanol, or about 15 to about 25 volume % ethanol. In certain embodiments, the hydrocarbon fuel is an E20 fuel or a gasoline fuel containing 20 volume % ethanol.

[0013] Diesel means at least mainly C 10 -C 25 It means an intermediate distillate fuel containing hydrocarbons. In one embodiment, diesel mainly consists of at least C 10 -C 25 It further means a composition that contains hydrocarbons and has a boiling point of about 165.6 °C (330 °F) to about 371.1 °C (700 °F). In an alternative embodiment, diesel, as defined above, mainly consists of at least C 10 -C 25 It is defined to mean a composition that contains hydrocarbons, has a boiling point of about 165.6 °C (330 °F) to about 371.1 °C (700 °F), and further meets ASTM D975.

[0014] 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 less than 100% by weight.

[0015] The gasoline used in this 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.

[0016] The fuel composition of this disclosure comprises one or more guanidine-based or amidine-based surfactants.

[0017] Guanidine-based surfactants Guanidine-based surfactants can be represented by the following generalized structure: [ka] In the formula, R 1 , R 2 , R 3 , R 4 and R 5 Each of these independently contains, in the form of a group or part in which hydrogen, a monovalent organic group (e.g., an aromatic or aliphatic group), or a monovalent heterovalent organic group (e.g., an aromatic or aliphatic group containing one or more N, O, S, or P) is bonded via a carbon atom.

[0018] In some embodiments, the guanidine-based surfactant includes a cyclic moiety, where R 1 , R 2 , R 3 , R 4 , and R 5Any two or more of these can be selectively 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. Organic and heteroorganic groups may have 1 to 10 carbon atoms (e.g., 1 to 6 carbon atoms).

[0019] In some embodiments, R 1 , R 2 , R 3 , R 4 and R 5 One or more of these are aromatic groups, such as phenyl, substituted phenyl, heteroaryl, or substituted heteroaryl. 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.

[0020] Suitable examples of guanidine-based surfactants include monosubstituted guanidines, polysubstituted guanidines, cyclic guanidines, imidazoles (including benzimidazoles), and N-guanidinosuccinimide. In some cases, guanidine-based surfactants may be classified into several guanidine groups.

[0021] monosubstituted guanidine The fuel compositions of this disclosure may comprise one or more monosubstituted guanidines. In some embodiments, the monosubstituted guanidine may have the following generalized structure: [ka] Here, R is alkyl(C n H 2n+1, n ≥ 1), aryl (substituted or unsubstituted carbocyclic or heterocyclic aromatic group), unsaturated hydrocarbyl (C n H 2m+1 , where m < n, n ≥ 2), alkoxyalkyl (C n H 2n+1 OC m H 2m n ≥ 1, m ≥ 2), polyalkoxyalkyl (C n H 2n+1 (OC m H 2m ) q n ≥ 1, m ≥ 2, q ≥ 2), or aryloxyalkyl (C n H 2n+1 C6H4OC m H 2m n ≥ 1, m ≥ 2) group.

[0022] Non-limiting examples of monosubstituted guanidines include the following.

Chemical formula

[0023] Polysubstituted guanidine The fuel compositions of the present disclosure may include one or more polysubstituted guanidines. In some embodiments, the polysubstituted guanidine may have the following generalized structure:

Chemical formula

[0024] Non-restrictive examples of polysubstituted guanidines include the following: [ka] [ka] [ka]

[0025] Cyclic guanidine The fuel compositions of this disclosure may comprise one or more cyclic guanidines. The cyclic structures may be aromatic or non-aromatic, and may vary from fully saturated to fully unsaturated, and may include partially saturated or partially unsaturated structures.

[0026] In some embodiments, cyclic guanidine may have one of the following generalized structures: [ka] In the formula, R 1 and R 2 is hydrogen, alkyl (C n H 2n+1 n≧1), aryl (substituted or unsubstituted carbocyclic or heterocyclic aromatic group), unsaturated hydrocarbyl (C n H 2m+1 , here, m <n、n≧2)、アルコキシアルキル(C n H 2n+1 OC m H 2m n≧1, m≧2), polyalkoxyalkyl(C) n H 2n+1 (OC m H 2m ) q n≧1, m≧2, q≧2), or aryloxyalkyl(C n H 2n+1 C6H4OC m H2m a group where n ≥ 1, m ≥ 2; and R 3 is hydrogen, alkyl (C n H 2n+1 , n ≥ 1), aryl (a substituted or unsubstituted carbocyclic or heterocyclic aromatic group), hydroxyalkyl (C n H 2n OH, n ≥ 1), aminoalkyl (C n H 2n NH2, n ≥ 1) group. In some embodiments, n is 2 - 6, for example, 3 - 6 or 3 - 6. Alternatively, the cyclic guanidine may have the following generalized structure:

Chemical formula

[0027] Non-restrictive examples of cyclic guanidines include: [ka] [ka] [ka]

[0028] Imidazole The fuel compositions of this disclosure may comprise one or more imidazoles. In some embodiments, the imidazole may have one of the following generalized structures: [ka] (In the formula, R 1 and R 2 R is independently hydrogen, alkyl, aryl, unsaturated hydrocarbyl, alkoxyalkyl, or aryloxyalkyl group; 3 is hydrogen, alkyl (C n H 2n+1 n≧1), aryl (substituted or unsubstituted carbocyclic or heterocyclic aromatic group), hydroxyalkyl (C n H 2n OH (1 ≤ n ≤ 6), or aminoalkyl (C n H 2n NH2 (1 ≤ n ≤ 6) group, or [ka] In the formula, R 1 is hydrogen, alkyl (C n H 2n+1 n≧1), aryl (substituted or unsubstituted carbocyclic or heterocyclic aromatic group), unsaturated hydrocarbyl (Cn H 2m+1 , where m <n、n≧2)、アルコキシアルキル(C n H 2n+1 OC m H 2m n≧1, m≧2), polyalkoxyalkyl(C) n H 2n+1 (OC m H 2m ) q n≧1, m≧2, q≧2), or aryloxyalkyl(C n H 2n+1 C6H4OC m H 2m n≧1, m≧2) group; and R 2 and R 3 These are independently hydrogen and alkyl (C n H 2n+1 , n≧1), aryl (substituted or unsubstituted carbocyclic or heterocyclic aromatic group), hydroxyalkyl (C n H 2n OH (1≦n≧6), or aminoalkyl(C n H 2n It is an NH2 group (1 ≤ n ≤ 6).

[0029] Non-specific examples of imidazoles include: [ka]

[0030] N-guanidinosuccinimide The fuel compositions of this disclosure may comprise one or more N-guanidinosuccinimides. In some embodiments, the N-guanidinosuccinimid may have the following generalized structure: [ka] In the formula, R is hydrogen, alkyl group (C n H 2n+1 , n≧1), or an unsaturated hydrocarbyl group (C n H 2m+1 , here, m <n、n≧2である)である。

[0031] Non-specific examples of N-guanidinosuccinimide include: [ka]

[0032] Amidine-based surfactants The fuel compositions of this disclosure may comprise one or more amidines. In some embodiments, the amidines may comprise the following generalized structures: [ka] In the formula, R 1 is hydrogen, alkyl (C n H 2n+1 n≧1), aryl (substituted or unsubstituted carbocyclic or heterocyclic aromatic group), unsaturated hydrocarbyl (C n H 2m+1 , where m <n、n≧2)、アルコキシアルキル(C n H 2n+1 OC m H 2m n≧1, m≧2), polyalkoxyalkyl(C) n H 2n+1 (OC m H 2m ) q n≧1, m≧2, q≧2), or aryloxyalkyl(C n H 2n+1 C6H4OC m H 2m n≧1, m≧2), hydroxyalkyl(C n H 2n OH (1 ≤ n ≤ 6), or aminoalkyl (C n H 2n This is the NH2 group (1 ≤ n ≤ 6).

[0033] Non-exclusive examples of amidines include: [ka]

[0034] Amidine-based surfactants can be represented by the following generalized formula 15: [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 a group or part that is bonded via a carbon atom and does not contain an acidic functional group such as a carboxyl or sulfone, and includes nitrogen, oxygen, sulfur, or phosphorus), and combinations thereof, where R 8 , R 9 , R 10 , and R 11 Any two or more of these can bond to each other to form a cyclic structure (e.g., a 5-, 6-, or 7-membered ring). The cyclic structure may be aromatic or aromatic, and may vary from fully saturated to fully unsaturated. Organic and heteroorganic groups may have 1 to 10 carbon atoms (e.g., 1 to 6 carbon atoms).

[0035] 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.

[0036] Each amine surfactant may be present in the exemplary composition in amounts based on the total fuel composition, ranging from approximately 10 ppm to approximately 3000 ppm, for example, approximately 1000 to approximately 2500, approximately 1250 to approximately 2250, 1500 to approximately 2000, and 10 ppm to approximately 750 ppm (for example, 20 to 700, 30 to 650, 50 to 600, 100 to 500, 200 to 400, 250 to 350, etc.).

[0037] Other additives Fuel compositions may include other generally known fuel additives. Suitable examples include, but are not limited to, antioxidants, metal deactivators, emulsifiers, oxygen additives, anti-knock agents, dispersants, carrier fluids, and other surfactants. In diesel fuels, other well-known additives such as pour point depressants and flow improvers may be used.

[0038] 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.

[0039] 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 10 to 70% by weight (e.g., 20 to 40% by weight).

[0040] In one embodiment, the concentrated composition comprises about 30 to 90% by weight of an organic solvent with a boiling point of 65°C to 205°C, and about 10 to 70% by weight of a surfactant mixture comprising one or more guanidine-based or amidine-based surfactants as described herein.

[0041] How to use Nitrogen-containing surfactants can be advantageously used in compositions and methods for improving engine performance, specifically, improving deposit cleaning performance, and / or reducing 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 a concentrate composition, for the purpose of controlling, preventing, or reducing carbon deposits. In particular, a significant improvement in deposit control can be achieved through the use of compositions comprising at least (iii) one or more nitrogen-containing surfactants disclosed herein.

[0042] In one embodiment, the method is a method for controlling carbon deposits in an internal combustion engine.

[0043] In one embodiment, the method comprises supplying fuel to an internal combustion engine, wherein the fuel comprises: i) a hydrocarbon fuel including gasoline, diesel, or a mixture of gasoline and ethanol; and ii) one or more guanidine-based or amidine-based surfactants disclosed herein.

[0044] The following examples are intended to be non-limiting. [Examples]

[0045] Deposition control for direct injection spark ignition (DISI) engines Diphenylguanidinium oleate was blended into premium unleaded fuel (PUL) and tested for deposition control (Table 1). Each example also contained the same amount of commonly used fuel additives, such as surfactants. [Table 1]

[0046] Figures 1A-1C show the injector deposit removal capability of cyclic guanidine (formula 8A). More specifically, Figure 1A shows a photograph of the injector nozzle after 50 hours of operation with baseline fuel. Figure 1B shows a photograph of the injector nozzle after treatment with cyclic guanidine. Figure 1C shows a clean injector nozzle.

[0047] 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. Although several forms of this disclosure have been illustrated and described, as is evident 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.

[0048] 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.

[0049] 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.

[0050] As used herein, the terms "a" and "the" are understood to include both singular and plural forms.

[0051] 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.

[0052] 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.

[0053] Where combinations, subsets, or groups of elements (for example, combinations of components in a composition or combinations of steps in a method) are disclosed, even if specific references to various individual and collective combinations and permutations of these elements are not explicitly disclosed, each is understood to be specifically intended and described herein.

[0054] 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. i) Hydrocarbon fuels, including gasoline or diesel; ii) A fuel composition comprising one or more guanidine-based or amidine-based surfactants, or acceptable salts thereof.

2. The fuel composition according to claim 1, wherein the guanidine-based surfactant or an acceptable salt thereof is based on the following structure: 【Chemistry 1】 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 heterovalent organic group, in the form of a group or part that is bonded via a carbon atom and does not contain acidic functionalities such as carboxylic acids or sulfonic acids; and R １ , R ２ , R ３ , R ４ and R ５ Any two or more of them may optionally be joined together to form a cyclic structure.

3. The fuel composition according to claim 1, wherein the guanidine-based surfactant is a monosubstituted guanidine, a polysubstituted guanidine, a cyclic guanidine, a benzimidazole, or N-guanidinosuccinimide.

4. The fuel composition according to claim 3, wherein the benzimidazole is aminobenzimidazole or iminobenzimidazole.

5. The fuel composition according to claim 1, wherein the guanidine-based surfactant is guanidium oleate or guanidium palmitate.

6. 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 the guanidine-based surfactant in an amount of about 500 ppmW to about 3000 ppmW.

7. 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 the amidine-based surfactant in an amount of about 500 ppmW to about 3000 ppmW.

8. 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 or diesel; and ii) The method comprising one or more guanidine-based or amidine-based surfactants, or acceptable salts thereof.

9. The method according to claim 8, wherein the guanidine-based surfactant or an acceptable salt thereof is based on the following structure: 【Chemistry 2】 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 heterovalent organic group, in the form of a group or part that is bonded via a carbon atom and does not contain acidic functionalities such as carboxylic acids or sulfonic acids; and R １ , R ２ , R ３ , R ４ and R ５ Any two or more of these elements can be selectively joined together to form a ring structure.

10. The method according to claim 8, wherein the guanidine-based surfactant is a monosubstituted guanidine, a polysubstituted guanidine, a cyclic guanidine, a benzimidazole, or N-guanidinosuccinimide.

11. The method according to claim 10, wherein the benzimidazole is aminobenzimidazole or iminobenzimidazole.

12. The method according to claim 8, wherein the guanidine-based surfactant is guanidium oleate or guanidium palmitate.

13. The method according to claim 8, wherein the fuel composition comprises the carrier fluid in a quantity of about 35 ppmW to about 5000 ppmW and the guanidine-based surfactant in a quantity of about 500 ppmW to about 3000 ppmW.

14. The method according to claim 8, wherein the fuel composition comprises the carrier fluid in a quantity of about 35 ppmW to about 5000 ppmW and the amidine-based surfactant in a quantity of about 500 ppmW to about 3000 ppmW.

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