Fuel additives for reducing injector nozzle fouling and particulate matter emissions

Abstract

The present disclosure provides a fuel composition comprising: a hydrocarbon-based fuel having a boiling point within the gasoline or diesel range; an amine-based detergent given by the formula R1-O-(CH2) m -NHR2, wherein the additive is present at about 10 weight ppm to about 750 weight ppm based on the total weight of the fuel composition, wherein R1 is a hydrocarbon group having 8 to 20 carbons, R2 is hydrogen or (CH2) n NH2 moiety, and wherein m, n are independently integers having a value of 3 or greater; and one or more nitrogen-containing detergents.

Description

Technical Field

[0001] The present disclosure relates to fuel components that can improve engine performance. More specifically, the present disclosure describes compositions and methods for mitigating injector nozzle fouling and reducing particulate matter emissions in direct injection spark ignition engines. Background Art

[0002] Conventional fuel additives developed for port fuel injection (PFI) gasoline engines are typically not optimized for controlling deposit formation in direct injection spark ignition (DISI) engines, sometimes referred to as direct injection gasoline (DIG) or gasoline injection (GDI) engines. This is primarily because, unlike PFI engines, DISI engines deliver fuel directly into the combustion chamber. When fuel is injected directly, it is immediately exposed to high temperatures and pressures. In this environment, combustion products can accumulate on the exterior and / or interior surfaces of injectors and nozzles (known as injector fouling).

[0003] Deposits formed around the injector nozzle and inside the combustion chamber can have a significant negative impact on one or more of the fuel flow rate, injection duration and / or spray pattern. This in turn can lead to increased emissions, increased particulate matter (PM) formation, reduced fuel economy, power / performance loss, increased wear and / or shortened equipment life. Summary of the invention

[0004] In one aspect, a fuel composition is provided, comprising: a hydrocarbon-based fuel having a boiling point in the gasoline or diesel range; 1 -O-(CH 2 ) m -NHR 2 The amine-based detergent is present in an amount of about 10 ppm by weight to about 750 ppm by weight based on the total weight of the fuel composition; wherein R 1 is a hydrocarbon group having 8 to 20 carbon atoms, R 2 is hydrogen or (CH 2 ) n NH 2 moiety, and wherein m, n are independently integers having a value of 3 or greater; and one or more nitrogen-containing descaling agents.

[0005] In another aspect, a concentrated composition is provided, comprising: about 30% to 90% by weight of an organic solvent having a boiling point in the range of 65° C. to 205° C.; and about 10% to 70% by weight of a descaling agent mixture, the descaling agent mixture comprising: (1) a descaling agent of formula R 1 -O-(CH 2 ) m -NHR 2 Amine-based descaling agents are given, where R1 is a hydrocarbon group having 8 to 20 carbon atoms, R 2 is hydrogen or (CH 2 ) n NH 2 moiety, and wherein m, n are independently integers having a value of 3 or greater; and (2) one or more nitrogen-containing descaling agents.

[0006] In one aspect, a method for controlling injector fouling is provided, the method comprising: supplying a fuel composition to a direct injection engine, the fuel composition comprising: a hydrocarbon-based fuel having a boiling point in the gasoline or diesel range; a fuel having a formula R 1 -O-(CH 2 ) m -NHR 2 The amine-based detergent is present in an amount of about 10 ppm by weight to about 750 ppm by weight based on the total weight of the fuel composition, wherein R 1 is a hydrocarbon group having 8 to 20 carbon atoms, R 2 is hydrogen or (CH 2 ) n NH 2 moiety, and wherein m, n are independently integers having a value of 3 or greater; and one or more nitrogen-containing descaling agents. BRIEF DESCRIPTION OF THE DRAWINGS

[0007] Figure 1 is a diagram described in the Examples section.

[0008] Figure 2 is a diagram described in the Examples section.

[0009] Figure 3 is a diagram described in the Examples section.

[0010] Figure 4 is a diagram described in the Examples section.

[0011] FIG. 5A to FIG. 5C is a diagram described in the Examples section.

[0012] FIG. 6A to FIG. 6C is a diagram described in the Examples section.

[0013] 7A to 7C is a diagram described in the Examples section.

[0014] FIG. 8A to FIG. 8C is a diagram described in the Examples section.

[0015] 9A to 9C is a diagram described in the Examples section.

[0016] FIG. 10A to FIG. 10Cis a diagram described in the Examples section.

[0017] FIG. 11A to FIG. 11B is a diagram described in the Examples section.

[0018] Fig.12 is a diagram described in the Examples section. DETAILED DESCRIPTION

[0019] Compositions and methods for deposit control in direct injection engines are described. More specifically, the present invention provides detergent additive compositions useful as components of fuel compositions and methods of using the same.

[0020] The fuel composition of the present invention comprises (i) a hydrocarbon-based fuel, (ii) a primary fuel additive and (iii) one or more secondary fuel additives.

[0021] Hydrocarbon based fuels

[0022] Hydrocarbon based fuels include gasoline and diesel.

[0023] Gasoline fuel is a fuel that contains at least mainly C 4 -C 12 In one embodiment, gasoline or gasoline boiling range components are further defined as comprising at least primarily C 4 -C 12 hydrocarbons and also having a boiling range from about 37.8°C (100°F) to about 204°C (400°F). In an alternative embodiment, gasoline is defined as comprising at least primarily C 4 -C 12 A hydrocarbon having a boiling range from about 37.8°C (100°F) to about 204°C (400°F) and further defined as a composition conforming to ASTM D4814.

[0024] Diesel fuel is a fuel that contains at least mainly C 10 -C 25 In one embodiment, diesel is further defined as a fuel containing at least mainly C 10 -C 25 hydrocarbons, and also having a boiling range of from about 165.6°C (330°F) to about 371.1°C (700°F). In an alternative embodiment, diesel is defined as above and refers to diesel fuels containing at least primarily C 10 -C 25 A hydrocarbon having a boiling range from about 165.6°C (330°F) to about 371.1°C (700°F), and is further defined as a composition conforming to ASTM D975.

[0025] The hydrocarbon-based fuel is present in a major weight percent of the total fuel composition. In some embodiments, the hydrocarbon-based fuel is present in about 50 weight percent or greater, 55 weight percent or greater, 60 weight percent or greater, 65 weight percent or greater, 70 weight percent or greater, 75 weight percent or greater, 80 weight percent or greater, 85 weight percent or greater, 90 weight percent or greater, 95 weight percent or greater, or any range from about 50 weight percent to less than 100 weight percent.

[0026] According to some embodiments, the gasoline used in the present invention may be clean burning gasoline (CBG). CBG refers to a gasoline formulation containing reduced levels of sulfur, aromatics, and olefins. The exact formulation may vary depending on local regulatory definitions.

[0027] Fuel-soluble non-volatile carrier fluids or oils may also be used with the compounds of the present disclosure. The carrier fluid is a chemically inert hydrocarbon-soluble liquid carrier that significantly increases the non-volatile residue (NVR) or solvent-free liquid fraction of the fuel additive composition without significantly contributing to an increase in the octane demand. The carrier fluid may be a natural or synthetic oil, such as mineral oil, refined petroleum oil, synthetic polyalkanes and olefins, including hydrogenated and unhydrogenated polyalphaolefins, synthetic polyoxyalkylene derivative oils, such as U.S. Pat. Nos. 3,756,793, 4,191,537, and 5,004,478; and those described in European Patent Application Publication Nos. 356,726 and 382,159.

[0028] The carrier fluid may be used in an amount ranging from 35 to 5000 ppm by weight of the hydrocarbon fuel (e.g., 50 to 3000 ppm of the fuel). When used in a fuel concentrate, the carrier fluid may be present in an amount ranging from 20% to 60% by weight (e.g., 30% to 50% by weight).

[0029] Main fuel additives

[0030] The primary fuel additive of the present invention is an amine-based detergent (more specifically, a linear / branched aliphatic ether amine) having the formula:

[0031] R 1 -O-(CH 2 ) m -NHR 2

[0032] Formula I

[0033] Where R 1 is a hydrocarbon group having 8 to 20 carbon atoms, R 2 is hydrogen or (CH 2 ) nNH 2 moiety, and m, n are independently integers having a value of 3 or greater. The hydrocarbyl group may be saturated or unsaturated. In some embodiments, the hydrocarbyl group may contain more than one unsaturated bond.

[0034] As an advantage, the fuel additive of the present invention can deliver more basic nitrogen at the same treat rate than conventional amine-based fuel detergents (such as polyisobutylamine, polyetheramine, etc.). This feature is important in determining detergency. As another advantage, the low molecular weight of the additive of the present invention and its low decomposition temperature and high volatility prevent the additive from generating harmful deposits.

[0035] Particularly illustrative aliphatic ether amines compatible with the present invention include isotridecyloxypropylamine and 2-ethylhexyloxypropylamine. These are illustrative examples and are not intended to be limiting.

[0036] In some embodiments, the primary fuel additive may be present at about 10 ppm to about 750 ppm (such as 20 ppm to 700 ppm, 30 ppm to 650 ppm, 50 ppm to 600 ppm, 100 ppm to 500 ppm, 200 ppm to 400 ppm, 250 ppm to 350 ppm, etc.), based on the total fuel composition.

[0037] Supplementary fuel additives

[0038] The fuel compositions of the present invention include one or more auxiliary fuel additives. The auxiliary fuel additives are nitrogen-containing detergents that provide enhanced detergency when paired with the primary fuel additives of the present invention.

[0039] Suitable auxiliary fuel additives can be classified as aliphatic hydrocarbyl-substituted amines, hydrocarbyl-substituted poly(oxyalkylene)amines, hydrocarbyl-substituted succinimides, Mannich reaction products, polyalkylphenoxyaminoalkanes, nitro and aminoaromatic esters of polyalkylphenoxyalkanols, and nitrogen-containing carburetors / injector descalants. Each class of auxiliary fuel additives will be described in more detail herein.

[0040] In particular, the aliphatic hydrocarbyl substituted amines used in the present invention can be straight or branched chain hydrocarbyl substituted amines having at least one basic nitrogen, and wherein the hydrocarbyl group has a number average molecular weight of about 700 to 3,000. Specific examples of aliphatic hydrocarbyl substituted amines include polyisobutylene amines and polyisobutylamines. These amines can be derived as monoamines or polyamines. The preparation of aliphatic amines is generally known and described in detail in U.S. Patents Nos. 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 hereby incorporated by reference.

[0041] In particular, the hydrocarbyl-substituted poly(oxyalkylene)amines (also referred to as "polyetheramines") used in the present invention may include hydrocarbyl poly(oxyalkylene)amines (monoamines or polyamines) in which the hydrocarbyl group contains from about 1 to about 30 carbon atoms. The number of oxyalkylene units may range from about 5 to about 100. The amine moiety is derived from ammonia, a primary alkyl monoamine or a secondary dialkyl monoamine, or a polyamine having a terminal amino nitrogen atom. The oxyalkylene moiety may be propylene oxide or butylene oxide or a mixture thereof. Hydrocarbyl-substituted poly(oxyalkylene)amines are described in U.S. Pat. Nos. 6,217,624 and 5,112,364, which are hereby incorporated by reference. Specific examples of hydrocarbyl-substituted poly(oxyalkylene)monoamines include alkylphenyl poly(oxyalkylene)monoamines in which the poly(oxyalkylene) moiety contains propylene oxide units or butylene oxide units, or a mixture of propylene oxide and butylene oxide units. The alkyl group on the alkylphenyl moiety is a straight or branched chain alkyl group having from about 1 to about 24 carbon atoms. A preferred alkylphenyl moiety is tetrapropenylphenyl, wherein the alkyl group is a branched chain alkyl group having 12 carbon atoms derived from a propylene tetramer.

[0042] More specifically, additional hydrocarbyl substituted poly(oxyalkylene) amines include the hydrocarbyl substituted poly(oxyalkylene) aminocarbamates disclosed in U.S. Pat. Nos. 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 hereby incorporated by reference. These hydrocarbyl 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. Preferred aminocarbamates are alkylphenyl poly(oxybutylene) aminocarbamates wherein the amine portion is derived from ethylenediamine or diethylenetriamine.

[0043] In particular, the hydrocarbyl-substituted succinimides useful in the present invention include polyalkyl succinimides and polyalkenyl succinimides, wherein the polyalkyl or polyalkenyl group has an average molecular weight of about 500 to 5,000, preferably about 700 to 3,000. The hydrocarbyl-substituted succinimides are typically prepared by reacting a hydrocarbyl-substituted succinic anhydride with an amine or polyamine having at least one reactive hydrogen bonded to an amine nitrogen atom. Preferred hydrocarbyl-substituted succinimides include polyisobutenyl succinimides and polyisobutylene succinimides, and derivatives thereof. Hydrocarbyl substituted succinimides are described in U.S. Pat. Nos. 5,393,309, 5,588,973, 5,620,486, 5,916,825, 5,954,843, 5,993,497, and 6,114,542, and British Patent No. 1,486,144, all of which are hereby incorporated by reference.

[0044] In particular, the Mannich reaction products used in the present invention include products obtained by the Mannich condensation of hydroxyaromatic compounds, amines containing at least one reactive hydrogen, and aldehydes, which are usually substituted with high molecular weight alkyls. The hydroxyaromatic compounds substituted with high molecular weight alkyls are preferably polyalkylphenols, such as polypropylphenol and polybutylphenol, especially polyisobutylphenol, wherein the polyalkyl groups have an average molecular weight of about 600 to 3,000. The amine reactants are usually polyamines, such as alkylene polyamines, especially ethylene or polyethylene polyamines, for example ethylenediamine, diethylenetriamine, triethylenetetramine, etc. The aldehyde reactants are usually fatty aldehydes, such as formaldehyde, including paraformaldehyde and formalin, and acetaldehyde. The preferred Mannich reaction products are obtained by condensing polyisobutylphenol with formaldehyde and diethylenetriamine, wherein the polyisobutyl groups have an average molecular weight of about 1,000. Mannich reaction products suitable for use in the present invention are described, for example, in US Pat. Nos. 4,231,759 and 5,697,988, the disclosures of each of which are incorporated herein by reference.

[0045] A further class of detergent additives suitable for use in the present invention are polyalkylphenoxyaminoalkanes. Preferred polyalkylphenoxyaminoalkanes include those having the formula:

[0046]

[0047] Where R 5 is a polyalkyl group having an average molecular weight in the range of about 600 to 5,000; R 6 and R 7is independently hydrogen or a lower alkyl group having 1 to 6 carbon atoms; and A is amino, N-alkylamino having from about 1 to about 20 carbon atoms in the alkyl group, N,N-dialkylamino having from about 1 to about 20 carbon atoms in each alkyl group, or a polyamine moiety having from about 2 to about 12 amine nitrogen atoms and from about 2 to about 40 carbon atoms. The polyalkylphenoxyaminoalkane of Formula II above and its preparation are described in detail in U.S. Pat. No. 5,669,939, which is hereby incorporated by reference herein.

[0048] Certain descaling agent mixtures are particularly useful as auxiliary additives according to the invention.

[0049] In some embodiments, mixtures of polyalkylphenoxyaminoalkane and poly(oxyalkylene)amines may be used. These mixtures are described in detail in U.S. Pat. No. 5,851,242, which is hereby incorporated by reference.

[0050] In some embodiments, mixtures of nitro and amino aromatic esters of polyalkylphenoxyalkanols may be used. Preferred nitro and amino aromatic esters of polyalkylphenoxyalkanols include those having the formula:

[0051]

[0052] Where: R 8 is nitro or -(CH 2 )-NR 13 R 14 , where R 13 and R 14 are independently hydrogen or lower alkyl having 1 to 6 carbon atoms; R 9 is hydrogen, hydroxyl, nitro or -NR 15 R 16 , where R 15 and R 16 are independently hydrogen or lower alkyl having 1 to 6 carbon atoms; R 10 and R 11 are independently hydrogen or lower alkyl having 1 to 6 carbon atoms; and R 12 is a polyalkyl group having an average molecular weight in the range of about 450 to 5000. Aromatic esters of polyalkylphenoxyalkanols represented by Formula III above and their preparation are described in detail in US Pat. No. 5,618,320, which is hereby incorporated by reference.

[0053] Mixtures of nitro and amino aromatic esters of polyalkylphenoxyalkanols and hydrocarbyl-substituted poly(oxyalkylene)amines are also useful in the present invention. These mixtures are described in detail in U.S. Pat. No. 5,749,929, which is hereby incorporated by reference. Preferred hydrocarbyl-substituted poly(oxyalkylene)amines useful as detergent additives in the present invention include those having the formula:

[0054]

[0055] Where: R 17 is a hydrocarbon group having from about 1 to about 30 carbon atoms; R 18 and R 19 are each independently hydrogen or a lower alkyl group having from about 1 to about 6 carbon atoms and each R 18 and R 19 Independently selected from each -O-CHR 18 -CHR 19 -unit; m is from about 5 to about 100; B is amino, N-alkylamino having from about 1 to about 20 carbon atoms in the alkyl group, N,N-dialkylamino having from about 1 to about 20 carbon atoms in each alkyl group, or a polyamine moiety having from about 2 to about 12 amine nitrogen atoms and from about 2 to about 40 carbon atoms; and m is an integer from about 5 to about 100. The hydrocarbyl-substituted poly(oxyalkylene)amines of formula IV above and their preparation are described in detail in U.S. Pat. No. 6,217,624, which is hereby incorporated herein by reference. The hydrocarbyl-substituted poly(oxyalkylene)amines of formula IV are preferably used alone or in combination with other detergent additives, particularly in combination with polyalkylphenoxyaminoalkanes, or nitro and amino aromatic esters of polyalkylphenoxyalkanols. More preferably, the detergent additives used in the present invention will be a combination of hydrocarbyl-substituted poly(oxyalkylene)amines and nitro and amino aromatic esters of polyalkylphenoxyalkanols. A particularly preferred hydrocarbyl-substituted poly(oxyalkylene) amine detergent additive is dodecylphenoxypoly(oxybutylene) amine, and a particularly preferred detergent additive combination is a combination of dodecylphenoxypoly(oxybutylene) amine and 4-polyisobutylphenoxyethyl p-aminobenzoate.

[0056] Another class of detergent additives suitable for use in the present invention includes nitrogen-containing carburetor / injector detergents. The carburetor / injector detergent additives are typically low molecular weight compounds having a number average molecular weight of about 100 to about 600 and having at least one polar portion and at least one non-polar portion. The non-polar portion is typically a linear or branched alkyl or alkenyl group having about 6 to about 40 carbon atoms. The polar portion is typically nitrogen-containing. Typical nitrogen-containing polar portions include amines (e.g., as described in U.S. Pat. No. 5,139,534 and PCT International Publication No. WO 90 / 10051), etheramines (e.g., as described in U.S. Pat. No. 3,849,083 and PCT International Publication No. WO 90 / 10051), amides, polyamides and esteramides (e.g., as described in U.S. Pat. Nos. 2,622,018, 4,729,769 and 5,139,534; and European Patent Publication No. 149,486), imidazolines (e.g., as described in U.S. Pat. No. 4,518,782), amine oxides (e.g., as described in U.S. Pat. Nos. 4,810,263 and 4,836,829), hydroxylamines (e.g., as described in U.S. Pat. No. 4,409,000), and succinimides (e.g., as described in U.S. Pat. No. 4,292,046). Each of these references is hereby incorporated by reference.

[0057] Each auxiliary fuel additive can be present in the fuel composition at about 50 ppm to about 2500 ppm by weight, such as 100 ppm to 2000 ppm by weight, 200 ppm to 1500 ppm by weight, 300 ppm to 1000 ppm by weight, etc. More preferably, the auxiliary fuel additive is present in the fuel composition at about 50 ppm to about 1000 ppm by weight.

[0058] Other additives

[0059] The fuel composition may contain other well-known fuel additives. Suitable examples include, but are not limited to, antioxidants, metal deactivators, demulsifiers, oxygenates, antiknock agents, dispersants and other detergents. In diesel fuels, other well-known additives may be used, such as pour point depressants, flow improvers, etc.

[0060] When used, each of the aforementioned additives is used with a functionally effective amount to impart the desired properties of the fuel composition. Usually, unless otherwise noted, when used, the concentration of each of these additives can be in the range of about 0.001 % by weight to about 20 % by weight, such as in the range of about 0.01 % by weight to about 10 % by weight.

[0061] Concentrates

[0062] The compounds of the present disclosure can be formulated into concentrates using inert stable oleophilic (i.e., soluble in hydrocarbon fuels) organic solvents having a boiling point in the range of 65° C. to 205° C. Aliphatic or aromatic hydrocarbon solvents such as benzene, toluene, xylene, or higher boiling aromatic compounds or aromatic diluents can be used. Combinations of aliphatic alcohols containing 2-8 carbon atoms (such as ethanol, isopropanol, methyl isobutanol, n-butanol, etc.) and hydrocarbon solvents are also suitable for use with the additives of the present invention. In the concentrate, the amount of the additive can be in the range of from 10% to 70% by weight (e.g., 20% to 40% by weight).

[0063] The following examples are intended to be non-limiting.

[0064] Example

[0065] Table 1 below summarizes the additives used to test injector fouling and / or deposit control performance. The additives used in the following tests included isotridecyloxypropylamine (Example 1) and polyoxybutyleneamine (Example 2). The baseline fuel was a gasoline composition without additives.

[0066] Table 1

[0067] name Example 1 Isotridecyloxypropylamine Example 2 Polyoxybutylene amine

[0068] Example 1 was blended in gasoline and tested for its ability to mitigate DISI injector fouling in a test vehicle using the test methods described herein. A 2017 VW Jetta SE equipped with a 1.4L turbocharged DISI 4-cylinder gasoline was the test vehicle used in this example.

[0069] Figure 1 The engine speed and load test conditions observed during the vehicle drive cycle are illustrated. The vehicle drive cycle is based on 10 hills extracted from the transient phase of the Environmental Protection Agency (EPA) Urban Dynamometer Drive Schedule (UDDS), with additional idle periods added. The total drive cycle is 20 minutes and the total test duration is 2,000 miles.

[0070] Additive testing is conducted in a "stay clean" configuration, which starts with clean injectors and combustion chambers. This test configuration evaluates the ability of a given deposit control additive to keep the injectors and combustion chambers clean for the duration of the test.

[0071] Test fuel samples were formulated with the target deposit control additive. Three injector "keep clean" tests were conducted: (i) two tests using a baseline fuel with no additives and (ii) one test using the same baseline fuel as in (i) blended with 200 ppmw of Example 1. Table 2 below summarizes the injector fuel limits (averages) after the indicated driving cycles.

[0072] As shown, the injector fuel restriction during the use of the added fuel was significantly reduced compared to the use of the fuel without addition. The injector fuel restriction measurement represents the reduction in fuel flow from the injector with the presence of deposits in the injector hole. Injector restriction forces the engine controller to make additional control adjustments to maintain proper engine fuel delivery, and the presence of deposits in the injector hole affects the fuel mixture, resulting in reduced engine performance and increased particulate matter emissions. The injector face images for each recipe after the test were completed are shown in Figure 2 and corresponds to Table 2.

[0073] Table 2

[0074]

[0075] The test engine was also used to evaluate the PM emissions of Example 1. A 2016 BMW B48ODISI 2.0L 16-valve turbocharged engine was used for this test.

[0076] The engine drive cycle duration was 360 seconds, the engine speed ranged from idle to 3000-RPM, and the load variation was up to 100-Nm. The total test duration was 96 hours. Figure 3 Engine speed and load test conditions are illustrated.

[0077] PM measurements are performed on an engine test bench using an AVL Micro Soot Sensor (MSS). The MSS provides a continuous, fast-response measurement of the amount of solid particulate matter and correlates very well with traditional gravimetric methods of PM measurement.

[0078] exist Figure 4In the PM emissions trace shown (a small 2000 second segment of the larger test), it is possible to observe how quickly PM emissions rise and fall as engine conditions change. To provide a useful metric for this data, one can look at the official measurement methods used to regulate vehicle emissions certification (such as the US Federal Test Procedure, or FTP). In these cases, regulators will simply report the total amount of vehicle tailpipe emissions over the entire driving cycle. Applying a similar strategy to the PM dataset, we integrate the PM emissions over the course of one test driving cycle. This integration is then repeated for each driving cycle, resulting in a PM emissions trend line over the entire test duration.

[0079] FIG. 5A to FIG. 5C The fuel composition of Example 2 containing 150 ppmw ( Figure 5A ), a fuel composition containing 150 ppmw of Example 2 and 150 ppmw of Example 1 ( Figure 5B ), and a fuel composition containing 150 ppmw of Example 2 and 750 ppmw of Example 1 ( Figure 5C ) results of PM emission trend line (96-hour test).

[0080] FIG. 6A to FIG. 6C The fuel composition of Example 3 containing 2000 ppmw ( Fig. 6A ), a fuel composition containing 2000 ppmw of Example 2 and 150 ppmw of Example 1 ( Figure 6B ), and a fuel composition containing 2000 ppmw of Example 2 and 750 ppmw of Example 1 ( Figure 6C ) results of PM emission trend line (96-hour test).

[0081] 7A to 7C and FIG. 8A to FIG. 8C The results of direct injection spark ignition (DISI) rig injector flow tests are illustrated. The graphs show the restriction percentage relative to the clean injector flow at different pulse widths (1.5 ms, 2.5 ms, 3.5 ms and 4.5 ms) at 100 bar injection pressure. The samples tested included the fuel composition of Example 2 ( Fig. 7A ), a fuel composition containing 150 ppmw of Example 2 and 150 ppmw of Example 1 ( Figure 7B ), and a fuel composition containing 150 ppmw of Example 2 and 750 ppmw of Example 1 ( Figure 7C The sample also included the fuel composition of Example 2 containing 2000 ppmw ( Fig. 8A), a fuel composition containing 2000 ppmw of Example 2 and 150 ppmw of Example 1 ( Figure 8B ), and a fuel composition containing 2000 ppmw of Example 2 and 750 ppmw of Example 1 ( Figure 8C ).

[0082] 9A to 9C A sample corresponding to the fuel composition of Example 2 containing 150 ppmw of Fig.9A ), a sample containing 150 ppmw of the fuel composition of Example 2 and 150 ppmw of Example 1 ( Fig. 9B ), and a sample containing 150 ppmw of the fuel composition of Example 2 and 750 ppmw of Example 1 ( Fig. 9C )’s injector face image.

[0083] FIG. 10A to FIG. 10C A sample corresponding to the fuel composition of Example 2 containing 2000 ppmw of Fig. 10A ), a sample containing 2000 ppmw of the fuel composition of Example 2 and 150 ppmw of Example 1 ( Fig. 10B ), and a sample containing 2000 ppmw of the fuel composition of Example 2 and 750 ppmw of Example 1 ( Fig. 10C )’s injector face image.

[0084] Fig.11A The average injector tip deposit volume (mm2) is shown for a fuel composition containing 150 ppmw of Example 2 (left bar), a fuel composition containing 150 ppmw of Example 2 and 150 ppmw of Example 1 (middle bar), and a fuel composition containing 150 ppmw of Example 2 and 750 ppm of Example 1 (right bar). 3 ). Fig. 11B The average injector tip deposit volume (mm2) is shown for a fuel composition containing 2000 ppmw of Example 2 (left bar), a fuel composition containing 2000 ppmw of Example 2 and 150 ppmw of Example 1 (middle bar), and a fuel composition containing 2000 ppmw of Example 2 and 750 ppmw of Example 1 (right bar). 3 ). These measurements are taken at the end of the vehicle or engine test (before the flow test).

[0085] Table 3 below summarizes the samples tested and rated for corrosion resistance using the NACE TM0172 standard test method. The baseline fuel is the fuel with no additives. Fig.12 Provides visual confirmation of corrosion resistance testing.

[0086] Table 3

[0087]

[0088]

[0089] All documents described herein are incorporated herein by reference, including any priority documents and / or test procedures, as long as they are not inconsistent with this text. It is obvious from the above general description and specific embodiments that although the form of the present disclosure has been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Therefore, it is not intended to limit the present disclosure thereby.

[0090] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, the range from any lower limit can be combined with any upper limit to list a range that is not explicitly listed, and the range from any lower limit can be combined with any other lower limit to list a range that is not explicitly listed, and similarly, the range from any upper limit can be combined with any other upper limit to list a range that is not explicitly listed. In addition, each point or individual value between its endpoints is included in a range, even if it is not explicitly listed. Therefore, each point or single value can be combined as its own lower limit or upper limit with any other point or single value or any other lower limit or upper limit to list a range that is not explicitly listed.

[0091] Likewise, the term “comprising” is considered synonymous with the term “including.” Likewise, whenever a composition, element, or group of elements is followed by the transitional phrase “comprising,” it should be understood that we also contemplate the same composition or group of elements preceded by the transitional phrases “consisting essentially of,” “consisting of,” “selected from the group consisting of,” or “being,” and vice versa.

[0092] As used herein, the terms "a", "an" and "the" shall be construed to include the plural as well as the singular.

[0093] Various terms have been defined above. If a term used in a claim is not defined above, it should be given the broadest definition persons in the relevant art have given that term as reflected in at least one printed publication or issued patent. In addition, all patents, test procedures, and other documents cited in this application are fully incorporated by reference to the extent such disclosure is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted.

[0094] The foregoing description of the present disclosure illustrates and describes the present disclosure. In addition, the present disclosure shows and describes only preferred embodiments, but, as mentioned above, it should be understood that the present disclosure can be used in various other combinations, modifications and environments, and can be changed or modified commensurate with the above teachings and / or the skills or knowledge of the relevant fields within the scope of the concepts expressed herein. Although the foregoing is directed to embodiments of the present disclosure, other and further embodiments of the present disclosure can be designed without departing from the basic scope of the present disclosure, and the scope of the present disclosure is determined by the appended claims.

[0095] It should be understood that when combinations, subsets, groups, etc. of elements are disclosed (e.g., combinations of components in a composition, or combinations of steps in a method), while specific reference to each of the various individual and collective combinations and arrangements of these elements may not be explicitly disclosed, each is specifically contemplated and described herein.

[0096] The embodiments described above are further intended to explain the known best mode of practicing it, and to enable others skilled in the art to utilize the present disclosure in this or other embodiments and with various modifications required for a particular application or use. Therefore, the description is not intended to be limited to the form disclosed herein. In addition, it is intended that the appended claims be interpreted as including alternative embodiments.

Claims

1. A fuel composition comprising: hydrocarbon-based fuels with boiling points in the gasoline or diesel range; Amine based descaling agents are given by the formula: R 1 -O-(CH 2 ) m -NHR 2 wherein the amine-based detergent is present in an amount of 10 ppm to 750 ppm by weight based on the total weight of the fuel composition; wherein R 1 is a hydrocarbon group having 8 to 20 carbon atoms, R 2 is hydrogen or (CH 2 ) n NH 2 moiety, and wherein m, n are independently integers having a value of 3 or greater; and One or more nitrogen-containing detergents, wherein the one or more nitrogen-containing detergents are aliphatic hydrocarbyl amines, hydrocarbyl-substituted poly(oxyalkylene)amines, hydrocarbyl-substituted succinimides, Mannich reaction products, nitro and amino aromatic esters of polyalkylphenoxyalkanols, or polyalkylphenoxyaminoalkanes.

2. The fuel composition of claim 1, wherein R 1 Is linear or branched.

3. The fuel composition of claim 1, wherein the one or more nitrogen-containing detergents are monoamines or polyamines.

4. The fuel composition of claim 1, wherein the amine-based detergent is present in an amount of 20 ppm to 700 ppm by weight of the fuel composition.

5. The fuel composition of claim 1, wherein the one or more nitrogen-containing detergents are present in an amount of 50 ppm to 2500 ppm by weight of the fuel composition.

6. The fuel composition of claim 1, further comprising an antioxidant, a metal deactivator, a demulsifier, an oxygen-containing compound, an antiknock agent, a dispersant, or a flow improver.

7. The fuel composition of claim 1 further comprising a pour point depressant.

8. A concentrate composition comprising: 30 to 90 wt% of an organic solvent having a boiling point in the range of 65°C to 205°C; and 10% to 70% by weight of a descaling agent mixture, the descaling agent mixture comprising: (1) Amine-based descaling agents given by the formula: R 1 -O-(CH 2 ) m -NHR 2 Where R 1 is a hydrocarbon group having 8 to 20 carbon atoms, R 2 is hydrogen or (CH 2 ) n NH 2 moiety, and wherein m, n are independently integers having a value of 3 or greater, and (2) one or more nitrogen-containing detergents, wherein the one or more nitrogen-containing detergents are aliphatic hydrocarbyl amines, hydrocarbyl-substituted poly(oxyalkylene)amines, hydrocarbyl-substituted succinimides, Mannich reaction products, nitro and amino aromatic esters of polyalkylphenoxyalkanols or polyalkylphenoxyaminoalkanes.

9. The concentrate composition of claim 8, wherein R 1 Is linear or branched.

10. The concentrate composition of claim 8, wherein the one or more nitrogen-containing detergents are monoamines or polyamines.

11. A method of controlling injector fouling in an engine equipped with a GDI, the method include: A direct injection engine is supplied with a fuel composition comprising: hydrocarbon-based fuels with boiling points in the gasoline or diesel range; Amine based descaling agents are given by the formula: R 1 -O-(CH 2 ) m -NHR 2 wherein the amine-based detergent is present in an amount of 10 ppm to 750 ppm by weight based on the total weight of the fuel composition; wherein R 1 is a hydrocarbon group having 8 to 20 carbon atoms, R 2 is hydrogen or (CH 2 ) n NH 2 moiety, and wherein m, n are independently integers having a value of 3 or greater; and One or more nitrogen-containing detergents, wherein the one or more nitrogen-containing detergents are aliphatic hydrocarbyl amines, hydrocarbyl-substituted poly(oxyalkylene)amines, hydrocarbyl-substituted succinimides, Mannich reaction products, nitro and amino aromatic esters of polyalkylphenoxyalkanols or polyalkylphenoxyaminoalkanes.

12. The method of claim 11, wherein R 1 Is linear or branched.

13. The method of claim 11, wherein the one or more nitrogen-containing descaling agents are monoamines or polyamines.

14. The method of claim 11, wherein the amine-based detergent is present in an amount of 20 ppm to 700 ppm by weight of the fuel composition.

15. The method of claim 11, wherein the one or more nitrogen-containing detergents are present in an amount of 50 ppm to 2500 ppm by weight of the fuel composition.

16. The method of claim 11, wherein the fuel composition further comprises an antioxidant, a metal deactivator, a demulsifier, an oxygen-containing compound, an antiknock agent, a dispersant, or a flow improver.

17. The method of claim 11, wherein the fuel composition further comprises a pour point depressant.

Images