Fuel additive to reduce injector nozzle contamination and decrease particulate matter emissions.

Abstract

The present invention provides a composition and method for reducing injector nozzle contamination and particle emission in direct injection spark-ignition engines. [Solution] A hydrocarbon fuel that boils in the range of gasoline or diesel, and the formula R1-O-(CH2) m - An amine-based detergent provided by NHR2, which is present in an additive concentration of approximately 10 ppm to approximately 750 ppm based on the total weight of the fuel composition [wherein R1 is a hydrocarbyl group having 8 to 20 carbon atoms, and R2 is hydrogen or (CH2)] n The present invention provides a fuel composition comprising an NH2 portion, where m and n are independent integers having a value of 3 or greater, and one or more nitrogen-containing detergents.

Description

[Technical Field]

[0001] This disclosure relates to fuel components that can improve engine performance. More specifically, this disclosure describes compositions and methods for reducing injector nozzle contamination and decreasing particulate emissions in direct injection spark-ignition engines. [Background technology]

[0002] Conventional fuel additives developed for port fuel injection (PFI) gasoline engines are generally not optimized to control deposit formation in direct injection spark ignition (DISI) engines, sometimes called direct injection gasoline (DIG) engines or gasoline injection (GDI) engines. This is primarily due to the fact that DISI engines, unlike PFI engines, deliver fuel directly to the combustion chamber. When fuel is directly injected, 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 contamination).

[0003] When deposits form both around the injector nozzle and inside the combustion chamber, it can have a significant adverse effect on one or more of the following: fuel flow rate, injection time, and / or spray pattern. This can result in increased emissions, increased particulate matter (PM) formation, reduced fuel economy, power / performance loss, increased wear, and / or reduced equipment lifespan. [Overview of the project]

[0004] In one embodiment, a fuel composition comprising a hydrocarbon fuel that boils in the range of gasoline or diesel, and the formula R1-O-(CH2) m - An amine-based detergent provided by NHR2, present in an amount of approximately 10 ppm to approximately 750 ppm based on the total weight of the fuel composition [wherein R1 is a hydrocarbyl group having 8 to 20 carbon atoms, and R2 is hydrogen or (CH2)] nA fuel composition is provided comprising an NH2 portion, where m and n are integers having a value of 3 or more, and one or more nitrogen-containing detergents.

[0005] In another embodiment, the concentrated composition comprises about 30 to 90% by weight of an organic solvent that boils in the range of 65°C to 205°C and about 10 to 70% by weight of a detergent mixture, wherein the detergent mixture is (1) formula R1-O-(CH2) m -Amine-based detergents provided by NHR2 [wherein R1 is a hydrocarbyl group having 8 to 20 carbon atoms, and R2 is hydrogen or (CH2) n A concentrated composition is provided comprising (1) an NH2 portion, where m and n are integers having a value of 3 or more independently, and (2) one or more nitrogen-containing detergents.

[0006] In yet another embodiment, a method for controlling injector contamination comprises supplying a fuel composition to a direct injection engine, wherein the fuel composition comprises a boiling hydrocarbon fuel in the range of gasoline or diesel and a fuel of the formula R1-O-(CH2) m - An amine-based detergent provided by NHR2, present in an amount of approximately 10 ppm to approximately 750 ppm based on the total weight of the fuel composition [wherein R1 is a hydrocarbyl group having 8 to 20 carbon atoms, and R2 is hydrogen or (CH2)] n A method is provided comprising an NH2 portion, where m and n are integers having a value of 3 or more independently, and one or more nitrogen-containing detergents. [Brief explanation of the drawing]

[0007] [Figure 1] This is a figure described in the Examples section. [Figure 2] This is a figure described in the Examples section. [Figure 3] This is a figure described in the Examples section. [Figure 4] This is a figure described in the Examples section. [Figure 5A] This is a figure described in the Examples section. [Figure 5B] It is a figure described in the Example section. [Figure 5C] It is a figure described in the Example section. [Figure 6A] It is a figure described in the Example section. [Figure 6B] It is a figure described in the Example section. [Figure 6C] It is a figure described in the Example section. [Figure 7A] It is a figure described in the Example section. [Figure 7B] It is a figure described in the Example section. [Figure 7C] It is a figure described in the Example section. [Figure 8A] It is a figure described in the Example section. [Figure 8B] It is a figure described in the Example section. [Figure 8C] It is a figure described in the Example section. [Figure 9A] It is a figure described in the Example section. [Figure 9B] It is a figure described in the Example section. [Figure 9C] It is a figure described in the Example section. [Figure 10A] It is a figure described in the Example section. [Figure 10B] It is a figure described in the Example section. [Figure 10C] It is a figure described in the Example section. [Figure 11] A and B are figures described in the Example section. [Figure 12] It is a figure described in the Example section.

Mode for Carrying Out the Invention

[0008] The present invention describes a composition and method for deposit control in a direct injection engine. More particularly, the present invention provides a detergent additive composition that can be utilized as a component of a fuel composition, and a method of using the composition.

[0009] The fuel composition of the present invention comprises (i) a hydrocarbon fuel, (ii) a primary fuel additive, and (iii) one or more secondary fuel additives.

[0010] Hydrocarbon fuel Hydrocarbon fuels include gasoline and diesel. <00001​​​​​​​​​​​​​​​​​​​​​​​​

[0013] Hydrocarbon fuels are present in large amounts by weight percentage relative to 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.

[0014] 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 the definitions of local regulations.

[0015] A fuel-soluble, non-volatile carrier fluid or carrier oil may be used with the compounds of this disclosure. The carrier fluid is a chemically inert hydrocarbon-soluble liquid vehicle that substantially increases the non-volatile residue (NVR) or solvent-free liquid fraction of the fuel additive composition but does not significantly increase the octane requirement. The carrier fluid may be natural or synthetic oils, such as mineral oil, refined petroleum, synthetic polyalkanes and alkenes including hydrogenated and unhydrogenated polyalphaolefins, and synthetic polyoxyalkylene-derived oils, such as those described in U.S. Patents No. 3,756,793, 4,191,537, and 5,004,478, and European Patent Publications No. 356,726 and 382,159.

[0016] The carrier fluid can be used in amounts ranging from 35 to 5000 ppm (e.g., 50 to 3000 ppm of the fuel) depending on the weight of the hydrocarbon fuel. When used in fuel concentrates, the carrier fluid can be present in amounts ranging from 20 to 60% by weight (e.g., 30 to 50% by weight).

[0017] Primary fuel additives The primary fuel additive of the present invention is given by the following formula: R1-O-(CH2) m-NHR2 (Equation I) An amine-based detergent having (more specifically, a linear / branched aliphatic etheramine), where R1 is a hydrocarbyl group having 8 to 20 carbon atoms, and R2 is hydrogen or (CH2) n The NH2 portion is where m and n are independent integers with a value of 3 or greater. The hydrocarbyl group may be saturated or unsaturated. In some embodiments, the hydrocarbyl group may contain two or more unsaturated bonds.

[0018] One advantage is that the fuel additive of the present invention can deliver more basic nitrogen at the same processing rate compared to conventional amine-based fuel detergents (e.g., polyisobutylamine, polyetheramine, etc.). This characteristic is important in determining the cleaning power. Another advantage is that the low molecular weight of the additive of the present invention, along with its low decomposition temperature and high volatility, prevents the additive from forming harmful deposits.

[0019] Aliphatic etheramines that are particularly useful for illustrating the present invention include isotridecyloxypropylamine and 2-ethylhexyloxypropylamine. These are examples for illustrative purposes only and are not intended to be limiting.

[0020] In some embodiments, the primary fuel additive may be present in concentrations of about 10 ppm to about 750 ppm based on the overall fuel composition (e.g., 20-700, 30-650, 50-600, 100-500, 200-400, 250-350, etc.).

[0021] Secondary fuel additives The fuel composition of the present invention comprises one or more secondary fuel additives. The secondary fuel additive is a nitrogen-containing detergent that, when combined with the primary fuel additive of the present invention, provides increased cleaning power.

[0022] Suitable secondary fuel additives can be classified into aliphatic hydrocarbyl-substituted amines, hydrocarbyl-substituted poly(oxyalkylene)amines, hydrocarbyl-substituted succinimides, Mannich reaction products, polyalkylphenoxyaminoalkanes, nitro and amino aromatic esters of polyalkylphenoxyalkanols, and nitrogen-containing carburetor / injector cleaners. Each type of secondary fuel additive is described in more detail herein.

[0023] In particular, the aliphatic hydrocarbyl-substituted amines used in the present invention may be linear or branched hydrocarbyl-substituted amines having at least one basic nitrogen and the hydrocarbyl group having 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 obtained as monoamines or polyamines. The preparation of aliphatic amines is generally known and is described in detail 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.

[0024] In particular, the hydrocarbyl-substituted poly(oxyalkylene)amines (also called "polyetheramines") used in the present invention may include hydrocarbyl poly(oxyalkylene)amines (monoamines or polyamines) in which the hydrocarbyl group contains 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, primary alkyl or secondary dialkyl monoamines, or polyamines having terminal amino nitrogen atoms. 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 in which the poly(oxyalkylene) portion contains oxypropylene units, oxybutylene units, or a mixture of oxypropylene and oxybutylene units. The alkyl group of the alkylphenyl portion is a linear or branched alkyl group having about 1 to about 24 carbon atoms. A preferred alkylphenyl portion is tetrapropenylphenyl, where the alkyl group is a branched alkyl group having 12 carbon atoms derived from a propylene tetramer.

[0025] More specifically, further 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. Preferred aminocarbamates are alkylphenyl poly(oxybutylene)aminocarbamates in which the amine portion is derived from ethylenediamine or diethylenetriamine.

[0026] In particular, the hydrocarbyl-substituted succinimides used in the present invention include polyalkyl succinimides and polyalkenyl succinimides, in which the polyalkyl group or polyalkenyl group has an average molecular weight of about 500 to 5,000, preferably about 700 to 3,000. Hydrocarbyl-substituted succinimides are typically prepared by reacting an amine or polyamine having at least one reactive hydrogen bonded to an amine nitrogen atom with hydrocarbyl-substituted succinic anhydride. Preferred hydrocarbyl-substituted succinimides include polyisobutenyl succinimides and polyisobutanyl succinimides, as well as their derivatives. Hydrocarbyl-substituted succinimides are described in U.S. Patents No. 5,393,309, 5,588,973, 5,620,486, 5,916,825, 5,954,843, 5,993,497, and 6,114,542, as well as British Patent No. 1,486,144, all of which are incorporated herein by reference.

[0027] In particular, the Mannich reaction products used in the present invention include products typically obtained from the Mannich condensation of a high molecular weight alkyl-substituted hydroxyaromatic compound, an amine containing at least one reactive hydrogen, and an aldehyde. The high molecular weight alkyl-substituted hydroxyaromatic compound is preferably a polyalkylphenol such as polypropylphenol and polybutylphenol, particularly polyisobutylphenol, where the polyalkyl group has an average molecular weight of about 600 to 3,000. The amine reactant is typically an alkylene polyamine, particularly an ethylene polyamine or polyethylene polyamine, such as ethylenediamine, diethylenetriamine, or triethylenetetramine. The aldehyde reactant is generally an aliphatic aldehyde, such as paraformaldehyde and formaldehyde containing formalin, as well as acetaldehyde. A preferred Mannich reaction product is obtained by condensing polyisobutylphenol with formaldehyde and diethylenetriamine, where the polyisobutyl group has an average molecular weight of about 1,000. Suitable Mannich reaction products for use in the present invention are described, for example, in U.S. Patent Nos. 4,231,759 and 5,697,988, the disclosures of which are incorporated herein by reference.

[0028] Further types of cleaning additives suitable for use in the present invention are polyalkylphenoxyaminoalkanes. Preferred polyalkylphenoxyaminoalkanes are given by the following formula: [ka] This includes having the following, where R5 is a polyalkyl group having an average molecular weight in the range of about 600 to 5,000, R6 and R7 are independently hydrogen or a lower alkyl group having 1 to 6 carbon atoms, and A is an amino, an N-alkylamino having about 1 to about 20 carbon atoms in the alkyl group, an N,N-dialkylamino having about 1 to about 20 carbon atoms in each alkyl group, or a polyamine moiety having about 2 to about 12 amine nitrogen atoms and about 2 to about 40 carbon atoms. The polyalkylphenoxyaminoalkanes of Formula II described above and their preparations are described in detail in U.S. Patent No. 5,669,939, which is incorporated herein by reference.

[0029] Certain detergent mixtures may be particularly useful as secondary additives according to the present invention.

[0030] In some embodiments, mixtures of polyalkylphenoxyaminoalkanes and poly(oxyalkylene)amines may be used. These mixtures are described in detail in U.S. Patent No. 5,851,242, which is incorporated herein by reference.

[0031] In some embodiments, a mixture of nitro and amino aromatic esters of polyalkylphenoxyalkanols may be used. Preferred nitro and amino aromatic esters of polyalkylphenoxyalkanols are given by the following formula: [ka] This includes those having -(CH2)-NR, where R8 is nitro or -(CH2)-NR 13 R 14 (Here, R 13 and R 14 R9 is independently hydrogen, or a lower alkyl having 1 to 6 carbon atoms, and R9 is hydrogen, hydroxy, nitro, or -NR 15 R 16 (Here, R 15 and R 16R is independently a lower alkyl group having hydrogen or 1 to 6 carbon atoms. 10 and R 11 R is independently a lower alkyl having hydrogen or 1 to 6 carbon atoms. 12 This is a polyalkyl group having an average molecular weight in the range of approximately 450 to 5,000. Aromatic esters of polyalkylphenoxyalkanols represented by Formula III above and preparations thereof are described in detail in U.S. Patent No. 5,618,320, which is incorporated herein by reference.

[0032] Mixtures of nitro and amino aromatic esters of polyalkylphenoxyalkanols and hydrocarbyl-substituted poly(oxyalkylene)amines can also be used in the present invention. These mixtures are described in detail in U.S. Patent No. 5,749,929, which is incorporated herein by reference. Preferred hydrocarbyl-substituted poly(oxyalkylene)amines that can be used as cleaning additives in the present invention are given by the following formula: [ka] Includes those having, in the formula, R 17 R is a hydrocarbyl group having approximately 1 to approximately 30 carbon atoms. 18 and R 19 Each is independently a lower alkyl having hydrogen or about 1 to about 6 carbon atoms, and R 18 and R 19 Each of these is -O-CHR 18 -CHR 19-The units are independently selected, where m is about 5 to about 100, and B is an amino, an N-alkylamino having about 1 to about 20 carbon atoms in the alkyl group, an N,N-dialkylamino having about 1 to about 20 carbon atoms in each alkyl group, or a polyamine moiety having about 2 to about 12 amine nitrogen atoms and about 2 to about 40 carbon atoms, where m is an integer from about 5 to about 100. The hydrocarbyl-substituted poly(oxyalkylene)amines of formula IV described above and their preparations are described in detail in U.S. Patent No. 6,217,624, which is incorporated herein by reference. The hydrocarbyl-substituted poly(oxyalkylene)amines of formula IV are preferably used alone or in combination with other cleaning additives, in particular in combination with nitro and amino aromatic esters of polyalkylphenoxyaminoalkanes or polyalkylphenoxyalkanols. More preferably, the cleaning additive used in the present invention is a combination of a hydrocarbyl-substituted poly(oxyalkylene)amine and a nitro and amino aromatic ester of a polyalkylphenoxyalkanol. A particularly preferred hydrocarbyl-substituted poly(oxyalkylene)amine cleaning additive is dodecylphenoxypoly(oxybutylene)amine, and a particularly preferred combination of cleaning additives is dodecylphenoxypoly(oxybutylene)amine and 4-polyisobutylphenoxyethyl para-aminobenzoate.

[0033] Another type of cleaning additive suitable for use in the present invention includes nitrogen-containing carburetor / injector cleaning agents. Carburetor / injector cleaning 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 moiety and at least one nonpolar moiety. The nonpolar moiety is typically a linear or branched alkyl or alkenyl group having about 6 to about 40 carbon atoms. The polar moiety typically contains nitrogen. Typical nitrogen-containing polar moieties include amines (e.g., as described in U.S. Patent No. 5,139,534 and PCT International Publication No. WO90 / 10051), etheramines (e.g., as described in U.S. Patent No. 3,849,083 and PCT International Publication No. WO90 / 10051), amides, polyamides and amide esters (e.g., U.S. Patents No. 2,622,018, No. 4,729,769 and No. 5,139,534, and European Patent Publication No. These include (as described in U.S. Patent Publication No. 149,486), imidazolines (e.g., as described in U.S. Patent No. 4,518,782), amine oxides (e.g., as described in U.S. Patents No. 4,810,263 and 4,836,829), hydroxyamines (e.g., as described in U.S. Patent No. 4,409,000), and succinimide (e.g., as described in U.S. Patent No. 4,292,046). Each of these references is incorporated herein by reference.

[0034] Each secondary fuel additive may be present in an amount of about 50 ppm to about 2500 ppm (e.g., 100-2000, 200-1500, 300-1000, etc.) depending on the weight of the fuel composition. More preferably, the secondary fuel additive is present in an amount of about 50 ppm to about 1000 ppm depending on the weight of the fuel composition.

[0035] Other additives The fuel composition may also contain other commonly known fuel additives. Preferred examples include, but are not limited to, antioxidants, metal deactivators, anti-emulsifiers, oxygen-containing agents, anti-knock agents, dispersants, and other detergents. Other well-known additives, such as pour point depressants and fluidity improvers, may be used in diesel fuels.

[0036] Each of the aforementioned additives, when used, is used in a functionally effective amount that imparts 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.

[0037] concentrate The compounds of this disclosure can be prepared as concentrates using an inert, stable, lipophilic (i.e., soluble in hydrocarbon fuels) organic solvent that boils in the range of 65°C to 205°C. Aliphatic or aromatic hydrocarbon solvents, such as benzene, toluene, xylene, or high-boiling aromatic or aromatic thinners may be used. Aliphatic alcohols containing 2 to 8 carbon atoms, such as ethanol, isopropanol, methyl isobutylcarbinol, and n-butanol, in combination with the hydrocarbon solvent are also suitable for use with the additives. 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).

[0038] The following examples are intended to be non-limiting. [Examples]

[0039] Table 1 below summarizes the additives used to test the injector contamination and / or deposit control performance. The additives used in the following tests include isotridecyloxypropylamine (Example 1) and polyoxybutyleneamine (Example 2). The base fuel is a gasoline composition without additives. [Table 1]

[0040] Example 1 was blended with gasoline and tested for its ability to reduce DISI injector contamination in a test vehicle using the test method described herein. The test vehicle used in this example was a 2017 VW Jetta SE equipped with a 1.4L turbocharged DISI 4-cylinder gasoline engine.

[0041] Figure 1 shows the engine speed and load test conditions observed during the vehicle's driving cycle. The vehicle's driving cycle was based on 10 driving sections (hills) extracted from the transition phase of the U.S. Environmental Protection Agency (EPA) Urban Dynamometer Drive Schedule (UDDS), with additional idle periods added. The total driving cycle was 20 minutes, and the overall test period was 2,000 miles.

[0042] The additive testing will be conducted in a "keep clean" configuration, starting with a clean injector and combustion chamber. This test configuration evaluates the ability of a given deposit control additive to keep the injector and combustion chamber clean during the test period.

[0043] Test fuel samples were prepared using the target deposit control additive. Three injector "keep clean" tests were performed: (i) two tests using base fuel without additives, and (ii) one test using the same base fuel as (i), blended with Example 1 at 200 ppmw. The average injector fuel limits after the specified operating cycles are summarized in Table 2 below.

[0044] As shown, injector fuel limiting was substantially reduced when using fuel with additives compared to when using fuel without additives. Injector fuel limiting measures the reduction in fuel flow from the injector, which represents the presence of deposits in the injector orifice. Injector limiting may require the engine controller to make further control adjustments to maintain proper engine fuel delivery, as the presence of deposits in the injector orifice can affect the fuel mixture, leading to reduced engine performance and increased particulate emissions. Images of the injector surface for each formulation after the completion of the test are shown in Figure 2, corresponding to Table 2. [Table 2]

[0045] The PM emissions for Example 1 were also evaluated using the test engine. This test used a 2016 BMW B48O DISI 2.0L 16-valve turbocharged engine.

[0046] The engine operating cycle was 360 seconds, the engine speed ranged from idle to 3000 RPM, and the load was varied up to a maximum of 100 Nm. The total test period was 96 hours. Figure 3 shows the engine speed and load test conditions.

[0047] PM measurements were performed on an engine test stand using an AVL Micro Soot Sensor (MSS). The MSS provides continuous, high-speed response measurements of solid particle mass and correlates well with conventional gravimetric methods for PM measurement.

[0048] The PM emission trace shown in Figure 4 (a small 2000-second segment of a larger test) allows us to observe how rapidly PM emissions rise and fall as engine conditions change. To establish useful metrics for this data, we can refer to official measurement methods used by regulatory bodies in certifying vehicle emissions (e.g., the US Federal Test Procedure, i.e., FTP). In these cases, regulatory bodies simply report the total amount of emissions from the vehicle exhaust over the entire driving cycle. By applying a similar method to the PM dataset, we can aggregate the PM emissions over the course of one test driving cycle. By repeating this aggregation for each driving cycle, we can obtain a trend line of PM emissions over the entire test period.

[0049] Figures 5A to 5C show the PM emission trend lines (96-hour test) for fuel compositions including Example 2 at 150 ppmw (Figure 5A), Example 2 at 150 ppmw and Example 1 at 150 ppmw (Figure 5B), and Example 2 at 150 ppmw and Example 1 at 750 ppmw (Figure 5C).

[0050] Figures 6A to 6C show the PM emission trend lines (96-hour test) for fuel compositions including Example 3 (2000 ppmw) (Figure 6A), Example 2 (2000 ppmw) and Example 1 (150 ppmw) (Figure 6B), and Example 2 (2000 ppmw) and Example 1 (750 ppmw) (Figure 6C).

[0051] Figures 7A–7C and 8A–8C show the results of direct injection spark ignition (DISI) rig injector flow rate tests. These graphs show the limiting factor to the flow rate of the clean injector at various pulse widths (1.5 ms, 2.5 ms, 3.5 ms, and 4.5 ms) at an injection pressure of 100 bar. The tested samples include fuel compositions including Example 2 at 150 ppmw (Figure 7A), Example 2 at 150 ppmw and Example 1 at 150 ppmw (Figure 7B), and Example 2 at 150 ppmw and Example 1 at 750 ppmw (Figure 7C). The samples also include fuel compositions including Example 2 at 2000 ppmw (Figure 8A), Example 2 at 2000 ppmw and Example 1 at 150 ppmw (Figure 8B), and Example 2 at 2000 ppmw and Example 1 at 750 ppmw (Figure 8C).

[0052] Figures 9A to 9C show images of the injector surface corresponding to samples containing fuel compositions including Example 2 at 150 ppmw (Figure 9A), Example 2 at 150 ppmw and Example 1 at 150 ppmw (Figure 9B), and Example 2 at 150 ppmw and Example 1 at 750 ppmw (Figure 9C), taken after the completion of vehicle or engine tests (before flow tests).

[0053] Figures 10A to 10C show images of the injector surface corresponding to samples containing fuel compositions including Example 2 of 2000 ppmw (Figure 10A), Example 2 of 2000 ppmw and Example 1 of 150 ppmw (Figure 10B), and Example 2 of 2000 ppmw and Example 1 of 750 ppmw (Figure 10C), taken after the completion of vehicle or engine tests (before flow tests).

[0054] Figure 11A shows the average volume (mm³) of deposits at the injector tip for fuel compositions including Example 2 at 150 ppmw (left bar), Example 2 at 150 ppmw and Example 1 at 150 ppmw (center bar), and Example 2 at 150 ppmw and Example 1 at 750 ppm (right bar). 3Figure 11B shows the average volume (mm³) of deposits at the injector tip for fuel compositions including Example 2 of 2000 ppmw (left bar), Example 2 of 2000 ppmw and Example 1 of 150 ppmw (center bar), and Example 2 of 2000 ppmw and Example 1 of 750 ppmw (right bar). 3 These measurements were obtained at the end of the vehicle or engine test (before the flow test).

[0055] Table 3 below summarizes the samples tested and evaluated for corrosion protection properties using the NACE TM0172 standard test method. The base fuel is a fuel without additives. Figure 12 shows the visual confirmation of the corrosion protection test. [Table 3]

[0056] All documents described herein, including any priority documents and / or test procedures, are incorporated herein by reference, to the extent that they do not conflict with this document. While the forms of this disclosure have been described and illustrated as evident from the preceding general description and specific embodiments, 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.

[0057] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, a range from any lower bound may be combined with any upper bound to describe an unexpressed range, and a range from any lower bound may be combined with any other lower bound to describe an unexpressed range, and similarly, a range from any upper bound may be combined with any other upper bound to describe an unexpressed range. Furthermore, a range includes all points or individual values ​​between its endpoints, even if not explicitly described. Thus, all points or individual values ​​can function as their own lower or upper bounds, which can be combined with any other points or individual values ​​or any other lower or upper bounds to describe an unexpressed range.

[0058] Similarly, the term “comprising” is considered synonymous with the term “including.” Likewise, whenever a composition, element, or group of elements is preceded by the transition phrase “comprising,” it is assumed that the same composition or group of elements is preceded by the transition phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is,” and vice versa.

[0059] As used herein, the terms "a" and "the" are understood to include both singular and plural nouns.

[0060] Various terms have been defined above. If a term used in a claim is not defined above, that term should be given the broadest definition that a person skilled in the art in the relevant field has given it, as reflected in at least one printed publication or granted patent. Furthermore, all patents, test procedures, and other documents referenced in this application are fully incorporated by reference in all jurisdictions where their incorporation is permitted, provided that their disclosure does not conflict with this application.

[0061] The preceding statements in this disclosure are illustrative and illustrative. Furthermore, while this disclosure shows and describes only preferred embodiments, as stated above, this disclosure can be used 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, corresponding to the teachings and / or the art or knowledge of the relevant technical field. The preceding statements cover embodiments of this disclosure, but other embodiments and further embodiments of this disclosure can be devised without departing from its basic scope, which is determined by the following claims.

[0062] 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 explicitly disclosed, but each is understood to be specifically assumed and described herein.

[0063] Furthermore, the embodiments described above are intended to illustrate the best known embodiments and to enable those skilled in the art to utilize the disclosure by making various modifications required for specific uses or applications in such embodiments or other embodiments. Therefore, this description is not intended to limit the scope to the forms disclosed herein. The appended claims are also intended to be interpreted as including alternative embodiments.

Claims

1. A fuel composition for use in an engine equipped with direct gasoline injection (GDI), Hydrocarbon fuels that boil in the range of gasoline or diesel, Formula R １ -O-(CH ２ ) ｍ -NHR ２ is an amine-based detergent provided by, and the amine-based detergent is present at 10 ppm to 750 ppm by weight based on the total weight of the fuel composition [wherein, R １ is a hydrocarbyl group having 8 to 20 carbons, R ２ is hydrogen or (CH ２ ) ｎ NH ２ moiety, and m and n are 3], and The following comprises one or more nitrogen-containing cleaning agents selected from the group consisting of: • Polyisobutenylamine, • Hydrocarbyl-substituted poly(oxybutylene)amines, • Polyoxybutyleneamine having a number average molecular weight of 700 to 3,000 - Mannich reaction products derived from polyisobutylphenol having an average molecular weight of 600 to 3,000 polyisobutyl groups, and • Polyalkylphenoxyaminoethane, The one or more nitrogen-containing detergents are present in an amount of 50 to 1,000 ppm based on the total weight of the fuel composition. Fuel composition.

2. R １ The fuel composition according to claim 1, wherein the elements are linear or branched.

3. The fuel composition according to claim 1, wherein the amine-based detergent is present in the fuel composition at an concentration of 20 ppm to 700 ppm.

4. The fuel composition according to claim 1, wherein the one or more nitrogen-containing detergents are present in the fuel composition at an amount of 100 ppm to 500 ppm.

5. The fuel composition according to claim 1, further comprising one or more antioxidants, metal deactivators, anti-emulsifiers, oxygen-containing agents, anti-knock agents, dispersants, pour point depressants, or fluidity improvers.

6. A concentrated composition for use in an engine equipped with direct gasoline injection (GDI), A 30-90% by weight organic solvent that boils in the range of 65°C to 205°C, It contains a mixture of detergents in an amount of 10 to 70% by weight, The aforementioned cleaning agent mixture is (1) Formula R １ -O-(CH ２ ) ｍ - NHR ２ Amine-based detergents provided by [in the formula, R １ R is a hydrocarbyl group having 8 to 20 carbon atoms. ２ is hydrogen or (CH ２ ) ｎ NH ２ [It is a part, and m and n are 3] (2) comprising one or more nitrogen-containing detergents selected from the group consisting of the following: • Polyisobutenylamine, • Hydrocarbyl-substituted poly(oxybutylene)amines, • Polyoxybutyleneamine having a number average molecular weight of 700 to 3,000 - Mannich reaction products derived from polyisobutylphenol having an average molecular weight of 600 to 3,000 polyisobutyl groups, and • Polyalkylphenoxyaminoethane, Concentrated composition.

7. R １ The concentrated composition according to claim 6, wherein the chain is linear or branched.

8. A method for controlling injector contamination in an engine equipped with direct gasoline injection (GDI), The process includes supplying a fuel composition to a direct injection engine, wherein the fuel composition is Hydrocarbon fuels that boil in the range of gasoline or diesel, Formula R １ -O-(CH ２ ) ｍ - NHR ２ An amine-based detergent provided by, wherein the amine-based detergent is present in an amount of 10 ppm to 750 ppm based on the total weight of the fuel composition [wherein R １ R is a hydrocarbyl group having 8 to 20 carbon atoms. ２ is hydrogen or (CH ２ ) ｎ NH ２ [It is a part, and m and n are 3] The following comprises one or more nitrogen-containing cleaning agents selected from the group consisting of: • Polyisobutenylamine, • Hydrocarbyl-substituted poly(oxybutylene)amines, • Polyoxybutyleneamine having a number average molecular weight of 700 to 3,000 - Mannich reaction products derived from polyisobutylphenol having an average molecular weight of 600 to 3,000 polyisobutyl groups, and • Polyalkylphenoxyaminoethane, The one or more nitrogen-containing detergents are present in an amount of 50 to 1,000 ppm based on the total weight of the fuel composition. method.

9. R １ The method according to claim 8, wherein is linear or branched.

10. The method according to claim 8, wherein the amine-based detergent is present in the fuel composition at a concentration of 20 ppm to 700 ppm.

11. The method according to claim 8, wherein the one or more nitrogen-containing detergents are present in the fuel composition at a concentration of 100 ppm to 500 ppm.

12. The method according to claim 8, wherein the fuel composition further comprises one or more antioxidants, metal deactivators, anti-emulsifiers, oxygen-containing agents, anti-knock agents, dispersants, pour point depressants, or fluidity improvers.

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