JP2023533737A - Fuel additive to reduce injector nozzle fouling and reduce particulate emissions - Google Patents

Abstract

The present disclosure is a fuel composition comprising a hydrocarbon-based fuel boiling in the gasoline or diesel range and an amine-based detergent given by the formula R1-O-(CH2)m-NHR2, wherein the fuel composition comprises: additives present from about 10 ppm to about 750 ppm by weight based on the total weight of [wherein R1 is a hydrocarbyl group having 8 to 20 carbons, R2 is hydrogen or (CH2)nNH2 moieties, m, n are independently integers having a value of 3 or greater] and one or more nitrogen-containing detergents. [Selection figure] None

Description

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

Conventional fuel additives developed for port fuel injection (PFI) gasoline engines are commonly used for direct injection spark ignition (DISI), sometimes referred to as direct injection gasoline (DIG) or gasoline injection (GDI) engines. Not optimized to control deposit formation in the engine. This is primarily due to the fact that DISI engines deliver fuel directly to the combustion chamber, unlike PFI engines. Fuel, when directly injected, is immediately exposed to high temperatures and pressures. In this environment, combustion products can accumulate on the external and/or internal surfaces of the injector and nozzle (known as injector fouling).

The formation of deposits both around the injector nozzle and inside the combustion chamber can have a significant adverse effect on one or more of fuel flow rate, injection time, and/or spray pattern. This can result in increased emissions, increased particulate matter (PM) formation, reduced fuel economy, loss of power/performance, increased wear, and/or reduced equipment life.

In one aspect, a fuel composition comprising a hydrocarbonaceous fuel boiling in the gasoline or diesel range and an amine-based detergent given by the formula R ₁ —O—(CH ₂ ) _m —NHR ₂ , comprising: A detergent present from about 10 ppm to about 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 and R ₂ is hydrogen or (CH ₂ ) _n NH ₂ moieties and m, n are independently integers having a value of 3 or greater] and one or more nitrogen-containing detergents are provided.

In another aspect, a concentrated composition comprising about 30-90% by weight of an organic solvent boiling in the range of 65° C. to 205° C. and about 10-70% by weight of a detergent mixture, wherein the detergent mixture is (1) an amine-based detergent given by the formula R ₁ —O—(CH ₂ ) _m —NHR ₂ , where R ₁ is a hydrocarbyl group having 8 to 20 carbons and R ₂ is , hydrogen or (CH ₂ ) _n NH ₂ moieties, where m, n are independently integers having a value of 3 or greater]; and (2) one or more nitrogen-containing detergents. , a concentrated composition is provided.

In yet another aspect, a method of controlling injector fouling comprises supplying a fuel composition to a direct injection engine, the fuel composition comprising a hydrocarbonaceous fuel boiling in the gasoline or diesel range and a formula An amine detergent given by R ₁ —O—(CH ₂ ) _m —NHR ₂ , wherein the amine detergent is present at from about 10 ppm to about 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 moieties, m, n are independently integers having a value of 3 or greater is] and one or more nitrogen-containing detergents.

FIG. 4 is a diagram described in the Examples section; FIG. 4 is a diagram described in the Examples section; FIG. 4 is a diagram described in the Examples section; FIG. 4 is a diagram described in the Examples section; FIG. 4 is a diagram described in the Examples section; FIG. 4 is a diagram described in the Examples section; FIG. 4 is a diagram described in the Examples section; FIG. 4 is a diagram described in the Examples section; FIG. 4 is a diagram described in the Examples section; FIG. 4 is a diagram described in the Examples section; FIG. 4 is a diagram described in the Examples section; FIG. 4 is a diagram described in the Examples section; FIG. 4 is a diagram described in the Examples section; FIG. 4 is a diagram described in the Examples section; FIG. 4 is a diagram described in the Examples section; FIG. 4 is a diagram described in the Examples section; FIG. 4 is a diagram described in the Examples section; FIG. 4 is a diagram described in the Examples section; FIG. 4 is a diagram described in the Examples section; FIG. 4 is a diagram described in the Examples section; FIG. 4 is a diagram described in the Examples section; FIG. 4 is a diagram described in the Examples section; A and B are diagrams described in the Examples section. FIG. 4 is a diagram described in the Examples section;

The present invention describes compositions and methods for deposit control in direct injection engines. More particularly, the present invention provides detergent additive compositions that can be utilized as components of fuel compositions, and methods of using the compositions.

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

Hydrocarbon Fuels Hydrocarbon fuels include gasoline and diesel.

Gasoline fuel refers to compositions containing at least predominantly C ₄ -C ₁₂ hydrocarbons. In one embodiment, the gasoline or gasoline boiling range component further contains at least predominantly _C4 to _C12 hydrocarbons and further contains from about 100°F to about 400°F defined to refer to a composition having a boiling range. In an alternative embodiment, the gasoline is a composition containing at least predominantly _C4 - _C12 hydrocarbons and having a boiling range of about 100°F to about 400°F. and further defined as meeting ASTM D4814.

Diesel fuel refers to a middle distillate fuel containing at least predominantly C ₁₀ -C ₂₅ hydrocarbons. In one embodiment, the diesel further contains at least primarily C ₁₀ -C ₂₅ hydrocarbons and further has a boiling range of from about 165.6° C. (330° F.) to about 371.1° C. (700° F.) defined to refer to a composition. In an alternative embodiment, the diesel contains at least primarily C ₁₀ -C ₂₅ hydrocarbons and has a temperature of about 165.6° C. (330° F.) to about 371.1° C. (700° F.), as defined above. F) and is further defined as meeting ASTM D975.

Hydrocarbon fuels are present in large amounts in weight percent of the total fuel composition. In some embodiments, the hydrocarbonaceous fuel is about 50 wt% or greater, 55 wt% or greater, 60 wt% or greater, 65 wt% or greater, 70 wt% or greater, 75 wt% or greater, 80 wt% or greater, 85 wt% or greater Weight percent or more, 90 weight percent or more, 95 weight percent or more, or any range from about 50 weight percent to less than 100 weight percent.

According to some embodiments, the gasoline used in the present invention may be clean burning gasoline (CBG). CBG refers to gasoline formulations containing reduced levels of sulfur, aromatics, and olefins. Exact formulations may vary according to local regulatory definitions.

A fuel-soluble, non-volatile carrier fluid or oil may be used with the compounds of the present 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 reduces the octane requirement. It does not contribute significantly to the increase. Carrier fluids include natural or synthetic oils such as mineral oils, refined petroleum oils, synthetic polyalkanes and alkenes, including hydrogenated and unhydrogenated polyalphaolefins, synthetic polyoxyalkylene-derived oils, such as U.S. Pat. 793, 4,191,537, and 5,004,478, and EP-A-356,726 and EP-A-382,159.

Carrier fluids may be used in amounts ranging from 35 to 5000 ppm by weight of the hydrocarbon fuel (eg, 50 to 3000 ppm of the fuel). When used in fuel concentrates, carrier fluids may be present in amounts ranging from 20 to 60 weight percent (eg, 30 to 50 weight percent).

Primary Fuel Additive The primary fuel additive of the present invention has the formula:
R ₁ —O—(CH ₂ ) _m —NHR ₂
(Formula I)
wherein R ₁ is a hydrocarbyl group having 8 to 20 carbons and R ₂ is a hydrogen or (CH ₂ ) _n NH ₂ moiety and m, n are independently integers having a value of 3 or greater. Hydrocarbyl groups may be saturated or unsaturated. In some embodiments, hydrocarbyl groups can contain two or more unsaturated bonds.

As an advantage, the fuel additives of the present invention can deliver more basic nitrogen at the same throughput rate compared to conventional amine-based fuel detergents (e.g., polyisobutylamine, polyetheramine, etc.). can. This feature is important in determining cleaning power. As another advantage, the low molecular weight of the additive of the present invention, along with its low decomposition temperature and high volatility, prevent the additive from forming harmful deposits.

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

In some embodiments, the primary fuel additive is from about 10 ppm to about 750 ppm (eg, 20-700, 30-650, 50-600, 100-500, 200-400, 250-350 ppm) based on the total fuel composition. etc.).

Secondary Fuel Additives The fuel compositions of the present invention contain one or more secondary fuel additives. A secondary fuel additive is a nitrogen-containing detergent that provides increased detergency when combined with the primary fuel additive of the present invention.

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

Specifically, the aliphatic hydrocarbyl-substituted amines used in the present invention are 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. can be Specific examples of aliphatic hydrocarbyl-substituted amines include polyisobutenylamine and polyisobutylamine. These amines can be obtained as monoamines or polyamines. The preparation of aliphatic amines is generally known, see U.S. Pat. Nos. 3,438,757; 3,565,804; 3,574,576; Nos. 3,960,515, 4,832,702, and 6,203,584, all of which are incorporated herein by reference. is

Specifically, hydrocarbyl-substituted poly(oxyalkylene)amines (also called "polyetheramines") for use in the present invention include hydrocarbylpoly(oxyalkylene)amines in which the hydrocarbyl groups contain from about 1 to about 30 carbon atoms. (monoamines or polyamines) may be included. The number of oxyalkylene units can range from about 5 to about 100. The amine portion is derived from ammonia, primary alkyl or secondary dialkyl monoamines, or polyamines with terminal amino nitrogen atoms. The oxyalkylene moiety can be oxypropylene or oxybutylene or mixtures thereof. Hydrocarbyl-substituted poly(oxyalkylene)amines are described in U.S. Pat. No. 6,217,624 and U.S. Pat. No. 5,112,364, which are incorporated herein by reference. It has been incorporated. Specific examples of hydrocarbyl-substituted poly(oxyalkylene) monoamines include alkylphenyl poly(oxyalkylene) monoamines wherein the poly(oxyalkylene) portion contains oxypropylene or oxybutylene units or a mixture of oxypropylene and oxybutylene units. is included. The alkyl group of the alkylphenyl moiety is a straight or branched chain alkyl having from about 1 to about 24 carbon atoms. A preferred alkylphenyl moiety is tetrapropenylphenyl, where the alkyl group is a branched chain alkyl with 12 carbon atoms derived from propylene tetramer.

More specifically, additional hydrocarbyl-substituted poly(oxyalkylene)amines include 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, hydrocarbyl-substituted poly(oxyalkylene) amino carbamates. These hydrocarbyl poly(oxyalkylene) amino carbamates contain at least one basic nitrogen atom and have a has an average molecular weight of Preferred amino carbamates are alkylphenyl poly(oxybutylene) amino carbamates in which the amine moiety is derived from ethylenediamine or diethylenetriamine.

In particular, hydrocarbyl-substituted succinimides for use in the present invention include polyalkylsuccinimides and polyalkenylsuccinimides, wherein the polyalkyl or polyalkenyl groups have an average molecular weight of about 500-5,000, preferably about 700-3,000. included. Hydrocarbyl-substituted succinimides are typically prepared by reacting a hydrocarbyl-substituted succinic anhydride with an amine or polyamine having at least one reactive hydrogen attached to the amine nitrogen atom. Preferred hydrocarbyl-substituted succinimides include polyisobutenyl succinimide and polyisobutanyl succinimide, and derivatives thereof. Hydrocarbyl-substituted succinimides are disclosed in U.S. Patent Nos. 5,393,309, 5,588,973, 5,620,486, 5,916,825, 5,954,843 , Nos. 5,993,497 and 6,114,542, and British Patent No. 1,486,144, all of which are incorporated herein by reference. incorporated into the book.

In particular, Mannich reaction products for use in the present invention include products typically obtained from the Mannich condensation of high molecular weight alkyl-substituted hydroxyaromatic compounds, amines containing at least one reactive hydrogen, and aldehydes. High molecular weight alkyl-substituted hydroxyaromatic compounds are preferably polyalkylphenols, such as polypropylphenols and polybutylphenols, especially polyisobutylphenol, wherein the polyalkyl groups have an average molecular weight of about 600-3,000. The amine reactant is typically a polyamine such as an alkylenepolyamine, particularly an ethylenepolyamine or a polyethylenepolyamine such as ethylenediamine, diethylenetriamine, triethylenetetramine. Aldehyde reactants are generally aliphatic aldehydes such as formaldehyde, including paraformaldehyde and formalin, and acetaldehyde. A preferred Mannich reaction product is obtained by condensing polyisobutylphenol with formaldehyde and diethylenetriamine, wherein 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. Pat. Nos. 4,231,759 and 5,697,988, the disclosures of each of which are incorporated herein by reference. incorporated herein by

を有するものを含み、式中、Ｒ_５は、約６００～５，０００の範囲の平均分子量を有するポリアルキル基であり、Ｒ_６及びＲ_７は、独立して、水素、または１～６個の炭素原子を有する低級アルキルであり、Ａは、アミノ、アルキル基に約１～約２０個の炭素原子を有するＮ－アルキルアミノ、各アルキル基に約１～約２０個の炭素原子を有するＮ，Ｎ－ジアルキルアミノ、または約２～約１２個のアミン窒素原子及び約２～約４０個の炭素原子を有するポリアミン部分である。上記の式ＩＩのポリアルキルフェノキシアミノアルカン及びそれらの調製物は、米国特許第５，６６９，９３９号に詳細に記述されており、この特許は、ここで参照することにより本明細書に組み込まれている。 A still further class of detergent additives suitable for use in the present invention are polyalkylphenoxyaminoalkanes. A preferred polyalkylphenoxyaminoalkane has the formula:

wherein R ₅ is a polyalkyl group having an average molecular weight ranging from about 600 to 5,000, and R ₆ and R ₇ are independently hydrogen, or 1 to 6 wherein A is amino, N-alkylamino having from about 1 to about 20 carbon atoms in the alkyl group, N having from about 1 to about 20 carbon atoms in each alkyl group; , N-dialkylamino, or polyamine moieties having from about 2 to about 12 amine nitrogen atoms and from about 2 to about 40 carbon atoms. Polyalkylphenoxyaminoalkanes of Formula II above and their preparation are described in detail in U.S. Pat. No. 5,669,939, which is incorporated herein by reference. ing.

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

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

を有するものを含み、式中、Ｒ_８は、ニトロまたは－（ＣＨ_２）－ＮＲ_１３Ｒ_１４（ここで、Ｒ_１３及びＲ_１４は、独立して、水素、または１～６個の炭素原子を有する低級アルキルである）であり、Ｒ_９は、水素、ヒドロキシ、ニトロ、または－ＮＲ_１５Ｒ_１６（ここで、Ｒ_１５及びＲ_１６は、独立して、水素、または１～６個の炭素原子を有する低級アルキルである）であり、Ｒ_１０及びＲ_１１は、独立して、水素、または１～６個の炭素原子を有する低級アルキルであり、Ｒ_１２は、約４５０～５，０００の範囲の平均分子量を有するポリアルキル基である。上記の式ＩＩＩに示されるポリアルキルフェノキシアルカノールの芳香族エステル及びそれらの調製物は、米国特許第５，６１８，３２０号に詳細に記述されており、この特許は、ここで参照することにより本明細書に組み込まれている。 In some embodiments, mixtures of nitro and amino aromatic esters of polyalkylphenoxyalkanols may be used. Preferred nitro and amino aromatic esters of polyalkylphenoxyalkanols are represented by the following formulae:

wherein R ₈ is nitro or —(CH ₂ )—NR ₁₃ R ₁₄ where R ₁₃ and R ₁₄ are independently hydrogen or 1 to 6 carbon atoms and R ₉ is hydrogen, hydroxy, nitro, or —NR ₁₅ R ₁₆ (wherein R ₁₅ and R ₁₆ are independently hydrogen or 1-6 carbons R ₁₀ and R ₁₁ are independently hydrogen or lower alkyl having 1 to 6 carbon atoms, and R ₁₂ is about 450 to 5,000 It is a polyalkyl group with a range of average molecular weights. Aromatic esters of polyalkylphenoxyalkanols shown in Formula III above and their preparation are described in detail in U.S. Pat. No. 5,618,320, which is incorporated herein by reference. incorporated into the specification.

を有するものを含み、式中、Ｒ_１７は、約１～約３０個の炭素原子を有するヒドロカルビル基であり、Ｒ_１８及びＲ_１９は、各々独立して、水素、または約１～約６個の炭素原子を有する低級アルキルであり、Ｒ_１８及びＲ_１９の各々は、各－Ｏ－ＣＨＲ_１８－ＣＨＲ_１９－単位において独立して選択され、ｍは、約５～約１００であり、Ｂは、アミノ、アルキル基に約１～約２０個の炭素原子を有するＮ－アルキルアミノ、各アルキル基に約１～約２０個の炭素原子を有するＮ，Ｎ－ジアルキルアミノ、または約２～約１２個のアミン窒素原子及び約２～約４０個の炭素原子を有するポリアミン部分であり、ｍは、約５～約１００の整数である。上記の式ＩＶのヒドロカルビル置換ポリ（オキシアルキレン）アミン及びそれらの調製物は、米国特許第６，２１７，６２４号に詳細に記述されており、この特許は、ここで参照することにより組み込まれている。式ＩＶのヒドロカルビル置換ポリ（オキシアルキレン）アミンは、好ましくは、単独で、または他の清浄添加剤と組み合わせて、特にポリアルキルフェノキシアミノアルカンもしくはポリアルキルフェノキシアルカノールのニトロ及びアミノ芳香族エステルと組み合わせて利用される。より好ましくは、本発明で用いられる清浄添加剤は、ヒドロカルビル置換ポリ（オキシアルキレン）アミンと、ポリアルキルフェノキシアルカノールのニトロ及びアミノ芳香族エステルとの組み合わせである。特に好ましいヒドロカルビル置換ポリ（オキシアルキレン）アミン清浄添加剤は、ドデシルフェノキシポリ（オキシブチレン）アミンであり、清浄添加剤の特に好ましい組み合わせは、ドデシルフェノキシポリ（オキシブチレン）アミンと４－ポリイソブチルフェノキシエチルパラアミノベンゾエートとの組み合わせである。 Mixtures of nitro and amino aromatic esters of polyalkylphenoxyalkanols and hydrocarbyl-substituted poly(oxyalkylene)amines can also be used in this invention. These mixtures are described in detail in US Pat. No. 5,749,929, which is incorporated herein by reference. Preferred hydrocarbyl-substituted poly(oxyalkylene)amines that may be used as detergent additives in the present invention have the formula:

wherein R ₁₇ is a hydrocarbyl group having from about 1 to about 30 carbon atoms and R ₁₈ and R ₁₉ are each independently hydrogen, or from about 1 to about 6 carbon atoms, each of R ₁₈ and R ₁₉ is independently selected in each —O—CHR ₁₈ —CHR ₁₉ — unit, m is from about 5 to about 100, and 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 from about 2 to about 12 amine nitrogen atoms and a polyamine moiety having from about 2 to about 40 carbon atoms, where m is an integer from about 5 to about 100. 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 incorporated herein by reference. there is The hydrocarbyl-substituted poly(oxyalkylene)amines of Formula IV are preferably used alone or in combination with other detergent additives, especially in combination with nitro and amino aromatic esters of polyalkylphenoxyaminoalkanes or polyalkylphenoxyalkanols. used. More preferably, the detergent additive used in the present invention is 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 combination of detergent additives is dodecylphenoxypoly(oxybutylene)amine and 4-polyisobutylphenoxyethyl. Combination with para-aminobenzoate.

Another class of detergent additives suitable for use in the present invention includes nitrogen-containing carburetor/injector detergents. Carburetor/injector detergent additives are typically low molecular weight compounds having a number average molecular weight of from about 100 to about 600 and having at least one polar portion and at least one non-polar portion. Non-polar moieties are typically straight or branched chain alkyl or alkenyl groups having from about 6 to about 40 carbon atoms. The polar portion typically contains nitrogen. Typical nitrogen-containing polar moieties include amines (e.g., as described in U.S. Pat. No. 5,139,534 and PCT International Publication No. WO 90/10051), ether amines (e.g., U.S. Pat. 849,083 and PCT International Publication No. WO 90/10051), amides, polyamides and amide esters (e.g., 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), as well as succinimides (eg, as described in US Pat. No. 4,292,046). Each of these references is hereby incorporated by reference.

Each secondary fuel additive may be present from about 50 ppm to about 2500 ppm (eg, 100-2000, 200-1500, 300-1000, etc.) by weight of the fuel composition. More preferably, the secondary fuel additive is present from about 50 ppm to about 1000 ppm by weight of the fuel composition.

Other Additives The fuel composition may contain other commonly known fuel additives. Suitable examples include, but are not limited to, antioxidants, metal deactivators, demulsifiers, oxygenates, anti-knock agents, dispersants, and other detergents. Other well-known additives such as pour point depressants, flow improvers, etc. may be used in diesel fuel.

Each of the foregoing additives, when used, are used in functionally effective amounts 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 weight percent, such as from about 0.01 to about 10 weight percent, unless otherwise specified.

Concentrates Compounds of the present disclosure may be formulated as concentrates using inert, stable, lipophilic (i.e., soluble in hydrocarbon fuels) organic solvents boiling in the range of 65°C to 205°C. can be done. 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, methylisobutylcarbinol, n-butanol, etc., in combination with hydrocarbon solvents are also suitable for use with the instant additives. In concentrates, the amount of additive may range from 10 to 70 wt% (eg, 20 to 40 wt%).

The following examples are intended to be non-limiting.

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

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

FIG. 1 shows the engine speed and load test conditions observed during the driving cycle of the vehicle. The vehicle drive cycle was based on 10 hills extracted from the transition phase of the US Environmental Protection Agency (EPA) Urban Dynamometer Drive Schedule (UDDS) with additional idle periods added. The total driving cycle is 20 minutes and the total test duration is 2,000 miles.

Additive testing is done 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 injectors and combustion chamber clean during the test period.

Test fuel samples were formulated with targeted deposit control additives. Three injector "keep clean" tests were performed: (i) two tests using base fuel with no additives and (ii) the same base as (i) blended with Example 1 at 200 ppmw. One test with fuel. The injector fuel limits (average) after the specified drive cycles are summarized in Table 2 below.

As shown, injector fuel restriction was substantially reduced during use of the additive-containing fuel as compared to use of the additive-free fuel. Injector fuel limit measures the reduction in fuel flow from the injector, indicative of the presence of deposits in the injector orifice. Injector restrictions can require the engine controller to make further control adjustments to maintain proper engine fuel delivery, and the presence of deposits in the injector orifices can affect fuel mixture and reduce engine This can lead to decreased performance and increased particulate emissions. Images of the injector face for each formulation after the test was completed are shown in FIG. 2 and correspond to Table 2.

The PM emissions of Example 1 were also evaluated using a test engine. A 2016 BMW B48O DISI 2.0L 16-valve turbocharged engine was used in this test.

The engine operating cycle is 360 seconds, the engine speed ranges from idle to 3000 RPM, and the load varies up to 100 Nm. The total test duration is 96 hours. FIG. 3 shows the engine speed and load test conditions.

PM measurements were made on the engine test bench using an AVL Micro Soot Sensor (MSS). MSS provides a continuous, fast-response measurement of solid particle mass and correlates well with conventional gravimetric methods of PM measurement.

In the PM emissions trace shown in FIG. 4 (a small 2000 second segment of the larger test), it can be observed how quickly PM emissions rise and fall as engine conditions change. Official metrics used in certifying vehicle emissions by regulatory agencies (e.g., the U.S. Federal Test Procedure, or FTP) can be consulted to establish useful metrics for these data. can. In these cases, the regulatory agency simply reports the total amount of emissions from the vehicle tailpipe over the entire driving cycle. A similar scheme is applied to the PM dataset to integrate PM emissions over the course of one test drive cycle. This integration is repeated for each driving cycle to obtain a trend line of PM emissions over the test period.

Figures 5A-5C include 150 ppmw Example 2 (Figure 5A), 150 ppmw Example 2 and 150 ppmw Example 1 (Figure 5B), and 150 ppmw Example 2 and 750 ppmw Example 1 (Figure 5C). Figure 2 shows PM emission trend line (96 hour test) results for fuel compositions.

Figures 6A-6C include 2000 ppmw Example 3 (Figure 6A), 2000 ppmw Example 2 and 150 ppmw Example 1 (Figure 6B), and 2000 ppmw Example 2 and 750 ppmw Example 1 (Figure 6C). Figure 2 shows PM emission trend line (96 hour test) results for fuel compositions.

Figures 7A-7C and Figures 8A-8C show the results of Direct Injection Spark Ignition (DISI) rig injector flow tests. These graphs show the rate of restriction versus clean injector flow at various pulse widths (1.5 ms, 2.5 ms, 3.5 ms, and 4.5 ms) at an injection pressure of 100 bar. Samples tested included 150 ppmw Example 2 (Figure 7A), 150 ppmw Example 2 and 150 ppmw Example 1 (Figure 7B), and 150 ppmw Example 2 and 750 ppmw Example 1 (Figure 7C). A fuel composition is included. The samples included 2000 ppmw Example 2 (Figure 8A), 2000 ppmw Example 2 and 150 ppmw Example 1 (Figure 8B), and 2000 ppmw Example 2 and 750 ppmw Example 1 (Figure 8C). things are also included.

9A-9C are 150 ppmw Example 2 (FIG. 9A), 150 ppmw Example 2 and 150 ppmw Example 1 (FIG. 9B) taken after completion of vehicle or engine testing (before flow test). , and fuel compositions containing 150 ppmw Example 2 and 750 ppmw Example 1 (FIG. 9C).

10A-10C are 2000 ppmw Example 2 (FIG. 10A), 2000 ppmw Example 2 and 150 ppmw Example 1 (FIG. 10B) taken after completion of vehicle or engine testing (before flow test). , and fuel compositions containing 2000 ppmw Example 2 and 750 ppmw Example 1 (FIG. 10C).

FIG. 11A shows 150 ppmw Example 2 (left bar), 150 ppmw Example 2 and 150 ppmw Example 1 (middle bar), and 150 ppmw Example 2 and 750 ppmw Example 1 (right bar). Figure 3 shows the average injector tip deposit volume (mm ³ ) for the containing fuel composition. FIG. 11B shows 2000 ppmw Example 2 (left bar), 2000 ppmw Example 2 and 150 ppmw Example 1 (middle bar), and 2000 ppmw Example 2 and 750 ppmw Example 1 (right bar). Figure 3 shows the average injector tip deposit volume (mm ³ ) for the containing fuel composition. These measurements were taken at the end of vehicle or engine testing (before flow testing).

Table 3 below summarizes the samples that were tested and evaluated for anticorrosion properties using the NACE TM0172 standard test method. A base fuel is a fuel without additives. FIG. 12 presents visual confirmation of the corrosion protection test.

All documents mentioned herein, including any priority documents and/or testing procedures, are hereby incorporated by reference unless inconsistent with this text. While the forms of the disclosure have been illustrated and described, as is apparent from the foregoing general description and specific embodiments, various changes can be made without departing from the spirit and scope of the disclosure. Accordingly, it is not intended that the disclosure be limited thereby.

For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit may be combined with any upper limit to describe ranges not explicitly recited, and ranges from any lower limit may be combined with any other lower limit to describe ranges not explicitly stated. Ranges not explicitly recited may be recited, and ranges from any upper limit may be combined with any other upper limit to describe ranges not explicitly recited. Further, a range includes every point or individual value between its endpoints even if not explicitly recited. Therefore, every point or individual value may have its own lower or upper limit combined with any other point or individual value or any other lower or upper limit to describe a range not explicitly recited. can function as

Similarly, the term "comprising" is considered synonymous with the term "including." Similarly, whenever a composition, element, or group of elements is preceded by the transitional phrase "comprising," a composition, element, or group of elements is preceded by "consisting essentially." the same composition or element with the transitional phrase "of", "consisting of", "selected from the group of consisting of", or "is" Groups are also envisioned and vice versa.

As used herein, the terms "a" and "the" are understood to include the singular as well as the plural.

Various terms have been defined above. If a term used in a claim is not defined above, that term shall have the meaning defined by one of ordinary skill in the relevant art as reflected in at least one printed publication or issued patent. should be given the broadest definition given to Further, all patents, testing procedures, and other documents cited in this application are fully incorporated by reference in all jurisdictions where their incorporation is permitted, to the extent that their disclosures do not contradict this application. ing.

The foregoing description of the disclosure illustrates and describes the disclosure. Furthermore, while the disclosure shows and describes only preferred embodiments, as noted above, the disclosure is capable of use in various other combinations, modifications, and environments and incorporates the teachings and/or associations above. It is to be understood that changes or modifications within the scope of the concepts expressed herein are possible commensurate with the skill or knowledge in the art. While the foregoing is directed to embodiments of the present disclosure, other and further embodiments of the present disclosure can be devised without departing from its basic scope, which covers the following claims: is determined by the range of

Where combinations, subsets, groups, etc. of elements are disclosed (eg, combinations of ingredients in compositions or combinations of steps in methods), specific references are provided for each of the various individual and collective combinations and permutations of these elements. Although specific references may not be explicitly disclosed, it is understood that each is specifically contemplated and described herein.

Furthermore, the embodiments described above are intended to illustrate the best known embodiment and also to those skilled in the art that various modifications may be required for a particular application or use in such or other embodiments. to make the present disclosure available. Accordingly, the description is not intended to be limited to the forms disclosed herein. Also, it is intended that the appended claims be interpreted to include alternative embodiments.

Claims (18)

A fuel composition comprising:
a hydrocarbonaceous fuel boiling in the gasoline or diesel range;
an amine detergent given by the formula R ₁ —O—(CH ₂ ) _m —NHR ₂ , wherein said amine detergent is present at from about 10 ppm to about 750 ppm by weight based on the total weight of said fuel composition [ wherein R ₁ is a hydrocarbyl group having 8 to 20 carbons, R ₂ is hydrogen or (CH ₂ ) _n NH ₂ moieties, and m, n independently have a value of 3 or greater. is an integer with
and one or more nitrogen-containing detergents. 2. The fuel composition of claim ₁ , wherein R1 is linear or branched. The one or more nitrogen-containing detergents are aliphatic hydrocarbylamines, hydrocarbyl-substituted poly(oxyalkylene)amines, hydrocarbyl-substituted succinimides, Mannich reaction products, nitro and amino aromatic esters of polyalkylphenoxyalkanols, or polyalkyl 2. The fuel composition according to claim 1, which is a phenoxyaminoalkane. 2. The fuel composition of claim 1, wherein said aminic detergent or said one or more nitrogen-containing detergents are monoamines or polyamines. 2. The fuel composition of claim 1, wherein said amine-based detergent is present from about 10 ppm to 750 ppm of said fuel composition. 2. The fuel composition of claim 1, wherein said one or more nitrogen-containing detergents are present from about 50 ppm to about 2500 ppm of said fuel composition. 2. The fuel composition of claim 1, further comprising an antioxidant, metal deactivator, demulsifier, oxygenator, anti-knock agent, dispersant, pour point depressant, or flow improver. A concentrated composition comprising:
about 30-90% by weight of an organic solvent boiling in the range of 65°C to 205°C;
about 10-70% by weight of a detergent mixture, said detergent mixture comprising:
(1) Aminic detergents given by the formula R ₁ —O—(CH ₂ ) _m —NHR ₂ , where R ₁ is a hydrocarbyl group having 8 to 20 carbons and R ₂ is hydrogen or (CH ₂ ) _n NH ₂ moieties, where m, n are independently integers having a value of 3 or greater];
(2) one or more nitrogen-containing detergents; 8. The concentrate composition of claim 7, wherein _R1 is linear or branched. The one or more nitrogen-containing detergents are aliphatic hydrocarbylamines, hydrocarbyl-substituted poly(oxyalkylene)amines, hydrocarbyl-substituted succinimides, Mannich reaction products, nitro and amino aromatic esters of polyalkylphenoxyalkanols, or polyalkyl 8. A concentrate composition according to claim 7, which is a phenoxyaminoalkane. 8. The concentrate composition of claim 7, wherein said aminic detergent or said one or more nitrogen-containing detergents are monoamines or polyamines. A method of controlling injector contamination comprising:
supplying a fuel composition to a direct injection engine, said fuel composition comprising:
a hydrocarbonaceous fuel boiling in the gasoline or diesel range;
an amine detergent given by the formula R ₁ —O—(CH ₂ ) _m —NHR ₂ , wherein said amine detergent is present at from about 10 ppm to about 750 ppm by weight based on the total weight of said fuel composition [ wherein R ₁ is a hydrocarbyl group having 8 to 20 carbons, R ₂ is hydrogen or (CH ₂ ) _n NH ₂ moieties, and m, n independently have a value of 3 or greater. is an integer with
and one or more nitrogen-containing detergents. 12. The method of claim 11, wherein _R1 is linear or branched. The one or more nitrogen-containing detergents are aliphatic hydrocarbylamines, hydrocarbyl-substituted poly(oxyalkylene)amines, hydrocarbyl-substituted succinimides, Mannich reaction products, nitro and amino aromatic esters of polyalkylphenoxyalkanols, or polyalkyl 12. The method of claim 11, which is a phenoxyaminoalkane. 12. The method of claim 11, wherein the amine-based detergent or the one or more nitrogen-containing detergents are monoamines or polyamines. 12. The method of claim 11, wherein the amine-based detergent is present from about 10 ppm to 750 ppm of the fuel composition. 12. The method of claim 11, wherein the one or more nitrogen-containing detergents are present from about 50 ppm to about 2500 ppm of the fuel composition. 12. The fuel composition of claim 11, wherein the fuel composition further comprises an antioxidant, metal deactivator, demulsifier, oxygenator, anti-knock agent, dispersant, pour point depressant, or flow improver. Method.

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