JP2024533830A - Fuel Additive for Reducing Deposits and Particulate Emissions - Patent application - Google Patents

Abstract

Fuel compositions are described that comprise a carrier fluid comprising an alkyl polyethoxylate having the following structure (I): where each R2 and R3 is independently hydrogen, a C1-C4 hydrocarbyl group, or a C1-C3 alcohol, R1 is a C4-C100 hydrocarbyl group, a carboxyl group, an ether group, a thioether group, or an aromatic group, and x is 1 to 20; or an alkyl polyethoxylate having the following structure (II): where R is a C4-C10 0 hydrocarbyl group, an amine detergent represented by formula 2, R4-O-(CH2)y-NHR5, where the amine detergent is present at about 10 ppm by weight to about 750 ppm by weight based on the total weight of the fuel composition, R4 is a hydrocarbyl group having from 8 to 20 carbons, R5 is hydrogen or a (CH2)zNH2 moiety, and y, z are independently integers having a value of 2 or greater, and one or more nitrogen-containing detergents.

Description

The present disclosure relates to fuel additives. More specifically, the present disclosure relates to compositions and methods that promote deposit cleaning performance and reduce particulate emissions.

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

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

［式中、各Ｒ^２及びＲ^３は独立して、水素、Ｃ_１－Ｃ_４ヒドロカルビル基、またはＣ_１－Ｃ_３アルコールであり、Ｒ^１は、Ｃ_４－Ｃ_１００ヒドロカルビル基、カルボキシル基、エーテル基、チオエーテル基、または芳香族基であり、ｘは１～２０である］
を有するアルキルポリエトキシレートを含むキャリア流体、または、以下の式：

を有するヒドロカルビルフェノール［式中、Ｒは、Ｃ_４－Ｃ_１００のヒドロカルビル基である］
ｉｉｉ）以下の式：
Ｒ^４－Ｏ－（ＣＨ_２）_ｙ－ＮＨＲ^５
［式中、アミン系洗剤は、燃料組成物の総重量に対して約１０重量ｐｐｍ～約７５０重量ｐｐｍで存在し、Ｒ^４は、８～２０個の炭素を有するヒドロカルビル基であり、Ｒ^５は、水素または（ＣＨ_２）_ｚＮＨ_２部分であり、ｙ、ｚは独立して、２以上の値を有する整数である］で示されるアミン系洗剤、ならびに、ｉｖ）１種以上の窒素含有洗剤を含む、燃料組成物を提供する。 In one aspect, a compound having: i) a hydrocarbonaceous fuel boiling point in the gasoline or diesel range; ii) the following structure:

wherein each R ² and R ³ is independently hydrogen, a C ₁ -C ₄ hydrocarbyl group, or a C ₁ -C ₃ alcohol; R ¹ is a C ₄ -C ₁₀₀ hydrocarbyl group, a carboxyl group, an ether group, a thioether group, or an aromatic group; and x is 1 to 20.
or a carrier fluid comprising an alkyl polyethoxylate having the following formula:

where R is a C ₄ -C ₁₀₀ hydrocarbyl group.
iii) a compound of the formula:
R ⁴ -O-(CH ₂ ) _y -NHR ⁵
wherein the amine detergent is present in an amount of from about 10 ppm by weight to about 750 ppm by weight, based on the total weight of the fuel composition, R ⁴ is a hydrocarbyl group having from 8 to 20 carbons, R ⁵ is hydrogen or a (CH ₂ ) _z NH ₂ moiety, and y, z are independently integers having a value of 2 or greater; and iv) one or more nitrogen-containing detergents.

［式中、各Ｒ^２及びＲ^３は独立して、水素、Ｃ_１－Ｃ_４ヒドロカルビル基、またはＣ_１－Ｃ_３アルコールであり、Ｒ^１は、Ｃ_４－Ｃ_１００ヒドロカルビル基、カルボキシル基、エーテル基、チオエーテル基、または芳香族基であり、ｘは１～２０である］
を有するアルキルポリエトキシレート化を含むキャリア流体、または、以下の式：

［式中、Ｒは、Ｃ_４－Ｃ_１００のヒドロカルビル基である］
を有するヒドロカルビルフェノール；
ｉｉｉ）以下の式：を有するアミン系洗剤
Ｒ^４－Ｏ－（ＣＨ_２）_ｙ－ＮＨＲ^５
［式中、アミン系洗剤は、燃料組成物の総重量に対して約１０重量ｐｐｍ～約７５０重量ｐｐｍで存在し、Ｒ^４は、８～２０個の炭素を有するヒドロカルビル基であり、Ｒ^５は、水素または（ＣＨ_２）_ｚＮＨ_２部分であり、ｙ、ｚは独立して、２以上の値を有する整数である］で示されるアミン系洗剤、ならびに、ｉｖ）１種以上の窒素含有洗剤、を含む、上記方法を提供する。 In another aspect, a method for controlling carbon deposits in an internal combustion engine includes providing a fuel to said internal combustion engine, said fuel having i) a hydrocarbonaceous fuel boiling point in the gasoline or diesel range; ii) a carbon-containing amine having the following structure:

wherein each R ² and R ³ is independently hydrogen, a C ₁ -C ₄ hydrocarbyl group, or a C ₁ -C ₃ alcohol; R ¹ is a C ₄ -C ₁₀₀ hydrocarbyl group, a carboxyl group, an ether group, a thioether group, or an aromatic group; and x is 1 to 20.
or a carrier fluid comprising an alkyl polyethoxylated having the following formula:

[wherein R is a C ₄ -C ₁₀₀ hydrocarbyl group]
a hydrocarbyl phenol having the formula:
iii) Amine-based detergents having the formula: R ⁴ -O-(CH ₂ ) _y -NHR ⁵
wherein the amine based detergent is present at about 10 ppm to about 750 ppm by weight based on the total weight of the fuel composition, R ⁴ is a hydrocarbyl group having from 8 to 20 carbons, R ⁵ is hydrogen or a (CH ₂ ) _z NH ₂ moiety, and y, z are independently integers having a value of 2 or greater; and iv) one or more nitrogen-containing detergents.

［式中、各Ｒ^２及びＲ^３は独立して、水素、Ｃ_１－Ｃ_４ヒドロカルビル基、またはＣ_１－Ｃ_３アルコールであり、Ｒ^１は、Ｃ_４－Ｃ_１００ヒドロカルビル基、カルボキシル基、エーテル基、チオエーテル基、または芳香族基であり、ｘは１～２０である］
を有するアルキルポリエトキシレート化を含むキャリア流体、または、以下の式：

［式中、Ｒは、Ｃ_４－Ｃ_１００のヒドロカルビル基である］；ｉｉ）以下の式：
Ｒ^４－Ｏ－（ＣＨ_２）_ｙ－ＮＨＲ^５
［式中、アミン系洗剤は、燃料組成物の総重量に対して約１０重量ｐｐｍ～約７５０重量ｐｐｍで存在し、Ｒ^４は、８～２０個の炭素を有するヒドロカルビル基であり、Ｒ^５は、水素または（ＣＨ_２）_ｚＮＨ_２部分であり、ｙ、ｚは独立して、２以上の値を有する整数である］により示されるアミン系洗剤、ならびに、ｉｉｉ）１種以上の窒素含有洗剤、を含む、約１０～７０重量％の洗剤混合物；を含む、濃縮組成物を提供する。 In another embodiment, about 30-90% by weight of an organic solvent boiling point in the range of 65° C. to 205° C.; and
i) a compound having the following structure:

wherein each R ² and R ³ is independently hydrogen, a C ₁ -C ₄ hydrocarbyl group, or a C ₁ -C ₃ alcohol; R ¹ is a C ₄ -C ₁₀₀ hydrocarbyl group, a carboxyl group, an ether group, a thioether group, or an aromatic group; and x is 1 to 20.
or a carrier fluid comprising an alkyl polyethoxylated having the following formula:

wherein R is a C ₄ -C ₁₀₀ hydrocarbyl group; ii) a compound of the formula:
R ⁴ -O-(CH ₂ ) _y -NHR ⁵
and iii) about 10 to 70 wt. % of a detergent mixture comprising an amine-based detergent represented by the formula: wherein the amine-based detergent is present at about 10 ppm to about 750 ppm by weight based on the total weight of the fuel composition, R ⁴ is a hydrocarbyl group having 8 to 20 carbons, R ⁵ is hydrogen or a (CH ₂ ) _z NH ₂ moiety, and y, z are independently integers having a value of 2 or greater; and iii) one or more nitrogen-containing detergents.

This is described in the Examples section. This is described in the Examples section. This is described in the Examples section. This is described in the Examples section. This is described in the Examples section. This is described in the Examples section. This is described in the Examples section. This is described in the Examples section. This is described in the Examples section.

The present disclosure provides compositions and methods for improving engine performance, specifically improving deposit cleaning performance and/or reducing particulate emissions. The present invention may be effective in controlling carbon deposits in internal combustion engines.

Generally, the fuel compositions of the present invention include (i) a hydrocarbon-based fuel, (ii) a carrier fluid, (iii) an amine-based detergent, and (iv) one or more nitrogen-containing detergents.

Hydrocarbon-Based Fuels Hydrocarbon-based fuels include gasoline and diesel.

Gasoline fuel means a composition containing at least primarily _C4 - _C12 hydrocarbons. In one embodiment, gasoline or gasoline boiling range components is further defined to mean a composition containing at least primarily _C4 - _C12 hydrocarbons and further having a boiling range of about 37.8°C (100°F) to about 204°C (400°F). In an alternative embodiment, gasoline is defined to mean a composition containing at least primarily _C4 - _C12 hydrocarbons and having a boiling range of about 37.8°C (100°F) to about 204°C (400°F), and further defined as meeting ASTM D4814.

Diesel fuel means a middle distillate fuel containing at least primarily _C10 - _C25 hydrocarbons. In one embodiment, diesel is further defined to mean a composition containing at least primarily _C10 - _C25 hydrocarbons and further having a boiling range of about 165.6°C (330°F) to about 371.1°C (700°F). In an alternative embodiment, diesel means a composition containing at least primarily _C10 - _C25 hydrocarbons as defined above and having a boiling range of about 165.6°C (330°F) to about 371.1°C (700°F), and further defined as meeting ASTM D975.

The hydrocarbon-based fuel is present in a major amount by weight percent of the total fuel composition. In some embodiments, the hydrocarbon-based fuel is present in an amount of about 50 wt% or more, 55 wt% or more, 60 wt% or more, 65 wt% or more, 70 wt% or more, 75 wt% or more, 80 wt% or more, 85 wt% or more, 90 wt% or more, 95 wt% or more, or any range between about 50 wt% and 100 wt% or less.

According to some embodiments, the gasoline used in the present invention is clean burning gasoline (CBG). CBG refers to a gasoline blend that contains low amounts of sulfur, aromatics, and olefins. The exact blend may vary depending on local regulatory definitions.

Carrier Fluids Fuel-soluble, non-volatile carrier fluids or oils may also be used with the compounds of the present disclosure. Carrier fluids are chemically inert, hydrocarbon-soluble liquid vehicles that aid in some increase in octane requirement, but substantially increase the non-volatile residue (NVR) or solvent-free fluid fraction of the fuel additive composition. In some embodiments, the carrier fluid is a surfactant.

［式中、各Ｒ^２及びＲ^３は独立して、水素、Ｃ_１－Ｃ_４ヒドロカルビル基、またはＣ_１－Ｃ_３アルコールであり、Ｒ^１は、Ｃ_４－Ｃ_１００ヒドロカルビル基、カルボキシル基、エーテル基、チオエーテル基、または芳香族基であり、ｘは１～２０である］。 The carrier fluid of the present invention may be an alkyl polyethoxylate represented by Formula 1 below:

wherein each R ² and R ³ is independently hydrogen, a C ₁ -C ₄ hydrocarbyl group, or a C ₁ -C ₃ alcohol; R ¹ is a C ₄ -C ₁₀₀ hydrocarbyl group, a carboxyl group, an ether group, a thioether group, or an aromatic group; and x is 1 to 20.

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

［式中、Ｒは、Ｃ_４－Ｃ_１００のヒドロカルビル基である］。ヒドロカルビルフェノールの具体例としては、テトラプロペニルフェノール、ＰＩＢフェノール、ブチルフェノール、オクチルフェノールなどが挙げられる。 In some embodiments, the carrier fluid of the present invention can be a hydrocarbyl phenol having the following structure:

[wherein R is a C ₄ -C ₁₀₀ hydrocarbyl group]. Specific examples of hydrocarbyl phenols include tetrapropenylphenol, PIB phenol, butylphenol, octylphenol, and the like.

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

Amine-Based Detergents The amine-based detergents of the present invention (more specifically, the linear/branched aliphatic ether amines) are represented by the formula:
R ⁴ -O-(CH ₂ ) _y -NHR ⁵
Equation 2
where R ⁴ is a hydrocarbyl group having 8 to 20 carbons, R ⁵ is hydrogen or a (CH ₂ ) _z NH ₂ moiety, and y, z are independently integers having a value of 2 or greater. The hydrocarbyl group may be saturated or unsaturated. In some embodiments, the hydrocarbyl group may contain 2 or more unsaturated bonds.

As an advantage, the fuel additive of the present invention can deliver more basic nitrogen at the same treatment rate compared to conventional amine-based fuel detergents (e.g., polyisobutylamine, polyetheramine, etc.). This property is important in measuring detergency. As another advantage, 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.

Particularly exemplary 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 can be present from about 10 ppm to about 750 ppm (e.g., 20-700, 30-650, 50-600, 100-500, 200-400, 250-350, etc.) based on the total fuel composition.

Nitrogen-Containing Detergents The fuel compositions of the present invention include one or more nitrogen-containing detergents. Suitable secondary fuel additives can be classified as 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 detergents. Each class of secondary fuel additive will be described in more detail herein.

Specifically, the aliphatic hydrocarbyl-substituted amines used in the present invention may be linear or branched chain hydrocarbyl-substituted amines having at least one basic nitrogen, where the hydrocarbyl group has a number average molecular weight of about 700 to 3,000. Specific examples of aliphatic hydrocarbyl-substituted amines include polyisobutenylamine and polyisobutylamine. These amines can be derived as monoamines or polyamines. The preparation of aliphatic amines is generally well known and is described in detail in U.S. Pat. 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 incorporated herein by reference.

Specifically, the hydrocarbyl-substituted poly(oxyalkylene)amines (also referred to as "polyether amines") used in the present invention can 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 can range from about 5 to about 100. The amine portion is derived from ammonia, a primary alkyl or secondary dialkyl monoamine, or a polyamine having a terminal amino nitrogen atom. The oxyalkylene portion can be oxypropylene or oxybutylene, 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 incorporated herein by reference. Specific examples of hydrocarbyl-substituted poly(oxyalkylene) monoamines include alkylphenyl poly(oxyalkylene) monoamines, where the poly(oxyalkylene) moiety contains oxypropylene or oxybutylene units, or a mixture of oxypropylene and oxypropylene units. The alkyl group on the alkylphenyl moiety is a straight or branched chain alkyl of about 1 to about 24 carbon atoms. A preferred alkylphenyl moiety is tetrapropenylphenyl, where the alkyl group is a branched chain alkyl of 12 carbon atoms derived from propylene tetramer.

More specifically, additional hydrocarbyl-substituted poly(oxyalkylene) amines include the hydrocarbyl-substituted poly(oxyalkylene) aminocarbamates disclosed in U.S. Patent 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 incorporated herein 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, where the amine moiety is derived from ethylenediamine or diethylenetriamine.

Specifically, the hydrocarbyl-substituted succinimides used in the present invention include polyalkyl and polyalkenyl succinimides, where the polyalkyl or polyalkenyl group has an average molecular weight of about 500 to 5,000, and preferably about 700 to 3,000. 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 and polyisobutanyl 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 incorporated herein by reference.

Specifically, the Mannich reaction products used in the present invention typically include products 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, especially polyisobutylphenol, where the polyalkyl group has an average molecular weight of about 600 to 3,000. The amine reactant is typically a polyamine, such as an alkylene polyamine, especially an ethylene or polyethylene polyamine, such as ethylenediamine, diethylenetriamine, triethylenetetramine, etc., for example, 1-(2-aminoethyl)piperazine. The aldehyde reactant is generally an aliphatic aldehyde, such as formaldehyde, including paraformaldehyde and formalin, and 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. Mannich reaction products suitable for use in the present invention are described, for example, in U.S. Pat. Nos. 4,231,759, 5,697,988, and 6,749,651, the disclosures of each of which are incorporated herein by reference.

［式中、Ｒ^６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^７及びＲ^８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と、約２～約４０個の炭素原子とを有するポリアミン部分である。］。上記式３のポリアルキルフェノキシアミノアルカン類、及びこれらの調製物は、米国特許第５，６６９，９３９号明細書に詳細に記載されており、参照により本明細書に援用されている。 Yet a further class of detergent additives suitable for use in the present invention are the polyalkylphenoxyaminoalkanes. Preferred polyalkylphenoxyaminoalkanes include those having the formula:

wherein R ⁶ is a polyalkyl group having an average molecular weight in the range of about 600 to 5,000; R ⁷ and R ⁸ are independently hydrogen or lower alkyl having 1 to 6 carbon atoms; and A is amino, N-alkylamino having about 1 to about 20 carbon atoms in the alkyl group, 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 3 above, and their preparation, are described in detail in U.S. Pat. No. 5,669,939, incorporated herein by reference.

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

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

［式中、Ｒ^９はニトロ、または－（ＣＨ_２）－ＮＲ^１４Ｒ^１５（式中、Ｒ^１４及びＲ^１５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は水素、ヒドロキシ、ニトロ、または－ＮＲ^１６Ｒ^１７（式中、Ｒ^１６及びＲ^１７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^１１及びＲ^１２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^１３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］。上記式４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類、及びこれらの調製物は、米国特許第５，６１８，３２０に詳細に記載されており、参照により本明細書に援用されている。 In some embodiments, mixtures of nitro and amino aromatic esters of polyalkylphenoxyalkanols can be used. Preferred nitro and amino aromatic esters of polyalkylphenoxyalkanols include those having the formula:

wherein R ⁹ is nitro, or -(CH ₂ )-NR ¹⁴ R ¹⁵ , where R ¹⁴ and R ¹⁵ are independently hydrogen or lower alkyl having 1 to 6 carbon atoms; R ¹⁰ is hydrogen, hydroxy, nitro, or -NR ¹⁶ R ¹⁷ , where R ^{16 and} R ¹⁷ are independently hydrogen or lower alkyl having 1 to 6 carbon atoms; R ¹¹ and R ¹² are independently hydrogen or lower alkyl having 1 to 6 carbon atoms; and R ¹³ is a polyalkyl group having an average molecular weight in the range of about 450 to 5,000. The aromatic esters of polyalkylphenoxyalkanols shown in formula 4 above, and their preparation, are described in detail in U.S. Patent No. 5,618,320, incorporated herein by reference.

［式中：Ｒ^１８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^１９及びＲ^２０は独立して、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、各－Ｏ－ＣＨＲ^１９－ＣＨＲ^２０－単位は、他の－Ｏ－ＣＨＲ^１９－ＣＨＲ^２０－単位と独立しており；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と、約２～約４０個の炭素原子と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］。上記式５のヒドロカルビル置換ポリ（オキシアルキレン）アミン類、及びこれらの調製物は、米国特許第６，２１７，６２４号に詳細に記載されており、参照により本明細書に援用されている。式５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、これら自身により、または、他の洗剤添加剤、特に、ポリアルキルフェノキシアミノアルカンと、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使用される。より好ましくは、本発明で用いられる洗剤添加剤は、ヒドロカルビル置換ポリ（オキシアルキレン）アミンの、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）アミン洗剤添加剤は、ドデシルフェノキシポリ（オキシブチレン）アミンであり、洗剤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の組み合わせである。 Mixtures of nitroaromatic and aminoaromatic esters of polyalkylphenoxyalkanols with 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 detergent additives in the present invention include those having the following formula:

where R ¹⁸ is a hydrocarbyl group having from about 1 to about 30 carbon atoms; R ¹⁹ and R ²⁰ are independently hydrogen or lower alkyl having from about 1 to about 6 carbon atoms, each -O-CHR ¹⁹ -CHR ²⁰ - unit being independent of the other -O-CHR ¹⁹ -CHR ²⁰ - units; 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; m is an integer from about 5 to about 100. The hydrocarbyl-substituted poly(oxyalkylene)amines of formula 5 above, and their preparation, are described in detail in U.S. Patent No. 6,217,624, incorporated herein by reference. The hydrocarbyl-substituted poly(oxyalkylene)amines of formula 5 are preferably used by themselves or in combination with other detergent additives, particularly with polyalkylphenoxyaminoalkanes or with nitro and amino aromatic esters of polyalkylphenoxyalkanols. More preferably, the detergent additives used in the present invention are combinations of hydrocarbyl-substituted poly(oxyalkylene)amines with 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 the combination of dodecylphenoxypoly(oxybutylene)amine and 4-polyisobutylphenoxyethyl 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 about 100 to about 600 and having at least one polar moiety and at least one non-polar moiety. The non-polar moiety is typically a straight or branched chain alkyl or alkenyl group having about 6 to about 40 carbon atoms. The polar moiety is typically nitrogen-containing. Exemplary nitrogen-containing polar moieties include amines (described, for example, in U.S. Pat. No. 5,139,534 and WO 90/10051), ether amines (described, for example, in U.S. Pat. No. 3,849,083 and WO 90/10051), amides, polyamides, and amide esters (described, for example, in U.S. Pat. Nos. 2,622,018; 4,729,769; and 5,139,534; and European Patent Publication No. 149,486), imidazolines (described, for example, in U.S. Pat. No. 4,518,782), amine oxides (described, for example, in U.S. Pat. Nos. 4,810,263 and 4,836,829), hydroxyamines (described, for example, in U.S. Pat. No. 4,409,000), and succinimides (described, for example, in U.S. Pat. No. 4,292,046). Each of these references is incorporated herein by reference.

Each secondary fuel additive can be present at about 50 ppm to about 2500 ppm (e.g., 100-2000, 200-1500, 300-1000, etc.) by weight of the fuel composition. More preferably, the secondary fuel additive is present at 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, oxygen additives, anti-knock agents, dispersants, and other detergents. In diesel fuels, other well-known additives may be used, such as pour point depressants, flow improvers, etc.

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

Concentrates The compounds of the present disclosure can be formulated as concentrates using an inert, stable, oleophilic (i.e., soluble in hydrocarbon fuels) organic solvent boiling 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 may be used. Aliphatic alcohols containing 2 to 8 carbon atoms, such as ethanol, isopropanol, methyl isobutyl carbinol, n-butanol, and the like, in combination with hydrocarbon solvents are also suitable for use with the present additives. In concentrates, the amount of additive may be 10 to 70% by weight (e.g., 20 to 40% by weight).

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. The base fuel is a neat gasoline composition.

Testing was conducted on a 2012 2.0L GM LHU with an in-line 4-cylinder turbocharged engine. The test was a dirty-up/clean-up (DU/CU) test in which the engine first completed a 100-hour DU segment to build up deposits and foul the injectors, followed by a one-tank CU segment.

Formulation Testing: The formula contained polyetheramine (PEA), 1000 ppmw of nonionic surfactants (Surfactant A and Surfactant B), and 150 ppmw of isotridecyloxypropylamine. Surfactant A is an ethoxylated ( _C12 - _C14 ) secondary alcohol. Surfactant B is a nonylphenol ethoxylate.

DU fuel: New model, high sulfur, E0 fuel

DU cycle: steady state 2000 rpm/100 Nm

1 Tank CU Fuel: This test was completed using unadditive base fuel in PUL E0 49 condition.

One tank CU cycle: 5 stages of cycle: idle, low speed and load segment, and medium speed and load segment. A base fuel run was performed with both fuel and cycle conditions changed between the DU and CU test phases to ensure that there was no CU in the injector without additive. The formulation is shown in Table 1 and images are shown in Figures 1A-1I.

All documents described herein are incorporated by reference, including any priority documents and/or test procedures, unless inconsistent with the text. As is apparent from the general description and specific embodiments set forth above, although several forms of the present disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, the present disclosure is not intended to be limited thereby.

For brevity, only certain ranges are explicitly disclosed herein. However, a range from any lower limit may be combined with any upper limit to recite a range not expressly stated, and similarly, a range from any lower limit may be combined with any other lower limit to recite a range not expressly stated, and similarly, a range from any upper limit may be combined with any other upper limit to recite a range not expressly stated. Furthermore, a range includes every point or individual value between its endpoints, even if not expressly recited. Thus, every point or individual value may be combined with any other point or individual value, or with any other lower or upper limit, to act as its own lower or upper limit and recite a range not expressly stated.

Similarly, the term "comprising" is considered synonymous with the term "including." Similarly, whenever the transitional phrase "comprising" precedes a composition, element, or group of elements, it is understood to also contemplate the same composition or group of elements with the transitional phrase "consisting essentially of," "consisting of," "selected from the group consisting of," or "is" preceding the description of the composition, element, or group of elements, and vice versa.

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

Various terms are defined above. To the extent a term used in the claims is not defined above, it should be given the broadest definition given to that term by one skilled in the relevant art as reflected in at least one printed publication or issued patent. Furthermore, all patents, test methods, and other documents cited in this application are incorporated by reference in their entirety to the extent such disclosure is not inconsistent with this application and in all jurisdictions where such incorporation is permitted.

The foregoing description of the disclosure illustrates and describes the disclosure. Moreover, the disclosure shows and describes only the preferred embodiments, but as noted above, it is to be understood that the disclosure can be used in various other combinations, modifications, and environments, and that changes or modifications are possible within the scope of the concepts expressed herein, consistent with the teachings above and/or the skill or knowledge of the relevant art. While the foregoing is directed to embodiments of the disclosure, other and further embodiments of the disclosure may be devised without departing from the basic scope thereof, the scope of which is determined by the claims which follow.

When combinations, subsets, groups, etc. of elements (e.g., combinations of components in a composition or combinations of steps in a method) are disclosed, it is understood that specific reference to each of the various individual and collective combinations and permutations of these elements is specifically contemplated and described herein, even though they may not be expressly disclosed.

The embodiments described herein above are further intended to further describe the best modes known for carrying out the invention and to enable others skilled in the art to utilize the present disclosure in such or other embodiments, with various modifications necessary for a particular application or use. Therefore, the description is not intended to be limited to the forms disclosed herein. It is also intended that the appended claims be construed to include alternative embodiments.

Claims (16)

i) Hydrocarbon fuel boiling point in the gasoline or diesel range;
ii) a molecule having the following structure:

wherein each R ² and R ³ is independently hydrogen, a C ₁ -C ₄ hydrocarbyl group, or a C ₁ -C ₃ alcohol; R ¹ is a C ₄ -C ₁₀₀ hydrocarbyl group, a carboxyl group, an ether group, a thioether group, or an aromatic group; and x is 1 to 20.
or a carrier fluid comprising an alkyl polyethoxylate having the following formula:

[wherein R is a C ₄ -C ₁₀₀ hydrocarbyl group]
a hydrocarbyl phenol having the formula:
iii) An amine-based detergent having the formula:
R ⁴ -O-(CH ₂ ) _y -NHR ⁵
wherein the amine based detergent is present in an amount of from about 10 ppm to about 750 ppm by weight based on the total weight of the fuel composition, R ⁴ is a hydrocarbyl group having from 8 to 20 carbons, R ⁵ is hydrogen or a (CH ₂ ) _z NH ₂ moiety, and y, z are independently integers having a value of 2 or greater; and iv) a fuel composition comprising one or more nitrogen-containing detergents. The fuel composition of claim 1, wherein the carboxyl group is a carboxylic acid, an ester, an amide or a ketone. The _C1 - _C3 alcohol is
-[CH ₂ ] _w -OH
2. The fuel composition of claim 1, having a structure represented by the formula: in which w is 1 to 3. The alkyl polyethoxylate has the following structure:

wherein each R ²² and R ²³ is independently hydrogen, a C ₁ -C ₄ hydrocarbyl group, or a C ₁ -C ₃ alcohol; p is 1 to 20, q is 1 to 3, s is 1 to 3, and q+s<6; and R ²¹ is a C ₁ -C ₁₀₀ hydrocarbyl group, a carboxyl group, an ether group, a thioether group, an aminoalkyl group, or a hydroxyl group.
The method of claim 1 , wherein the The fuel composition of claim 1, wherein the fuel composition comprises from about 50 ppmw to about 2000 ppmw of the carrier fluid. The fuel composition of claim 1, wherein the fuel composition contains about 100 ppmw to 750 ppmw of the amine detergent. 1. A method for controlling carbon deposits in an internal combustion engine, comprising:
providing a fuel to the internal combustion engine, the fuel comprising:
i) Hydrocarbon fuel boiling point in the gasoline or diesel range;
ii) a molecule having the following structure:

wherein each R ² and R ³ is independently hydrogen, a C ₁ -C ₄ hydrocarbyl group, or a C ₁ -C ₃ alcohol; R ¹ is a C ₄ -C ₁₀₀ hydrocarbyl group, a carboxyl group, an ether group, a thioether group, or an aromatic group; and x is 1 to 20.
or a carrier fluid comprising an alkyl polyethoxylated having the following formula:

[wherein R is a C ₄ -C ₁₀₀ hydrocarbyl group]
a hydrocarbyl phenol having the formula:
iii) An amine-based detergent having the formula:
R ⁴ -O-(CH ₂ ) _y -NHR ⁵
wherein the amine based detergent is present at about 10 ppm to about 750 ppm by weight based on the total weight of the fuel composition, R ⁴ is a hydrocarbyl group having 8 to 20 carbons, R ⁵ is hydrogen or a (CH ₂ ) _z NH ₂ moiety, and y, z are independently integers having a value of 2 or greater; and iv) one or more nitrogen-containing detergents. The method of claim 7, wherein the carboxyl group is a carboxylic acid ester, an amide, or a ketone. The _C1 - _C3 alcohol is
-[CH ₂ ] _w -OH
The method of claim 7, having a structure represented by the formula: [wherein w is 1 to 3]. The alkyl polyethoxylate has the following structure:

wherein each R ²² and R ²³ is independently hydrogen, a C ₁ -C ₄ hydrocarbyl group, or a C ₁ -C ₃ alcohol; p is 1 to 20, q is 1 to 3, s is 1 to 3, and q+s<6; and R ²¹ is a C ₁ -C ₁₀₀ hydrocarbyl group, a carboxyl group, an ether group, a thioether group, an aminoalkyl group, or a hydroxyl group.
The method of claim 7 , wherein the compound is represented by: The method of claim 7, wherein the fuel composition comprises about 50 ppmw to about 2000 ppmw of the carrier fluid. The method of claim 7, wherein the fuel composition comprises about 100 ppmw to 750 ppmw of the amine detergent. About 30-90% by weight of an organic solvent boiling point in the range of 65° C. to 205° C., and;
i) a compound having the following structure:

wherein each R ² and R ³ is independently hydrogen, a C ₁ -C ₄ hydrocarbyl group, or a C ₁ -C ₃ alcohol; R ¹ is a C ₄ -C ₁₀₀ hydrocarbyl group, a carboxyl group, an ether group, a thioether group, or an aromatic group; and x is 1 to 20.
or a carrier fluid comprising an alkyl polyethoxylated having the following formula:

[wherein R is a C ₄ -C ₁₀₀ hydrocarbyl group]
a hydrocarbyl phenol having the formula:
ii) An amine-based detergent having the formula:
R ₄ -O-(CH ₂ ) _y -NHR ₅
wherein the amine detergent is present in an amount of from about 10 ppm to about 750 ppm by weight based on the total weight of the fuel composition; _R4 is a hydrocarbyl group having from 8 to 20 carbons; _R5 is hydrogen or _a ( _CH2 ) _zNH2 moiety; and y, z are independently integers having a value of 2 or greater.
iii) A concentrated composition comprising about 10-70% by weight of a detergent mixture comprising one or more nitrogen-containing detergents. The concentrate of claim 13, wherein the carboxyl group is a carboxylic acid ester, an amide, or a ketone. The _C1 - _C3 alcohol is
-[CH ₂ ] _w -OH
[Wherein, w is 1 to 3]
14. The concentrate of claim 13 having a structure represented by: The alkyl polyethoxylate is represented by the formula 6

14. The concentrate of claim 13, represented by the formula: wherein each R ²² and R ²³ is independently hydrogen, a C ₁ -C ₄ hydrocarbyl group, or a C ₁ -C ₃ alcohol; p is 1 to 20, q is 1 to 3, s is 1 to 3, and q+s<6; and R ²¹ is a C ₁ -C ₁₀₀ hydrocarbyl group, a carboxyl group, an ether group, a thioether group, an aminoalkyl group, or a hydroxyl group.

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