Polyether amine fuel additives and related methods and compositions

Abstract

A fuel additive including a combination of a nitrogen-containing fuel detergent and a polyether amine. The foregoing combination capable of use with hydrocarbon fuels (e.g., gasoline optionally with ethanol therein) or in fuel additive concentrate compositions to be diluted by a hydrogen fuel. The combination of the polyether amine and the nitrogen-containing fuel detergent may prevent or remove carbonaceous deposits in internal combustion engines, especially gasoline direct injection engines.

Description

POLYETHER AMINE FUEL ADDITIVES AND RELATED METHODS AND COMPOSITIONSCROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Patent Application Serial Number 63 / 640,379 filed April 30, 2024. The noted application is incorporated herein by reference.FIELD

[0002] The present disclosure generally relates to fuel additives and, more specifically, to fuel additives that prevent or reduce carbonaceous deposits in internal combustion engines.BACKGROUND

[0003] The performance of an internal combustion engine may be adversely affected by the formation of carbonaceous deposits in or around the fuel injection system and combustion chamber. Even when present in minor amounts, these carbonaceous deposits can cause a noticeable reduction in the performance of the engine, an increase in fuel consumption, and an increase in the production of exhaust pollutants.

[0004] Increasingly, new motor vehicles use gasoline direct injection (GDI) engines for better fuel economy rather than to port fuel injection (PF1) engines. However, fuel additives designed to mitigate or reduce the formation of carbonaceous deposits in PFI gasoline engines may not perform as well in GDI engines, which is largely due to the different engine design. GDI engines deliver fuel directly into the combustion chamber. When fuel is directly injected, 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 injector and nozzle, which is known as injector fouling. The formation of carbonaceous deposits, both around the injector nozzle and inside the combustion chamber, can negatively impact fuel flow rate, injection duration, and spray pattern. The carbonaceous deposits can lead to poor performance in drivability, increased fuel consumption, higher exhaust emissions, and shorter engine lifetime.SUMMARY

[0005] A nonlimiting example fuel composition of the present disclosure may comprise: a hydrocarbon fuel comprising gasoline and optionally ethanol; a nitrogen-containing fuel detergent; and a polyether amine according to Formula I (described above) having a weight average molecular weight (Mw) of 500 g / mol or lessFormula I wherein R is a linear or branched C4-C22 alkyl, alkylphenyl with a C4-C12 alkyl, or dialkylphenyl with a C4-C12 alkyl; R’ is hydrogen, methyl, ethyl, or a combination thereof; and n is from 1 to 8 (preferably 1 to 4). As described below, the alcohol used as a reactant for the RO- group can be a linear or branched alcohol, alkylphenol, or dialkylphenol.

[0006] A nonlimiting example fuel additive concentrate composition of the present disclosure may comprise: about 30 to 90 wt % of an organic solvent boiling in a range of from 65°C to 205°C based on the total weight of the concentrate; and about 10 to 70 wt % of a polyether amine and a nitrogen-containing fuel detergent, cumulatively, based on the total weight of the concentrate, wherein the polyether amine is according to Formula I (described above) and has a weight average molecular weight of 500 g / mol or less.

[0007] A nonlimiting example method of the present disclosure may comprise: supplying to an engine a fuel composition comprising: a hydrocarbon fuel comprising gasoline and optionally ethanol; a polyether amine according to Formula I (described above) having a weight average molecular weight of 500 g / mol or less; and a nitrogen-containing fuel detergent.DETAILED DESCRIPTION

[0008] The present disclosure generally relates to fuel additives and related compositions and methods where the fuel additives may prevent the formation of or remove carbonaceous deposits in internal combustion engines, especially GDI engines. The fuel additives of the present disclosure include low molecular weight polyether amines.

[0009] The carbonaceous deposits on the fuel injectors include partially oxidized hydrocarbons from fuels or lubricants. There can be a lot of acid group on these carbonaceous deposits. Advantageously, the amine head group in the polyether amines in the fuel additives of the present disclosure can have strong interaction with these acid sites. The hydrophobic tail of the polyether amines may increase the hydrophobicity of the carbonaceous deposits and facilitate suspension of the carbonaceous deposits in the fuel for removal.

[0010] Additionally, the polyether amines of the present disclosure are low molecular weight polymers and, therefore, have a distribution of molecular weights. In contrast, anti-fouling additives are commonly a chemical compound with a specific molecular weight, not a distribution of molecular weights. Because the carbonaceous deposits are not uniform in size, shape, or number of acid groups, the distribution of molecular weights of the polyether amines gives the additive a distribution of properties (e.g., solubility, detergency, etc.) that may advantageously improve the removal of the non-uniform carbonaceous deposits in the engine. In contrast, an anti-fouling fuel additive with a single chemical compound or mixture of two or three chemical compounds does not have a distribution of properties and may remove some carbonaceous deposits with good efficacy but not impact the formation or removal other carbonaceous deposits.

[0011] Further, a single chemical compound often has higher production costs related to lower reaction yield and more purification requirements compared to a product where multiple species over a variety of molecular weights. Accordingly, the cost to produce the poly ether amines for fuel additives of the present disclosure can be lower than other additives that are a single chemical compound.

[0012] Before explaining aspects of the present disclosure in detail, it is to be understood that the present disclosure is not limited in its application to the details of construction and the arrangement of components or steps, or methodologies set forth in the following description. The present disclosure is capable of other embodiments or of being practiced or carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein is for the purpose of description and should not be regarded as limiting.

[0013] If appearing herein, the term “comprising” and derivatives thereof are not intended to exclude the presence of any additional component, step, or procedure, whether or not the same is disclosed herein. In order to avoid any doubt, all compositions claimed herein through use of the term “comprising” may include any additional additive, adjuvant, or compound, unless stated tothe contrary. In contrast, the term, “consisting essentially of’ if appearing herein, excludes from the scope of any succeeding recitation any other component, step, or procedure, except those that are not essential to operability and the term “consisting of’, if used, excludes any component, step or procedure not specifically delineated or listed. The terms “or” and “and / or”, unless stated otherwise, refer to the listed members individually as well as in any combination. For example, the expressions A or B and A and / or B refer to A alone, B alone, or to both A and B.

[0014] The articles “a” and “an” are used herein to refer to one or to more than one (i.e., to at least one) of the grammatical objects of the article. By way of example, “a solvent” means one solvent or more than one solvent. The phrases “in one embodiment”, “according to one embodiment” and the like generally mean the feature, structure, or characteristic following the phrase is included in at least one embodiment of the present disclosure and may be included in more than one embodiment of the present disclosure. Importantly, such phrases do not necessarily refer to the same embodiment. If the specification states a component or feature “may”, “can”, “could”, or “might” be included or have a characteristic, that component or feature is not required to be included or have the characteristic.

[0015] The terms “preferred” and “preferably” refer to embodiments that may afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful and is not intended to exclude other embodiments from the scope of the present disclosure.

[0016] The term “about” as used herein can allow for a degree of variability in a value or range, for example, it may be within 10%, within 5%, or within 1% of a stated value or of a stated limit of a range.

[0017] The use of ordinal number terminology (i.e., “first”, “second”, “third”, “fourth”, etc.) is solely for the purpose of differentiating between two or more items and, unless otherwise stated, is not meant to imply any sequence or order or importance to one item over another or any order of addition.

[0018] Values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but to also include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a range such as from 1 to 6, should beconsidered to have specifically disclosed sub-ranges, such as, from 1 to 3, from 2 to 4, from 3 to 6, etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.

[0019] In the methods described herein, the acts can be carried out in any order without departing from the principles of the present disclosure, except when a temporal or operational sequence is explicitly recited. Furthermore, specified acts can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed act of doing X and a claimed act of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.

[0020] The term “optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

[0021] The term “alkyl” as a group or part of a group as used herein refers to branched or straight (linear) or cyclic hydrocarbon with no site of unsaturation.

[0022] As used herein, the term “cycloalkyl” as a group or part of a group refers to a saturated or partially saturated cyclic alkyl radical. Examples of C3-C6 cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.

[0023] The term “aryl” as a group or part of a group refers to a polyunsaturated, aromatic hydrocarbyl group having a single ring (i.e., phenyl) or multiple aromatic rings fused together (e.g. naphthyl) or linked covalently wherein at least one ring is aromatic. Aryl groups typically contain 6 to 24 carbon atoms, preferably 6 to 10 carbon atoms, wherein at least one ring is aromatic. The aromatic ring may optionally include one to two additional rings fused thereto. For example, a Ce- C10 aryl refers to an aryl containing 6 to 10 atoms; wherein at least one ring is aromatic. Examples of Ce-Cio aryl include phenyl, naphthyl, indanyl, or 1,2,3,4-tetrahydro-naphthyl.

[0024] A polyether amine and a nitrogen-containing fuel detergent may be included in combination as additives (e.g., anti-fouling additives) in fuel compositions and related compositions like fuel additive concentrate compositions.

[0025] The polyether amines suitable for use in the compositions and methods of the present disclosure have a structure according to Formula I:Formula I wherein R is a linear or branched C4-C22 alkyl, alkylphenyl with a C4-C12 alkyl, or dialkylphenyl with a C4-C12 alkyl; R’ is hydrogen, methyl, ethyl, or a combination thereof (where n is greater than 1); and n is from 1 to 8 (preferably 1 to 4). As described below, the alcohol used as a reactant for the RO- group can be a linear or branched alcohol, alkylphenol, or dialkylphenol.

[0026] The polyether amines in the present disclosure are hydrophobic and easily miscible with a hydrocarbon fuel. It is noted that Formula I is not a salt and that the compositions described herein do not include a salt derivative of Formula I.

[0027] The polyether amines may generally be prepared by reaction of a monohydric initiator (e.g., a linear or branched C4-C22 alkyl, alkylphenol with a C4-C12 alkyl, or dialkylphenol with a C4-C12 alkyl) with one or more of ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO). This reaction is followed by conversion of the resulting terminal hydroxyl group to an amine, thereby providing a polyether backbone (comprising EO, PO, BO, or any mixture thereof) and a terminal primary amino group. Based on the composition of Formula I, one skilled in the art will recognize the reactant suitable for producing the various embodiments of Formula I.

[0028] When using two or more of EO, PO, and BO, any mole ratio between the components may be used and, consequently, be present in the poly ether amine product at the [O-CH2-CHR’]nunits in a similar ratio. One skilled in the art will recognize that referring to EO, PO, and BO in a polyether amine product refers to the corresponding reacted monomeric unit in the polyether amine.

[0029] Where the polyether amine includes EO and PO units, a mole ratio of EO:PO in the polyether amines may range from about 10: 1 to about 1 : 10 (e.g., about 10: 1 to about 1 : 1, about 5: 1 to about 1 :5, about 3: 1 to about 1 :3, or about 1: 1 to about 1: 10). Where the polyether amine includes EO and BO units, a mole ratio of EO:BO in the poly ether amines may range from about 10: 1 to about 1 : 10 (e.g., about 10: 1 to about 1 :1, about 5: 1 to about 1 :5, about 3: 1 to about 1 :3, or about 1 :1 to about 1 : 10). Where the poly ether amine includes PO and BO units, a mole ratio of PO:BO in the polyether amines may range from about 10: 1 to about 1 : 10 (e.g., about 10: 1 to about1 : 1, about 5 : 1 to about 1 : 5, about 3 : 1 to about 1 :3, or about 1 : 1 to about 1 : 10). Where all three of EO, PO, and BO units are included in the polyether amine, a mole ratio of EO:PO may range from about 10: 1 to about 1 : 10 (e.g., about 10: 1 to about 1 : 1, about 5: 1 to about 1 :5, about 3: 1 to about 1 :3, or about 1 :1 to about 1 : 10), and a mole ratio of EO:BO may range from about 10: 1 to about 1 : 10 (e.g., about 10: 1 to about 1 : 1, about 5: 1 to about 1 :5, about 3: 1 to about 1:3, or about 1 : 1 to about 1 : 10).

[0030] The polyether amines may have a weight average molecular weight (Mw) of about 500 g / mol or less (e g., about 100 g / mol to about 500 g / mol, about 100 g / mol to about 200 g / mol, about 150 g / mol to about 250 g / mol, about 200 g / mol to about 300 g / mol, about 250 g / mol to about 350 g / mol, about 300 g / mol to about 400 g / mol, about 350 g / mol to about 450 g / mol, or about 400 g / mol to about 500 g / mol).

[0031] The polyether amines may have a poly dispersity index (PDI) of about 3 or less (e.g., about 1 to about 3, about 1 to about 2, about 1.5 to about 2.5, about 2 to about 3).

[0032] Gel permeation chromatography per ASTM D6474 can be used to determine the Mw, number average molecular weight (Mn), and PDI (equal to Mw divided by Mn, i.e., Mw / Mn).

[0033] Examples of nitrogen-containing fuel detergents suitable for use in the compositions and methods of the present disclosure may include, but are not limited to, aliphatic hydrocarbyl- substituted amines, Mannich amines, hydrocarbyl-substituted poly(oxyalkylene)amine, hydrocarbyl-substituted succinimide, nitro and amino aromatic ester of polyalkylphenoxyalkanol, polyalkylphenoxyaminoalkane, the like, and any mixture thereof. Such nitrogen-containing fuel detergents are more particularly described in the following patents: British Pat. No. 1,083,610, British Pat. No. 1,094,020, European Pat. No. 0476 485B1, U.S. Pat. No. 3,753,670, U.S. Pat. No. 3,756,793, U.S. Pat. No. 3,948,619, U.S. Pat. No. 4,231,759, U.S. Pat. No. 4,832,702, U.S. Pat. No. 5,112,364, U.S. Pat. No. 5,810,894, and U.S. Pat. No. 5,851,242, which are incorporated by reference. Preferably, the nitrogen-containing fuel detergents comprises an aliphatic hydrocarbyl- substituted amine, a Mannich amine, or a combination of both an aliphatic hydrocarbyl-substituted amine and a Mannich amine.

[0034] Aliphatic hydrocarbyl-substituted amines may be straight or branched chain hydrocarbyl-substituted amines with at least one basic nitrogen. Examples of aliphatic hydrocarbyl-substituted amines may include, but are not limited to, polyisobutenyl amines, polyisobutyl amines, the like, and any combination thereof.

[0035] Aliphatic hydrocarbyl -substituted amines may have a weight average molecular weight (Mw) of about 700 g / mol or greater (e.g., about 700 g / mol to about 5000 g / mol, about 700 g / mol to about 1500 g / mol, about 1000 g / mol to about 2500 g / mol, or about 2500 g / mol to about 5000 g / mol).

[0036] Mannich amines may be a reaction product of a hydrocarbyl -substituted phenol, an aldehyde, and an amine or ammonia. Polybutene-based Mannich amines may be preferred. Examples may include, but are not limited to, the Mannich reaction product of polyisobutylphenol and ethylene amine, the Mannich reaction product of polyisobutylphenol and dimethylaminopropylamine, the like, and any combination thereof.

[0037] Mannich amines may have a weight average molecular weight (Mw) of about 600 g / mol or greater (e.g., about 600 g / mol to about 5000 g / mol, about 600 g / mol to about 2000 g / mol, about 1500 g / mol to about 3000 g / mol, or about 2500 g / mol to about 5000 g / mol).

[0038] In the compositions described herein (e.g., a fuel composition and a fuel additive concentrate composition), a weight ratio of the polyether amine to the nitrogen-containing fuel detergent (cumulatively if more than one nitrogen-containing fuel detergent is used) may be about 10: 1 to about 1 : 10 (e.g., about 10: 1 to about 1 : 1, about 5: 1 to about 1 :5, about 3: 1 to about 1:3, or about 1 : 1 to about 1 : 10).

[0039] A polyether amine and a nitrogen-containing fuel detergent, in combination, may be included as additives in fuel compositions and related compositions like fuel additive concentrate compositions. Optionally, the fuel compositions and related compositions may further include other fuel additives, discussed in more detail below.

[0040] A fuel composition may comprise a hydrocarbon fuel, a polyether amine, a nitrogencontaining fuel detergent, and optionally other fuel additives.

[0041] The hydrocarbon fuel may be a petroleum distillate, including a gasoline as defined by ASTM specification D4814. The gasoline may be non-leaded gasoline. The hydrocarbon fuel may be a blend of gasoline and ethanol (e.g., E5-E20).

[0042] The poly ether amine may be present in the fuel composition from about 10 ppm to about 5000 ppm (e.g., about 10 ppm to about 500 ppm, about 10 ppm to about 250 ppm, about 10 ppm to about 100 ppm, about 250 ppm to about 1000 ppm, about 500 ppm to about 2000 ppm, about 1000 ppm to about 2500 ppm, about 2000 ppm to about 3500 ppm, or about 2500 ppm to about 5000 ppm), based on the total weight of the fuel composition. The nitrogen-containing fueldetergent may be present in the fuel composition from about 10 ppm to about 5000 ppm (e g., about 10 ppm to about 500 ppm, about 10 ppm to about 250 ppm, about 10 ppm to about 100 ppm, about 250 ppm to about 1000 ppm, about 500 ppm to about 2000 ppm, about 1000 ppm to about 2500 ppm, about 2000 ppm to about 3500 ppm, or about 2500 ppm to about 5000 ppm), based on the total weight of the fuel composition. The weight ratio of the polyether amine to the nitrogencontaining fuel detergent described above is applicable to the fuel composition.

[0043] In some instances, the polyether amine and the nitrogen-containing fuel detergent may be used to maintain a clean engine and mitigate the formation of carbonaceous deposits. In such embodiments, the concentration of the poly ether amine may preferably be about 500 ppm or less (e.g., about 10 ppm to about 500 ppm or about 100 ppm to about 500 ppm), and the nitrogencontaining fuel detergent may preferably be about 500 ppm or less (e.g., about 10 ppm to about 500 ppm or about 100 ppm to about 500 ppm). In some instances, the polyether amine and the nitrogen-containing fuel detergent may be used to clean an engine with existing carbonaceous deposits where a higher concentration of said components is preferable. In such embodiments, the concentration of the polyether amine may preferably be about 500 ppm or greater (e.g., about 500 ppm to about 5000 ppm or about 500 ppm to about 2500 ppm), and the nitrogen-containing fuel detergent may preferably be about 500 ppm or greater (e.g., about 500 ppm to about 5000 ppm or about 500 ppm to about 2500 ppm).

[0044] Methods of the present disclosure for controlling injector fouling may include supplying a fuel composition described herein to an engine (e.g., to a direct injection engine like a GIP engine).

[0045] A fuel additive concentrate composition may comprise a polyether amine, a nitrogencontaining fuel detergent, an organic solvent having a boiling point from about 65°C to about 205°C, and optionally other fuel additives. The organic solvent may solubilize polyether amine and a nitrogen-containing fuel detergent so that said components readily mix homogenously into a hydrocarbon fuel. The hydrocarbon fuel acts as a diluent to the fuel additive concentrate composition. The fuel additive concentrate composition may be added to an amount of hydrocarbon fuel to affect any desired dilution of the fuel additive concentrate composition. That is, the dilution of the fuel additive concentrate composition may be at least about 5 times (e.g., at least about 10 times, at least about 25 times, at least about 50 times, at least about 100 times, at least about 500 times, at least about 1000 times, or more) in the hydrocarbon fuel.

[0046] Methods of the present disclosure may include diluting a fuel additive concentrate composition described herein in a hydrocarbon fuel to produce a fuel composition described herein.

[0047] Examples of organic solvents having a boiling point from about 65°C to about 205°C may include, but are not limited to, benzene, toluene, xylene, gasoline fuel, kerosene fuel, diesel fuel, other aromatic solvents such as aromatic 100 and aromatic 150, C7-C16 alkane such as isooctane, the like, and any combination thereof.

[0048] The solvent may be present in the fuel additive concentrate composition from about 30 wt% to about 90 wt% (e.g., about 40 wt% to about 90 wt%, about 50 wt% to about 90 wt%, about 50 wt% to about 80 wt%, or about 60 wt% to about 80 wt%), based on the total weight of the fuel additive concentrate composition. The polyether amine and the nitrogen-containing fuel detergent (cumulatively) may be present in the fuel additive concentrate composition from about 10 wt% to about 70 wt% (e.g., about 10 wt% to about 60 wt%, about 10 wt% to about 50 wt%, about 20 wt% to about 50 wt%, or about 20 wt% to about 40 wt%), based on the total weight of the fuel additive concentrate composition. The weight ratio of the polyether amine to the nitrogen-containing fuel detergent described above is applicable to the fuel additive concentrate composition.

[0049] As discussed herein, other additives may be present in fuel compositions and / or fuel additive concentrate composition. Examples of other fuel additives may include, but are not limited to, anti-knocking agents, antioxidants, metal deactivators, demulsifiers, lubricators, auxiliary dispersants, pour point depressants, flow improver, oxygenates, lead scavengers, dyes, rust inhibitors, bacteriostatic agents, gum inhibitors, the like, and any combination thereof. Generally, each of the other fuel additives, individual, may be present in a fuel composition from about 0.001 wt% to about 20 wt% (e.g., about 0.001 wt% to about 1 wt%, about 0.1 wt% to about 5 wt%, about 1 wt% to about 10 wt%, or about 5 wt% to about 20 wt%), based on a total weight of the fuel composition.

[0050] Each of the other fuel additives, individually, may be present in a fuel additive concentrate composition from 0 wt% to about 60 wt% (e.g., about 0.01 wt% to about 5 wt%, about 0.1 wt% to about 10 wt%, about 1 wt% to about 20 wt%, about 5 wt% to about 30 wt%, about 15 wt% to about 45 wt%, or about 30 wt% to about 60 wt%), based on a total weight of the fuel additive concentrate composition. The fuel additive concentrate composition may be absent otherfuel additives and consist of the organic solvent, the polyether amine, and the nitrogen-containing fuel detergent.

[0051] Each of the other fuel additives may be added to the hydrocarbon fuel as part of the fuel additive concentrate composition with the polyether amine and the nitrogen-containing fuel detergent or may be added to the hydrocarbon fuel separately from the fuel additive concentrate composition. For example, producing a fuel composition may include adding a fuel additive concentrate composition comprising a polyether amine, a nitrogen-containing fuel detergent, and a first other fuel additive to a hydrocarbon fuel, and adding a second other fuel additive to the hydrocarbon fuel separately from the fuel additive concentrate composition.

[0052] Non-limiting examples of anti-knocking agents may include, but are not limited to, methylcyclopentadienyl manganese tricarbonyl, ferrocene, tetramethyl lead, tetraethyl lead, the like, and any combination thereof.

[0053] Non-limiting examples of antioxidants may include, but are not limited to, butylated hydroxy toluene, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butylphenol, phenylene diamine, ethylene diamine, 0-carotene, the like, and any combination thereof.

[0054] Non-limiting examples of metal deactivators may include, but are not limited to, aromatic triazoles, derivatives of aromatic triazoles, the like, and any combination thereof.

[0055] Non-limiting examples of demulsifiers may include, but are not limited to, polyalkoxylated alcohols, polydimethyl siloxane, the like, and any combination thereof.

[0056] Non-limiting examples of lubricators may include, but are not limited to, fatty carboxylic acids, the like, and any combination thereof.

[0057] Non-limiting examples of pour point depressants may include, but are not limited to, polymethacrylates, polyacrylates, polyarylamides, condensation products of haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers, and terpolymers of dialkylfumarates, vinyl esters of fatty acids, allyl vinyl ethers, the like, and any combination thereof.

[0058] Non-limiting examples of oxygenates may include, but are not limited to, methanol, ethanol, isopropyl alcohol, n-butanol, gasoline-grade t-butanol, methyl tert-butyl ether, tertiary amyl methyl ether, tertiary hexyl methyl ether, ethyl tertiary butyl ether, tertiary amyl ethyl ether, diisopropyl ether, the like, and any combination thereof.

[0059] Non-limiting examples of lead scavengers may include, but are not limited to, tri cresyl phosphate, 1,2-dibromoethane, 1,2-dichloroethane, the like, and any combination thereof.

[0060] Nonlimiting embodiments of the present disclosure include the following.

[0061] Embodiment 1. A fuel composition comprising: a hydrocarbon fuel comprising gasoline and optionally ethanol; a polyether amine according to Formula I (described above) having a weight average molecular weight (Mw) of 500 g / mol or less; and a nitrogen-containing fuel detergent.

[0062] Embodiment 2. The fuel composition of Embodiment 1, wherein the nitrogencontaining fuel detergent comprises an aliphatic hydrocarbyl-substituted amine, aMannich amine, a hydrocarbyl-substituted poly(oxyalkylene)amine, a hydrocarbyl-substituted succinimide, a nitro and amino aromatic ester of polyalkylphenoxyalkanol, a polyalkylphenoxyaminoalkane, or any mixture thereof.

[0063] Embodiment 3. The fuel composition of any preceding Embodiment, wherein the nitrogen-containing fuel detergent comprises two or more of: (i) polyisobutene, (ii) a Mannich reaction product of poly isobutylphenol and ethylene amine, and (iii) a Mannich reaction product of polyisobutylphenol and dimethylaminopropylamine.

[0064] Embodiment 4. The fuel composition of any preceding Embodiment, wherein the poly ether amine is not a salt derivative of Formula I.

[0065] Embodiment 5. The fuel composition of any preceding Embodiment, wherein the polyether amine has a poly dispersity index of 3 or less.

[0066] Embodiment 6. The fuel composition of any preceding Embodiment, wherein the R’ of Formula I is a mixture of hydrogen and methyl, and wherein a mole ratio of propylene oxide to butylene oxide for R’ is 10: 1 to 1 : 10.

[0067] Embodiment 7. The fuel composition of any preceding Embodiment, wherein the polyether amine is present from 100 ppm to 5000 ppm, based on a total weight of the fuel composition.[006S] Embodiment 8. The fuel composition of any preceding Embodiment, wherein the nitrogen-containing fuel detergent is present from 100 ppm to 5000 ppm, based on a total weight of the fuel composition.

[0069] Embodiment 9. The fuel composition of any preceding Embodiment, wherein a weight ratio of the polyether amine to the nitrogen-containing fuel detergent is 10: 1 to 1 : 10.

[0070] Embodiment 10. The fuel composition of any preceding Embodiment, further comprising one or more other fuel additives selected from the group consisting of: an anti-knocking agent, an antioxidant, a metal deactivator, a demulsifier, an auxiliary dispersant, a pour point depressant, a flow improver, an oxygenate, a lead scavenger, a dye, a rust inhibitor, a bacteriostatic agent, and a gum inhibitor.

[0071] Embodiment 11. A fuel additive concentrate composition comprising: about 30 wt % to about 90 wt % of an organic solvent boiling in a range of from about 65 °C to about 205 °C; and about 10 wt % to about 70 wt % of a poly ether amine and a nitrogen-containing fuel detergent, cumulatively, wherein the polyether amine is according to Formula I (described above) and has a weight average molecular weight of about 500 g / mol or less.

[0072] Embodiment 12. The fuel additive concentrate composition of Embodiment 11, wherein the nitrogen-containing fuel detergent comprises an aliphatic hydrocarbyl-substituted amine, a Mannich amine, a hydrocarbyl-substituted poly(oxyalkylene)amine, a hydrocarbyl- substituted succinimide, a nitro and amino aromatic ester of polyalkylphenoxyalkanol, a polyalkylphenoxyaminoalkane, or any mixture thereof.

[0073] Embodiment 13. The fuel additive concentrate composition of Embodiment 11 or 12, wherein the R’ of Formula I is a mixture of hydrogen and methyl, and wherein a mole ratio of ethylene oxide to propylene oxide for R’ is 10: 1 to 1 : 10.

[0074] Embodiment 14. The fuel additive concentrate composition of one of Embodiments 11- 13, wherein a weight ratio of the polyether amine to the nitrogen-containing fuel detergent is 10: 1 to 1 :10.

[0075] Embodiment 15. A method comprising: supplying to an engine a fuel composition comprising: a hydrocarbon fuel comprising gasoline and optionally ethanol; a polyether amine according to Formula I (described above) having a weight average molecular weight of about 500 g / mol or less; and a nitrogen-containing fuel detergent.

[0076] Embodiment 16. The method of Embodiment 15, wherein the R’ of Formula I is a mixture of hydrogen and methyl, and wherein a mole ratio of ethylene oxide to propylene oxide forR’ is 10: 1 to 1 : 10.

[0077] Embodiment 17. The method of Embodiment 15 or 16, wherein the polyether amine is present from about 100 ppm to about 5000 ppm, and the nitrogen-containing fuel detergent is present from about 100 ppm to about 5000 ppm, each based on a total weight of the fuel composition.

[0078] Embodiment 18. The method of one of Embodiments 15-17, wherein a weight ratio of the poly ether amine to the nitrogen-containing fuel detergent is 10: 1 to 1 : 10.

[0079] Embodiment 19. The method of one of Embodiments 15-18, wherein the fuel composition further comprises one or more other fuel additives selected from the group consisting of: an anti-knocking agent, an antioxidant, a metal deactivator, a demulsifier, an auxiliary dispersant, a pour point depressant, a flow improver, an oxygenate, a lead scavenger, a dye, a rust inhibitor, a bacteriostatic agent, and a gum inhibitor.

[0080] Embodiment 20. The method of one of Embodiments 15-19, wherein the engine is a gasoline direct injection engine.

[0081] While the foregoing is directed to embodiments of the present disclosure, other and further embodiments of the disclosure may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims

WHAT IS CLAIMED IS:

1. A fuel composition comprising: a hydrocarbon fuel comprising gasoline and optionally ethanol; a polyether amine according to Formula I having a weight average molecular weight (Mw) of about 500 g / mol or less;Formula I wherein R is a linear or branched C4-C22 alkyl, alkylphenyl with a C4-C12 alkyl, or dialkylphenyl with a C4-C12 alkyl; R’ is hydrogen, methyl, ethyl, or a combination thereof; and n is from 1 to 8; and a nitrogen-containing fuel detergent.

2. The fuel composition of claim 1, wherein the nitrogen-containing fuel detergent comprises an aliphatic hydrocarbyl-substituted amine, a Mannich amine, a hydrocarbyl -substituted poly(oxyalkylene)amine, a hydrocarbyl-substituted succinimide, a nitro and amino aromatic ester of polyalkylphenoxyalkanol, a polyalkylphenoxyaminoalkane, or any mixture thereof.

3. The fuel composition of any preceding claim, wherein the nitrogen-containing fuel detergent comprises two or more of: (i) polyisobutene, (ii) a Mannich reaction product of poly isobutylphenol and ethylene amine, and (iii) a Mannich reaction product of polyisobutylphenol and dimethylaminopropylamine.

4. The fuel composition of any preceding claim, wherein the polyether amine is not a salt derivative of Formula I.

5. The fuel composition of any preceding claim, wherein the poly ether amine has a poly dispersity index of 3 or less.

6. The fuel composition of any preceding claim, wherein the R’ of Formula I is a mixture of hydrogen and methyl, and wherein a mole ratio of propylene oxide to butylene oxide for R’ is from 10: 1 to 1 : 10.

7. The fuel composition of any preceding claim, wherein the polyether amine is present from 100 ppm to 5000 ppm, based on a total weight of the fuel composition.

8. The fuel composition of any preceding claim, wherein the nitrogen-containing fuel detergent is present from about 100 ppm to about 5000 ppm, based on a total weight of the fuel composition.

9. The fuel composition of any preceding claim, wherein a weight ratio of the polyether amine to the nitrogen-containing fuel detergent is from 10: 1 to 1 : 10.

10. The fuel composition of any preceding claim, further comprising one or more other fuel additives selected from the group consisting of: an anti-knocking agent, an antioxidant, a metal deactivator, a demulsifier, an auxiliary dispersant, a pour point depressant, a flow improver, an oxygenate, a lead scavenger, a dye, a rust inhibitor, a bacteriostatic agent, and a gum inhibitor.

11. A fuel additive concentrate composition comprising: about 30 wt % to about 90 wt % of an organic solvent boiling in a range of from about 65°C to about 205°C; and about 10 wt % to about 70 wt % of a poly ether amine and a nitrogen-containing fuel detergent, cumulatively, wherein the polyether amine is according to Formula I and has a weight average molecular weight of about 500 g / mol or lessFormula Iwherein R is a linear or branched C4-C22 alkyl, alkylphenyl with a C4-C12 alkyl, or dialkylphenyl with a C4-C12 alkyl; R’ is hydrogen, methyl, ethyl, or a combination thereof; and n is from 1 to 8.

12. The fuel additive concentrate composition of claim 11, wherein the nitrogen-containing fuel detergent comprises an aliphatic hydrocarbyl -substituted amine, a Mannich amine, a hydrocarbyl-substituted poly(oxyalkylene)amine, a hydrocarbyl-substituted succinimide, a nitro and amino aromatic ester of polyalkylphenoxyalkanol, a polyalkylphenoxyaminoalkane, or any mixture thereof.

13. The fuel additive concentrate composition of claim 11 or 12, wherein the R’ of Formula I is a mixture of hydrogen and methyl, and wherein a mole ratio of ethylene oxide to propylene oxide for R’ is from 10: 1 to 1 : 10.

14. The fuel additive concentrate composition of one of claims 11-13, wherein a weight ratio of the poly ether amine to the nitrogen-containing fuel detergent is from 10: 1 to 1: 10.

15. A method compri sing : supplying to an engine a fuel composition comprising: a hydrocarbon fuel comprising gasoline and optionally ethanol; a poly ether amine according to Formula I having a weight average molecular weight of about 500 g / mol or lessFormula I wherein R is a linear or branched C4-C22 alkyl, alkylphenyl with a C4-C12 alkyl, or dialkylphenyl with a C4-C12 alkyl; R’ is hydrogen, methyl, ethyl, or a combination thereof; and n is from 1 to 8; and a nitrogen-containing fuel detergent.

16. The method of claim 15, wherein the R’ of Formula l is a mixture of hydrogen and methyl, and wherein a mole ratio of ethylene oxide to propylene oxide for R’ is from 10: 1 to 1 : 10.

17. The method of claim 15 or 16, wherein the polyether amine is present from about 100 ppm to about 5000 ppm, and the nitrogen-containing fuel detergent is present from about 100 ppm to about 5000 ppm, each based on a total weight of the fuel composition.

18. The method of one of claims 15-17, wherein a weight ratio of the polyether amine to the nitrogen-containing fuel detergent is from 10: 1 to 1 : 10.

19. The method of one of claims 15-18, wherein the fuel composition further comprises one or more other fuel additives selected from the group consisting of: an anti-knocking agent, an antioxidant, a metal deactivator, a demulsifier, an auxiliary dispersant, a pour point depressant, a flow improver, an oxygenate, a lead scavenger, a dye, a rust inhibitor, a bacteriostatic agent, and a gum inhibitor.

20. The method of one of claims 15-19, wherein the engine is a gasoline direct injection engine.

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