Fuel composition

Abstract

A detergent additive package comprising a quaternary ammonium inner salt detergent and a Mannich base detergent mixture, wherein the quaternary ammonium inner salt is derived from an amine or polyamine substantially free of any free anionic species, wherein the Mannich base detergent mixture comprises a first Mannich base detergent component derived from a diamine or polyamine and a second Mannich base detergent component derived from a monoamine, wherein the weight ratio of the first Mannich base detergent to the second Mannich base detergent mixture is in the range of about 1:6 to about 3:1, and wherein the weight ratio of the quaternary ammonium inner salt detergent to the Mannich base detergent mixture is in the range of about 1:10 to about 1:100.

Description

Technical Field

[0001] This invention relates to fuel compositions containing certain fuel additives for providing enhanced engine and / or injector performance, fuel additive packages, and methods for using said fuel compositions to improve engine and / or injector performance. Background Technology

[0002] Fuel compositions for vehicles are constantly being improved to enhance various fuel properties to suit their use in newer, more advanced engines, including both port-injection and direct-injection engines. Typically, improvements to fuel compositions focus on improving fuel additives and other components used in the fuel. For example, friction modifiers may be added to the fuel to reduce friction and wear in the engine's fuel delivery system. Other additives may be included to reduce the fuel's corrosion potential or to improve its electrical conductivity. Other additives may also be blended with the fuel to improve fuel economy. Engine and fuel delivery system deposits represent another problem in modern internal combustion engines, and therefore other fuel additives often include various deposit control additives to control and / or mitigate engine deposit problems. Thus, fuel compositions often consist of complex mixtures of additives.

[0003] However, challenges remain when attempting to balance such a complex array of additives. For example, some conventional fuel additives may benefit one characteristic or type of engine while simultaneously harming another fuel characteristic. In some cases, a fuel additive effective in a port-injection gasoline engine may not provide comparable performance in a direct-injection engine, and vice versa. In other cases, fuel additives often require unreasonably high processing rates to achieve the desired effect, which can undesirably limit the amount of other additives available in the fuel composition. However, other fuel additives are often expensive and / or difficult to manufacture or blend into the fuel. These disadvantages are particularly pronounced in the case of quaternary ammonium salt fuel additives, which are typically difficult or expensive to manufacture and / or require relatively high processing rates for performance. Summary of the Invention

[0004] According to the present invention, an unleaded gasoline fuel is provided, comprising a fuel composition containing a major amount of a base fuel and a detergent additive package, wherein the detergent additive package comprises a mixture of a quaternary ammonium salt detergent and a Mannich base detergent, wherein the quaternary ammonium salt is obtained from an amine or polyamine substantially free of any free anionic substances, and wherein the Mannich base detergent mixture comprises a first Mannich base detergent component derived from a diamine or polyamine and a second Mannich base detergent component derived from a monoamine, wherein the weight ratio of the first Mannich base detergent to the second Mannich base detergent mixture is in the range of about 1:6 to about 3:1, and wherein the weight ratio of the quaternary ammonium salt detergent to the Mannich base detergent mixture is in the range of about 1:10 to about 1:100.

[0005] According to the present invention, the use of an unleaded gasoline fuel composition for improving engine and / or injector performance in a direct injection engine is also provided, wherein the unleaded gasoline fuel composition comprises a major amount of a gasoline base fuel and a detergent additive package, wherein the detergent additive package comprises a mixture of a quaternary ammonium salt detergent and a Mannich base detergent, wherein the quaternary ammonium salt is obtained from an amine or polyamine substantially free of any free anionic substances, and wherein the Mannich base detergent mixture comprises a first Mannich base detergent component derived from a diamine or polyamine and a second Mannich base detergent component derived from a monoamine, wherein the weight ratio of the first Mannich base detergent to the second Mannich base detergent mixture is in the range of about 1:6 to about 3:1, and wherein the weight ratio of the quaternary ammonium salt detergent to the Mannich base detergent mixture is in the range of about 1:10 to about 1:100.

[0006] According to the present invention, a method for improving engine performance and / or injector performance in a direct injection engine is also provided, the method comprising supplying the engine an unleaded gasoline fuel composition comprising a major amount of a gasoline base fuel and a detergent additive package, wherein the detergent additive package comprises a mixture of a quaternary ammonium salt detergent and a Mannich base detergent, wherein the quaternary ammonium salt is obtained from an amine or polyamine substantially free of any free anionic substances, and wherein the Mannich base detergent mixture comprises a first Mannich base detergent component derived from a diamine or polyamine and a second Mannich base detergent component derived from a monoamine, wherein the weight ratio of the first Mannich base detergent to the second Mannich base detergent mixture is in the range of about 1:6 to about 3:1, and wherein the weight ratio of the quaternary ammonium salt detergent to the Mannich base detergent mixture is in the range of about 1:10 to about 1:100.

[0007] The preceding method or use may include optional steps, features, or any combination thereof. The method or implementation of the method or use may include one or more of the following: wherein the improved injector performance is one of improved fuel flow rate, improved fuel economy, improved engine efficiency, or a combination thereof; and / or wherein the improved injector performance is measured by one of injector pulse width, injection duration, injector flow rate, or a combination thereof. Attached Figure Description

[0008] Figure 1 This is a diagram illustrating the Long-Term Fuel Compensation (LTFT) of embodiments of the present invention and Comparative Examples 1 and 2. Detailed Implementation

[0009] The unleaded gasoline fuel compositions of the present invention comprise Mannich detergents and quaternary ammonium salts, and particularly combinations of Mannich detergents and hydrocarbon-substituted quaternary ammonium internal salts, have been found to effectively provide improved engine and / or injector performance in gas direct injection (GDI) engines. Methods for using or burning fuels containing the fuel additive combinations described herein to achieve improved engine and / or injector performance are also provided herein.

[0010] The inventors have discovered that the unleaded gasoline fuel composition of the present invention provides improved engine and / or injector performance, including control or reduction of fuel injector deposits. Improved injector performance can also result in improved fuel flow, improved fuel economy, and / or improved engine efficiency, as determined by one or more of injector pulse width, injection duration, and / or injector flow rate.

[0011] In one aspect of the invention, the unleaded gasoline fuel composition comprises a gasoline base fuel and a detergent additive package. The detergent additive package is typically used at a concentration of 6 PTB (23 ppmw) to 528 PTB (2000 ppmw), preferably 8 PTB (30 ppmw) to 300 PTB (1125 ppmw), and more preferably 30 PTB (113 ppmw) to 250 PTB (942 ppmw) (where PTB represents pounds of additive per thousand barrels of gasoline).

[0012] The cleaning additive package used herein comprises a Mannich base cleaning agent mixture containing a mixture of a quaternary ammonium salt cleaning agent and a Mannich base cleaning agent, wherein the quaternary ammonium salt is obtained from an amine or polyamine that is substantially free of any free anionic substances, and wherein the Mannich base cleaning agent mixture comprises a first Mannich base cleaning agent component derived from a diamine or polyamine and a second Mannich base cleaning agent component derived from a monoamine, wherein the weight ratio of the first Mannich base cleaning agent to the second Mannich base cleaning agent mixture is in the range of about 1:6 to about 3:1, preferably about 1:4 to about 2:1, more preferably about 1:2 to about 2:1, for example 1:1, and wherein the weight ratio of the quaternary ammonium salt cleaning agent to the Mannich base cleaning agent mixture is in the range of about 1:10 to about 1:100, preferably about 1:20 to about 1:50, more preferably about 1:25 to about 1:35, for example about 1:25, about 1:30 or about 1:35. Suitable Mannich base cleaning agent mixtures used herein are disclosed in US2016 / 0289584. The package may also contain solvents. Examples of suitable solvents include aromatic solvents (e.g., xylene, Aromatic 100, Aromatic 150, and Aromatic 200), alkane solvents, alcohols, petroleum distillates (e.g., gasoline), esters, or mixtures thereof. The package may also contain one or more of demulsifiers, corrosion inhibitors, anti-wear additives, antioxidants, metal passivators, antistatic additives, anti-fogging agents, antiknock additives, lubricating additives, and / or combustion improvers. In one aspect, the quaternary ammonium salt cleaner and the Mannich base cleaning agent mixture together constitute 5%–90% of the package.

[0013] In one embodiment of this document, a suitable fuel additive package comprises (i) a Mannich base cleaner mixture comprising (a) a first Mannich base cleaner component derived from a diamine or polyamine, (b) a second Mannich base cleaner component derived from a monoamine; (ii) a quaternary ammonium salt; and (iii) an optional carrier fluid component selected from the group consisting of polyether monohydric alcohols and polyether polyhydric alcohols. The weight ratio of the first Mannich base cleaner to the second Mannich base cleaner in the fuel additive package is in the range of about 1:6 to about 3:1, such as about 1:4 to about 2:1, or about 1:3 to about 1:1. The weight ratio of the Mannich base cleaner mixture to the quaternary ammonium salt in the cleaner additive package is in the range of about 1:10 to about 1:100, preferably about 1:20 to about 1:50, more preferably about 1:25 to about 1:35, for example, in the range of about 1:25, about 1:30, or about 1:35.

[0014] In another aspect of the invention, the gasoline fuel composition comprises a combination of Mannich base detergent additives and quaternary ammonium internal salt detergents, rather than a detergent additive package. In this aspect of the invention, the Mannich base detergent additive is added to the gasoline base fuel by premixing the individual detergent additives together, optionally with one or more anti-wear additives and / or one or more succinimidyl detergents and / or one or more carrier fluids, and then adding the premix to the gasoline base fuel; or by adding the individual detergent additives and the individual anti-wear additives and carrier fluids directly to the gasoline base fuel.

[0015] Mannich Alkali Cleaner:

[0016] The Mannich base cleaners applicable to this invention are reaction products of alkyl-substituted hydroxy aromatic compounds, aldehydes, and amines. The alkyl-substituted hydroxy aromatic compounds, aldehydes, and amines used to prepare the reaction products of the Mannich cleaners described herein can be any such compounds known and used in the art, provided that the Mannich-based cleaner comprises at least one first Mannich base cleaner derived from a diamine or polyamine and at least one second Mannich base cleaner derived from a dialkyl monoamine.

[0017] Representative alkyl-substituted hydroxy aromatic compounds that can be used to form Mannich base reaction products are polypropylene / cresol (formed by alkylation of phenol / cresol with polypropylene), polybutylphenol or polybutylphenol (formed by alkylation of phenol / cresol with polybutene and / or polyisobutylene), and polybutyl-co-polypropylene / cresol (formed by alkylation of phenol / cresol with butene and / or copolymers of butene and propylene). Other similar long-chain alkylphenols may also be used. Examples include phenol / cresol alkylated with copolymers of butene and / or isobutylene and / or propylene, and one or more monoolefin comonomers (e.g., ethylene, 1-pentene, 1-hexene, 1-octene, 1-decene, etc.) that can be copolymerized therewith, wherein the copolymer molecule contains at least 50% by weight of butene and / or isobutylene and / or propylene units. The comonomers polymerized with propylene, butene, and / or isobutene may be aliphatic and may also contain non-aliphatic groups, such as styrene, o-methylstyrene, p-methylstyrene, divinylbenzene, etc. Therefore, in any case, the resulting polymers and copolymers used to form alkyl-substituted hydroxy aromatic compounds are essentially aliphatic hydrocarbon polymers. In one embodiment herein, polybutylphenol or polybutylcresol (formed by alkylating phenol / cresol with polybutene) is used to form Mannich base cleaners. Unless otherwise stated herein, the term "polybutene" is used in a general sense to include polymers made from "pure" or "substantially pure" 1-butene or isobutene, as well as polymers made from mixtures of two or all of 1-butene, 2-butene, and isobutene. Commercial grades of such polymers may also contain small amounts of other olefins. So-called highly reactive polybutenes, formed by methods such as those described, for example, in U.S. Patent 4,152,499 and German Publication 2,904,314, having a relatively high proportion of terminal vinylidene polymer molecules, are also suitable for forming long-chain alkylated phenol / cresol reactants.

[0018] Alkylation of hydroxy aromatic compounds is typically carried out in the presence of an alkylation catalyst at temperatures ranging from about 50°C to about 200°C. Acidic catalysts are commonly used to facilitate Friedel-Crafts alkylation. Typical catalysts used in commercial production include sulfuric acid, BF3, aluminum phenolate, methanesulfonic acid, cation exchange resins, acidic clays, and modified zeolites.

[0019] The long-chain alkyl substituents on the benzene ring of the phenolic compound are derived from polyolefins with a number-average molecular weight (MW) of about 500 Daltons to about 3000 Daltons (preferably about 500 Daltons to about 2100 Daltons), as determined by gel permeation chromatography (GPC). It is also desirable that the polydispersity (weight-average molecular weight / number-average molecular weight) of the polyolefin used, as determined by GPC, is in the range of about 1 to about 4 (suitably about 1 to about 2).

[0020] Mannich cleaners can be prepared from long-chain alkylphenols or long-chain alkylcresols. However, other phenolic compounds, including high molecular weight alkyl-substituted derivatives of resorcinol, hydroquinone, catechol, hydroxydiphenyl, benzylphenol, phenethylphenol, naphthol, tolylnaphthol, etc., can be used. Polyalkylphenol and polyalkylcresol reactants, such as polypropylphenol, polybutylphenol, polypropylcresol, polyisobutylcresol, and polybutylcresol, are particularly suitable for preparing Mannich condensation products, wherein the number average molecular weight of the alkyl group is from about 500 to about 2100, and the most suitable alkyl group is the polybutyl group derived from polybutene with a number average molecular weight in the range of about 800 Daltons to about 1300 Daltons.

[0021] The alkyl-substituted hydroxy aromatic compounds have a para-substituted monoalkylphenol or para-substituted monoalkyl o-cresol configuration. However, any alkylphenol that readily reacts in the Mannich condensation reaction can be used. Therefore, Mannich products prepared from alkylphenols having only one cycloalkyl substituent or two or more cycloalkyl substituents are suitable for preparing the Mannich base cleaners described herein. Long-chain alkyl substituents may contain some residual unsaturated groups, but are generally substantially saturated alkyl groups. Long-chain alkylphenols according to this disclosure include cresols. Representative reactants include, but are not limited to, straight-chain, branched, or cyclic alkylene monoamines and diamines or polyamines having at least one suitably reactive primary or secondary amino group in the molecule. Other substituents, such as hydroxyl, cyano, amide, etc., may be present in the amine compound. In one embodiment, the first Mannich base cleaner is derived from an alkylene diamine or polyamine. Such diamines or polyamines may include, but are not limited to, polyethylene polyamines, such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexethyleneheptamine, heptaethyleneoctamine, heptaethylenenonamine, octaethylenenonamine, nonaethylenedecamine, decaethyleneundecamine, and having the formula H2N-(A-NH--). n H is a mixture of amines of this type with a nitrogen content of alkylene polyamine, wherein A is a divalent ethylene and n is an integer from 1 to 10. Alkylene polyamines can be obtained by reacting ammonia with dihaloalkanes, such as dichloroalkanes. Therefore, alkylene polyamines obtained by reacting 2 to 11 moles of ammonia with 1 to 10 moles of dichloroalkanes having 2 to 6 carbon atoms and chlorine at different carbon atoms are suitable alkylene polyamine reactants.

[0022] In one embodiment, the first Mannich base cleaner is derived from an aliphatic straight-chain, branched, or cyclic diamine or polyamine having a primary or secondary amino group and a tertiary amino group in the molecule. Examples of suitable polyamines include N,N,N",N"-tetraalkyldialkylenetriamine (two terminal tertiary amino groups and one central secondary amino group), N,N,N",N"-tetraalkyltrialkyltetraamine (one terminal tertiary amino group, two internal tertiary amino groups and one terminal primary amino group), N,N,N,N",N"-pentaalkyltrialkyltetraamine (one terminal tertiary amino group, two internal tertiary amino groups and one terminal secondary amino group), N,N-dihydroxyalkyl-α,ω-alkylenediamine (one terminal tertiary amino group and one terminal primary amino group), N,N,N'-trihydroxyalkyl-α,ω-alkylenediamine (one terminal tertiary amino group and one terminal secondary amino group), tris(dialkylaminoalkyl)aminoalkylmethane (three terminal tertiary amino groups and one terminal primary amino group), and similar compounds, wherein the alkyl groups are the same or different, and generally each contains no more than about 12 carbon atoms, and suitably each contains 1 to 4 carbon atoms. In one embodiment, the alkyl group of the polyamine is a methyl and / or ethyl group. Therefore, the polyamine reactants can be selected from N,N-dialkylα,ω-alkylene diamines, such as those having 3 to about 6 carbon atoms in the alkylene groups and 1 to about 12 carbon atoms in each alkyl group. Particularly useful polyamines are N,N-dimethyl-1,3-propanediamine and N-methylpiperazine.

[0023] Examples of polyamines having a reactive primary or secondary amino group that can participate in the Mannich condensation reaction and at least one sterically hindered amino group that cannot directly participate in the Mannich condensation reaction to any significant extent include N-(tert-butyl)-1,3-propanediamine, N-neopentyl-1,3-propanediamine, N-(tert-butyl)-1-methyl-1,2-ethylenediamine, N-(tert-butyl)-1-methyl-1,3-propanediamine, and 3,5-di(tert-butyl)aminoethyl-1-piperazine.

[0024] Second Mannich base cleaners can be derived from alkyl monoamines, including but not limited to dialkyl monoamines such as methylamine, dimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, dipropylamine, diisopropylamine, butylamine, isobutylamine, dibutylamine, diisobutylamine, pentanamine, dipentanamine, neopentanamine, dinepentanamine, hexylamine, dihexylamine, heptamine, diheptamine, octylamine, dioctylamine, 2-ethylhexylamine, di-2-ethylhexylamine, nonylamine, dinonylamine, decylamine, didecylamine, dicyclohexylamine, etc.

[0025] Representative aldehydes used to prepare Mannich base products include aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, pentanal, hexanal, heptanal, and stearaldehyde. Aromatic aldehydes that can be used include benzaldehyde and salicylaldehyde. Illustrative heterocyclic aldehydes used in this invention include furfural and thiophene aldehyde. Formaldehyde-producing reagents, such as paraformaldehyde, or aqueous solutions of formaldehyde, such as formalin, can also be used. Particularly suitable aldehydes may be selected from formaldehyde and formalin.

[0026] The condensation reaction between alkylphenols, specific amines, and aldehydes can be carried out at temperatures ranging from about 40°C to about 200°C. The reaction can be carried out in bulk (without diluent or solvent) or in solvent or diluent. Water escapes and can be removed during the reaction by azeotropic distillation. Typically, the Mannich reaction products are formed by reacting an alkyl-substituted hydroxyl aromatic compound, an amine, and an aldehyde in a molar ratio of 1.0:0.5–2.0:1.0–3.0, respectively.

[0027] Suitable Mannich base cleaners for use in the disclosed embodiments include those cleaners taught in U.S. Patents 4,231,759, 5,514,190, 5,634,951, 5,697,988, 5,876,468, 6,800,103, and 10,457,884, the disclosure of which is incorporated herein by reference.

[0028] When formulating the fuel compositions used herein, a mixture of Mannich base cleaners is used. The mixture of Mannich base cleaners comprises a first Mannich base cleaner and a second Mannich base cleaner in a weight ratio of about 1:6 to about 3:1. In another embodiment, the mixture of Mannich base cleaners comprises a first Mannich base cleaner and a second Mannich base cleaner in a weight ratio of about 1:4 to about 2:1, such as about 1:3 to about 1:1. The total amount of Mannich base cleaner in the gasoline fuel compositions according to this disclosure can range from about 10 ppmw to about 400 ppmw based on the total weight of the fuel composition.

[0029] An optional component of the fuel compositions and / or additive packages described herein is a succinimide cleaner. Succinimide cleaners suitable for use in various embodiments of this disclosure, when added in an amount effective for the stated purpose, can impart a dispersant effect to the fuel composition. Compared to the performance of succinimide together with a first Mannich base cleaner or a second Mannich base cleaner, the presence of succinimide in the fuel composition with a mixture of Mannich base cleaners has been observed to result in enhanced deposit formation control.

[0030] Succinimide cleaners include, for example, alkenyl succinimides, which comprise reaction products obtained by reacting an alkenyl succinic anhydride, acid, acid-ester, or lower alkyl ester with an amine containing at least one primary amine group.

[0031] Suitable succinimide base cleaners used herein include those disclosed in US2016 / 0289584, which is incorporated herein by reference.

[0032] When the succinimide cleaner is present in the fuel composition / additive package described herein, the weight ratio of the succinimide cleaner to the Mannich base cleaner mixture is preferably in the range of about 0.04:1 to about 0.2:1.

[0033] In another embodiment, the Mannich base cleaning agent mixture and succinimide cleaning agent can be used with a liquid carrier or inducing agent. Such carriers can be of various types, such as liquid poly-α-olefin oligomers, mineral oils, liquid poly(oxyalkylene) compounds, liquid alcohols or polyols, polyolefins, liquid esters, and similar liquid carriers. Mixtures of two or more such carriers can be used. Suitable carrier fluids used herein include those disclosed in US2016 / 0289584, which is incorporated herein by reference.

[0034] When a carrier fluid is present, the weight ratio of the carrier fluid to the Mannich base cleaning agent mixture is preferably in the range of about 0.25:1 to about 1:1.

[0035] The fuel composition and / or detergent additive packages described herein may also contain anti-wear components, optionally selected from hydrocarbon amides and hydrocarbon imides.

[0036] In one embodiment, the hydrocarbon amide is an alkanolamide derived from diethanolamine and oleic acid. In another embodiment, the hydrocarbon imide is a succinimide derived from polyisobutylene succinic anhydride and ammonia. In one embodiment, the hydrocarbon amide compound may be one or more fatty acid alkanolamide compounds.

[0037] Suitable anti-wear additives used herein include those disclosed in US2016 / 0289584, which is incorporated herein by reference.

[0038] Quaternary ammonium inner salt

[0039] The cleaning additive packages or fuel compositions described herein comprise quaternary ammonium salts, and preferably quaternary ammonium inner salts or betaine compounds. As used herein, the term "inner salt" means a molecule containing equal numbers of positively and negatively charged functional groups. The term "inner salt" may be used interchangeably with the term "zwitterion." As used herein, the term betaine is a zwitterion that cannot isomerize to a completely neutral form, such as when the positive change is located on the quaternary ammonium group. Quaternary ammonium salt additives can be any hydrocarbon-substituted quaternary ammonium inner salt (or betaine) obtained from amines or polyamines that are substantially free of any free anionic substances. For example, such additives can be made by making tertiary amines having the following structure

[0040]

[0041] Each R group in the above structure is independently selected from a hydrocarbon group containing 1 to 200 carbon atoms, and is prepared by reacting with a halogen-substituted C2-C8 carboxylic acid, ester, amide, or a salt thereof. Quaternizing agents, typically avoided in the method, are selected from the group consisting of hydrocarbon-substituted carboxylic acid esters, carbonates, cyclic carbonates, phenolic esters, epoxides, or mixtures thereof. In one embodiment, the halogen-substituted C2-C8 carboxylic acid, ester, amide, or a salt thereof may be selected from chloro-, bromo-, fluorine-, and iodine-C2-C8 carboxylic acids, esters, amides, and their salts. The salt may be an alkali metal or alkaline earth metal salt selected from sodium, potassium, lithium, calcium, and magnesium salts. Particularly useful halogen-substituted compounds for the reaction are sodium or potassium salts of chloroacetic acid.

[0042] As used herein, the term "substantially free of free anions" means that the anions are mostly covalently bound to the product, such that the prepared reaction product does not contain any significant amount of free anions or anions bound to the product ions. In one embodiment, "substantially free" means the range of 0% by weight to less than about 2% by weight, less than about 1.5% by weight, less than about 1% by weight, less than about 0.5% by weight, or none.

[0043] In another embodiment, tertiary amines, including monoamines and polyamines, can react with halogen-substituted acetic acid, esters, or other derivatives thereof to provide the quaternary ammonium inner salt additive described herein. Suitable tertiary amine compounds are those having the structures described above, wherein, as mentioned above, each R group is independently selected from hydrocarbon groups containing 1 to 200 carbon atoms. Each hydrocarbon group R can be independently linear, branched, substituted, cyclic, saturated, unsaturated, or containing one or more heteroatoms. Suitable hydrocarbon groups can include, but are not limited to, alkyl, aryl, alkylaryl, aralkyl, alkoxy, aryloxy, amide, ester, imino, and similar groups. Any of the aforementioned hydrocarbon groups may also contain heteroatoms, such as oxygen or nitrogen atoms. Particularly suitable hydrocarbon groups can be linear or branched alkyl groups. In some embodiments, the tertiary amine can be the product of the reaction of a diamine or triamine with a tertiary amine and a hydrocarbon-substituted carboxylic acid. In other embodiments, some representative examples of amine reactants that can react to produce compounds of the present disclosure include, but are not limited to, trimethylamine, triethylamine, tri-n-propylamine, dimethylethylamine, dimethyllauroamine, dimethyloleylamine, dimethylstearamide, dimethyleicosylamine, dimethyloctadecylamine, N,N-dimethylpropanediamine, N-methylpiperidine, N,N'-dimethylpiperazine, N-methyl-N-ethylpiperazine, N-methylmorpholine, N-ethylmorpholine, N-hydroxyethylmorpholine, pyridine, triethanolamine, triisopropanolamine, methyldiethanolamine, dimethylethanolamine, lauryl diisopropanolamine, stearoyl diethanolamine, and others. Dioleoethanolamine, dimethylisobutanolamine, methyldiisooctanolamine, dimethylpropenylamine, dimethylbutenylamine, dimethyloctenylamine, ethyleicosenoenylamine, dibutyleicosenoenylamine, triethylenediamine, hexamethyltetramine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl-propanediamine, N,N,N',N'-tetraethyl-1,3-propanediamine, methyldicyclohexylamine, 2,6-dimethylpyridine, dimethylcyclohexylamine, C10-C30 alkyl or alkenyl-substituted amide-propyl dimethylamine, C12-C200 alkyl or alkenyl-substituted succinic acid-carbonyl-dimethylamine, etc. In embodiments, a suitable quaternary ammonium inner salt additive may be an inner salt of oleamide-propyl dimethylamino or oleodimethylamine.

[0044] If the amine contains only a primary or secondary amino group, it may be necessary to alkylate at least one of the primary or secondary amino groups to a tertiary amino group before reacting with a halogen-substituted C2-C8 carboxylic acid, ester, amide, or salt thereof. In one embodiment, the alkylation of a primary amine and a secondary amine, or a mixture of both, may be fully or partially alkylated to a tertiary amine. It may also be necessary to take into account the hydrogen on the nitrogen and provide a base or acid as needed (e.g., alkylation until the tertiary amine requires the removal (neutralization) of hydrogen (protons) from the alkylation product). If an alkylating agent, such as an alkyl halide or a dialkyl sulfate, is used, the alkylation product of the primary or secondary amine is a protonated salt, and a base source is required to release the amine for further reactions.

[0045] Halogenated C2-C8 carboxylic acids, esters, amides, or salts thereof used to prepare quaternary salt additives may be derived from mono-, di-, or trichloro-, bromo-, fluoro-, or iodo-carboxylic acids, esters, amides, or salts thereof selected from the group consisting of: halogenated acetic acid, propionic acid, butyric acid, isopropionic acid, isobutyric acid, tert-butyric acid, valeric acid, heptanoic acid, octanoic acid, halomethylbenzoic acid and its isomers, esters, amides, and salts. Carboxylic acid salts may include alkali metal salts or alkaline earth metal salts or ammonium salts, including but not limited to Na, Li, K, Ca, Mg, triethylammonium, and triethanolamine salts of halogenated carboxylic acids. Particularly suitable halogenated carboxylic acids, esters, or salts thereof may be selected from chloroacetic acid or its esters and sodium or potassium chloroacetate. The amount of halogenated C2-C8 carboxylic acids, esters, amides, or salts thereof relative to the amount of tertiary amine reactant may be in a molar ratio ranging from about 1:0.1 to about 0.1:1.0.

[0046] In other embodiments, the inner salt of the mixture herein may be prepared according to the foregoing procedure and may include, but is not limited to, (1) a hydrocarbon-substituted compound of formula R"-NMe2CH2COO, wherein R" is a C1 to C30 or a substituted amide group; (2) a fatty amide-substituted inner salt; and (3) a hydrocarbon-substituted imide, amide, or ester inner salt, wherein the hydrocarbon group has 8 to 40 carbon atoms. Particularly suitable inner salts may be selected from the group consisting of: polyisobutylene-substituted succinimide, succinamide, and succinate diester inner salts; C8-C40 alkenyl-substituted succinimide, succinamide, and succinate diester inner salts; oleamide-propyl dimethylamino inner salts; and oleyl dimethylamino inner salts.

[0047] In another embodiment, the fuel additive and the quaternary ammonium inner salt of the fuel described herein are inner salts or betaine compounds having the structure of Formula II:

[0048]

[0049] In the above structure, R and R' are independently alkylene linkages having 1 to 10 carbon atoms (1 to 3 carbon atoms in other methods); R8 is a saturated alkylene, unsaturated olefin, or a straight-chain, branched, or cyclic hydrocarbon group or an optionally substituted or unsubstituted C12-C100 hydrocarbon group, or an aryl group or an optionally substituted aryl group (in one method, R8 is a C8-C20 hydrocarbon group); each R9 is independently a straight-chain or branched C1 to C4 alkyl group; and R 10 It consists of hydrogen atoms or C1 to C4 alkyl groups. As discussed above, the inner salt of Formula II may also be substantially free of free anions.

[0050] In another embodiment, the quaternary ammonium salt additive comprises a compound of formula II above, wherein R is a propylene linkage group, R' is a methylene linkage group, R8 is a C8 to C20 hydrocarbon group, each R9 is a methyl group, and R 10 The form is hydrogen. In other embodiments, the quaternary ammonium salt inner salt is selected from oleamide-propyl dimethylamine inner salt or oleo-dimethylamino inner salt. In some embodiments, such additives may be substantially free of the free anionic substances described above.

[0051] An exemplary reaction scheme for preparing the quaternary ammonium inner salt is shown in the exemplary process of reaction scheme I below: Of course, other methods for preparing the first quaternary ammonium salt additive described herein can also be used:

[0052]

[0053] In the above reaction scheme, R8 can be, as described above, or in one method, an alkyl group, such as a C12-C100 hydrocarbon group; R and R' are independently alkylene linkages having 1 to 10 carbon atoms; each R9 is independently an alkyl group or a straight-chain or branched C1 to C4 group; and R”' is an alkyl group or hydrogen.

[0054] The fuel additive package described herein may contain about 1% to about 15% by weight of a quaternary ammonium salt, about 1% to about 10% by weight of a quaternary ammonium salt, or about 1.5% to about 5% by weight of a quaternary ammonium salt (based on the total active weight of the quaternary ammonium salt in the fuel additive). When blended into gasoline fuel, the fuel composition may contain about 0.1 ppmw to about 10 ppmw of an active quaternary ammonium salt, about 0.3 ppmw to about 5 ppmw, or about 1 ppmw to about 3 ppmw of an active quaternary ammonium salt by weight of the fuel composition.

[0055] fuel:

[0056] The fuel compositions described herein contain a principal amount of base fuel. As used herein, the term 'principal amount' in relation to base fuel preferably means a level greater than 50% v / v, more preferably greater than 60% v / v, even more preferably greater than 70% v / v, and especially greater than 80% v / v. In a preferred embodiment herein, the 'principal amount' of base fuel means a level greater than 90% v / v, more preferably greater than 95% v / v, and even more preferably greater than 98% v / v based on the total fuel composition. If the liquid fuel composition of the present invention contains gasoline base fuel, then the liquid fuel composition is a gasoline fuel composition. Gasoline can be any gasoline suitable for spark-ignition (gasoline) type internal combustion engines known in the art, including automobile engines and other types of engines, such as off-road engines and aircraft engines. The gasoline used as base fuel in the liquid fuel compositions of the present invention may also be conveniently referred to as 'base gasoline'.

[0057] Gasoline typically contains a mixture of hydrocarbons with boiling points ranging from 25°C to 230°C (EN-ISO 3405). The optimal range and distillation profile generally vary depending on the climate and season throughout the year. The hydrocarbons in gasoline can be obtained by any means known in the art. Conveniently, the hydrocarbons can be derived in any known manner from straight-run gasoline, synthetically produced aromatic hydrocarbon mixtures, thermally or catalytically cracked hydrocarbons, hydrocracked petroleum fractions, catalytically reformed hydrocarbons, or mixtures thereof.

[0058] The specific distillation profile, hydrocarbon composition, research octane number (RON), and motor octane number (MON) of gasoline are not crucial.

[0059] Conveniently, the research octane number (RON) of gasoline can be at least 80, for example, in the range of 80 to 110. Preferably, the RON of gasoline will be at least 90, for example, in the range of 90 to 110. More preferably, the RON of gasoline will be at least 91, for example, in the range of 91 to 105. Even more preferably, the RON of gasoline will be at least 92, for example, in the range of 92 to 103. Even more preferably, the RON of gasoline will be at least 93, for example, in the range of 93 to 102. And the most preferred gasoline will have an RON of at least 94, for example, in the range of 94 to 100 (EN 25164). The motor octane number (MON) of gasoline can conveniently be at least 70, for example, in the range of 70 to 110. Preferably, the MON of gasoline will be at least 75, for example, in the range of 75 to 105. More preferably, the MON of gasoline will be at least 80, for example, in the range of 80 to 100. The most preferred gasoline will have a MON of at least 82, for example, in the range of 82 to 95 (EN25163).

[0060] Typically, gasoline contains components selected from one or more of the following groups: saturated hydrocarbons, alkenes, aromatic hydrocarbons, and oxygenated hydrocarbons. Conveniently, gasoline may contain a mixture of saturated hydrocarbons, alkenes, aromatic hydrocarbons, and optionally oxygenated hydrocarbons.

[0061] Typically, the olefin content of gasoline is based on gasoline in the range of 0% to 40% by volume (ASTM D1319); preferably, the olefin content of gasoline is based on gasoline in the range of 0% to 30% by volume, and more preferably, the olefin content of gasoline is based on gasoline in the range of 0% to 20% by volume.

[0062] Typically, the aromatic hydrocarbon content of gasoline is based on gasoline in the range of 0% to 70% by volume (ASTM D1319), for example, the aromatic hydrocarbon content of gasoline is based on gasoline in the range of 10% to 60% by volume; preferably, the aromatic hydrocarbon content of gasoline is based on gasoline in the range of 0% to 50% by volume, for example, the aromatic hydrocarbon content of said gasoline is based on gasoline in the range of 10% to 50% by volume.

[0063] The benzene content of gasoline is based on gasoline being at most 10% by volume, more preferably at most 5% by volume, and especially at most 1% by volume.

[10055] Gasoline preferably has a low or very low sulfur content, for example at most 1000 ppmw (parts per million by weight), preferably not more than 500 ppmw, more preferably not more than 100 ppmw, even more preferably not more than 50 ppmw, and most preferably not more than 10 ppmw.

[0064] Gasoline is also preferably low in total lead, such as at most 0.005 g / l, and most preferably lead-free – without the addition of lead compounds (i.e., lead-free).

[0065] When gasoline contains oxygenated hydrocarbons, at least a portion of the non-oxygenated hydrocarbons are replaced by oxygenated hydrocarbons. The oxygen content of gasoline can be up to 35% by weight (EN 1601) (e.g., ethanol itself). For example, the oxygen content of gasoline can be up to 25% by weight, preferably up to 10% by weight. Conveniently, the concentration of oxygenated compounds will have a minimum concentration selected from any one of 0% by weight, 0.2% by weight, 0.4% by weight, 0.6% by weight, 0.8% by weight, 1.0% by weight, and 1.2% by weight, and a maximum concentration selected from any one of 5% by weight, 4.5% by weight, 4.0% by weight, 3.5% by weight, 3.0% by weight, and 2.7% by weight.

[0066] Examples of oxygenated hydrocarbons that can be blended into gasoline include alcohols, ethers, esters, ketones, aldehydes, carboxylic acids and their derivatives, as well as oxygenated heterocyclic compounds. Preferably, the oxygenated hydrocarbons that can be blended into gasoline are selected from alcohols (such as methanol, ethanol, propanol, 2-propanol, butanol, tert-butanol, isobutanol and 2-butanol), ethers (preferably ethers containing 5 or more carbon atoms per molecule, such as methyl tert-butyl ether and ethyl tert-butyl ether), and esters (preferably esters containing 5 or more carbon atoms per molecule); a particularly preferred oxygenated hydrocarbon is ethanol.

[0067] When oxygenated hydrocarbons are present in gasoline, the amount of oxygenated hydrocarbons in the gasoline can vary within a wide range. For example, gasolines containing a major proportion of oxygenated hydrocarbons are currently commercially available in countries such as Brazil and the United States, such as ethanol itself and E85, as well as gasolines containing a minor proportion of oxygenated hydrocarbons, such as E10 and E5. Thus, gasoline can contain up to 100% by volume of oxygenated hydrocarbons. This document also includes E100 fuel used in Brazil. Preferably, the amount of oxygenated hydrocarbons present in gasoline is selected from the following amounts: up to 85% by volume; up to 70% by volume; up to 65% by volume; up to 30% by volume; up to 20% by volume; up to 15% by volume; and up to 10% by volume, depending on the desired final gasoline formulation. Conveniently, gasoline can contain at least 0.5% by volume, 1.0% by volume, or 2.0% by volume of oxygenated hydrocarbons.

[0068] Examples of suitable gasoline include gasoline with an olefin content of 0% to 20% by volume (ASTM D1319), an oxygen content of 0% to 5% by weight (EN 1601), an aromatic hydrocarbon content of 0% to 50% by volume (ASTM D1319), and a benzene content of up to 1% by volume.

[0069] Also applicable here are gasoline blends that can be derived from biological sources. Examples of such gasoline blends can be found in WO2009 / 077606, WO2010 / 028206, WO2010 / 000761, European patent applications 09160983.4, 09176879.6, 09180904.6 and U.S. patent application serial number 61 / 312,307.

[0070] Although not critical to the present invention, the base gasoline or gasoline composition of the present invention may conveniently contain one or more optional fuel additives in addition to the essential Mannich and quaternary ammonium detergents described above. The concentration and properties of the optional fuel additives that may be included in the base gasoline or gasoline composition of the present invention are not critical. Non-limiting examples of suitable types of fuel additives that may be included in the base gasoline or gasoline composition of the present invention include antioxidants, corrosion inhibitors, anti-wear additives or surface modifiers, flame speed additives, detergents, anti-fogging agents, anti-knock additives, metal passivators, valve seat return protection compounds, dyes, solvents, carrier fluids, diluents, and markers. Examples of suitable such additives are generally described in U.S. Patent 5,855,629.

[0071] Conveniently, the fuel additive can be blended with one or more solvents to form an additive concentrate, which can then be mixed with the base gasoline or gasoline composition of the present invention.

[0072] The concentration of any optional additive (active substance) present in the base gasoline or gasoline composition of the present invention is preferably at most 1% by weight, more preferably in the range of 5 ppmw to 2000 ppmw, advantageously in the range of 300 ppmw to 1500 ppmw, such as 300 ppmw to 1000 ppmw.

[0073] Example

[0074] The following examples illustrate exemplary embodiments of this disclosure. In these examples and elsewhere in this application, all ratios, parts, and percentages are by weight unless otherwise indicated. These examples are intended to be presented for illustrative purposes only and are not intended to limit the scope of the invention disclosed herein. The specifications of the base fuels in the examples are shown in Table 1 below.

[0075] Table 1: Fuel Specifications.

[0076]

[0077] Example 1

[0078] Oleamidopropyl dimethylammonium betaine quaternary ammonium inner salt can be prepared by the method described in U.S. Patent 8,894,726 (Example 3 of the present invention), which is incorporated herein by reference.

[0079] Example 2

[0080] Two Mannich cleaners and a quaternary ammonium salt were blended into the base fuel described in Table 1 at the treatment rates listed in Table 2 below. The first Mannich cleaner was prepared from highly reactive polyisobutylene cresol, a diamine, and formaldehyde according to a known method (see, for example, US 6,800,103, which is incorporated herein by reference). The second Mannich cleaner was prepared using the same method but with a monoamine. The quaternary ammonium inner salt was oleamidopropyl dimethylammonium from Example 1.

[0081] Table 2

[0082]

[0083] A series of three contamination / cleaning (DU / CU) tests were conducted to evaluate the effects of the fuels in Table 2 on fuel injector deposits in vehicles equipped with gas direct injection (GDI) engines. All tests were performed using the base fuels from Table 1 during the contamination (DU) and cleaning (CU) phases of the respective tests. The fuels were tested to evaluate the ability of each type of additive, Mannich cleaner mixture, and quaternary ammonium salt to improve injector performance by reducing injector deposits in GDI engines, individually (Comparative Examples 1 and 2) and together (Examples of the present invention).

[0084] Base fuels were previously evaluated in bench engines to determine their tendency to foul or contaminate injectors. The fouling level can be indirectly measured using engine control management (ECM) algorithm parameters such as variations in injector pulse width or long-term fuel trim (LTFT). The test bench used for this evaluation was a direct injection GM LHU engine, conforming to the RIFT method described in Smith, S. and Imoehl, W., "Measurement and Control of Fuel Injector Deposits in Direct Injection Gasoline Vehicles," SAE Technical Paper 2013-01-2616, 2013, doi:10.4271 / 2013-01-2616 and / or Shanahan, C., Smith, S. and / or Sears, B., "A General Method for Fouling Injectors in Gasoline Direct Injection Vehicles and the Effects of Deposits on Vehicle Performance," SAE Int. J. Fuels Lubr. 10(3): 2017, doi:10.4271 / 2017-01-2298, which is incorporated herein by reference.

[0085] To accelerate the DU stage of the base fuel, a combination of di-tert-butyl disulfide (DTBDS 406.1 ppmw) and tert-butyl hydrogen peroxide (TBHP, 286 ppmw) is added to the base fuel to provide fouling in the range of 5%–12% during the time allocated to the DU stage. The percentage of fouling in the GM engine based on the injector pulse width is calculated as follows:

[0086]

[0087] A series of three GDI CU deposit tests were conducted to demonstrate the removal of deposits that had formed in the fuel injectors during the DU phase. The base fuels in Table 1, treated with DTBDS and TBHP, were used for the DU. The vehicle-based test procedure used a 2008 Pontiac Solstice car mounted on a chassis dynamometer. The procedure was first described in DuMont, R. et al., “Test and Control of Fuel Injector Deposits in Direct Injected Spark Ignition Vehicles,” SAE Technical Paper 2009-01-2641, 2009, doi:10.4271 / 2009-01-2641. It consisted of a 48-hour DU cycle with continuous monitoring of the LTFT to maintain a stoichiometric air / fuel ratio. After the DU cycle, the fuel was changed to one of the additive formulations described in Table 2, and then a 48-hour CU cycle was run. The percentage increase in LTFT during the DU cycle and the subsequent percentage decrease during the CU cycle are parameters used to evaluate the fouling or cleaning effect of fuel candidates at the treatment rates listed in Table 3 below, demonstrating a cleaning (CU) of 62% over 48 hours for the embodiments of the invention. CU is calculated according to the following equation:

[0088]

[0089] Table 3

[0090]

[0091] As shown in Table 3 above, the embodiments of the present invention exhibit improved injector cleaning compared to the comparative examples. In the combination of the first and second Mannich cleaners with a quaternary ammonium salt, the CU% is 62%, while the two Mannich cleaners alone provide 6.2% GDI CU and the quaternary ammonium salt provides 28.1%. Figure 1 This is a graphical representation of the data in Table 3. Figure 1The embodiments of the present invention, as well as Long-Term Fuel Compensation (LTFT) of Comparative Examples 1 and 2, are shown.

[0092] It should be noted that, unless explicitly and definitively limited to one indicator, the singular forms “a / an” and “the” as used in this specification and the appended claims include multiple indicators. Thus, for example, a reference to “antioxidant” includes two or more different antioxidants. The term “comprising” and its grammatical variations as used herein are intended to be non-limiting, such that the description of an item in the list does not exclude other similar items that may be substituted for or added to the listed items.

[0093] For the purposes of this specification and the appended claims, unless otherwise stated, all figures and other numerical values ​​used in the specification and claims to express quantities, percentages or proportions should be understood to be modified by the term "about" in all cases. Therefore, unless indicated to the contrary, the numerical parameters set forth in the following specification and the appended claims are approximations that may vary depending on the desired characteristics sought to be obtained through this disclosure. To a minimum, and without attempting to limit the application of the equivalence principle to the scope of the claims, each numerical parameter should be interpreted at least according to the number of significant figures reported and by applying general rounding techniques.

[0094] It should be understood that each component, compound, substituent or parameter disclosed herein should be interpreted as disclosed for use alone or in combination with one or more of each other component, compound, substituent or parameter disclosed herein.

[0095] It should also be understood that each range disclosed herein should be interpreted as a disclosure of each specific value within the disclosed range having the same significant digits. Thus, for example, the range 1 to 4 should be interpreted as an explicit disclosure of the values ​​1, 2, 3, and 4, and any range of such values.

[0096] It should also be understood that each lower limit of each range disclosed herein should be interpreted as a combination of each upper limit of each range and each specific value within each range disclosed herein for the same component, compound, substituent, or parameter. Therefore, this disclosure should be interpreted as the disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range or with each specific value within each range, or by combining each upper limit of each range with each specific value within each range. That is, it should also be understood that this document also discusses any range between endpoint values ​​within a wide range. Therefore, the range 1 to 4 also means the range 1 to 3, 1 to 2, 2 to 4, 2 to 3, etc.

[0097] Furthermore, the specific amounts / values ​​of components, compounds, substituents, or parameters disclosed in this specification or examples should be interpreted as disclosures of a lower or upper limit of a range, and therefore can be combined with any other lower or upper limit or specific amount / value of the range of the same components, compounds, substituents, or parameters disclosed elsewhere in this disclosure to form such a range of components, compounds, substituents, or parameters.

Claims

1. A gasoline fuel additive package, said gasoline fuel additive package comprising: (i) a mixture of quaternary ammonium salt cleaner and (ii) Mannich base cleaner. The quaternary ammonium internal salt is obtained from an amine that contains virtually no free anions. The Mannich base cleaning agent mixture comprises (a) a first Mannich base cleaning agent component derived from a polyamine and (b) a second Mannich base cleaning agent component derived from a monoamine. The weight ratio of the first Mannich base cleaning agent component to the second Mannich base cleaning agent component is in the range of 1:6 to 3:1, and The weight ratio of the mixture of the quaternary ammonium salt cleaner and the Mannich base cleaner is in the range of 1:20 to 1:

100.

2. The gasoline fuel additive package according to claim 1, wherein the quaternary ammonium internal salt is obtained from a polyamine that is substantially free of any free anionic substances.

3. The gasoline fuel additive package according to claim 1, wherein the first Mannich base cleaner component is derived from diamine.

4. The gasoline fuel additive package according to claim 1, wherein the weight ratio of the first Mannich base cleaner component to the second Mannich base cleaner component is in the range of 1:1 to 1:

3.

5. The gasoline fuel additive package of claim 1, wherein the first Mannich base cleaner component and the second Mannich base cleaner component are derived from polyisobutylene-substituted hydroxy aromatics, and wherein the polyisobutylene group has a molecular weight in the range of 500 Daltons to 1000 Daltons as determined by gel permeation chromatography.

6. The gasoline fuel additive package according to claim 5, wherein the polyisobutylene-substituted hydroxy aromatic is a polyisobutylene-substituted phenol or cresol.

7. The gasoline fuel additive package according to claim 6, wherein the polyisobutylene-substituted hydroxy aromatic is a polyisobutylene-substituted cresol.

8. The gasoline fuel additive package according to claim 1, wherein the quaternary ammonium internal salt has the structure of Formula II. Wherein R and R' are independently alkylene linkages having 1 to 10 carbon atoms; R8 is a C12 to C100 hydrocarbon group; each R9 is independently a straight-chain or branched C1 to C4 alkyl group; and R 10 It consists of a hydrogen atom or a C1 to C4 alkyl group.

9. The gasoline fuel additive package according to claim 8, wherein R8 is a C12 to C100 alkyl, alkenyl, aryl group or optionally substituted aryl group.

10. The gasoline fuel additive package according to claim 7, wherein the quaternary ammonium internal salt has the structure of Formula II. Wherein R and R' are independently alkylene linkages having 1 to 10 carbon atoms; R8 is a C12 to C100 hydrocarbon group; each R9 is independently a straight-chain or branched C1 to C4 alkyl group; and R 10 It consists of a hydrogen atom or a C1 to C4 alkyl group.

11. The gasoline fuel additive package according to claim 10, wherein R8 is a C12 to C100 alkyl, alkenyl, aryl group or optionally substituted aryl group.

12. The gasoline fuel additive package according to claim 1, wherein the gasoline fuel additive package further comprises a solvent, and the quaternary ammonium salt cleaner (i) and the Mannich base cleaner mixture (ii) comprise 5% to 90% by weight of the gasoline fuel additive package.

13. The gasoline fuel additive package according to claim 10, wherein the gasoline fuel additive package further comprises a solvent, and the quaternary ammonium salt cleaner (i) and the Mannich base cleaner mixture (ii) constitute 5% to 90% by weight of the gasoline fuel additive package.

14. The gasoline fuel additive package according to claim 1, wherein the gasoline fuel additive package further comprises one or more of a demulsifier, a corrosion inhibitor, an antioxidant, a metal passivator, an antistatic additive, a defogging agent, an antiknock additive, a lubricating additive, and a combustion improver.

15. The gasoline fuel additive package according to claim 10, wherein the gasoline fuel additive package further comprises one or more of a demulsifier, a corrosion inhibitor, an antioxidant, a metal passivator, an antistatic additive, a defogging agent, an antiknock additive, a lubricating additive, a polyether monohydric alcohol or a polyether polyhydric alcohol carrier fluid, and a combustion improver.

16. The gasoline fuel additive package according to claim 15, wherein the gasoline fuel additive package further comprises a solvent, and the quaternary ammonium salt cleaner (i) and the Mannich base cleaner mixture (ii) constitute 5% to 90% by weight of the gasoline fuel additive package.

17. The gasoline fuel additive package of claim 1, wherein the first Mannich base cleaner component is derived from N,N-dimethyl-1,3-propanediamine, and the second Mannich base cleaner component is derived from dialkyl monoamine.

18. The gasoline fuel additive package of claim 1, wherein the gasoline fuel additive package further comprises a polyether monohydric alcohol or a polyether polyhydric alcohol carrier fluid.

19. The gasoline fuel additive package of claim 10, wherein the gasoline fuel additive package further comprises a polyether monohydric alcohol or a polyether polyhydric alcohol carrier fluid.

20. The gasoline fuel additive package according to claim 1, wherein the weight ratio of the mixture of the quaternary ammonium salt cleaner and the Mannich base cleaner is in the range of 1:25 to 1:

35.

21. The gasoline fuel additive package according to claim 14 or 15, wherein the gasoline fuel additive package further comprises an anti-wear additive.

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