Title:
Fuel Additives for Use in High Level Alcohol-Gasoline Blends
Kind Code:
A1


Abstract:
The present invention provides a fuel additive concentrate comprising a polyetheramine, antioxidant; and a friction modifier selected from the group consisting of an alkoxylated fatty amine, a fatty acid or derivative thereof, and mixture thereof. Additionally, the present invention further provides for a fuel composition comprising a fuel which is a liquid at room temperature; and additive, wherein the additive is selected from the group consisting of: a polyetheramine; antioxidant; friction modifier selected from the group consisting of an alkoxylated fatty amine, a fatty acid or derivative thereof, and mixture thereof; and mixtures thereof.



Inventors:
Vilardo, Jonathan S. (Chardon, OH, US)
Application Number:
12/519589
Publication Date:
12/17/2009
Filing Date:
12/14/2007
Assignee:
THE LUBRIZOL CORPORATION (Wickliffe, OH, US)
Primary Class:
International Classes:
C10L1/18
View Patent Images:
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Primary Examiner:
TOOMER, CEPHIA D
Attorney, Agent or Firm:
The Lubrizol Corporation (29400 Lakeland Blvd., Wickliffe, OH, 44092-2298, US)
Claims:
What we claim:

1. A fuel additive concentrate comprising: a. polyetheramine; b. antioxidant; and c. a friction modifier selected from the group consisting of an alkoxylated fatty amine, a fatty acid or derivative thereof, and mixture thereof.

2. The fuel additive concentrate of claim 1, wherein the polyethermamine is represented by the formula RO(AO)mR1NR2R3; wherein R is a hydrocarbyl group of about 8 to about 30 carbon atoms; A is an alkylene group having 2 to 6 carbon atoms; m is a number from 1 to about 50; R1 is an alkylene group having 2 to 6 carbon atoms; and R2 and R3 are independently hydrogen, a hydrocarbyl group or —[R4N(R5)]nR6 wherein R4 is an alkylene group having 2 to 6 carbon atoms, R5 and R6 are independently hydrogen or a hydrocarbyl group, and n is a number from 1 to 7.

3. The fuel additive concentrate of claim 2, wherein the polyetheramine is represented by the formula RO[CH2CH(CH2CH3)O]mCH2CH2CH2NH2; wherein R is an aliphatic group or alkyl-substituted phenyl group of about 8 to about 30 carbon atoms; and m is a number from about 12 to about 30.

4. The fuel additive concentrate of claim 3, wherein the polyetheramine is represented by the formula CH3CH(CH3)[CH2CH(CH3)]2CH(CH3)CH2CH2O[CH2CH(CH2CH3)O]mCH2CH2CH2NH2; wherein m is a number from about 16 to about 28.

5. The fuel additive concentrate of claim 1, wherein the antioxidant is selected from the group consisting of hindered phenol or derivatives thereof, hindered amines or derivatives thereof, and mixtures thereof.

6. The friction modifier of claim 1, wherein the friction modifier is glycerol monooleate.

7. A fuel composition comprising: a. a fuel which is a liquid at room temperature; and b. additive wherein the additive is selected from the group consisting of: a polyetheramine; antioxidant; friction modifier selected from the group consisting of an alkoxylated fatty amine, a fatty acid or derivative thereof, and mixture thereof; and mixtures thereof.

8. The fuel composition of claim 7, wherein the fuel comprises a blend of ethanol and gasoline having a ratio from 25:75 to 90:10.

9. A method of fueling an internal combustion engine comprising: a. supplying to the internal combustion engine: i. a fuel which is a liquid at room temperature; ii. polyetheramine; iii. antioxidant; and iv. a friction modifier selected from the group consisting of an alkoxylated fatty amine, a fatty acid or derivative thereof, and mixture thereof.

Description:

BACKGROUND OF THE INVENTION

The present invention relates to fuel additive concentrate, the fuel additive concentrate in an ethanol-gasoline blended fuel and the method for fueling an internal combustion engine, providing improved fuel economy and retention of fuel economy, deposit control, oxidation control, and wear and friction reduction.

Governments around the world are implementing the use of oxygenates in gasoline for economic and environmental reasons. Ethanol in particular is gaining ground as the oxygenate of choice as it presents a renewable and environmentally friendly alternative to other octane boosters, such as, tetra ethyl lead (TEL) and methyl tert-butyl ether (MTBE). Additionally, ethanol benefits the agricultural sector and therefore, has the backing of political and pricing support. This in combination with rises in crude oil, desire for energy independence, and fears of global warming explains the recent growth in the ethanol energy market. In the United States, ethanol has been available since the late 1970's and is added at 10% (E10) to approximately one-third of all gasoline used in North America. The production of ethanol blended fuels has begun in Europe with Spain and Sweden at the forefront. Brazil has a long history of using ethanol and ethanol blends. Other countries in Latin America have varied but growing levels of E10. In the Asia Pacific region, Thailand has lead the way and E10 is widely available. Other countries with regional (but not national) mandates include China and India while Japan, Australia and the Philippines are not far behind.

Ethanol blended gasoline have a long history and are widely understood to present certain technical challenges which have been successfully addressed in most cases. New markets will likely face the traditional issues associated with ethanol blended gasoline, such as, the tendency for increased deposits formation, fuel system corrosion, loss of fuel economy and, an increase in inlet valve sticking. In most cases, formulation adjustments and/or increases in additive level is the remedy, but new high level ethanol blended gasoline (>50% Ethanol−E50 or greater) has entered the marketplace and may present new challenges. Some issues have been addressed through the development of new vehicle technology, while other issue will require new inventive additives technology.

The present invention, therefore, solves the problem of ethanol-gasoline blend fuels tendency for engine deposits formation, lubricant oxidation, and a loss of fuel economy by providing fuel additives to the ethanol-gasoline blends that prevent engine deposits, slows lubricant oxidation and improves fuel economy.

SUMMARY OF THE INVENTION

The present invention provides a fuel additive concentrate comprising:

    • a. polyetheramine;
    • b. antioxidant; and
    • c. a friction modifier selected from the group consisting of an alkoxylated fatty amine, a fatty acid or derivative thereof, and mixture thereof.

The present invention further provides for a fuel composition comprising:

    • a. a fuel which is a liquid at room temperature; and
    • b. additive

wherein the additive is selected from the group consisting of: a polyetheramine; antioxidant; friction modifier selected from the group consisting of an alkoxylated fatty amine, a fatty acid or derivative thereof, and mixture thereof; and mixtures thereof.

The present invention further provides a method for fueling an internal combustion engine, comprising:

A. supplying to an internal combustion engine:

    • i. a fuel which is a liquid at room temperature;
    • ii. polyetheramine;
    • iii. antioxidant; and
    • iv. a friction modifier selected from the group consisting of an alkoxylated fatty amine, a fatty acid or derivative thereof, and mixture thereof.

DETAILED DESCRIPTION OF THE INVENTION

Various preferred features and embodiments will be described below by way of non-limiting illustration.

FIELD OF THE INVENTION

This invention involves fuel additive concentrate that includes: a polyetheramine, antioxidant, and a friction modifier selected the group consisting of an alkoxylated fatty amine, a fatty acid or derivative thereof, and mixture thereof; a fuel composition that includes a fuel which is a liquid at room temperature and an additive wherein the additive is selected from the group consisting of: a polyetheramine; antioxidant; friction modifier selected from the group consisting of an alkoxylated fatty amine, a fatty acid or derivative thereof, and mixture thereof; and mixtures thereof, and a method of operating an internal combustion engine with the fuel composition. The concentrates, compositions and methods of the present invention promote engine cleanliness and fuel economy, while controlling lubricant oxidation, which enables optimal engine operation.

Fuel

The fuel composition of the present invention can comprise the fuel additive concentrate, as described above, and a fuel which is a liquid at room temperature and is useful in fueling an engine. The fuel is normally a liquid at ambient conditions e.g., room temperature (20 to 30° C.). The fuel can be a hydrocarbon fuel, a nonhydrocarbon fuel, or a mixture thereof. The hydrocarbon fuel can be a petroleum distillate to include a gasoline as defined by ASTM specification D4814 or a diesel fuel as defined by ASTM specification D975. In an embodiment of the invention, the fuel is a gasoline, and in other embodiment, the fuel is a leaded gasoline, or a nonleaded gasoline. In another embodiment of this invention, the fuel is a diesel fuel. The hydrocarbon fuel can be a hydrocarbon prepared by a gas to liquid process to include, for example, hydrocarbons prepared by a process, such as, the Fischer-Tropsch process. The nonhydrocarbon fuel can be an oxygen containing composition, often referred to as an oxygenate, which can include an alcohol, an ether, a ketone, an ester of a carboxylic acid, a nitroalkane, or a mixture thereof. The nonhydrocarbon fuel can include, for example, methanol, ethanol, propanol, butanol, methyl t-butyl ether, methyl ethyl ketone, transesterified oils and/or fats from plants and animals such as rapeseed methyl ester and soybean methyl ester, and nitromethane. In several embodiments of this invention, the fuel can have an oxygenate content on a weight basis that is 15 percent by weight, or 25 percent by weight, or 50 percent by weight, or 65 percent by weight, or 85 percent by weight, or 90 percent by weight. Mixtures of hydrocarbon and nonhydrocarbon fuels can include, for example, gasoline and methanol and/or ethanol, diesel fuel and ethanol, and diesel fuel and a transesterified plant oil such as rapeseed methyl ester, fuels referred to as E85 or M85, fuels referred to as AlCool™. In one embodiment, mixtures of hydrocarbon and nonhydrocarbon fuels can be defined by ASTM D-5798-99. In several embodiments of this invention, the mixtures of hydrocarbon and nonhydrocarbon fuels can have an oxygenate content on a weight basis that is 15 percent by weight, or 25 percent by weight, or 50 percent by weight, or 65 percent by weight, or 85 percent by weight, or 90 by weight. In another embodiment, the fuel comprises a blend of ethanol and gasoline having a ratio from 25:75 to 90:10. In an embodiment of the invention, the fuel can be an emulsion of water in a hydrocarbon fuel, a nonhydrocarbon fuel, or a mixture thereof. In several embodiments of this invention, the fuel can have a sulfur content on a weight basis that is 5000 ppm or less, 1000 ppm or less, 300 ppm or less, 200 ppm or less, 30 ppm or less, or 10 ppm or less. In another embodiment, the fuel can have a sulfur content on a weight basis of 1 to 100 ppm. In one embodiment, the fuel contains 0 ppm to 1000 ppm, or 0 to 500 ppm, or 0 to 100 ppm, or 0 to 50 ppm, or 0 to 25 ppm, or 0 to 10 ppm, or 0 to 5 ppm of alkali metals, alkaline earth metals, transition metals or mixtures thereof. In another embodiment, the fuel contains 1 to 10 ppm by weight of alkali metals, alkaline earth metals, transition metals or mixtures thereof. It is well known in the art that a fuel containing alkali metals, alkaline earth metals, transition metals or mixtures thereof have a greater tendency to form deposits and therefore foul or plug injectors. The fuel of the invention can be present in a fuel composition in a major amount that is generally greater than 50 percent by weight, and in other embodiments is present at greater than 90 percent by weight, greater than 95 percent by weight, greater than 99.5 percent by weight, or greater than 99.8 percent by weight.

Polyetheramine

Polyetheramines of this invention include compounds having two or more consecutive ether groups and at least one primary, secondary or tertiary amine group where the amine nitrogen has some basicity. The polyetheramines of this invention include poly(oxyalkylene)amines having a sufficient number of repeating oxyalkylene units to render the poly(oxyalkylene)amine soluble in a normally liquid fuel, such as, in hydrocarbons boiling in a gasoline or diesel fuel range and blends of hydrocarbon fuel with non-hydrocarbon fuel. Generally, poly(oxyalkylene)amines having at least about 5 oxyalkylene units are suitable for use in the present invention. Poly(oxyalkylene)amines can include: hydrocarbylpoly(oxyalkylene)amines, hydrocarbylpoly(oxyalkylene)polyamines, hydropoly(oxyalkylene)amines, hydropoly(oxyalkylene)polyamines, and derivatives of polyhydric alcohols having at least two poly(oxyalkylene)amine and/or poly(oxyalkylene)polyamine chains on the molecule of the derivative. In one embodiment, the poly(oxyalkylene)amine for use in the invention is represented by the formula RO(AO)mR1NR2R3 (I) wherein R is a hydrocarbyl group of 1 to 50 carbon atoms, or about 8 to about 30 carbon atoms; A is an alkylene group having 2 to 18 carbon atoms and preferably 2 to 6 carbon atoms; m is a number from 1 to about 50; R1 is an alkylene group having 2 to 18 carbon atoms or preferably 2 to 6 carbon atoms; and R2 and R3 are independently hydrogen, a hydrocarbyl group or —[R4N(R5)]nR6 wherein R4 is an alkylene group having 2 to 6 carbon atoms, R5 and R6 are independently hydrogen or a hydrocarbyl group, and n is a number from 1 to 7.

In another embodiment, the poly(oxyalkylene)amine of the present invention can be represented by the formula: RO[CH2CH(CH2CH3)O]mCH2CH2CH2NH2 (II) wherein R is an aliphatic group or alkyl-substituted phenyl group of about 8 to about 30 carbon atoms; and m is a number from about 12 to about 30. In yet another embodiment, the poly(oxyalkylene)amine of the present invention can be represented by the formula: CH3CH(CH3)[CH2CH(CH3)]2CH(CH3)CH2CH2O—[CH2CH(CH2CH3)O]mCH2CH2CH2NH2 (III) wherein m is a number from about 16 to about 28. Poly(oxyalkylene)amines of the present invention can have a molecular weight in the range from about 300 to about 5,000.

The polyetheramines of the present invention can be prepared by initially condensing an alcohol or alkylphenol with an alkylene oxide, mixture of alkylene oxides or with several alkylene oxides in sequential fashion in a 1:1-50 mole ratio of hydric compound to alkylene oxide to form a polyether intermediate. U.S. Pat. Nos. 5,112,364 and 5,264,006 provide reaction conditions for preparing a polyether intermediate.

The alcohol can be monohydric or polyhydric, linear or branched, saturated or unsaturated and having 1 to 50 carbon atoms, or from 8 to 30 carbon atoms, or from 10 to 16 carbon atoms. Branched alcohols of the present invention can include Guerbet alcohols, as described in U.S. Pat. No. 5,264,006, which generally contain between 12 and 40 carbon atoms and can be represented by the formula RCH(CH2CH2R)CH2OH (IV) where R is a hydrocarbyl group. In one embodiment, the alkyl group of the alkylphenols can be 1 to 50 carbon atoms, or 2 to 24 carbon atoms, or 10 to 20 carbon atoms.

In one embodiment, the alkylene oxides include 1,2-epoxyalkanes having 2 to about 18 carbon atoms, or 2 to about 6 carbon atoms. In yet another embodiment, the alkylene oxides can be ethylene oxide, propylene oxide and butylene oxide. Especially useful is propylene oxide, butylene oxide, or a mixture thereof. The number of alkylene oxide units in the polyether intermediate can be 1-50, or 12-30, or 16-28.

The polyether intermediates can be converted to polyetheramines by several methods. The polyether intermediate can be converted to a polyetheramine by a reductive amination with ammonia, a primary amine or a polyamine as described in U.S. Pat. Nos. 5,112,364 and 5,752,991. In one embodiment, the polyether intermediate can be converted to a polyetheramine via an addition reaction of the polyether to acrylonitrile to form a nitrile which is then hydrogenated to form the polyetheramine. U.S. Pat. No. 5,264,006 provides reaction conditions for the cyanoethylation of the polyether with acrylonitrile and the subsequent hydrogenation to form the polyetheramine. In yet another embodiment, the polyether intermediate or poly(oxyalkylene) alcohol is converted to the corresponding poly(oxyalkylene) chloride via a suitable chlorinating agent followed by displacement of chlorine with ammonia, a primary or secondary amine, or a polyamine as described in U.S. Pat. No. 4,247,301.

In one embodiment, the polyetheramine in the fuel composition may be present in an amount from about 1 to about 10000 ppm, or about 5 to about 5000, or about 20 to about 4000 or about 40 to about 3500 ppm.

In one embodiment, the polyetheramine can be present in the fuel additive concentration in an amount from about 1 to about 99 percent by weight, or about 10 to about 80 percent by weight, about 20 to about 60 percent by weight and about 20 to about 50 percent by weight.

Friction Modifier

The fuel additive concentrate of the present invention can comprise a friction modifier. The friction modifier can be selected from the group consisting of an alkoxyalted fatty amine, fatty acid or derivative thereof, and mixtures thereof.

Alkoxylated Fatty Amine

The alkoxylated fatty amine of the present invention can include amines represented by the formula:

wherein R is a hydrocarbyl group having about 4 to 30 carbon atoms, A1 and A2 are vicinal alkylene groups, and the sum of x and y is an integer that is at least 1. The hydrocarbyl group is a univalent radical of carbon atoms that is predominantly hydrocarbon in nature, but can have nonhydrocarbon substituent groups and can have heteroatoms. The hydrocarbyl group R can be an alkyl or alkylene group of about 4 to 30 carbon atoms, or about 10 to 22 carbon atoms. The vicinal alkylene groups A1 and A2 can be the same or different and include: ethylene(—CH2CH2—), propylene (—CH2CH2CH2—) and butylene (—CH2CH2CH2CH2—) having the carbon to nitrogen and carbon to oxygen bonds on adjacent or neighboring carbon atoms. Examples of alkoxylated fatty amines can include: diethoxylated tallowamine, diethoxylated oleylamine, diethoxylated stearylamine, and the diethoxylated amine from soybean oil fatty acids. Alkoxylated fatty amines are commercially available from Akzo under the Ethomeen® series.

Fatty Acid or Derivative Thereof

In one embodiment, the fatty acid or derivative thereof can have about 4 to 30 carbon atoms, or 8 to 26 carbon atoms, or 12 to 22 carbon atoms. Saturated and unsaturated monocarboxylic acids are useful and include capric, lauric, myristic, palmitic, stearic, behenic, oleic, petroselinic, elaidic, palmitoleic, linoleic, linolenic and erucic acid. Typical fatty acids are those derived from natural oil typically containing C6 or C22 fatty acid esters, i.e., glycerol fatty acid esters or triglycerides derived from natural sources, for use herein include, but are not limited to beef tallow oil, lard oil, palm oil, castor oil, cottonseed oil, corn oil, peanut oil, soybean oil, sunflower oil, olive oil, whale oil, coconut oil, palm oil, rape oil, and soya oil.

In another embodiment of this invention, the fatty acid can be the partial ester of a fatty carboxylic acid. The partial ester of the present invention has at least one free hydroxyl group and is formed by reacting at least one fatty carboxylic acid and at least one polyhydric alcohol.

The fatty carboxylic acid used to form the partial ester can be saturated or unsaturated aliphatic, can be branched or straight chain, can be a monocarboxylic or polycarboxylic acid, and can be a single acid or mixture of acids. The fatty carboxylic acid can have about 4 to 30 carbon atoms, or 8 to 26 carbon atoms, or 12 to 22 carbon atoms. Saturated and unsaturated monocarboxylic acids are useful and include, for example, capric, lauric, myristic, palmitic, stearic, behenic, oleic, petroselinic, elaidic, palmitoleic, linoleic, linolenic and erucic acid.

The polyhydric alcohol used to form the partial ester has two or more hydroxyl groups and includes alkylene glycols, polyalkylene glycols, triols, polyols having more than three hydroxyl groups, and mixtures thereof. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, neopentyl glycol, glycerol, trimethylol propane, pentaerythritol, and sorbitol.

The partial esters having at least one free hydroxyl group are commercially available or can be formed by a variety of methods well known in the art. These esters are derived from any of the above described fatty carboxylic acids and polyhydric alcohols or mixtures thereof. Preferred esters are derived from fatty carboxylic acids having about 12 to 22 carbon atoms and glycerol, and will usually be mixtures of mono- and diglycerides, such as, a mixture of glycerol monooleate and glycerol dioleate. In one embodiment, the friction modifier of the present invention is glycerol monoleate.

Another derivative of the fatty carboxylic acid is the amide of the fatty carboxylic acid. In general, these compounds are the reaction product of the natural fatty acid oils containing 6 to 22 carbon atoms and an amine. The fatty carboxylic acid of these amides can be saturated or unsaturated aliphatic, can be branched or straight chain, can be a monocarboxylic or polycarboxylic acid, and can be a single acid or mixture of acids. The fatty carboxylic acid can have about 4 to 30 carbon atoms, or 8 to 26 carbon atoms, or 12 to 22 carbon atoms. Saturated and unsaturated monocarboxylic acids are useful and include, for example, capric, lauric, myristic, palmitic, stearic, behenic, oleic, petroselinic, elaidic, palmitoleic, linoleic, linolenic and erucic acid.

The amine can be an alkyl amine having from about 2 to about 10 carbon atoms, or about 4 to about 6 carbon atoms. A typical amine can be the alkanol amines. The alkanolamine used in the reaction with the fatty acid can be a primary or secondary amine, which possesses at least one hydroxy group. The alkanolamine corresponds to the general formula HN(R1OH)2-xHx wherein R1 is a lower hydrocarbyl having from about two to about six carbon atoms and x is 0 or 1. The expression “alkanolamine” is used in its broadest sense to include compounds containing at least one primary or secondary amine and at least one hydroxy group, such as, for example, monoalkanolamines, dialkanolamines, and so forth. It is believed that almost any alkanolamine can be used, although preferred alkanolamines are lower alkanolamines having form about two to about six carbon atoms. The alkanolamine can possess an O or N functionality, in addition to the one amino group (that group being a primary of secondary amino group), and at least one hydroxy group. Suitable alkanolamines for use herein include: monoethanolamine, diethanolamine, propanolamine, isopropanolamine, dipropanolamine, di-isopropanolamine, butanolamines, aminoethylaminoethanols, e.g., 2-(2-aminoethoamino)ethanol, and the like with diethanolamine being preferred. It is also contemplated that mixtures of two or more alkanolamines can be employed.

In one embodiment, the friction modifier can be present in the fuel additive concentrate in an amount from about 1 to about 99 percent by weight, or about 2 to about 50 percent by weight, or about 5 to about 40 percent by weight, or about 5 to about 30 percent by weight, in yet another embodiment from about 8 to about 25 percent by weight.

In one embodiment, the friction modifier of this invention can be present in a fuel composition on a weight basis from about 1 to about 10,000 ppm (parts per million), and in other embodiment from about 5 to about 8,000 ppm, or about 10 to about 7000 ppm, or about 20 to about 5000 ppm, or about 30 to about 2000 ppm, or about 50 to about 1500, or about 40 to about 1000 ppm, or about 40 to about 650 ppm.

Antioxidant

The present invention also includes one or more antioxidants. The antioxidants for use in the present invention are well known and include a variety of chemical types including phenate sulfides, phosphosulfurized terpenes, sulfurized esters, aromatic amines, and hindered phenols.

Aromatic amines are typically of the formula

wherein R5 is a phenyl group or a phenyl group substituted by R7, and R6 and R7 are independently a hydrogen or an alkyl group containing 1 to 24 carbon atoms. Preferably R5 is a phenyl group substituted by R7 and R6 and R7 are alkyl groups containing from 4 to 20 carbon atoms. In one embodiment, the antioxidant can be an alkylated diphenylamine, such as, nonylated diphenylamine containing typically some of the formula

Hindered phenol antioxidants are typically alkyl phenols of the formula

wherein R4 is an alkyl group containing 1 to 24 carbon atoms and m is an integer of 1 to 5. In certain embodiments, R contains 4 to 18 carbon atoms or 4 to 12 carbon atoms. R4 may be either straight chained or branched chained, especially branched. Suitable values of m include 1 to 4, such as 1 to 3 or, particularly, 2. In certain well-known embodiments, the phenol is a butyl substituted phenol containing 2 or 3 t-butyl groups. When a is 2, the t-butyl groups may occupy the 2,6-positions, that is, the phenol is sterically hindered:

The antioxidant can be, and typically is, further substituted at the 4-position with any of a number of substituents, such as hydrocarbyl groups or groups bridging to another hindered phenolic ring.

Also included among the antioxidants are hindered ester substituted phenols such as those represented by the formula:

wherein t-alkyl can be, among others, t-butyl, R3 is a straight chain or branched chain alkyl group containing about 1 to about 22 carbon atoms, or about 2 to about 22, or about 2 to about 8, or about 4 to about 8 carbon atoms. R3 may be a 2-ethylhexyl group or an n-butyl or n-octyl group. Hindered ester substituted phenols can be prepared by heating a 2,6-dialkylphenol with an acrylate ester under base catalysis conditions, such as, aqueous KOH.

The antioxidants of the present invention can also include sulfurized olefins, such as, mono-, or disulfides or mixtures thereof. These materials generally have sulfide linkages having 1 to 10 sulfur atoms, or 1 to 4, or 1 or 2 sulfur atoms. Materials, which can be sulfurized to form the sulfurized organic compositions of the present invention, include: oils, fatty acids and esters, olefins and polyolefins made thereof, terpenes, or Diels-Alder adducts. Details of methods of preparing some such sulfurized materials can be found in U.S. Pat. Nos. 3,471,404 and 4,191,659. Molybdenum compounds can also serve as antioxidants. The use of molybdenum and sulfur containing compositions as antioxidants is known.

In certain embodiment, a mixture of antioxidants are employed, such as, both a phenolic and an aromatic amine antioxidant, or mixtures thereof, or alternatively phenolic, or aromatic amine, or phosphosulfurized olefin antioxidants or molybdenum antioxidant or mixtures thereof.

In one embodiment, the amount of the antioxidant in the fuel composition can be present in an amount from about 1 to about 1000 ppm, or about 1 to about 5000, or about 2 to about 500, or about 4 to about 200 or about 5 to about 100 ppm.

In one embodiment, the amount of antioxidant can be present in the fuel additive concentration in an amount from about 1 to about 99 percent by weight, or from about 1 to about 40 percent by weight, or from about 2 to about 30 percent by weight, or from about 2 to about 20 percent by weight.

Fuel Composition

In one embodiment, the fuel composition contains a fuel, which is a liquid at room temperature, and an additive wherein the additive is selected from the group consisting of: a polyetheramine; antioxidant; friction modifier selected from the group consisting of an alkoxylated fatty amine, a fatty acid or derivative thereof, and mixture thereof; and mixtures thereof. The fuel, which is a liquid at room temperature, and additives of the fuel composition are described above.

Fuel Additive Concentrate

In one embodiment, the fuel additive concentrate of the present invention can be present in a fuel composition in an amount from about 1 to about 10000 ppm, in another embodiment about 5 to about 8000 ppm, in another embodiment about 10 to about 5000 ppm or about 20 to about 5000 ppm, in yet another embodiment about 100 to about 4000 ppm, and in another embodiment about 200 to about 2000, or about 300 to about 2000 or about 300 to about 1000 ppm.

Miscellaneous

The fuel additive concentrate compositions and fuel compositions of the present invention can contain other additives that are well known to those of skill in the art. These can include anti-knock agents such as tetra-alkyl lead compounds and MMT (methylcyclopentadienyl manganese tricarbonyl), lead scavengers such as halo-alkanes, corrosion inhibitors, dyes, bacteriostatic agents, auxiliary, gum inhibitors, marking agents, metal deactivators, detergents, demulsifiers, or mixtures thereof. The fuel compositions of this invention can be lead-containing or lead-free fuels.

INDUSTRIAL APPLICATION

In one embodiment the invention is useful for a liquid fuel or for an internal combustion engine. The internal combustion engine includes a 2-stroke or 4-stroke engine fuelled with gasoline, diesel, a natural gas or a mixed gasoline/alcohol. The diesel engine includes both light duty and heavy duty diesel engines. The gasoline engine includes a direct injection gasoline engine.

As used herein, the term “hydrocarbyl substituent” or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include: hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring); substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy); hetero substituents, that is, substituents which, while having a predominantly hydrocarbon character, in the context of this invention, contain other than carbon in a ring or chain otherwise composed of carbon atoms. Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituents as pyridyl, furyl, thienyl and imidazolyl. In general, no more than two, preferably no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; typically, there will be no non-hydrocarbon substituents in the hydrocarbyl group.

It is known that some of the materials described above may interact in the final formulation, so that the components of the final formulation may be different from those that are initially added. For instance, metal ions (of, e.g., a detergent) can migrate to other acidic or anionic sites of other molecules. The products formed thereby, including the products formed upon employing the composition of the present invention in its intended use, may not be susceptible of easy description. Nevertheless, all such modifications and reaction products are included within the scope of the present invention; the present invention encompasses the composition prepared by admixing the components described above.

Each of the documents referred to above is incorporated herein by reference. Except in the Examples, or where otherwise explicitly indicated, all numerical quantities in this description specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, and the like, are to be understood as modified by the word “about.” Unless otherwise indicated, each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade. However, the amount of each chemical component is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, unless otherwise indicated. It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined. Similarly, the ranges and amounts for each element of the invention can be used together with ranges or amounts for any of the other elements. As used herein, the expression “consisting essentially of” permits the inclusion of substances that do not materially affect the basic and novel characteristics of the composition under consideration.