Patent Publication Number: US-8974551-B1

Title: Fuel additive for improved performance in fuel injected engines

Description:
TECHNICAL FIELD 
     The disclosure is directed to fuel compositions and to fuel additive and additive concentrates that include a synergistic combination of ingredients that is useful for improving the performance of fuel injected engines. In particular the disclosure is directed to a synergistic fuel additive that is effective to enhance the performance of fuel injectors for internal combustion engines. 
     BACKGROUND AND SUMMARY 
     It has long been desired to maximize fuel economy, power and driveability in vehicles while enhancing acceleration, reducing emissions, and preventing hesitation. Accordingly, fuel additives have been developed to improve fuel delivery system performance in order to improve engine performance. For example certain additives are used to keep fuel injectors for diesel and spark ignited engines operating under optimal condition by either keeping them clean or cleaning up dirty injectors. Such additives may include additives that are effective to reduce internal deposits in the injectors. 
     Hydrocarbyl substituted anhydrides such as polyisobutenyl succinic anhydride (PIBSA) and derivatives are known fuel additives detergents for cleaning up deposits on various parts of a fuel delivery systems. However the cleaning performance of such detergents is often found insufficient for use in newer engines and with fuels designed for such newer engines. For example, engines are now being designed to run on alternative renewable fuels. Such renewal fuels may include fatty acid esters and other biofuels which are known to cause deposit formation in the fuel supply systems for the engines. Such deposits may reduce or completely bock fuel flow, leading to undesirable engine performance. 
     Also, low sulfur fuels and ultra low sulfur fuels are now common in the marketplace for internal combustion engines. A “low sulfur” fuel means a fuel having a sulfur content of 50 ppm by weight or less based on a total weight of the fuel. An “ultra low sulfur” fuel means a fuel having a sulfur content of 15 ppm by weight or less based on a total weight of the fuel. Low sulfur fuels tend to form more deposits in engines than conventional fuels, for example, because of the need for additional friction modifiers and/or corrosion inhibitors in the low sulfur fuels. 
     Conventional quaternary ammonium compounds have been found effective in cleaning up certain fuels but are not effective in other fuels. In addition, such compounds have non-covalently bound anions that may lead to other problems such as deposit formation in the fuel from the anionic part of the compound. 
     Certain quaternary ammonium internal salts have been found to be effective where conventional quaternary ammonium salts lack the performance. However quaternary ammonium internal salts may be ineffective in certain petroleum fuels. Accordingly, there is a need for fuel additives, additive concentrates and fuel compositions that provide improved engine performance in a variety of fuels and engines. 
     In accordance with the disclosure, exemplary embodiments provide a fuel additive concentrate, a method for cleaning fuel injectors, a method for restoring power to a diesel fuel injected engine, a fuel composition, and a method of operating a fuel injected diesel engine. The additive concentrate includes (a) a hydrocarbyl substituted quaternary ammonium internal salt; and (b) a hydrocarbyl substituted dicarboxylic anhydride derivative selected from a diamide, acid/amide, acid/ester, diacid, amide/ester, diester, and imide. The hydrocarbyl substituent of component (b) has a number average molecular weight ranging from about 450 to about 1500. A weight ratio of (a) to (b) in the additive concentrate ranges from about 1:20 to about 2:1. The additive concentrate is devoid of a reaction product of a hydrocarbyl substituted dicarboxylic acid, anhydride or ester and an amine compound of the formula 
                         
wherein R 2  is selected from hydrogen and a hydrocarbyl group containing from about 1 to about 15 carbon atoms, and R 3  is selected from hydrogen and a hydrocarbyl group containing from about 1 to about 20 carbon atoms.
 
     Another embodiment of the disclosure provides a method of improving the injector performance of a fuel injected diesel engine. The method includes operating the engine on a fuel composition that includes a major amount of fuel and from about 5 to about 500 ppm by weight based on a total weight of the fuel of a synergistic fuel additive. The synergistic fuel additive includes (a) a hydrocarbyl substituted quaternary ammonium internal salt; and (b) a hydrocarbyl substituted dicarboxylic anhydride derivative selected from a diamide, acid/amide, acid/ester, diacid, amide/ester, diester, and imide. The hydrocarbyl substituent of component (b) has a number average molecular weight ranging from about 450 to about 1500. A weight ratio of (a) to (b) in the fuel additive ranges from about 1:20 to about 2:1. When the synergistic additive(s) is present in the fuel, at least about 49% of the power lost during a dirty up phase of a CEC F98-08 DW10 test conducted in the absence of the synergistic additive(s) is recovered. In another embodiment, at least 70% of the lost power is recovered. In still another embodiment at least 100% of the lost power is recovered. The additive concentrate is devoid of a reaction product of a hydrocarbyl substituted dicarboxylic acid, anhydride or ester and an amine compound of the formula 
                         
wherein R 2  is selected from hydrogen and a hydrocarbyl group containing from about 1 to about 15 carbon atoms, and R 3  is selected from hydrogen and a hydrocarbyl group containing from about 1 to about 20 carbon atoms.
 
     A further embodiment of the disclosure provides a method of operating a fuel injected engine. The method includes combusting in the engine a fuel composition containing a major amount of fuel and from about 5 to about 500 ppm by weight based on a total weight of the fuel of a synergistic fuel additive. The synergistic fuel additive includes (a) a hydrocarbyl substituted quaternary ammonium internal salt; (b) a reaction product derived from (i) a hydrocarbyl substituted dicarboxylic acid, anhydride, or ester, wherein the hydrocarbyl substituent of component (b) has a number average molecular weight ranging from about 450 to about 1500 and (ii) a polyamine of the formula H 2 N—((CHR 1 —(CH 2 ) n —NH) m —H, wherein R 1  is hydrogen, n is 1 and m is 4, wherein a molar ratio of (i) reacted with (ii) ranges from about 0.5:1 to about 2:1; and (c) a metal deactivator selected from the group consisting of tolyltriazole and N,N-bis(2-ethylhexyl)-ar-methyl-1H-benzotriazole-1-methanamine. A weight ratio of (a) to (b) in the fuel additive ranges from about 1:20 to about 2:1 and a weight ratio of (b) to (c) ranges from 0.5:1 to 5:1. The fuel additive is devoid of a reaction product of a hydrocarbyl substituted dicarboxylic acid, anhydride or ester and an amine compound of the formula 
                         
wherein R 2  is selected from hydrogen and a hydrocarbyl group containing from about 1 to about 15 carbon atoms, and R 3  is selected from hydrogen and a hydrocarbyl group containing from about 1 to about 20 carbon atoms.
 
     Another embodiment of the disclosure provides a fuel additive composition that includes a) an oleyl amidopropyl dimethylamino internal salt; (b) a reaction product derived from (i) a hydrocarbyl substituted succinic anhydride, wherein the hydrocarbyl substituent of component (b) has a number average molecular weight of about 950, and (ii) a tetraethylene pentamine, wherein a molar ratio of (i) reacted with (ii) is about 1.6:1; and c) a metal deactivator selected from tolyltriazole and N,N-bis(2-ethylhexyl)-ar-methyl-1H-benzotriazole-1-methanamine. 
     It was surprisingly found the hydrocarbyl substituted anhydrides and derivatives in combination with certain hydrocarbyl quaternary ammonium internal salts may be synergistically more effective for improving injector performance and power recovery (power restoration) than each of the components (a) and (b) alone in the fuel. Hydrocarbyl substituted anhydride derivatives may include among others diacid, mono acid/ester, mono acid/amide, amide, ester, imide, and mixtures. 
     An advantage of the fuel additive described herein is that the additive may not only reduce the amount of deposits forming on fuel injectors, but the additive may also be effective to clean up dirty fuel injectors sufficient to provide improved power recovery to the engine. The combination of components (a) and (b) may also be effective for improving the fuel delivery system including, but not limited to, reducing fuel filter blockage. 
     Additional embodiments and advantages of the disclosure will be set forth in part in the detailed description which follows, and/or can be learned by practice of the disclosure. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure, as claimed. 
    
    
     DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS 
     Components (a), (b), and/or (c) of the fuel additive may be used in a minor amount in a major amount of fuel and may be added to the fuel directly or added as components of an additive concentrate to the fuel. 
     Component (a) 
     Component (a) of the fuel additive for improving the operation of internal combustion engines may be made by a wide variety of well known reaction techniques with amines or polyamines. For example, such additive component (a) may be made by reacting a tertiary amine of the formula 
                         
wherein each of R 1 , R 2 , and R 3  is selected from hydrocarbyl groups containing from 1 to 200 carbon atoms, with a halogen substituted C 2 -C 8  carboxylic acid, ester, amide, or salt thereof. What is generally to be avoided in the reaction is quaternizing agents selected from the group consisting of hydrocarbyl substituted carboxylates, carbonates, cyclic-carbonates, phenates, epoxides, or mixtures thereof. In one embodiment, the halogen substituted C 2 -C 8  carboxylic acid, ester, amide, or salt thereof may be selected from chloro-, bromo-, fluoro-, and iodo-C 2 -C 8  carboxylic acids, esters, amides, and salts thereof. The salts may be alkali or alkaline earth metal salts selected from sodium, potassium, lithium calcium, and magnesium salts. A particularly useful halogen substituted compound for use in the reaction is the sodium or potassium salt of a chloroacetic acid.
 
     As used herein, the term “hydrocarbyl group” or “hydrocarbyl” 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 a molecule and having a predominantly hydrocarbon character. Examples of hydrocarbyl groups include:
         (1) 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 an alicyclic radical);   (2) substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups which, in the context of the description herein, do not alter the predominantly hydrocarbon substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, amino, alkylamino, and sulfoxy);   (3) hetero-substituents, that is, substituents which, while having a predominantly hydrocarbon character, in the context of this description, contain other than carbon in a ring or chain otherwise composed of carbon atoms. Hetero-atoms include sulfur, oxygen, nitrogen, and encompass substituents such as carbonyl, amido, imido, pyridyl, furyl, thienyl, ureyl, and imidazolyl. In general, no more than two, or as a further example, no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; in some embodiments, there will be no non-hydrocarbon substituent in the hydrocarbyl group.       

     As used herein, the term “major amount” is understood to mean an amount greater than or equal to 50 wt. %, for example from about 80 to about 98 wt. % relative to the total weight of the composition. Moreover, as used herein, the term “minor amount” is understood to mean an amount less than 50 wt. % relative to the total weight of the composition. 
     As used herein the term “substantially devoid of free anion species” means that the anions, for the most part are covalently bound to the product such that the reaction product as made does not contain any substantial amounts of free anions or anions that are ionically bound to the product. In one embodiment, “substantially devoid” means from 0 to less than about 2 wt. % of anion species. 
     As used herein the term “ultra-low sulfur” means fuels having a sulfur content of 15 ppm by weight or less. 
     In one embodiment, a tertiary amine including monoamines and polyamines may be reacted with the halogen substituted acetic acid or derivative thereof to provide component (a). Suitable tertiary amine compounds of the formula 
                         
wherein each of R 1 , R 2 , and R 3  is selected from hydrocarbyl groups containing from 1 to 200 carbon atoms may be used. Each hydrocarbyl group R 1  to R 3  may independently be linear, branched, substituted, cyclic, saturated, unsaturated, or contain one or more hetero atoms. Suitable hydrocarbyl groups may include, but are not limited to alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, alkoxy groups, aryloxy groups, amido groups, ester groups, imido groups, and the like. Any of the foregoing hydrocarbyl groups may also contain hetero atoms, such as oxygen or nitrogen atoms. Particularly suitable hydrocarbyl groups may be linear or branched alkyl groups. Some representative examples of amine reactants which can be reacted to yield compounds of this invention are: trimethyl amine, triethyl amine, tri-n-propyl amine, dimethylethyl amine, dimethyl lauryl amine, dimethyl oleyl amine, dimethyl stearyl amine, dimethyl eicosyl amine, dimethyl octadecyl amine, N-methyl piperidine, N,N′-dimethyl piperazine, N-methyl-N-ethyl piperazine, N-methyl morpholine, N-ethyl morpholine, N-hydroxyethyl morpholine, pyridine, triethanol amine, triisopropanol amine, methyl diethanol amine, dimethyl ethanol amine, lauryl diisopropanol amine, stearyl diethanol amine, dioleyl ethanol amine, dimethyl isobutanol amine, methyl diisooctanol amine, dimethyl propenyl amine, dimethyl butenyl amine, dimethyl octenyl amine, ethyl didodecenyl amine, dibutyl eicosenyl amine, triethylene diamine, hexamethylene tetramine, N,N,N′,N′-tetramethylethylenediamine, N,N,N′,N′-tetramethylpropylenediamine, N,N,N′,N′-tetraethyl-1,3-propanediamine, methyldi-cyclohexyl amine, 2,6-dimethylpyridine, dimethylcylohexylamine, C 10 -C 30 -alkyl or alkenyl-substituted amidopropyldimethylamine, C 12 -C 200 -alkyl or alkenyl-substituted succinic-carbonyldimethylamine, and the like.
 
     If the amine contains solely primary or secondary amino groups, it is necessary to alkylate at least one of the primary or secondary amino groups to a tertiary amino group prior to the reaction with the halogen substituted C 2 -C 8  carboxylic acid, ester, amide, or salt thereof. In one embodiment, alkylation of primary amines and secondary amines or mixtures with tertiary amines may be exhaustively or partially alkylated to a tertiary amine. It may be necessary to properly account for the hydrogens on the nitrogens and provide base or acid as required (e.g., alkylation up to the tertiary amine requires removal (neutralization) of the hydrogen (proton) from the product of the alkylation). If alkylating agents, such as, alkyl halides or dialkyl sulfates are used, the product of alkylation of a primary or secondary amine is a protonated salt and needs a source of base to free the amine for further reaction. 
     The halogen substituted C 2 -C 8  carboxylic acid, ester, amide, or salt thereof for use in making component (a) may be derived from a mono-, di-, or trio- chloro- bromo-, fluoro-, or iodo-carboxylic acid, ester, amide, or salt thereof selected from the group consisting of halogen-substituted acetic acid, propanoic acid, butanoic acid, isopropanoic acid, isobutanoic acid, tert-butanoic acid, pentanoic acid, heptanoic acid, octanoic acid, halo-methyl benzoic acid, and isomers, esters, amides, and salts thereof. The salts of the carboxylic acids may include the alkali or alkaline earth metal salts, or ammonium salts including, but not limited to the Na, Li, K, Ca, Mg, triethyl ammonium and triethanol ammonium salts of the halogen-substituted carboxylic acids. A particularly suitable halogen substituted carboxylic acid, or salt thereof may be selected from chloroacetic acid and sodium or potassium chloroacetate. The amount of halogen substituted C 2 -C 8  carboxylic acid, ester, amide, or salt thereof relative to the amount of tertiary amine reactant may range from a molar ratio of about 1:0.1 to about 0.1:1.0. 
     The internal salts made according to the foregoing procedure may include, but are not limited to (1) hydrocarbyl substituted compounds of the formula R—NMe 2 CH 2 COO where R is from C 1  to C 30 ; (2) fatty amide substituted internal salts; and (3) hydrocarbyl substituted imide, amide, or ester internal salts wherein the hydrocarbyl group has 8 to 40 carbon atoms. Particularly suitable internal salts may be selected from the group consisting of polyisobutenyl substituted succinimide, succinic diamide, and succinic diester internal salts; C 8 -C 40  alkenyl substituted succinimide, succinic diamide, and succinic diester internal salts; oleyl amidopropyl dimethylamino internal salts; and oleyl dimethylamino internal salts. 
     Component (b) 
     Component (b) of the additive composition is, in one embodiment, a derivative of hydrocarbyl substituted dicarboxylic anhydride, wherein the hydrocarbyl substituent has a number average molecular weight ranging from about 450 to about 1500. The derivative may be selected from a diamide, acid/amide, acid/ester, diacid, amide/ester, diester, and imide. Such derivative may be made from (i) hydrocarbyl substituted dicarboxylic anhydride and (ii) water, an alcohol, ammonia, amine of the formula H 2 N—((CHR 1 —(CH 2 ) n —NH) m —H, wherein R 1  is hydrogen or an alkyl group having from 1 to 4 carbon atoms, n is an integer of from 1 to 4 and m is an integer of from 1-6, and mixtures thereof, wherein a molar ratio of (i) reacted with (ii) ranges from about 0.5:1 to about 2:1. 
     The hydrocarbyl substituted dicarboxylic anhydride may be a hydrocarbyl carbonyl compound of the formula 
                         
wherein R 4  is a hydrocarbyl group derived from a polyolefin. In some aspects, the hydrocarbyl carbonyl compound may be a polyalkylene succinic anhydride reactant wherein R 4  is a hydrocarbyl moiety, such as for example, a polyalkenyl radical having a number average molecular weight of from about 450 to about 1500. For example, the number average molecular weight of R 4  may range from about 600 to about 1300, or from about 700 to about 1000, as measured by GPC. A particularly useful R 4  has a number average molecular weight of about 950 Daltons and comprises polyisobutylene. Unless indicated otherwise, molecular weights in the present specification are number average molecular weights.
 
     The R 4  hydrocarbyl moiety may comprise one or more polymer units chosen from linear or branched alkenyl units. In some aspects, the alkenyl units may have from about 2 to about 10 carbon atoms. For example, the polyalkenyl radical may comprise one or more linear or branched polymer units chosen from ethylene radicals, propylene radicals, butylene radicals, pentene radicals, hexene radicals, octene radicals and decene radicals. In some aspects, the R 4  polyalkenyl radical may be in the form of, for example, a homopolymer, copolymer or terpolymer. In one aspect, the polyalkenyl radical is isobutylene. For example, the polyalkenyl radical may be a homopolymer of polyisobutylene comprising from about 10 to about 60 isobutylene groups, such as from about 20 to about 30 isobutylene groups. The polyalkenyl compounds used to form the R 4  polyalkenyl radicals may be formed by any suitable methods, such as by conventional catalytic oligomerization of alkenes. 
     In some aspects, high reactivity polyisobutenes having relatively high proportions of polymer molecules with a terminal vinylidene group may be used to form the R 4  group. In one example, at least about 60%, such as about 70% to about 90%, of the polyisobutenes comprise terminal olefinic double bonds. There is a general trend in the industry to convert to high reactivity polyisobutenes, and well known high reactivity polyisobutenes are disclosed, for example, in U.S. Pat. No. 4,152,499, the disclosure of which is herein incorporated by reference in its entirety. 
     In some aspects, approximately one mole of maleic anhydride may be reacted per mole of polyalkylene, such that the resulting polyalkenyl succinic anhydride has about 0.8 to about 1 succinic anhydride group per polyalkylene substituent. In other aspects, the molar ratio of succinic anhydride groups to polyalkylene groups may range from about 0.5 to about 3.5, such as from about 1 to about 1.1. 
     The hydrocarbyl carbonyl compounds may be made using any suitable method. Methods for forming hydrocarbyl carbonyl compounds are well known in the art. One example of a known method for forming a hydrocarbyl carbonyl compound comprises blending a polyolefin and maleic anhydride. The polyolefin and maleic anhydride reactants are heated to temperatures of, for example, about 150° C. to about 250° C., optionally, with the use of a catalyst, such as chlorine or peroxide. Another exemplary method of making the polyalkylene succinic anhydrides is described in U.S. Pat. No. 4,234,435, which is incorporated herein by reference in its entirety. 
     In component (b) the polyamine reactant may be an alkylene polyamine. For example, the polyamine may be selected from ethylene polyamine, propylene polyamine, butylenes polyamines, and the like. In one embodiment, the polyamine is an ethylene polyamine that may be selected from ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, and pentaethylene hexamine. A particularly useful ethylene polyamine is a compound of the formula H 2 N—((CHR 1 —(CH 2 ) n —NH) m —H, wherein R 1  is hydrogen, n is 1 and m is 4. The molar ratio of reactant (i) to (ii) in the reaction mixture for making component (b) may range from 0.5:1 to about 2:1. For example, a suitable molar ratio may range from about 1:1 to about 1.6:1. 
     In embodiments of the disclosure, the fuel, fuel additive and additive concentrate is desirably devoid of a reaction product derived from (c) a hydrocarbyl substituted dicarboxylic acid, anhydride, or ester and (d) an amine compound or salt thereof of the formula 
                         
wherein R 2  is selected from the group consisting of hydrogen and a hydrocarbyl group containing from about 1 to about 15 carbon atoms, and R 3  is selected from the group consisting of hydrogen and a hydrocarbyl group containing from about 1 to about 20 carbon atoms.
 
     In the foregoing reaction product, the hydrocarbyl substituted dicarboxylic acid, anhydride, or ester may also be a hydrocarbyl carbonyl compound of the formula 
                         
wherein R 4  is a hydrocarbyl group having a number average molecular weight ranging from about 200 to about 3000, wherein the hydrocarbyl group R 4  is described above.
 
     The amount of components (a) and (b) in the fuel or fuel additive concentrate may range from a weight ratio of 1:20 to about 2:1, for example from about 1:15 to about 1.5:1 by weight. Other useful weight ratios of (a) to (b) in a fuel may range from 1:10 to 1:1 and from 1:5 to 1:1. 
     In some aspects of the present application, the components (a) and (b) of the additive compositions of this disclosure may be used in combination with a fuel soluble carrier. Such carriers may be of various types, such as liquids or solids, e.g., waxes. Examples of liquid carriers include, but are not limited to, mineral oil and oxygenates, such as liquid polyalkoxylated ethers (also known as polyalkylene glycols or polyalkylene ethers), liquid polyalkoxylated phenols, liquid polyalkoxylated esters, liquid polyalkoxylated amines, and mixtures thereof. Examples of the oxygenate carriers may be found in U.S. Pat. No. 5,752,989, issued May 19, 1998 to Henly et. al., the description of which carriers is herein incorporated by reference in its entirety. Additional examples of oxygenate carriers include alkyl-substituted aryl polyalkoxylates described in U.S. Patent Publication No. 2003/0131527, published Jul. 17, 2003 to Colucci et. al., the description of which is herein incorporated by reference in its entirety. 
     In other aspects, the additive compositions of (a) and (b) may not contain a carrier. For example, some additive compositions of the present disclosure may not contain mineral oil or oxygenates, such as those oxygenates described above. 
     One or more additional optional compounds may be present in the fuel compositions of the disclosed embodiments. For example, the fuels may contain conventional quantities of cetane improvers, corrosion inhibitors, cold flow improvers (CFPP additive), pour point depressants, solvents, demulsifiers, lubricity additives, friction modifiers, amine stabilizers, combustion improvers, dispersants, antioxidants, heat stabilizers, conductivity improvers, metal deactivators, marker dyes, organic nitrate ignition accelerators, cyclomatic manganese tricarbonyl compounds, and the like. In some aspects, the compositions described herein may contain about 10 weight percent or less, or in other aspects, about 5 weight percent or less, based on the total weight of the additive concentrate, of one or more of the above additives. Similarly, the fuels may contain suitable amounts of conventional fuel blending components such as methanol, ethanol, dialkyl ethers, and the like. 
     In some aspects of the disclosed embodiments, organic nitrate ignition accelerators that include aliphatic or cycloaliphatic nitrates in which the aliphatic or cycloaliphatic group is saturated, and that contain up to about 12 carbons may be used. Examples of organic nitrate ignition accelerators that may be used are methyl nitrate, ethyl nitrate, propyl nitrate, isopropyl nitrate, allyl nitrate, butyl nitrate, isobutyl nitrate, sec-butyl nitrate, tert-butyl nitrate, amyl nitrate, isoamyl nitrate, 2-amyl nitrate, 3-amyl nitrate, hexyl nitrate, heptyl nitrate, 2-heptyl nitrate, octyl nitrate, isooctyl nitrate, 2-ethylhexyl nitrate, nonyl nitrate, decyl nitrate, undecyl nitrate, dodecyl nitrate, cyclopentyl nitrate, cyclohexyl nitrate, methylcyclohexyl nitrate, cyclododecyl nitrate, 2-ethoxyethyl nitrate, 2-(2-ethoxyethoxy)ethyl nitrate, tetrahydrofuranyl nitrate, and the like. Mixtures of such materials may also be used. 
     Suitable optional cyclomatic manganese tricarbonyl compounds which may be used in the compositions of the present application include, for example, cyclopentadienyl manganese tricarbonyl, methylcyclopentadienyl manganese tricarbonyl, indenyl manganese tricarbonyl, and ethylcyclopentadienyl manganese tricarbonyl. Yet other examples of suitable cyclomatic manganese tricarbonyl compounds are disclosed in U.S. Pat. No. 5,575,823, issued Nov. 19, 1996, and U.S. Pat. No. 3,015,668, issued Jan. 2, 1962, both of which disclosures are herein incorporated by reference in their entirety. 
     Component (c) 
     Examples of suitable optional metal deactivators useful in the compositions of the present application are disclosed in U.S. Pat. No. 4,482,357 issued Nov. 13, 1984, the disclosure of which is herein incorporated by reference in its entirety. Such metal deactivators include, for example, salicylidene-o-aminophenol, disalicylidene ethylenediamine, disalicylidene propylenediamine, and N,N′-disalicylidene-1,2-diaminopropane. 
     Other metal deactivators that may be used with components (a) and (b) described above, include, but are not limited to derivatives of benzotriazoles such as tolyltriazole; N,N-bis(heptyl)-ar-methyl-1H-benzotriazole-1-methanamine; N,N-bis(nonyl)-ar-methyl-1H-benzotriazole-1-methanamine; N,N-bis(decyl)-ar-methyl-1H-benzotriazole-1-methanamine; N,N-bis(undecyl)-ar-methyl-1H-benzotriazole-1-methanamine; N,N-bis(dodecyl)-ar-methyl-1H-benzotriazole-1-methanamine; N,N-bis(2-ethylhexyl)-ar-methyl-1H-benzotriazole-1-methanamine and mixtures thereof. In one embodiment the metal deactivator is selected from N,N-bis(2-ethylhexyl)-ar-methyl-1H-benzotriazole; 1-methanamine; 1,2,4-triazoles; benzimidazoles; 2-alkyldithiobenzimidazoles; 2-alkyldithiobenzothiazoles; 2-(N,N-dialkyldithiocarbamoyl)benzothiazoles; 2,5-bis(alkyl-dithio)-1,3,4-thiadiazoles such as 2,5-bis(tert-octyldithio)-1,3,4-thiadiazole; 2,5-bis(tert-nonyldithio)-1,3,4-thiadiazole; 2,5-bis(tert-decyldithio)-1,3,4-thiadiazole; 2,5-bis(tert-undecyldithio)-1,3,4-thiadiazole; 2,5-bis(tert-dodecyldithio)-1,3,4-thiadiazole; 2,5-bis(tert-tridecyldithio)-1,3,4-thiadiazole; 2,5-bis(tert-tetradecyldithio)-1,3,4-thiadiazole; 2,5-bis(tert-pentadecyldithio)-1,3,4-thiadiazole; 2,5-bis(tert-hexadecyldithio)-1,3,4-thiadiazole; 2,5-bis(tert-heptadecyldithio)-1,3,4-thiadiazole; 2,5-bis(tert-octadecyldithio)-1,3,4-thiadiazole; 2,5-bis(tert-nonadecyldithio)-1,3,4-thiadiazole; 2,5-bis(tert-eicosyldithio)-1,3,4-thiadiazole; and mixtures thereof; 2,5-bis(N,N-dialkyldithiocarbamoyl)-1,3,4-thiadiazoles; 2-alkyldithio-5-mercapto thiadiazoles; and the like. The metal deactivator may be present in the range of about 0% to about 90%, and in one embodiment about 0.0005% to about 50% and in another embodiment about 0.0025% to about 30% of the fuel additive. A suitable amount of metal deactivator may range from about 5 ppm by weight to about 15 ppm by weight of a total weight of a fuel composition. A ratio of component (b) to component (c) in fuels and fuel additive compositions according to the disclosure may range from about 0.5:1 to about 5:1 such as from about 1:1 to about 3:1 or from about 1:1 to about 2:1. 
     In one embodiment, the metal deactivator is tolyltriazole which is used in the fuel at a concentration of about 5 ppmw based on a total weight of the fuel composition. Accordingly, a premium fuel composition may include 10 ppmw of component (a), 85 ppmw of component (b) and 5 ppmw of component (c). 
     Other commercially available detergents may be used in combination with additive components (a) and (b) as described herein. Such detergents include but are not limited to succinimides, Mannich base detergents, and quaternary ammonium detergents. When formulating the fuel compositions of this application, the additive composition of (a) and (b) may be employed in amounts sufficient to reduce or inhibit deposit formation in a fuel system or combustion chamber of an engine and/or crankcase. In some aspects, the fuels may contain minor amounts of the above described additive composition that controls or reduces the formation of engine deposits, for example injector deposits in diesel and/or gasoline engines. For example, the fuels of this application may contain, on an active ingredient basis, a total amount of the additive composition of components (a) and (b) in the range of about 5 mg to about 500 mg of additive composition per Kg of fuel, such as in the range of about 10 mg to about 150 mg of per Kg of fuel or in the range of from about 30 mg to about 100 mg of the additive composition per Kg of fuel. In aspects, where a carrier is employed, the fuel compositions may contain, on an active ingredients basis, an amount of the carrier in the range of about 1 mg to about 100 mg of carrier per Kg of fuel, such as about 5 mg to about 50 mg of carrier per Kg of fuel. The active ingredient basis excludes the weight of (i) unreacted components associated with and remaining in additive composition, and (ii) solvent(s), if any, used in the manufacture of the additive composition either during or after its formation but before addition of a carrier, if a carrier is employed. 
     The additive compositions of the present application, including components (a) and (b) described above, and optional additives used in formulating the fuels of this invention may be blended into the base fuel individually or in various sub-combinations. In some embodiments, the additive components of the present application may be blended into the fuel concurrently using an additive concentrate, as this takes advantage of the mutual compatibility and convenience afforded by the combination of ingredients when in the form of an additive concentrate. Also, use of a concentrate may reduce blending time and lessen the possibility of blending errors. 
     The fuels of the present application may be applicable to the operation of diesel and gasoline engines. The engines include both stationary engines (e.g., engines used in electrical power generation installations, in pumping stations, etc.) and ambulatory engines (e.g., engines used as prime movers in automobiles, trucks, road-grading equipment, military vehicles, etc.). For example, the fuels may include any and all gasoline and middle distillate fuels, diesel fuels, biorenewable fuels, biodiesel fuel, gas-to-liquid (GTL) fuels, jet fuel, alcohols, ethers, kerosene, low sulfur fuels, synthetic fuels, such as Fischer-Tropsch fuels, liquid petroleum gas, bunker oils, coal to liquid (CTL) fuels, biomass to liquid (BTL) fuels, high asphaltene fuels, fuels derived from coal (natural, cleaned, and petcoke), genetically engineered biofuels and crops and extracts therefrom, and natural gas. “Biorenewable fuels” as used herein is understood to mean any fuel which is derived from resources other than petroleum. Such resources include, but are not limited to, corn, maize, soybeans and other crops; grasses, such as switchgrass, miscanthus, and hybrid grasses; algae, seaweed, vegetable oils; natural fats; and mixtures thereof. In an aspect, the biorenewable fuel can comprise monohydroxy alcohols, such as those comprising from 1 to about 5 carbon atoms. Non-limiting examples of suitable monohydroxy alcohols include methanol, ethanol, propanol, n-butanol, isobutanol, t-butyl alcohol, amyl alcohol, and isoamyl alcohol. 
     Diesel fuels that may be used include low sulfur diesel fuels and ultra low sulfur diesel fuels. A “low sulfur” diesel fuel means a fuel having a sulfur content of 50 ppm by weight or less based on a total weight of the fuel. An “ultra low sulfur” diesel fuel (ULSD) means a fuel having a sulfur content of 15 ppm by weight or less based on a total weight of the fuel. In another embodiment, the diesel fuels are substantially devoid of biodiesel fuel components. 
     Accordingly, aspects of the present application are directed to methods for reducing the amount of injector deposits of engines having at least one combustion chamber and one or more direct fuel injectors in fluid connection with the combustion chamber. In another aspect, the additive containing components (a) and (b) described herein may be combined with component (c) and with other succinimide detergents, derivatives of succinimide detergents, and/or quaternary ammonium salts having one or more polyolefin groups; such as quaternary ammonium salts of polymono-olefins, polyhydrocarbyl succinimides; polyhydrocarbyl Mannich compounds: polyhydrocarbyl amides and esters. The foregoing quaternary ammonium salts may be disclosed for example in U.S. Pat. Nos. 3,468,640; 3,778,371; 4,056,531; 4,171,959; 4,253,980; 4,326,973; 4,338,206; 4,787,916; 5,254,138: 7,906,470; 7,947,093; 7,951,211; U.S. Publication No. 2008/0113890; European Patent application Nos. EP 0293192; EP 2033945; and PCT Application No. WO 2001/110860. 
     In some aspects, the methods comprise injecting a hydrocarbon-based fuel comprising the additive composition of the present disclosure through the injectors of the engine into the combustion chamber, and igniting the fuel. In some aspects, the method may also comprise mixing into the fuel at least one of the optional additional ingredients described above. 
     The fuel compositions described herein are suitable for both direct and indirect injected engines. The direct injected diesel engines include high pressure common rail direct injected engines. Spark ignition engines include, but are not limited to, port fuel injected engines. 
     EXAMPLES 
     The following examples are illustrative of exemplary embodiments of the disclosure. In these examples as well as elsewhere in this application, all parts and percentages are by weight unless otherwise indicated. It is intended that these examples are being presented for the purpose of illustration only and are not intended to limit the scope of the invention disclosed herein. 
     Component (a) Example 1 
     A mixture of oleyl amidopropyl dimethylamine (366 grams) and sodium chloroacetate (SCA, 113 grams) was heated in a mixture of isopropanol (125 mL) and water (51 grams) at 80° C. for 5.5 hours. Isopropanol (600 mL) and 2-ethylhexanol (125 grams) were added and the mixture was concentrated by heating to remove water. The resultant mixture was filtered through CELITE 512 filter medium to give product as yellow oil. 
     Component (a) Example 2 
     The reaction product was made similar to Component (a) Example 1 with the exception that oleyl amidopropyl dimethylamine was replaced with oleyl dimethylamine. The reaction product was mixed with an aromatic solvent and 2-ethylhexanol to provide a yellow liquid. 
     Component (b) Example 3 
     A component (b) was produced by mixing 435 grams of 950 number average molecular weight polyisobutylene succinic anhydride (PIBSA) with aromatic solvent 150 (195 grams) in a round bottom flask. Water (11.4 grams) was added to the mixture. The mixture was then heated at 80° C. for 3 hours. Residual water was removed by a rotary evaporator under vacuum at 70° C. The mixture was then filtered through a diatomaceous earth filter to give a clear oil product. 
     Component (b) Example 4 
     A component (b) was produced from the reaction of a 950 number average molecular weight polyisobutylene succinic anhydride (PIBSA) with tetraethylenepentamine (TEPA) in a molar ratio of PIBSA/TEPA=1/1. PIBSA (551 g) was diluted in 200 grams of aromatic 150 solvent under nitrogen atmosphere. The mixture was heated to 115° C. TEPA was then added through an addition funnel. The addition funnel was rinsed with additional 50 grams of aromatic 150 solvent. The mixture was heated to 180° C. for about 2 hours under a slow nitrogen sweep. Water was collected in a Dean-Stark trap. The reaction mixture was further vacuum stripped to remove volatiles to give a brownish oil product. 
     Component (b) Example 5 
     A component (b) was made similar to that of Example 4 except that the molar ratio of PIBSA/TEPA was 1.6:1. 
     Component (b) Example 6 
     A component (b) was made similar to that of Example 5 except that the molar ratio of PIBSA/TEPA was 1.3:1 and the number average molecular weight of the PIBSA was 750 instead of 950. 
     Component (b) Example 7 
     A component (b) was made similar to that of Example 6 except that the molar ratio of PIBSA/TEPA was 1.5:1. 
     In the following example, an injector deposit test was performed on a diesel engine using an industry standard diesel engine fuel injector test, CEC F-98-08 (DW10) as described below. 
     Diesel Engine Test Protocol 
     A DW10 test that was developed by Coordinating European Council (CEC) was used to demonstrate the propensity of fuels to provoke fuel injector fouling and was also used to demonstrate the ability of certain fuel additives to prevent or control these deposits. Additive evaluations used the protocol of CEC F-98-08 for direct injection, common rail diesel engine nozzle coking tests. An engine dynamometer test stand was used for the installation of the Peugeot DW10 diesel engine for running the injector coking tests. The engine was a 2.0 liter engine having four cylinders. Each combustion chamber had four valves and the fuel injectors were DI piezo injectors have a Euro V classification. 
     The core protocol procedure consisted of running the engine through a cycle for 8-hours and allowing the engine to soak (engine off) for a prescribed amount of time. The foregoing sequence was repeated four times. At the end of each hour, a power measurement was taken of the engine while the engine was operating at rated conditions. The injector fouling propensity of the fuel was characterized by a difference in observed rated power between the beginning and the end of the test cycle. 
     Test preparation involved flushing the previous test&#39;s fuel from the engine prior to removing the injectors. The test injectors were inspected, cleaned, and reinstalled in the engine. If new injectors were selected, the new injectors were put through a 16-hour break-in cycle. Next, the engine was started using the desired test cycle program. Once the engine was warmed up, power was measured at 4000 RPM and full load to check for full power restoration after cleaning the injectors. If the power measurements were within specification, the test cycle was initiated. The following Table 1 provides a representation of the DW10 coking cycle that was used to evaluate the fuel additives according to the disclosure. 
     
       
         
           
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                 One hour representation of DW10 coking cycle. 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 Duration 
                 Engine speed 
                 Load 
                 Torque 
                 Boost air after 
               
               
                 Step 
                 (minutes) 
                 (rpm) 
                 (%) 
                 (Nm) 
                 Intercooler (° C.) 
               
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 1 
                 2 
                 1750 
                 20 
                 62 
                 45 
               
               
                 2 
                 7 
                 3000 
                 60 
                 173 
                 50 
               
               
                 3 
                 2 
                 1750 
                 20 
                 62 
                 45 
               
               
                 4 
                 7 
                 3500 
                 80 
                 212 
                 50 
               
               
                 5 
                 2 
                 1750 
                 20 
                 62 
                 45 
               
               
                 6 
                 10 
                 4000 
                 100 
                 * 
                 50 
               
               
                 7 
                 2 
                 1250 
                 10 
                 25 
                 43 
               
               
                 8 
                 7 
                 3000 
                 100 
                 * 
                 50 
               
               
                 9 
                 2 
                 1250 
                 10 
                 25 
                 43 
               
               
                 10 
                 10 
                 2000 
                 100 
                 * 
                 50 
               
               
                 11 
                 2 
                 1250 
                 10 
                 25 
                 43 
               
               
                 12 
                 7 
                 4000 
                 100 
                 * 
                 50 
               
               
                   
               
            
           
         
       
     
     Various fuel additives were tested using the foregoing engine test procedure in an ultra low sulfur diesel fuel containing zinc neodecanoate, 2-ethylhexyl nitrate, and a fatty acid ester friction modifier (base fuel). A “dirty-up” phase consisting of base fuel only with no additive was initiated, followed by a “clean-up” phase consisting of the base fuel plus additive(s). All runs were made with 8 hour dirty-up and 8 hour clean-up unless indicated otherwise. The percent power recovery was calculated using the power measurement at end of the “dirty-up” phase and the power measurement at end of the “clean-up” phase. The percent power recovery was determined by the following formula
 
Percent Power recovery=(DU−CU)/DU×100
 
wherein DU is a percent power loss at the end of a dirty-up phase without the additive, CU is the percent power loss at the end of a clean-up phase with the fuel additive, and power is measured according to CEC F98-08 DW10 test.
 
     
       
         
           
               
               
               
               
               
             
               
                 TABLE 2 
               
               
                   
               
               
                   
                   
                 DU % 
                 CU % 
                 %  
               
               
                 Run 
                 Additives and treat rate 
                 Power 
                 Power 
                 power 
               
               
                 No. 
                 (ppm by weight) 
                 Change 
                 Change 
                 Recovery 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 1 
                   
                   
                   
                   
               
               
                 2 
                 Component (a) Example 1 (50 ppm) 
                 −5.10 
                 −5.22 
                 −2 
               
               
                 4 
                 Component (a) Example 1 (20 ppm) 
                 −4.60 
                 −5.86 
                 −27 
               
               
                 5 
                 Component (b) Example 3 (150 ppm) 
                 −11.01 
                 −5.42 
                 51 
               
               
                 6 
                 Component (b) Example 4 (85 ppm) 
                 −4.78 
                 −4.07 
                 15 
               
               
                 7 
                 Component (b) Example 5 (85 ppm) 
                 −5.70 
                 −5.40 
                 5 
               
               
                 8 
                 Component (b) Example 6 (85 ppm) 
                 −5.12 
                 −2.57 
                 50 
               
               
                 9 
                 Component (b) Example 7 (85 ppm) 
                 −5.89 
                 −3.26 
                 45 
               
               
                 10 
                 Mixture of Component (a) Example 1 
                 −2.7 
                 0.3 
                 111 
               
               
                   
                 (20 ppm) and Component (b)  
                   
                   
                   
               
               
                   
                 Example 3 (125 ppm) 
                   
                   
                   
               
               
                 11 
                 Mixture of Component (a) Example 1  
                 −4.07 
                 −0.65 
                 84 
               
               
                   
                 (10 ppm) and Component (b)  
                   
                   
                   
               
               
                   
                 Example 4 (85 ppm) 
                   
                   
                   
               
               
                 12 
                 Mixture of Component (a) Example 1  
                 −5.40 
                 −2.78 
                 49 
               
               
                   
                 (10 ppm) and Component (b)  
                   
                   
                   
               
               
                   
                 Example 5 (85 ppm) 
                   
                   
                   
               
               
                 13 
                 Mixture of Component (a) Example 1  
                 −2.57 
                 1.04 
                 140 
               
               
                   
                 (10 ppm) and Component (b)  
                   
                   
                   
               
               
                   
                 Example 6 (85 ppm) 
                   
                   
                   
               
               
                 14 
                 Mixture of Component (a) Example 1  
                 −3.26 
                 1.19 
                 137 
               
               
                   
                 (10 ppm) and Component (b)  
                   
                   
                   
               
               
                   
                 Example 7 (85 ppm) 
               
               
                   
               
            
           
         
       
     
     As shown by the foregoing Runs 10-14, a detergent mixture containing components (a) and (b) provides significant improvement in power loss recovery compared to the power recovery of each of the individual components of the mixture as shown in Runs 1-9 at comparable treat rates. Each of the Runs 10-14 showed a synergistic increase in power recovery over what would be expected from adding the power recovery of the individual components (a) and (b). 
     It is noted that, as used in this specification and the appended claims, the singular forms “a,” “an,” and “the,” include plural referents unless expressly and unequivocally limited to one referent. Thus, for example, reference to “an antioxidant” includes two or more different antioxidants. As used herein, the term “include” and its grammatical variants are intended to be non-limiting, such that recitation of items in a list is not to the exclusion of other like items that can be substituted or added to the listed items 
     For the purposes of this specification and appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. 
     While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or can be presently unforeseen can arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they can be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.