BE1018579A5 - FUEL ADDITIVES TO MAINTAIN OPTIMAL INJECTOR PERFORMANCE. - Google Patents

Abstract

There is provided a fuel, a concentrate of diesel fuel additives and a method of improving the performance of the fuel injector of a diesel engine. Diesel fuel includes a major amount of middle distillate fuel; and a reaction product of a hydrocarbyl substituted dicarboxylic acid or anhydride and an amine compound or its salt. The amine compound of the formula wherein R is selected from the group consisting of hydrogen and a hydrocarbyl group containing from about 1 to about 15 carbon atoms, and R1 is selected from the group consisting of hydrogen and a hydrocarbyl group containing from about 1 to about 20 carbon atoms. The reaction product contains at least one aminotriazole group and is present in the fuel in an amount sufficient to improve the performance of diesel fuel injectors.

Description

Description

Fuel Additives to Maintain Optimum Injector Performance

Technical area

The present invention relates to certain diesel fuel additives and diesel fuels and diesel fuel additive concentrates that include the additive. In particular, the disclosure relates to a diesel fuel additive that is effective in increasing the performance of diesel fuel injectors.

Background and summary

It has long been desired to maximize fuel economy, horsepower and driveability in diesel powered vehicles while increasing acceleration, reducing emissions and preventing hesitation. While gasoline engine performance can be increased by using dispersants to keep valves and fuel injectors clean, such gasoline dispersants are not necessarily effective in diesel fuel applications. The reasons for this unpredictability are based on many differences between the way the diesel engine and the gasoline engine operate and the chemical differences between diesel and gasoline.

Over the years, dispersant compositions for diesel fuel have been developed. Dispersant compositions known in the art for use in diesel fuel include compositions which may include polyalkylene succinimides, which are the products of the reaction of succinic anhydrides of polyalkylene and amines. Dispersants are suitable for maintaining soot and sludge in suspension in the fluid, however, they are not particularly effective at cleaning surfaces once deposits have formed on the surfaces. Thus, diesel fuel compositions that include dispersants often still produce undesirable deposits on diesel engine injectors. Therefore, improved compositions that can prevent, deposit build-up, maintaining a clean "as new" for the life of. vehicles are desired. Ideally, the same composition that can clean the soiled fuel injectors by restoring the performance of the previous state "as good as new" would also be desirable and valuable for the purpose of reducing emissions to the atmosphere.

Embodiments of the invention provide diesel fuel, a diesel fuel additive concentrate, and a method for improving the fuel injector performance of a diesel engine. Diesel fuel includes a major amount of middle distillate fuel; and a reaction product of a hydrocarbyl-substituted dicarboxylic acid or anhydride and an amine compound or salt thereof. The amine compound has the formula

wherein R is selected from the group consisting of hydrogen and a hydrocarbyl group containing from about 1 to about 15 carbon atoms, and R 1 is selected from the group consisting of hydrogen and a hydrocarbyl group containing from about 1 to about 20 carbon atoms. The reaction product contains at least one aminotriazole moiety and is present in the fuel in an amount sufficient to improve the performance of the fuel injectors.

Another embodiment of the invention provides a method of improving the performance of the injector of a diesel engine. The method includes operating the diesel engine with a fuel having a major amount of fuel and a minor amount of a reaction product derived from an amine compound or salt thereof of the formula

wherein R is selected from the group consisting of hydrogen and a hydrocarbyl group containing from about 1 to about 15 carbon atoms, and R 1 is selected from the group consisting of hydrogen and a hydrocarbyl group containing from about 1 to about 20 carbon atoms and a hydrocarbyl carbonyl compound of the formula

wherein R2 is a hydrocarbyl group having a number average molecular weight ranging from about 200 to about 3000.

Another embodiment of the invention provides a method of cleaning the fuel injectors of a diesel fuel injection engine. The method includes operating the diesel engine with a fuel having a major amount of fuel and a minor amount of a reaction product derived from an amine compound or salt thereof of the formula

wherein R is selected from the group consisting of hydrogen and a hydrocarbyl group containing from about 1 to about 15 carbon atoms, and R 1 is selected from the group consisting of hydrogen and a hydrocarbyl group containing from about 1 to about 20 carbon atoms, and a hydrocarbyl carbonyl compound of the formula

wherein R2 is a hydrocarbyl group having a number average molecular weight ranging from about 200 to about 3000.

An advantage of the fuel additive described herein is that the additive can not only reduce the amount of deposits. forming on direct and / or indirect diesel fuel injection systems, but the additive can also be effective in cleaning dirty fuel injection systems. Deposition reduction and the cleaning effect of the additive are demonstrated in engine technology in the post-2007 years.

Additional embodiments and advantages of the invention will be set forth in part in the following detailed description, and / or may be learned by the practice of the invention. It should be understood that both the foregoing general description and the following detailed description are only exemplary and explanatory and are not restrictive for the invention as claimed. Detailed description of exemplary embodiments

The compositions of the present application may be used in a minor amount in a major amount of diesel fuel and may be obtained by reaction of an amine compound or salt thereof of formula

wherein R is selected from the group consisting of hydrogen and a hydrocarbyl group containing from about 1 to about 15 carbon atoms, and R 1 is selected from the group consisting of hydrogen and a hydrocarbyl group containing from about 1 to about 20 carbon atoms, with a hydrocarbyl carbonyl compound of the formula

wherein R2 is a hydrocarbyl group having a number average molecular weight ranging from about 200 to about 3000. Without being bound by theoretical considerations, it is believed that the reaction product of the amine and the hydrocarbyl carbonyl compound is an aminotriazole, such as a bis-aminotriazole compound of the formula

including tautomers having a number average molecular weight ranging from about 200 to about 3000 containing from about 40 to about 80 carbon atoms. The five-membered ring of triazole is considered to be aromatic. Aminotriazoles are fairly stable to oxidizing agents and are extremely resistant to hydrolysis. It is believed, although not certain, that the reaction product is a polyalkenyl bis-3-amino-1,2,4-triazole. Such a product contains a relatively high nitrogen content in the range of about 1.8 wt% to about 2.9 wt% nitrogen.

As used herein, the term "hydrocarbyl group" or "hydrocarbyl" is used in its ordinary meaning, 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 predominant hydrocarbon character. Examples of hydrocarbyl groups include: (1) hydrocarbon substituents, i.e., aliphatic, (eg, alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and substituted aromatic substituents by aromatic, aliphatic and alicyclic groups, as well as cyclic substituents in which the ring is supplemented by another portion of the molecule (for example, two substituents together form an alicyclic radical); (2) substituted hydrocarbon substituents, i.e., substituents containing nonhydrocarbon moieties which, in the context of the description herein, do not alter the predominant hydrocarbon substituent (e.g., halogen (especially, chloro 'and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso and sulfoxy); (3) heterosubstituents, i.e., substituents which, although having a predominant hydrocarbon character, in the context of this specification, contain an atom other than carbon in a ring or chain otherwise composed of carbon atoms. The heteroatoms include sulfur, oxygen, nitrogen and include substituents such as pyridyl, furyl, thienyl and imidazolyl. In general, not more than two, or as another example, no more than one non-hydrocarbon substituent will be present per 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" means an amount greater than or equal to 50% by weight, for example from about 80 to about 98% by weight based on the total weight of the composition. In addition, as used herein, the term "minor amount" means less than 50% by weight based on the total weight of the composition.

Amine compound

Suitable amine compounds of formula

may be chosen from guanidines and aminoguanidines or salts thereof in which R and R1 are as defined above. Therefore, the amine compound can be selected from the inorganic salts of guanidines, such as the halide, carbonate, nitrate, phosphate and orthophosphate salts of guanidines. The term "guanidines" refers to guanidines and guanidine derivatives, such as aminoguanidine. In one embodiment, the guanidine compound for the preparation of the additive is aminoguanidine bicarbonate. Aminoguanidine bicarbonates are readily obtainable from commercial sources or can be prepared in a well-known manner.

Hydrocarbonyl carbonyl compound

The hydrocarbyl carbonyl reactant compound of the additive may be any suitable compound having a hydrocarbyl moiety and a carbonyl moiety and which is capable of binding with the amine compound to form the disclosure additives. Non-limiting examples of such suitable hydrocarbyl carbonyl compounds include, but are not limited to, hydrocarbyl substituted succinic anhydrides, hydrocarbyl substituted succinic acids, and hydrocarbyl substituted succinic acid esters.

In certain aspects, the hydrocarbyl carbonyl compound may be a polyalkylene succinic anhydride reactant having the following formula:

wherein R2 is a hydrocarbyl moiety, such as, for example, a polyalkenyl radical having a number average molecular weight of from about 100 to about 5000. For example, the number average molecular weight of R2 may range from about 200 to about 3000. , as measured by GPC. Unless otherwise indicated, the molecular weights herein are number average molecular weights.

The polyalkenyl radicals R 2 may comprise one or more polymer units chosen from linear or branched alkenyl units. In some aspects, 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, radicals of octene and decene radicals. In some aspects, the polyalkenyl radical R 2 may be in the form of, for example, a homopolymer, a copolymer or a terpolymer. In one aspect, the polyalkenyl radical is. isobutylene. For example, the polyalkenyl radical may be a polyisobutylene homopolymer 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 polyalkenyl radicals R 2 can be formed by any suitable method, such as conventional catalytic oligomerization of alkenes.

In an additional aspect, the hydrocarbyl moiety R 2 may be derived from a linear alpha olefin or an acid-isomerized alpha olefin obtained by oligomerization of ethylene by methods well known in the art. These hydrocarbyl moieties may vary from about 8 carbon atoms to more than 40 carbon atoms. For example, alkenyl moieties of this type may be derived from C18 linear alpha olefins or a mixture thereof C20-24 or C16 alpha-olefins acid-isomerized.

In some aspects, high reactivity polyisobutenes having relatively high proportions of polymer molecules with a terminal vinylidene moiety can be used to form the R2 moiety. In one example, at least about 60%, such as about 70% to about 90%, of the polyisobutenes comprise terminal olefinic double bonds. This is a general trend in the industry to convert to high reactivity polyisobutenes and well-known high reactivity polyisobutenes are disclosed, for example, in US Patent No. 4,152,499, the disclosure of which is incorporated herein by reference. reference in its entirety.

Specific examples of hydrocarbyl carbonyl compounds include such compounds as dodecenyl succinic anhydrides, C 16-18 alkenyl succinic anhydrides and polyisobutenyl succinic anhydride (PIBSA). In some embodiments, the PIBSA may have a portion of polyisobutylene with a vinylidene content ranging from about 4% to greater than about 90%. In some embodiments, the ratio of the number of carbonyl groups to the number of hydrocarbyl moieties in the hydrocarbyl carbonyl compound may range from about 1: 1 to about 6: 1.

In some aspects, approximately one mole of maleic anhydride can be reacted per mole of polyalkylene, so that the resulting polyalkenyl succinic anhydride has from about 0.8 to about 1 succinic anhydride group per polyalkylene substituent. In other aspects, the weight ratio of succinic anhydride moieties to alkylene moieties may vary from about 0.5 to about. 3.5, as from about 1 to about 1.1.

The hydrocarbyl carbonyl compounds can be prepared by any suitable method. Processes for preparing hydrocarbyl carbonyl compounds are well known in the art. An example of a known method for forming a hydrocarbyl carbonyl compound comprises mixing a polyolefin and maleic anhydride. The polyolefin and maleic anhydride reactants are heated at temperatures, for example, from about 150 ° C to about 250 ° C, optionally using a catalyst, such as chlorine or peroxide. Another exemplary process for the preparation of polyalkylene succinic anhydrides is described in U.S. Patent No. 4,234,435, which is incorporated herein by reference in its entirety.

The hydrocarbyl carbonyl and amine compounds described above may be mixed together under appropriate conditions to provide the aminotriazole compounds of the desired product of the present disclosure. In one aspect of the present disclosure, the reactive compounds may be mixed together in a mole ratio of hydrocarbyl carbonyl to amine ranging from about 1: 1 to about 1: 2.5. For example, the molar ratio of the reactants can range from about 1: 1 to about 1: 2.2.

Suitable reaction temperatures can range from about 155 ° C to about 200 ° C at atmospheric pressure. For example, the reaction temperatures may vary from about 160 ° C to about 190 ° C. Any suitable reaction pressures may be used, such as, including subatmospheric pressures or supra-atmospheric pressures. However, the temperature range may be different from those listed if the reaction is performed at a pressure other than atmospheric pressure. The reaction may be carried out for a period of time in the range of about 1 hour to about 8 hours, preferably in the range of about 2 hours to about 6 hours.

In some aspects of the present application, the dispersants of this application can be used in combination with a soluble diesel fuel carrier. These supports can be of various types, such as liquids or solids, for example, waxes. Examples of liquid carriers include, but are not limited to, mineral oils and oxygenates, such as polyalkoxylated liquid ethers (also known as polyalkylene glycols or polyalkylene ethers), polyalkoxylated liquid phenols, polyalkoxylated liquid esters, polyalkylated liquid amines, and mixtures thereof. Examples of oxygenate supports can be found in U.S. Patent No. 5,752,989, issued May 19, 1998, to Henly et al., The disclosure of which is incorporated herein by reference in its entirety. Additional examples of oxygenate supports include alkyl-substituted aryl polyalkoxylates disclosed in US Patent Publication No. 2003/0131,527, published July 17, 2003, by Colucci et al., The disclosure of which is incorporated. here as a reference in its entirety.

In other aspects, the compositions of the present application may not contain support. For example, some compositions of the present application may not contain mineral oil or oxygenates, such as those oxygenates described above.

One or more optional additional compounds may be present in the fuel compositions of the disclosed embodiments. For example, the fuels may contain conventional amounts of cetane number improvers, corrosion inhibitors, cold flow improvers (filterability limit additives, CFPP), flow, solvents, demulsifiers, lubricity additives, friction modifiers, amine stabilizers, combustion improvers, dispersants, antioxidants, heat stabilizers, conductivity improvers, metal deactivators, marker dyes, organic nitrate combustion accelerators, cyclomatic manganese tricarbonyl compounds, and others. In some aspects, the compositions described herein may contain about 10 percent by weight or less, or in other aspects, about 5 percent by weight or less, based on the total weight of the additive concentrate, one or several of the additives above. Similarly, the fuels may contain appropriate amounts of conventional fuel blend components such as methanol, ethanol, dialkyl ethers and others.

In some aspects of the disclosed embodiments, organic nitrate combustion accelerators that include aliphatic or cycloaliphatic nitrates in which the aliphatic or cycloaliphatic moiety is saturated, and which contain up to about 12 carbons can be used. Examples of organic nitrate combustion accelerators that can be used are methyl nitrate, ethyl nitrate, propyl nitrate, isopropyl nitrate, allyl nitrate, butyl nitrate, nitrate isobutyl, sec-butyl nitrate, t-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, nitrate dodecyl, cyclopentyl nitrate, cyclohexyl nitrate, methylcyclohexyl nitrate, cyclododecyl nitrate, 2-ethoxyethyl nitrate, 2- (2-ethoxyethoxy) ethyl nitrate, tetrahydrofuranyl nitrate and 'other. Mixtures of these materials can also be used.

Examples of optional suitable metal deactivators useful in the compositions of the present application are disclosed in U.S. Patent No. 4,482,357, issued November 13, 1984, the disclosure of which is incorporated herein 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.

Suitable optional cyclomatic manganese tricarbonyl compounds which can be used in the compositions of the present application include, for example, manganese cyclopentadienyl tricarbonyl, manganese methylcyclopentadienyl tricarbonyl, manganese indenyl tricarbonyl and manganese ethylcyclopentadienyl tricarbonyl . Still other examples of suitable cyclomatic manganese tricarbonyl are disclosed in U.S. Patent No. 5,575,823, issued November 19, 1996 and U.S. Patent No. 3,015,668, issued January 2, 1962, disclosures of which are incorporated herein. as a reference in their entirety.

When formulating the fuel compositions of this application, the additives can be used in amounts sufficient to reduce or inhibit the formation of deposits in a diesel engine. In some aspects, the fuels may contain minor amounts of the bis-aminotriazole compound described above that controls or reduces the formation of deposits in the engine, for example, deposits in the injector in diesel engines. For example, the diesel fuels of this application may contain, on an active ingredient basis, an amount of the bis-aminotriazole compound in the range of about 5 mg to about 200 mg of bis-aminotriazole compound per kg of as in the range of about 20 mg to about 120 mg of bis-aminotriazole compound per kg of fuel. In aspects, or a carrier is used, the fuel compositions may contain, on a active ingredient, a carrier amount 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 dispersant per kg of fuel. The active ingredient base excludes the weight (i) of the unreacted components such as the polyalkylene compounds associated with and remaining in the product as produced and used, and (ii) the solvent (s), if present, used in the manufacture of the bis-aminotriazole compound either during or after its formation but before the addition of a carrier, if a carrier is used.

The additives of the present application, including the bis-aminotriazole compound described above, and the optional additives used in the formulation of the fuels of this invention can be blended into the base diesel fuel individually or in various subcombinations. In certain embodiments, the additive components of the present application can be mixed in the diesel fuel simultaneously using an additive concentrate, thereby taking advantage of the mutual compatibility and suitability provided by the combination of ingredients. when they are in the form of an additive concentrate. Similarly, the use of a concentrate can reduce the mixing time and reduce the possibility of mixing errors.

Thus, in certain embodiments, the present application relates to a diesel fuel additive, comprising the bis-aminotriazole compound, the compound being the product of the reaction of at least one guanidine and at least one polyalkylene succinic anhydride. as described above. The additive may comprise one or more of the additive ingredients listed above. The additive can be packaged and sold separately from diesel fuel, for example, in a concentrated form. The additive can then be mixed with the diesel fuel by the customer as desired.

The diesel fuels of the present application may be applicable to the operation of both stationary diesel engines (e.g., engines used in power generation facilities, pumping stations, etc.) and ambulatory diesel engines ( for example, engines used as a prime mover in automobiles, trucks, road gradation equipment, military vehicles, etc.). For example, fuels may include any and all middle distillate fuels, diesel fuels, bio-renewable fuels, biodiesel fuels, gas-to-liquids fuels (GTLs), jet fuels, alcohols, ethers, kerosene, low-sulfur fuels, synthetic fuels, such as Fischer-Tropsch fuels, liquefied petroleum gas, heavy fuel oil, fuels from the coal industry to liquids (CTL), biomass to liquid (BTL) fuels, high asphaltene fuels, coal derived fuels (natural, cleaned and petroleum coke), genetically modified biofuels and harvests and extracts these and natural gas. "Biorenewable fuels" as used. here are understood to mean any fuel that is derived from other resources than petroleum: These resources include, but are not limited to, cereals, corn, soybeans and other crops; grasses such as switchgrass, miscanthus and hybrid grasses; seaweed, kelp, vegetable oils; natural fats; and mixtures thereof. In one aspect, the bioreversible fuel may comprise monohydroxy alcohols, such as those comprising from 1 to about 5 carbon atoms. Non-limiting examples of monohydroxy alcohols include methanol, ethanol, propanol, n-butanol, isobutanol, t-butyl alcohol, amyl alcohol and isoamyl alcohol. Accordingly, the aspects of the present application relate to methods of reducing the amount of injector deposits of a diesel engine having at least one combustion chamber and one or more direct fuel injection systems in liquid connection with the combustion chamber. In another aspect, the improvements can too. be observed in indirect fuel injection systems. In some aspects, the methods include injecting a hydrocarbon-based combustion compression fuel comprising the bis-aminotriazole additive of the present application, by diesel engine injectors into the combustion chamber, and combustion. fuel compression combustion. In some aspects, the process may also include mixing in diesel fuel at least one of the additional optional ingredients described above.

In one embodiment, the diesel fuels of the present application may be essentially free, as lacking, of conventional succinimide dispersant compounds. The term "essentially free" is defined, for the purposes of this application, as concentrations with essentially no measurable effect on injector cleanliness or deposit formation.

In yet other aspects of the present application, the fuel additive may be free or essentially free of 1,2,4-triazoles other than the triazoles described above. For example, the compositions may be substantially free of triazoles of formula II,

where R4 and R5 are independently selected from hydrogen and hydrocarbyl groups, provided that at least one of R4 and R5 is not hydrogen. Examples of hydrocarbyl groups include straight, branched or cyclic C 2 -C 50 alkyl groups; straight-chain, branched or cyclic C 2 -C 20 alkenyl groups; and substituted or unsubstituted aryl groups, such as phenyl groups, tolyl groups and xylyl groups.

EXAMPLES

The following examples are illustrative of exemplary embodiments of the present invention. In these examples, as well as elsewhere in this application, all parts and percentages are by weight unless otherwise indicated. It should be understood that these examples are presented by way of illustration only and are not intended to limit the scope of the invention disclosed herein.

Example 1. Polybutenyl succinic anhydride of molecular weight 950 is heated to 95 ° C. An aminoguanidine bicarbonate oil slurry (AGBC) is added over a period of 45 minutes. The mixture is heated under vacuum at 160 ° C and maintained at this temperature for about 6 hours, removing water and carbon dioxide. The resulting mixture is filtered.

In the following example, an injector deposition test is performed on a diesel engine using a conventional diesel engine injector test as described below.

Test program

The test program used is described by Graupner et al. "Injector deposit test for modem diesel engines", Technische Akademie Esslingen, 5th International Colloquium, 12-13 January 2005, 3.10, p57, edited by Wilfried J. Bartz. Briefly, the program uses a modern diesel engine with a highlight of the formation of the deposit on the fuel injector, 1 / test is broken down into 5 steps: a) measurement of the power output of the engine b) a lap of 8 hours endurance c) a prolonged soaking period (3 to 8 hours) during which the engine is stopped and allowed to cool d) a second endurance lap of 8 hours e) measurement of the output power of the engine

For the data presented here, the above five steps are used, however, steps b), c) and d) can be repeated several times depending on the current testing program. Similarly, steps a) and e) may be omitted but are useful for improving the understanding of the results. The results are reported as the difference between a mean actual power at the start of the test during step a) and an average actual power at the end of the test during step e). Alternatively, if step a) and step e) of the above procedure are not performed, the difference measured between the actual starting power at full load / full speed and ultimate load / speed can be used. Differences in smoke production are also noted. The depot formation on the injector will have a negative influence on the final output power and will increase the amount of smoke observed. In order to replicate the expected conditions in a modern diesel engine, a small amount of metallic contamination in the form of zinc neodecanoate is added to the fuel used to run the engine. In the table, BAT is a bis-aminotriazole compound as described above.

As shown in the previous example, the bis-aminotriazole compound provides virtually no real power loss in a diesel fuel that has been doped with zinc. This result is surprising and totally unexpected. Therefore, it is believed that the bis-aminotriazole compositions as described herein can be effective in keeping the surfaces of the diesel fuel injectors clean.

It should be noted that, as used in this specification and the appended claims, the singular forms "a", "a" and "the", "la", include plural referents unless otherwise indicated and unequivocally limited to a referent . So, for example, the reference to "an antioxidant" includes two or more different antioxidants. As used herein, the term "includes" and its grammatical variants are meant to be non-limiting, as the recitation of the articles in a list is not to the exclusion of other articles that may be substituted or added to the listed articles.

For the purposes of this specification and the 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 to be modified in all cases by the term "about". Therefore, unless otherwise indicated, the numerical parameters given in the following specification and the appended claims are approximations which may vary depending on the desired properties contemplated to be obtained by the present disclosure. At the very least, and not as an attempt to limit the demand for equivalence doctrine to claims, each numerical parameter must at least be designed in light of the number of significant digits reported and by the application of ordinary rounding techniques. .

While the particular embodiments have been described, substantial variations, modifications, variations, improvements, and equivalents that are or may be presently provided may occur to the Applicant or other skilled persons. Therefore, the appended claims as filed and as they may be amended are assumed to embrace all such variations, modifications, variations, improvements and substantial equivalents.

Claims (31)

A diesel fuel for fuel injection comprising: a major amount of middle distillate fuel; and a reaction product of (a) a hydrocarbyl-substituted dicarboxylic acid or anhydride and (b) an amine compound or a salt thereof of the formula

wherein R is selected from the group consisting of hydrogen and a hydrocarbyl group containing from about 1 to about 15 carbon atoms, and R 1 is selected from the group consisting of hydrogen and a hydrocarbyl group containing from about 1 to about 20 carbon atoms and wherein the reaction product is prepared at a temperature of about 155 ° C to about 200 ° C at atmospheric pressure and contains at least one aminotriazole moiety and wherein product of the reaction is present. in an amount in the range of about 5 mg to about 200 mg per kg of fuel, said amount being sufficient to improve the performance of direct and / or indirect diesel fuel injection devices. 2. The fuel of claim 1, wherein the reaction product is substantially free of succinimide dispersants. The fuel of claim 1, wherein the reaction product comprises a compound of formula

and tautomers thereof, wherein R2 is a hydrocarbyl group having a number average molecular weight ranging from about 200 to about 3000. The fuel of claim 1, wherein the hydrocarbyl dicarboxylic anhydride comprises one or more hydrocarbyl-substituted succinic anhydrides. The fuel of claim 4, wherein R2 is a polyolefin radical having a number average molecular weight of from about 200 to about 3000. 6. Use of the fuel according to claim 5 for the direct injection of fuel into a diesel engine. The fuel according to claim 6, wherein the polyolefin radical comprises a polyisobutylene radical which is derived from high reactivity polyisobutylenes having at least 60% or more terminal olefinic double bonds. The fuel of claim 1, wherein a molar ratio of (a) to (b) is from about 1: 1 to about 1: 2.2. The fuel of claim 1, wherein the amine comprises an inorganic guanidine salt. The fuel of claim 1, wherein the amine comprises an aminoguanidine salt. The fuel of claim 1, wherein the amine comprises aminoguanidine bicarbonate. A method of improving the injection performance of a fuel-injected diesel engine comprising operating the diesel engine with a fuel composition comprising a major amount of fuel and from 5 mg to 200 mg per kg of fuel oil. a reaction product derived from (a) an amine compound or a salt thereof

wherein R is selected from the group consisting of hydrogen and a hydrocarbyl group containing from about 1 to about 15 carbon atoms, and R 1 is selected from the group consisting of hydrogen and a hydrocarbyl group containing from about 1 to about 20 carbon atoms and (b) a hydrocarbyl carbonyl compound of the formula

wherein R2 is a hydrocarbyl group having a number average molecular weight of from about 200 to about 3000, wherein the reaction product is prepared at a temperature in the range of about 155 ° C to about 200 ° C at the atmospheric pressure and the reaction product contains at least one aminotriazole group. The process of claim 12 wherein the reaction product is substantially free of succinimide dispersants. The process of claim 12 wherein R2 is a polyisobutylene having a number average molecular weight of from about 200 to about 3000. The method of claim 12, wherein the fuel injection diesel engine comprises a direct injection diesel engine. The process of claim 12, wherein a molar ratio of (a) to (b) is from about 1: 1 to about 2.2: 1. The process of claim 12, wherein the amine is aminoguanidine bicarbonate. A method of cleaning a fuel injector of a diesel fuel injection engine comprising operating the diesel engine with a fuel composition comprising a major amount of fuel and from 5 mg to 200 mg per kilogram of fuel oil. reaction product derived from (a) an amine compound or a salt thereof

wherein R is selected from the group consisting of hydrogen and a hydrocarbyl group containing from about 1 to about 15 carbon atoms, and R 1 is selected from the group consisting of hydrogen and a hydrocarbyl group containing about 1 to about 20 carbon atoms and (b) a hydrocarbyl carbonyl compound of the formula

wherein R2 is a hydrocarbyl group having a number average molecular weight of from about 200 to about 3000, wherein the reaction product is prepared at a temperature in the range of about 155 ° C to about 200 ° C at the atmospheric pressure and the reaction product contains at least one aminotriazole group. The process of claim 18, wherein the reaction product is substantially free of succinimide dispersants. The process of claim 18, wherein R2 is a polyolefin radical having a number average molecular weight of from about 200 to about 3000. 21. The method of claim 18, wherein the fuel injection diesel engine comprises a direct injection diesel engine. The method of claim 18, wherein a molar ratio of (a) to (b) is from about 1: 1 to about 2.2: 1. 23. The method of claim 12, wherein the amine is aminoguanidine bicarbonate. 24. A method for preparing a diesel fuel for use in a diesel engine comprising mixing a diesel fuel with a fuel additive concentrate comprising a reaction product derived from (a) an amine compound or a salt of this one of formula

wherein R is selected from the group consisting of hydrogen and a hydrocarbyl group containing from about 1 to about 15 carbon atoms, and R 1 is selected from the group consisting of hydrogen and a hydrocarbyl group containing about 1 to about 20 carbon atoms and (b) a hydrocarbyl carbonyl compound of the formula

wherein R2 is a hydrocarbyl group having a number average molecular weight of from about 200 to about 3000, wherein said reaction product is prepared at a temperature in the range of about 155 ° C to about 200 ° C at the atmospheric pressure and the reaction product contains at least one aminotriazole group and wherein the additive concentrate comprises an amount of reaction product sufficient to provide from 5 mg to 200 mg per kg of reaction product in the fuel. 25. The method of claim 24, wherein R2 is a polyolefin radical having a number average molecular weight of about 500 to about 1000 daltons. 26. The method of claim 25, wherein the polyolefin radical is a polyisobutylene radical. The method of claim 26, wherein the polyisobutylene radical is derived from high reactivity polyisobutenes having at least 60% or more terminal olefinic double bonds. The method of claim 24, wherein a molar ratio of (a) to (b) is from about 1: 1 to 2.2: 1. 29. The method of claim 24, wherein the amine comprises an inorganic guanidine salt. 30. The method of claim 24, wherein the diesel engine comprises a direct injection diesel engine. 31. A method according to any of claims 24 to 31, wherein the fuel is selected from the group consisting of middle distillate fuels, diesel fuels, biorevable fuels, biodiesel fuels, fuels from the gas stream to liquids (GTL), jet fuels, alcohols, ethers, kerosene, low sulfur fuels, synthetic fuels, such as fuels derived from the Fischer-Tropsch process, liquefied petroleum gas, oil heavy fuel, coal-to-liquids fuels (CTL), biomass-to-liquids fuels (BTL), high-asphaltene fuels, coal-derived fuels (natural, cleaned and petroleum coke) ), genetically modified biofuels and crops and extracts thereof and natural gas.