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    • 专利摘要:
    A method for cleaning internal components of a fuel injector for a diesel engine, which method includes operating the engine with a fuel composition comprising a major amount of fuel and from about 10 to about 500 ppm by weight a compound of formula: (NH2) - (N3C3H) - (CH R2) - CH2 - (N3C2H) - (NH2) and the tautomers and enantiomers thereof, with R2 a hydrocarbyl group having a number average molecular weight of 100 to 5,000 daltons.
    公开号:BE1021686B1
    申请号:E2013/0252
    申请日:2013-04-09
    公开日:2016-01-08
    发明作者:Julienne M. Galante-Fox；Scott D. Schwab；Xinggao Frang
    申请人:Afton Chemical Corportion；
    IPC主号:
    专利说明:

    Fuel additives to treat internal deposits of fuel injectors
    Related Applications
    This application is a continuation in part of application number 12/119 788, filed on May 13, 2008, currently pending and is a continuation in part of application serial number 13/111,364, filed May 19 2011, currently pending.
    Technical area
    This disclosure relates to certain diesel fuel additives and processes for cleaning and / or preventing internal deposits in injectors for engines running on diesel fuel. In particular, the disclosure relates to methods that are effective against internal deposits in injectors for engines operating with very low sulfur diesel fuels. Background and summary
    Recent changes in diesel fuels and diesel fuel additives have led to new injector performance issues with deposits, including a new type of deposit not yet experienced with older diesel fuel formulations. Injector performance issues affect all areas; engines for the road fleet, mining equipment, agricultural equipment, railway engines and marine engines, river boat engine.
    Vehicle drivers, fuel marketers and fuel manufacturers are now seeing deposits forming on the internal parts of the fuel injectors. If left untreated, these deposits can lead to significant power loss, reduced fuel economy and, in extreme cases, increased downtime and higher maintenance costs due to premature replacement of fuel. "Clogged injectors". It is thought that the new deposits may be the result of some common corrosion inhibitors, biofuel components, and acid friction modifier or other carboxylic components used in the reaction of fuels with trace amounts of transition metals, Alkaline and alkaline earth metals form salts that are less soluble in ultra-low sulfur diesel (ULSD) fuels than the higher sulfur fuels of the past. When these salts are present in a fuel that is used in a high-voltage common rail (HPCR) motor concept, these salts may tend to settle in the very tight tolerance zones of the injectors. These deposits can lead to low fuel injection, which in turn can lead to loss of power, loss of fuel economy, irregular engines, and possibly engine downtime and costs. excessive maintenance.
    ULSDs now account for about 79% of all distillates supplied in the United States. Similarly, the standard renewable fuel minimum for biodiesel was raised to one billion gallons in 2012. There are indications that the amount of biodiesel required to be used in fuel will be even higher in the future. As a result, the slate of fuel change continues to shift to more ULSD (with less solubility for salts that may form) and more biodiesel to the market (another potential source of materials causing deposits in the fuel system).
    According to this disclosure, exemplary embodiments provide a method for cleaning the internal components of a fuel injector for a diesel engine. The method includes operating a diesel fuel injection engine with a fuel composition comprising (A) a major amount of fuel, (B) from about 10 to about 500 ppm by weight based on the total weight of the composition of (A) a compound of formula:
    and tautomers and enantiomers thereof, wherein R2 is a polyisobutylene group having a number average molecular weight ranging from 100 to 5000 daltons, and (C) an amount of a hydrocarbyl succinimide dispersant in which a ratio of B: C weight in the fuel ranges from 1: 2 to 1:10.
    Another embodiment of the disclosure provides a method for reducing a quantity of salt deposits on the internal components of a fuel injector for a diesel fuel injection engine. The method includes operating the diesel engine with a fuel composition comprising: (A) a major amount of fuel, (B) from about 10 to about 100 ppm by weight and a compound of the formula:
    and tautomers and enantiomers thereof, wherein R2 is a polyisobutylene group having a number average molecular weight ranging from 100 to 5000 daltons, and an amount of a hydrocarbyl succinimide dispersant, wherein a weight ratio of A: B in the fuel varies from 1: 2 to 1:10.
    Another embodiment of this disclosure provides a method for preventing clogging of a fuel filter for fuel injectors of a diesel fuel injection engine. The method includes providing a major amount of fuel and a minor amount of (A) a compound of the formula:
    and tautomers and enantiomers thereof, wherein R2 is a polyisobutylene group having a number average molecular weight ranging from 100 to 5000 daltons and (B) an amount of hydrocarbyl succinimide dispersant, in which a weight ratio A: B in the fuel ranges from 1: 2 to 1:10, and wherein the fuel comprises from about 5 mg to about 200 mg of compound (A) per kg of fuel, on an active basis; and the flow of fuel through the fuel filter for the fuel injectors.
    An advantage of the fuel additive described herein is that the additive can not only reduce the amount of internal deposits forming on the direct and / or indirect diesel fuel injection devices, but the additive can also be effective for Clean dirty fuel injectors and can prevent clogging of the fuel filters in the fuel supply to the fuel injectors.
    Additional embodiments and benefits of disclosure may be set forth in part in the following detailed description, and / or may be learned by the practice of disclosure. It should be understood that both the preceding general description and the following detailed description are exemplary and explanatory only and are not restrictive of disclosure, as claimed. Brief description of the drawings
    Figure 1 is a graphical representation of the cylinder exhaust gas temperatures over time for a four-cylinder diesel engine at the beginning of a fuel additive test.
    Figure 2 is a graphical representation of the cylinder exhaust gas temperatures over time for a four-cylinder diesel engine after eight hours of testing using no fuel detergent.
    Figures 3 and 4 are graphical representations of the cylinder exhaust gas temperatures over time for a four-cylinder diesel engine using conventional fuel detergents.
    Figures 5 and 6 are graphical representations of the cylinder exhaust gas temperatures over time for a four-cylinder diesel engine using a fuel detergent according to the embodiments of the disclosure.
    Figure 7 is a graphical representation of the exhaust gas cylinder temperatures over time for a four-cylinder diesel engine using a fuel detergent according to an embodiment of the disclosure for cleaning dirty fuel injectors.
    Detailed description of exemplary embodiments
    The composition (A) of the present disclosure may be used in a minor amount in a major amount of diesel fuel and may be obtained by reacting an amine or salt 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 with a hydrocarbyl carbonyl compound of the formula
    wherein R2 is a polyisobutylene group having a number average molecular weight ranging from about 200 to about 3000 daltons. Without wishing to be bound by theoretical considerations, it is believed that the reaction product of the amine and the hydrocarbylcarbonyl 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 daltons. 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 product of the reaction is polyalkenyl bis-3-amino-1,2,4-triazole.
    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. In particular, it refers to a group having a carbon atom attached directly 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 aromatic substituents substituted with 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 non-hydrocarbon moieties which, in the context of the present specification, do not change the predominant hydrocarbon substituent (e.g., halo (in particular, chlorine); 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 a carbon atom in a ring or chain otherwise composed of carbon atoms. Heteroatoms include sulfur, oxygen, nitrogen, and include substituents such as pyridyl, furyl, thienyl, and imidazolyl. In general, no more than two, or as another example, no more than one, non-hydrocarbon substituents 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.
    The term "bio-renewable fuels" and "biodiesel fuels" as used herein refers to any fuel that is derived from resources other than petroleum. These resources include, but are not limited to, wheat, 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 bio-renewable fuel may include monohydroxy alcohols, such as those having 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. .
    As used herein, the term "major amount" is understood to mean 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" is understood to mean less than 50% by weight based on the total weight of the composition.
    As used herein, the term "salts or salt deposits" refers to metal carboxylates.
    Amine compound
    Suitable amine compounds of the formula
    may be selected from guanidines and aminoguanidines or salts thereof wherein R and R 1 are as defined above. Therefore, the amine compound can be selected from inorganic salts of guanidines, such as halide, carbonate, nitrate, phosphate and orthophosphate salts. The term "guanidines" refers to guanidine 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 available from commercial sources, or can be prepared in a well-known manner.
    Hydrocarbonylcarbonyl compound
    The hydrocarbylcarbonyl reactant compound (1) 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 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 hydrocarbylcarbonyl compound may be a polyalkylene succinic anhydride reactant having the following formula:
    wherein R2 is a polyisobutylene moiety 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 daltons, as measured by GPC. Unless otherwise indicated, the molecular weights herein are number average molecular weights.
    The polyalkenyl radicals R 2 can be 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 can be formed by any suitable method, such as conventional catalytic oligomerization of alkenes.
    In some aspects, high reactivity polyisobutenes having relatively high proportions of polymer molecules with a vinylidene end group can be used to form the R2 moiety. In one example, at least about 60 mole%, such as about 70 mole% to about 90 mole%, polyisobutenes include olefinic terminal double bonds. There is a general tendency in the industry to convert to high reactivity polyisobutenes, and well-known high reactivity polyisobutenes are disclosed, for example, in U.S. Pat. 4,152,499, the disclosure of which is hereby incorporated by reference in its entirety.
    Specific examples of hydrocarbylcarbonyl compounds include compounds such as dodecenylsuccinic anhydrides, C16-18 succinic alkenyl anhydride and polyisobutenyl succinic anhydride (PIBSA). In some embodiments, the PIBSA may have a polyisobutylene portion 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 hydrocarbylcarbonyl compound may range from about 1: 1 to about 6: 1.
    In some aspects, approximately one mole of maleic anhydride may be reacted per mole of polyalkylene, such 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 groups to alkylene groups may range from about 0.5 to about 3.5, such as from about 1 to about 1.1.
    The hydrocarbylcarbonyl compounds can be obtained using any suitable method. Processes for the formation of hydrocarbyl carbonyl compounds are well known in the art. An example of a known method for forming a hydrocarbylcarbonyl compound comprises mixing a polyolefin and maleic anhydride. The polyolefin and maleic anhydride reactants are heated at temperatures of, for example, about 150 ° C to about 250 ° C, optionally using a catalyst such as chlorine or peroxide. Another exemplary process for producing polyalkylene succinic anhydride is described in U.S. 4,234,435, which is incorporated herein by reference in its entirety.
    The hydrocarbylcarbonyl 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 molar ratio of the hydrocarbonylcarbonyl 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 may vary 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 reaction pressure may be used, such as, including subatmospheric pressures or supra-atmospheric pressures. However, the temperature range may be different from that 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 certain aspects of the present disclosure, compound (A) may 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 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 oxygenate supports can be found in U.S. Patent No. 5,752,989, published May 19, 1998, by Henly et al. al., the disclosure of which is hereby incorporated by reference in its entirety. Additional examples of oxygenate supports include alkyl-substituted aryl polyalkoxylates disclosed in U.S. Patent Publication No. 2003/0131527, published July 17, 2003 by Colucci et al. al., the disclosure of which is hereby incorporated by reference in its entirety.
    In other aspects, the compositions of the present disclosure may not contain support. For example, certain compositions of the present application 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 amounts of additives improving the cetane number, corrosion inhibitors, cold creep additive (CFPP additive), pour point depressants, solvents , emulsifiers, lubricity additives, friction coefficient-modifying feedstock, amine stabilizers, combustion improvers, dispersants, antioxidants, heat stabilizers, conductivity enhancing additives, metal deactivators, marker dyes, organic nitrate ignition 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 of several of the above additives. 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 ignition 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 ignition accelerators that can 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 'other. Mixtures of these materials can also be used.
    Examples of suitable optional metal deactivators useful in the compositions of the present application are disclosed in U.S. Patent No. 4,482,357, published 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.
    Optional cyclomatic manganese tricarbonyl compounds that can 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. Still other examples of suitable cyclomatic manganese tricarbonyl compounds are disclosed in US Pat. No. 5,575,823, published November 19, 1996, and U.S. 3,015,668, published January 2, 1962, the disclosures of which are both incorporated herein by reference in their entirety.
    In one embodiment, the fuel composition of the disclosure may include (B) a mixture of a hydrocarbyl substituted succinimide dispersant in combination with the component (A) described above. As used herein, the term "succinimide" is meant to encompass the product of the complete reaction reaction of an amine with a hydrocarbyl substituted succinic acid or anhydride (or succinic acylating agent), and is it is intended to encompass compounds in which the product may have amide linkages, and / or salt in addition to the imide bond of the type resulting from the reaction of or contact with an amine moiety and an anhydride moiety.
    Suitable hydrocarbyl substituted succinic anhydrides can be formed by first reacting an olefinically unsaturated hydrocarbon of a desired molecular weight with maleic anhydride. Reaction temperatures from about 100 ° C to about 250 ° C may be used.
    With olefinically unsaturated hydrocarbons having higher boiling points, good results can be obtained at about 200 ° C to about 250 ° C. This reaction can be promoted by the addition of chlorine.
    Typical olefins may include, but are not limited to, cracked wax olefins, linear alpha-olefins, branched chain alpha-olefins, lower olefin polymers and copolymers. The olefins may be selected from ethylene, propylene, butylene, such as isobutylene, 1-octane, 1-hexene, 1-decene and others. Useful polymers and / or copolymers may include, but are not limited to, polypropylene, polybutenes, polyisobutene, ethylene-propylene copolymers, ethylene-isobutylene copolymers, propylene-isobutylene copolymers. copolymers of ethylene-1-decene and others.
    In one aspect of the disclosed embodiments, the hydrocarbyl substituents of the hydrocarbyl-substituted succinic anhydrides are isobutylene polymers. Polyisobutenes suitable for use herein include those formed from HR-PIB having at least about 60%, such as about 70% to about 90% or more, of terminal vinylidene content. Suitable polyisobutenes may include those prepared using BF3 catalysts. The number average molecular weight of the polyisobutylene substituent may vary over a wide range, for example from about 100 to about 5000, such as from about 500 to about 5000 daltons, as determined by GPC.
    Carboxylic reagents other than maleic anhydride may be used such as maleic acid, fumaric acid, malic acid, tartaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, ethylmaleic anhydride, dimethylmaleic anhydride, ethylmaleic acid, dimethylmaleic acid, hexylmaleic acid and others, including the corresponding acid halides and the lower aliphatic esters. A molar ratio of maleic anhydride to olefin in the reaction mixture can vary widely. Therefore, the mole ratio can range from about 5: 1 to about 1.5, for example from about 3: 1 to about 1: 3, and as another example, maleic anhydride can be used in excess stoichiometric to force the reaction to completion. Unreacted maleic anhydride can be removed by vacuum distillation. Any of many polyamines can be used in the preparation of the hydrocarbyl-substituted succinimide dispersant. Exemplary non-limiting polyamines may include aminoguanidine bicarbonate (AGBC), diethylene triamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (ΤΕΡΑ), pentaethylenehexamine (PEHA), and heavy polyamines. A heavy polyamine may comprise a mixture of polyalkylene polyamines having small amounts of lower polyamine oligomers such as ΤΕΡΑ and PEHA, but mainly oligomers having seven or more nitrogen atoms, two or more primary amines per molecule, and more branching. extensively than conventional polyamine mixtures. Additional non-limiting polyamines that can be used to prepare the hydrocarbyl-substituted succinimide dispersant are disclosed in U.S. Patent No. 6,548,458, the disclosure of which is incorporated herein by reference in its entirety. In one embodiment of the disclosure, the polyamine may be selected from tetraethylenepentamine (ΤΕΡΑ).
    In one embodiment, the dispersant may include compounds of the formula:
    wherein n is 0 or an integer of 1 to 5, and R2 is a hydrocarbyl substituent as defined above. In one embodiment, n is 3 and R 2 is a polyisobutenyl substituent, such as that derived from polyisobutylenes having at least about 60 mole percent, such as about 70 mole percent to about 90 mole percent or more, of terminal vinylidene content. . The compounds of the preceding formula may be the product of the reaction of a hydrocarbyl-substituted succinic anhydride, such as a polyisobutenyl succinic anhydride (PIBSA) and a polyamine, for example tetraethylenepentamine (ΤΕΡΑ).
    When formulating the fuel compositions of this application, the additives can be used in amounts sufficient to reduce or inhibit deposition formation in a diesel engine. In some aspects, the fuels may contain minor amounts of the bis-aminotriazole compound described above which controls or reduces the formation of deposits on the engine, for example deposits on the injector in diesel engines. For example, the diesel fuels of this application may contain, on an active ingredient basis, a quantity of bis-aminotriazole compound in the range of about 5 mg to about 500 mg of bis-aminotriazole compound per kg of fuel. as in the range of about 20 mg to about 120 mg of bis-aminotriazole compound per kg of fuel. In some aspects, where a carrier is used, the fuel compositions may contain, based on active ingredients, an amount of carrier in the range of about 1 mg to about 100 mg of carrier per kg of fuel, as about 5 mg to about 50 mg of dispersant per kg of fuel. The active ingredient base excludes the weight (i) of unreacted components such as polyalkylene compounds associated with and remaining in the product as produced and used, and (ii) 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.
    In another aspect, the presently disclosed fuel compositions may contain, on an active ingredient basis, a dispersant (B) as herein described in an amount ranging from about 50 to about 500 ppm, such as from about 80 ppm to about 500 ppm. about 200 ppm by weight based on the total weight of the fuel composition.
    In aspects where a carrier is used, the fuel compositions may contain, based on the active ingredients, a carrier amount ranging from about 10 mg to about 1000 mg carrier per kg of fuel, such as about 25 mg to about 700 mg of carrier per kg of fuel. The active ingredient base excludes the weight of (i) unreacted components associated with and remaining in the disclosed additives as produced and used, and (ii) solvent (s), if present, used in the manufacture of the additives disclosed either during or after its formation but before the addition of a support, if a support is used.
    The additives of the present application, including the bis-aminotriazole compound described above, and 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, as this allows for benefit from the mutual compatibility and convenience offered by the present invention. 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 reaction product of at least one guanidine and at least one polyalkylene succinic anhydride, such as described above. The additive may include one or more of the additional 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 mobile diesel engines. (for example, engines used as a prime mover in automobiles, trucks, road leveling equipment, military vehicles, etc.). Accordingly, aspects of the present application relate to methods for 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 fluid connection with the engine. combustion chamber. In another aspect, improvements can also be observed in indirect diesel fuel injection systems. In some aspects, the methods include injecting a hydrocarbon-based ignition compression fuel comprising the bis-aminotriazole additive of the present application, by the diesel engine injectors into the combustion chamber, and ignition of fuel for compression ignition. In some aspects, the process may also include mixing in diesel fuel at least one of the optional additional 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 to be concentrations having virtually no measurable effect on the cleanliness of an injector or the formation of deposits.
    In yet other aspects of the present application, the fuel additive may be free or substantially 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, with the proviso that at least one of R4 and R5 is not hydrogen. Examples of hydrocarbyl groups include linear, branched or cyclic C 2 -C 5 alkyl groups; linear, branched or cyclic C2 to C50 alkenyl groups; and substituted or unsubstituted aryl groups, such as phenyl groups, tolyl groups and xylyl groups.
    Without wishing to be bound by theory, it is believed that the internal salt deposits in the fuel injectors can be caused by the contamination of metal ions in the fuel. The metal ions can come from the base fuel itself or additives introduced into the base fuel. When present, metal ions can react with functional carboxylate fuel additives such as corrosion inhibitors (e.g., a dodecylsuccinic acid corrosion inhibitor), and / or biodiesel fatty acid esters to form deposits. salt type. When modern injectors are manufactured for extremely tight tolerances, any of these deposits can severely restrict the movement of the internal components of the injectors. As a result, salt deposits can produce a significant loss of performance due to fouling of injection needles, reduced fuel economy, loss of power, and increased emissions. Internal deposits are typically less prevalent in conventional diesel fuels, but have manifested themselves in ULSD fuels. As stated above, the compound (A) alone or in combination with the component (B) has surprisingly been found to clean and / or prevent the formation of such deposits on the fuel injectors.
    EXAMPLES
    The following examples are illustrative of the exemplary embodiments of the disclosure. In these examples as well as throughout this application, all parts and percentages are by weight unless otherwise indicated. It is intended that these examples are presented for the purpose of illustration only and are not intended to limit the scope of the invention described herein.
    In the following examples, the effect of the additives of the compound (A) and / or (A) plus (B) on the diesel fuel contaminated with carboxylate salts for high pressure common rail diesel fuel systems is evaluated. An engine test is used to demonstrate the propensity of fuel to cause fouling of the fuel injector and is also used to demonstrate the ability of certain fuel additives to prevent or control internal deposition in injectors. A dynamometer test stand is used for the installation of the Peugeot DW10 diesel engine for the execution of injector fouling tests. The engine is a 2.0 liter engine having four cylinders. Each combustion chamber has four valves and the fuel injectors are piezo DI injectors of Euro V classification.
    The basic protocol procedure is to run the engine for an 8-hour cycle and leave the engine at temperature (engine off) for a prescribed period of time. The performance of the injector is then characterized by measuring the exhaust temperature of the cylinder for each cylinder. A test is stopped and considered to be missed (fouling of one or more injectors) if the exhaust temperature of any cylinder is more than 65 ° C higher than another cylinder exhaust temperature at any time in time. A test is also considered to be missed if, after allowing the engine to cool to room temperature, a cold start shows a temperature difference of 45 ° C or more in the cylinder exhaust temperatures. Fouling of the needle and thus rupture could also be confirmed by disassembling the injector and subjectively determining the force required to remove the needle from the nozzle body. The cleanliness tests are carried out for cleanliness maintenance performance as well as cleaning performance.
    The preparation of the test involves rinsing the fuel from the previous test from the engine before removing the injectors. The test injectors are inspected, cleaned and reinstalled in the engine. If new injectors are selected, the new injectors are subjected to a 16-hour adaptation cycle. Then the engine is started using the desired test cycle program. Once the engine has been warmed up, power is measured at 4000 rpm and full load to evaluate the full power restoration after injector cleaning. If the power measurements are in the specification, the test cycle is initiated. The following Table 1 provides a representation of the fouling test cycle DW10 that is used to evaluate the fuel additives according to the disclosure.
    Table 1 - One hour representation of DW10 bonding test cycle
    Example 1
    Engine injector fouling test
    The diesel engine nozzle fouling tests are carried out using the Peugeot DW10 engine according to the protocol in Table 1. For the cleanliness test, the engine runs on diesel fuel contaminated with metal carboxylate salts and with the detergent additive indicated in the example. For the cleaning test, the engine first runs on diesel fuel contaminated with metal carboxylate salts without a detergent additive to establish a baseline of fouled fuel injectors. Then the engine runs on the same fuel containing the indicated detergent additive. In all tests, the fuels tested contained 200 ppm by volume of lubricity modifier and 1600 ppm by volume of cetane number additive, 20 ppm by weight of dodecylsuccinic acid, 3 ppm by weight of NaOH, and ppm by weight volume of water. At the beginning of the test, no injector fouling is indicated by a
    uniform temperature of the exhaust gas for the 4 cylinders as shown (in Figure 1). However, a cold start of the engine after 8 hours shows a fouling of the injector as shown in FIG. 2. In all the figures, curve A corresponds to cylinder 1, curve B corresponds to cylinder 2, curve C corresponds to to the cylinder 3 and the curve D corresponds to the cylinder 4.
    Comparative Example 2
    In this example, a conventional dispersant succinimide additive is added to the fuel at a treatment rate of 75 ppm by weight. Figure 3 shows the fouling of the injectors after a 16 hour test with the fuel containing the conventional detergent.
    Comparative Example 3
    In this example, a quaternary ammonium salt diesel fuel additive formulation is added to the fuel at a treatment rate of 75 ppm by weight. Figure 4 shows the fouling of the injector after a 7-hour test with this fuel.
    Example 4
    Compound (A) is added to the fuel at a treatment rate of 75 ppm by weight. After a 16 hour test, Figure 5 shows that none of the injectors are dirty. The physical inspection of the injectors at the completion of the test confirms that none of the injectors is fouled.
    Example 5
    In this test, the compound (A) at 15 ppm by weight is combined with the compound (B) at 60 ppm by weight for a total treatment rate of 75 ppm by weight. Figure 6 shows that after a test of 16 hours, none of the injectors is dirty.
    Example 6
    In this test, the ability of the detergent additive to clean dirty fuel injectors is demonstrated. The dirty fuel injectors have exhaust temperatures similar to FIG. 2 before adding a mixture of compound (A) at 10 ppm by weight and compound (B) at 40 ppm by weight for a treatment rate total of 50 ppm by weight in the fuel. Figure 7 shows that after an 8 hour test, none of the injectors are glued.
    As indicated in the previous examples, the fuel additives containing the compound (A) or the compound (A) plus the compound (B) provide a significant reduction in internal deposits in the diesel fuel injectors when the engines run on ULSD fuels. compared to conventional fuel detergent additives.
    It should be noted that, as used in this disclosure and the accompanying claims, the singular forms "a", "a", and "the", "la" include several referents unless express and unequivocal indication limited to a single referent. As used herein, the term "include" and its grammatical variants are assumed to be nonlimiting, so that the enumeration of items in a list is not exclusive of other elements that may be substituted or added to the elements. listed.
    For 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 as being modified in all cases by the term "about". Therefore, unless otherwise indicated, the numerical parameters set forth in the following specification and the appended claims are approximations which may vary depending on the desired properties desired by the present disclosure. At the very least, and not as an attempt to limit the demand for equivalence doctrine to the scope of claims, each numerical parameter should at least be interpreted in light of the number of significant digits and by applying ordinary rounding techniques.
    Although particular embodiments have been described, substantial variations, modifications, variations, improvements and substantial equivalents that are or may be presently unforeseen may occur to the Applicant or other skilled persons. Therefore, the claims as filed, and as they may be amended, are intended to encompass such substantial variations, modifications, variations, improvements and equivalents.
    权利要求:
    Claims (18)
    [1]
    A method for cleaning internal components of a diesel fuel injector comprising operating a diesel fuel injection engine with a fuel composition comprising (A) a major amount of fuel, (B) d. from about 10 to about 500 ppm by weight, based on a total weight of the fuel composition of a compound of the formula:

    and tautomers and enantiomers thereof, wherein R2 is a polyisobutylene group having a number average molecular weight ranging from 100 to 5,000 daltons; and (C) an amount of a hydrocarbylsuccinimide dispersant in which a weight ratio of B: C in the fuel ranges from 1: 2 to 1:10.
    [2]
    2. The process of claim 1 wherein R2 is a polyisobutylene group having a number average molecular weight of from about 200 to about 3000 daltons.
    [3]
    3. - A method according to claim 1 or 2, wherein the diesel fuel injection engine comprises a diesel direct injection engine.
    [4]
    4. The process according to claim 1, wherein the hydrocarbyl succinimide dispersant comprises a product of the polyalkenylsuccinic acid or anhydride reaction with tetraethylene pentamine.
    [5]
    The method of claim 4, wherein the polyalkenylsuccinic acid or anhydride is derived from polyisobutylene having a number average molecular weight ranging from 800 to 1100 daltons.
    [6]
    The process according to claim 5, wherein the polyisobutylene comprises a high reactivity polyisobutylene having at least 70% by weight or more of terminal olefinic double bonds.
    [7]
    7. A process according to any one of the preceding claims, wherein the fuel comprises from 50 to 500 ppm by weight of a mixture of B and C.
    [8]
    A method for reducing a quantity of salt deposits on the internal components of a fuel injector for a diesel fuel injection engine comprising operating the diesel engine with a fuel composition comprising (A) a quantity of major diesel fuel with a very low sulfur content, (B) from about 10 to about 100 ppm by weight compound of formula:

    and tautomers and enantiomers thereof, wherein R2 is a polyisobutylene group having a number average molecular weight ranging from 100 to 5000; and (C) an amount of a hydrocarbylsuccinimide dispersant, wherein a weight ratio of B: C in the fuel ranges from 1: 2 to 1:10.
    [9]
    9. The process according to claim 8, wherein R2 is a polyisobutylene group having a number average molecular weight ranging from about 200 to about 3000 daltons.
    [10]
    The method of claim 9, wherein the hydrocarbyl succinimide dispersant comprises a product of the polyalkenylsuccinic acid or anhydride reaction with tetraethylene pentamine.
    [11]
    11. The process according to claim 10, wherein the polyalkenylsuccinic acid or anhydride is derived from polyisobutylene having a number average molecular weight ranging from 800 to 1100 daltons.
    [12]
    The process of claim 11, wherein the polyisobutylene comprises a high reactivity polyisobutylene having at least 70% by weight or more of terminal olefinic double bonds.
    [13]
    13. - Process according to any one of claims 9 to 12, wherein the fuel comprises from 50 to 500 ppm by weight of a mixture of B and C.
    [14]
    A method for preventing clogging of a fuel filter for fuel injectors of a diesel fuel injection engine comprising supplying a major amount of fuel and a minor amount of a fuel mixture. (A) a compound of formula

    and tautomers and enantiomers thereof, wherein R2 is a polyisobutylene group having a number average molecular weight of from 100 to 5000 daltons and (B) an amount of hydrocarbyl succinimide dispersant, wherein a ratio of A: B weight in fuel ranges from 1: 2 to 1:10 and wherein the fuel comprises from about 5 mg to about 200 mg of compound (A) per kg of fuel, on an active basis; and the flow of fuel through the fuel filter for the fuel injectors.
    [15]
    15. - The method of claim 14, wherein the fuel filter has openings of 2 microns for the flow of fuel.
    [16]
    The process of any one of claims 14 to 15, wherein the fuel comprises from about 20 mg to about 120 mg of compound (A) per kg of fuel.
    [17]
    17. - Process according to any one of claims 14 to 16, wherein the fuel comprises a diesel fuel with very low sulfur content (ULSD).
    [18]
    18. - Method according to any one of the preceding claims, wherein the diesel fuel injection engine is a diesel direct injection engine.
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    同族专利:
    公开号 | 公开日
    SG194314A1|2013-11-29|
    GB2504371B|2015-05-20|
    CN103602355A|2014-02-26|
    GB2504371A|2014-01-29|
    CN103602355B|2016-04-20|
    GB201307043D0|2013-05-29|
    GB2504371A8|2014-07-16|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20090282731A1|2008-05-13|2009-11-19|Afton Chemical Corporation|Fuel additives to maintain optimum injector performance|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US13/450,638|US8529643B2|2008-05-13|2012-04-19|Fuel additives for treating internal deposits of fuel injectors|
    US13/450638|2012-04-19|
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