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    • 专利摘要:
    A method of cleaning a fuel injector for a diesel engine comprising operating the diesel engine with a composition containing a major amount of diesel fuel and +/- 5 to 500 ppm by weight of a reaction product derived from (a ) a hydrocarbyl substituted dicarboxylic acid, anhydride or ester and (b) an amino compound or a salt thereof of the formula HR 1 NH 2 - C - NH - NHR with R and R1: H or a hydrocarbyl group .
    公开号:BE1022388B1
    申请号:E2013/0283
    申请日:2013-04-22
    公开日:2016-01-25
    发明作者:Xinggao Fang；Julienne M. Galante-Fox；Scott D. Schwab
    申请人:Afton Chemical Corporation；
    IPC主号:
    专利说明:

    FUEL ADDITIVES FOR TREATING INTERNAL DEPOSITS OF FUEL JETTERS
    RELATED APPLICATIONS
    This application is a continuation of part of the application number 13/240 233, filed on 22 September 2011, currently pending.
    TECHNICAL FIELD The invention relates to certain diesel fuel additives and a method for cleaning and / or preventing internal deposits in injectors for engines powered by diesel fuel. In particular, the invention relates to methods that are effective against internal deposits in injectors for engines operating with ultra-low sulfur diesel fuels.
    BACKGROUND AND SUMMARY
    Recent changes in diesel fuels and diesel fuel additives have given rise to new problems in the performance of injectors in deposits, including a new type of deposits not previously encountered with older diesel fuel formulations. Injector performance problems affect all areas: road vehicle fleets, mining equipment, agricultural equipment, railway engines, marine engines and engines for river navigation.
    Vehicle users, fuel producers and engine manufacturers are currently seeing deposits forming on internal parts of the fuel injectors. If left untouched, these deposits can lead to significant power loss, reduced fuel economy and, in extreme cases, increased downtime and increased maintenance costs due to premature replacement. "glued injectors". The new deposits are thought to be due to some common corrosion inhibitors, common biofuel components and a common acid friction modifier, or other carboxylic components used in the fuel, which react with trace amounts of metals alkali or alkaline earth metals, producing salts that are less soluble in ultra-low sulfur diesel (ULSD) fuels than in higher sulfur fuels. When such salts are present in the fuel that is used in a High Pressure Common Rail (HPCR) engine model, the salts may tend to settle in areas of very tight tolerance of the injectors. Such deposits can lead to poor fuel injection, which in turn can lead to loss of power, loss of fuel economy, inconsistent engine operation, and possibly excessive vehicle downtime and maintenance costs. excessive.
    ULSD currently accounts for about 79% of all distilled fuel dispensed in the United States. Similarly, the minimum Renewable Fuel Standard for biodiesel was raised to 1 billion gallons in 2012. There is evidence that the amount of biodiesel that will be required to be used will be even higher. the future. As a result, the changing fuel volume continues to evolve to more ULSD (with less solubility for potential salts) and more biodiesel to the market (another potential source of materials causing deposits in the fuel system). fuel).
    In accordance with the invention, exemplary embodiments provide a method of cleaning the internal components of a fuel injector for a diesel engine. The method comprises operating a fuel injection diesel engine with a fuel composition that contains a major amount of diesel fuel having a sulfur content of 50 ppm by weight or less and from about 5 to about 500 ppm by weight a reaction product derived from (a) a hydrocarbyl-substituted acid, anhydride or dicarboxylic ester and (b) an amino 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 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 is characterized by a FTIR spectrum having a peak intensity in a region of about 1630 cm -1 to about 1645 cm -1, which ranges from about 5 to about 45% peak intensities of other peaks. in a region of about 1500 cm -1 to about 1800 cm -1.
    Another embodiment of the invention provides a method for reducing a quantity of salt deposits on internal components of a fuel injector for a diesel fuel injection engine. The method comprises operating the diesel engine with a fuel composition that contains a major amount of fuel and a minor amount of a reaction product derived from (a) a hydrocarbyl-substituted acid, anhydride, or dicarboxylic ester, and b) an amino 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 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 less than one equivalent of an amino triazole group per molecule of reaction product.
    Another embodiment of the invention provides a method for preventing clogging of a fuel filter for fuel injectors of a diesel fuel injection engine. The method comprises providing a major amount of fuel and a minor amount of a reaction product derived from (a) a hydrocarbyl-substituted acid, anhydride or dicarboxylic ester and (b) an amino compound or a salt of it 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 is characterized by a FTIR spectrum having a peak intensity in a region of about 1630 cm -1 to about 1645 cm -1, which ranges from about 5 to about 45% peak intensities of other peaks. in a region of about 1500 cm -1 to about 1800 cm -1, and wherein the reaction product contains less than one equivalent of an amino triazole group per molecule of reaction product.
    An advantage of the fuel additive described herein is that the additive can not only reduce the amount of internal deposits forming on direct and / or indirect injectors of diesel fuel, but that the additive can also be effective for cleaning the Clogged fuel injectors and can prevent clogging of fuel filters in the fuel supply to the fuel injectors.
    Embodiments and additional advantages of the invention may be demonstrated in part in the detailed description which follows, and / or may also be acquired by the practice of the invention. It should be understood that the foregoing general description as well as the following detailed description are given only by way of example and explanation only and do not constitute a limitation of the invention as claimed.
    BRIEF DESCRIPTION OF THE DRAWINGS
    Fig. 1 is a part of an FTIR spectrum of a product of the prior art.
    Fig. 2 is a part of an FTIR spectrum of a reaction product according to the invention.
    Fig. Figure 3 is a graphical representation of the exhaust gas cylinder temperatures over time for a four-cylinder diesel engine at the beginning of a fuel additive test.
    Fig. 4 is a graphical representation of exhaust cylinder temperatures over time for a four-cylinder diesel engine after eight hours of testing by not using fuel detergent.
    Figs. Figures 5 and 6 are graphical representations of exhaust cylinder temperatures over time for a four-cylinder diesel engine using conventional fuel detergents.
    Fig. 7 is a graphical representation of the exhaust gas cylinder temperatures as a function of time using a fuel detergent according to one embodiment of the invention.
    Fig. 8 is a graphical representation of exhaust cylinder temperatures over time for a four-cylinder diesel engine at the end of a fouling test cycle.
    Fig. 9 is a graphical representation of the exhaust gas cylinder temperatures as a function of time for a four-cylinder engine using a fuel detergent according to an embodiment of the invention for cleaning fouled fuel injectors of the invention. Figure 6.
    DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
    The compositions of the present application can be used in a minor amount in a major amount of diesel fuel and can be produced by reacting an amino 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 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-substituted acid, anhydride or dicarboxylic ester, wherein the reaction product contains less than one equivalent of an amino triazole group per molecule of reaction product. The reaction product is characterized by a FTIR spectrum having a peak intensity in a region of about 1630 cm -1 to about 1645 cm -1, which ranges from about 5 to about 45% peak intensities of other peaks. in a region of about 1500 cm -1 to about 1800 cm -1. By way of comparison, Figure 1 shows an FTIR spectrum of a compound produced with a molar ratio of hydrocarbyl carbonyl to amine ranging from about 1: 1 to about 1: 2.5. The peak of about 1636 cm -1 is assumed to be an aminotriazole peak. In comparison, the reaction product produced according to the disclosed embodiments has an FTIR spectrum of the type shown in Figure 2, wherein the peak intensity at about 1636 cm -1 is substantially less than the peak intensity of other peaks in a region of about 1500 cm -1 to about 1800 cm -1. For example, the reaction product according to the invention has a peak intensity in the region of 1630 cm -1 to about 1645 cm -1. covers from about 5 to about 45% of the peak intensities of other peaks in a region of about 1500 cm -1 to about 1800 cm -1. In other embodiments, the reaction product has a typical peak intensity in the range of about 1630 cm -1 to about 1645 cm -1 which is not more than 30%, for example not more than 25%. %, and typically not more than 10% of the intensity of other peaks in the range of about 1500 cm -1 to about 1800 cm -1.
    As used herein, the term "hydrocarbyl" or "hydrocarbyl" is used in its usual sense, which is well known to those skilled in the art. Specifically, it refers to a group comprising 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 (e.g., alkyl or alkenyl), alicyclic (e.g. cycloalkyl, cycloalkenyl) substituents, and aromatic, aliphatically-substituted aromatic substituents and alicyclic, as well as cyclic substituents in which the ring is completed 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 groups which, in the context of the present description, do not alter the predominant hydrocarbon character (eg halo [especially chlorine and fluorine], hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, amino, alkylamino, and sulfoxy); (3) hetero-substituents, i.e., substituents which, while having a predominant hydrocarbon character, in the context of the present specification, contain atoms other than carbon in a ring or a compound chain (e) moreover carbon atoms. The hetero atoms 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 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.
    The terms "bio-renewable fuels" and "biodiesel fuels" used herein should be understood to mean any fuel that is derived from resources other than petroleum. Such resources include, but are not limited to, wheat, corn, soybeans, and other crop plants; herbs, such as switchgrass, miscanthus, and hybrid grasses; algae, kelp, vegetable oils; natural fats; and mixtures thereof. In one aspect, the bio-renewable fuel may comprise 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" should be 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" should be 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" should be understood to mean carboxylates of transition metals, alkali metals or alkaline earth metals.
    Amino compound
    Suitable amino compounds of the formula
    may be selected from guanidines and aminoguanidines or salts thereof, wherein R and R1 have already been defined above. Therefore, the amino compound can be selected from inorganic salts of guanidines, such as the halide, carbonate, nitrate, phosphate, and guanidine 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 can be readily obtained from different sources, or can be prepared in a well-known manner.
    Hvdrocarbvle-carbonvle compound
    The hydrocarbyl carbonyl reactant compound of the additive may be any suitable compound comprising a hydrocarbyl moiety and a carbonyl moiety, and which is capable of binding to the amine compound to form the additives of the invention. 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 some 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 5,000 daltons. 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.
    In the above formula, the hydrocarbyl moiety R 2 may comprise one or more polymer units selected 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 polyalkenyl radical R 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, especially by conventional catalytic oligomerization of alkenes.
    In an additional aspect, the R2 hydrocarbyl moiety may be derived from a linear alpha-olefin or an acid isomerized alpha-olefin produced by the oligomerization of ethylene by methods well known in the art. These hydrocarbyl moieties may range from about 8 carbon atoms to more than 40 carbon atoms. For example, alkenyl moieties of this type may be derived from a linear alpha-olefin or a mixture of C20-24 alpha-olefins or from acid-isomeric alpha-olefins.
    In some aspects, high reactivity polyisobutenes containing relatively high proportions of polymer molecules with a terminal vinylidene group can be used to form the R2 group. In one example, at least about 60%, such as from about 70% to about 90%, of the polyisobutenes comprise terminal olefinic double bonds. There is a general trend in the industry to switch to high reactivity polyisobutenes, and well known high reactivity polyisobutenes are disclosed, for example, in US Patent No. 4,152,499, the contents of which are incorporated herein. in full for reference.
    Specific examples of hydrocarbyl carbonyl compounds include compounds such as dodecenyl succinic anhydrides, C 16 -C 18 alkenyl succinic anhydride, and polyisobutenyl succinic anhydride (PIBSA), and derived acid and ester compounds. of these. In some embodiments, the PIBSA may comprise a polyisobutylene portion with a vinylidene content ranging from about 4% to greater than about 90%. In some embodiments, the molar ratio of the number of carbonyl groups to the number of hydrocarbyl moieties in the hydrocarbyl carbonyl compound can range from about 0.5: 1 to about 5: 1.
    In some aspects, about one mole of maleic anhydride may be reacted with one mole of polyalkylene, such that the polyalkenyl succinic anhydride obtained has from about 0.8 to about 1 group of succinic anhydride per polyalkylene substituent. In other aspects, the molar 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 hydrocarbyl carbonyl compounds can be produced using any suitable method. Methods for producing 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 of, for example, about 150 ° C to about 250 ° C, optionally using a catalyst, such as chlorine or peroxide. Another example of a process for producing polyalkylene succinic anhydrides is described in US Patent No. 4,234,435, which is incorporated herein in its entirety by reference.
    The hydrocarbyl carbonyl and amine compounds described above may be mixed with each other under appropriate conditions to provide the desired reaction product of the present invention. In one aspect of the present invention, the reactive compounds may be mixed with each other in a molar ratio of the hydrocarbyl carbonyl compound to the amine compound of from about 1: 0.5 to about 1: 1.5. For example, the molar ratio of reactants can range from about 1: 5 to about 1: 0.95.
    Suitable reaction temperatures can range from about 130 ° C to less than about 200 ° C at atmospheric pressure. For example, reaction temperatures can range from about 140 ° C to about 160 ° C. Any suitable reaction pressure may be used, such as those comprising sub-atmospheric or super-atmospheric pressures. However, the temperature range may be different from that quoted when the reaction is performed at a pressure other than atmospheric pressure. The reaction may be carried out for a period of time from about 1 hour to about 9 hours, for example from about 2 hours to about 6 hours.
    In some aspects of the present application, the dispersants of this application may be used in combination with a carrier soluble in diesel fuel. Such carriers 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 polyalkoxylated liquid ethers (also known as polyalkylene glycols or polyalkylene ethers), polyalkoxylated liquid phenols, liquid esters polyalkoxylated, polyalkoxylated liquid amines, and mixtures thereof. Examples of the oxygenates may be found in US Patent No. 5,752,989, issued May 19, 1998 to Henly et al, the description of which carriers are hereby incorporated by reference in its entirety. Additional examples of oxygenate carriers include alkyl-substituted aryl polyalkoxylates disclosed in US Patent Publication No. 2003/0131527, published July 27, 2003 for Colucci et al., The disclosure of which is incorporated herein by reference in its entirety. reference.
    In other aspects, compositions of the present application may not contain a carrier. For example, some compositions of this application may not contain mineral oil or oxygenates, such as the 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 cetane improvers, corrosion inhibitors, cold flow improvers (CFPP additives), pour point depressants, detergents, solvents, demulsifiers, lubricating additives, friction modifiers, amine stabilizers, combustion improvers, dispersants, antioxidants, heat stabilizers, conductivity enhancers, 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 percent by weight or less, and in other aspects, about 5 percent by weight or less, based on the total weight of the additive concentrate, a or more than one of the aforementioned additives. Similarly, the fuels may contain appropriate amounts of conventional fuel blend components such as methanol, ethanol, dialkyl ethers, and the like.
    In some aspects of the disclosed embodiments, organic nitrate type ignition accelerators, which include aliphatic or cycloaliphatic nitrates in which the aliphatic or cycloaliphatic group is saturated, and which contain up to about 12 carbon atoms, may be used. . Examples of organic nitrate ignition boosters that can be used include 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, nitrate of hexyl, 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, tetrabydrofuranyl nitrate, and like. Mixtures of these compounds 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, issued November 13, 1984, the contents of which are hereby 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.
    Suitable optional cyclomatic manganese tricarbonyl compounds which may be employed in the compositions of the present application include, for example, manganese cyclopentadienyl tricarbonyl, manganese methylcyclopentadienyl tricarbonyl, manganese indenyl tricarbonyl, and ethylcyclopentadienyl tricarbonyl of manganese. Still other examples of cyclomatic manganese tricarbonyl compounds are disclosed in U.S. Patent Nos. 5,575,823, issued November 19, 1996, and U.S. 3,015,668, issued January 2, 1962, both of which are incorporated herein by reference. incorporated herein by reference in their entirety.
    When formulating the fuel compositions of this application, the additives can be employed 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 reaction product described above which controls or reduces the formation of engine deposits, for example, deposits in the diesel engine injectors. For example, the diesel fuels of this application may contain, on an active ingredient basis, an amount of the reaction product in the range of about 5 mg to about 500 mg of reaction product per kg of fuel, for example in the range from about 20 mg to about 120 mg of reaction product per kg of fuel. In certain aspects, in which a carrier is used, the fuel compositions may contain, based on active ingredients, an amount of the carrier in a range of about 1 mg to about 100 mg carrier per kg of fuel per example from about 5 mg to about 50 mg carrier per kg of fuel. The active ingredient base excludes the weight of (i) unreacted components such as polyalkylene compounds associated with and remaining in the reaction product as it is produced and used, and (ii) solvent (s). ), if any, used in the production of the reaction product either during or after its formation but before the addition of a carrier, if a holder is employed.
    The additives of the present application, including the reaction product described above, and optional additives used in the formulation of the fuels of the present invention, may be blended into the base diesel fuel individually or in various sub-combinations. In some embodiments, the additive components of the present application can be blended into the diesel fuel concurrently using an additive concentrate, since this takes advantage of the mutual compatibility and convenience provided by the combination of ingredients. when 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.
    The diesel fuels of the present application can be used to operate both stationary diesel engines (e.g. engines used in power generation plants, pumping stations, etc.) and mobile diesel engines ( for example, motors used as sources of movement in automobiles, trucks, road-building equipment, military vehicles, etc.). For example, fuels may include any and all middle distillate fuels, diesel fuels, biorevable fuels, biodiesel fuel, liquefied gas fuels (GTL), jet fuel, alcohols, ethers, kerosene, low sulfur fuels, synthetic fuels, such as Fischer-Tropsch fuels, liquefied petroleum gas, bunker fuels, liquefied coal fuels (CTL), liquefied biomass fuels (BTL) , fuels with high asphaltene content, fuels derived from coal (natural, purified, petroleum coke), biofuels and plants and genetically modified extracts thereof, and natural gas. The term "bio-renewable fuels" used herein should be understood to mean any fuel that is derived from resources other than petroleum. Such resources include, but are not limited to, wheat, corn, soybeans, and other crop plants; herbs, such as switchgrass, miscanthus, and hybrid grasses; algae, kelp, vegetable oils; natural fats; and mixtures thereof. In one aspect, the bio-renewable fuel may comprise 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.
    Accordingly, aspects of the present application relate to methods for reducing the amount of diesel engine nozzle deposits having at least one combustion chamber and one or more direct fuel injectors in fluid connection with the combustion chamber. In another aspect, improvements can also be observed in indirect injectors of diesel fuel. In some aspects, the methods include injecting a hydrocarbon-based compression ignition fuel comprising the reaction product additive of the present invention through the diesel engine injectors into the combustion chamber. and ignition of the compression ignition fuel. 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 substantially free or free, for example free, of conventional succinimide dispersant compounds. The term "essentially free" is defined, for the purposes of this application, as being concentrations which have substantially no effect on the cleanliness or formation of injectors deposits.
    In still other aspects of the present application, the fuel additive may be free or substantially free or free of 1,2,4-triazoles. For example, the compositions may be substantially free of triazoles of formula II,
    wherein 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 C2 to C50 alkyl groups; linear, branched or cyclic C 1 -C 5 alkenyl groups; and substituted or unsubstituted aryl groups, such as phenyl groups, tolyl groups and xylyl groups.
    EXAMPLES
    The examples which follow illustrate by way of examples embodiments of the invention. In these examples and elsewhere in this application, all parts and percentages are by weight unless otherwise indicated. The intention is that these examples are presented for illustrative purposes only and are not intended to limit the scope of the invention disclosed herein.
    In the following examples, the effect of the detergent additive on a carboxylate salt contaminated diesel fuel for high pressure common rail diesel fuel systems was evaluated. An engine test was used to demonstrate the propensity of fuels to cause sticking of fuel injectors and was also used to demonstrate the ability of certain fuel additives to prevent or reduce the amount of internal deposits in the injectors. A dynamometer test bench for engines was used for the installation of the Peugeot DW10 diesel engine to perform injector bonding tests. The engine was a 2.0-liter four-cylinder engine. Each combustion chamber was equipped with four valves and the fuel injectors were DI piezoelectric injectors with a Euro V classification.
    The basic protocol procedure was to run the engine for an 8-hour cycle and then let it idle (engine off) for a prescribed period of time. The performance of the injectors was then characterized by measuring the outlet temperature of the cylinders for each cylinder. One test was stopped and was considered failed (one or more glue injectors) if the exit temperature of any of the cylinders was more than 65 ° C higher than any other cylinder outlet temperature at any one time. A test was also considered to have failed if, after allowing the engine to cool to room temperature, a cold start showed a difference of 45 ° C or more in the cylinder exit temperatures. Needle sticking and thus failure could also be confirmed by disassembling the injector and subjectively determining the force required to remove the needle from the injector housing. Cleanliness tests were performed to assess the cleanliness performance and cleaning performance.
    The test preparation included evacuating the fuel from the previous test out of the engine before removing the injectors. The injectors in the test were inspected, cleaned, and reinstalled in the engine. If new injectors were selected, the new injectors were subjected to a 16-hour break-in cycle. Then, the engine was started using the program of the desired test cycle. Once the engine was warm, power was measured at 4000 rpm and at full load to verify full power restoration after injector cleaning. If the power measurements were within the specifications, the test cycle was started. Table I below gives a representation of the bonding test cycle of the DW10, which was used to evaluate the fuel additives according to the invention.
    Table 1 - One Hour Representation of the DW10 Bonding Test Cycle
    Example 1 (Engine Test for Bonding the Injectors)
    Diesel engine injector bonding tests were carried out using the Peugeot DW10 engine following the protocol of Table 1. For the cleanliness test, the engine was powered with a diesel fuel doped with carboxylate salts. of metal and with the detergent additive indicated in the example. For the cleaning test, the engine was first powered with diesel fuel doped with metal carboxylate salts without a detergent additive to establish a baseline of the bonded fuel injectors. Then, the engine was powered with the same fuel containing the indicated detergent additive. In all of these tests, the fuels tested contained 200 ppm vol. friction modifier and 1600 ppm vol. cetane enhancer, 20 ppm by weight of dodecyl succinic acid, 3 ppm by weight of NaOH, and 25 ppm by weight. of water. At the beginning of the test, no injector bonding was indicated by a uniform exhaust gas temperature of all 4 cylinders, as shown in Figure 3. However, a cold start of the engine after 8 hours revealed a collage of injectors, as shown in Figure 4. In all figures, the curve A relates to the cylinder 1, the curve B the cylinder 2, the curve C the cylinder 3 and the curve D the cylinder 4.
    Comparative Example 2
    In this example, a conventional succinimide dispersant additive was added to the fuel at a treatment level of 75 ppm by weight. Figure 5 shows that the injectors were stuck after a 16 hour test with the conventional detergent fuel.
    Comparative Example 3
    In this example, a dose of quaternary ammonium salt diesel fuel additive was added to the fuel at a treatment level of 75 ppm by weight. Figure 6 shows that the injectors were stuck after a 7-hour test with this fuel.
    Example 4 The detergent additive of the invention was added to the fuel at a treatment level of 75 ppm by weight. After a 16 hour test, Figure 7 shows that none of the injectors were stuck. Line physical inspection of the injectors after the completion of the test confirmed that none of the injectors were glued.
    Example 5
    In this test, a base fuel containing the metal salts described above was used in the engine for 8 hours to foul the fuel injectors. Figure 8 shows that after a cold start of the engine, the injectors were glued.
    Example 6
    In this test, the ability of the detergent additive of the invention to clean the fouled fuel injectors of Figure 8 was demonstrated. In this example, 30 ppm by weight of the detergent additive of the invention was combined. with 120 ppm weight of a conventional succinimide dispersant, and this mixture was added to the fuel. Figure 9 shows that after a 16 hour test, none of the injectors were stuck.
    As the foregoing examples show, fuel additives containing the detergent additive according to the invention provide a significant reduction in internal deposits in diesel fuel injectors, when the engines are fueled with ULSD fuels, as compared to detergent additives. for conventional fuel, and that the detergent additive was effective in cleaning the fouled fuel injectors.
    Note that, as used in this application and in the appended claims, the singular forms "a", "an", and "the" include references to the plural, unless there is a express and unequivocal limitation to a reference to the singular. As used herein, the term "includes" and its grammatical variants have no intention of limitation, so that the enumeration of items in a list does not imply the exclusion of others. similar articles, which may replace or add to the listed articles.
    For the purposes of this application and the appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the application and claims, shall be understood to be modified in all cases by the term "about". Therefore, unless otherwise indicated, the numerical parameters presented in the following application and the appended claims are approximations which may vary depending on the desired properties sought to be achieved by the present invention. At the very least, and without this being an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be interpreted in light of the number of significant digits indicated and by applying the techniques Ordinary rounding.
    Although particular embodiments have been described, alternatives, modifications, variations, improvements, and important equivalents that are or may be currently unanticipated may be apparent to applicants or other skilled persons. Accordingly, the appended claims as filed and as may be amended are intended to encompass all such alternatives, modifications, variations, improvements and significant equivalents.
    权利要求:
    Claims (15)
    [1]
    A method of cleaning the internal components of a fuel injector for a diesel engine, comprising operating a diesel fuel injection engine with a fuel composition that contains a major amount of diesel fuel having a sulfur content of 50 ppm by weight or less and from about 5 to about 500 ppm by weight of a reaction product derived from (a) a hydrocarbyl-substituted acid, anhydride or dicarboxylic ester, wherein the hydrocarbyl group comprises a group polyisobutylene having a number average molecular weight of from about 200 to about 3000 daltons and (b) an amino 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 R1 is selected from the group consisting of hydrogen and a hydrocarbyl group containing from about 1 to about 20 carbon atoms, wherein the reaction product contains less than one equivalent of an amino triazole group per molecule of reaction product, and wherein the reaction product is characterized by a FTIR spectrum having a peak intensity in a region of about 1630 cm-1 to about 1645 cm-1, which ranges from about 5 to about 45 percent peak intensities of other peaks in a region of about 1500 cm -1 to about 1800 cm -1, wherein the reaction product is effective to prevent clogging of the fuel filter with salt deposits selected from the group consisting of carboxylates of transition metals, alkali metals and alkaline earth metals on internal components of the fuel injector.
    [2]
    The process according to claim 1, wherein a molar ratio of (a) to (b) in the reaction product is from about 1: 0.5 to about 1: 1.5.
    [3]
    The process according to claim 1 or 2, wherein the hydrocarbyl substituted acid, anhydride or dicarboxylic ester is selected from hydrocarbyl substituted succinic anhydrides, hydrocarbyl substituted succinic acids, and acid esters. hydrocarbyl substituted succinic compounds.
    [4]
    The method of any of the preceding claims, wherein the diesel fuel injection engine comprises a direct injection diesel engine.
    [5]
    The process according to any one of the preceding claims, wherein the amine is aminoguanidine bicarbonate.
    [6]
    A method for reducing a quantity of salt deposits on internal components of a fuel injector for a diesel fuel injection engine, comprising operating the diesel engine with a fuel composition that contains a major amount of fuel and a fuel composition. minor amount of a reaction product derived from (a) a hydrocarbyl-substituted dicarboxylic acid, anhydride or ester, wherein the hydrocarbyl group comprises a polyisobutylene group having a number average molecular weight of from about 200 to about 3 000 daltons and (b) an amino 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 R1 is selected from the group consisting of hydrogen and a hydrocarbyl group containing from about 1 to about 20 carbon atoms, wherein the reaction product contains less than one equivalent of an amino triazole group per molecule of reaction product, and wherein the salt deposits are selected from the group consisting of carboxylates of transition metals, alkali metals and alkaline earth metals.
    [7]
    The method of claim 5 or 6, wherein the diesel fuel injection engine is a direct injection diesel engine.
    [8]
    The process according to any one of claims 5 to 7, wherein a molar ratio of (a) to (b) in the reaction product is from about 1: 0.5 to 1: 1.5.
    [9]
    The process of any one of claims 5 to 8, wherein the fuel comprises from about 5 to about 200 ppm by weight of reaction product compound based on the total weight of the fuel composition.
    [10]
    The process of any one of claims 5 to 9, wherein the fuel is an ultra low sulfur diesel fuel.
    [11]
    A method for preventing clogging of a fuel filter for fuel injectors of a fuel injection diesel engine with salt deposits, comprising supplying a major amount of fuel and a minor amount of fuel. a reaction product derived from (a) a hydrocarbyl-substituted amino acid, anhydride or dicarboxylic ester, wherein the hydrocarbyl group comprises a polyisobutylene group having a number average molecular weight of from about 200 to about 3000 daltons and (b) a 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 R1 is selected from the group consisting of hydrogen and a hydrocarbyl group containing from about 1 to about 20 carbon atoms, wherein the reaction product is characterized by an FTIR spectrum having a peak intensity in a region of about 1630 cm -1 to about 1645 cm -1, which covers about At about 45% of the peak intensities of other peaks in a region of about 1500 cm -1 to about 1800 cm -1, and wherein the reaction product contains less than one equivalent of an amino triazole group per reaction product molecule, and wherein the salt deposits are selected from the group consisting of carboxylates of transition metals, alkali metals and alkaline earth metals.
    [12]
    The method of claim 11, wherein the fuel filter has 2 micron openings for fuel flow.
    [13]
    Process according to any one of claims 11 to 12, wherein the fuel contains from about 5 mg to about 200 mg of the reaction product per kg of fuel, on an active basis.
    [14]
    The process of any one of claims 11 to 13, wherein the fuel contains from about 20 mg to about 120 mg of reaction product per kg of fuel.
    [15]
    The method of any one of claims 11 to 14, wherein the fuel contains an ultra low sulfur diesel fuel (ULSD).
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    同族专利:
    公开号 | 公开日
    KR101586116B1|2016-01-15|
    AU2013201711B2|2014-10-30|
    TWI523944B|2016-03-01|
    EP2657322A1|2013-10-30|
    AU2013201711A1|2013-11-07|
    CA2810258A1|2013-10-24|
    CN103374421A|2013-10-30|
    CA2810258C|2016-03-22|
    SG194317A1|2013-11-29|
    TW201346022A|2013-11-16|
    CN103374421B|2016-01-06|
    MY158654A|2016-10-31|
    KR20130124193A|2013-11-13|
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    法律状态:
    2018-03-21| FG| Patent granted|Effective date: 20160125 |
    2018-03-21| MM| Lapsed because of non-payment of the annual fee|Effective date: 20170430 |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/454697|2012-04-24|
    US13/454,697|US8852297B2|2011-09-22|2012-04-24|Fuel additives for treating internal deposits of fuel injectors|
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