• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:
    Diesel fuel includes a major amount of low sulfur middle distillate fuel; and a reaction product of (a) a hydrocarbyl substituted dicarboxylic acid or anhydride or ester, and (b) an amino compound or a salt thereof of the formula NR 1 NHy-C-NH-NHR wherein R is H or a C1 to C15 hydrocarbyl group and R1 represents H or a C1 to C20 hydrocarbyl group, the reaction product containing less than one equivalent of an aminotriazole group per molecule of the reaction product.
    公开号:BE1021772B1
    申请号:E2012/0615
    申请日:2012-09-19
    公开日:2016-01-18
    发明作者:Xinggao Fang；Julienne M. Galante-Fox
    申请人:Afton Chemical Corporation；
    IPC主号:
    专利说明:

    The invention relates to certain diesel fuel additives and diesel fuels and diesel fuel additive concentrates which comprise the additive. BACKGROUND OF THE INVENTION In particular, the invention relates to a diesel fuel additive that is effective in increasing the performance of diesel fuel injectors, particularly for low sulfur and very low sulfur diesel fuels. BACKGROUND OF THE INVENTION AND SUMMARY: It has been a long time since we wish to maximize fuel economy, power and driveability of diesel fuel vehicles while increasing acceleration, reducing emissions and reducing fuel consumption. preventing hesitation. While gasoline engines are known to increase performance by using dispersants to keep valves and fuel injectors clean, these gasoline dispersants are not necessarily effective in diesel fuel applications. The reasons for this unpredictability lie in the many differences between the way diesel engines and gasoline engines operate and the chemical differences between diesel and gasoline.
    [0003] In addition, low-sulfur diesel, ultra low sulfur diesel and high pressure common rail diesel (RCHP) diesel engines are now widely available on the market. "Low sulfur" diesel fuel means a fuel with a sulfur content of 50 ppm or less based on the total weight of the fuel. A "very low sulfur" diesel fuel (DTFS) means a fuel with a sulfur content of 15 ppm or less based on the total weight of the fuel. RCHP engine fuel injectors operate at much higher pressures and temperatures than older-style engines and fuel injection systems. The combination of low sulfur engines or DTFS and RCHP has resulted in a change in the type of injector deposits and the frequency of formation of injector deposits now available on the market.
    [0004] Over the years, dispersant compositions for diesel fuel have been developed. Dispersant compositions known in the art for use in diesel fuel include those compositions which may include polyalkylene succinimides, which are the reaction products of succinic anhydrides of polyalkylene and amines. Dispersants are suitable for keeping soot and sludge suspended in a fluid, however dispersants are not particularly effective at cleaning surfaces once deposits have formed on the surfaces. Therefore, it is common for diesel fuel compositions containing low sulfur diesel fuels or DTFS used in new engine technologies to still produce undesirable deposits in diesel engine injectors. Therefore, improved compositions that can prevent build up of deposits, maintaining the "original" cleanliness of the vehicle are desirable to increase its service life. Ideally, the same composition that can clean the fouled fuel injectors while restoring their performance to the "original" condition would be both desirable and useful in reducing exhaust emissions in the environment. 'air.
    [0005] In accordance with the invention, exemplary embodiments describe a diesel fuel, a diesel fuel additive concentrate, and a method for improving the performance of fuel injectors for a diesel engine. The diesel fuel comprises a major amount of middle distillate fuel having a sulfur content of less than or equal to 50 ppm by weight; and a reaction product of (a) a hydrocarbyl-substituted anhydride or dicarboxylic acid ester, and b) an amino compound or a salt thereof having the formula
    wherein R is selected from hydrogen and a hydrocarbyl group containing from about 1 to about 15 carbon atoms, and R 1 is selected from a hydrogen atom and a hydrocarbyl group containing from about 1 to about 20 carbon atoms, wherein the reaction product contains less than one equivalent of aminotriazole group per molecule of reaction product, and the reaction product is present in an amount sufficient to improve the performance of direct and / or indirect injection diesel fuel injectors.
    Another embodiment of the invention describes a method for improving the performance of the injectors of a diesel engine with fuel injection. The method comprises using the diesel engine with a fuel composition that comprises a major amount of diesel fuel having a sulfur content of 50 ppm or less and a minor amount of a reaction product derived from (a) a hydrocarbylcarbonyl compound having the formula
    wherein R2 is a hydrocarbyl group having a number average molecular weight of from about 200 to about 3000 and (b) an amino compound or a salt thereof having the formula
    wherein R is selected from a hydrogen atom and a hydrocarbyl group containing from about 1 to about 15 carbon atoms, and R1 is selected from a hydrogen atom and a hydrocarbyl group containing from about 1 to about 20 atoms of carbon. The reaction product is characterized by an FTIR (Fourier Transform Infrared Spectroscopy) spectrum having a peak intensity in a region of from about 1,630 cm -1 to about 1,645 cm -1 ranging from about 5 to about 45 % of the maximum intensity of other peaks in a region from about 1500 cm -1 to about 1800 cm -1.
    Another embodiment of the invention is a method of cleaning fuel injectors of a diesel engine with fuel injection. The method comprises using the diesel engine with a fuel composition comprising a major amount of diesel fuel having a sulfur content of 50 ppm by weight or less and a minor amount of a reaction product derived from (a) a compound hydrocarbylcarbonyl corresponding to the formula
    and an acid or an ester thereof, wherein R2 is a hydrocarbyl group having a number average molecular weight of from about 200 to about 3000 and (b) an amino compound or a salt thereof. to the formula
    wherein R is selected from a hydrogen atom and a hydrocarbyl group containing from about 1 to about 15 carbon atoms, and R1 is selected from a hydrogen atom and a hydrocarbyl group containing from about 1 to about 20 atoms of carbon. The reaction product contains less than one equivalent of aminotriazole group per molecule of reaction product.
    [0008] 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 injection diesel fuel injectors, but can also be effective to clean dirty fuel injectors.
    Additional embodiments and advantages of the invention will be set forth in the following detailed description, and / or may be inferred from the practice of the invention. It is understood that the foregoing general description and detailed description are intended only to illustrate and explain the invention as claimed, not to restrict it.
    BRIEF DESCRIPTION OF THE DRAWINGS
    Figure 1 is a part of an FTIR spectrum of a product of the prior art and [00011] FIG. 2 is a part of an FTIR spectrum of a reaction product according to the invention.
    DETAILED DESCRIPTION OF EXAMPLES OF EMBODIMENTS
    The compositions of the present application may be used in a minor amount in a major amount of diesel fuel and may be prepared by reacting an amino compound or a salt thereof having 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 hydrocarbylcarbonyl compound having the formula
    or an acid or an ester thereof, wherein R2 is a hydrocarbyl group having a number average molecular weight of from about 200 to about 3000, the reaction product containing less than one equivalent of aminotriazole group per molecule of reaction product. The reaction product is characterized by a FTIR spectrum having a peak intensity in a region of from about 1,630 cm-1 to about 1,645 cm-1 which ranges from about 5 to about 45 percent of the maximum intensity of the others. peaks in a region from about 1500 cm -1 to about 1800 cm -1.
    By way of comparison, Figure 1 shows an FTIR spectrum of a compound prepared with a molar ratio of hydrocarbyl carbonyl to amine ranging from about 1/1 to about 1: 2.5. The peak at about 1636 cm-1 would be a peak corresponding to aminotriazole. By way of comparison, the reaction product prepared according to the described embodiments has an FTIR spectrum as shown in Figure 2, wherein the peak intensity at about 1636 cm-1 is substantially less than the peak intensity. other peaks in a region from 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 which varies from about 5 to about 45% of the maximum intensity of the other peaks. in a region of from about 1500 cm -1 to about 1800 cm -1. In other embodiments, the reaction product has a characteristic peak intensity in the range of 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 the other peaks in the range of about 1500 cm -1 to about 1800 cm -1.
    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 predominantly hydrocarbon character. Examples of hydrocarbyl groups include: (1) hydrocarbon substituents, namely aliphatic (e.g. alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic, aliphatic and alicyclic substituted aromatic substituents, as well as cyclic substituents in which the ring is supplemented by another part of the molecule (for example, two substituents together form an alicyclic radical); (2) substituted hydrocarbon substituents, that is to say substituents containing non-hydrocarbon groups which, in the context of the present description, do not modify the predominantly hydrocarbon substituent (for example, halo (in particular chloro and fluoro), hydroxy alkoxy, mercapto, alkylmercapto, nitro, nitroso, amino, alkylamino and sulfoxy); (3) hetero-substituents, namely substituents which, while having a predominantly hydrocarbon character, in the context of this specification, contain elements other than carbon in a ring or chain otherwise composed of carbon atoms; carbon. The hetero atoms include sulfur, oxygen, and nitrogen, and include substituents such as pyridyl, furyl, thienyl, and imidazolyl. In general, not more than two, or as a further example, no more than one non-hydrocarbon substituent is present per ten carbon atoms in the hydrocarbyl group; in some embodiments, no non-hydrocarbon substituent is present in the hydrocarbyl group.
    As used herein, the term "major amount" refers to 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. Furthermore, as used herein, the term "minor amount" is understood to mean less than 50% by weight based on the total weight of the composition.
    Amino compound [00016] Suitable amino compounds corresponding to the formula
    may be chosen from guanidines and aminoguanidines or their salts, in which formula R and R1 are as defined above. Therefore, the amino compound can be selected from the inorganic salts of guanidines, such as guanidine halide, carbonate, nitrate, phosphate and orthophosphate salts. The term "guanidines" refers to guanidine and guanidine derivatives, such as amincguanidine. In one embodiment, the guanidine compound for the preparation of the additive is aminoguanidine bicarbonate. The aminoguanidine bicarbonates are readily available from commercial sources, or prepared in a well-known manner.
    Hydrocarbonylcarbonyl Compound The hydrocarbylcarbonyl reactant compound of the additive may be any suitable compound having a hydrocarbyl group and a carbonyl group, and which is capable of bonding with 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 certain aspects, the hydrocarbylcarbonyl compound may be a polyalkylene succinic anhydride reactant having the following formula:
    wherein R2 represents a hydrocarbyl group, such as, for example, a polyalkenyl radical having a number average molecular weight of from about 100 to about 5,000. For example, the number average molecular weight of R2 may vary from about 200 to about 3. 000, as measured by GPC (gel permeation chromatography). Unless otherwise indicated, the molecular weights in this specification represent the number average molecular weights.
    The hydrocarbyl group R2 may comprise one or more polymer units chosen from linear or branched alkenyl units. In some aspects, the alkenyl units may have from about 2 to about 10 caron 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 2 can 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 a further aspect, the R2 hydrocarbyl moiety may be derived from a linear alpha-olefin or an isomerized alpha-olefin using an acid made by oligomerization of ethylene by well-known methods. in art. These hydrocarbyl groups can comprise from about 8 carbon atoms to more than 40 carbon atoms. For example, alkenyl groups of this type may be derived from a linear C18 alpha-olefin or from a mixture of C20 to C24 alpha-olefins or C6 alpha-olefins isomerized with the aid of an acid.
    In some aspects, high reactivity polyisobutenes comprising relatively high proportions of polymer molecules having a terminal vinylidene group can be used to form the R2 group. In one example, at least about 60%, for example from about 70% to about 90%, of the polyisobutenes comprise terminal olefinic double bonds. There is a general tendency in the industry to convert to high reactivity polyisobutenes, and well known high reactivity polyisobutenes are described, for example in US Pat. No. 4,152,499, the entire contents of which are incorporated. here by reference.
    Specific examples of hydrocarbylcarbonyl compounds include compounds such as dodecenylsuccinic anhydrides, C16 to C18 alkenylsuccinic anhydride, and polyisobutenylsuccinic anhydride (APIBS). In some embodiments, the APIBS may include a polyisobutylene moiety having a vinylidene content of 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 groups in the hydrocarbylcarbonyl compound may range from about 0.5: 1 to about 5: 1.
    In some aspects, about 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 molar ratio of succinic anhydride groups to alkylene groups may range from about 0.5 to about 3.5, for example from about 1 to about 1.1.
    [00024] The hydrocarbylcarbonyl compounds can be prepared using any suitable method. The processes for preparing the hydrocarbyl carbonyl compounds are well known in the art. An example of a known method for preparing a hydrocarbylcarbonyl 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 with the use of a catalyst, such as chlorine or peroxide. Another example of a 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 hydrocarbylcarbonyl and amine compounds described above may be mixed with each other under suitable conditions to provide the desired reaction product of this disclosure. In one aspect of the present disclosure, the reactive compounds may be mixed with each other in a molar ratio of hydrocarbylcarbonyl compound to amine of from about 1: 0.5 to about 1: 1.5. For example, the molar ratio of reactants may vary from about 1: 0.5 to about 1: 0.95.
    [0026] Suitable reaction temperatures can vary from about 130 ° C to less than about 200 ° C at atmospheric pressure. For example, the reaction temperatures may vary from about 140 ° C to about 160 ° C. Any suitable reaction pressures may be used, including, for example, subatmospheric pressures or superatmospheric pressures. However, the temperature range may be different from those listed where the reaction is carried out 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 carrier soluble in diesel fuels. 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, issued May 19, 1998 to Henly et al. al., the description of said supports being incorporated herein by reference in its entirety. Additional examples of oxygenate supports include the alkyl-substituted aryl polyalkoxylates disclosed in U.S. Patent Application No. 2003/0131,527, published July 17, 2003 and issued to Colucci et al. al., the disclosure of which is hereby incorporated by reference in its entirety.
    [00028] In other aspects, the compositions of the present application may not contain support. For example, certain compositions of the present application may not include 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 described embodiments. For example, the fuels may contain conventional amounts of cetane modifier additives, corrosion inhibitors, cold flow additives (CFPP additives), pour point depressants , solvents, demulsifiers, lubricating additives, friction modifiers, amine stabilizers, combustion improvers, dispersants, antioxidants, thermal stabilizers, conductivity improvers, deactivators metal 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, 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 listed above. Also, the fuels may contain adequate amounts of conventional fuel blend components such as methanol, ethanol, dialkyl ethers and the like.
    In certain aspects of the described embodiments, organic nitrate ignition accelerators which comprise aliphatic or cycloaliphatic nitrates in which the aliphatic or cycloaliphatic group is saturated, and which contain up to about 12 carbon atoms. , 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, 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, tetrahydrofuranyl nitrate and other. The mixtures of these compounds can also be used.
    Examples of suitable optional metal deactivators useful in the compositions of the present application are described in U.S. Patent 4,482,357, issued November 13, 1984, the entire contents of which are incorporated herein by reference. 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, cyclopentadienyl manganese tricarbonyl, methylcyclopentadienyl manganese tricarbonyl, indenyl manganese tricarbonyl and tricarbonyl of ethylcyclopentadienyl manganese. Still other examples of suitable cyclomatic manganese tricarbonyl compounds are described in US Patent No. 5,575,823, issued November 19, 1996, and US Patent No. 3,015,668, issued January 2, 1962, whose two presentations in their entirety are incorporated herein by reference.
    When preparing the fuel compositions of this application, the additives may be employed in amounts sufficient to reduce or inhibit deposition formation in a diesel engine. In some aspects, the fuels may contain minor amounts of the reaction product described above that limits or reduces the formation of deposits in the engine, for example injector deposits in diesel engines. For example, the diesel fuels of this application may contain, on the basis of the active substance, a quantity of reaction product in the range of about 5 mg to about 200 mg of reaction product per kg of fuel, for example in the range of from about 20 mg to about 120 mg of reaction product per kg of fuel. In certain aspects in which a carrier is employed, the fuel compositions may contain, based on the active ingredients, a carrier amount in the range of about 1 mg to about 100 mg of carrier per kg of fuel, e.g. about 5 mg to about 50 mg of carrier per kg of fuel. The active substance base excludes the weight (i) of the unreacted components such as product-associated polyalkylene compounds remaining in the product as produced and used, and (ii) solvent (s) , if any, used in the manufacture of the reaction product either during or after its formation but before the addition of a carrier, if a carrier is employed.
    The additives of the present application, including the reaction product described above, and the optional additives used in the formulation of the fuels of this invention can be incorporated into the base diesel fuel individually or in various sub-combinations. In some embodiments, the additive components of the present application can be incorporated into the diesel fuel simultaneously using an additive concentrate, since this allows to take advantage of the mutual compatibility and convenience afforded by the combination of ingredients when they are in the form of an additive concentrate. In addition, the use of a concentrate can reduce mixing time and reduce the risk of mixing errors.
    The diesel fuels of the present application may be applicable to the use both of stationary diesel engines (for example, engines used in power generation installations, pumping stations, etc.) than mobile diesel engines (eg engines used as the main driving force in automobiles, trucks, road grading equipment, military vehicles, etc.). For example, fuels may include any or all of the middle distillate fuels, diesel fuels, bio-renewable fuels, biodiesel fuel, gas-liquid fuels (GTL), jet fuel, alcohols, ethers, kerosene, low sulfur fuels, synthetic fuels, such as Fischer-Tropsch fuels, liquefied petroleum gas, bunker fuels, coal liquefaction fuels (CTL), fuels biomass liquefaction (BTL), high asphaltene fuels, coal fuels (natural, cleaned and petroleum coke), genetically modified biofuels and crops and extracts thereof, and natural gas . The term "bio-renewable fuels" as used herein refers to any fuel that is derived from resources other than petroleum. These resources include, but are not limited to, corn, corn, soybeans and other crops; herbs, such as switchgrass, miscanthus and hybrid grasses; algae, kelp, vegetable oils; natural fats; and their mixtures. In one aspect, the bio-renewable fuel may comprise monohydroxy alcohols, such as those comprising from 1 to about 5 carbon atoms. Non-limiting examples of suitable monohydroxy alcohols include methanol, ethanol, propanol, n-butanol, isobutanol, t-butyl alcohol, amyl alcohol and isoamyl alcohol.
    Therefore, aspects of the present application relate to methods for reducing the amount of deposits on injectors of a diesel engine having at least one combustion chamber and one or more direct injection fuel injectors in fluid connection. with the combustion chamber. In another aspect, improvements can also be observed in indirect injection diesel fuel injectors. In some aspects, the methods include injecting a hydrocarbon-based compression ignition fuel comprising the additive consisting of the reaction product of the present invention, by 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 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 purpose of this application as representing concentrations having substantially no measurable effect on injector cleanliness or deposit formation.
    In still other aspects of the present application, the fuel additive may be free or substantially 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, provided that at least one of R4 and R5 is not hydrogen. Examples of hydrocarbyl groups include linear, branched or cyclic C 2 to C 50 alkyl groups; C2 to C50 alkenyl groups, linear, branched or cyclic; and substituted or unsubstituted aryl groups, such as phenyl groups, tolyl groups and xylyl groups.
    EXAMPLES
    [00039] The following examples illustrate the exemplary embodiments of the presentation. In these examples and elsewhere in this application, all parts and percentages are by weight unless otherwise indicated. These examples are intended to be presented by way of illustration only, but not to limit the scope of the invention described herein.
    Comparative Example 1 Polybutenyl succinic anhydride of molecular weight 950 (295 grams) was mixed with 86 grams (2 equivalents) of aminoguanidine bicarbonate (AGBC) and 416 grams of aromatic solvent 150. The mixture was heated under vacuum at 165 ° C and held at this temperature for about 4 hours, extracting water and carbon dioxide. The resulting mixture was filtered. An FTIR spectrum of the product shows a peak at 1636 cm-1 which dominates the peaks in a region from 1500 cm -1 to 1800 cm -1 as shown in Figure 1.
    Example 2 Polybutenyl succinic anhydride of molecular weight 950 (553 g), aromatic solvent 150 (210 g), aminoguanidine bicarbonate (AGBC) (79.5 g) was introduced into a flask. 1 equivalent) and toluene (145g). The reaction mixture was heated to 145 ° C and held at this temperature for about 2 hours. No additional water was extracted by azeotropic distillation. A sample was extracted and diluted with approximately equal weight of heptane. The resulting mixture was filtered through Celite 512 and concentrated on a rotary evaporator to give the desired product as a brownish oil. An FTIR spectrum of the product showed peaks at 1724, 1689, 1637 and 1588 cm-1, the peak at 1637 cm-1 being the smallest.
    In the following example, an injector deposition test was performed on a diesel engine using a conventional diesel engine fuel injector test as described below.
    Test protocol [00043] A DW10 test developed by the CEC (Coordinating
    European Council) has been used to demonstrate the propensity of fuels to cause fouling of fuel injectors and has also been used to demonstrate the ability of certain fuel additives to prevent or limit such deposits. The additive evaluation was based on the CEC F-98-08 protocol for coking tests of common-rail and direct-injection diesel engines. A dynamometer test bench for the engine was used for the installation of the Peugeot DW10 diesel engine in order to carry out the coking tests of the injectors. The engine was a 2.0-liter four-cylinder engine. Each combustion chamber had four valves and the fuel injectors were piezo DI injectors meeting the Euro V classification.
    The central protocol procedure was to run the engine for an 8-hour cycle and leave the engine soaked (engine stopped) for a prescribed time. The previous sequence was repeated four times. At the end of each hour, a measure of engine power was taken while the engine was running at rated conditions. The propensity of the fuel to foul the injectors was characterized by the nominal power difference observed between the beginning and the end of the test cycle.
    The preparation of the test included the elimination of the fuel from the previous test of the engine before the extraction of the injectors. Injectors tested 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 desired test cycle program. Once the engine warmed up, power was measured at 4,000 rpm and full power to verify full power restoration after injector cleaning. If the power measurement was within specification, the test cycle was started. The following Table 1 illustrates the DW10 decoking cycle that was used to evaluate the fuel additives according to the invention.
    Table 1 - Representation of the DW10 decoking cycle for one hour.
    [0001] Various fuel additives were tested using the previous engine test procedure in a very low sulfur diesel fuel containing zinc neodecanoate, 2-ethylhexyl nitrate, and an ester type friction modifier. fatty acid (basic fuel). A "fouling" phase consisting solely of the basic fuel without additive was started, followed by a "cleaning" phase consisting of the base fuel with additive. All measurements were made with an 8-hour fouling phase and an 8-hour cleaning phase, unless otherwise specified. The percentage power recovery was calculated using the power measurement at the end of the "fouling" phase and the power measurement at the end of the "cleaning" phase. The percent power recovery was determined by the following formula Percentage power recovery = (EN) / E x 100 where E represents the percent power loss at the end of a fouling phase without the additive, N represents the percent power at the end of a cleaning phase with the fuel additive, and the power is measured according to the DW10 test, CEC protocol F98-08. The conventional succinimide dispersant has been generally prepared in accordance with the disclosure of U.S. Patent No. 5,752,989.
    Table 2
    1 Engine used for 16 hours without additive and for 16 hours with additive 2 Engine used for 32 hours without additive and for 32 hours with additive [00046] As illustrated in the previous example, the reaction product of Tests No. 5-9 provided a post-fouling power recovery in a very low sulfur diesel fuel substantially greater than the reaction product of Comparative Example 1. The results were surprising and totally unexpected. Therefore, it is believed that the reaction product as described herein can be effective in maintaining the cleanliness of the surface of the diesel fuel injectors and in cleaning the fouled fuel injectors.
    [00047] It should be noted that, as used in this specification and the related claims, the singular forms "a", "a", "the" and "the" include plural referents, unless expressly and unequivocally to a single refer. Thus, for example, the reference to "an antioxidant" includes two or more different antioxidants. As used herein, the term "understand" and its grammatical variants are intended to be nonlimiting, so that the enumeration of the elements of a list is not done by excluding other similar elements that may be substituted or add to the items listed.
    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, shall be understood to be modified. in any case by the term "about". Therefore, unless indicated otherwise, the numerical parameters set forth in this specification and the appended claims are approximations which may vary depending on the desired properties sought to be achieved by the present invention. Finally, and without attempting to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter must at least be interpreted in light of the number of significant digits indicated and by applying ordinary rounding techniques.
    Although particular embodiments have been described, alternatives, modifications, variations, improvements and substantial equivalents that are or may be presently unforeseen may be imposed on applicants and other skilled persons. Therefore, the appended claims as filed and as may be amended are intended to encompass all of these alternatives, modifications, variations, improvements and substantial equivalents.
    权利要求:
    Claims (27)
    [1]
    CLAIMS:
    A diesel fuel for fuel injection comprising: a major amount of middle distillate fuel having a sulfur content of less than or equal to 50 ppm by weight; and a reaction product of (a) a hydrocarbyl substituted acid, anhydride or dicarboxylic ester and (b) an amino compound or a salt thereof having 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 being prepared under conditions to obtain a reaction product containing less than one equivalent of aminotriazole group per molecule of reaction product, and the reaction product being present in an amount sufficient to improve the performance of direct and / or indirect injection diesel fuel injectors.
    [2]
    The fuel according to claim 1, wherein the reaction product is characterized by an FTIR (Fourier Transform Infrared Spectroscopy) spectrum having a peak intensity in a region of from about 1,630 cm -1 to about 1,645 cm -1. 1 which ranges from about 5 to about 45% of the maximum intensity of the other peaks in a region ranging from about 1500 cm -1 to about 1800 cm -1.
    [3]
    The fuel of claim 1 or 2, wherein the molar ratio of (a) to (b) in the reaction product ranges from about 1: 0.5 to about 1: 1.5.
    [4]
    A fuel according to any one of the preceding claims, wherein the hydrocarbyl substituted acid, anhydride or dicarboxylic ester is selected from hydrocarbyl substituted succinic anhydrides, hydrocarbyl substituted succinic acids and hydrocarbyl substituted succinic acids.
    [5]
    The fuel of claim 4, wherein the hydrocarbyl group of the hydrocarbyl-substituted acid, anhydride or dicarboxylic ester has a number average molecular weight of from about 200 to about 3000 (y. Fuel according to any one of the preceding claims, wherein the diesel fuel comprises a fuel for direct injection engine fuel.
    [7]
    A fuel according to any one of the preceding claims, wherein the hydrocarbyl group of the hydrocarbyl substituted dicarboxylic acid, anhydride or ester comprises a polyisobutylene radical which is derived from high reactivity polyisobutenes having at least one minus 60% or more terminal olefinic double bonds.
    [8]
    A fuel according to any one of the preceding claims wherein the amine comprises an inorganic salt of guanidine.
    [9]
    A fuel according to any one of the preceding claims, wherein the amine comprises an aminoguanidine salt.
    [10]
    A fuel according to any one of the preceding claims, wherein the amine comprises aminoguanidine bicarbonate.
    [11]
    A method for improving the performance of the injectors of a fuel-injected diesel engine comprising using the diesel engine with a fuel composition comprising a major amount of diesel fuel having a sulfur content of 50 ppm or less by weight and from 5 to 200 mg per kg of fuel of a reaction product derived from (a) a hydrocarbylcarbonyl compound having the formula

    or an acid or an ester thereof, wherein R is a hydrocarbyl group having a number average molecular weight of from about 200 to about 3000 and (b) an amino compound or a salt thereof. to 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 of a hydrocarbyl group containing from about 1 to about 20 carbon atoms, the reaction product being characterized by a FTIR spectrum having a peak intensity in a region of from about 1,630 cm-1 to about 1,645 cm-1 which varies from about 5 to about 45% of the maximum intensity of the other peaks in a region from about 1500 cm -1 to about 1800 cm -1, and that the reaction product is prepared under conditions to obtain a reaction product containing less than one equivalent of aminotriazole group per molecule of reaction product.
    [12]
    The process of claim 11 wherein the molar ratio of (a) to (b) in the reaction product ranges from about 1: 0.5 to about 1: 1.5.
    [13]
    The process of claim 11 or 12 wherein R is polyisobutylene having a number average molecular weight of from about 200 to about 3000.
    [14]
    The method of any one of claims 11 to 13, wherein the fuel injection diesel engine comprises a direct injection diesel engine.
    [15]
    The process of any one of claims 11 to 14, wherein the diesel fuel has a sulfur content less than or equal to 15 ppm by weight.
    [16]
    The process of any one of claims 11 to 15, wherein the amine is aminoguanidine bicarbonate.
    [17]
    A method of cleaning fuel injectors of a diesel fuel injection engine comprising using the diesel engine with a fuel composition comprising a major amount of diesel fuel having a sulfur content of 50 ppm or less weight, advantageously less than or equal to 15 ppm by weight, and from 5 to 200 mg per kg of fuel of a reaction product derived from (a) a hydrocarbylcarbonyl compound corresponding to the formula

    or an acid or an ester thereof, wherein R2 is a hydrocarbyl group having a number average molecular weight of from about 200 to about 3000 and (b) an amino compound or salt thereof. to 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 being prepared under conditions to obtain a reaction product containing less than one equivalent of aminotriazole group per molecule of reaction product. Λ
    [18]
    The process of claim 17, wherein R is a polyolefinic radical having a number average molecular weight of from about 200 to about 3000.
    [19]
    The method of claim 17 or 18, wherein the diesel fuel injection engine is a direct injection diesel engine.
    [20]
    The process of any one of claims 17 to 19, wherein the molar ratio of (a) to (b) in the reaction product ranges from about 1: 0.5 to about 1: 1.5.
    [21]
    21. The process according to any one of claims 17 to 20, wherein the amine is aminoguanidine bicarbonate.
    [22]
    22. A fuel additive concentrate for adding to a low sulfur diesel fuel to improve the performance of the fuel injectors for a diesel engine comprising a reaction product derived from (a) a hydrocarbylcarbonyl compound having the formula

    or an acid or an ester thereof, wherein R2 is a hydrocarbyl group having a number average molecular weight of from about 200 to about 3000 and (b) an amino compound or salt thereof. to 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 of a hydrocarbyl group containing from about 1 to about 20 carbon atoms, the reaction product being characterized by a FTIR spectrum having a peak intensity in a region of from about 1,630 cm -1 to about 1,645 cm -1 which ranges from about 5 to about 45% of the maximum intensity of the other peaks in a region of about 1500 cm -1 to about 1800 cm -1, and the reaction product being prepared under conditions to obtain reaction product containing less than one equivalent of aminotriazole group per molecule of reaction product, wherein the reaction product is effective for low sulfur diesel fuels to improve the performance of the fuel injectors at a concentration of about 5 to 200mg of reaction product per kg of fuel.
    [23]
    The additive concentrate of claim 22, wherein R is a polyolefinic radical having a number average molecular weight of about 500 to about 1300 daltons.
    [24]
    24. An additive concentrate according to claim 23, wherein the polyolefinic radical is a polyisobutylene radical.
    [25]
    An additive concentrate according to claim 24, wherein the polyisobutylene radical is derived from high reactivity polyisobutenes having at least 60% or more terminal olefinic double bonds.
    [26]
    26. An additive concentrate according to any one of claims 22 to 25, wherein the amine comprises an inorganic aminoguanidine salt.
    [27]
    An additive concentrate according to any one of claims 22 to 26, wherein the diesel engine comprises a direct injection diesel engine.
    [28]
    28. A diesel fuel having a sulfur content of less than or equal to 15 ppm by weight and an amount of additive concentrate according to any one of claims 22 to 27 sufficient to provide from about 5 mg to about 200 mg of the reaction product. per kg of fuel.
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    同族专利:
    公开号 | 公开日
    GB2494978B|2014-03-19|
    DE102012018514A1|2013-07-25|
    GB2494978A|2013-03-27|
    GB201216447D0|2012-10-31|
    TWI537376B|2016-06-11|
    CA2788313C|2015-11-24|
    US20130074874A1|2013-03-28|
    KR20130032249A|2013-04-01|
    AU2012227168B2|2014-12-18|
    SG188750A1|2013-04-30|
    CN103013593A|2013-04-03|
    US8758456B2|2014-06-24|
    AU2012227168A1|2013-04-11|
    KR101435270B1|2014-08-27|
    TW201326381A|2013-07-01|
    CN103013593B|2015-08-19|
    CA2788313A1|2013-03-22|
    MY153110A|2014-12-31|
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    法律状态:
    2017-11-20| FG| Patent granted|Effective date: 20160118 |
    2017-11-20| MM| Lapsed because of non-payment of the annual fee|Effective date: 20160930 |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/240233|2011-09-22|
    US13/240,233|US8758456B2|2011-09-22|2011-09-22|Fuel additive for improved performance of low sulfur diesel fuels|
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