• 专利附录
  • 专利说明
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    • 专利摘要:
    The fuel additive has a number average molecular weight (Mn) of about 500 to about 10,000 and is selected from a hydrocarbyl substituted succinic acid or anhydride or a derivative thereof and a Mannich base substituted with a hydrocarbyl. The additive has a molecular weight distribution such that less than about 25% by weight of the additive has a molecular weight of 400 or less as measured by gel permeation chromatography (GPC) based on a calibration curve of polystyrene.
    公开号:BE1021480B1
    申请号:E2011/0344
    申请日:2011-06-08
    公开日:2015-11-30
    发明作者:Xinggao Fang；Julie Galante-Fox
    申请人:Afton Chemical Corporation；
    IPC主号:
    专利说明:

    Description
    Diesel Fuel Additive Technical Area
    The disclosure relates to fuel additives and in particular diesel fuel additives which provide better injector performance.
    Background and summary
    The indirect injection diesel engine has moved into the market now almost entirely to more modern light-duty direct injection diesel engines for fuel economy, performance and low emissions. However, direct injection diesel engines are much more sophisticated than previous indirect injection engines and require more accurate calibration to be maintained to maintain their design performance. Injectors, pumps, filters and other components of the engine fuel system are likely to have their operation disrupted by fouling from deposits resulting from fuel combustion.
    Direct injection engines can also use a high pressure common rail fuel system. Recent problems have arisen with the use of ultra-low sulfur diesel fuels when used in these high-pressure common-rail fuel systems. By "high pressure" is meant here those pressures in diesel fuel systems that are equal to or greater than 1000 bar (equal to or greater than 15,000 psi). These problems are evident from the appearance of sediment in the fuel additive compositions, the internal jet deposits and the adhesion of the injector. Therefore, there is a need to discover the source of deposits and the problem of the injector when the engines operate with very low sulfur fuels, i.e., fuels containing about 15 ppm by weight sulfur or less.
    In order to meet the foregoing and other needs, one embodiment of the disclosure provides a diesel fuel additive composition that has a number average molecular weight (Mn) of about 500 to about 10,000. additive is selected from a hydrocarbyl-substituted succinic acid or anhydride or a derivative thereof, and a hydrocarbyl-substituted Mannich base, wherein the additive has a molecular weight distribution such that less than about 25% By weight of the additive have a molecular weight of 400 or less as measured by gel permeation chromatography (GPC) based on a polystyrene calibration curve.
    In another embodiment of the disclosure, there is provided a method for reducing or preventing injector adhesion or deposits in a high pressure common-rail diesel engine having injectors and burning diesel fuel containing 15 ppm by weight. sulfur weight or less. The method includes combustion in the engine of a composition containing the diesel fuel and a diesel fuel additive having a number average molecular weight (Mn) of about 500 to 10,000. The additive is selected from an acid or a hydrocarbyl-substituted succinic anhydride or a derivative thereof, and a hydrocarbyl-substituted Mannich base, wherein the additive has a molecular weight distribution such that less than about 25% by weight of the additive has a molecular weight of 400 or less as measured by gel permeation chromatography (GPC) based on a polystyrene calibration curve. The use of the fuel containing the additive is effective in reducing the occurrence of the adhesion of the injector relative to the occurrence of the adhesion of the injector in a comparable engine burning a fuel containing a fuel additive similar having a molecular weight distribution such that more than 25% by weight of the additive has a molecular weight of 400 or less as measured by GPC.
    Another embodiment of the disclosure provides a method for improving an additive for a very low sulfur diesel fuel to reduce the deposition and adhesion of the injector in a high pressure diesel fuel injection system. The method includes loading a hydrocarbyl component into a reaction vessel. The hydrocarbyl component is then vacuum distilled at a temperature greater than about 200 ° C for a period of time sufficient to remove at least a portion of the hydrocarbyl components such that a distillation residue of the distilled hydrocarbyl component is effective to provide an additive. for diesel fuel having a number average molecular weight (Mn) of about 500 to 10,000, wherein less than about 25% by weight of the additive has a molecular weight of 400 or less as measured by gel permeation chromatography (GPC) based on a polystyrene calibration curve. The additive is selected from a hydrocarbyl substituted succinic acid or anhydride or a derivative thereof, and a hydrocarbyl-substituted Mannich base. The distillation residue of the hydrocarbyl component is then reacted with a component selected from an unsaturated dicarboxylic acid or anhydride and a substituted phenol or phenol to provide a hydrocarbyl substituted component. The hydrocarbyl-substituted component is then reacted with a reagent selected from an amine and an amine plus an aldehyde to provide the additive having a molecular weight distribution of about 500 to about 10,000, where less than 25% The weight of the additive has a molecular weight of 400 or less as measured by GPC based on a polystyrene calibration curve.
    Yet another embodiment of the disclosure provides a method for improving an additive for a very low sulfur diesel fuel to reduce the deposition and adhesion of the injector in a high pressure injection system for a diesel engine . The method includes charging a hydrocarbyl component to a reaction vessel and reacting the hydrocarbyl component with a component selected from an unsaturated dicarboxylic acid or anhydride to provide a hydrocarbyl substituted component.
    The hydrocarbyl-substituted component is vacuum distilled at a temperature greater than about 200 ° C for a period of time sufficient to remove at least a portion of the hydrocarbyl-substituted component, so that a distillation residue of the substituted component of the Distillate hydrocarbyl is effective in providing a diesel fuel additive having a number average molecular weight (Mn) of about 500 to 10,000, wherein the additive has a molecular weight distribution such as less than about 25% by weight of the additive have a molecular weight of 400 or less as measured by gel permeation chromatography (GPC) based on a polystyrene calibration curve. The distillation residue of the hydrocarbyl substituted component is then reacted with a polar compound to provide the additive having a number average molecular weight (Mn) of about 500 to about 10,000, where less than 25% by weight of the additive have a molecular weight of 400 or less as measured by GPC. Other embodiments of the disclosure may provide increased stability of a diesel fuel additive composition containing a hydrocarbyl-substituted additive where less than 25% (by weight) of the additive has a molecular weight of 400 or less as determined by gel permeation chromatography (GPC) based on a polystyrene calibration curve. Still other embodiments of the disclosure may provide a method for reducing or preventing visible deposits on the internal parts of a diesel injector in a high pressure common rail diesel engine.
    Another embodiment can improve the stability of a diesel fuel additive composition containing a hydrocarbyl-substituted additive component by reducing a weight percent of the precursors of the additive having a relatively low molecular weight so that the resulting additive has a molecular weight distribution which contains less than 25% by weight of the additive having 400 molecular weight or less as determined by gel permeation chromatography (GPC) based on a polystyrene calibration curve.
    According to one or more of the embodiments of the disclosure, there may be a significant benefit in the occurrence of improved (reduced) injector adhesion in high pressure common rail diesel fuel systems. reducing or removing a percentage of fuel additive having a low molecular weight, i.e., a molecular weight of 400 or less as determined by GPC using a polystyrene standard. It has surprisingly been found that the deposits formed on the injectors are composed mainly of materials (lacquers, varnishes, salts, etc.) containing or derived from these low molecular weight portions of the typical distribution curve of the additive product. In fact, even a small amount, such as 10% by weight, or 5% by weight, or less of this relatively low molecular weight component in the fuel additive, if present, can lead to undesirable deposits, varnish and / or adhesion of the injector. Removal or significant reduction of a relatively low molecular weight fraction of the additive of an unmodified calibration curve for such an additive can dramatically improve the performance of the engine and the injector.
    Subject matters of the invention are claimed in the accompanying set of claims.
    Brief description of the drawings
    Fig. 1 is a graphical representation of the exhaust gas temperature over time for the cylinders in a Peugeot engine for a DW10 engine test with a baseline fuel containing no additive.
    Figs. 2 and 3 are graphical representations of exhaust gas temperatures over time for cylinders in a Peugeot engine for a DW10 engine test with additives with conventional fuel additives.
    DETAILED DESCRIPTION OF THE DISCLOSED EMBODIMENTS Other features, embodiments, and advantages thereof may also be provided by the following detailed description of the embodiments of the disclosure. An important feature of the embodiments described herein is that the low or lowest molecular weight additive species in the additive having an unmodified molecular weight distribution curve is desirably removed for example by distillation under void of the additive component in bulk. For example, a succinic imide dispersant or a hydrocarbyl-substituted Mannich base may have a molecular weight distribution having a polydispersity (Mw / Mn) of 1.5 to about 4.0, where Mw is an average molecular weight by weight and Mn is a number average molecular weight of the dispersant. In general, it is extremely difficult or expensive to produce dispersants having a polydispersity of less than about 1.5. Therefore, the distribution curves for these dispersants have one or more conventional bell-shaped portions containing dispersant components having molecular weights above or below the average. These dispersants are reported herein as "unmodified" dispersants or "conventional" dispersants.
    The molecular weight of the hydrocarbyl component and / or the fuel additive can be determined by gel permeation chromatography (GPC). The GPC separation method includes column chromatography in which the stationary phase is a heteroporous polymer network swollen in a polystyrene gel solvent of variable permeability by several orders of magnitude. When the liquid phase (tetrahydrofuran) containing the polymer sample passes through the gel, the polymer molecules diffuse into all parts of the gel that are not mechanically prohibited to it. Smaller molecules "spread" more completely and spend more time in the column; larger molecules "spread" less and pass through the column faster. The Mn and Mw values of the hydrocarbyl component can be obtained by comparing the distribution data obtained from the GPC with a series of calibration standards of known molecular weight polymers. The average molecular weight of the hydrocarbyl component or fuel additive according to the embodiments of the disclosure can be determined by GPC using a polystyrene calibration curve.
    For purposes of disclosure, the term "hydrocarbyl group" or "hydrocarbyl" is used in its ordinary meaning, which is well known to those skilled in the art. Specifically, hydrocarbyl refers to a group having a carbon atom directly attached to the remainder of a molecule and having a predominant hydrocarbon character. Examples of hydrocarbyl groups include: (1) hydrocarbon substituents, i.e., aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents and aromatic substituted aromatic substituents aliphatic 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 moieties which, in the context of the present specification, do not alter the predominant hydrocarbon substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso and sulfoxy); (3) heterosubstituents, i.e., substituents which, although having a predominant hydrocarbon character, in the context of this specification, contain atoms other than carbon in an otherwise composed ring or chain of carbon atoms. Heteroatoms include sulfur, oxygen, nitrogen and include substituents such as pyridyl, furyl, thienyl and imidazolyl. In general, not more than two, or as another example, no more than one non-hydrocarbon substituent will be present per ten carbon atoms in the hydrocarbyl group; in some embodiments, there will be no non-hydrocarbon substituent in the hydrocarbyl group.
    As used herein, the term "major amount" 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.
    The "middle distillate fuel" as used herein may be, for example, a naphtha, kerosene or diesel fuel composition. It may be heating oil, industrial gasoline, drilling oil, automotive diesel fuel, distillate fuel for ships, or kerosene fuel such as aviation fuel or heating kerosene. It can be in particular a composition of diesel fuel. More particularly, a middle distillate fuel is a fuel that is suitable and / or adapted and / or intended for use in an internal combustion engine; for example, an automobile fuel composition, and / or adapted and / or intended for use in a diesel engine (compression ignition). Such a middle distillate fuel may be an organically or synthetic derived gas oil, for example derived from petroleum or according to Fisher-Tropsch. An average distillate fuel may boil in the typical diesel range of 125 or 150 to 400 or 550 ° C, depending on the quality and use. A specific gravity of the middle distillate fuel can vary from 0.75 to 1.0 g / cm3, for example from 0.8 to 0.86 g / cm3, at 15 ° C (IP 365) and a measured cetane number. (ASTM D613) from 35 to 80, suitably 40 to 75 or 70. An initial boiling point of a middle distillate fuel may suitably be in the range of 150 to 230 ° C and the fuel may have a final boiling point in the range of 290 to 400 ° C. A kinematic viscosity of the middle distillate fuel at 40 ° C (ASTM D445) can suitably range from 1.5 to 4.5 mm 2 / s (centistokes).
    The diesel fuels of the embodiments disclosed may be applicable to the operation of both stationary diesel engines (e.g., engines used in power generation facilities, pumping stations, etc.) and ambulatory diesel engines. (for example, engines used as generators of motive power in automobiles, trucks, road equipment, military vehicles, etc.).
    It should be noted that, as used in this specification and the appended claims, the singular forms "a", "a" and "the", "la", include plural referents except expressly and not equivocally limited to a referent. So, for example, the reference to "an antioxidant" includes one or more different antioxidants. As used herein, the term "includes" and its grammatical variants are intended to be non-limiting, so that the recitation of articles in a list is not exclusive of other identical articles that may be substituted or added to articles listed.
    As stated above, it has been found, unexpectedly, that the reduction or removal of relatively low molecular weight components of the additives can provide significant advantages for certain very low sulfur diesel fuels, in particular particularly when used in diesel engines having a high pressure common rail injector system. In order to reduce or eliminate the relatively low molecular weight components of the additive, one or more precursors for the additive may be subjected in a reaction vessel to a vapor pressure reduction via a vacuum distillation process. with overheating. Heat can be applied to the reaction vessel during the vacuum distillation process to increase the process. During the vacuum distillation process, the lower molecular weight species, i.e. the more volatile species, is removed by boiling first leaving a mixture in which the remaining fractions or distillation residues are removed. may be reacted to provide a major amount of additive having a molecular weight greater than 400, as large as 500, more desirably greater than 600 as determined by GPC using a polystyrene standard. By controlling the amount of vacuum and the distillation temperature, the amount of relatively low molecular weight material removed from the reaction vessel can be easily controlled. For example, a vacuum of from about 700 to about 750 mm Hg at a temperature ranging from about 190 to about 250 ° C may be adequate to effect vacuum distillation on the precursor component. Other methods for removing the low molecular weight component may include, but are not limited to, high temperature inert gas stripping, thin layer distillation and / or evaporation, and others. In another form, the low molecular weight component can be removed under vacuum, by stripping, or by thin layer distillation of the final additive product. According to the embodiments of the disclosure, one or more hydrocarbyl component, hydrocarbyl substituted component or additive product may be subjected to one or more of the foregoing methods.
    In one embodiment, the additive contains less than about 10% by weight of additive components having a molecular weight of 400 or less by GPC using a polystyrene standard. In another embodiment, the additive contains less than about 5% by weight of additive components having a molecular weight of 400 or less by GPC using a polystyrene standard. From a practical point of view, it is not necessary to substantially eliminate all additive components having a molecular weight of 400 or less as determined by GPC of the additive to achieve the benefits of the disclosed embodiments. However, the stability of the additive can be improved and the performance of the diesel engine can be extended when the additive contains a relatively minor amount of relatively low molecular weight additive components.
    Unless specifically treated according to the embodiments of the disclosure to remove or eliminate additive components having a molecular weight of 400 or less by GPC using a polystyrene standard, the conventional additives as described above may have a which includes a substantial amount of relatively low molecular weight additive components. Even additives having a relatively high number average molecular weight (Mn) may contain additive components of low molecular weight to form deposits or foul the injectors of diesel engines having a high pressure common rail injector system. .
    In one aspect of the disclosed embodiments, the hydrocarbyl substituents of the hydrocarbyl substituted succinic acid or anhydride or derivatives thereof and Mannich bases may be derived from polyolefins, for example highly branched polyethylene, copolymers of ethylene and alpha olefin, polypropylene, and butene polymers, for example polymers of isobutylene. Polyisobutylenes suitable for use herein include those formed from polyisobutylene or highly reactive polyisobutylene having at least about 60%, such as about 70% to about 90% or more, of terminal vinylidene content. Suitable polyisobutylenes may include those prepared using BF3 catalysts. The number average molecular weight (Mn) of the hydrocarbyl substituent can vary over a wide range, for example, from about 500 to about 10,000, such as from about 500 to about 5,000, as determined by GPC as described above. .
    When the additive is a succinic acid derivative or a succinic anhydride derivative, carboxylic reagents other than maleic anhydride may be used such as maleic acid, fumaric acid, malic acid, acid itaconic anhydride, 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 lower aliphatic esters. A molar ratio of maleic anhydride to hydrocarbyl component in the reaction medium may 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, the maleic acid or anhydride can be used in a stoichiometric excess to force the reaction to completion. Unreacted maleic acid or anhydride can be removed by vacuum distillation.
    A hydrocarbyl-substituted Mannich base can be prepared by reacting the hydrocarbyl component with a phenol or substituted phenol, an aldehyde or its precursors and a polar compound.
    The polar compound may include one of many amines, amino alcohols, amino acids, polyamines, alcohols, polyols, alkoxy alcohols, alkoxyamines, hydrazines, and others. These polar compounds can be used in the preparation of hydrocarbyl-substituted succinic acid or anhydride or derivatives thereof or a Mannich base. Non-limiting examples of amines include methylamine, 2-ethylhexylamine, n-dodecylamine, stearylamine, N, N-dimethylpropanediamine, N- (3-aminopropyl) morpholine, N-dodecylpropanediamine, N-aminopropylpiperazine Ethanolamine, N-ethanolethylenediamine and others. Exemplary non-limiting polyamines may include aminoguanidine bicarbonate (AGBC), ethylenediamine, diethylenetriamine (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 a larger branching. than conventional polyamine blends. Additional non-limiting polyamines that can be used to prepare the hydrocarbyl substituted additive component 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 additive component may include compounds of the following formula:
    where 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 is a polyisobutenyl substituent, such as those derived from polyisobutylenes having at least about 60%, such as about 70% to about 90% or more, of terminal vinylidene content. The compounds of the above formula may be the reaction product of a hydrocarbyl-substituted succinic anhydride, such as polyisobutenyl succinic anhydride (PIBSA) and a polyamine, for example tetraethylenepentamine (ΤΕΡΑ). The foregoing additive may have a molar ratio of hydrocarbyl substituted succinic anhydride (A) to polyamine (B) in the plate of from about 3: 1 to about 1: 2 in the additive. A particularly useful additive contains a polyisobutenyl group of polyisobutenyl substituted succinic anhydride having a number average molecular weight (Mn) in the range of about 500 to 850 as determined by GPC and a polyamine (B) having a general formula H2N (CH2) m- [NH (CH2) m] n_NH2, wherein m is in the range of 2 to 4 and n is in the range of 1 to 3.
    When formulating the fuel containing the additive as described herein, the fuel may contain an amount of additive ranging from about 10 to about 10,000 ppmwv, such as from about 80 to about 200 ppmwv. In those aspects where a carrier is used to provide a composition containing the fuel additive, the additive compositions may contain, on an active ingredient basis, a carrier amount ranging from about 10 mg to about 1000 mg of carrier per kg of fuel, as approximately 25 mg to about 700 mg of carrier per kg of fuel. The base of the active ingredients excludes the weight (i) of the unreacted components associated with and remaining in the additives as produced and used, and (ii) the 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 additive of the present disclosure may be blended into a base fuel individually or in various sub-combinations. In some embodiments, the additive of the present disclosure may be mixed in a fuel simultaneously using an additive concentrate, as this benefits from the mutual compatibility and convenience afforded by the combination of ingredients when they are under the control. form of an additive concentrate. Similarly, the use of a concentrate can reduce the mixing time and reduce the possibility of mixing errors.
    One or more additional optional additives may be present in the fuel compositions disclosed herein. For example, the fuel compositions may contain antifoaming agents, additional dispersing agents, detergents, antioxidants, heat stabilizers, carrier fluids, metal deactivators, dyes, labels, corrosion inhibitors, biocides, and the like. , anti-static additives, friction-reducing agents, friction modifiers, demulsifiers, emulsifiers, fog, anti-icing additives, anti-knock additives, surfactants, cetane number improvers, corrosion inhibitors , cold flow improvers, pour point depressants, solvents, demulsifiers, lubricant additives, extreme pressure agents, viscosity index improvers, seal swelling agents, amine stabilizers, combustion improvers, dispersants, amine improvers tivity, organic nitrate ignition accelerators, manganese tricarbonyl compounds, and mixtures thereof. In some aspects, the fuel additive compositions described herein may contain about 10% by weight or less, or in other aspects, about 5% by weight or less, based on the total weight of the additive or fuel composition, of one or more additives above. Similarly, the fuel compositions may contain appropriate amounts of fuel blend components such as methanol, ethanol, dialkyl ethers and others.
    To further illustrate the features and advantages of the disclosed embodiments, the following non-limiting examples are provided. For purposes of the following examples, the molecular weight of the additives is measured by gel permeation chromatography (GPC) with tetrahydrofuran (THF) as the solvent. Polystyrene standards of the desired molecular weight ranges are used as standards.
    Example 1. A fuel additive is produced from the polyisobutylene succinic anhydride reaction (PIBSA) with tetraethylenepentamine (ΤΕΡΑ) in a molar ratio of PIBSA to ΤΕΡΑ of 1.1: 1.0. A modified procedure as described in U.S. Patent No. 5,752,989 is used to prepare the additive. During the preparation of the additive, high vacuum stripping is used to remove low molecular weight components at various stages of the process. The resulting product has a number average molecular weight (Mn) of 1387 as measured by GPC. The amount of components having a molecular weight of 400 or less as measured by GPC remaining in the product is 2.7% by weight. The resulting product is diluted with an aromatic process fluid at 25:75 weight ratio of the product to the oil of the process to form a clear, bright homogeneous solution in a glass jar. The solution is exposed to atmospheric conditions at 22 ° C to determine the stability of the additive. After 16 hours, the solution remains clear and bright without sedimentation.
    Example 2.-
    An additive is made in a manner similar to that of Example 1 except that the ratio of PIBSA to ΤΕΡΑ is 1.0: 1.0. The product has an Mn of 1420 and the amount of components having a molecular weight of 400 or less as measured by GPC remaining in the product is 2.8% by weight. When it is diluted and exposed to the same atmospheric conditions as in Example 1, the mixture remains clear and bright without sedimentation. Example 3 (Comparative Example)
    An additive is made in the same manner as described in Example 2 except that no high vacuum stripping is used during the reaction to remove low molecular weight components other than vacuum stripping to remove the maleic anhydride which has not reacted. The product has an Mn of 1092 and the amount of components having a molecular weight of less than 400 as measured by GPC is 5.9% by weight. When exposed to the same atmospheric conditions as in Example 2, a brownish sediment forms at the bottom of the glass jar.
    In the following examples, the effect that additives obtained according to the methods of Examples 1-3 have on diesel fuel for high pressure common rail diesel fuel systems is evaluated. A DW10 test developed by the Coordination European Council (CEC) is used to demonstrate the propensity of fuels to cause fouling of the fuel injector and is also used to demonstrate the ability of certain fuel additives to prevent or control these fuel additives. deposits. The injector adhesion evaluation uses the CEC F-98-08 protocol for coking tests of direct injection common-rail diesel engine nozzles. An engine dynamometer test stand is used to install the Peugeot DW10 diesel engine to perform coking tests on the injector. The engine is a 2.0-liter engine with four cylinders. Each combustion chamber has four valves and the diesel injectors are DI piezo injectors with a Euro V classification.
    The central protocol procedure is to operate the engine for an 8-hour cycle and allow the engine to stand (engine off) for a prescribed amount of time. The previous sequence is repeated four times. At the end of each hour, a power measurement is taken from the motor while the motor is operating at rated conditions. The fouling propensity of the fuel injector is characterized by a difference in the nominal power observed between the beginning and the end of the test cycle.
    Test preparation includes rinsing the fuel from previous engine tests before removing the injectors. Test injectors are inspected, cleaned, and reinstalled in the engine. If new injectors are selected, the new injectors are subjected to an interrupt cycle of 16 hours. Then the engine is started using the desired test cycle program. Once the engine has warmed up, the power is measured at 4000 rpm and full load to verify the restoration of full power after cleaning the injectors. If the power measurements are in the specifications, the test cycle is initiated. The following Table 1 provides a representation of the DW10 coking cycle that is used to evaluate the fuel additives according to the disclosure.
    Table 1 - DW10 One Hour Coking Cycle Representation
    Example 4 (adhesion test of the engine injector)
    The coking tests of the diesel engine nozzles are carried out using the Peugeot DW10 engine according to CEC protocol F-98-08 of Table 1. The engine is powered with diesel fuel (PC10) without additives to establish a baseline. No adhesion of the injector is observed, as indicated by a uniform exhaust gas temperature for the 4 cylinders as shown in FIG. 1. In Fig. 1, the curve A is the cylinder 1, the curve B is the cylinder 2, the curve C is the cylinder 3 and the curve D is the cylinder 4.
    Example 5.-
    In this example, an additive made according to Examples 1 and 2 having a GPC Mn of 1462 and having 2.5% by weight of components having a molecular weight of 400 or less is mixed in the fuel in the amount of 180 ppmwv. (weight per volume of diesel fuel). The engine runs for 32 hours without adhesion of the injector.
    Example 6 (Comparative Example)
    An additive made without high vacuum stripping according to the method of Comparative Example 3 is added to a diesel fuel in the amount of 112 ppmwv. The additive has a Mn of 610 according to the GPC, a molecular weight distribution (Mw / Mn) of 1.61, and contains 18.0% by weight of components having a molecular weight of 400 or less. The engine runs for 8 hours on the fuel and restarts after cooling the engine. Two injectors (curves B and C) are blocked as indicated by the low exhaust temperatures at the end of the 8 hours as shown in FIG. 2. The physical inspection of the injectors at the completion of the test confirms that both injectors are blocked.
    Example 7 (Comparative Example)
    Another comparative example is carried out in a manner similar to that of Example 6 except that the additive is used in an amount of 113 ppmwv. Two injectors were found blocked after 8 hours as shown in FIG. 3.
    As indicated by the previous examples, fuel additives containing a large amount of components having a molecular weight of 400 per GPC or less may lead to adhesion of the injector. Unexpectedly, when the additive has only a minor amount of components having a molecular weight of 400 or less per GPC, the fuel behaves exceptionally well in the DW10 test without any adhesion of the injector
    Although the preceding examples illustrate the use of additives containing the reaction product with ΤΕΡΑ as the polar head of the additive component, it is expected that the use of a less polar head as a reaction product obtained with a monoamine, a diamine or an alcohol provide improved performance of the injector even if the additive contains up to about 25% by weight of low molecular weight component.
    For the purposes of this specification and the appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values in the specification and claims, are to be understood as being varied in all case 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 application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be designed in light of the number of significant digits reported and by applying the techniques of ordinary rounding.
    Although particular embodiments have been described, variants, modifications, variations, improvements and substantial equivalents that are or may be presently unforeseen may be apparent to the Applicant and others skilled in the art. Therefore, the claims as filed and as amended may be intended to encompass all such variations, modifications, variations, improvements and all such substantial equivalents.
    权利要求:
    Claims (20)
    [1]
    A diesel fuel additive composition comprising: a diesel fuel additive having a number average molecular weight of about 500 to about 10,000 and being selected from the group consisting of a hydrocarbyl-substituted succinic acid or anhydride or a derivative thereof, and a hydrocarbyl-substituted Mannich base, wherein the additive has a molecular weight distribution such that less than about 25% by weight of the additive has a molecular weight of 400 or less as measured by gel permeation chromatography (GPC) based on a polystyrene calibration curve.
    [2]
    The diesel fuel additive composition according to claim 1, wherein less than about 10% by weight of the additive has a molecular weight of 400 or less as measured by GPC.
    [3]
    The diesel fuel additive composition according to claim 1, wherein less than about 5% by weight of the additive has a molecular weight of 400 or less as measured by GPC.
    [4]
    The diesel fuel additive composition according to any one of claims 1 to 3, wherein the additive comprises a polyisobutenyl-substituted imide acid or anhydride which is prepared by the reaction of a substituted succinic acid or anhydride. by polyisobutenyl and polyamine.
    [5]
    The diesel fuel additive composition according to claim 4, wherein the additive has a molar ratio of the polyisobutenyl (A) substituted succinic acid or anhydride moiety to the polyamine (B) moiety. in the range of about 3: 1 to about 1: 2, wherein the polyisobutenyl group of the polyisobutenyl-substituted succinic acid or anhydride has a number average molecular weight (Mn) in the range of about 500 to 850 and the polyamine (B) has a general formula H2N (CH2) ra- [NH (CH2) m] n -NH2, wherein m is in the range of 2 to 4 and n is in the range of 1 to 3.
    [6]
    The diesel fuel additive composition according to any one of the preceding claims, wherein the additive comprises a polyisobutenyl substituted Mannich base prepared by the reaction of a phenol or a substituted phenol, with a aldehyde or its precursor, and an amine.
    [7]
    The diesel fuel additive composition according to any one of the preceding claims, wherein the hydrocarbyl-substituted succinic acid or anhydride or a derivative thereof comprises a product of the reaction of an acid. or polyisobutenyl substituted succinic anhydride with a polar compound selected from the group consisting of a hydrazine, an alcohol, an amino alcohol, an alkoxylated amine, an alkoxylated alcohol and a polyol.
    [8]
    A very low sulfur diesel fuel comprising the diesel fuel additive composition of any one of the preceding claims.
    [9]
    9. - A method for reducing the appearance of the adhesion of the injector in a high pressure diesel fuel injection system in a diesel engine having injectors and burning a diesel fuel containing 15 ppm by weight or less of sulfur said method comprising burning in said engine a composition comprising said diesel fuel and a diesel fuel additive having a number average molecular weight (Mn) of from about 500 to about 10,000, and being selected from the group consisting of hydrocarbyl-substituted succinic acid or anhydride or a derivative thereof, and a hydrocarbyl-substituted Mannich base, wherein the additive has a molecular weight distribution such as less than about 25% by weight. The weight of the additive has a molecular weight of 400 or less as measured by gel permeation chromatography (GPC), whereby the appearance of the adhesion of the injector is reduced compared to the app. injection of the injector into a comparable fuel-burning engine comprising a fuel additive having a molecular weight distribution such that more than 25% by weight of the fuel additive has a molecular weight of 400 or less as measured by gel permeation chromatography (GPC) based on a polystyrene calibration curve.
    [10]
    The method of claim 9, wherein less than about 5% by weight of the additive has a molecular weight of 400 or less horn measured by GPC.
    [11]
    The process according to claims 9 or 10, wherein the additive comprises a polyisobutenyl-substituted succinic acid or anhydride derivative prepared by reacting a polyisobutenyl-substituted succinic acid or anhydride with a polyamine.
    [12]
    The process according to any one of claims 9 to 11, wherein the additive comprises a polyisobutenyl substituted Mannich base prepared by reacting a phenol or a substituted phenol with an aldehyde or its precursor, and an amine.
    [13]
    A process for improving a fuel additive for a very low sulfur diesel fuel to reduce the deposition and adhesion of the injector in a high pressure diesel fuel injection system for a diesel engine comprising: loading a hydrocarbyl component to a reaction vessel; vacuum distillation of the hydrocarbyl component at a temperature above about 200 ° C for a period of time sufficient to remove at least a portion of the hydrocarbyl component, a distillation residue of said distillate hydrocarbyl component being effective to provide a diesel fuel additive having a number average molecular weight (Mn) of about 500 to 10,000, wherein the additive has a molecular weight distribution such that less than about 25% by weight of the additive has a molecular weight of 400 or less as measured by gel permeation chromatography using a polystyrene calibration curve; reacting the distillation residue with a component selected from the group consisting of an unsaturated dicarboxylic acid or anhydride and a phenol or substituted phenol to provide a hydrocarbyl substituted component; and reacting the hydrocarbyl-substituted component with an amine or amine plus aldehyde to provide the additive selected from the group consisting of a hydrocarbyl-substituted succinic acid or anhydride imide and a hydrocarbyl-substituted Mannich base having a number average molecular weight (Mn) of about 500 to 10,000, wherein less than about 25% by weight of the additive has a molecular weight of 400 or less as measured by gel permeation chromatography (GPC) ) using a polystyrene calibration curve.
    [14]
    The method of claim 13, wherein less than about 5% by weight of the additive has a molecular weight of 400 or less as measured by GPC.
    [15]
    15. The process according to claim 13 or 14, wherein the additive comprises a polyisobutenyl-substituted succinic anhydride prepared by the reaction of a polyisobutenyl-substituted succinic anhydride with a polyamine.
    [16]
    16. - Process according to any one of claims 13 to 15, wherein the additive comprises a polyisobutenyl-substituted Mannich base.
    [17]
    A method for improving a fuel additive for a very low sulfur diesel fuel to reduce the deposits and adhesion of the injector in a high pressure diesel fuel injection system for a diesel engine comprising: loading a hydrocarbyl component to a reaction vessel; reacting the hydrocarbyl component with a component selected from the group consisting of an unsaturated dicarboxylic acid or anhydride to provide a hydrocarbyl substituted component; vacuum distillation of the hydrocarbyl-substituted component at a temperature above about 200 ° C for a period of time sufficient to remove at least a portion of the hydrocarbyl substituted component, a distillation residue of said distillate substituted hydrocarbyl component being effective to provide a diesel fuel additive having a number average molecular weight (Mn) of about 500 to 10,000, wherein the additive has a molecular weight distribution such that less than about 25% by weight of the additive have a molecular weight of 400 or less as measured by gel permeation chromatography (GPC) using a polystyrene calibration curve; and reacting the distillate-substituted hydrocarbyl substituted component with a polar compound to provide the number average molecular weight (Mn) additive of about 500 to 10,000, wherein less than about 25% by weight of the additive have a molecular weight of 400 or less as measured by gel permeation chromatography (GPC) using a polystyrene calibration curve.
    [18]
    The method of claim 17, wherein less than about 5% by weight of the additive has a molecular weight of 400 or less as measured by GPC.
    [19]
    19. - Process according to claims 17 or 18, wherein the additive comprises a polyisobutenyl-substituted succinic anhydride prepared by reaction of a polyisobutenyl-substituted succinic anhydride with a polyamine.
    [20]
    The method of any one of claims 17 to 19, wherein the polar compound is selected from the group consisting of an amine, a hydrazine, an alcohol, an amino alcohol, an amine alkoxylated, an alkoxylated alcohol and a polyol.
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    同族专利:
    公开号 | 公开日
    CN102277213B|2015-08-19|
    GB2481278B|2012-05-30|
    GB2481278A|2011-12-21|
    CN102277213A|2011-12-14|
    US8475541B2|2013-07-02|
    GB201108558D0|2011-07-06|
    US20110302828A1|2011-12-15|
    SG177090A1|2012-01-30|
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    法律状态:
    优先权:
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    US12/815,033|US8475541B2|2010-06-14|2010-06-14|Diesel fuel additive|
    US12/815033|2010-06-14|
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