EP1051462B1 - Solid fuel additive - Google Patents
Solid fuel additive Download PDFInfo
- Publication number
- EP1051462B1 EP1051462B1 EP99904864A EP99904864A EP1051462B1 EP 1051462 B1 EP1051462 B1 EP 1051462B1 EP 99904864 A EP99904864 A EP 99904864A EP 99904864 A EP99904864 A EP 99904864A EP 1051462 B1 EP1051462 B1 EP 1051462B1
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- Prior art keywords
- additive
- composition
- weight
- fuel
- solid
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
Definitions
- the present invention relates to solid or pasty additive compositions for fuels.
- Carburetors and intake systems of gasoline engines, but also injection systems for fuel metering in petrol and diesel engines are increasingly contaminated.
- the Impurities are caused by dust particles from the Air sucked in by the engine, unburned hydrocarbon residues from the combustion chamber and the ventilation gases led into the carburetor from the crankcase.
- Such detergents belonging to a variety of chemical substance classes can generally come in combination with carrier oils and possibly other additive components, such as. Corrosion inhibitors and demulsifiers, for use.
- These liquid additive formulations are usually used appropriate metering devices added to the fuel where they take effect.
- cases also occur during storage and distribution of fuels where no suitable Dosing options for liquid fuel additives available is.
- the existence of fuel additives would be more solid Form that dissolves in fuels, helpful and cheap. You would see a significant improvement over liquid additives represent because of the technical and costly effort a dosing device is not required.
- DE-A-44 31 409 is a pumpable fuel additive paste known, which can be metered directly into the fuel supply line is.
- the paste has an additive content of approximately 5 to 35% by weight. and contains 10 to 60 wt .-% oils, fats and / or waxes as well 1 to 10% by weight of a thickening agent, e.g. Bentonite.
- a thickening agent e.g. Bentonite.
- the disadvantage of such fuel additive formulations is poor handling of the pasty product, as well as the high technical effort for metering the paste into the fuel.
- CA-A-2 143 140 describes solid additives for internal combustion engines known.
- the solid formulation is made by a liquid additive on a porous, solid, fuel-soluble Carrier, preferably a naphthalene-based carrier, adsorbed and the pores of the carrier after adsorption of the additive closes.
- a disadvantage of these solid additives is their cumbersome Production method.
- Another serious one The disadvantage is the limited adsorption capacity of the used Naphthalene pellets. For example, it describes that a 1.6 g pellet is typically only an amount of additive can accommodate a third of its volume.
- Embodiment provides a pelletized additive formulation which have an additive content of about 25 to about 75 % By weight based on the weight of the composition.
- the Additive is in a solidifying agent dispersible in fuel, such as B. paraffin wax, and the additive pellets are sealed on their surface.
- Examples of preferred additives are hydrogenated polybutenes with a molecular weight from about 700 to about 1100 and reaction products from one or several vegetable oils and a polyethyleneimine, in addition derivatized with a sulfonic acid.
- US-A-4 639 255 describes continue solid fuel additive formulations that as Solidifying agent an aromatic hydrocarbon, such as e.g.
- Another solid additive formulation contains one Solidification agent also as a long-chain alcohol Modifier for increasing the melting point.
- Another solid additive formulation has an additive content of about 5 to 40 % By weight, the additive pellets being a coating of foamed Have paraffin wax.
- US-A-4 describes 639 255 additive formulations with foamed carrier. All the solid additive formulations described above are related on their additive content and / or because of their relatively complicated Manufacturing still not entirely satisfactory.
- highly concentrated, solid or pasty detergent additive formulations are provided become.
- This object is surprisingly achieved through provision one that is non-liquid, solid or non-liquid under normal conditions pasty fuel additive composition, which in particular in Gasoline is usable, preferably from a homogeneous Mixture of a solid, fuel-soluble or dispersible Solidifying agent and at least one liquid fuel additive, the composition, based on their total weight, an additive content of more than 40 to about 99% by weight, preferably about 50 to 95% by weight, e.g. about 60 to 90 % By weight or approximately 75 to 90% by weight, characterized in that that the liquid fuel additive is at least one among polyether amines and polyalkenamines and functional derivatives thereof selected detergent additive in a proportion of more than about 10% by weight, based on the total weight of the composition, contains.
- the present invention relates to a fuel additive composition from a homogeneous mixture of a solid, in Fuel-soluble solidifying agent and at least one liquid fuel additive, the composition based an additive content of more than about 40 on their total weight Wt .-% to about 99 wt .-%, solid under normal conditions or pasty, characterized in that the liquid Fuel additive at least one of polyether amines and polyalkenamines and functional derivatives thereof, detergent additive selected in a proportion of more than about 10% by weight on the total weight of the composition.
- the additive compositions according to the invention have the advantage that they have a clear due to their increased additive content have improved performance. Furthermore, they own the advantage that they are easy to manufacture by using the or the additives e.g. in a melt of at ambient temperature solid solidifying agent incorporated, the mixture homogenized, if necessary, allow to cool and suitably packaged. It is not necessary to add the solidifying agent still foam the z. B. processed into pellets, solid formulation to undergo a surface treatment.
- the invention Formulations also offer the advantage of no pumping device can be used for fuel additive to be able to. Furthermore, the dosage level can be adjusted more easily and the viscosity requirements for the additive product are easier to accomplish.
- Has a "solid” or “pasty” composition according to the invention a melting range or melting point in the range of about 25-95 ° C, preferably about 30-90 ° C, especially about 35 - 70 ° C, e.g. about 35 to 50 ° C.
- a "homogeneous" composition exists if there are no phase boundaries or areas of segregation visually in the solid according to the invention are recognizable.
- the inventive Compositions as the main additive component at least one Detergent additive.
- such additives are used which both the formation of deposits on the intake valves prevent as well as remove already formed deposits. They therefore show both a keep-clean effect and one clean-up effect.
- Additives suitable according to the invention are selected from polyether amines, such as, for example, poly-C 2 -C 6 -alkylene oxide amines, and polyalkenamines, such as, for example, poly-C 2 -C 6 -alkenamine, and functional derivatives thereof.
- Particularly preferred detergent additives are selected from polyisobutenamines and functional derivatives thereof.
- the polyisobutene content of such additives can be based, for example, on the C 4 cut with a high polyisobutene content, typically obtained in the case of thermal or catalytic cracking.
- B. be produced by cationic polymerization.
- the polyisobutene part can also from mixtures of n-butene and i-butene, for. B.
- a functional derivative is understood to mean chemically modified detergent additives which show a cleaning effect of a detergent additive which is qualitatively comparable but not necessarily completely identical in terms of level or strength.
- the detergent additives preferably used according to the invention are known per se from the prior art. Polyisobutenamines are described, for example, in EP-A-0 244 616 and EP-A-0 578 323. Further detergent additives suitable according to the invention are described, for example, in European Patent Applications EP-A-0 277 345, 0 356 725, 0 476 485, 0 484 736, 0 539 821, 0 543 225, 0 548 617, 0 561 214, 0 567 810 and 0 568 873; in German patent applications DE-A-39 42 860, 43 09 074, 43 09 271, 43 13 088, 44 12 489, 0 44 25 834, 195 25 938, 196 06 845, 196 06 846, 196 15 404, 196 06 844, 196 16 569, 196 18 270 and 196 14 349; and in WO-A-96/03479. Particularly useful liquid detergent additives are sold by BASF AG
- Detergent additives used according to the invention in particular those preferred polyisobutenamine additives used usually have a number average molecular weight Mn in the range of about 150 to about 5000, preferably about 500 to about 2000, in particular about 800 to 1500 g per mole.
- the content of detergent additive e.g. Polyisobutenamines and the functional derivatives thereof is about 20 to 100 % By weight, preferably more than 30% by weight, in particular more than 40 % By weight, such as. B. about 45 to 70 wt .-%, based on the total weight of those contained in the composition according to the invention
- Additives Is the detergent additive component in one Share before, one speaks in the context of the present invention of a "major additive component" of the composition.
- the detergent additive fraction e.g. more than about 10% by weight, e.g. 15 to 30% by weight or more, e.g. about 40 up to 99% by weight or 50 to 95% by weight, or 60 to 90% by weight or 75 to 90% by weight.
- detergent additive In addition to the detergent additive, other customary ones may be used Contain fuel additives and additives such as Corrosion inhibitors, Demulsifiers and dyes. Furthermore, if necessary Carrier oils can be added.
- mineral carrier oils examples include synthetic carrier oils and Mixtures of which with the additive (s) used and the Are fuel compatible.
- Suitable mineral carrier oils are fractions, such as kerosene, that occur during oil processing or naphtha, brightstock or mineral oils with viscosity in the range SN 500 - 900; but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols.
- Suitable synthetic carrier oils are polyolefins, (poly) esters, (poly) alkoxylates, and in particular aliphatic polyethers, aliphatic polyetheramines, alkylphenol-started polyethers and alkylphenol-started polyetheramines.
- Suitable carrier oil systems are described, for example, in DE-A-38 38 918, DE-A-38 26 608, DE-A-41 42 241, DE-43 09 074, US-A-4 877 416 and EP-A-0 452 328, to which express reference is hereby made.
- particularly suitable synthetic carrier oils are alcohol-initiated polyethers with about 15 to 30, for example about 20 to 25, C 3 -C 6 alkylene oxide units, such as, for example, selected from propylene oxide, n-butylene oxide and i-butylene oxide units or mixtures thereof ,
- Solidifying agent is preferably fuel-soluble and has usually a melting point or softening point above the corresponding values of the finished composition, e.g. in the range of about 30 to 100 ° C, preferably about 30 to 90 ° C, especially 40 to 70 ° C.
- the solidifying agent selected from fuel-soluble (a) natural waxes, such as e.g. petrochemical waxes, in particular paraffin wax and petroleum jelly; (b) chemically modified waxes, e.g. Hard waxes, and (c) synthetic waxes such as e.g. Polyethylene wax and high molecular weight polyisobutene (see e.g.
- Solidifying agents suitable according to the invention have a Fuel solubility up to about 10% by weight of the fuel used.
- the fuel additive compositions according to the invention are in simply using well known techniques produced.
- the solidifying agent is preferably heated at its softening temperature, there is stirring Fuel additive or the additive mixture and optionally that Add carrier oil and stir until a homogeneous mixture is formed is.
- the liquid mixture is then allowed to solidify.
- the incorporation of the additive into the hardening agent is the same usable by kneading or by melt extrusion.
- the finished composition is then extruded or made up into tablets. There is also the possibility to provide the compositions in pill or powder form. Encapsulation of pellets or pills is possible however not required.
- the additive compositions according to the invention can the fuel without special technical devices e.g. right away after loading into the tanker.
- the dosing units such as. Pellets are added in an amount that is required to have a detergent additive concentration of approximately 20 to 5000 mg / kg fuel, e.g. about 400 - 900 mg / kg Fuel.
- Example 1 Preparation of a solid additive composition
- Example 2 Preparation of a solid additive composition
- Example 3 Determination of the cleaning action of a solid additive formulation
- test results show that inlet valve deposits in the Significantly reduced compared to the non-additive basic value were.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft feste oder pastöse Additivzusammensetzungen für Kraftstoffe.The present invention relates to solid or pasty additive compositions for fuels.
Vergaser und Einlaßsysteme von Ottomotoren, aber auch Einspritzsysteme für die Kraftstoffdosierung in Otto- und Dieselmotoren werden in zunehmendem Maße durch Verunreinigungen belastet. Die Verunreinigungen werden verursacht durch Staubteilchen aus der vom Motor angesaugten Luft, unverbrannte Kohlenwasserstoffreste aus dem Brennraum und die in den Vergaser geleiteten Entlüftungsgase aus dem Kurbelwellengehäuse.Carburetors and intake systems of gasoline engines, but also injection systems for fuel metering in petrol and diesel engines are increasingly contaminated. The Impurities are caused by dust particles from the Air sucked in by the engine, unburned hydrocarbon residues from the combustion chamber and the ventilation gases led into the carburetor from the crankcase.
Diese Rückstände verschieben das Luft-Kraftstoffverhältnis im Leerlauf und im unteren Teillastbereich, so daß das Gemisch fetter und die Vorbrennung unvollständiger wird. Als Folge davon erhöht sich der Anteil unverbrannter oder teilverbrannter Kohlenwasserstoffe im Abgas und der Benzinverbrauch steigt.These residues shift the air-fuel ratio in the Idling and in the lower part load range, so that the mixture fatter and the pre-firing becomes incomplete. As a result, increased the percentage of unburned or partially burned hydrocarbons in exhaust gas and gasoline consumption increases.
Es ist bekannt, daß zur Vermeidung dieser Nachteile Kraftstoffadditive zur Reinhaltung von Ventilen und Vergaser- bzw. Einspritzsystemen verwendet werden (vgl. z.B.: M. Rossenbeck in Katalysatoren, Tenside, Mineralöladditive, Hrsg. J. Falbe, U. Hasserodt, S. 223, G. Thieme Verlag, Stuttgart 1978). Je nach Wirkungsweise und bevorzugtem Wirkort solcher Detergens-Additive unterscheidet man heute zwei Additiv-Generationen. Die erste Additiv-Generation konnte nur die Bildung von Ablagerungen im Ansaugsystem verhindern, nicht aber bereits vorhandene Ablagerungen wieder entfernen. Die Additive der zweiten Generation können dagegen Ablagerungen verhindern und beseitigen. Sie zeigen somit sowohl einen keep-clean-Effekt als auch einen clean-up-Effekt. Dies wird insbesondere durch deren hervorragende Thermostabilität an Zonen höherer Temperatur, wie insbesondere an den Einlaßventilen, ermöglicht.It is known that to avoid these disadvantages, fuel additives for keeping valves and carburetor or injection systems clean can be used (see e.g. M. Rossenbeck in catalysts, Surfactants, mineral oil additives, ed. J. Falbe, U. Hasserodt, P. 223, G. Thieme Verlag, Stuttgart 1978). Depending on the mode of action and preferred site of action of such detergent additives today two generations of additives. The first generation of additives could only prevent the formation of deposits in the intake system, but do not remove any existing deposits. The second generation additives, however, can deposit prevent and eliminate. They therefore show both keep-clean effect as well as a clean-up effect. This will be particularly due to their excellent thermal stability in zones higher Temperature, such as in particular at the inlet valves, allows.
Derartige Detergenzien, die einer Vielzahl chemischer Substanzklassen entstammen können, gelangen im allgemeinen in Kombination mit Trägerölen und gegebenenfalls weiteren Additivkomponenten, wie z.B. Korrosionsinhibitoren und Demulgatoren, zur Anwendung. Diese flüssigen Additivformulierungen werden in der Regel mittels geeigneter Dosiervorrichtungen dem Kraftstoff zugesetzt, wo sie ihre Wirkung entfalten. Allerdings treten auch Fälle bei der Lagerung und Verteilung von Kraftstoffen auf, bei denen keine geeignete Dosierungsmöglichkeit für flüssige Kraftstoffadditive vorhanden ist. Hier wäre die Existenz von Kraftstoffadditiven in fester Form, die sich in Kraftstoffen lösen, hilfreich und günstig. Sie würden eine erhebliche Verbesserung gegenüber flüssigen Additiven darstellen, da der technische und kostenintensive Aufwand einer Dosiervorrichtung entfällt.Such detergents belonging to a variety of chemical substance classes can generally come in combination with carrier oils and possibly other additive components, such as. Corrosion inhibitors and demulsifiers, for use. These liquid additive formulations are usually used appropriate metering devices added to the fuel where they take effect. However, cases also occur during storage and distribution of fuels where no suitable Dosing options for liquid fuel additives available is. Here the existence of fuel additives would be more solid Form that dissolves in fuels, helpful and cheap. You would see a significant improvement over liquid additives represent because of the technical and costly effort a dosing device is not required.
Aus der DE-A-44 31 409 ist eine pumpfähige Kraftstoffadditiv-Paste bekannt, welche direkt in die Kraftstoffzuleitung zudosierbar ist. Die Paste weist einen Additivgehalt von etwa 5 bis 35 Gew.-% auf und enthält 10 bis 60 Gew.-% Öle, Fette und/oder Wachse sowie 1 bis 10 Gew.-% eines Verdickgungsmittels, wie z.B. Bentonit. Nachteilig bei derartigen Kraftstoffadditivformulierungen ist die schlechte Handhabbarkeit des pastösen Produkts, sowie der hohe technische Aufwand für die Zudosierung der Paste zum Kraftstoff.DE-A-44 31 409 is a pumpable fuel additive paste known, which can be metered directly into the fuel supply line is. The paste has an additive content of approximately 5 to 35% by weight. and contains 10 to 60 wt .-% oils, fats and / or waxes as well 1 to 10% by weight of a thickening agent, e.g. Bentonite. The disadvantage of such fuel additive formulations is poor handling of the pasty product, as well as the high technical effort for metering the paste into the fuel.
Aus der CA-A-2 143 140 sind Feststoffadditive für Verbrennungsmotoren bekannt. Die feste Formulierung wird hergestellt, indem man ein flüssiges Additiv auf einem porösen, festen, kraftstofflöslichen Träger, vorzugsweise einem Träger auf Naphthalinbasis, adsorbiert und die Poren des Trägers nach Adsorption des Additivs verschließt. Ein Nachteil dieser Feststoffadditive ist deren umständliches Herstellungsverfahren. Ein weiterer gravierender Nachteil besteht in der begrenzten Adsorptionsfähigkeit der verwendeten Naphthalinpellets. So wird beispielsweise beschrieben, daß ein 1,6 g-Pellet typischerweise lediglich eine Additivmenge aufnehmen kann, die einem Drittel seines Volumens entspricht.CA-A-2 143 140 describes solid additives for internal combustion engines known. The solid formulation is made by a liquid additive on a porous, solid, fuel-soluble Carrier, preferably a naphthalene-based carrier, adsorbed and the pores of the carrier after adsorption of the additive closes. A disadvantage of these solid additives is their cumbersome Production method. Another serious one The disadvantage is the limited adsorption capacity of the used Naphthalene pellets. For example, it describes that a 1.6 g pellet is typically only an amount of additive can accommodate a third of its volume.
Aus der US-A-4 639 255 sind verschiedene feste Kraftstoffadditivzusammensetzungen bekannt. Gemäß einer ersten darin beschriebenen Ausführungsform wird eine pelletierte Additivformulierung bereitgestellt, welche einen Additivgehalt von etwa 25 bis etwa 75 Gew.-% bezogen auf das Gewicht der Zusammensetzung aufweist. Das Additiv ist in einem in Kraftstoff dispergierbaren Verfestigungsmittel, wie z. B. Paraffinwachs, enthalten und die Additivpellets sind an ihrer Oberfläche versiegelt. Beispiele für bevorzugte Additive sind hydrogenierte Polybutene mit einem Molekulargewicht von etwa 700 bis etwa 1100 und Reaktionsprodukte aus einem oder mehreren pflanzlichen Ölen und einem Polyethylenimin, zusätzlich derivatisiert mit einer Sulfonsäure. Die US-A-4 639 255 beschreibt weiterhin feste Kraftstoffadditivformulierungen, die als Verfestigungsmittel einen aromatischen Kohlenwasserstoff, wie z.B. Naphthalin oder das leicht sublimierende Durene (1,2,4,5-Tetramethylbenzol), in einem Anteil von etwa 50 bis 95 Gew.-% enthalten. Eine weitere feste Additivformulierung enthält neben einem Verfestigungsmittel zusätzlich einen langkettigen Alkohol als Modifikator zur Schmelzpunktserhöhung. Eine andere feste Additivformulierung besitzt einen Additivgehalt von etwa 5 bis 40 Gew.-%, wobei die Additivpellets eine Beschichtung aus geschäumtem Paraffinwachs aufweisen. Schließlich beschreibt die US-A-4 639 255 Additivformulierungen mit geschäumtem Träger. Sämtliche der oben beschriebenen festen Additivformulierungen sind in bezug auf ihren Additivgehalt und/oder aufgrund ihrer relativ komplizierten Herstellung noch nicht völlig zufriedenstellend. Der Fachmann wird in der US-A-4 639 255 ausdrücklich darauf hingewiesen, daß der Additivgehalt in unbeschichteten Formulierungen bei nicht mehr als 40 Gew.-% liegen darf und vorzugsweise etwa 10 bis 30 Gew.-% und insbesondere etwa 15 bis 25 Gew.-% betragen sollte.Various solid fuel additive compositions are disclosed in US-A-4,639,255 known. According to a first described therein Embodiment provides a pelletized additive formulation which have an additive content of about 25 to about 75 % By weight based on the weight of the composition. The Additive is in a solidifying agent dispersible in fuel, such as B. paraffin wax, and the additive pellets are sealed on their surface. Examples of preferred additives are hydrogenated polybutenes with a molecular weight from about 700 to about 1100 and reaction products from one or several vegetable oils and a polyethyleneimine, in addition derivatized with a sulfonic acid. US-A-4 639 255 describes continue solid fuel additive formulations that as Solidifying agent an aromatic hydrocarbon, such as e.g. Naphthalene or the slightly subliming durene (1,2,4,5-tetramethylbenzene), contained in a proportion of about 50 to 95 wt .-%. Another solid additive formulation contains one Solidification agent also as a long-chain alcohol Modifier for increasing the melting point. Another solid additive formulation has an additive content of about 5 to 40 % By weight, the additive pellets being a coating of foamed Have paraffin wax. Finally, US-A-4 describes 639 255 additive formulations with foamed carrier. All the solid additive formulations described above are related on their additive content and / or because of their relatively complicated Manufacturing still not entirely satisfactory. The A person skilled in the art is expressly advised in US-A-4,639,255 that that the additive content in uncoated formulations not more than 40% by weight, and preferably about 10 to 30 wt .-% and in particular about 15 to 25 wt .-% should be.
Es ist deshalb Aufgabe der vorliegenden Erfindung feste oder pastöse Kraftstoffadditivformulierungen bereitzustellen, welche sich sowohl durch einen hohen Additivgehalt als auch durch einfache Herstellung auszeichnen. Insbesondere sollen hochkonzentrierte, feste oder pastöse Detergensadditivformulierungen bereitgestellt werden.It is therefore an object of the present invention to be solid or pasty To provide fuel additive formulations which both by a high additive content and by simple Award manufacturing. In particular, highly concentrated, solid or pasty detergent additive formulations are provided become.
Diese Aufgabe wird überraschenderweise gelöst durch Bereitstellung einer unter Normalbedingungen nicht-flüssigen, festen oder pastösen Kraftstoffadditivzusammensetzung, welche insbesondere in Ottokraftstoffen verwendbar ist, aus einem vorzugsweise homogenen Gemisch eines festen, in Kraftstoff löslichen oder dispergierbaren Verfestigungsmittels und wenigstens eines flüssigen Kraftstoffadditivs, wobei die Zusammensetzung, bezogen auf ihr Gesamtgewicht, einen Additivgehalt von mehr als 40 bis etwa 99 Gew.-%, vorzugsweise etwa 50 bis 95 Gew.-%, wie z.B. etwa 60 bis 90 Gew.-% oder etwa 75 bis 90 Gew.-%, aufweist, dadurch gekennzeichnet, dass das flüssige Kraftstoffadditiv wenigstens ein unter Polyetheraminen und Polyalkenaminen und funktionellen Derivaten davon ausgewähltes Detergens-Additiv in einem Anteil von mehr als etwa 10 Gew.-%, bezogen auf das Gesamtgewicht der Zusammensetzung, enthält. This object is surprisingly achieved through provision one that is non-liquid, solid or non-liquid under normal conditions pasty fuel additive composition, which in particular in Gasoline is usable, preferably from a homogeneous Mixture of a solid, fuel-soluble or dispersible Solidifying agent and at least one liquid fuel additive, the composition, based on their total weight, an additive content of more than 40 to about 99% by weight, preferably about 50 to 95% by weight, e.g. about 60 to 90 % By weight or approximately 75 to 90% by weight, characterized in that that the liquid fuel additive is at least one among polyether amines and polyalkenamines and functional derivatives thereof selected detergent additive in a proportion of more than about 10% by weight, based on the total weight of the composition, contains.
Demgemäß betrifft die vorliegende Erfindung eine Kraftstoffadditivzusammensetzung aus einem homogenen Gemisch eines festen, in Kraftstoff löslichen Verfestigungsmittels und wenigstens eines flüssigen Kraftstoffadditivs, wobei die Zusammensetzung bezogen auf ihr Gesamtgewicht einen Additivgehalt von mehr als etwa 40 Gew.-% bis etwa 99 Gew.-% aufweist, bei Normalbedingungen fest oder pastös ist, dadurch gekennzeichnet, dass das flüssige Kraftstoffadditiv wenigstens ein unter Polyetheraminen und Polyalkenaminen und funktionellen Derivaten davon ausgewähltes Detergens-Additiv in einem Anteil von mehr als etwa 10 Gew.-%, bezogen auf das Gesamtgewicht der Zusammensetzung, enthält.Accordingly, the present invention relates to a fuel additive composition from a homogeneous mixture of a solid, in Fuel-soluble solidifying agent and at least one liquid fuel additive, the composition based an additive content of more than about 40 on their total weight Wt .-% to about 99 wt .-%, solid under normal conditions or pasty, characterized in that the liquid Fuel additive at least one of polyether amines and polyalkenamines and functional derivatives thereof, detergent additive selected in a proportion of more than about 10% by weight on the total weight of the composition.
Die erfindungsgemäßen Additivzusammensetzungen besitzen den Vorteil, daß sie aufgrund ihres erhöhten Additivgehaltes eine deutlich verbesserte Performance aufweisen. Weiterhin besitzen sie den Vorteil, daß sie einfach herstellbar sind, indem man das oder die Additive z.B. in eine Schmelze des bei Umgebungstemperatur festen verfestigungsmittels einarbeitet, das Gemisch homogenisiert, gegebenenfalls abkühlen läßt und in geeigneter Weise konfektioniert. Es ist weder erforderlich das Verfestigungsmittel zu schäumen noch die, z. B. zu Pellets verarbeitete, feste Formulierung einer Oberflächenbehandlung zu unterziehen. Die erfindungsgemäßen Formulierungen bieten außerdem den Vorteil, ohne Pumpvorrichtung für die Additivierung von Kraftstoff verwendet werden zu können. Weiterhin kann die Dosierhöhe leichter eingestellt werden und die Viskositätsanforderungen an das additivierte Produkt sind leichter zu erfüllen. The additive compositions according to the invention have the advantage that they have a clear due to their increased additive content have improved performance. Furthermore, they own the advantage that they are easy to manufacture by using the or the additives e.g. in a melt of at ambient temperature solid solidifying agent incorporated, the mixture homogenized, if necessary, allow to cool and suitably packaged. It is not necessary to add the solidifying agent still foam the z. B. processed into pellets, solid formulation to undergo a surface treatment. The invention Formulations also offer the advantage of no pumping device can be used for fuel additive to be able to. Furthermore, the dosage level can be adjusted more easily and the viscosity requirements for the additive product are easier to accomplish.
Angaben zum Aggregatszustand, wie "fest", "flüssig" oder "pastös" erfolgen im Rahmen der vorliegenden Beschreibung unter Bezugnahme auf Normalbedingungen, also etwa 20 °C und etwa 1 atm Druck.Information on the state of matter, such as "solid", "liquid" or "pasty" are made within the scope of the present description with reference on normal conditions, i.e. about 20 ° C and about 1 atm pressure.
Eine erfindungsgemäße "feste" oder "pastöse" Zusammensetzung besitzt einen Schmelzbereich bzw. einen Schmelzpunkt im Bereich von etwa 25 - 95°C, vorzugsweise etwa 30 - 90°C, insbesondere etwa 35 - 70°C, wie z.B. etwa 35 bis 50 °C.Has a "solid" or "pasty" composition according to the invention a melting range or melting point in the range of about 25-95 ° C, preferably about 30-90 ° C, especially about 35 - 70 ° C, e.g. about 35 to 50 ° C.
Die im Rahmen der vorliegenden Erfindung angebenen "Additivgehalte" stellen, sofern keine anderen Angaben gemacht werden, die Summe der Gehaltswerte aller vom Verfestigungsmittel verschiedenen Bestandteile der jeweiligen Formulierung dar.The "additive contents" specified in the context of the present invention unless otherwise specified, the Sum of the salary values of all other than the solidifying agent Components of the respective formulation.
Eine "homogene" Zusammensetzung liegt vor, wenn keine Phasengrenzen oder Entmischungsbereiche im erfindungsgemäßen Feststoff visuell erkennbar sind.A "homogeneous" composition exists if there are no phase boundaries or areas of segregation visually in the solid according to the invention are recognizable.
In einer bevorzugten Ausführungsform enthalten die erfindungsgemäßen Zusammensetzungen als Hauptadditivkomponente wenigstens ein Detergensadditiv. Insbesondere werden solche Additive verwendet, welche sowohl die Bildung von Ablagerungen an den Einlaßventilen verhindern als auch bereits gebildete Ablagerungen beseitigen. Sie zeigen somit sowohl einen keep-clean-Effekt als auch einen clean-up-Effekt.In a preferred embodiment, the inventive Compositions as the main additive component at least one Detergent additive. In particular, such additives are used which both the formation of deposits on the intake valves prevent as well as remove already formed deposits. They therefore show both a keep-clean effect and one clean-up effect.
Erfindungsgemäß geeignete Additive sind ausgewählt unter Polyetheraminen, wie z.B. Poly-C2-C6-alkylenoxidamine, und Polyalkenaminen, wie z.B. Poly-C2-C6-alkenamine, und funktionellen Derivaten davon. Besonders bevorzugte Detergensadditive sind ausgewählt unter Polyisobutenaminen und funktionellen Derivaten davon. Der Polyisobutenanteil derartiger Additive kann beispielsweise ausgehend von dem bei thermischem oder katalytischem Cracken typischerweise anfallenden C4-Schnitt mit hohem Polyisobutenanteil, z. B. durch kationische Polymerisation, hergestellt sein. Der Polyisobutenteil kann aber auch aus Gemischen von n-Buten und i-Buten, z. B. durch kationische Polymerisation, abgeleitet sein, wobei das molare Verhältnis von i-Buten zu n-Buten frei wählbar und beispielsweise im Bereich von etwa 1:20 bis etwa 20:1, wie z. B. etwa 1:10 bis 10:1, frei einstellbar ist. Der Polyisobutenanteil kann aber auch aus im Wesentlichen reinem i-Buten, z. B. durch kationische Polymerisation, abgeleitet sein und somit etwa zu 100 % i-Buteneinheiten in einpolymerisierter Form enthalten. Bevorzugt werden obige Polyalkenamine ausgehend von sogenanntem, aus dem Stand der Technik bekannten reaktiven Polyalken hergestellt. Dieses weist vorzugsweise einen hohen Gehalt an endständigen Doppelbindungen, wie z. B. von etwa ≥ 50 % oder ≥ 70 % oder ≥ 90 % auf. Unter einem funktionellen Derivat versteht man erfindungsgemäß chemisch modifizierte Detergensadditive welche einen qualitativ vergleichbaren, jedoch nicht notwendigerweise in der Höhe bzw. Stärke völlig identischen Reinigungseffekt eines Detergensadditivs zeigen.Additives suitable according to the invention are selected from polyether amines, such as, for example, poly-C 2 -C 6 -alkylene oxide amines, and polyalkenamines, such as, for example, poly-C 2 -C 6 -alkenamine, and functional derivatives thereof. Particularly preferred detergent additives are selected from polyisobutenamines and functional derivatives thereof. The polyisobutene content of such additives can be based, for example, on the C 4 cut with a high polyisobutene content, typically obtained in the case of thermal or catalytic cracking. B. be produced by cationic polymerization. The polyisobutene part can also from mixtures of n-butene and i-butene, for. B. by cationic polymerization, where the molar ratio of i-butene to n-butene is freely selectable and for example in the range from about 1:20 to about 20: 1, such as. B. about 1:10 to 10: 1, is freely adjustable. However, the polyisobutene fraction can also consist of essentially pure i-butene, e.g. B. by cationic polymerization, and thus contain about 100% i-butene units in copolymerized form. The above polyalkenamines are preferably prepared starting from so-called reactive polyalkene known from the prior art. This preferably has a high content of terminal double bonds, such as. B. of about ≥ 50% or ≥ 70% or ≥ 90%. According to the invention, a functional derivative is understood to mean chemically modified detergent additives which show a cleaning effect of a detergent additive which is qualitatively comparable but not necessarily completely identical in terms of level or strength.
Die erfindungsgemäß bevorzugt verwendeten Detergensadditive sind an sich aus dem Stand der Technik bekannt. Polyisobutenamine sind beispielsweise beschrieben in der EP-A-0 244 616 sowie der EP-A-0 578 323. Weitere erfindungsgemäß geeignete Detergensadditive sind beispielsweise beschrieben in den Europäischen Patentanmeldungen EP-A-0 277 345, 0 356 725, 0 476 485, 0 484 736, 0 539 821, 0 543 225, 0 548 617, 0 561 214, 0 567 810 und 0 568 873; in den Deutschen Patentanmeldungen DE-A-39 42 860, 43 09 074, 43 09 271, 43 13 088, 44 12 489, 0 44 25 834, 195 25 938, 196 06 845, 196 06 846, 196 15 404, 196 06 844, 196 16 569, 196 18 270 und 196 14 349; sowie in der WO-A-96/03479. Besonders brauchbare flüssige Detergensadditive werden von der BASF AG, Ludwigshafen unter der Handelsbezeichnung Kerocom®PIBA vertrieben. Diese enthalten Polyisobutenamine gelöst in aliphatischen C10-14-Kohlenwasserstoffen.The detergent additives preferably used according to the invention are known per se from the prior art. Polyisobutenamines are described, for example, in EP-A-0 244 616 and EP-A-0 578 323. Further detergent additives suitable according to the invention are described, for example, in European Patent Applications EP-A-0 277 345, 0 356 725, 0 476 485, 0 484 736, 0 539 821, 0 543 225, 0 548 617, 0 561 214, 0 567 810 and 0 568 873; in German patent applications DE-A-39 42 860, 43 09 074, 43 09 271, 43 13 088, 44 12 489, 0 44 25 834, 195 25 938, 196 06 845, 196 06 846, 196 15 404, 196 06 844, 196 16 569, 196 18 270 and 196 14 349; and in WO-A-96/03479. Particularly useful liquid detergent additives are sold by BASF AG, Ludwigshafen, under the trade name Kerocom®PIBA. These contain polyisobutenamines dissolved in aliphatic C 10-14 hydrocarbons.
Erfindungsgemäß verwendete Detergensadditive, inbesondere die bevorzugt verwendeten Polyisobutenamin-Additive, besitzen gewöhnlich ein zahlenmittleres Molekulargewicht Mn im Bereich von etwa 150 bis etwa 5000, vorzugsweise etwa 500 bis etwa 2000, insbesondere etwa 800 bis 1500 g pro Mol.Detergent additives used according to the invention, in particular those preferred polyisobutenamine additives used usually have a number average molecular weight Mn in the range of about 150 to about 5000, preferably about 500 to about 2000, in particular about 800 to 1500 g per mole.
Der Gehalt an Detergensadditiv, wie z.B. Polyisobutenaminen und den funktionellen Derivaten davon, beträgt etwa 20 bis 100 Gew.-%, vorzugsweise mehr als 30 Gew.-%, insbesondere mehr als 40 Gew.-%, wie z. B. etwa 45 bis 70 Gew.-%, bezogen auf das Gesamtgewicht der in der erfindungsgemäßen Zusammensetzung enthaltenen Additive. Liegt die Detergensadditiv-Komponente in einem solchen Anteil vor, so spricht man im Rahmen der vorliegenden Erfindung von einer "Hauptadditivkomponente" der Zusammensetzung.The content of detergent additive, e.g. Polyisobutenamines and the functional derivatives thereof is about 20 to 100 % By weight, preferably more than 30% by weight, in particular more than 40 % By weight, such as. B. about 45 to 70 wt .-%, based on the total weight of those contained in the composition according to the invention Additives. Is the detergent additive component in one Share before, one speaks in the context of the present invention of a "major additive component" of the composition.
Bezogen auf das Gesamtgewicht der festen oder pastösen Additivformulierung kann der Detergensadditivanteil z.B. mehr als etwa 10 Gew.-%, wie z.B. 15 bis 30 Gew.-% oder mehr, wie z.B. etwa 40 bis 99 Gew.-% oder 50 bis 95 Gew.-%, oder 60 bis 90 Gew.-% oder 75 bis 90 Gew.-%, betragen.Based on the total weight of the solid or pasty additive formulation can the detergent additive fraction e.g. more than about 10% by weight, e.g. 15 to 30% by weight or more, e.g. about 40 up to 99% by weight or 50 to 95% by weight, or 60 to 90% by weight or 75 to 90% by weight.
Neben dem Detergensadditiv sind gegebenenfalls weitere übliche Kraftstoffadditive und Zusätze enthalten, wie z.B. Korrosionsinhibitoren, Demulgatoren und Farbstoffe. Weiterhin können gebenenenfalls Trägeröle zugesetzt sein. In addition to the detergent additive, other customary ones may be used Contain fuel additives and additives such as Corrosion inhibitors, Demulsifiers and dyes. Furthermore, if necessary Carrier oils can be added.
Als Beispiele für brauchbare Trägeröle oder Trägerflüssigkeiten sind zu nennen mineralische Trägeröle, synthetische Trägeröle und Gemische davon, welche mit dem/den verwendeten Additiv/en und dem Kraftstoff verträglich sind. Geeignete mineralische Trägeröle sind bei der Erdölverarbeitung anfallende Fraktionen, wie Kerosin oder Naphtha, Brightstock oder Mineralöle mit Viskosität im Bereich SN 500 - 900 ; aber auch aromatische Kohlenwasserstoffe, paraffinische Kohlenwasserstoffe und Alkoxyalkanole.As examples of usable carrier oils or carrier liquids mineral carrier oils, synthetic carrier oils and Mixtures of which with the additive (s) used and the Are fuel compatible. Suitable mineral carrier oils are fractions, such as kerosene, that occur during oil processing or naphtha, brightstock or mineral oils with viscosity in the range SN 500 - 900; but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols.
Beispiele für geeignete synthetische Trägeröle sind Polyolefine, (Poly)ester, (Poly)alkoxylate, und insbesondere aliphatische Polyether, aliphatische Polyetheramine, alkylphenolgestartete Polyether und alkylphenolgestartete Polyetheramine. Geeignete Trägerölsysteme sind beispielsweise beschrieben in DE-A- 38 38 918, DE-A-38 26 608, DE-A- 41 42 241, DE-43 09 074, US-A- 4 877 416 und EP-A-0 452 328, worauf hiermit ausdrücklich Bezug genommen wird. Beispiele für besonders geeignete synthetische Trägeröle sind alkoholgestartete Polyether mit etwa 15 bis 30, wie z.B. etwa 20 bis 25, C3-C6-Alkylenoxideinheiten, wie z.B. ausgewählt unter Propylenoxid-, n- Butylenoxid- und i-Butylenoxid-Einheiten oder Gemischen davon.Examples of suitable synthetic carrier oils are polyolefins, (poly) esters, (poly) alkoxylates, and in particular aliphatic polyethers, aliphatic polyetheramines, alkylphenol-started polyethers and alkylphenol-started polyetheramines. Suitable carrier oil systems are described, for example, in DE-A-38 38 918, DE-A-38 26 608, DE-A-41 42 241, DE-43 09 074, US-A-4 877 416 and EP-A-0 452 328, to which express reference is hereby made. Examples of particularly suitable synthetic carrier oils are alcohol-initiated polyethers with about 15 to 30, for example about 20 to 25, C 3 -C 6 alkylene oxide units, such as, for example, selected from propylene oxide, n-butylene oxide and i-butylene oxide units or mixtures thereof ,
Ein typisches in einer erfindungsgemäßen Zusammensetzung enthaltenes
Additivgemisch umfaßt beispielsweise
Das für die Herstellung der erfindungsgemäßen Additive verwendete Verfestigungsmittel ist vorzugsweise kraftstofflöslich und besitzt gewöhnlich einen Schmelzpunkt oder Erweichungspunkt über den entsprechenden Werten der fertigen Zusammensetzung, wie z.B. im Bereich von etwa 30 bis 100°C, vorzugsweise etwa 30 bis 90°C, insbesondere 40 bis 70°C. Insbesondere ist das Verfestigungsmittel ausgewählt unter kraftstofflöslichen (a) natürlichen Wachsen, wie z.B. petrochemischen Wachsen, insbesondere Paraffinwachs und Vaseline; (b) chemisch modifizierten Wachsen, wie z.B. Hartwachsen, und (c) synthetischen Wachsen, wie z.B. Polyethylenwachs und hochmolekularem Polyisobuten (vgl. z.B. Ullmann's Encyclopädie der Technischen Chemie, Dritte Auflage, Bd. 18, S. 262 ff.). Einige Beispiele geeigneter kraftstofflöslicher Wachse sind auch aus der US-A-4 639 255 bekannt. Auf oben genannte Druckschriften wird hiermit ausdrücklich Bezug genommen. Es sind auch Mischungen obiger Verfestigungsmittel brauchbar.The one used for the production of the additives according to the invention Solidifying agent is preferably fuel-soluble and has usually a melting point or softening point above the corresponding values of the finished composition, e.g. in the range of about 30 to 100 ° C, preferably about 30 to 90 ° C, especially 40 to 70 ° C. In particular, the solidifying agent selected from fuel-soluble (a) natural waxes, such as e.g. petrochemical waxes, in particular paraffin wax and petroleum jelly; (b) chemically modified waxes, e.g. Hard waxes, and (c) synthetic waxes such as e.g. Polyethylene wax and high molecular weight polyisobutene (see e.g. Ullmann's Encyclopedia der Technische Chemie, Third Edition, Vol. 18, pp. 262 ff.). Some Examples of suitable fuel-soluble waxes are also known from US-A-4 639 255. On the above mentioned documents is hereby expressly referred to. They are also mixtures above hardening agent usable.
Erfindungsgemäß geeignete Verfestigungsmittel besitzen eine Kraftstofflöslichkeit von bis zu etwa 10 %, bezogen auf das Gewicht des verwendeten Kraftstoffs.Solidifying agents suitable according to the invention have a Fuel solubility up to about 10% by weight of the fuel used.
Die erfindungsgemäßen Kraftstoffadditivzusammensetzungen sind in einfacher Weise unter Anwendung allgemein bekannter Techniken herstellbar. Vorzugsweise erwärmt man hierzu das Verfestigungsmittel auf dessen Erweichungstemperatur, gibt unter Rühren das Kraftstoffadditiv bzw. die Additivmischung und gegebenenfalls das Trägeröl hinzu und rührt, bis eine homogene Mischung entstanden ist. Anschließend läßt man das flüssige Gemisch erstarren. In gleicher Weise ist die Einarbeitung des Additivs in das Verfestigungsmittel durch Kneten oder durch Schmelzextrusion brauchbar. Die fertige Zusammensetzung wird anschließend durch Extrudieren oder Tablettieren konfektioniert. Außerdem besteht die Möglichkeit, die Zusammensetzungen pillen- oder pulverförmig bereitzustellen. Eine Verkapselung von Pellets oder Pillen ist möglich, jedoch nicht erforderlich.The fuel additive compositions according to the invention are in simply using well known techniques produced. For this purpose, the solidifying agent is preferably heated at its softening temperature, there is stirring Fuel additive or the additive mixture and optionally that Add carrier oil and stir until a homogeneous mixture is formed is. The liquid mixture is then allowed to solidify. In the incorporation of the additive into the hardening agent is the same usable by kneading or by melt extrusion. The finished composition is then extruded or made up into tablets. There is also the possibility to provide the compositions in pill or powder form. Encapsulation of pellets or pills is possible however not required.
Die erfindungsgemäßen Additivzusammensetzungen können dem Kraftstoff ohne besondere technische Vorrichtungen z.B. unmittelbar nach Verladung in den Tankwagen, zugesetzt werden. Die Dosiereinheiten, wie z.B. Pellets, werden in einer Menge zugesetzt, die erforderlich ist, um eine Detergensadditivkonzentration von etwa 20 bis 5000 mg/kg Kraftstoff, wie z.B. etwa 400 - 900 mg/kg Kraftstoff, einzustellen. The additive compositions according to the invention can the fuel without special technical devices e.g. right away after loading into the tanker. The dosing units, such as. Pellets are added in an amount that is required to have a detergent additive concentration of approximately 20 to 5000 mg / kg fuel, e.g. about 400 - 900 mg / kg Fuel.
Die vorliegende Erfindung wird nun anhand der folgenden Beispiele näher erläutert. Werden keine anderen Angaben gemacht, so erfolgt die Dichtebestimmung nach DIN 51757 und die Viskositätsbestimmung nach DIN 51562.The present invention will now be illustrated by the following examples explained in more detail. If no other information is given, it is done the density determination according to DIN 51757 and the viscosity determination according to DIN 51562.
80 g eines Polyisobutenamins (Mn = 1000) werden mit der gleichen Menge eines Hartparaffins (Smp. = 55°C) in einem Kneter (200 ml-Kneter von Werner & Pfleiderer) eine Stunde bei 20 °C geknetet. Nach dieser Verarbeitungsstufe liegt das Detergens in fester Form vor (Schmelzbereich 35-40°C).80 g of a polyisobutenamine (Mn = 1000) are made with the same Amount of a hard paraffin (mp = 55 ° C) in a kneader (200 ml kneader by Werner & Pfleiderer) kneaded at 20 ° C for one hour. After this processing stage, the detergent is in solid form before (melting range 35-40 ° C).
Die Prüfung der erfindungsgemäßen festen Kraftstoffadditive, insbesondere
hinsichtlich ihrer Eignung als Einlaßventilreiniger,
geschieht mit Hilfe von Motorentests, die in Prüfstandsversuchen
mit einem Opel Kadett-Motor gemäß CEC F-04-A-87 durchgeführt werden.
Dabei wurde die gemäß Beispiel 1b) hergestellte feste Additivzusammensetzung
handelsüblichem Ottokraftstoff in einer Menge
zugesetzt, die 600 mg Keropur/kg Kraftstoff entspricht. Die Ergebnisse
sind in folgender Tabelle 1 zusammengefaßt.
Die Versuchsergebnisse zeigen, daß Einlaßventilablagerungen im Vergleich zum nicht-additivierten Grundwert deutlich reduziert wurden.The test results show that inlet valve deposits in the Significantly reduced compared to the non-additive basic value were.
In Anlehnung an die Versuchsvorschrift von Beispiel 1 wurden weitere erfindungsgemäße Additivformulierungen hergestellt und auf Schmelzverhalten, Kraftstofflöslichkeit und Ausbluten getestet. Die ermittelten Versuchsergebnisse sind in Tabelle 2 zusammengefaßt.Based on the test instructions of Example 1, others were Additive formulations according to the invention produced and on Melting behavior, fuel solubility and bleeding tested. The test results obtained are summarized in Table 2.
Aus den ermittelten Versuchsergebnissen ist zu erkennen, daß aus flüssigen Kraftstoffadditiven erfindungsgemäße hochkonzentrierte, stabile Additivformulierungen in einfacher Weise herstellbar sind.
It can be seen from the determined test results that highly concentrated, stable additive formulations according to the invention can be produced in a simple manner from liquid fuel additives.Claims (10)
- A fuel additive composition comprising a homogeneous mixture of a solid compacting agent soluble in fuel and at least one liquid fuel additive, the composition having an additive content of from more than about 40 to about 99% by weight, based on its total weight, being solid or pasty under standard conditions of temperature and pressure, wherein the liquid fuel additive contains at least one detergent additive selected from polyetheramines and polyalkeneamines and functional derivatives thereof, in an amount of more than about 10% by weight, based on the total weight of the composition.
- A composition as claimed in claim 1, which melts in the range from about 25 to 95°C.
- A composition as claimed in claim 1, wherein the detergent additive is selected from polyisobuteneamines, and functional derivatives thereof.
- A composition as claimed in claim 3, wherein the content of detergent additive is from about 20 to about 100% by weight, based on the total weight of the additives contained in the composition.
- A composition as claimed in claim 4, which contains at least one further additive, selected from corrosion inhibitors, demulsifiers and dyes, and, if required, at least one carrier oil.
- A composition as claimed in any of the preceding claims, wherein the compacting agent has a melting point from about 30 to 100°C.
- A composition as claimed in any of the preceding claims, wherein the compacting-agent is selected from fuel-soluble natural waxes, chemically modified waxes and synthetic waxes, in particular paraffin wax, polyethylene wax, high molecular weight polyisobutene and vaseline, and mixtures thereof.
- A composition as claimed in any of the preceding claims, containing an additive mixture comprising abouta) 20-80% by weight of at least one polyisobuteneamine,b) 20-80% by weight of at least one synthetic carrier liquid or one carrier oil based on mineral oil andc) 0-5% by weight of at least one further additive,
- A composition as claimed in any of the preceding claims, containing at least one polyisobuteneamine having an Mn of about 150-5000.
- A composition as claimed in any of the preceding claims, fabricated as solid, preferably uncoated dosage units.
Applications Claiming Priority (3)
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DE19804756A DE19804756A1 (en) | 1998-02-06 | 1998-02-06 | Solid fuel additives |
DE19804756 | 1998-02-06 | ||
PCT/EP1999/000778 WO1999040166A1 (en) | 1998-02-06 | 1999-02-05 | Solid fuel additive |
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EP1051462A1 EP1051462A1 (en) | 2000-11-15 |
EP1051462B1 true EP1051462B1 (en) | 2003-06-18 |
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EP99904864A Expired - Lifetime EP1051462B1 (en) | 1998-02-06 | 1999-02-05 | Solid fuel additive |
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EP (1) | EP1051462B1 (en) |
JP (1) | JP2002502910A (en) |
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AT (1) | ATE243245T1 (en) |
AU (1) | AU754706B2 (en) |
BR (1) | BR9910386A (en) |
CA (1) | CA2319526A1 (en) |
DE (2) | DE19804756A1 (en) |
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EP1753528A1 (en) * | 2004-06-11 | 2007-02-21 | Honeywell International, Inc. | Automotive additive composition |
US20060229215A1 (en) * | 2005-03-29 | 2006-10-12 | Burrington James D | Solid additive compostion and method thereof |
US7919185B2 (en) * | 2006-02-15 | 2011-04-05 | Chaiko David J | Polymer composites, polymer nanocomposites and methods |
US20090000186A1 (en) * | 2007-06-28 | 2009-01-01 | James Kenneth Sanders | Nano-sized metal and metal oxide particles for more complete fuel combustion |
US8545577B2 (en) * | 2009-03-31 | 2013-10-01 | James K. And Mary A. Sanders Family Llc | Catalyst component for aviation and jet fuels |
US8182554B2 (en) * | 2009-03-31 | 2012-05-22 | James Kenneth Sanders | Fuels for cold start conditions |
US8182555B2 (en) | 2009-03-31 | 2012-05-22 | James Kenneth Sanders | Nano-sized zinc oxide particles for fuel |
US8377290B2 (en) * | 2009-03-31 | 2013-02-19 | James K. and Mary A. Sanders Family L.L.C. | Low sulfur fuels |
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US9382490B2 (en) | 2012-12-27 | 2016-07-05 | Shell Oil Company | Compositions |
WO2016050636A1 (en) * | 2014-09-30 | 2016-04-07 | Sicpa Holding Sa | Method for liquid authentication by detection of flavonoid derivatives |
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US4639255A (en) * | 1980-01-15 | 1987-01-27 | Phillips Petroleum Company | Solid form additives and method of forming same |
IT1206306B (en) * | 1980-02-22 | 1989-04-14 | Giudice Maria Assunta | SOLID COMPLEX WITH FUEL ADDITIVE. |
US4515740A (en) * | 1980-10-16 | 1985-05-07 | Phillips Petroleum Company | Method of forming solid form fuel additives |
IT1156129B (en) * | 1982-12-02 | 1987-01-28 | Anic Spa | CHEMICAL COMPOUNDS TO BE USED AS SOLID SUPPORTS OF FUEL ADDITIVES |
FR2557587B1 (en) * | 1984-01-04 | 1986-10-17 | Polaroil Sa | HYDROCARBON ADDITIVE, PROCESS FOR THEIR PREPARATION, USE FOR LOWERING THE LIMIT TEMPERATURE OF FILTERABILITY OF FUELOILS AND GASOILS |
DE4128381A1 (en) * | 1991-08-27 | 1993-03-04 | Mobil Oil Deutschland | CARBURETTOR FUEL ADDITIVE |
GB9318908D0 (en) * | 1993-09-13 | 1993-10-27 | Exxon Research Engineering Co | Additive concentrate for use with gasolines |
DE4431409A1 (en) * | 1994-09-02 | 1996-05-15 | Svendborg Dampskibs As | Pumpable paste for the additive of liquid fuels |
DE4434603A1 (en) * | 1994-09-28 | 1996-04-04 | Basf Ag | Mixture of amines, hydrocarbon polymers and carrier oils suitable as a fuel and lubricant additive |
CA2143140A1 (en) | 1995-02-22 | 1996-08-23 | Roger Paradis | Solid fuel additive and method |
-
1998
- 1998-02-06 DE DE19804756A patent/DE19804756A1/en not_active Withdrawn
-
1999
- 1999-02-05 ES ES99904864T patent/ES2203066T3/en not_active Expired - Lifetime
- 1999-02-05 TR TR2000/02269T patent/TR200002269T2/en unknown
- 1999-02-05 CA CA002319526A patent/CA2319526A1/en not_active Abandoned
- 1999-02-05 EE EEP200000457A patent/EE04197B1/en not_active IP Right Cessation
- 1999-02-05 NZ NZ505969A patent/NZ505969A/en unknown
- 1999-02-05 JP JP2000530583A patent/JP2002502910A/en not_active Withdrawn
- 1999-02-05 BR BR9910386-9A patent/BR9910386A/en not_active IP Right Cessation
- 1999-02-05 AT AT99904864T patent/ATE243245T1/en not_active IP Right Cessation
- 1999-02-05 DE DE59905998T patent/DE59905998D1/en not_active Expired - Lifetime
- 1999-02-05 KR KR1020007008515A patent/KR20010040643A/en not_active Application Discontinuation
- 1999-02-05 AU AU25224/99A patent/AU754706B2/en not_active Ceased
- 1999-02-05 PL PL99342230A patent/PL342230A1/en unknown
- 1999-02-05 WO PCT/EP1999/000778 patent/WO1999040166A1/en not_active Application Discontinuation
- 1999-02-05 EP EP99904864A patent/EP1051462B1/en not_active Expired - Lifetime
- 1999-02-05 HU HU0102107A patent/HUP0102107A3/en unknown
- 1999-02-05 SK SK1111-2000A patent/SK11112000A3/en unknown
- 1999-02-05 US US09/601,018 patent/US6312480B1/en not_active Expired - Fee Related
- 1999-02-05 IL IL13740099A patent/IL137400A/en not_active IP Right Cessation
-
2000
- 2000-08-03 NO NO20003935A patent/NO20003935D0/en not_active Application Discontinuation
Also Published As
Publication number | Publication date |
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EE04197B1 (en) | 2003-12-15 |
ES2203066T3 (en) | 2004-04-01 |
IL137400A0 (en) | 2001-07-24 |
ATE243245T1 (en) | 2003-07-15 |
KR20010040643A (en) | 2001-05-15 |
PL342230A1 (en) | 2001-06-04 |
WO1999040166A1 (en) | 1999-08-12 |
EE200000457A (en) | 2001-12-17 |
HUP0102107A3 (en) | 2002-02-28 |
HUP0102107A2 (en) | 2001-09-28 |
DE19804756A1 (en) | 1999-08-12 |
IL137400A (en) | 2004-02-08 |
SK11112000A3 (en) | 2001-04-09 |
JP2002502910A (en) | 2002-01-29 |
EP1051462A1 (en) | 2000-11-15 |
NO20003935L (en) | 2000-08-03 |
AU754706B2 (en) | 2002-11-21 |
CA2319526A1 (en) | 1999-08-12 |
BR9910386A (en) | 2001-01-16 |
NO20003935D0 (en) | 2000-08-03 |
AU2522499A (en) | 1999-08-23 |
US6312480B1 (en) | 2001-11-06 |
NZ505969A (en) | 2003-01-31 |
TR200002269T2 (en) | 2000-12-21 |
DE59905998D1 (en) | 2003-07-24 |
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