EP1051462B1 - Solid fuel additive - Google Patents

Abstract

Solid or pasty fuel additive compositions comprise a homogeneous mixture of a solid compacting agent soluble in fuel and at least one liquid fuel additive, the compositions having an additive content of from more than about 40 to 99% by weight, based on their total weight.

Description

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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 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.

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.

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.

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.

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.

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.

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.

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 ,

a) etwa 20 bis 80 Gew.-%, vorzugsweise etwa 60 bis 80 Gew.-%, wenigstens eines Polyisobutenamins oder eines funktionellen Derivates davon,

b) etwa 20 bis 80 Gew.-%, vorzugsweise etwa 20 bis 40 Gew.-%, wenigstens einer synthetischen Trägerflüssigkeit, wie z.B. ein alkylphenolgestarteter Polyether, z.B. aufgebaut aus etwa 15 bis 30, wie z.B. etwa 20 bis 25, C₃-C₆-Alkylenoxideinheiten, wie z.B. Propylenoxid-, n- und i-Butylenoxid-Einheiten oder Gemische davon, und/oder wenigstens eines Trägeröls auf Mineralölbasis und

c) 0 bis etwa 5 Gew.-%, vorzugsweise etwa 1 bis 4 Gew.-%, wenigstens eines weiteren von a) verschiedenen Additivs des oben genannten Typs;

wobei die Gewichtsangaben auf das Gesamtgewicht der dem Verfestigungsmittel zugesetzten Komponenten a), b) und c) bezogen sind. Geeignete Additivgemische besitzen beispielsweise einen Siedepunkt im Bereich von über 120°C, wie z.B. von über 150 oder 180 °C, eine Dichte (15°C, DIN 51757) von etwa 0,8 bis 0,9 g/ cm³ und eine Viskosität (20°C, DIN 51562) von etwa 50 bis 200 mm²/s, wie z.B. etwa 70 bis 160mm²/s. Derartige Additivgemische sind als Handelsprodukte, wie z.B. unter der Handelsbezeichnung Keropur® von der Firma BASF AG, Ludwigshafen, erhältlich. Konkrete Beispiele für geeignete Handelsprodukte sind Keropur® 3222, 3131 und ES 3401.A typical additive mixture contained in a composition according to the invention comprises, for example

a) about 20 to 80% by weight, preferably about 60 to 80% by weight, of at least one polyisobutenamine or a functional derivative thereof,

b) about 20 to 80% by weight, preferably about 20 to 40% by weight, of at least one synthetic carrier liquid, such as, for example, an alkylphenol-started polyether, for example composed of about 15 to 30, such as, for example, about 20 to 25, C ₃ - C ₆ -alkylene oxide units, such as propylene oxide, n- and i-butylene oxide units or mixtures thereof, and / or at least one mineral oil-based carrier oil and

c) 0 to about 5% by weight, preferably about 1 to 4% by weight, of at least one further additive of the type mentioned above which is different from a);

wherein the weight data are based on the total weight of components a), b) and c) added to the solidifying agent. Suitable additive mixtures have, for example, a boiling point in the range above 120 ° C., such as above 150 or 180 ° C., a density (15 ° C., DIN 51757) of approximately 0.8 to 0.9 g / cm ³ and a viscosity (20 ° C, DIN 51562) from about 50 to 200 mm ² / s, such as about 70 to 160mm ² / s. Such additive mixtures are available as commercial products, such as, for example, under the trade name Keropur® from BASF AG, Ludwigshafen. Specific examples of suitable commercial products are Keropur® 3222, 3131 and ES 3401.

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.

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. 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.

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.

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.

Example 1: Preparation of a solid additive composition

a) 100 g of a conventional additive composition for petrol (Keropur ®3222) (bp:> 165 ° C, density (15 ° C) = 0.865 g / ml; viscosity (20 ° C) = 120 mm ² / s; 25 wt. -% polyisobutenamine, Mn = 1000, as detergent) is mixed with stirring with half the amount of a melted commercial paraffin wax (mp. = 55 ° C). After the mixture has been homogenized, the mixture is allowed to cool to room temperature, the paraffin becoming solid again and the additive enclosed. The solid fuel additive thus produced is soluble in conventional fuels.

b) Example 1a) was repeated, except that additive and Use hard paraffin in a 1: 1 ratio. You get also a solid, fuel-soluble fuel additive composition.

Example 2: Preparation of a solid additive composition

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).

Example 3: Determination of the cleaning action of a solid additive formulation

The testing of the solid fuel additives according to the invention, in particular with regard to their suitability as an inlet valve cleaner, is carried out with the aid of engine tests which are carried out in test bench tests with an Opel Kadett engine in accordance with CEC F-04-A-87. The solid additive composition prepared according to Example 1b) was added in an amount corresponding to 600 mg Keropur / kg fuel. The results are summarized in Table 1 below. additive Dosage [mg / kg] Intake valve deposits [mg / valve] 1 2 3 4 basic value - 510 277 250 467 solid petrol additive according to Example 1b) 1200 6 7 9 45

The test results show that inlet valve deposits in the Significantly reduced compared to the non-additive basic value were.

Examples 4 to 8

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.

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)

1. 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.
2. A composition as claimed in claim 1, which melts in the range from about 25 to 95°C.
3. A composition as claimed in claim 1, wherein the detergent additive is selected from polyisobuteneamines, and functional derivatives thereof.
4. 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.
5. 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.
6. A composition as claimed in any of the preceding claims, wherein the compacting agent has a melting point from about 30 to 100°C.
7. 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.
8. A composition as claimed in any of the preceding claims, containing an additive mixture comprising about

   a) 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 and

   c) 0-5% by weight of at least one further additive,

   the stated contents each being based on the total weight of the components a), b) and c) added to the compacting agent.
9. A composition as claimed in any of the preceding claims, containing at least one polyisobuteneamine having an Mn of about 150-5000.
10. A composition as claimed in any of the preceding claims, fabricated as solid, preferably uncoated dosage units.