EP1612257A2 - Fuel composition - Google Patents

Abstract

Fuel composition contains an Otto fuel and a small amount of an Otto fuel additive containing a hydrophobic hydrocarbon residue and a specified polar group. Fuel composition comprises an Otto fuel containing a maximum of 42 vol.% aromatics and a sulfur content of a maximum of 150 wt. ppm, and a small amount of an Otto fuel additive with effective detergency and valve seat antiwear properties. The additive comprises a hydrophobic hydrocarbon residue and a specified polar group selected from: (a) mono- and polyamino groups with up to 6 nitrogen atoms, (b) nitro groups optionally in combination with hydroxyl groups, (c) hydroxyl groups in combination with mono- and polyamino groups, (d) carboxyl groups or their alkali metal or alkaline earth metal salts, (e) sulfonic acid groups or their alkali metal or alkaline earth metal salts, (f) polyoxy 2-4C alkylene groups, (g) carboxylic acid ester groups, (h) groups derived from succinic acid anhydride with hydroxy and/or amino and/or amido and/or imido groups, and (i) groups obtained by Mannich conversion of phenolic hydroxyl groups with aldehydes and mono- and polyamines.

Description

The present invention relates to a fuel composition comprising in a larger amount a specific gasoline fuel and in a smaller amount selected gasoline additives, in particular detergent additives having at least one polar grouping selected from the groups (a), (b), (c), (g ), (h) and (i).

Carburettors and intake systems of gasoline engines, as well as injection systems for fuel metering, are increasingly burdened by contaminants caused by dust particles from the air, unburned hydrocarbon residues from the combustion chamber and the crankcase vent gases directed into the gasifier.

These residues shift the air-fuel ratio at idle and in the lower part-load range, so that the mixture leaner, the incomplete combustion and turn the proportions of unburned or partially combusted hydrocarbons in the exhaust gas and gasoline consumption increases.

It is known that in order to avoid these disadvantages, fuel additives are used for keeping valves and carburetors or injection systems of gasoline engines clean (cf., for example: M. Rossbach in Catalysts, Surfactants, Mineral Oil Additives, Ed. J. Falbe, U. Hasserodt, S. 223, G. Thieme Verlag, Stuttgart 1978).

Furthermore emerges in gasoline engines of older design, the problem of valve seat wear when operating with unleaded gasoline. Against this, valve seat wear-inhibiting additives based on alkali metal or alkaline earth metal compounds have been developed.

Modern gasoline engines require for a trouble-free use fuels with a complex property profile, which can be guaranteed only in combination with appropriate gasoline additives. Such gasoline fuels usually consist of a complex mixture of chemical compounds and are characterized by physical quantities. However, the interaction between gasoline fuels and corresponding additives is still in need of improvement in the case of the known fuel compositions with regard to the cleaning and / or retention effect and the valve seat wear-inhibiting effect.

The object of the present invention was therefore to find a more effective gasoline-petrol fuel additive composition.

• (a) Mono- oder Polyaminogruppen mit bis zu 6 Stickstoffatomen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat,
• (b) Nitrogruppen, ggf. in Kombination mit Hydroxylgruppen,
• (c) Hydroxylgruppen in Kombination mit Mono- oder Polyaminogruppen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat,
• (d) Carboxylgruppen oder deren Alkalimetall- oder Erdalkalimetallsalzen,
• (e) Sulfonsäuregruppen oder deren Alkalimetall- oder Erdalkalimetallsalzen,
• (f) Polyoxy-C₂- bis C₄-alkylengruppierungen, die durch Hydroxylgruppen, Mono- oder Polyaminogruppen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat, oder durch Carbamatgruppen terminiert sind,
• (g) Carbonsäureestergruppen,
• (h) aus Bernsteinsäureanhydrid abgeleitete Gruppierungen mit Hydroxy- und/oder Amino- und/oder Amido- und/oder Imidogruppen und
• (i) durch Mannich-Umsetzung von substituierten Phenolen mit Aldehyden und Mono- oder Polyaminen erzeugte Gruppierungen

aufweist.Accordingly, a fuel composition has been found which contains in a larger amount a gasoline having an aromatic content of at most 42 vol .-% and a sulfur content of at most 150 ppm by weight, and in a smaller amount at least one gasoline additive with detergent effect or valve seat wear-inhibiting effect wherein said gasoline additive comprises at least one hydrophobic hydrocarbon radical having a number average molecular weight (M _N ) of from 85 to 20,000 and at least one polar moiety selected from

• (a) mono- or polyamino groups having up to 6 nitrogen atoms, at least one nitrogen atom having basic properties,
• (b) nitro groups, optionally in combination with hydroxyl groups,
• (c) hydroxyl groups in combination with mono- or polyamino groups, where at least one nitrogen atom has basic properties,
• (d) carboxyl groups or their alkali metal or alkaline earth metal salts,
• (e) sulphonic acid groups or their alkali metal or alkaline earth metal salts,
• (f) polyoxy-C ₂ - to C ₄ -alkylene groups terminated by hydroxyl groups, mono- or polyamino groups, wherein at least one nitrogen atom has basic properties, or terminated by carbamate groups,
• (g) carboxylic ester groups,
• (h) succinic anhydride-derived moieties having hydroxy and / or amino and / or amido and / or imido groups and
• (i) moieties generated by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines

having.

The aromatic content of the gasoline is preferably not more than 40% by volume, in particular not more than 38% by volume. Preferred ranges for the aromatic content are from 20 to 42% by volume, in particular from 25 to 40% by volume.

The sulfur content of the gasoline is preferably not more than 100 ppm by weight, in particular not more than 50 ppm by weight. Preferred ranges for the sulfur content are from 0.5 to 150 ppm by weight, in particular from 1 to 100 ppm by weight.

In a preferred embodiment, the gasoline has an olefin content of not more than 21% by volume, preferably not more than 18% by volume, in particular not more than 10% by volume. Preferred ranges for the olefin content are from 6 to 21% by volume, in particular from 7 to 18% by volume.

In a further preferred embodiment, the gasoline has a benzene content of not more than 1.0% by volume, in particular not more than 0.9% by volume. Preferred ranges for the benzene content are from 0.5 to 1.0% by volume, in particular from 0.6 to 0.9% by volume.

In a further preferred embodiment, the gasoline has an oxygen content of at most 2.7 wt .-%, preferably from 0.1 to 2.7 wt .-%, especially from 1.0 to 2.7 wt .-%, in particular from 1.2 to 2.0 wt .-%, on.

Particular preference is given to a gasoline fuel which simultaneously has an aromatics content of not more than 38% by volume, an olefin content of not more than 21% by volume, a sulfur content of not more than 50 ppm by weight, a benzene content of not more than 1.0% by volume and a Having oxygen content of 1.0 to 2.7 wt .-%.

The content of alcohols and ethers in gasoline is usually relatively low. Typical maximum contents for methanol are 3% by volume, for ethanol 5% by volume, for isopropanol 10% by volume, for tert-butanol 7% by volume, for isobutanol 10% by volume and for ethers 5 or more C atoms in the molecule 15 vol .-%.

The summer vapor pressure of the gasoline is usually not more than 70 kPa, in particular 60 kPa (each at 37 ° C).

The research octane number ("RON") of the gasoline is typically 90 to 100. A common range for the corresponding engine octane number ("MOZ") is 80 to 90.

The specified specifications are determined by conventional methods (DIN EN 228).

The hydrophobic hydrocarbon radical in the gasoline additives, which provides sufficient solubility in the fuel, has a number average molecular weight (M _N ) of from 85 to 20,000, especially from 113 to 10,000, especially from 300 to 5,000. As a typical hydrophobic hydrocarbon radical , in particular in connection with the polar groupings (a), (c), (h) and (i), the polypropenyl, polybutenyl and polyisobutenyl radical having in each case M _N = 300 to 5000, in particular 500 to 2500, especially 750 to 2250, into consideration.

As individual gasoline additives with detergent effect or with valve seat wear-inhibiting effect, the following may be mentioned.

Mono- or polyamino (a) -containing additives are preferably polyalkene mono- or Polyalkenpolyamine based on polypropene or highly reactive (ie with predominantly terminal double bonds - usually in the α- and β-position) or conventional (ie with predominantly central double bonds) polybutene or Polyisobutene with M _n = 300 to 5000. Such additives based on highly reactive polyisobutene, which from the polyisobutene, which may contain up to 20 wt .-% of n-butene units, by hydroformylation and reductive amination with ammonia, monoamines or polyamines such Dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine can be prepared, are known in particular from EP-A 244 616. If one proceeds in the preparation of the additives of polybutene or polyisobutene with predominantly intermediate double bonds (usually in the β and γ position), the preparation route by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to carbonyl or Carboxyl compound and subsequent amination under reductive (hydrogenating) conditions. For amination, the same amines as described above can be used for the reductive amination of the hydroformylated highly reactive polyisobutene. Corresponding additives based on polypropene are described in particular in WO-A 94/24231.

Further preferred monoamino groups (a) containing additives are the hydrogenation products of the reaction products of polyisobutenes having an average degree of polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A 97/03946.

Further preferred monoamino groups (a) containing additives are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in DE-A 196 20 262.

Nitro groups, optionally in combination with hydroxyl groups, (b) containing additives are preferably reaction products of polyisobutenes of average degree of polymerization P = 5 to 100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A 96/03367 and WO-A 96/03479. These reaction products typically are mixtures of pure nitropolyisobutanes (e.g., α, β-dinitropolyisobutane) and mixed hydroxynitropolyisobutanes (e.g., α-nitro-β-hydroxy polyisobutane).

Hydroxyl groups in combination with mono- or polyamino groups (c) containing additives are in particular reaction products of polyisobutene epoxides obtainable from preferably predominantly terminal double bonds polyisobutene having M _N = 300 to 5000, with ammonia, mono- or polyamines, as described in particular in EP-A 476 485 are described.

Carboxyl groups or their alkali metal or alkaline earth metal salts (d) containing additives are preferably copolymers of C ₂ -C _4O- olefins with maleic anhydride having a total molecular weight of 500 to 20,000, the carboxyl groups wholly or partly to the alkali metal or alkaline earth metal salts and a remaining Rest of the carboxyl groups are reacted with alcohols or amines. Such additives are known in particular from EP-A 307 815. Such additives are primarily used to prevent valve seat wear and, as described in WO-A 87/01126, can be advantageously used in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.

Sulfonic acid groups or their alkali metal or alkaline earth metal salts (e) containing additives are preferably alkali metal or alkaline earth metal salts of a Sulfobernsteinsäurealkylesters, as described in particular in EP-A 639 632. Such additives are primarily for preventing valve seat wear and can be used to advantage in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.

Polyoxy-C ₂ - to C ₄ -alkylene (f) additives are preferably polyethers or polyetheramines which are obtainable by reaction of C ₂ - to C ₆₀ alkanols, C ₆ - to C ₃₀ alkanediols, mono- or di-C ₂ C ₃₀ -alkylamines, C ₁ -C ₃₀ -alkylcyclohexanols or C ₁ -C ₃₀ -alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines are available. Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416. In the case of polyethers, such products also meet carrier oil properties. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.

Carboxylic ester groups (g) containing additives are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, especially those having a minimum viscosity of 2 mm ² / s at 100 ° C, as described in particular in DE-A 38 38 918 are. As mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable long-chain representatives having, for example, 6 to 24 carbon atoms as ester alcohols or polyols. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and of isotridecanol. Such products also meet carrier oil properties.

Succinic anhydride-derived moieties containing hydroxy and / or amino and / or amido and / or imido (h) additives are preferably corresponding derivatives of polyisobutenyl succinic anhydride. which are obtainable by reaction of conventional or highly reactive polyisobutene with M _N = 300 to 5000 with maleic anhydride by thermal means or via the chlorinated polyisobutene. Of particular interest here are derivatives with aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. Such gasoline additives are described in particular in US Pat. No. 4,849,572.

By Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated groupings (i) containing additives are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine. The polyisobutenyl-substituted Phenols may stem from conventional or highly reactive polyisobutene having an M _N of from 300 to 5000th Such "polyisobutene-Mannich bases" are described in particular in EP-A 831 141.

For a more detailed definition of the individual listed petrol additives, reference is made here expressly to the disclosures of the abovementioned prior art documents.

The fuel composition of the invention may further contain other conventional components and additives. Here are primarily carrier oils without pronounced detergent action to name, for example mineral carrier oils (base oils), especially those of the viscosity class "Solvent Neutral (SN) 500 to 2000", and synthetic carrier oils based on olefin polymers with M _N = 400 to 1800, before all based on polybutene or polyisobutene (hydrogenated or non-hydrogenated), polyalphaolefins or poly-internal alolefins.

Suitable solvents or diluents (when providing additive packages) are aliphatic and aromatic hydrocarbons, e.g. Solvent naphtha, into consideration.

Further customary additives are corrosion inhibitors, for example those based on film-forming ammonium salts of organic carboxylic acids or heterocyclic aromatics in non-ferrous metal corrosion protection, antioxidants or stabilizers, for example based on amines such as p-phenylenediamine, dicyclohexylamine or derivatives thereof or on phenols such as 2,4-diester .-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid, demulsifiers, antistatic agents, metallocenes such as ferrocene or methylcyclopentadienyl manganese tricarbonyl, lubricity additives such as certain fatty acids, alkenyl succinic esters, bis (hydroxyalkyl) fatty amines, hydroxyacetamides or castor oil as well as dyes (markers). Sometimes amines are also added to lower the pH of the fuel.

In particular combinations of the described gasoline fuel with a mixture of gasoline fuel additives with the polar grouping (f) and corrosion inhibitors and / or lubricity improvers based on carboxylic acids or fatty acids, which may be present as monomeric and / or dimeric species, come into consideration for the novel fuel composition. Typical mixtures of this type contain polyisobutene amines in combination with alkanol-initiated polyethers such as tridecanol or isotridecanol butoxylates or propoxylates, polyisobuteneamines in combination with alkanol-started polyetheramines such as tridecanol or isotridecanol butoxylate ammonia reaction products and alkanol-started polyetheramines such as tridecanol or isotridecaol butoxylate ammonia reaction products in combination with alkanol-started polyethers such as tridecanol or isotridecanol butoxylates or propoxylates, in each case together with the cited corrosion inhibitors or lubricity improvers.

The aforementioned gasoline additives with the polar groups (a) to (i) and the other components mentioned are added to the gasoline and unfold their effect there. The components or additives can be added to the gasoline fuel individually or as a previously prepared concentrate ("additive package").

The above gasoline additives with the polar groups (a) to (i) are added to the gasoline usually in an amount of 1 to 5000 ppm by weight, in particular 5 to 3000 ppm by weight, especially 10 to 1000 ppm by weight , The other components and additives mentioned are added, if desired, in customary amounts.

In the fuel composition of the present invention, surprisingly, with significantly less detergent or valve seat wear-inhibiting agent, the same cleaning or valve seat wear-inhibiting effect can be obtained as in conventional fuel compositions of the prior art. Furthermore, when using the same amounts of detergent or valve seat wear-inhibiting agent in the inventive fuel composition over conventional fuel compositions surprisingly results in a significantly better cleansing or retaining or valve seat wear-inhibiting effect.

Furthermore, the fuel composition according to the invention additionally has the advantage that fewer deposits are formed in the combustion chamber of the gasoline engine and that less additive is added via the fuel dilution in the engine oil.

The following examples are intended to illustrate the invention without, however, limiting it.

Examples:

As gasoline fuels those listed in Table 1 were used with the specified specification, wherein OK 1 represents a typical commercial fuel. Table 1 specification OK1 (for comparison) OK2 (according to the invention) Aromatic content [% by volume] 48.4 41.8 Benzene content [Vol. -%] 2.0 1.0 Olefin content [Vol .-%] 22.6 7.8 Oxygen content [% by weight] 0.5 1.7 Sulfur content [ppm by weight] 245 90 Summer vapor pressure (at 37 ° C) [kPa] 78.4 69.3

Preparation of fuel compositions Example 1 (comparative experiment)

700 mg of a polyisobuteneamine prepared by hydroformylation and subsequent reductive amination with ammonia of highly reactive polyisobutene with M _N = 1000 and dilution to equal parts by weight with C ₁₀ -C ₁₄ paraffin (Kerocom® PIBA from BASF Aktiengesellschaft) dissolved in 1 kg of OK1 according to Table 1.

Example 2 (according to the invention)

700 mg of the same polyisobutene amine as in Example 1 were dissolved in 1 kg of OK 2 according to Table 1.

Example 3 (comparative experiment)

600 mg of a commercial Additvzusammensetzung for gasoline fuels, containing in a conventional amount of a detergent with carbamate groups according to grouping (f), were dissolved in 1 kg of OK1 according to Table 1.

Example 4 (according to the invention)

600 mg of the same commercial additive composition for gasoline fuels as in Example 3 were dissolved in 1 kg of OK2 according to Table 1.

Example 5 (comparative experiment)

400 mg of a commercially available additive composition for gasoline fuels, containing a detergent, prepared by chlorination and subsequent amination of polyisobutene with M _N = 950 with predominantly central double bonds, were dissolved in 1 kg of OK1 according to Table 1.

Example 6 (according to the invention)

400 mg of the same commercial additive composition for gasoline fuels as in Example 5 were dissolved in 1 kg of OK2 according to Table 1.

Example 7 (comparative experiment)

750 m of a commercial additive composition for gasoline fuels, containing 50 wt .-% of the same polyisobutene amine as in Example 1 and mineral and synthetic carrier oils and corrosion protection in customary amounts (Keropur® 3222 Fa. BASF Aktiengesellschaft), were in 1 kg OK1 according to Table 1 solved.

Example 8 (according to the invention)

350 mg of the same commercial additive composition for gasoline fuels as in Example 7 were dissolved in 1 kg of OK2 according to Table 1.

Example 9 (comparative experiment)

500 mg of a commercially available additive composition for gasoline containing 60 wt .-% of the same polyisobutene amine as in Example 1 and mineral carrier oil and corrosion protection in customary amounts (Keropur® 3233 Fa. BASF Aktiengesellschaft) were in 1 kg 0K1 according to Table 1 solved.

Example 10 (according to the invention)

500 mg of the same commercial additive composition for gasoline fuels as in Example 9 were dissolved in 1 kg of OK2 according to Table 1.

Example 11 (comparative experiment)

700 mg of a mixture of 50% by weight of the same polyisobutene amine as in Example 1 and 50% by weight of a commercial wear protection additive (Kerocom® 3280 from BASF Aktiengesellschaft) were dissolved in 1 kg 0K1 according to Table 1.

Example 12 (according to the invention)

700 mg of the same additive composition for gasoline fuels as in Example 11 were dissolved in 1 kg of OK 2 according to Table 1.

Application engineering investigations Example 13 (comparative experiment)

Gasoline according to Example 1 was tested for its suitability for intake system cleanliness. This was done with the help of engine tests, which were carried out in test bench tests with a Mercedes-Benz engine according to CEC F-05-A-93. As expected, the inlet valve deposits were significantly reduced compared to the non-additive base value according to Table 2 below.

Example 14 (according to the invention)

Gasoline according to Example 2 was tested for its suitability for intake system cleanliness. This was done with the help of engine tests, which were carried out in test bench trials with a Mercedes-Benz engine CEC F-05-A-93. As expected, the intake valve deposits were significantly reduced compared to the non-additized base value according to Table 2 below. Surprisingly, it has been found that in comparison to Example 13 with the same amount of fuel additive complete purification of the intake valves is achieved.

Example 15 (comparative experiment)

Gasoline according to Example 3 was tested for its suitability for inlet system cleanliness. This was done with the help of engine tests in bench tests with a Mercedes-Benz engine CEC F-05-A-93. As expected, the intake valve deposits were significantly reduced compared to the non-additized base value according to Table 2 below.

Example 16 (according to the invention)

Gasoline according to Example 4 was tested for its suitability for intake system cleanliness. This was done with the help of engine tests, which were carried out in test bench trials with a Mercedes-Benz engine CEC F-05-A-93. As expected, the intake valve deposits were significantly reduced compared to the non-additized base value according to Table 2 below. Surprisingly, it has been found that in comparison with Example 15 with the same amount of fuel additive, a virtually complete purification of the intake valves is achieved.

Example 17 (comparative experiment)

Gasoline according to Example 5 was tested for its suitability for intake system cleanliness. This was done with the help of engine tests, which were carried out in test bench trials with a Mercedes-Benz engine CEC F-05-A-93. As expected, the intake valve deposits were significantly reduced compared to the non-additized base value according to Table 2 below.

Example 18 (according to the invention)

Gasoline according to Example 6 was tested for its suitability for intake system cleanliness. This was done with the help of engine tests, which were carried out in test bench trials with a Mercedes-Benz engine CEC F-05-A-93. As expected, the intake valve deposits were significantly reduced compared to the non-additized base value according to Table 2 below. Surprisingly, it has been found that in comparison with Example 17 with the same amount of fuel additive, a virtually complete keeping clean of the intake valves is achieved.

Example 19 (comparative experiment)

Gasoline according to Example 7 was tested for its suitability for intake system cleanliness. This was done with the help of engine tests, which were carried out in test bench trials with a Mercedes-Benz engine CEC F-05-A-93. As expected, the intake valve deposits were not compared to Additive basic value according to Table 2 below significantly reduced.

Example 20 (according to the invention)

Gasoline according to Example 8 was tested for its suitability for intake system cleanliness. This was done with the help of engine tests, which were carried out in test bench trials with a Mercedes-Benz engine CEC F-05-A-93. As expected, the intake valve deposits were significantly reduced compared to the non-additized base value according to Table 2 below. Surprisingly, it has been found that significantly less fuel additive compared to Example 19 is needed to the same order of magnitude cleanliness of the intake valves.

Example 21 (comparative experiment)

Gasoline according to Example 9 was tested for its suitability for intake system cleanliness. This was done with the help of engine tests, which were carried out in test bench trials with a Mercedes-Benz engine CEC F-05-A-93. As expected, the intake valve deposits were significantly reduced compared to the non-additized base value according to Table 2 below.

Example 22 (according to the invention)

Gasoline according to Example 10 was tested for its suitability for intake system cleanliness. This was done with the help of engine tests, which were carried out in test bench trials with a Mercedes-Benz engine CEC F-05-A-93. As expected, the intake valve deposits were significantly reduced compared to the non-additized base value according to Table 2 below. Surprisingly, it was found that in comparison to Example 21 with the same amount of fuel additive significantly better cleanliness of the intake valves is achieved.

Example 23 (comparative experiment)

Gasoline according to Example 11 was tested for its suitability for intake system cleanliness. This was done with the help of engine tests, which were carried out in test bench trials with a Mercedes-Benz engine CEC F-05-A-93. As expected, the intake valve deposits were not compared to Additive basic value according to Table 2 below significantly reduced.

Example 24 (according to the invention)

Gasoline according to Example 12 was tested for its suitability for intake system cleanliness. This was done with the help of engine tests, which were carried out in test bench trials with a Mercedes-Benz engine CEC F-05-A-93. As expected, the intake valve deposits were significantly reduced compared to the non-additized base value according to Table 2 below. Surprisingly, it was found that in comparison to Example 23 with the same amount of fuel additive significantly better cleanliness of the intake valves is achieved. Table 2 additive Dosage [mg / kg] Inlet valve deposits [mg / valve] Valve 1 Valve 2 Valve 3 Valve 4 on average Example 13 700 40 157 7 87 73 (547) Example 14 700 0 0 0 0 0 (239) Example 15 600 19 60 86 34 50 (274) Example 16 600 0 1 0 2 1 (239) Example 17 400 0 75 17 182 69 (402) Example 18 400 0 2 2 0 1 (239) Example 19 750 31 120 111 30 73 (592) Example 20 350 46 68 38 67 55 (239) Example 21 500 181 95 26 68 93 (475) Example 22 500 27 33 14 77 38 (239) Example 23 700 123 12 98 55 72 (558) Example 24 700 82 12 23 22 35 (239) (in brackets the basic value of the non-added fuel)

Claims (14)

A fuel composition comprising in a larger amount a gasoline having an aromatic content of at most 42% by volume and a sulfur content of at most 150 ppm by weight, and in a smaller amount at least one gasoline additive with detergent action optionally in combination with a gasoline additive with valve seat wear-inhibiting effect, wherein these gasoline additives have at least one hydrophobic hydrocarbon radical having a number average molecular weight (M _N ) of from 85 to 20,000, the detergent additive at least one polar grouping selected from (a) mono- or polyamino groups having up to 6 nitrogen atoms, at least one nitrogen atom having basic properties, (b) nitro groups, optionally in combination with hydroxyl groups, (c) hydroxyl groups in combination with mono- or polyamino groups, where at least one nitrogen atom has basic properties, (g) carboxylic ester groups, (h) succinic anhydride-derived moieties having hydroxy and / or amino and / or amido and / or imido groups and (i) moieties generated by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines
and the valve seat wear inhibiting additive comprises at least one polar moiety selected from (d) carboxyl groups or their alkali metal or alkaline earth metal salts, and (e) sulphonic acid groups or their alkali metal or alkaline earth metal salts,
having. A fuel composition according to claim 1, containing as petrol additive with polar groups (a) Polyalkene mono- or Polyalkenpolyamine based on polypropene, polybutene or polyisobutene with M _N = 300 to 5000. A fuel composition according to claim 1, comprising as petrol additive with polar groups (b) reaction products of polyisobutenes of average degree of polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen. A fuel composition according to claim 1, comprising as petrol additive with polar groups (c) reaction products of polyisobutene epoxides obtainable from predominantly terminal double bonds polyisobutene having M _N = 300 to 5000, with ammonia, mono- or polyamines. A fuel composition according to claim 1, containing as gasoline additive with polar groups (d) copolymers of C ₂ -C ₄₀ -olefins with maleic anhydride having a total molecular weight of 500 to 20 000, their carboxyl groups wholly or partly to the alkali metal or alkaline earth metal salts and a remaining Rest of the carboxyl groups are reacted with alcohols or amines. A fuel composition according to claim 1 containing as a gasoline additive with polar groups (e) alkali metal or alkaline earth metal salts of a sulfosuccinic acid alkyl ester. A fuel composition according to claim 1, containing as gasoline additive with polar groups (g) esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols. A fuel composition according to claim 1, containing as petrol additive with polar groups (h) derivatives of polyisobutenyl succinic anhydride, obtainable by reaction of conventional or highly reactive polyisobutene with M _n = 300 to 5000 with maleic anhydride by thermal means or via the chlorinated polyisobutene. A fuel composition according to claim 1, containing as petrol additive with polar groups (i) reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines. A fuel composition according to claims 1 to 9, containing a gasoline having an olefin content of at most 21% by volume. A fuel composition according to claims 1 to 10, containing a gasoline having a benzene content of at most 1.0% by volume. A fuel composition according to claims 1 to 11, containing a gasoline having an oxygen content of at most 2.7% by weight. A fuel composition according to claims 1 to 12, containing the gasoline fuel additives having the polar groups (a) to (e), (h) and (i) in an amount of 1 to 5,000 ppm by weight. Use of a polar compound having at least one polar group (a), (b), (c), (g), (h) or (i) as defined above as a detergent additive for gasoline fuels having an aromatic content of not more than 42% by volume and a sulfur content of at most 150 ppm by weight and optionally with an olefin content of not more than 21% by volume, a maximum benzene content of 1.0% by volume and an oxygen content of not more than 2.7% by weight.