DE10251312A1 - Additive mixture useful for improving antifoam performance of fuels comprises a silicone antifoam and a lubricity improver selected from neutralized fatty acids and long-chain carboxylic acids and their esters - Google Patents

Abstract

Additive mixture comprises a silicone antifoam and a lubricity improver selected from (partially) neutralized fatty acids and long-chain carboxylic acids and their esters. Independent claims are included for: (1) fuel composition comprising a hydrocarbon fuel, an additive mixture as above and optionally another additive; (2) additive concentrate comprising an additive mixture as above, a diluent and optionally another additive.

Description

The present invention relates to an additive mixture containing at least one polysiloxane antifoam and at least one partially or fully neutralized fatty acid.

An important part of fuel additive packages are anti-foaming agents that affect the natural foaming behavior of Fuels, especially when filling, for example during the Refueling at the petrol pump, dampen should. Frequently Antifoams used are polysiloxanes, in particular polysiloxane alkoxylates.

So describes the US 6,093,222 Antifoam compositions for diesel fuels comprising different polysiloxanes. The polysiloxanes are substituted with long-chain polyether groups, organic polyols, hydrocarbon residues and / or phenol residues. Due to the high costs for the production of the polysiloxane antifoam, however, these represent a not insignificant cost factor in the amount in which they are required to achieve an antifoam performance.

WO 95/04117 describes an additive composition which is an anti-foam agent and a nitrogen-containing ash free burning dispersant contains. The nitrogenous one Ash-free burning dispersants are said to provide long-term storage stability for the anti-foam agent increase. However, the dispersant does not lower the damping effect Foaming of a fuel required amount of anti-foaming agent.

Object of the present invention was to provide an additive mixture that has an improved anti-foam effect compared to prior art anti-foam agents.

• i) als Komponente A wenigstens ein Polysiloxan-Antischaummittel und
• ii) als Komponente B wenigstens eine teilweise oder vollständig neutralisierte Fettsäure, eine langkettige Carbonsäure, einen Ester einer solchen Carbonsäure oder eine wenigstens eine dieser Verbindungen umfassende Mischung.

The object was achieved by an additive mixture containing

• i) as component A at least one polysiloxane antifoam and
• ii) as component B at least one partially or completely neutralized fatty acid, a long-chain carboxylic acid, an ester of such a carboxylic acid or a mixture comprising at least one of these compounds.

Suitable polysiloxane anti-foaming agents are all common antifoam agents known to those skilled in the art Polysiloxane. Such anti-foam agents are, for example in the ATC Doc. 52 "fuel Additives and the Environment ".

worin die Reste R jeweils unabhängig voneinander für einen Rest R¹, R², R³, R⁴ oder R⁵ stehen, worin
R¹ für einen aromatischen oder gesättigten aliphatischen Kohlenwasserstoffrest steht,
R² für ein organisches Polyol steht,
R³ für einen Polyetherrest steht,
R⁴ für einen Phenolrest steht,
R⁵ für einen Rest R² steht, wobei jedoch die Hydroxygruppen ganz oder teilweise zu Diestern, Diethern, Acetalen und/oder Ketalen umgesetzt sind, w = 2 + y + 2 z,y und z jeweils unabhängig für eine Zahl von 0 bis 2 stehen, wobei die Summe aus y und z einer Zahl von 0 bis 2 entspricht und w + x + y + z = 20 bis 60. A preferred antifoam agent is a polysiloxane of the general formula I

wherein the radicals R each independently represent a radical R ¹ , R ² , R ³ , R ⁴ or R ⁵ , wherein
R ^{1 represents} an aromatic or saturated aliphatic hydrocarbon radical,
R ^{2 represents} an organic polyol,
R ^{3 represents} a polyether radical,
R ^{4 represents} a phenol radical,
R ^{5 represents} a radical R ² , but the hydroxyl groups have been wholly or partly converted to diesters, diethers, acetals and / or ketals, w = 2 + y + 2 z, y and z each independently represent a number from 0 to 2, the sum of y and z corresponding to a number from 0 to 2 and w + x + y + z = 20 to 60.

In R ¹ , the aromatic or saturated aliphatic hydrocarbon radical is preferably C ₁ -C ₂₄ alkyl, in particular for methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl or stearyl; C ₃ -C ₂₄ cycloalkyl, in particular for cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl or cyclodecyl; C ₄ -C ₂₄ alkylcycloalkyl, especially for methylcyclohexyl, dimethylcyclohexyl or ethylcyclohexyl; C ₆ -C ₁₀ aryl, especially for phenyl; or C ₇ -C ₁₈ arylalkyl, in particular for methylphenyl, dimethylphenyl or phenylethyl. R ¹ particularly preferably represents C ₁ -C ₂₄ -alkyl, in particular methyl.

In R ² , the organic polyol preferably represents a saturated or unsaturated, branched or unbranched aliphatic hydrocarbon radical with at least two hydroxyl groups, which is optionally interrupted by one or more O atoms. The hydrocarbon residue is preferably saturated. The radical R ² preferably has a molecular weight of 100 to 700, particularly preferably 130 to 650 and in particular approximately 400.

The R ² radicals are introduced into the polysiloxane skeleton, for example, by reacting an unsaturated polyol with a polysiloxane which contains hydrogen atoms bonded to silicon. Examples of suitable polyols for the production of saturated radicals R ² are trimethylolpropane monoallyl ether, ethoxylated pentaerythritol allyl ether, propoxylated pentaerythritol allyl ether, triisopropanolamine allyl ether, ethoxylated allyl sorbitol and 1,3-allyloxypropanediol. An example of a polyol suitable for producing an unsaturated radical R ² is 2-butyne-1,4-diol.

R ³ preferably represents a polyether radical which contains at least 50% by weight, particularly preferably at least 75% by weight and in particular 100% by weight, of copolymerized ethylene oxide units. R ³ preferably has a molecular weight of up to 1,500, particularly preferably from 100 to 350.

R ⁴ preferably represents a phenol radical which is substituted by mono- or polyunsaturated alkene and / or alkyne radicals. Suitable examples are eugenol, vinylphenol, vinylguaiacol and 4-allylphenol.

In preferred polysiloxanes of the formula I, the quotient of the number of R ¹ groups and the number of R ² groups (R ¹ / R ² ) is 3 to 19.

In addition, in preferred polysiloxanes I the quotient of the sum of the number of R ³ , R ⁴ and R ⁵ groups and the number of R ² groups is [(R ³ + R ⁴ + R ⁵ ) / R ² ] 0 up to 2.

In a preferred embodiment contains Component A several different polysiloxanes I.

worin die Reste R* jeweils unabhängig voneinander für einen Rest R¹ oder R³ stehen, wobei R¹ und R³ wie bei Polysiloxan I definiert sind; a = 2 + c + 2 d;c + d jeweils unabhängig für eine Zahl von 0 bis 2 stehen und a + b + c + d = 15 bis 50,und/oder mit einem Polysiloxan der allgemeinen Formel I.2

worin R, w, x, y und z wie bei Polysiloxan I definiert sind, wobei R2 für ein gesättigtes Polyol steht und wobei der Quotient aus der Anzahl an R³-Gruppen und der Anzahl an R²-Gruppen (R³/R²) und der Quotient aus der Anzahl an R⁴-Gruppen und aus der Anzahl der R²-Gruppen (R⁴/R²) größer 0 ist.In a particularly preferred embodiment, a polysiloxane I as defined above is used with a polysiloxane of the general formula I.1

wherein the radicals R * each independently represent a radical R ¹ or R ³ , where R ¹ and R ^{3 are} as defined for polysiloxane I; a = 2 + c + 2 d; c + d each independently represent a number from 0 to 2 and a + b + c + d = 15 to 50, and / or with a polysiloxane of the general formula I.2

wherein R, w, x, y and z are as defined for polysiloxane I, where R2 is a saturated polyol and where the quotient of the number of R ³ groups and the number of R ² groups (R ³ / R ² ) and the quotient of the number of R ⁴ groups and the number of R ² groups (R ⁴ / R ² ) is greater than 0.

Such polysiloxane combinations are, for example, from the US 6,093,222 known, to which reference is hereby made in full.

In preferred polysiloxanes I.1, the quotient of the number of R ¹ groups and the number of R ³ groups (R ¹ / R ³ ) is 3 to 19.

In preferred polysiloxanes I.2, the quotient (R ³ / R ² ) is 0.25 to 5.

Component B is preferably one partially or completely neutralized with amines Fatty acid.

worin
R für C₇-C₂₃-Alkyl oder ein- oder mehrfach ungesättigtes C₇-C₂₃-Alkenyl, die gegebenenfalls durch eine oder mehrere Hydroxygruppen substituiert sind, steht;
A für C₂-C₈-Alkylen steht;
Z für C₁-C₈-Alkylen, C₃-C₈-Cycloalkylen oder C₆-C₁₂-Arylen oder C₇-C₂₀-Arylalkylen steht;
m für eine Zahl von 0 bis 5 steht; und
x¹, x², x³ und x⁴ jeweils unabhängig für eine Zahl von 0 bis 24 stehen, wobei wenigstens ein x nicht für 0 steht,
und gegebenenfalls wenigstens eine weitere Fettsäure RCOOH, worin R wie vorstehend definiert ist.Component B particularly preferably comprises at least one fatty acid salt of the formula II

wherein
R represents C ₇ -C ₂₃ alkyl or mono- or polyunsaturated C ₇ -C ₂₃ alkenyl, which are optionally substituted by one or more hydroxyl groups;
A represents C ₂ -C ₈ alkylene;
Z represents C ₁ -C ₈ alkylene, C ₃ -C ₈ cycloalkylene or C ₆ -C ₁₂ arylene or C ₇ -C ₂₀ arylalkylene;
m represents a number from 0 to 5; and
x ¹ , x ² , x ³ and x ⁴ each independently represent a number from 0 to 24, at least one x not representing 0,
and optionally at least one further fatty acid RCOOH, where R is as defined above.

Such fatty acid salts II are for example described in WO 01/38463, to the full extent Reference is made.

The longer-chain radical R occurring in the carboxylate anion RCOO or in the fatty acid RCOOH denotes, for example, branched or preferably linear C ₇ to C ₂₃ , preferably C ₁₁ to C ₂₁ , especially C ₁₅ to C ₁₉ alkyl groups, which can additionally carry hydroxyl groups. Examples of underlying carboxylic acids are octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid, iso-tridecanoic acid, tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid) and e. The acids mentioned can be of natural or synthetic origin. Mixtures of the acids mentioned can also form the basis of the carboxylate anions.

However, the longer-chain radical R occurring in the carboxylate anion RCOO or in the fatty acid RCOOH preferably denotes mono- or polyunsaturated C ₇ to C ₂₃ radicals, in particular mono- or polyunsaturated C ₁₁ to C ₂₁ , especially C ₁₅ to C ₁₉ alkenyl groups, which can additionally carry hydroxyl groups. These unsaturated residues are preferably linear. Monounsaturated fatty acids are, for example, palmitoleic, oleic and erucic acid. In the case of polyunsaturated alkenyl groups, these preferably contain two or three double bonds. Examples of underlying carboxylic acids are elaidic acid, ricinoleic acid, linoleic acid and linolenic acid. Particularly good results are achieved with oleic acid. Mixtures of such unsaturated carboxylic acids with one another and with the above-mentioned saturated carboxylic acids can also form the basis of the carboxylate anions. Such mixtures are, for example, tall oil, tall oil fatty acid and rapeseed oil fatty acid. The unsaturated carboxylic acids and the mixtures mentioned are generally of natural origin.

The alkylene group A in compounds Formula II is preferably derived from corresponding alkylene oxides such as ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide and cis or trans-2,3-butylene oxide. However, it can also be used for 1,3-propylene, 1,4-butylene, 1,6-hexylene or 1,8-octylene. A can also be a mixture represent from different of the groupings mentioned. Especially be preferred for A ethylene, 1,2-propylene or 1,2-butylene groups.

The variable Z means in particular C ₁ - to C ₄ -alkylene groupings such as methylene, 1,2-propylene, 1,2-butylene, 1,3-butylene or 2,3-butylene, C ₅ - to C ₆ -cycloalkylene groupings such as 1 , 3-Cyclo pentylidene or 1,3- or 1,4-cyclohexylidene or C ₆ - to C ₈ -arylene or arylalkylene groups such as 1,3- or 1,4-phenylene, 2-methyl-l, 4-phenylene or 1,3- or 1,4-bismethylene phenylene.

However, the variable Z preferably means polymethylene groupings of the formula - (CH ₂ ) n- with n = 2 to 8, in particular with n = 2 to 6, that is to say in particular 1,2-ethylene, 1,3-propylene, 1,4-butylene , 1,5-pentylene and 1,6-hexylene, but also 1,7-heptylene and 1,8-octylene.

If the variable m stands for 0, as a rule, depending on the sum (Σ) of all variables x ¹ , x ² and x ³ , mixtures of mono-, di- and / or trialkanolamines or pure trialkanolamines are the cationic fatty acid salts used according to the invention Component. Examples of such alkanolamines are Monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine and the associated mixtures. In this group, the oleic acid salt of triethanolamine is [(x ¹ + x ² + x ³ ) = 3; A = ethylene] of particular interest.

However, the variable m is preferably for the Number 1 or 2. For m = 1 lie completely and / or partially alkoxylated alkylenediamines such as 1,2-ethylenediamine, 1,3-propylenediamine or 1,4-butylenediamine. For m = 2 are usually complete and / or partially alkoxylated dialkylenetriamines such as di- (1,2-ethylene) -triamine, Di- (1,3-propylene) -triamine or di- (1,4-butylene) -triamine. In this group are the bis oleic acid salts of N, N, N ', N'-tetrakis (2'-hydroxyethyl) -1,2-ethylenediamine (xΣ = 4) and N, N, N ', N'-tetrakis (2'-hydroxypropyl) -1,2-ethylenediamine (Σx = 4) as well as the tris oleic acid salts of reacted with 4 to 5 moles of ethylene oxide or 1,2-propylene oxide Di- (1,2-ethylene) -triamine of particular interest.

However, it is also possible to have higher homologues of the alkylenediamines and dialkylenetriamines mentioned, for example Triethylene tetramine (m = 3), tetraethylene pentamine (m = 4) or pentaethylene hexamine (m = 5) as an amine component for those used according to the invention fatty acid salts taken as a basis.

In a preferred embodiment, the number x, ie the sum of x ¹ , x ² , x ³ and x ⁴ (Σx), of the alkylene oxide units (OA) introduced per amine molecule is the number of NH bonds in the underlying amine dependent and can correspond to the number of NH bonds (Σx = m + 3). However, more or fewer OA units can also be installed. In the case of superstoichiometric incorporation, triple alkoxylation per NH bond [300% of (m + 3)] is a preferred upper limit with regard to the properties of the resulting fatty acid salts. In the case of sub-stoichiometric incorporation, a statistical average 50% alkoxylation [50% of (m + 3)) is a corresponding preferred lower limit; here mostly mixtures of species with different degrees of alkoxylation are present.

In a particularly preferred embodiment has the sum (Σ) of all variables x a value from 75% to 125 of (m + 3).

The fatty acid salts of the general formula II can usually easily by alkoxylation of the underlying amines according to the usual Methods and subsequent neutralization with the fatty acids of the formula Make RCOOH.

When using C ₂ to C ₄ alkylene oxides, the alkoxylation is expediently used for introducing the first alkylene oxide unit into the NH bond in the presence of small amounts of water (usually 0.5 to 5% by weight, based on the amount on amine used) without catalyst at temperatures from 80 to 140 ° C and for the introduction of further alkylene oxide units with the exclusion of water in the presence of basic catalysts such as alkali metal hydroxides, for. As sodium or potassium hydroxide, carried out at temperatures from 100 to 150 ° C.

The neutralization takes place in the Usually by heating the alkoxylated amine thus obtained with the appropriate stoichiometric or slightly sub-stoichiometric Quantity (i.e. 90 to 100%, especially 95 to 100% of theory) of fatty acid at temperatures from 30 to 100 ° C, in particular 40 to 80 ° C, for one Duration of 15 minutes to 10 hours, especially 30 minutes up to 5 hours. The neutralization reaction should be carried out that no Carbonsäureester Shares arise in the product. In many cases, both the alkoxylated Amine as well as the fatty acid as liquids are used, which is the implementation of the corresponding fatty acid salt designed particularly simple. The order of joining of alkoxylated amine and fatty acid is not critical, i.e. one can submit both the alkoxylated amine and the fatty acid admit as well the fatty acid submit and add the alkoxylated amine.

In principle, however, it is also possible that alkoxylated amine and the fatty acid as individual components, additive concentrates or mineral oil products add and let the salt formation take place there.

As useful components B for the additive mixtures according to the invention are also long chain carboxylic acids, Esters thereof or mixtures of substances usable, which at least one of these components included.

Long chain carboxylic acids in For the purposes of the present invention, saturated and unsaturated mono- or polycarboxylic acids with 4 to 50 carbon atoms, preferably 8 to 24 carbon atoms. Are the carboxylic acids in dimerized form, the number of carbon is corresponding doubled. Polycarboxylic acids according to the invention include preferably 2 to 4 carboxyl groups. Unsaturated carboxylic acids according to the invention include one or more, preferably one, two or three, in particular non-cumulative, double bonds.

Preferred preferred examples of saturated or unsaturated long-chain monocarboxylic acids are the saturated or unsaturated C ₈ -C ₂₄ -monocarboxylic acids given in connection with the above definition for the compound of the formula II.

Examples of suitable polycarboxylic acids are saturated or unsaturated dicarboxylic acids to name, such as the dimerized variant of oleic acid.

The carboxylic acids used can be of natural or synthetic origin. They can be used as a pure substance or as a mixture of substances which contain one or more of these carboxylic acids, optionally together with other substances. Tall oil fatty acids can be used as non-limiting examples be called creations. These typically include a mixture of saturated, monounsaturated and polyunsaturated C ₁₈ carboxylic acids and varying proportions of a saponifiable resin. Suitable products are described, for example, in WO-A-98/04656, to which reference is hereby expressly made.

The long-chain useful according to the invention Carbonsäureester are in more conventional Way by reacting the above long-chain carboxylic acids with monohydric or polyhydric alcohols available.

The alcohols contained in the esters according to the invention are preferably derived from straight-chain or branched C ₁ to C ₂₀ alkanes and carry 1 to 8, such as 1 to 4, hydroxyl groups. Cyclic alcohols containing 6 to 12 carbon atoms are also useful.

Preferred noncyclic one or polyhydric alcohols include 2 to 12, such as 2 to 5, Carbon atoms, are straight-chain or branched and have 1 to 4 hydroxyl groups. As non-limiting examples are too name monohydric alcohols, such as methanol, ethanol, n- and iso-propanol and polyhydric alcohols such as glycol, glycerin, trimethylolpropane, Pentaerytritol, sorbitol, mannitol, inositol, glucose and fructose. The hydrocarbyl radical of the alcohols which can be used according to the invention can optionally one or more heteroatoms, such as oxygen, sulfur, Nitrogen or phosphorus contained in the carbon chain.

When using polyhydric alcohols can these in the esters according to the invention in part or in full esterified form. Mono and diester esters are preferred.

As non-limiting examples for usable Esters are methyl esters of the above saturated or unsaturated Monocarboxylic acids to name, as well as the corresponding esterification products of naturally occurring fatty acids or fatty acid mixtures to call. In particular can monoesters or diesters such as glycerol monooleate are mentioned, Glycerol dioleate and glycerol monostearate.

In the additive mixture according to the invention, component A and component B in a weight ratio of preferably 1: 200 to 1:10, particularly preferably from 1: 100 to 1:10 and in particular from 1:50 to 1:10.

Another subject of the present The invention is the use of the additive mixture according to the invention for additivation of fuel compositions, in particular to improve the Anti-foam performance of a fuel composition.

Suitable fuels are petrol and middle distillates, such as diesel fuels, heating oil or kerosene, diesel fuels are preferred.

It deals with diesel fuels for example, oil refinements, the usual have a boiling range of 100 to 400 ° C. These are mostly distillates with a 95% point up to 360 ° C or even above out. You can but also so-called "Ultra Low Sulfur Diesel "or" City Diesel " by a 95% point of, for example, a maximum of 345 ° C and one Sulfur content of up to 0.005% by weight or through a 95% point of, for example, 285 ° C and a sulfur content of at most 0.001% by weight. In addition to through Refining available Diesel fuels are those produced by coal gasification or gas liquefaction ("gas to liquid (GTL) fuels) available are suitable. Mixtures of the aforementioned ge are also suitable Diesel fuels with renewable fuels, such as biodiesel.

The additive mixture according to the invention is particularly preferred for the additivation of diesel fuels with low sulfur content, d. H. with a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, in particular less than 0.005% by weight and especially less than 0.001 wt% sulfur.

It is also the subject of the present Invention a fuel composition containing a major amount of a hydrocarbon fuel and an effective amount of the additive mixture according to the invention and optionally at least one additional additive. Regarding more suitable Fuels are the same as said before.

The additive mixture according to the invention is in the Fuel preferably in an amount of 1 to 1000 ppm by weight, particularly preferably from 20 to 300 ppm by weight and in particular from 50 to 150 ppm by weight, based on the total amount of additiv Fuel, before.

Another subject of the present The invention is an additive concentrate containing the additive mixture according to the invention, at least one diluent and optionally at least one further additive.

Suitable diluents are, for example, fractions obtained in petroleum processing, such as kerosene, naphtha or brightstock. Aromatic and aliphatic hydrocarbons and alkoxyalkanols are also suitable. In the case of middle distillates, particularly preferred diluents for diesel fuels, naphtha, kerosene, diesel fuels, aromatic hydrocarbons, such as heavy solvent naphtha, Solvesso ^® or Shellsol ^® and mixtures of these solvents and diluents.

The additive mixture according to the invention is present in the concentrate in a concentration of 0.1 to 80 wt .-%, especially preferably from 0.1 to 60% by weight and in particular from 15 to 50% by weight, based on the total weight of the concentrate.

Suitable additives in the fuel according to the invention or concentrate in addition to the additive mixtures according to the invention could be, especially for Diesel fuels include detergents, corrosion inhibitors, Dehazer, demulsifiers, other usual Anti-foaming agents ("Antifoam"), antioxidants, Metal deactivators, multifunctional stabilizers, cetane number improvers, Combustion improvers, dyes, markers, solubilizers, antistatic agents, lubricity, the cold properties improving additives such as flow improvers ("MDFI"), paraffin dispersants ("WASA") and the combination of the last two additives mentioned ("WAFI"). Suitable additives are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry (1990) Vol. A 16, pp. 719 ff., Whereupon expressly Reference is made.

To the usual anti-foaming agents belong the polysiloxanes, acylated polyamines mentioned above and their Mixtures with different N-acyl compounds, such as polyalkenylsuccinic acid amides.

The synergistically effective combination of components A and B in the additive mixture according to the invention leads to a significant improvement in the anti-foam performance of additives added with it Fuels compared to additives of the prior art.

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

• – Dieselkraftstoff gemäß DIN EN 590 mit einem Schwefelgehalt von 48 ppm: Diesel I
• – Dieselkraftstoff gemäß DIN EN 590 mit einem Schwefelgehalt von 15 ppm (ULSD): Diesel II
• – Dieselkraftstoff gemäß DIN EN 590 mit einem Schwefelgehalt von 4 ppm (MK1): Diesel III
• – Blend aus 5% Biodiesel in 95% Diesel I: Blend I
• – Blend aus 8% Ethanol in 91% Diesel I (1% Stabilisatorpaket): Blend II
• – Gas to Liquid-Kraftstoff: GTL
• – Blend aus 20% GTL in 80% Diesel I: Blend III

The tests described below were determined with the following fuels:

• - Diesel fuel according to DIN EN 590 with a sulfur content of 48 ppm: Diesel I
• - Diesel fuel according to DIN EN 590 with a sulfur content of 15 ppm (ULSD): Diesel II
• - Diesel fuel according to DIN EN 590 with a sulfur content of 4 ppm (MK1): Diesel III
• - Blend from 5% biodiesel in 95% Diesel I: Blend I
• - Blend from 8% ethanol in 91% Diesel I (1% stabilizer package): Blend II
• - Gas to liquid fuel: GTL
• - Blend from 20% GTL in 80% Diesel I: Blend III

The following products were used as lubricity improvers:
Lubricity I: Product manufactured according to Example 1
Lubricity II: tall oil fatty acid mixture available under the trade name Kerocom LA 99 from BASF AG
Lubricity III: fatty acid ester mixture with glycein monooleate as the main component.

An anti-foaming agent became a standard Polysiloxane derivative called anti-foam is used.

Example 1: Synthesis of a oiliness (Lubricity I)

58.4 g (0.2 mol) of N, N, N ', N'-tetrakis (2'-hydroxypropyl) -1,2-ethylenediamine (obtained from 1,2-ethylenediamine and 4 mol of propylene oxide in the presence of 3% by weight of water based on the amount of the amine used) were heated to 60-80 ° C and 110.4 (0.4 mol) of oleic acid were added with stirring within two hours. The pH did not drop below 7. Finally, it was two hours touched. The product obtained had one N titer of 2.39 mmol / g.

Example 2: Attempts to Determination of anti-foam performance

Determining antifoam performance was according to the BNPe test carried out according to standard NF M 07-075.

The additive fuels or Blends were made by adding the above Combinations of 5 mg / kg each Antifoam and 120 mg / kg lubricity improver Lubricity 7 to III received. In the table below they are determined values for the foam volume and foam breakdown time in dry fuels listed.

The lubricity improver alone had no positive impact the foam effect.

The combinations of antifoam according to the invention and Lubricity I, II and III showed in comparison to the effect from antifoam alone a significantly improved antifoam performance, with the same lubricity-improving Effect. Particularly excellent results are achieved when using lubricity type Lubricity I.

Claims (13)

Additive mixture containing i) as a component A at least one polysiloxane antifoam and ii) as a component B at least one partially or completely neutralized fatty acid, one long chain carboxylic acid, an ester of such carboxylic acid or a mixture comprising at least one of these compounds. Additive mixture according to claim 1, wherein component A contains at least one polysiloxane of the general formula I,

wherein the radicals R each independently represent a radical R ¹ , R ² , R ³ , R ⁴ or R ⁵ , wherein R ^{1 represents} an aromatic or saturated aliphatic hydrocarbon radical, R ^{2 represents} an organic polyol, R ^{3 represents} one Is a polyether radical, R ^{4 is} a phenol radical, R ^{5 is} a radical R ² , but all or part of the hydroxyl groups have been converted to diesters, diethers, acetals and / or ketals, w = 2 + y + 2 z, y and z each independently represent a number from 0 to 2, the sum of y and z corresponding to a number from 0 to 2 and w + x + y + z = 20 to 60. Additive mixture according to claim 2, wherein in component AR ¹ for C ₁ -C ₂₄ alkyl, C ₃ -C ₂₄ cycloalkyl, C ₄ -C ₂₄ alkylcycloalkyl, C ₆ -C ₁₀ aryl or C ₇ -C ₁₈ - Arylalkyl, R ^{2 represents} a saturated or unsaturated, branched or unbranched aliphatic hydrocarbon radical which is substituted by at least two hydroxyl groups and is optionally interrupted by one or more O atoms, R ^{3 represents} a polyether radical which has at least 50% by weight .-% copolymerized ethylene oxide units and has a molecular weight of up to 1,500, the quotient of the number of R ¹ groups and the number of R ² groups (R ¹ / R ² ) is 3 to 19 and the quotient from the sum of the number of R ³ , R ⁴ and R ⁵ groups and the number of R ² groups [(R ³ + R ⁴ + R ⁵ ) / R ² ] is 0 to 2. Additive mixture according to one of the preceding claims, wherein Component B at least one neutralized with at least one amine fatty acid includes. Additive mixture according to claim 4, wherein component B at least one fatty acid salt of formula II

wherein R is C ₇ -C ₂₃ alkyl or mono- or polyunsaturated C ₇ -C ₂₃ alkenyl, which are optionally substituted by one or more hydroxyl groups; A represents C ₂ -C ₈ alkylene; Z represents C ₁ -C ₈ alkylene, C ₃ -C ₈ cycloalkylene or C ₆ -C ₁₂ arylene or C ₇ -C ₂₀ arylalkylene; m represents a number from 0 to 5; and x ¹ , x ² , x ³ and X ⁴ each independently represent a number from 0 to 24, and optionally comprises at least one further fatty acid RCOOH, in which R is as defined above. Additive mixture according to one of claims 1 to 3, wherein component B with at least one saturated or unsaturated mono- or polycarboxylic acid 4 to 50 carbon atoms or at least one ester thereof carboxylic acid with a one or polyhydric alcohol with 1 to 20 carbon atoms and 1 to 8 Includes hydroxyl groups. Additive mixture according to one of the preceding claims, wherein Component A and component B in a weight ratio of 1: 200 to 1:10. Use of the additive mixture, as in a of the preceding claims is defined for the additive of fuel compositions. Use according to claim 8 to improve the Anti-foaming performance a fuel composition. Fuel composition containing a major amount of a hydrocarbon fuel and an effective amount of one Additive mixture as defined in any one of claims 1 to 7, and optionally at least one additional additive. A fuel composition according to claim 10 or Use according to claim 8 or 9, wherein it is the fuel about diesel fuel, heating oil or kerosene. Fuel composition or use according to claim 11, the diesel fuel being one that available through refining, coal gasification or gas liquefaction, or a mixture deals with renewable fuels. Additive concentrate containing an additive mixture as defined in one of the claims 1 to 7 and at least one diluent and optionally at least one further additive.