EA045457B1 - COMPOSITIONS AND METHODS FOR DISPERSING PARAFFINS IN LOW-SULFUR FUEL OILS - Google Patents

Description

Mineral oils and mineral oil distillates such as gas oil, diesel fuel or heating oil usually contain some dissolved n-paraffins. At low temperatures, solid waxes precipitate when the cloud point (CP) is reached. Upon further cooling, the plate-shaped n-paraffin crystals form a house of cards structure, causing the mineral oil or mineral oil distillate to lose fluidity even though it is still predominantly liquid. As a result of the precipitation of n-paraffins in the range from the cloud point to the pour point (PP), the fluidity, in particular of middle distillate fuel, is significantly deteriorated; paraffins clog filters and lead to uneven supply or complete stop of fuel supply to combustion units. Similar violations occur in the case of light heating oil.

Due to the decrease in global oil reserves and discussions about the environmental consequences of consumption of fossil and mineral fuels, there is increasing interest in the additional use of alternative energy sources based on renewable raw materials (biofuels). In addition to the traditional fatty acid esters as first generation biodiesel, various synthetic fuel production methods have been developed over the past few years. They can be used to produce virtually aromatic-free paraffinic hydrocarbons, especially from waste fats and residue fractions from the food industry, fishing industry and slaughterhouses, as well as from fractions of other vegetable oils not intended for the food industry. Such synthetic fuels include, for example, hydrotreated vegetable oils (HVOs), which can be obtained by hydrodeoxygenation of vegetable oils, optionally followed by isomerization of the crude products. The next example is synthetic fuel produced by the Fischer-Tropsch method. The components of these second-generation biofuels are very similar to conventional fossil-based middle distillates and can therefore replace fossil-based middle distillates in virtually any blending ratio regardless of the quality of the particular fuel.

As with fossil fuel oils, when these synthetic fuels cool, they produce wax crystals that can also clog car filters and metering devices. Due to the high proportion of paraffinic components, the synthetic fuels mentioned above, as well as their mixtures with middle distillates of mineral or fossil origin, generally have less favorable low-temperature characteristics than middle distillates of only fossil origin. In the context of the present invention, middle distillates of mineral or fossil origin, second generation biofuels and mixtures thereof are collectively referred to as fuel oil.

In addition to the usual methods of eliminating problems associated with waxes (thermal, mechanical or using solvents), which only refer to the removal of precipitates that have already formed, a number of chemical additives (wax inhibitors) have been developed which, by physically interacting with the precipitated wax crystals, change their shape, size and adhesive properties. In particular, polymers having paraffin-like structural elements, such as ethylene vinyl ester and/or acrylic ester copolymers and especially ethylene vinyl acetate copolymers, have been found to be useful wax inhibitors or low temperature improvers/middle distillate flow improvers (MDFI) of this type. polymers (EVA) and their combinations with comb-shaped polymers containing long alkyl side chains. Such additives serve as additional crystal nuclei and partially crystallize together with paraffins. In this case, small individual crystals are formed, which, even with a further decrease in temperature, pass through filters in cars and heating systems, or at least form a layer on the filter that is permeable to the liquid part of the fuel oil, thus ensuring uninterrupted operation. Additive fuel oils can still be pumped and processed at temperatures that are often more than 20°C lower than unadditive fuels. The effectiveness of wax inhibitors is usually expressed, in accordance with the European standard EN 116, indirectly by determining the cold filter plug point (CFPP) for fuels with additives.

One of the disadvantages of these additives for improving fluidity at low temperatures is that the paraffin crystals modified with their help, due to their higher density compared to the liquid part of the fuel oil, settle to an even greater extent at the bottom of the tank during fuel storage. This results in the formation of a homogeneous phase with a low wax content in the upper part of the reservoir and a two-phase wax-rich layer in the lower part. Since, both in the case of automotive fuel tanks and storage tanks or service tanks, fuel is usually withdrawn slightly above the base of the tank, there is a risk that high concentrations of solid waxes will lead to clogging of filters and metering devices. This risk increases as storage temperatures drop below the wax deposition temperature because the amount of wax precipitated increases with decreasing temperature.

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These problems can be reduced through the additional use of wax dispersants or wax anti-sedimentation additives (WASA). Various paraffin dispersants of both monomeric and polymeric structures are known.

Examples of known monomeric wax dispersants include the reaction products of alkenyl spirobislactones with amines described in EP-A-0413279.

In addition, EP-A-0061894 discloses oil-soluble nitrogen compounds, for example the reaction products of phthalic anhydride with amines, used in mixtures with ethylene-vinyl acetate copolymers.

In addition, EP-A-0597278 describes reaction products of aminoalkylenecarboxylic acids with primary or secondary amines.

EP-A-0436151 discloses middle distillates of mineral oils with improved low-temperature properties, which contain the reaction product of copolymers based on maleic anhydride and α,β-unsaturated compounds with dialkanolamines.

EP-A-0283293 describes copolymers based on aliphatic olefins and maleic anhydride, where the copolymer must contain both ester and amide groups, each of which contains an alkyl group having at least 10 carbon atoms. In addition, this application discloses copolymers obtained by reacting a secondary amine with a polymer containing anhydride groups to form an amide and ammonium salts in equal proportions from the anhydride groups.

EP-A-0606055 describes terpolymers based on α,β-unsaturated dicarboxylic acid anhydrides, α,β-unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols, and their use as wax inhibitors for waxy petroleum products. In addition, EP-A-0688796 describes copolymers based on α,β-unsaturated olefins containing at least three carbon atoms and α,β-unsaturated dicarboxylic acid anhydrides, where the dicarboxylic acid anhydride units are converted to imide, amide or ammonium units by polymer-analogous reaction with polyetheramines or alkanolamines.

WO 2008/113757 describes a mixture containing:

(a) from 5 to 95% by weight of at least one organic compound capable of improving the low temperature flow characteristics of the fuel, and (b) from 5 to 95% by weight of at least one amine of general formula (I)

R1R2HN (I), in which R ¹ represents a hydrocarbyl radical which contains from 6 to 40 carbon atoms and may also contain primary and/or secondary and/or tertiary amine functional groups, and R ² represents a hydrocarbyl radical containing from 6 to 40 carbon atoms, where R ¹ and R ² together can form a 5-7 membered ring, where the total sum of components (a) and (b) is 100 wt.%.

DE-2557793 describes a middle distillate fuel composition having improved low-temperature flow properties, comprising:

(1) from about 0.005 to 0.10 wt.% (based on the weight of the entire fuel composition) dialkyl-substituted secondary amine, in which each alkyl group is linear and contains from 8 to 30 carbon atoms, (2) from about 0.003 to 0 .20 wt.% pour point depressant; and (3) about 0.025 to 0.50 wt.% amorphous petrolatum having a melting point of about 25 to 60° C. and a number average molecular weight of about 600 to 1100, which practically does not contain normal paraffins, in which the depressant additive consists of:

(A) an oil-soluble ethylene copolymer, the number average molecular weight of which is from about 1000 to 50,000, which is a copolymer containing from 3 to 40 mole parts of ethylene and 1 mole part of a comonomer, namely a C ₃ -C ₁₆ -α-monoolefin or unsaturated ester having the following formula:

R.H

I I s=s I I

R ₃ in which R1 represents hydrogen or a methyl radical,

R2 represents -OOCR4 or -COOR4, where R4 represents hydrogen or an alkyl group containing from 1 to 16 carbon atoms, R3 represents hydrogen or the radical -COOR4; or (B) a chlorine-substituted polyethylene having a number average molecular weight of from 1000 to 20,000 and a chlorine content of from 4 to 35% by weight; or (C) a hydrocarbyl-substituted succinamic acid derivative having the formula

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R--CH—COX ²

CH ₂ -COX ² in which R is a linear aliphatic hydrocarbyl radical that contains 0 or 1 olefinic unsaturation and from 14 to 40 carbon atoms, and is linked to the succinyl group at a secondary carbon atom, one of the two X ² and X ³ radicals represents -NYY ¹ where Y ¹ denotes aliphatic hydrocarbyl groups containing from 14 to 40 carbon atoms, and the other of the radicals X ² and X ³ denotes a radical of the formula

-OH(NHY ² Y ³ )n, in which n is 0 or 1, Y ² and Y ³ represent hydrogen or aliphatic or oxyaliphatic hydrocarbons containing from 1 to 30 carbon atoms, or, together with the nitrogen atom to which they are bonded , form a 5-7-membered heterocycle, or (D) a hydrogenated copolymer of butadiene and styrene.

US 8,287,608 discloses a composition containing a mixture of at least one amine containing at least one alicyclic group and at least one monocarboxylic acid or fatty acid containing from eight to 22 carbon atoms. The composition addresses the technical problem that commercially available fatty acids and mixtures of fatty acids tend to freeze or form crystals at temperatures common in winter conditions. Freezing or crystal formation makes additives difficult to handle, especially when added to fuel. Therefore, there is a need to improve lubricating additives to reduce the cloud point of the lubricating additives themselves without negatively affecting other desirable properties.

As demands for environmental friendliness of fuels and their combustion products continually increase, the sulfur content of middle distillate has been gradually reduced since the 1990s and is now limited to a maximum of 10 ppm in most regions. However, the refinery processes used to desulphurize fossil fuel oils reduce not only the concentration of undesirable sulfur compounds, but also the content of other components, such as polycyclic aromatic compounds and other polar compounds, which are necessary for certain engine parts, such as the injection pump. Therefore, a so-called lubricity additive must be added to low-sulfur fuels to ensure sufficient lubricity. Typically it contains fatty acids, their esters, for example partial esters of polyols, and/or their amides, for example alkanolamides. Since second-generation biofuels as a result of synthesis contain virtually no polar components capable of exerting a lubricating effect, the need for lubricating additives is especially high in the case of fuels containing or consisting of second-generation biofuels.

However, it is often the case that the addition of a lubricating additive to fuel oil reduces the effectiveness of wax dispersants containing ammonium polycarboxylic acid as the active ingredient. This is manifested, for example, in that the low temperature properties achieved by using such wax dispersants are degraded when a lubricant is added, or the low temperature properties that can be obtained with the wax dispersant are not achieved. In particular, this antagonism is observed in cases where it is necessary to ensure the dispersion of paraffins under very critical conditions, for example, when storing fuel oil at a temperature not just 5 K, as usual, but 10 K or more, for example, 15 K below the temperature cloudiness of the fuel oil and/or for extended periods of time ranging from days to weeks. By increasing the dosage of wax dispersant, this antagonistic effect can usually only be partially overcome, if at all.

It is therefore an object of the present invention to provide a wax dispersant, an improvement over the prior art, the effectiveness of which is not impaired by the addition of a lubricant selected from fatty acids, partial esters of fatty acids with polyols, and/or fatty acid amides with alkanolamides , into fuel oil containing a paraffin dispersant.

A further object of the invention is to improve the response characteristics of wax dispersants in such a low sulfur fuel oil containing a lubricant selected from fatty acids, partial fatty acid esters of polyols and/or fatty acid amides and alkanolamides. By improved response characteristics, as used herein, we mean that the improvement in low temperature properties achieved at a given dosage of wax dispersant is comparable or even superior to the absence or presence of a lubricant additive in the fuel oil. By comparable efficiency we mean that the properties at low temperatures in their totality are as close as possible to the values obtained without the addition of a lubricating additive.

Furthermore, the present invention provides a fuel oil which, by virtue of the addition of a wax dispersant and a lubricant selected from fatty acids, partial fatty acid esters of polyols and/or fatty acid amides and alkanolamides, has the same or at least at least comparable properties at low temperatures compared to the same fuel oil after adding only a wax dispersant.

It has now been surprisingly discovered that the effectiveness of a wax dispersant containing not only an oil-soluble amido-ammonium salt of a polycarboxylic acid but also an oil-soluble amine is not reduced by adding a lubricating additive to a fuel oil containing the wax dispersant and the oil-soluble amine. Likewise, the response characteristics of a wax dispersant containing an ammonium ammonium salt of a polycarboxylic acid, which were degraded by the presence of a lubricating additive in the fuel oil, can be improved by adding an oil-soluble amine to the wax dispersant. In addition, the antagonistic effect exerted by the lubricant on the performance or response characteristics of the ammonium polycarboxylic acid ammonium salt-containing wax dispersant can be suppressed by adding an oil-soluble amine to the fuel oil.

The present invention firstly provides a fuel oil having a sulfur content of less than 50 ppm, containing:

i. at least one oil-soluble amido-ammonium salt (A) of a polycarboxylic acid with mono and/or dialkylamine, ii. 5-100 wt.% oil-soluble amine (B) based on ammonium ammonium salt (A), and iii. a lubricant (C) selected from fatty acids, partial esters of fatty acids and polyols, and fatty acid amides and alkanolamides, wherein the fuel oil consists of mineral fuel oil, synthetic fuel, or a mixture thereof.

Secondly, the invention provides the use of a low temperature additive containing:

i. at least one oil-soluble amido-ammonium salt (A) of a polycarboxylic acid with mono and/or dialkylamine, and ii. 5-100% by weight of an oil-soluble amine (B) based on ammonium ammonium salt (A), to improve the low temperature properties of a fuel oil having a sulfur content of less than 50 ppm containing a lubricant additive (C) selected from fatty acids , partial esters of fatty acids and polyols, and fatty acid amides and alkanolamides, wherein the fuel oil consists of mineral fuel oil, synthetic fuel or a mixture thereof.

Third, the invention provides the use of an oil-soluble amine (B), taken in an amount of 5-100 wt.% based on the ammonium salt (A), to improve the low-temperature properties of fuel oil having a sulfur content of less than 50 ppm containing:

i. at least one oil-soluble amido-ammonium salt (A) of a polycarboxylic acid with mono and/or dialkylamine; and iii. a lubricant (C) selected from fatty acids, partial esters of fatty acids and polyols, and fatty acid amides and alkanolamides, wherein the fuel oil consists of mineral fuel oil, synthetic fuel or a mixture thereof.

Fourth, the invention provides a method for improving the response characteristics of a fuel oil containing a lubricating additive (C) and having a sulfur content of less than 50 ppm to the addition of ammonium ammonium salt (A), characterized in that 5 to 100% by weight of an oil-soluble amine (B) based on ammonium ammonium salt (A), wherein the lubricant (C) is selected from fatty acids, partial esters of fatty acids and polyols, and fatty acid amides and alkanolamides, and wherein Fuel oil consists of mineral fuel oil, synthetic fuel or a mixture of both.

Fifth, the invention provides a method for improving the low temperature properties of a fuel oil having a sulfur content of less than 50 ppm containing a lubricant additive (C) selected from fatty acids, partial fatty acid esters of polyols and fatty acid amides of alkanolamides by adding a low-temperature additive to the fuel oil containing:

i. at least one oil-soluble amido-ammonium salt (A) of a polycarboxylic acid with mono and/or dialkylamine; and ii. 5-100 wt.% oil-soluble amine (B) based on the ammonium salt (A), and wherein the fuel oil consists of mineral fuel oil, synthetic fuel or a mixture thereof.

The combination of (A) and (B) is also referred to as the additive of the invention hereinafter. The oil-soluble amido-ammonium salt (A) of a polycarboxylic acid with mono and/or dialkylamine is also called amido-ammonium salt (A) in the context of the present invention.

In accordance with the invention, by improving the response characteristics of low-temperature additives is meant that at least one low-temperature property of the fuel oil that has been or can be imparted by the presence of ammonium ammonium salt (A) and is deteriorated by the addition of a lubricating additive (C), is improved or restored by the addition of an oil-soluble amine (B). In particular, the addition of an oil-soluble amine (B) achieves the low temperature properties that were or can be imparted by the presence of the ammonium ammonium salt (A) in the absence of a lubricant (C). Low temperature properties as used herein refer, alone or in combination, to cloud point, cold filter plug point (CFPP), wax dispersibility, and pour point (PP) of fuel oils.

The response characteristics of low temperature additives containing amido-ammonium salts (A) are particularly degraded in fuel oils containing more than 10 ppm of lubricant additive (C), especially more than 50 ppm and especially more than 100 ppm of lubricant additive (WITH).

Amido-ammonium salt (A).

Oil-soluble amido-ammonium salt (A) is the reaction product of a polycarboxylic acid with mono- and/or dialkylamine. Preferably, the polycarboxylic acid is selected from monomeric dicarboxylic acids, monomeric polycarboxylic acids and copolymerized dicarboxylic acids. Preferred polycarboxylic acids contain 2 or more, for example 3, 4 or more carboxyl groups; in the case of copolymerized dicarboxylic acids, the polymer molecule contains the number of carboxyl groups corresponding to twice the degree of polymerization. The polycarboxylic acid may also include heteroatoms such as oxygen, sulfur and/or nitrogen. Preferred polycarboxylic acids containing carboxyl groups contain from 3 to 20 carbon atoms, and preferably from 4 to 10 carbon atoms, for example from 3 to 10 or from 4 to 20 carbon atoms. The carbon skeleton containing carboxyl groups can be aliphatic or aromatic. It can be interrupted by heteroatoms such as N, O and S.

Examples of monomeric dicarboxylic acids include maleic acid, fumaric acid, crotonic acid, itaconic acid, succinic acid, C ₁ -C 4 ₀ -alkenyl succinic acid, adipic acid, glutaric acid, pimelic acid, sebacic acid and malonic acid, as well as phthalic acid, isophthalic acid acid and terephthalic acid. Examples of monomeric polycarboxylic acids include trimellitic acid, pyromellitic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, methylglycine diacetic acid, glutamic acid-N,N-diacetic acid, and mixtures thereof. Particularly preferred monomeric polycarboxylic acids are maleic acid, phthalic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid.

Examples of copolymerized dicarboxylic acids include copolymers of ethylenically unsaturated dicarboxylic acids, such as maleic acid or fumaric acid and/or itaconic acid. Particular preference is given to copolymers of maleic anhydride. Preferred are comonomers that impart oil solubility to the copolymer. The term oil-soluble means that the copolymer, after interaction with mono- and/or dialkylamine, dissolves without residue in the fuel oil, into which the additive will be added in doses of practical importance. Particularly suitable comonomers are, for example, olefins, alkyl esters of acrylic acid and methacrylic acid, alkyl vinyl esters and alkyl vinyl ethers. Preferred olefins are α-olefins and styrene. Particular preference is given to comonomers containing alkyl radicals containing from 2 to 40, preferably containing from 6 to 24, in particular containing from 8 to 20 and in particular containing from 10 to 16 carbon atoms, for example comonomers containing from 2 to 24, containing from 2 to 20, containing from 2 to 16, containing from 6 to 40, containing from 6 to 20, containing from 6 to 16, containing from 8 to 40, containing from 8 to 24, containing from 8 to 20, containing from 10 to 40, containing from 10 to 24 or containing from 10 to 20 carbon atoms in the alkyl radical. Alkyl radicals can be linear or branched, preferably they are linear. In the case of olefins, the number of carbon atoms is calculated based on the alkyl radical associated with the double bond. Preferred α-olefins are dodecene, tetradecene, hexadecene, octadecene, and mixtures thereof. The copolymers can be random copolymers, block copolymers, or other alternating polymers. Taking into account the polymerization properties of maleic anhydride, preference is given to its alternating co- and terpolymers. Examples of suitable co- and terpolymers include poly(maleic anhydride-a-co-olefin), poly(maleic anhydride-co-styrene), poly(maleic anhydride-co-a-alkyl acrylate) and poly(maleic anhydride-co-olefin- co-a-alkyl acrylate). The weight average molecular weight of the polymer copolymers is preferably from 400 to 20,000, more preferably from 500 to 10,000, for example from 1000 to 5000 g/mol (as determined by GPC in THF relative to polystyrene standards).

Ammonium ammonium salts (A) can be prepared by reacting a mono- and/or dialkylamine with a polycarboxylic acid. It has been repeatedly noted that it is advantageous to start from a reactive polycarboxylic acid derivative, for example an ester, anhydride or an acid halide. In this case, particular preference is given to acid anhydrides.

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Mono- and/or dialkylamines preferred for the preparation of amido-ammonium salts (A) from polycarboxylic acids or reactive derivatives thereof are compounds of the formula NR ¹ R2R ³ in which R ¹ , R ² and R ³ may be the same or different, and at least one of these groups is C ₈ -C ₃₆ -alkyl, C ₆ -C ₃₆ -cycloalkyl, C ₈ -C ₃₆ -alkenyl, especially C ₁₂ -C ₂₄ -alkyl, C ₁₂ -C ₂₄ -alkenyl or cyclohexyl , and the remaining groups are either hydrogen, C ₁ -C ₃₆ -alkyl, C ₂ -C ₃₆ alkenyl, cyclohexyl, or a group of the formula (A-O) _x -E or -(CH ₂ ) _n -NYZ, in which A represents ethyl or propyl group, x represents a number from 1 to 50, E = H, C ₁ -C ₃₀ -alkyl, C ₅ -C ₁₂ -cycloalkyl or C ₆ -C ₃₀ -aryl, and n = 2, 3 or 4, a Y and Z independently represent H, C ₁ -C ₃₀ -alkyl or -(A-O) _x . Polyamines of the formula are also suitable as mono- and/or dialkylamines

-[N-(CH2)n]m-NR ¹ R ² in which m represents a number from 1 to 20, an, R ¹ and R ² are defined above. Alkyl and alkylene radicals can be linear or branched and contain up to two double bonds. Preferably they are linear and substantially saturated, which means that their iodine number is less than 75 g I2/100 g, preferably less than 60 g I2/100 g, and especially from 1 to 10 g I2/100 g. Preference is given to secondary amines in which two of the groups R ¹ , R ² and R ³ represent C ₈ -C ₃₆ -alkyl, C ₆ -C ₃₆ -cycloalkyl, C ₈ -C ₃₆ -alkenyl, in particular C ₁₂ -C ₂₄ -alkyl , C ₁₂ -C ₂₄ -alkenyl or cyclohexyl. Suitable monoalkylamines are, for example, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosylamine, behenylamine; preferred dialkylamines are, for example, didecylamine, didodecylamine, ditetradecylamine, dihexadecylamine, dioctadecylamine, diecosylamine, dibehenylamine and mixtures thereof. In particular, mono- and dialkylamines contain fragment chains based on natural raw materials, such as cocoamine, tallowamine, hydrogenated tallowamine, dicocoamine, ditallowamine and di(hydrogenated tallowamine). Particularly preferred amine derivatives are amine salts, imides and/or amides, for example ammonium amido salts of secondary fatty amines, in particular dicocoamine, dithallowamine and distearylamine.

Particularly preferred ammonium salts (A) have been found to be oil-soluble polar nitrogen compounds which are prepared by the reaction of aliphatic amines, preferably single-chain aliphatic amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their anhydrides (see US 4211534). Equally suitable as oil-soluble polar nitrogen compounds are amides and ammonium salts of aminoalkylene polycarboxylic acids, such as nitrilotriacetic acid or ethylenediaminetetraacetic acid, with secondary amines (see EP 0398101). Other oil-soluble polar nitrogen compounds are copolymers of maleic anhydride with α,β-unsaturated compounds, which can optionally be reacted with primary monoalkylamines and/or aliphatic alcohols (see EP-A-0154177, EP-0777712), reaction products of alkenyl spirobislactones with amines (see EP-A-0413279 B1) and in accordance with EP-A-0606055 A2, reaction products of terpolymers based on anhydrides of α, β-unsaturated dicarboxylic acids, α, β-unsaturated compounds and polyoxyalkylene ethers with lower unsaturated alcohols.

To improve low temperature properties, ammonium ammonium salt (A) is added to the low sulfur fuel oil to be treated, preferably in an amount of 1 to 100 ppm, more preferably in an amount of 5 to 75 ppm, and especially in an amount of 10 to 50 ppm, for example in an amount of 1 to 75 ppm, in an amount of 1 to 50 ppm, in an amount of 5 to 100 ppm, in an amount of 5 up to 50 ppm, in an amount from 10 to 100 ppm, or in an amount from 10 to 75 ppm (w/w in each case).

Oil-soluble amine (B).

According to the invention, the preferred oil-soluble amines (B) are amines whose boiling point is higher than the initial boiling point of the low sulfur fuel oil to be added to the additive. By initial boiling point we mean the boiling point at normal pressure. The boiling characteristics of middle distillates can be determined, for example, by boiling analysis in accordance with DIN EN ISO 3405. Particular preference is given to amines with a boiling point of at least 110°C, in particular amines with a boiling point of at least at least 150°C, for example at least 175°C. This prevents loss of amine from the treated low sulfur fuel oil during transportation and/or storage.

Preferred oil-soluble amines (B) have formula (1) in which R ⁴ represents an alkyl radical containing from 8 to 22 carbon atoms, or a group of formula -(CH2)n-[NR ⁷ -(CH2)n]m-NH2,

R ⁵ represents hydrogen or an alkyl radical containing from 1 to 22 carbon atoms, or

- 6 045457 group of formula -(CH ₂ ) _n -[NR ⁷ -(CH ₂ ) _n ] _m -NH2,

R ⁶ represents hydrogen or an alkyl radical containing from 1 to 22 carbon atoms,

R ⁷ represents H or an alkyl radical containing from 1 to 22 carbon atoms, n is 2 or 3, and m is 0 or an integer from 1 to 10.

In a first preferred embodiment, the oil-soluble amine (B) is a fatty amine (Bi) containing at least one alkyl radical containing at least 8 carbon atoms, preferably containing from 12 to 22 carbon atoms and in particular containing from 14 up to 20 carbon atoms, for example containing from 8 to 22 carbon atoms, containing from 12 to 20 carbon atoms, or 14 to 22 carbon atoms. Preferred fatty amines (Bi) have formula (1), in which

R ⁴ represents an alkyl radical containing from 8 to 22 carbon atoms,

R ⁵ represents hydrogen or an alkyl radical containing from 1 to 22 carbon atoms, and

R ⁶ represents hydrogen or an alkyl radical containing from 1 to 22 carbon atoms.

Suitable fatty amines (Bi) include primary, secondary and/or tertiary amines and mixtures thereof.

In a first preferred embodiment, the fatty amine (Bi) is a primary amine in which R ⁴ is an alkyl radical containing from 8 to 22 carbon atoms and R ⁵ and R ⁶ are hydrogen. In a particularly preferred embodiment, the fatty amine (Bi) is a mixture of different primary amines.

In a second preferred embodiment, the fatty amine (Bi) is a secondary amine in which R ⁴ is an alkyl radical containing from 10 to 22 carbon atoms, R ⁵ is an alkyl radical containing from 1 to 22 carbon atoms, and R ⁶ is hydrogen. In particularly preferred secondary amines, R ⁵ is an alkyl radical containing from 10 to 22 carbon atoms. In a particularly preferred embodiment, R ⁴ and R ⁵ are a mixture of chains of different lengths. In an even more preferred embodiment, the fatty amine (Bi) is a mixture of different secondary amines of formula (1).

In a third preferred embodiment, the fatty amine (Bi) is a tertiary amine in which R ⁴ is an alkyl radical containing from 10 to 22 carbon atoms, and R ⁵ and R ⁶ independently represent an alkyl radical containing from 1 to 22 carbon atoms. In particularly preferred tertiary amines of formula (1), R ⁴ and R ⁵ independently represent an alkyl radical containing from 10 to 22 carbon atoms, and R ⁶ represents an alkyl radical containing from 1 to 6 carbon atoms. In a particularly preferred embodiment, R ⁴ , R ⁵ and R ⁶ are independently a mixture of chains of different lengths. In an even more preferred embodiment, the fatty amine (Bi) is a mixture of different tertiary amines of formula (1).

The alkyl radicals R ⁴ , R ⁵ and R ⁶ can independently be linear or branched; if they contain at least 5 carbon atoms, they may also be cyclic or contain cyclic structural elements. Preferably they are linear. In addition, the alkyl radicals R ⁴ , R ⁵ and R ⁶ can independently be saturated or unsaturated. More preferably, they are saturated or substantially saturated. By essentially saturated it is meant that the amines containing them have a Wiis iodine value of no more than 20 g I2/100 g, more preferably no more than 10 g _I2 /100 g and especially no more than 5 g _I2 /100 g.

Examples of preferred alkyl radicals R ⁴ , R ⁵ and R ⁶ containing from 10 to 20 carbon atoms include decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, oleyl and eicosyl radicals and mixtures thereof. In the case where R ⁴ , R ⁵ and R ⁶ contain mixtures of different alkyl radicals, each of the individual chain lengths is preferably present in the mixtures in an amount of from 1 to 99 wt.%, and more preferably from 5 to 95 wt.%. Particular preference is given to mixtures of alkyl radicals obtained from renewable raw materials, for example cocoalkyl, tallovalkyl and behenyl radicals. Examples of preferred alkyl radicals R ⁵ and R ⁶ containing from 1 to 9 carbon atoms are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octal and nonyl radicals and mixtures thereof. A particularly preferred alkyl radical R ⁵ and R ⁶ containing 1-9 carbon atoms is a methyl radical.

Examples of primary fatty amines (Bi) that are preferred in accordance with the invention are decylamine, dodecylamine, tridecylamine, tetradecylamine, hexadecylamine, octadecylamine and eicosylamine, and mixtures thereof. Particular preference is given to amines obtained from chain fragments of renewable raw materials, such as cocoamine, tallowamine, hydrogenated tallowamine and behenylamine.

Examples of secondary fatty amines (Bi) that are preferred according to the invention are di(decyl)amine, didodecylamine, ditridecylamine, ditetradecylamine, dihexadecylamine, dioctadecylamine, dieicosylamine, dodecyltetradecylamine, dodecylhexadecylamine, tetradecylhexadecylamine, hexadecyloctadecylamine and mixtures thereof. Particular preference is given to amines obtained from chain fragments of renewable raw materials, for example dicocoamine, ditallowamine, dehydrogenated tallowamine) and dibehenylamine.

Examples of tertiary fatty amines (Bi) that are preferred according to the invention are N-methyldidecylamine, N-methyldidodecylamine, N-methylditridecylamine, N-methylditetradecylamine, N-methyldihexadecylamine, N-methyldioctadecylamine, N-methyldieicosylamine, Nmethyl-N-dodecyltetradecylamine, N-methyl-N-dodecylhexadecylamine, N-methyl-N-tetradecylhexadecylamine, N-methyl-N-hexadecyloctadecylamine and mixtures thereof. Particular preference is given to fatty amines (Bi) obtained from chain fragments of renewable raw materials, for example N-methyldicocofettamine, N-methylditalghfettamine, N-methyldi(hydrogenated tallowamine) and N-methyldibehenylamine.

In the case of fatty amines (Bi), in which the radicals R ⁴ , R ⁵ and/or R ⁶ have different definitions, and also in the case of mixtures of fatty amines (Bi), the average alkyl chain length (in molar terms) of the radicals R ⁴ , R ⁵ and R ⁶ , if not hydrogen, is preferably from 10 to 18, and especially from 12 to 17.5, for example from 10 to 17.5 or from 12 to 18. Fatty amines which are particularly preferred according to the invention , are dicoamine, di(hydrogenated tallow)amine, distearylamine and mixtures thereof.

In a second preferred embodiment, the oil-soluble amine (B) is a polyamine (Bii) containing at least one group of the formula -(CH ₂ ) _p -[NR ⁷ -(CH ₂ ) _p ]m-NH ₂ in which R ⁷ represents H or an alkyl radical containing from 1 to 22 carbon atoms, p is 2 or 3, am is 0 or an integer from 1 to 10. Preferably, R ⁷ is H. As a consequence, polyamines (Bii) include at least two nitrogen atoms linked through an alkylene radical containing two or three carbon atoms. Particularly preferred polyamines contain from 2 to 10, for example two, three or four nitrogen atoms. Examples of preferred polyamines are ethylene diamine, propylene diamine, diethylenetriamine, dipropylene triamine, triethylene tetraamine, tetraethylene pentamine, lauryl propylene diamine, tallow propylene diamine, lauryl dipropylene triamine, tallow dipropylene triamine and oleyl tripropylene tetramine.

The oil-soluble amine (B) is present in the additive and in the low-sulfur fuel oil to which it is added in an amount of 5-100 wt.% based on the amount of ammonium ammonium salt (A). The additive preferably contains from 10 to 100 wt.%, more preferably from 15 to 70 wt.% and, in particular, from 20 to 50 wt.%, for example from 5 to 100 wt.%, from 5 to 70 wt.%, from 5 to 50 wt.%, from 10 to 100 wt.%, from 10 to 70 wt.%, from 10 to 50 wt.%, from 15 to 100 wt.%, from 15 to 50 wt.%, from 20 up to 100 wt.% or from 30 to 70 wt.% oil-soluble amine (B) based on the amount of ammonium ammonium salt (A).

When using an oil-soluble amine (B) to improve the low temperature properties of a low sulfur fuel oil according to a third aspect of the invention, as well as to improve the response characteristics of a low sulfur fuel oil containing a lubricant additive (C) to the addition of ammonium ammonium salt (A ), 5 to 100 wt%, preferably 10 to 75 wt%, more preferably 15 to 70 wt%, and especially 20 to 65 wt%, such as 5 to 75, are added to the low sulfur fuel oil. wt.%, from 5 to 70 wt.%, from 5 to 65 wt.%, from 10 to 100 wt.%, from 10 to 70 wt.%, from 10 to 65 wt.%, from 15 to 100 wt.% %, from 15 to 75 wt.%, from 15 to 65 wt.%, from 20 to 100 wt.%, from 20 to 75 wt.% or from 30 to 70 wt.% oil-soluble amine (B) based on the amount amido-ammonium salt (A) present in the fuel oil or to be added to it.

In a third aspect of the invention, an oil-soluble amine (B) is added to a low sulfur fuel oil containing an ammonium ammonium salt (A) and a lubricant additive (C). This improves low temperature properties, such as further reducing the CFPP value and/or improving wax dispersion.

Alternatively, the oil-soluble amine (B) according to the quaternary aspect of the invention can also be added to the low sulfur fuel oil before the amido ammonium salt (A) and lubricant (C) are added thereto to prevent an antagonistic effect from occurring when the amido is subsequently added -ammonium salt (A) and lubricating additive (C).

Lubricating additive (C).

Lubricants are oil additives that improve the lubricity of low sulfur fuel oils. At the dose used, they preferentially reduce the amount of frictional wear (R; in µm) when tested using the HFRR (High Frequency Reciprocating Lubricity Test) test in a fuel oil compared to the same fuel without the addition of a lubricant additive by at least 10%, more preferably at least 20% and especially at least 25%. The amount of frictional wear can be determined, for example, using the HFRR test in accordance with DIN ISO 12156-1. Standard lubricating additives are oil-soluble amphiphilic compounds that form a film on engine parts to be lubricated.

- 8 045457

The lubricating additives (C) critical to the degradation of the low temperature properties imparted by the ammonium amido salts (A) are in particular amphiphiles having an alkyl or alkenyl radical containing from 10 to 28 carbon atoms, preferably from 12 to 22 carbon atoms to which the polar terminal group is bonded and which are fatty acids, partial esters of fatty acids and polyols, and fatty acid amides with alkanolamides. The most pronounced effect is observed in the case of fatty acids.

Examples of lubricating additives (C), the antagonistic effect of which is overcome in accordance with the invention, are saturated and especially unsaturated fatty acids containing from 10 to 20 carbon atoms, and preferably containing from 12 to 22 carbon atoms, for example containing from 10 to 22 atoms carbon or containing from 12 to 18 carbon atoms in the alkyl or alkenyl radical. In addition, the antagonistic effect caused by alk(en)ylsuccinic acids containing alk(en)yl radicals in the mentioned chain length range is also overcome. The alk(en)yl radical of fatty acids and/or alk(en)ylsuccinic acids can be linear, branched or cyclic. In addition, the antagonistic effect caused by partial esters of the mentioned fatty acids with polyhydroxyl compounds, for example, ethylene glycol or glycerol, is overcome. In addition, the antagonistic effect caused by amides of the above fatty acids with primary or secondary alkanolamines, each containing from 2 to 4 carbon atoms per alkyl group, such as ethanolamine, propanolamine, N-methylethanolamine, diethanolamine, is overcome. The term alk(en)yl includes alkyl and alkenyl radicals, where alkenyl radicals may be mono- or polyunsaturated.

Examples of lubricating additives within the scope of the present invention include lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, palmitoleic acid, maleic acid, elaidic acid, erucic acid, linolenic acid, dodecenyl succinic acid, tetradecenyl succinic acid, hexadecenyl succinic acid, ok tadecenylsuccinic acid and mixtures of them. In a preferred embodiment, the lubricating additive is a mixture of fatty acids derived from natural raw materials, for example coconut oil fatty acids, palm oil fatty acids, soybean oil fatty acids, rapeseed oil fatty acids, tall oil fatty acids or tall oil fatty acids.

Optionally, said fatty acids can be used in mixture with at least one polycyclic hydrocarbon compound. Preferred polycyclic hydrocarbon compounds are rosin acids extracted from tree resins, in particular conifer resins. The resin acids are preferably selected from the group consisting of abietic acid, dihydroabietic acid, tetrahydroabietic acid, dehydroabietic acid, neoabietic acid, pimaric acid, levopimaric acid, palustric acid and derivatives thereof.

The above-described saturated and especially unsaturated fatty acids containing from 10 to 20 carbon atoms, as well as alk(en)ylsuccinic acids containing C ₁₀ -C ₂₈ -alk(en)yl radicals and preferred embodiments thereof, are also preferred starting materials for the production of partial esters of polyols and alkanolamides.

Preferred polyols contain from 2 to 10 carbon atoms and from 2 to 6 OH groups, but not more than one OH group per carbon atom. Examples of preferred polyols include ethylene glycol, propylene glycol, butylene glycol, glycerin, pentaerythritol and sorbitol. By partial esters it is meant that at least one OH group of the polyol is not esterified. Examples of partial esters of fatty acids with polyhydroxy compounds are ethylene glycol monostearate, ethylene glycol monotallowate, glycerol monooleate and glycerol monotallowate.

Preferred alkanolamines are primary and secondary amines containing one and two hydroxyalkyl radicals, respectively. Preferred hydroxyalkyl radicals contain from two to 4 carbon atoms and, in particular, 2 or 3 carbon atoms. Examples of preferred alkanolamines include ethanolamine, propanolamine, diethanolamine and dipropanolamine. Examples of fatty amides derived from fatty acids and hydroxyamines include stearic acid monoethanolamide, tall oil fatty acid monoethanolamide, tall oil fatty acid monopropanolamide, stearic acid diethanolamide, tall oil fatty acid diethanolamide and tall oil fatty acid dipropanolamide.

Preferred low sulfur fuel oils contain from 20 to 2000 ppm, especially preferably from 50 to 1000 ppm and especially preferably from 100 to 500 ppm, for example from 10 to 2000 ppm, from 10 to 1000 ppm, from 10 to 500 ppm, from 20 to 1000 ppm, from 20 to 500 ppm, from 50 to 2000 ppm, from 50 to 500 h ./million, 100 to 2000 ppm, or 100 to 1000 ppm (each w/w) of lubricant additive (C).

Low sulfur fuel oil.

By fuel oils with low sulfur content in the context of the invention we mean fuel oils whose sulfur content does not exceed 50 ppm, preferably does not exceed 20 ppm, and especially fuels with a sulfur content of not more than 10 ppm (w/w). The sulfur content of fuel oils can be determined, for example, according to EN ISO 20846 or EN ISO 20884.

Fuel oils are of mineral or synthetic origin. They are essentially composed of hydrocarbons and do not contain esters.

Preferred fuel oils are middle distillates. More specifically, middle distillates refer to mineral oils obtained from the distillation of crude oil and having a boiling point in the range of from about 150 to 450°C and, in particular, in the range from about 170 to 390°C, for example kerosene, aviation fuel, diesel fuel and heating oil. Middle distillates typically contain from about 5 to 50 wt.%, for example from about 10 to 35 wt.% nparaffins, from which long-chain paraffins can crystallize during cooling and impair the fluidity of the middle distillate. The low temperature additives according to the invention are particularly preferred for middle distillates where the aromatic content is less than 40% by weight, for example less than 30% by weight. The compositions of the invention are also particularly preferred in the case of middle distillates having a low final boiling point, i.e. in the case of middle distillates, 90% of whose distillation temperatures are below 350°C, in particular below 340°C and in special cases below 335°C, and in addition in the case of middle distillates whose boiling range for the distillation volume is from 20 to 90 % is below 140°C and in particular below 125°C and especially from 80 to 120°C, for example from 80 to 140°C or from 80 to 125°C. By aromatic compounds we mean the total amount of mono-, di- and polycyclic aromatic compounds that can be determined by HPLC (high performance liquid chromatography) according to DIN EN 12916 (2001 edition).

Preferred fuel oils may also contain or consist of one or more synthetic fuels. In a preferred embodiment, the fuel oils contain a total of 1 to 50% by volume, more preferably from 2 to 30% by volume and especially from 3 to 20% by volume of one or more synthetic fuels. Examples of preferred synthetic fuels include hydrotreated vegetable oils (HVOs). They can be obtained, for example, by the catalytic hydrodeoxygenation of vegetable oils and fats, as well as animal fats. It is not necessarily possible to subject hydrogenated vegetable oils to isomerization to adjust low temperature properties. Another example is synthetic fuels produced by Fischer-Tropsch synthesis.

According to the invention, low sulfur fuel oils having improved cold flow properties preferably contain from 1 to 100 ppm, more preferably from 5 to 75 ppm and in particular from 10 to 50 ppm ./million, for example from 1 to 75 ppm, from 1 to 50 ppm, from 5 to 100 ppm, from 5 to 50 ppm, from 10 to 100 ppm, or from 10 to 75 ppm, (in wt./wt. each) ammonium ammonium salt (A) and 5-100 wt.%, preferably from 10 to 70 wt.% and, in particular, from 15 to 65 wt.%, for example from 5 to 70 wt.%, from 5 to 65 wt.%, from 10 to 100 wt.%, from 10 to 65 wt.%, from 15 to 100 wt.% or from 15 to 70 wt.% oil-soluble amine (B) based on the amount of amidoammonium salt.

To improve low temperature properties and in particular CFPP value and/or wax dispersion, preferably 1 to 100 ppm, more preferably 5 to 75 ppm, and especially 10 to 10 ppm are added to the low sulfur fuel oil. 50 ppm, for example 1 to 75 ppm, 1 to 50 ppm, 5 to 100 ppm, 5 to 50 ppm, 10 to 100 ppm ppm, or 10 to 75 ppm (w/w each) of ammonium ammonium salt (A) and 5 to 100 wt%, preferably 10 to 70 wt% and especially 15 to 65 wt .%, for example from 5 to 70 wt.%, from 5 to 65 wt.%, from 10 to 100 wt.%, from 10 to 65 wt.%, from 15 to 100 wt.% or from 15 to 70 wt. % oil-soluble amine (B) based on the amount of ammonium ammonium salt (A).

Other components (D)-(G).

In a preferred embodiment, ammonium ammonium salt (A) is added to a low sulfur fuel oil in combination with one or more other known cold flow additives. Each of the amido-ammonium salt (A), the additive of the invention consisting of (A) and (B), and other cold flow additives may be added to the fuel oil individually or as a component of a composition additives Preferred additive compositions and/or fuel oils treated therewith accordingly also contain one or more additional additives to improve cold fluidity. Preferred additional cold flow additives are:

D) resins obtained from aromatic compounds containing at least one alkyl radical, and aldehydes and/or ketones;

E) oil-soluble polyoxyalkylene compounds;

F) comb polymers;

G) ethylene copolymers.

Still other preferred cold flow additives are resins (D) derived from aromatic compounds containing at least one alkyl radical and aldehydes and/or ketones. The alkyl radical can be

- 10 045457 is connected to the aromatic system directly or through an ester or ether group.

Preferred alkyl radicals may be saturated or unsaturated. They preferably contain from 1 to 20, in particular from 4 to 16 and especially from 6 to 12 carbon atoms, for example from 1 to 16, from 1 to 12, from 4 to 20, from 4 to 12, from 6 to 20 or from 6 to 16 carbon atoms. Examples of preferred alkyl radicals are n-, iso- and tert-butyl, n- and isopentyl, n- and isohexyl, n- and isooctyl, n- and isononyl, n- and isodecyl, n- and isododecyl, tetradecyl, hexadecyl, octadecyl, tripropenyl , tetrapropenyl, tributenyl, tetrabutenyl, poly(propenyl) and poly(isobutenyl) radical.

Preferred resins are primarily alkylphenolaldehyde resins derived from alkylphenols containing one or two alkyl radicals in the ortho and/or para position to the OH group. Particularly preferred starting materials are alkylphenols containing at least two hydrogen atoms capable of condensation with aldehydes in the aromatic system, and especially monoalkylated phenols. More preferably, the alkyl radical is in the para position to the phenolic OH group. In a preferred embodiment, alkylphenol resins (D) are prepared using mixtures of alkylphenols with various alkyl radicals. Alkyl radicals, for example, may include chains of different lengths and/or different branching patterns (isomers). For example, suitable resins have been found to be resins based on butylphenol on the one hand, and octyl-, nonyl- and/or dodecylphenol in a molar ratio of 1:10 to 10:1 on the other hand.

Other preferred alkylphenol resins contain structural units of phenol analogues such as salicylic acid, hydroxybenzoic acid and derivatives thereof such as esters, amides and salts. Particularly preferred are esters, amides and salts derived from alcohols or amines containing an alkyl radical with the above number of carbon atoms.

Suitable aldehydes for condensation with aromatic compounds containing an alkyl radical are aldehydes containing from 1 to 12 carbon atoms, and preferably aldehydes containing from 1 to 4 carbon atoms, for example formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 2-ethylhexanal , benzaldehyde, glyoxylic acid and their reactive equivalents such as paraformaldehyde and trioxane. Particular preference is given to formaldehyde in the form of paraformaldehyde and especially formalin.

The molecular weight of the resin (D), determined by gel permeation chromatography relative to poly(styrene) standards in THF, is preferably 500 to 25,000 g/mol, more preferably 800 to 10,000 g/mol, and especially 1,000 to 5,000 g/mol , for example from 1500 to 3000 g/mol. A prerequisite here is that the resin (D) must be oil-soluble, at least in concentrations appropriate to the application, which range from 0.001 to 1 wt.%.

In a preferred embodiment, the resin (D) prepared from an aromatic compound containing at least one alkyl radical and an aldehyde and/or ketone is an oligomer or polymer comprising a repeating unit of formula (2)

in which R ⁸ represents C1-C ₂₄ -alkyl, OR ⁹ , OC(O)-R ⁹ or -C(O)-OR ⁹ ,

R ⁹ is C1 -C ₂₂ -alkyl or C ₂ -C ₂₂ -alkenyl, and n is a number from 2 to 100.

Preferably, R ⁸ is C1-C20 alkyl, and especially C4-C16-, eg C6-C12 alkyl. Even more preferably, R ⁹ is C1-C20 alkyl or C ₂ -C ₂₀ alkenyl, and especially C ₄ -C ₁₆ alkyl or alkenyl, for example C6-C ₁₂ alkyl or alkenyl. Preferably, n is a number from 2 to 50 and especially a number from 3 to 25, for example a number from 5 to 15.

Resins (D) based on aromatic compounds containing at least one alkyl radical and aldehydes and/or ketones can be prepared by known methods, for example by condensation of the corresponding alkylphenols with formaldehyde, i.e. using 0.5 to 1.5 moles, preferably 0.8 to 1.2 moles of formaldehyde per mole of alkylphenol. The condensation can be carried out without a solvent, but is preferably carried out in the presence of an inert organic solvent with zero or only partial miscibility with water, such as mineral oil, alcohol, ether, etc. Particular preference is given to solvents that are capable of forming azeotropic mixtures with water. Solvents of this type used are, in particular, aromatic compounds such as toluene, xylene, diethylbenzene and high boiling industrial solvent mixtures such as Shell sol® AB and Solvent Naphtha. In addition, fatty acids and their derivatives are suitable as solvents, for example esters with lower alcohols containing from 1 to 5 carbon atoms, for example ethanol and especially methanol. Condensation

- 11 045457 is preferably carried out at a temperature of from 70 to 200°C, for example from 90 to 160°C. Typically it is catalyzed by bases in an amount of 0.05 to 5% by weight, or preferably by an acid in an amount of 0.05 to 5% by weight. Catalysts commonly used as acid catalysts, as well as carboxylic acids such as acetic acid and oxalic acid, are in particular strong mineral acids such as hydrochloric acid, phosphoric acid and sulfuric acid, and sulfonic acids. Particularly suitable catalysts are sulfonic acids containing at least one sulfo group and at least one saturated or unsaturated, linear, branched and/or cyclic hydrocarbon radical containing from 1 to 40 carbon atoms, and preferably containing from 3 to 24 carbon atoms. Particular preference is given to aromatic sulfonic acids, in particular alkylaromatic monosulfonic acids containing one or more C1- _C28 alkyl radicals and especially those containing _C3 - _C22 alkyl radicals, for example containing C1- _C22 alkyl radicals. Suitable examples include methanesulfonic acid, butanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, 2-mesitylenesulfonic acid, 4-ethylbenzenesulfonic acid, isopropylbenzenesulfonic acid, 4-butylbenzenesulfonic acid, 4-octylbenzenesulfonic acid, dodecylbenzenesulfonic acid , didodecylbenzenesulfonic acid, naphthalene sulfonic acid. In addition, mixtures of the above sulfonic acids are suitable. They usually remain in the product as such or in neutralized form after the reaction is complete. Neutralization is preferably carried out using amines and/or aromatic bases, since these may remain in the product; salts containing metal ions and therefore forming ash are usually separated.

In a further preferred embodiment, the low temperature additives according to the invention and/or the fuel oils to which they are added contain an oil-soluble polyoxyalkylene compound (E) as an additional flow improver. Examples of preferred oil-soluble polyoxyalkylene compounds (E) include esters, ethers and ethers of polyols containing at least one alkyl radical containing from 12 to 30 carbon atoms. In a preferred embodiment, the oil-soluble polyoxyalkylene compounds (E) contain at least 2, for example 3, 4 or 5 aliphatic hydrocarbon radicals. These radicals preferably independently contain from 16 to 26 carbon atoms, for example from 17 to 24 carbon atoms. These radicals of oil-soluble polyoxyalkylene compounds (E) are preferably linear. Even more preferably, they are substantially saturated and, in particular, are alkyl radicals. Esters are especially preferred.

Polyols particularly suitable for preparing the preferred polyoxyalkylene compounds (E) are polyethylene glycols, polypropylene glycols, polybutylene glycols and copolymers thereof with an average molecular weight of from 100 to 5000 g/mol, and preferably from 200 to 2000 g/mol. In a preferred embodiment, the oil-soluble polyoxyalkylene compounds (E) are derived from polyols containing 3 or more OH groups, more preferably from polyols containing from 3 to 50 OH groups, and especially from polyols containing from 4 to 10 OH groups, e.g. containing from 3 to 10 OH groups or from 4 to 50 OH groups. Examples of preferred polyols include neopentyl glycol, glycerol, trimethylolethane, trimethylolpropane, sorbitol, pentaerythritol, and oligomers containing from 2 to 10 monomer units obtained by condensation, such as glycerol. In addition, higher polyols such as sorbitol, sucrose, glucose, fructose and their oligomers, such as cyclodextrin, are suitable as polyols, provided that their ester or alkoxylates are oil soluble, at least in quantities appropriate for the application. Preferred polyoxyalkylene compounds are based on a branched polyoxyalkylene framework to which numerous alkyl radicals are associated, imparting oil solubility to the final compound.

Typically, the polyols are reacted with an alkylene oxide in an amount of from 3 to 70 moles, preferably from 4 to 50 and especially from 5 to 20 moles of alkylene oxide, for example from 3 to 50, from 3 to 20, from 4 to 70, from 4 to 30, from 5 to 70 or from 5 to 20 mol of alkylene oxide per hydroxyl group of the polyol. Preferred alkylene oxides include ethylene oxide, propylene oxide and/or butylene oxide. Alkoxylation is carried out by known methods.

Fatty acids preferred for carrying out the esterification of alkoxylated polyols contain from 12 to 30 and especially from 16 to 26 carbon atoms, for example from 12 to 26 or from 16 to 30 carbon atoms. Suitable fatty acids are, for example, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, isostearic acid, arachidic acid and behenic acid, oleic acid and erucic acid, palmitoleic acid, myristoleic acid, ricinoleic acid and mixtures of fatty acids obtained from natural fats and oils. Preferred fatty acid mixtures contain greater than 50 mol% fatty acids containing at least 20 carbon atoms. Preferably, less than 50 mol.% of the fatty acids used for esterification contain double bonds, in particular less than 10 mol.%; in particular, they are saturated in

- 12 045457 to a very significant extent. Esterification can also occur with the participation of reactive fatty acid derivatives such as lower alcohol esters (eg methyl or ethyl esters) or anhydrides.

In the context of the present invention, saturated to a very significant extent means the iodine value (according to Wijs, similar to EN 14111) of the fatty acid or fatty alcohol used, up to 5 g I2 per 100 g of fatty acid or fatty alcohol.

The polyol and fatty acids are used for esterification, based on the content of hydroxyl groups on the one hand or carboxyl groups on the other hand, in a ratio of 1.5:1 to 1:1.5, preferably in a ratio of 1.1:1 up to 1:1.1, and especially in equimolar quantities. The acid number of the esters formed is typically less than 15 mg KOH/g, preferably less than 10 mg KOH/g, especially less than 5 mg KOH/g. The hydroxyl number in the esters is preferably less than 20 mg KOH/g and especially less than 10 mg KOH/g.

In a further preferred embodiment, after alkoxylation of the polyol, the terminal hydroxyl groups are converted to terminal carboxyl groups, for example by oxidation or reaction with dicarboxylic acids. By reaction with fatty alcohols containing from 8 to 50, in particular from 12 to 30 and especially from 16 to 26 carbon atoms, the polyoxyalkylene esters of the invention are similarly obtained. Preferred fatty alcohols or fatty acid mixtures contain greater than 50 mol% fatty alcohols containing at least 20 carbon atoms. Preferably, less than 50 mol.% of the fatty alcohols used for esterification include double bonds, in particular less than 10 mol.%; in particular, they are saturated to a very significant extent. Also suitable according to the invention are fatty acid esters of alkoxylated fatty alcohols which contain the above proportions of poly(alkylene oxides) and whose fatty alcohol and fatty acid have the above alkyl chain lengths and saturation levels.

In a further preferred embodiment, the alkoxylated polyols described above are converted into polyoxyalkylene compounds (E) by esterification with fatty alcohols containing from 8 to 50, in particular from 12 to 30 and especially from 16 to 26 carbon atoms, for example containing from 8 to 30, containing from 8 to 26, containing from 12 to 50, containing from 12 to 26, containing from 16 to 50, or containing from 16 to 30 carbon atoms. Fatty alcohols preferred for this purpose are linear and highly saturated. The esterification is preferably carried out completely or at least to a very significant extent completely. Esterification is carried out by known methods.

Particularly preferred polyoxyalkylene compounds (E) are derived from polyols containing 3, 4 and 5 OH groups, which contain from about 5 to 10 mol.% ethylene oxide-based structural units per hydroxyl group of the polyol and which have been esterified to a very significant extent with ₁₇ - With ₂₄ fatty acids, saturated to a very significant extent. Still other particularly preferred polyoxyalkylene compounds (E) are polyethylene glycols which have been esterified with highly saturated C ₁₇ -C ₂₄ fatty acids and have a molecular weight of from about 350 to 1000 g/mol. Examples of particularly suitable polyoxyalkylene compounds (E) include polyethylene glycols esterified with stearic acid and especially behenic acid, and having a molecular weight of from 350 to 800 g/mol, such as neopentyl glycol 14-ethylene oxide distearate (neopentyl glycol alkoxylated with 14 moles of ethylene oxide and then esterified with 2 moles of stearic acid), neopentyl glycol 14ethylene oxide dibehenate, glycerol 20-ethylene oxide tristearate, glycerol 20-ethylene oxide dibehenate, glycerol 20-ethylene oxide tribehenate, trimethylolpropane 22-ethylene oxide tristearate, sorbitol 25-ethylene oxide tristearate, sorbitol 25-ethylene oxide tetrastearate, sorbitol 25-ethylene oxide tribehenate , sorbitol 25ethylene oxide tetrabehenate; pentaerythritol 30-ethylene oxide tribehenate, pentaerythritol 30-ethylene oxide tetrastearate, pentaerythritol 30-ethylene oxide tetrabehenate and pentaerythritol 20-ethylene oxide 10-propylene oxide tetrabehenate.

In a further preferred embodiment, the low temperature additives according to the invention and/or fuel oils treated therewith contain a comb polymer (F) as an additional additive to improve fluidity under low temperature conditions. Preferred comb polymers (F) can be, for example, described by formula (3)

In this formula

A represents R ¹⁰ , COOR ¹⁰ , OCOR ¹⁰ , R11-COOR ¹⁰ , OR ¹⁰ ;

D is H, CH ₃ , A or R ¹¹ ;

- 13 045457

E represents H, A;

G represents H, R ¹¹ , R11-COOR ¹⁰ , an aryl radical or a heterocyclic radical;

M represents H, COOR ¹¹ , OCOR ¹¹ , OR ¹¹ , COOH;

N represents H, R ¹¹ , COOR ¹¹ , OCOR ¹¹ , aryl radical;

R ¹⁰ represents a hydrocarbon chain containing from 8 to 20, preferably from 10 to 18 carbon atoms;

R ¹¹ represents a hydrocarbon chain containing from 1 to 10 carbon atoms;

m represents a number from 0.4 to 1.0; and k represents a number between 0 and 0.6.

Preferred comb polymers (F) are, for example, copolymers of ethylenically unsaturated dicarboxylic acids, eg maleic or fumaric acid esters, with other ethylenically unsaturated monomers such as olefins or vinyl esters, eg vinyl acetate. Particularly preferred in the present invention are aolefins containing from 10 to 20 and especially from 12 to 18 carbon atoms, for example 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and mixtures thereof. In addition, long-chain olefins derived from oligomerized C ₂ -C ₆ olefins, for example poly(isobutylene) with a high proportion of total double bonds, are suitable comonomers. Typically, these copolymers are esterified to a degree of at least 50 mol.%, based on the carboxyl groups contained therein, with alcohols containing from 10 to 20 and especially from 12 to 18 carbon atoms. Suitable alcohols include n-decan-1-ol, n-decan-1-ol, n-tetradecan-1-ol, n-hexadecan-1-ol, n-octadecan-1-ol, and mixtures thereof. Particularly preferred are mixtures of n-tetradecan-1-ol and n-hexadecan-1-ol.

Equally suitable as comb polymers (F) are poly(alkyl acrylates), poly(alkyl methacrylates) and poly(alkyl vinyl ethers), which are derived from fatty alcohols containing from 10 to 20 and especially from 12 to 18 carbon atoms, and poly( vinyl esters), which are derived from fatty acids containing from 10 to 20 and especially from 12 to 18 carbon atoms. Preferred comb polymers (F) have a weight average molecular weight of from 10,000 to 200,000 g/mol.

In a further preferred embodiment, the low temperature additives of the invention and/or fuel oils treated therewith contain ethylene copolymer (G) as an additional additive to improve fluidity under low temperature conditions. Preferred ethylene copolymers (G) are copolymers of ethylene and ethylenically unsaturated compounds. Suitable ethylene copolymers (G) are in particular copolymers which, in addition to ethylene, contain from 8 to 21 mol% and especially from 10 to 18 mol% of one or more ethylenically unsaturated compounds as comonomers. Preferred ethylenically unsaturated compounds are vinyl esters, acrylic esters, methacrylic esters, alkyl vinyl ethers and/or alkenes.

Preferred comonomer vinyl esters have the formula (4) CH2=CH-OCOR ¹² (4), in which R ¹² is C ₁ -C ₃₀ alkyl, preferably C ₄ -C ₁₆ alkyl and especially C ₆ -C ₁₂ -alkyl, for example C1-C ₁₆ -alkyl or C1-C ₁₂ -alkyl. In a further embodiment, said alkyl group may be replaced by one or more hydroxyl groups. In a further preferred embodiment, R ¹² is a linear or branched alkyl radical, and more preferably a neoalkyl radical containing from 7 to 11 carbon atoms, especially containing 8, 9 or 10 carbon atoms. Particularly preferred are vinyl esters derived from secondary and especially tertiary carboxylic acids, in which the branching is in the alpha position to the carboxyl group. Suitable vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl hexanoate, vinyl heptanoate, vinyl octanoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl laurate, vinyl stearate and versatic acid esters such as vinyl neononanoate, vinyl neodecanoate, vinyl neoundecanoate.

In a further preferred embodiment, the ethylene copolymers (G) comprise vinyl acetate and at least one additional vinyl ester of formula 4, wherein R ¹² is C ₄ -C ₃₀ alkyl, preferably C ₄ -C ₁₆ alkyl, preferably C ₆ -C ₁₂ -alkyl.

Acrylic esters preferred as comonomer are those of formula (5)

CH2=CR ¹³ -COOR ¹⁴ (5), in which R ¹³ represents hydrogen or methyl, and R ¹⁴ represents C ₁ -C ₃₀ -alkyl, preferably C ₄ -C ₁₆ -alkyl and especially C ₆ -C ₁₂ -alkyl, for example, C1-C ₁₆ -alkyl or C ₁ -C ₁₂ -alkyl. Suitable acrylic esters include, for example, methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, n- and isobutyl(meth)acrylate, hexyl(meth)acrylate, octyl(meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl(meth)acrylate, dodecyl(meth)acrylate, tetradecyl(meth)acrylate, hexadecyl(meth)acrylate, octadecyl(meth)acrylate and mixtures of these comonomers.

Alkyl vinyl ethers, preferred as a comonomer, are compounds

- 14 045457 explanation of formula (6)

CH2=CH-OR ¹⁵ (6), in which R ¹⁵ is C ₁ -C ₃₀ alkyl, preferably C ₄ -C ₁₆ alkyl and especially C ₆ -C ₁₂ alkyl, for example C1-C ₁₆ alkyl or C ₁ -C ₁₂ -alkyl. Suitable alkyl vinyl ethers include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether. In a further embodiment, said alkyl groups may be replaced by one or more hydroxyl groups.

Alkenes preferred as comonomer are monounsaturated hydrocarbons containing from 3 to 30 carbon atoms, in particular containing from 4 to 16 carbon atoms and especially containing from 5 to 12 carbon atoms, for example containing from 3 to 16 or from 3 to 12 carbon atoms. Preferred alkenes include propene, butene, isobutene, pentene, hexene, 4-methylpentene, octene, diisobutene and norbornene, and derivatives thereof such as methylnorbornene and vinylnorbornene.

In particular, preferred ethylene comonomers (G) are terpolymers which, in addition to ethylene, contain from 3.5 to 20 mol.%, especially from 8 to 15 mol.% vinyl acetate and from 0.1 to 12 mol.%, especially from 0.2 to 5 mol% of at least one relatively long-chain and preferably branched vinyl ester, for example vinyl 2-ethylhexanoate, vinyl neononanoate or vinyl neodecanoate, where the total comonomer content of the terpolymers is preferably from 8 to 21 mol%, especially from 12 to 18 mol.%, for example from 8 to 18 mol.% or from 12 to 21 mol.%. Still other preferred copolymers contain, in addition to ethylene, from 8 to 18 mol.% vinyl ester of C ₂ -C ₁₂ carboxylic acids, from 0.5 to 10 mol.% olefins such as propene, butene, isobutene, hexene, 4-methylpentene , octene, diisobutene and/or norbornene.

Preferably, the melt viscosity of the ethylene copolymers (G) at 140° C. is from 20 to 10,000 mPa-s, in particular from 30 to 5,000 mPa-s, especially from 50 to 2,000 mPa-s. The weight average molecular weight determined by gel permeation chromatography in THF relative to poly(styrene) standards is preferably from 3000 to 30,000 g/mol, and more preferably from 5000 to 15,000 g/mol. The degree of branching, as determined by 1H NMR spectroscopy, is preferably 1 to 9 CH3/100 CH2 groups, especially 2 to 6 CH3/100 CH2 groups, which is not derived from comonomers.

In a preferred embodiment, mixtures of two or more of the above-mentioned ethylene copolymers (G) are used. The ethylene copolymers (G) forming the basis of such mixtures differ in at least one way, for example they may contain different comonomers or have different comonomer contents, molecular weights and/or degrees of branching.

The mixing ratio between the additive according to the invention and additional components (D), (E), (F) and/or (G) may vary depending on the application. In preferred additives, the mixing ratio between the additive according to the invention, on the one hand, and additional components (D), (E), (F) and/or (G), based on the active ingredients, is in each case preferably from 1:20 to 20:1, more preferably 1:10 to 10:1 and especially 1:5 to 5:1 (w/w), for example 1:20 to 10:1, 1:20 to 5:1, 1:10 to 20:1, 1:10 to 5:1, 1:5 to 20:1 or 1:5 to 10:1.

To facilitate use, low temperature additives are preferably used in the form of concentrates containing, in addition to the low temperature additive, from 10 to 95 wt.%, preferably from 20 to 80 wt.% and especially from 25 to 60 wt.% solvent, for example from 10 to 80 wt.%, from 10 to 60 wt.%, from 20 to 95 wt.%, from 20 to 60 wt.%, from 25 to 95 wt.% or from 25 to 80 wt.% solvent. Preferred solvents include high boiling aliphatic, aromatic hydrocarbons, alcohols, esters, ethers and mixtures thereof.

The low temperature additives according to the invention can be used alone or in combination with other additives, for example additional cold flow additives, dewaxing auxiliaries, detergent additives, antioxidants, cetane improvers, haze inhibitors, anti-emulsifiers, foam inhibitors , dyes, corrosion inhibitors, lubricants, sludge reducers, odorants and/or cloud point reducers.

The additive according to the invention improves the low temperature properties of low sulfur fuel oils, such as kerosene, aviation fuel, diesel fuel, marine diesel fuel and heating oil, which contain a lubricating additive (C). This improvement is manifested, for example, in a decrease in cloud point, pour point, CFPP value and/or in improved dispersion of waxes. In particular, it is effective for fuel oils with a low aromatic content and especially for fuel oils with an aromatic content of less than 40 wt.%, for example less than 30 wt.%. In addition, the additive according to the invention is particularly effective for fuel oils with a low end boiling point and especially for fuel oils whose boiling points are 90% below 350°C, in particular below 340°C and especially below 335°C. The additive according to the invention is also particularly effective for fuel oils with a boiling range from 20 to 90% of the distillation volume at a temperature of less than 140°C and, in particular, less than 125°C and especially from 100 to 120°C, for example from 100 up to 140°C or from 100 to 125°C. The additive according to the invention is particularly effective for fuel oils that have both a low content of aromatic compounds and a low end boiling point.

The benefits of various aspects of the present invention with respect to wax dispersibility are particularly noticeable when cooling of the fuel oil occurs rapidly, for example at a cooling rate of -0.5°C/min towards an accelerated cooling rate, for example at -1.5°C/min or -3°C /min. The benefits of various aspects of the present invention are also particularly noticeable during long-term storage of more than 16 hours, such as 24, 60 hours or longer. The benefits are also particularly noticeable when the fuel oil with additives is stored at a temperature of 5°C or lower, such as 8°C or lower, and especially 10°C or lower than the cloud point of the fuel oil. The additives according to the invention are particularly preferred in case of long-term storage at very low temperatures.

Examples

To evaluate the improvement in low-temperature properties of fuel oils due to the additives of the invention, the fuel oils described in Table 1 were used. 1. Cloud points were determined according to ISO 3015 and CFPP values according to EN 116. Molecular weight values were determined by gel permeation chromatography (GPC) in THF relative to poly(styrene) standards. The amounts of oil-soluble amine B (ppm) used in the experiments shown in table. 3-8 are further presented in wt.% based on the amount (active ingredient content) of ammonium ammonium salt (A) added to the fuel oil.

The dispersibility of waxes was determined during sedimentation tests, which were carried out as follows: 350 ml of fuel oil was heated to 60 ° C in a graduated cylinder and the quantities of additives described in tables 2A to 2D were added, which are given in table. 4, 7 and 8. The doses given in the tables represent the masses of active ingredients added in each case, based on the amount of fuel oil (ppmw).

The fuel oil thus treated was cooled to room temperature. To determine CFPP and cloud point (previously), a 50 ml sample was taken. The 300 ml residue in the graduated cylinder was cooled to the appropriate storage temperature at a cooling rate of -1.5°C/min in the refrigerator. After the storage time specified in table. 4 and 7, the sample was assessed visually. This included determining and assessing the volume of the deposited wax phase and the appearance of the overlying fuel oil phase. Quantitative determination was carried out as a percentage of the sediment volume. A small amount of sediment and a fuel oil phase with maximum turbidity uniformity indicate good dispersibility of waxes.

In addition, immediately after refrigerated storage, 20 vol.% samples of the upper and lower phases were taken and their cloud point and CFPP value were determined.

The sedimentation test was considered passed if the following five criteria were met.

Criterion 1: When visually assessing dispersion (vis), the sample must have uniform turbidity or sediment volume < 1% (n). If there is more sediment (m), the test is considered failed.

Criterion 2: The CP of the lower phase can be no more than 2 K higher than the CP of the fuel before storage (ACP _u ).

Criterion 3: The CP of the upper phase can be no more than 2 K below the CP of the fuel before storage (ACPo).

Criterion 4: The lower phase CFPP can be no more than 2 K higher than the CFPP of the fuel before storage (ACFPPu).

Criterion 5: The CFPP of the upper phase can be no more than 2 K below the CFPP of the fuel before storage (ACFPPo).

Only a slight deviation of the cloud point and the clogging point of the cold filter for the lower and upper phases from the control oil value indicates good dispersibility of paraffins.

- 16 045457

Table 1. Characteristics of the test fuels used

Test fuel 1 Test fuel 2 Test fuel 3 Test fuel 4 Test fuel 5 Test fuel 6 Distillation TNK [°C] 196.7 176.8 176.2 187.3 201.4 173.2 20% [°C] 240.8 219.6 223.1 246.7 249.7 223.2 90% [°C] 327.2 318.9 331.0 332.8 333.8 332.9 (90-20)% [°C] 86.4 99.3 107.9 86.1 84.1 109.7 TKK [°C] 355.1 340.1 358.1 360.6 354.9 357.4 Cloud point [°C] -11.2 -16.0 -7.1 -7.1 -8 -7.8 CFPP [°C] -eleven -18 -10 -8 -8 -8 Pour point [°C] -21 -24 -15 -15 -12 -18 Density at 15 °C [g/cm] 0.8398 0.8412 0.8304 0.838 0.8563 0.8328 Sulfur content [ppm] 9 7 9 8 7 9 Aromatic content [wt.%] 32.75 29.9 24.7 28.67 23.94 19.09 in which mono [wt.%] 26.4 24.3 22.5 23.8 20.76 17.89 di [wt.%] 5.87 4.32 2.0 4.53 3.01 1.2 poly [wt.%] 0.48 0.38 0.2 0.34 0.17 0 Content of n-paraffins [wt.%]] 23.2 24.3 26.5 23.7 26.3 22.5

Table 2A. Characteristics of the used ammonium salts (A)

A1 Reaction product of a copolymer of Cm/Cm-a-olefin and maleic anhydride with 2 equivalents of hydrogenated dithallowamine A2 Reaction product of ethylenediaminetetraacetic acid with 4 equivalents of dithallowamine to give ammonium amido salt AZ Reaction product of phthalic anhydride with 2 equivalents of di(hydrogenated thal)amine

Table 2B. Characteristics of used oil-soluble amines (B)

IN 1 Di(tallowamine) Wb Tallow propylene diamine AT 2 Di(stearylamine) AT 7 Dimethylhexadecylamine VZ Tallowamine AT 8 Dimethylcocoamine AT 4 Dimethyllaurylamine AT 9 Triethylene tetraamine AT 5 Dimethyltetradecylamine

Table 2C. Characteristics of the lubricating additives used (C)

C1 Tall oil fatty acid C2 Bis(ethylene glycol ether) C ι8-alkenyl succinic acid NW Oleic acid diethanolamide C4 Oleic acid

Table 2D. Characteristics of additional additives used (D)-(G) to improve fluidity at low temperatures

D1 Nonylphenol-formaldehyde resin, M _w = 4500 g/mol, 60% in high boiling aromatic solvent D2 Dodecyl benzoate-formaldehyde resin, M _w = 2100 g/mol, 50% in high boiling aromatic solvent E1 Behenyl ester of alkoxylated glycerol, M _p = 3100 g/mol, 50% in high boiling aromatic solvent E2 PEG 400-dibehenate, 50% in high boiling aromatic solvent F1 Ditetradecyl fumarate copolymer, 50% in high boiling aromatic solvent F2 Poly(C12/14-alkyl acrylate), M _w = 85000 g/mol, 50% in high boiling aromatic solvent G1 Copolymer of ethylene and 13.5 mol.% vinyl acetate with a melt viscosity Vuo measured at 140°C and 125 mPa-s, 65% in kerosene. Density (40°C) = 0.85 g/ ^cm3

- 17 045457

G2 Ethylene terpolymer, 13 mol.% vinyl acetate and 2 mol.% vinyl neodecanoate with melt viscosity Vuo measured at 140°C and 95 mPa-s, 65% in kerosene. Density (40°C) = 0.86 g/ ^cm3 G3 Mixture of equal parts G1 and G2 G4 Ethylene terpolymer, 13 mol.% vinyl acetate and 5 mol.% propylene with melt viscosity Vy0 measured at 140°C and 110 mPa-s, 65% in kerosene. Density (40°C) = 0.87 g/ ^cm3

Both ammonium ammonium salts (A) and oil-soluble amines (B) were used as 60% concentrates in a mixture of high boiling aromatic solvents for ease of use. Lubricating additives (C) were used without prior dilution. Doses indicated in table. 3-8 are based on the amount of active ingredient added in each case.

Table 3. Amine Suppression of Lubricant Additive Antagonism to CFPP Values in Test Fuel 1

Example A1 IN 1 C1 CFPP [h/million] [h/million] [wt.%] [h/million] [°C] 1 (compared) 24 - - - -29 2 (compared) 24 4 17 - -29 3 (compared) 24 10 42 - -29 4 (compared) 24 20 83 - -29 5 (compared) 24 - - 200 -24 6 24 4 17 200 -26 7 24 10 42 200 -28 8 24 20 83 200 -29 9 (compared) 24 - - 350 -22 10 24 4 17 350 -24 AND 24 10 42 350 -26 12 24 20 83 350 -29

As an additional flow improver, the test fuel contained 260 ppm by volume of a mixture consisting of 1 part by weight. D1 and 6 parts by weight G4 (CFI1; density at 40°C = 0.91 g/cm ³ ).

Table 4. Suppression of antagonism caused by lubricating additives by amines in relation to the dispersibility of waxes in test fuel 2

Example A [h/million] In [wt.%; ppm] C1 [ppm] Sediment Cloud point [°C] ACP ₀ ACP _and CFPP [°C] ACFPPo ACFPP _U Grade visa about.% before top bottom [°C] [°C] before top bottom [°C] [°C] 0(C) A1 [54] - - P 0 -16.7 -16.9 -16.4 0.2 0.3 -38 -37 -37 1.0 1.0 + KS) A1 [54] - 350 m 8 -16.5 -18.5 -12.5 2.0 4.0 -33 -34 -25 1.0 8.0 - 2 A1 [54] B1 [31; 17] 350 P 0 -16.7 -16.4 -16.7 0.3 0.0 -37 -35 -35 2.0 2.0 + 3 A1 [54] B2[31; 17] 350 P < 1 -16.4 -17.0 -15.3 0.6 1.1 -36 -38 -37 2.0 1.0 + 4 A1 [54] B4 [31; 17] 350 P 0 -16.3 -16.8 -15.6 0.5 0.7 -35 -35 -34 0.0 1.0 + 5 A1 [54] B9 [31;17] 350 P 2 -16.2 -17.7 -14.5 1.5 17 -33 -35 -31 2.0 2.0 + 6 A1 [72] - - P 0 -16.7 -16.9 -16.4 0.2 0.3 -36 -36 -35 0.0 1.0 - 7 A1 [72] - 350 P 0 -16.5 -18.9 -14.1 2.4 2.1 -34 -34 -21 0.0 13.0 - 8 A2 [72] - 350 P 0 -16.6 -18.6 -15.3 2.0 1.3 -34 -36 -28 2.0 6.0 - 9 AZ [72] - 350 P 2 -16.2 -16.4 -14.1 0.2 2.1 -33 -33 -28 0.0 5.0 - 10 A2 [72] B1 [21; 15] 350 P 0 -16.5 -16.6 -16.3 0.1 0.3 -35 -35 -34 0.0 1.0 + eleven AZ [72] B1 [21; 15] 350 P < 1 -16.3 -16.4 -15.6 0.1 0.7 -35 -34 -33 1.0 2.0 +

As an additional additive to improve fluidity, the test fuel contained 210 vol. ppm mixture containing 3.5 parts by weight. D1, 1 part by weight E2 and 17 parts by weight G3 (CFI2; density at 40°C = 0.90 g/cm ³ ). The storage temperature was -22°C and the storage duration was 16 hours.

- 18 045457

Table 5. Suppression of antagonism caused by lubricant additives by amines in relation to the CFPP value in test fuel 3

Example A IN WITH CFPP [h/million] [h/million] wt.% [h/million] [°C] 1 (compared) A1 [24] - - -27 2 (compared) A1 [24] B2 [7.5] B2 [31] - -27 3 (compared) A1 [24] B4 [7.5] B4 [31] - -26 4 (compared) A1 [24] B5 [7.5] B5 [31] - -27 5 (compared) A1 [24] Wb [7.5] Wb [31] - -28 6 (compared) A1 [24] B7 [7.5] B7 [31] - -27 7 (compared) A1 [24] B8 [7.5] B8 [31] - -27 8 (compared) A1 [24] - - C1 [200] -13 9 A1 [24] B2 [7.5] B2 [31] C1 [200] -27 10 A1 [24] B4 [7.5] B4 [31] C1 [200] -26 eleven A1 [24] B5 [7.5] B5 [31] C1 [200] -27 12 A1 [24] Wb [7.5] Wb [31] C1 [200] -27 13 A1 [24] B7 [7.5] B7 [31] C1 [200] -26 14 A1 [24] B8 [7.5] B8 [31] C1 [200] -26 15 (compared) A1 [24] - - C1 [350] -15 16 A1 [24] B1 [7.5] B1 [31] C1 [350] -27 17 A1 [24] B5 [7.5] B4 [31] C1 [350] -27 18 A1 [24] Wb [7.5] B5 [31] C1 [350] -27 19 A1 [24] B4 [7.5] Wb [31] C1 [350] -26 20 A1 [24] B7 [7.5] B7 [31] C1 [350] -27 21 A1 [24] B8 [7.5] B8 [31] C1 [350] -26

As a fluidity additive, the test fuel contained 260 vol. ppm mixture containing 3.5 parts by weight. D1, 1 part by weight E1 and 15 parts by weight. G2 (CFI3; density at 40°C = 0.91 g/cm ³ ).

Table 6. Suppression of antagonism caused by lubricating additives by amines in relation to the CFPP value in test fuel 4

Example A IN WITH CFI4 CFPP [h/million] [h/million] [wt.%] [h/million] [about. ppm] [°C] 1 (compared) A1 [30] - - - 250 -27 2 (compared) A1 [36] - - - 300 -27 3 (compared) A1 [30] B2 [9] B2 [31] - 250 -27 4 (compared) A1 [30] B8 [9] B8 [31] - 250 -27 5 (compared) A1 [30] - - C1 [200] 250 -23 6 (compared) A1 [36] - - C1 [200] 300 -23 7 A1 [30] B2 [9] B2 [31] C1 [200] 250 -27 8 A1 [30] B8 [9] B8 [31] C1 [200] 250 -26 9 (compared) A1 [30] C1 [350] 250 -22 10 (compared) A1 [36] C1 [350] 300 -22 eleven A1 [30] B2 [9] B2 [31] C1 [350] 250 -27 12 A1 [30] B8 [9] B8 [31] C1 [350] 250 -28

As an additional additive to improve fluidity, a mixture was added to the test fuel, including 3 parts by weight. D1, 1 part by weight E1 and 17 parts by weight. G4 (CFI4; density at 40°C = 0.91 g/cm ³ ).

-

Claims (25)

Table 7. Suppression of Lubricant Antagonism of Wax Dispersibility by Amines in Test Fuel 5 Example A [ppm] in [wt.%; ppm] C [ppm] Sediment Cloud point [°C] ACP ₀ ACP _and CFPP [°C] ACFPP ₀ ACFPP _U Visa rating. vol.% to top bottom [°C] [°C] to top bottom [°C] [°C] 0(C) A1 [36] - - P 0 -7.9 -8.1 -7.6 0.2 0.3 -25 -26 -25 1.0 0.0 + 1(C) A1 [36] - C1 [350] m 4 -7.7 -9.3 -5.5 1.6 2.2 -22 -22 -18 0.0 4.0 - 2(C) A1 [36] - C2 [350] m 9 -7.9 -9.5 -5.3 1.6 2.6 -23 -22 -18 1.0 5.0 - 3(C) A1 [36] - NW [350] m 7 -7.8 -9.6 -5.5 1.8 2.3 -22 -21 -18 1.0 4.0 - 4 A1 [36] B1 [31; 9] C1 [350] P 0 -7.9 -7.9 -7.6 0.0 0.3 -26 -25 -25 1.0 ι,ο + 5 A1 [36] B1 [31; 9] C2 [350] P > 1 -7.8 -7.9 -7.5 0.1 0.3 -25 -25 -24 0.0 ι,ο + 6 A1 [36] B1 [31; 9] NW [350] P 0 -7.7 -7.9 -7.6 0.2 0.1 -25 -26 -24 1.0 ι,ο + 7 A2 [36] B8 [31; 9] C1 [350] P < 1 -7.8 -8.1 -7.5 0.3 0.3 -26 -25 -25 1.0 ι,ο + 8 A2 [36] B8 [31; 9] C2 [350] P 0 -7.7 -8.2 -7.3 0.5 0.4 -25 -26 24 1.0 ι,ο + 9 A2 [36] B8 [31; 9] NW [350] P 2 -7.8 -8.2 -7.5 0.4 0.3 -26 -24 -24 2.0 2.0 + As an additional flow improver, the test fuel contained 280 ppm of a mixture containing 4.0 parts by weight. D1, 0.5 parts by weight F1 and 1 part by weight E4 (CFI5; density at 40°C = 0.90 g/cm ³ ). The storage temperature was -18°C, the storage duration was 24 hours. Table 8. Suppression by amines of antagonism caused by lubricating additives in relation to the dispersibility of waxes in test fuel 6 Example A [ppm] B [wt.%; ppm] C [ppm] Sediment Cloud point [°C] ACPO ACPi CFPP [°C] ACFPPo ACFPP _U Rating VIZ. about.% BEFORE top BOTTOM [°C] [°C] BEFORE top BOTTOM [°C] [°C] 0(C) A1 [48] - - And 0 -8.0 -7.6 -8.2 0.4 0.2 -25 -26 -25 1 0 + KS) A1 [48] - C1 [300] m 8 -7.7 -5.1 -5.3 2.6 2.4 -21 -23 -18 4 3 - 2(C) A1 [48] - C2 [300] m 9 -7.6 -5.2 -3.5 2.4 4.1 -20 -22 -17 2 h - 3(C) A1 [48] - NW [300] m 7 -7.5 -4.4 -1.8 3.1 5.8 -22 -18 -16 4 6 - 4(C) A1 [48] - C4 [300] m 10 -7.9 -5.2 -4.8 2.7 3.1 -23 -20 -21 3 1 - 5 A1 [48] B1 [50; 24] C1 [300] P 0 -7.9 -8.0 -7.9 0.1 0.0 -25 -24 -26 1 1 + 6 A1 [48] B1 [50; 24] C2 [300] P > 1 -8.0 -8.3 -7.4 0.7 0.6 -26 -26 -25 0 1 + 7 A1 [48] B1 [50; 24] NW [300] P 0 -7.8 -8.1 -8.0 0.3 0.2 -27 -26 -27 1 0 + 8 A1 [48] B1 [50; 24] C4 [300] P 1 -7.9 -8.1 -7.5 0.2 0.4 -26 -25 -26 1 0 + 9 A1 [48] VZ [50; 24] C4 [300] P 1 -8.0 -8.5 -7.3 0.5 0.7 -25 -25 -24 0 1 + As an additional flow improver, the test fuel contained a 320 ppm mixture containing 3.5 parts by weight. G3, 1 part by weight D2, 1 part by weight F2 and 1 part by weight El (CFI6; density at 40°C = 0.90 g/cm ³ ). The storage temperature was -18°C and the storage duration was 24 hours. CLAIM 1. Fuel oil having a sulfur content of less than 50 ppm, containing fuel of mineral origin, or synthetic fuel obtained by catalytic hydrodeoxygenation of vegetable oils and fats or animal fats, or synthetic fuel obtained by Fischer-Tropsch synthesis, or a mixture thereof, optionally containing: i. at least one oil-soluble amido-ammonium salt (A) of a polycarboxylic acid with mono- and/or dialkylamine; and ii. 5-100 wt.% oil-soluble amine (B) based on the amount of ammonium ammonium salt (A); and iii. a lubricant (C) selected from fatty acids, partial esters of fatty acids with polyols and amides of fatty acids with alkanolamides, wherein the fatty acid has 10-28 carbon atoms. 2. The fuel oil according to claim 1, wherein the polycarboxylic acid is selected from monomeric dicarboxylic acids, monomeric polycarboxylic acids and copolymerized dicarboxylic acids. 3. Fuel oil according to claim 1 or 2, wherein said fuel oil contains from 1 to 95 wt.% ammonium salt (A). 4. Fuel oil according to any one of claims 1 to 3, wherein the oil-soluble amine (B) has the formula (1) - 20 045457 in which R ⁴ represents an alkyl radical containing from 8 to 22 carbon atoms, or a group of the formula -(CH ₂ ) _n -[NR ⁷ -(CH ₂ ) _n ] _m -NH ₂ , R ⁵ represents hydrogen, an alkyl radical containing from 1 to 22 carbon atoms, or a group of the formula -(CH2)n-[NR ⁷ -(CH2) _n ]m-NH ₂ R ⁶ represents hydrogen or an alkyl radical containing from 1 to 22 carbon atoms, R ⁷ represents hydrogen or an alkyl radical containing from 1 to 22 carbon atoms, n is 2 or 3, and m is from 0 to 10. 5. Fuel oil according to any one of claims 1 to 4, wherein said fuel oil contains from 15 to 70 wt.%, and preferably from 20 to 50 wt.% oil-soluble amine (B) based on the amount of ammonium ammonium salt (A ). 6. Fuel oil according to any one of claims 1 to 5, wherein the oil-soluble amine (B) is a primary, secondary or tertiary fatty amine. 7. Fuel oil according to any one of claims 4-6, in which in formula (1) R ⁴ represents an alkyl radical containing from 8 to 22 carbon atoms, R ⁵ represents hydrogen or an alkyl radical containing from 1 to 22 carbon atoms, and R ⁶ represents hydrogen or an alkyl radical containing from 1 to 22 carbon atoms. 8. Fuel oil according to any one of claims 1 to 7, wherein the oil-soluble amine (B) contains at least one alkyl radical containing from 10 to 22 carbon atoms. 9. Fuel oil according to any one of claims 1 to 5 or 8, wherein the oil-soluble amine (B) is a polyamine. 10. Fuel oil according to any one of claims 1 to 9, wherein said fuel oil further contains an alkylphenol resin and/or a hydroxybenzoate resin (D). 11. Fuel oil according to any one of claims 1 to 10, wherein said fuel oil further contains a polyoxyalkylene compound (E). 12. Fuel oil according to any one of claims 1 to 11, wherein said fuel oil further comprises a comb polymer (F). 13. Fuel oil according to any one of claims 1 to 12, wherein said fuel oil further contains an ethylene copolymer (G). 14. Fuel oil according to any one of claims 1 to 13, wherein the sulfur content of the fuel is less than 20 ppm and particularly preferably less than 10 ppm. 15. Fuel oil according to any one of claims 1 to 14, wherein said fuel oil is a middle distillate. 16. Fuel oil according to any one of claims 1 to 15, wherein said fuel oil is diesel fuel or heating oil. 17. Fuel oil according to any one of claims 1 to 16, which further contains one or more additional additives selected from cold flow improvers, dewaxing auxiliaries, detergent additives, antioxidants, cetane number improvers, haze inhibitors , anti-emulsifiers, foam inhibitors, dyes, corrosion inhibitors, sediment reducers, odorants and/or cloud point reducers. 18. Use of a low-temperature additive containing: i. at least one oil-soluble amido-ammonium salt (A) of a polycarboxylic acid with mono- and/or dialkylamine; and ii. 5-100 wt.% oil-soluble amine (B) based on the amount of ammonium salt (A), to improve the low-temperature properties of a fuel oil having a sulfur content of less than 50 ppm, containing a lubricant additive (C) selected from fatty acids acids, partial esters of fatty acids with polyols and amides of fatty acids with alkanolamides, wherein the fatty acid has 10-28 carbon atoms, and the fuel oil consists of fuel of mineral origin, or synthetic fuel obtained by catalytic hydrodeoxygenation of vegetable oils and fats or animal fats , or synthetic fuel obtained by Fischer-Tropsch synthesis. 19. The use of oil-soluble amine (B) to improve the low-temperature properties of fuel oil having a sulfur content of less than 50 ppm, containing: i. at least one oil-soluble amido-ammonium salt (A) of a polycarboxylic acid with mono- and/or dialkylamine; and iii. lubricant additive (C) selected from fatty acids, partial esters of fatty acids - 21 045457 acids with polyols and fatty acid amides with alkanolamides, wherein the fatty acid has 10-28 carbon atoms, and the amount of oil-soluble amine (B) is 5-100 wt.% based on the amount of ammonium ammonium salt (A), wherein the fuel oil consists of fuel of mineral origin, or synthetic fuel obtained by catalytic hydrodeoxygenation of vegetable oils and fats or animal fats, or synthetic fuel obtained by Fischer-Tropsch synthesis. 20. Use according to claim 19, wherein the lubricant (C) is a fatty acid having 10 to 28 carbon atoms. 21. Application according to any one of paragraphs. 18-20, in which 15 to 70 wt.% and preferably 20 to 50 wt.% of oil-soluble amine (B) are added based on the amount of ammonium ammonium salt (A). 22. A method for improving the low-temperature properties of a fuel oil having a sulfur content of less than 50 ppm, containing a lubricant additive (C) selected from fatty acids, partial esters of fatty acids with polyols and fatty acid amides with alkanolamides, wherein the fatty acid has 10-28 carbon atoms, due to the addition of a low-temperature additive to the fuel oil containing: i. at least one oil-soluble amido-ammonium salt (A) of a polycarboxylic acid with mono- and/or dialkylamine; and ii. 5-100 wt.% oil-soluble amine (B) based on the amount of ammonium salt (A), wherein the fuel oil consists of fuel of mineral origin, or synthetic fuel obtained by catalytic hydrodeoxygenation of vegetable oils and fats or animal fats, or synthetic fuel , obtained by Fischer-Tropsch synthesis. 23. The method according to claim 22, wherein the fuel oil contains from 50 to 1000 ppm of lubricating additive (C). 24. The method according to claim 22 or 23, wherein the lubricating additive (C) is a fatty acid having 10-28 carbon atoms. 25. A method for improving the response characteristics of a fuel oil containing a lubricating additive (C) and having a sulfur content of less than 50 ppm to the addition of ammonium amido salt (A), characterized in that from 5 to 100 wt. are added to the fuel oil. % oil-soluble amine (B) based on ammonium ammonium salt (A), wherein the lubricating additive (C) is selected from fatty acids, partial esters of fatty acids with polyols and fatty acid amides with alkanolamides, wherein the fatty acid has 10-28 carbon atoms, and wherein the fuel oil consists of a fuel of mineral origin, or a synthetic fuel obtained by the catalytic hydrodeoxygenation of vegetable oils and fats or animal fats, or a synthetic fuel obtained by Fischer-Tropsch synthesis, whereby by improving response characteristics it is meant that at least one low temperature property of a fuel oil which has been or can be imparted by the presence of an ammonium salt (A) and has been impaired by the addition of a lubricant (C) is improved or restored by the addition of an oil-soluble amine (B). Eurasian Patent Organization, EAPO Russia, 109012, Moscow, Maly Cherkassky lane, 2