EP0857776B2 - Mineral oil and mineral oil distillate flowability improvement using alkylphenol-aldehyde resins - Google Patents

Abstract

Process for improving the flowability of paraffin-containing mineral oil (distillates) comprises reacting them with (A) ethylene/vinyl ester co- or ter-polymer, (B) alkyl phenol-aldehyde resin containing 10% alkyl phenols and more than one alkyl groups, and opt. (C) a paraffin dispersant different from B. A mixture containing (B) and (C) and a mixture containing (A), (B), and (C) are also claimed.

Description

The invention relates to a process for improving the flowability of paraffin-containing mineral oils and mineral oil distillates by adding flow improvers based on ethylene-vinyl ester copolymers and terpolymers, alkylphenol-aldehyde resins and optionally further paraffin dispersants.

Depending on the origin of the crude oils, crude oils and middle distillates obtained by distillation of crude oils, such as gas oil, diesel oil or fuel oil, contain different amounts of n-paraffins which crystallize out as platelet-shaped crystals when the temperature is lowered and partly agglomerate with the inclusion of oil. As a result of this crystallization and agglomeration, the flow properties of the oils or distillates deteriorate, which can lead to disruptions in the extraction, transport, storage and / or use of the mineral oils and mineral oil distillates. When transporting mineral oils through pipelines, the phenomenon of crystallization, especially in winter, can lead to deposits on the pipe walls, in individual cases, e.g. at standstill of a pipeline, even lead to their complete blockage. During storage and further processing of the mineral oils, it may also be necessary in winter to store the mineral oils in heated tanks. In the case of mineral oil distillates, as a result of the crystallization, blockages of the filters in diesel engines and firing systems may occur, as a result of which reliable metering of the fuels is prevented and, under certain circumstances, a complete interruption of the fuel or heating agent supply occurs.

In addition to the classical methods for removing the crystallized paraffins (thermal, mechanical or with solvents), which relate only to the removal of already formed precipitates, chemical additives (so-called flow improvers) have been developed in recent years. These cause physical interaction with the precipitated paraffin crystals that their shape, size and adhesion properties are modified. The additives act as additional nuclei and partially crystallize out with the paraffins, resulting in a larger number of smaller paraffin crystals with altered crystal form. The modified paraffin crystals are less prone to agglomeration, so that the oils added with these additives can still be pumped or processed at temperatures that are often more than 20 ° lower than with non-additive oils.

Typical flow improvers for crude oils and middle distillates are copolymers and terpolymers of ethylene with carboxylic acid esters of vinyl alcohol.

Another object of flow improver additives is the dispersion of paraffin crystals, i. the delay or prevention of the sedimentation of paraffin crystals and thus the formation of a paraffin-rich layer at the bottom of storage containers.

Various paraffin dispersants of both monomeric and polymeric structure are known.

Examples of monomeric paraffin dispersants which are known from EP-A-0 413 279 are reaction products of alkenyl spiro-bis-lactones with amines. Furthermore, EP-A-0 061 894 discloses oil-soluble nitrogen-containing compounds, e.g. Reaction products of phthalic anhydride with amines described, which are used in admixture with ethylene-vinyl acetate copolymers. Furthermore, from EP-A-0 597 278 reaction products of aminoalkylenecarboxylic acids with primary or secondary amines are known.

As polymeric paraffin dispersants, for example, the following are described in the literature.

EP-A-0 688 796 discloses copolymers based on α, β-unsaturated olefins having at least 3 C atoms and α, β-unsaturated dicarboxylic acid anhydrides, the dicarboxylic anhydride units being prepared by polymer-analogous reaction with polyetheramines or alkanolamines in imide, Amide or ammonium units are transferred.

Further, EP-A-0 606 055 discloses terpolymers based on α, β-unsaturated dicarboxylic acid anhydrides, α, β-unsaturated compounds and polyoxyalkylene ethers of lower, unsaturated alcohols and their use as paraffin inhibitors for paraffinic petroleum products.

EP-A-0 154 177 describes reaction products of alternating copolymers based on maleic anhydride and α, β-unsaturated compounds with primary monoalkylamines and aliphatic alcohols. These copolymers are particularly useful as paraffin inhibitors of paraffinic petroleum products, for example, crude oils and distillation residues from petroleum processing.

EP-A-0 436 151 discloses reaction products of copolymers based on maleic anhydride and α, β-unsaturated compounds with dialkylamines.

EP-A-0 283 293 discloses copolymers based on aliphatic olefins and maleic anhydride, which copolymer must have both ester and amide groups, each containing an alkyl group of at least 10 carbon atoms, and copolymers obtained by reacting a secondary amine with a polymer containing anhydride groups, wherein the anhydride groups in equal parts amides or ammonium salts.

These paraffin dispersants are usually used together with other flow improvers, in particular ethylene-vinyl ester copolymers.

From WO 93/14178 it is also known that the cold flow properties of mineral oils and mineral oil distillates can be significantly improved by using known as flow improvers known polyaddition products (eg ethylene / vinyl ester copolymers) or polycondensation products in combination with so-called Emulsionsspaltem.

These emulsion breakers have the ability to break an oil / water emulsion to form separate oil and water phases. They must therefore contain both hydrophobic and hydrophilic structural units in order to dissolve sufficiently in the oil of the oil / water emulsion on the one hand, in order to split the latter, and on the other hand to enrich after the phase separation in the aqueous phase.

As emulsion breakers with flow-improving / paraffin-inhibiting action, according to WO 93/14178, oxalkylated alkylphenol-formaldehyde resins are suitable. In this case, the oxalkyl side chain representing the hydrophilic structural portion contains up to 50 oxalkyl units, each having 2-6 C atoms.

EP-A-0 311 452 discloses condensation products of at least 80 mole% of difunctional, alkylated phenol and aldehydes comprising from 1 to 30 carbon atoms as flow improvers for mineral oils. The use of condensation products of monoalkylated phenols with aldehydes as flow improvers or paraffin dispersants is not disclosed.

The paraffin-dispersing effect of the known paraffin dispersants described above is not always sufficient, so that on cooling the oils sometimes form large paraffin crystals, which sediment over time due to their higher density and thus lead to the formation of a paraffin-rich layer at the bottom of Lagerbehältem , Problems occur especially in the addition of paraffin-rich narrow distillation cuts with boiling ranges of 20-90% by volume less than 110 ° C, especially less than 100 ° C. Even with distillates with more than 20 ° C, especially more than 25 ° C large difference in temperature between the boiling point and the temperature at which distilled 90% by volume, can be achieved by the addition of known additives often no sufficient paraffin dispersion.

It was therefore an object to improve the flowability, in particular the paraffin dispersion in mineral oils or mineral oil distillates by the addition of suitable additives.

Furthermore, the solubility of paraffin-dispersing polar nitrogen compounds in the paraffinic or aromatic solvents is often unsatisfactory. The object was therefore also to find a solubilizer between the polar nitrogen compounds and the paraffinic or aromatic solvents.

Surprisingly, it has been found that alkylphenol-aldehyde resins, which themselves have a paraffin-dispersing action, are excellent solubilizers between these substances.

The invention relates to a process for improving the flowability of paraffin-containing mineral oils and mineral oil distillates, according to claim 1.

The alkylphenols are preferably para-substituted. They are preferably substituted at most 7 mol%, in particular at most 3 mol%, with more than one alkyl group.

The use of the alkylphenol-aldehyde resins B in combination with the ethylene / vinyl ester co- / terpolymers A and optionally the paraffin dispersants C other than B has a positive effect on the paraffin dispersion, i. the accumulation of paraffin crystals precipitated on cooling, e.g. on the tank bottom or the fuel filter, is delayed or prevented. As a result of the uniform dispersion of the paraffin crystals, a homogeneously turbid phase is obtained. There is also an improvement in the cold flow properties, in particular the filterability of the additized paraffinic mineral oils and in particular mineral oil distillates below the cloud point.

1. A) mit 10 - 5000 ppm, bevorzugt 10 - 2000 ppm, bezogen auf das Mineralöl bzw. Mineralöldestillat, mindestens eines Ethylenvinylester-Co- oder -Terpolymeren,
2. B) 10 - 2000 ppm, bevorzugt 10 - 1000 ppm, bezogen auf das Mineralöl bzw. Mineralöldestillat, mindestens eines Alkylphenol-Aldehyd-Harzes und gegebenenfalls
3. C) bis zu 2000 ppm, bevorzugt bis zu 1000 ppm, bezogen auf das Mineralöl bzw. Mineralöldestillat mindestens eines von B verschiedenen Paraffin-Dispergators, versetzt.

A preferred embodiment of the method according to the invention is characterized in that the paraffin-containing mineral oil or mineral oil distillate

1. A) with 10 - 5000 ppm, preferably 10 - 2000 ppm, based on the mineral oil or mineral oil distillate, of at least one ethylene vinyl ester co- or terpolymer,
2. B) 10 - 2000 ppm, preferably 10 - 1000 ppm, based on the mineral oil or mineral oil distillate, of at least one alkylphenol-aldehyde resin and optionally
3. C) up to 2000 ppm, preferably up to 1000 ppm, based on the mineral oil or mineral oil distillate of at least one of B different paraffin dispersant added.

The additives A, B and, if appropriate, C may be the paraffin-containing mineral oils or mineral oil distillates be added separately.

• B) 10 - 90 Gew.-% mindestens eines der oben genannten Alkylphenol-Aldehyd-Harzes und
• C) 90 - 10 Gew.-% mindestens eines der oben genannten von B verschiedenen Paraffin-Dispergatoren,

wobei die Summe der Additive B und C immer 100 Gew.-% beträgt. Additiv B kann dabei auch lösevermittelnd für Additiv C in organischen Lösemitteln wirken.Alternatively, one can add the additive A individually and the additives B and C in a mixture. Such mixtures contain

• B) 10 - 90 wt .-% of at least one of the above-mentioned alkylphenol-aldehyde resin and
• C) 90-10% by weight of at least one of the abovementioned paraffin dispersants other than B,

wherein the sum of the additives B and C is always 100 wt .-%. Additive B can also act as a solubilizer for additive C in organic solvents.

1. A) 5 - 90, vorzugsweise 10 - 90 Gew.-% mindestens eines Ethylen/Vinylester-Co- oder -Terpolymers,
2. B) 5 - 90, vorzugsweise 10 - 90 Gew.-% mindestens eines der oben genannten Alkylphenol-Aldehyd-Harzes sowie gegebenenfalls
3. C) 5 - 90, vorzugsweise 10 - 90 Gew.-% mindestens eines der oben genannten von B verschiedenen Paraffin-Dispergatoren,

wobei die Summe der Additive A, B sowie gegebenenfalls C immer 100 Gew.-% betragen muß.It is also possible that the mineral oil or mineral oil distillate with a common mixture of additives A, B and optionally C added. Such mixtures contain

1. A) from 5 to 90, preferably from 10 to 90,% by weight of at least one ethylene / vinyl ester co- or terpolymer,
2. B) 5-90, preferably 10-90 wt .-% of at least one of the above-mentioned alkylphenol-aldehyde resin and optionally
3. C) 5-90% by weight, preferably 10-90% by weight of at least one of the abovementioned paraffin dispersants other than B,

where the sum of the additives A, B and optionally C must always be 100 wt .-%.

In a preferred embodiment, the individual additives or the corresponding mixtures are dissolved or dispersed in an organic solvent or dispersion medium before addition to the mineral oils or mineral oil distillates. In the case of the mixture of additives A, B and optionally C and the mixture of additives B and C, the solution or dispersion contains 5-90, preferably 5-75 wt .-% of the respective mixture.

Suitable solvents or dispersants are aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, e.g. Gasoline fractions, kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or commercial solvent mixtures such as ®Solvent Naphtha, ®Shellsol AB, ®Solvesso 150, ®Solvesso 200, ®Exxsol, ®ISOPAR and Shellsol D types.

Optionally, polar solubilizers such as 2-ethylhexanol, decanol, iso-decanol or iso-tridecanol can be added.

The invention further mineral oils or mineral oil distillates, according to claim 13.

1. A) 10 - 5000 ppm, bevorzugt 10-2000 ppm mindestens eines Ethylenvinylester-Co- oder -Terpolymeren,
2. B) 10 - 2000 ppm, bevorzugt 10-1000 ppm mindestens eines der oben gennanten Alkylphenol-Aldehyd-Harzes und gegebenenfalls
3. C) bis zu 2000 ppm, bevorzugt bis zu 1000 ppm mindestens eines der oben genannten von B verschiedenen Paraffin-Dispergatoren enthalten.

Preference is given to mineral oils or mineral oil distillates, the

1. A) 10 to 5000 ppm, preferably 10 to 2000 ppm of at least one ethylene vinyl ester co- or terpolymer,
2. B) 10 - 2000 ppm, preferably 10-1000 ppm of at least one of the above-mentioned alkylphenol-aldehyde resin and optionally
3. C) up to 2000 ppm, preferably up to 1000 ppm, of at least one of the abovementioned paraffin dispersants other than B,

The mineral oils or mineral oil distillates may also contain other conventional additives such as dewaxing aids, corrosion inhibitors, antioxidants, lubricity additives, sludge inhibitors, Cetanzahlverbesserer, detergent additives, dehazers, conductivity improvers or dyes.

The invention further provides an additive mixture for paraffin dispersion in paraffin-containing mineral oils and mineral oil distillates containing at least one paraffin dispersant and at least one aliphatic or aromatic liquid hydrocarbon as solvent, characterized in that at least one alkylphenol-aldehyde resin is added as a solubilizer.

Another object of the invention is a process for the preparation of solutions of paraffin dispersants in aliphatic or aromatic liquid hydrocarbons by adding an alkylphenol-aldehyde resin to the mixture of these substances.

Alkylphenol-aldehyde resins B are known in principle and, for example, in Römpp Chemie Lexikon, 9th edition, Thieme Verlag 1988-92, Volume 4, p 3351ff. described.

The alkyl radicals of the o- or p-alkylphenol especially have 6-12 carbon atoms; it is preferably n-, iso- and tert. Butyl, n- and iso-pentyl, n- and iso-hexyl, n- and iso-octyl, n- and iso-nonyl, n- and iso-decyl, n- and iso-dodecyl. The alkylphenol-aldehyde may also contain up to 50 mol% phenol units. For the alkylphenol-aldehyde resin, the same or different alkylphenols may be used. The aliphatic aldehyde in the alkylphenol-aldehyde resin B has 1-4 carbon atoms and is preferably formaldehyde. The molecular weight of the alkylphenol-aldehyde resins is 400-10,000, preferably 400-5,000, g / mol. requirement here is that the resins are oil-soluble.

The preparation of the alkylphenol-aldehyde resins B takes place in a known manner by basic catalysis, resulting in condensation products of the resol type, or by acid catalysis, resulting in condensation products of the novolac type.

The condensates obtained according to both types are suitable as additives B in the process according to the invention. Preferably, the condensation is in the presence of acidic catalysts.

For the preparation of the alkylphenol-aldehyde resins are a bifunctional o- or p-alkylphenol having 4 to 12 carbon atoms, in particular 6 to 12 carbon atoms per alkyl group, or mixtures thereof and an aliphatic aldehyde having 1 to 4 carbon atoms with each other reacted, wherein per mole of alkylphenol about 0.5 to 2 mol, preferably 0.7 to 1.3 mol and in particular equimolar amounts of aldehyde are used.

Suitable alkylphenols are C ₄ -C ₁₂ -alkylphenols such as, for example, o- or p-cresol, n-, sec- and tert. Butylphenol, n- and i-pentylphenol, n- and iso-hexylphenol, n- and iso-octylphenol, n- and iso-nonylphenol, n- and iso-decylphenol, n- and iso-dodecylphenol

The alkylphenols to be used may contain small amounts, preferably up to about 10 mol%, in particular up to 7 mol% and especially up to 3 mol% of dialkylphenols.

Particularly suitable aldehydes are formaldehyde, acetaldehyde and butyraldehyde, with formaldehyde being preferred.

The formaldehyde may be used in the form of paraformaldehyde or in the form of a preferably 20-40% by weight aqueous formalin solution. Corresponding amounts of trioxane can also be used.

The reaction of alkylphenol and aldehyde is usually carried out in the presence of alkaline catalysts, for example alkali metal hydroxides or alkylamines, or of acidic catalysts, for example inorganic or organic acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, sulfonic acid, sulfamido acids or haloacetic acids, and in the presence of one with water Azeotrope-forming organic solvent, for example toluene, xylene, higher aromatics or mixtures thereof. The reaction mixture is heated to a temperature of 90 to 200 ° C, preferably 100 to 160 ° C, wherein the resulting reaction water is removed during the reaction by azeotropic distillation. Solvents that do not release protons under condensation conditions may remain in the products after the condensation reaction. The resins may be used directly or after neutralization of the catalyst, optionally after further dilution of the solution with aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, e.g. Gasoline fractions, kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or solvents such as ®Solvent Naphtha, ®Shellsol AB, ®Solvesso 150, ®Solvesso 200, ®Exxsol, ®ISOPAR and Shellsol D types.

• Ethylen-Vinylacetat-Copolymere mit 10 - 40 Gew.-% Vinylacetat und 60 - 90 Gew.-% Ethylen;
• Die aus der DE-OS 34 43 475 bekannten Ethylen-Vinylacetat-Hexen-Terpolymere;
• Die in der EP-B-0 203 554 beschriebenen Ethylen-Vinylacetat-Diisobutylen-Terpolymere;
• Die aus der EP-B-0 254 284 bekannte Mischung aus einem Ethylen-Vinylacetat-Diisobutylen-Terpolymerisat und einem EthylenNinylacetat-Copolymer;
• Die in der EP-B-0 405 270 offenbarten Mischungen aus einem Ethylen-Vinylacetat-Copolymer und einem Ethylen-Vinylacetat-N-Vinylpyrrolidon-Terpolymerisat;
• Die in der EP-B-0 463 518 beschriebenen Ethylen/Vinylacetat/iso-Butylvinylether-Terpolymere;
• Die in der EP-B-0 491 225 offenbarten Mischpolymerisate des Ethylens mit Alkylcarbonsäurevinylestern;
• Die aus der EP-B-0 493 769 bekannten Ethylen/Vinylacetat/Neononansäurevinylester bzw. Neodecansäurevinylester-Terpolymere, die außer Ethylen 10 - 35 Gew.-% Vinylacetat und 1 - 25 Gew.-% der jeweiligen Neoverbindung enthalten;
• Die in DE-A-196 20 118. beschriebenen Terpolymere aus Ethylen, dem Vinylester einer oder mehrerer aliphatischer C₂ - C₂₀-Monocarbonsäuren und 4-Methylpenten-1;
• Die in DE-A-196 20 119 offenbarten Terpolymere aus Ethylen, dem Vinylester einer oder mehrerer aliphatischer C₂ - C₂₀-Monocarbonsäuren und Bicyclo[2.2.1]hept-2-en.

As ethylene / vinyl ester copolymers or terpolymers A, it is possible to use all known copolymers or terpolymers of this type which, taken alone, improve the cold flow properties of mineral oils or mineral oil distillates. Suitable copolymers or terpolymers A include, for example:

• Ethylene-vinyl acetate copolymers with 10-40% by weight of vinyl acetate and 60-90% by weight of ethylene;
• The known from DE-OS 34 43 475 ethylene-vinyl acetate-hexene terpolymers;
• The ethylene-vinyl acetate-diisobutylene terpolymers described in EP-B-0 203 554;
• The mixture known from EP-B-0 254 284 comprising an ethylene-vinyl acetate-diisobutylene terpolymer and an ethylene-vinyl acetate copolymer;
• The blends of an ethylene-vinyl acetate copolymer and an ethylene-vinyl acetate-N-vinylpyrrolidone terpolymer disclosed in EP-B-0 405 270;
• The ethylene / vinyl acetate / isobutyl vinyl ether terpolymers described in EP-B-0 463 518;
• The copolymers of ethylene with alkylcarboxylic acid vinyl esters disclosed in EP-B-0 491 225;
• The ethylene / vinyl acetate / vinyl neononanoate or vinyl neodecanoate terpolymers known from EP-B-0 493 769, which contain, in addition to ethylene, 10-35% by weight of vinyl acetate and 1-25% by weight of the respective neo compound;
• The terpolymers of ethylene, the vinyl ester of one or more aliphatic C ₂ -C ₂₀ monocarboxylic acids and 4-methylpentene-1 described in DE-A-196 20 118.
• The terpolymers of ethylene, the vinyl ester of one or more aliphatic C ₂ -C ₂₀ monocarboxylic acids and bicyclo [2.2.1] hept-2-ene disclosed in DE-A-196 20 119.

Preferred are such ethylene-vinyl ester copolymers or terpolymers having an ethylene content of 60-90% by weight.

• eine oder mehrere mit mindestens einer C₈ - C₂₆-Alkylkette substituierte Ester-, Amid- und/oder Imidgruppen enthalten
• und/oder eine oder mehrere Ammoniumgruppen tragen, die sich von Aminen mit einer oder zwei C₈ - C₂₆ Alkylgruppen ableiten.

As B different paraffin dispersants C are polar, low molecular weight or polymeric, oil-soluble nitrogen compounds suitable, the

• one or more with at least one C ₈ - C ₂₆ alkyl chain substituted ester, amide and / or imide groups
• and / or carry one or more ammonium groups derived from amines having one or two C ₈ -C ₂₆ alkyl groups.

As monomeric polar nitrogen-containing compounds according to claim 1 C, for example, the following substances can be used.

EP-A-0 413 279 describes suitable reaction products of alkenyl spiro-bis-lactones with amines.

Also, the oil-soluble reaction products of phthalic anhydride with amines disclosed in EP-A-0 061 894 can be used in admixture with ethylene-vinyl acetate copolymers.

Furthermore, the reaction products of aminoalkylenecarboxylic acids with primary or secondary amines known from EP-A-0 597 278 are suitable as monomeric nitrogen-containing compounds according to claim 1 C.

As polymeric polar nitrogen-containing compounds according to claim 1 C, preference is given to using copolymers or terpolymers based on α, β-unsaturated compounds and maleic acid. Suitable examples are:

The terpolymers described in EP-A-0 606 055 based on α, β-unsaturated dicarboxylic acid anhydrides, α, β-unsaturated compounds and polyoxyalkylene ethers of lower, unsaturated alcohols;

The reaction products of alternating copolymers based on α, β-unsaturated compounds and maleic anhydride known from EP-A-0 154 177 with primary monoalkylamines and aliphatic alcohols;

The statistical co- and terpolymers described in DE-A-196 45 603 based on ethylene, α, β-unsaturated dicarboxylic anhydrides and optionally further α, β-unsaturated compounds, wherein the dicarboxylic anhydride units are present in a high proportion as imide units and in lesser Proportion as amide / ammonium salt units;

The copolymers based on α, β-unsaturated olefins having at least 3 C atoms and α, β-unsaturated dicarboxylic acid anhydrides known from EP-A-0 688 796, where the dicarboxylic acid anhydride units are prepared by polymer-analogous reaction with polyetheramines or alkanolamines in imide, Amide and ammonium units were transferred;

The reaction products of copolymers based on maleic anhydride and α, β-unsaturated compounds such as styrene with dialkylamines known from EP-A-0 436 151;

The copolymers based on aliphatic olefins and maleic anhydride disclosed in EP-A-0 283 293, which copolymer has both ester and amide groups, each containing an alkyl group of at least 10 carbon atoms.

The same applies equally to all three additives A, B and C: as additive A it is also possible to use mixtures of different ethylene vinyl ester copolymers or terpolymers which have a different qualitative and / or quantitative composition and / or different (measured at 140 ° C.) Have viscosities. As additive B, mixtures of alkylphenol-aldehyde resins are also usable which contain various alkylphenols and / or aldehydes as components. Similarly, mixtures of several of B different paraffin dispersants C can be used. In this way, the flow improvers can be adapted to individual requirements.

With the additives A, B and, if appropriate, C oils of animal, vegetable or mineral origin can be added in the process according to the invention.

Paraffin-containing mineral oils and mineral oil distillates in the context of the invention are, for example, crude oils, petroleum refining residues or other paraffin-containing oils. (See, for example, Compositions and Properties of Petroleum, F. Enke Publishers, Stuttgart 1981, page 1-37). Paraffin-containing mineral oil products, especially middle distillates such as jet fuel, diesel, fuel oil EL and heavy fuel oil are characterized by a boiling range of 120-500 ° C, preferably 150-400 ° C. The paraffins are straight-chain or branched alkanes having about 10 to 50 carbon atoms.

Examples Paraffin dispersion in middle distillates

1. A) Ethylen-Vinylester-Terpolymere (Fl)
   1. A1) Ethylen-Vinylacetat-Versaticsäurevinylester-Terpolymer mit ca. 31 Gew.-% Vinylacetat und einer bei 140°C gemessenen Schmelzviskosität von 110 mPas, 50%ig in Kerosin.
   2. A2) Ethylen-Vinylacetat-Versaticsäurevinylester-Terpolymer mit ca. 31 Gew.-% Vinylacetat und einer bei 140°C gemessenen Schmelzviskosität von 280 mPas, 50%ig in Kerosin.
   3. A3) Ethylen-Vinylacetat-Versaticsäurevinylester-Terpolymer mit ca. 31.5 Gew.-% Vinylacetat und einer bei 140°C gemessenen Schmelzviskosität von 170 mPas, 55%ig in Kerosin.
   4. A4) Mischung von 2 Teilen des Terpolymers gemäß Beispiel A1 und 1 Teil des Terpolymers gemäß Beispiel A2
2. B) Alkylphenol-Aldehyd-Harze (PD)
   1. B1) Nonylphenol-Formaldehyd-Harz
      Zur Herstellung dieses Formaldehyd-Harzes wurde p-Nonylphenol in Gegenwart katalytischer Mengen Alkylbenzolsulfonsäure mit einer äquimolaren Menge einer 35 Gew.-%igen Formalinlösung zur Reaktion gebracht, das Reaktionsgemisch durch Auskreisen mit einer Mischung höher siedender aromatischer Kohlenwasserstoffe (Siedebereich 185-215°C) vom Wasser befreit und mit Kaliumhydroxid neutralisiert. Das rotbraune Harz wurde in ®Solvent Naphtha auf einen Feststoffgehalt von 50% verdünnt. Das gelchromatographisch bestimmte Molekulargewicht (Eichung gegen Polystyrol-Standards) liegt bei 2000 g/mol.
   2. B2) Nonyl-Butylphenol-Formaldehyd-Harz
      Analog zu Beispiel B1 wurden äquimolare Mengen Nonylphenol und Butylphenol unter saurer Katalyse mit Formaldehyd kondensiert. Das Molekulargewicht des rotbraunen Harzes liegt bei 1800 g/mol.
   3. B3) (Vergleichsbeispiel)
      Mit 5,5 mol Ethylenoxid unter saurer Katalyse umgesetztes Nonylphenol-Formaldehydharz gemäß Beispiel B1, 50%ig in Solvent Naphtha.
   4. B4) Analog Beispiel B1 unter saurer Katalyse aus Dodecylphenol hergestelltes Harz
   5. B5) Mit NaOH neutralisiertes Harz gemäß B4
   6. B6) Analog Beispiel B1 unter saurer Katalyse aus equimolarer Mengen Phenol und Nonylphenol hergestelltes Harz.
   7. B7) In Anlehnung an Beispiel B1 werden equimolare Mengen Nonylphenol und Formalinlösung in Gegenwart katalytischer Mengen KOH zur Reaktion gebracht.
3. C) Polare stickstoffhaltige Verbindungen (PN)
   1. C1) Umsetzungsprodukt eines Terpolymers aus einem C_14/16-α-Olefin, Maleinsäureanhydrid und Allylpolyglykol mit 2 Äquivalenten Ditalgfettamin, 50%ig in Solvent Naphtha (hergestellt gemäß EP-A-0606055).
   2. C2) Umsetzungsprodukt eines Dodecenyl-Spirobislactons mit einer Mischung aus primärem und sekundärem Talgfettamin, 60 %ig in Solvent Naphtha (hergestellt gemäß EP-A-0413279).

The following substances were used as additives A, B and C in Examples 1 to 63:

1. A) Ethylene Vinyl Ester Terpolymers (Fl)
   1. A1) ethylene-vinyl acetate-Versaticsäurevinylester terpolymer with about 31 wt .-% vinyl acetate and a measured at 140 ° C melt viscosity of 110 mPas, 50% in kerosene.
   2. A2) Ethylene vinyl acetate Versaticsäureesterester terpolymer with about 31 wt .-% vinyl acetate and measured at 140 ° C melt viscosity of 280 mPas, 50% in kerosene.
   3. A3) Ethylene vinyl acetate Versaticsäureesterester terpolymer with about 31.5 wt .-% vinyl acetate and a measured at 140 ° C melt viscosity of 170 mPas, 55% in kerosene.
   4. A4) Mixture of 2 parts of the terpolymer according to Example A1 and 1 part of the terpolymer according to Example A2
2. B) Alkylphenol-Aldehyde Resins (PD)
   1. B1) nonylphenol-formaldehyde resin
      To prepare this formaldehyde resin, p-nonylphenol was reacted in the presence of catalytic amounts of alkylbenzenesulfonic acid with an equimolar amount of a 35% strength by weight formalin solution, and the reaction mixture was removed by centrifuging with a mixture of higher-boiling aromatic hydrocarbons (boiling range 185-215 ° C.). freed from water and neutralized with potassium hydroxide. The reddish-brown resin was diluted to a solids content of 50% in ® Solvent Naphtha. Gelchromatographisch determined molecular weight (calibration against polystyrene standards) is 2000 g / mol.
   2. B2) Nonyl-butylphenol-formaldehyde resin
      Analogously to Example B1, equimolar amounts of nonylphenol and butylphenol were condensed under acidic catalysis with formaldehyde. The molecular weight of the red-brown resin is 1800 g / mol.
   3. B3) (comparative example)
      Nonylphenol-formaldehyde resin reacted with 5.5 mol of ethylene oxide under acid catalysis according to Example B1, 50% strength in solvent naphtha.
   4. B4) Resin produced analogously to Example B1 under acid catalysis from dodecylphenol
   5. B5) NaOH neutralized resin according to B4
   6. B6) Resin produced analogously to Example B1 under acid catalysis from equimolar amounts of phenol and nonylphenol.
   7. B7) Following Example B1, equimolar amounts of nonylphenol and formalin solution are reacted in the presence of catalytic amounts of KOH.
3. C) Polar nitrogen-containing compounds (PN)
   1. C1) Reaction product of a terpolymer of a C _14/16 α-olefin, maleic anhydride and allyl polyglycol with 2 equivalents of ditallow fatty amine, 50% in solvent naphtha (prepared according to EP-A-0606055).
   2. C2) Reaction product of a dodecenyl spirobislactone with a mixture of primary and secondary tallow fatty amine, 60% in solvent naphtha (prepared according to EP-A-0413279).

The addition of these additives A, B and C was to representative winter diesel fuels from German refineries, which are characterized in Table 1. The boiling analyzes were carried out according to ASTM D-86. Table 1: Characterization of the test oils test oil 1 2 3 4 5 6 7 8th Initial boiling point ° C 175 172 174 159 159 176 170 169 20% boiling point ° C 223 217 212 230 222 254 247 201 30% boiling point ° C 236 228 224 239 231 261 257 215 50% boiling point ° C 261 253 252 276 273 282 281 242 90% boiling point ° C 326 322 342 328 329 327 328 330 Boiling ° C 354 348 370 357 359 355 356 361 Cloud Point ° C -8.5 -9.9 -5.6 -6.0 -5.7 -6.7 -6.5 -5.6 CFPP ° C -12 -12 -10 -9 -9 -10 -10 -8th

The cold flow behavior was determined as follows:

The abovementioned test oils were admixed at room temperature with the amounts of the additives heated to 60 ° C. in Table 2, warmed to 40 ° C. for 15 minutes with occasional shaking and then cooled to room temperature. The CFPP value (cold filter plugging point) was determined in accordance with EN 116 from the middle distillate so additized.

The paraffin dispersion in middle distillates was detected in the short sediment test as follows:

150 ml of the middle distillates, which were additized as described above, were cooled to -13 ° C. in a cold cabinet at -2 ° C./hour in 200 ml graduated cylinders and stored at this temperature for 16 hours. Subsequently, the volume and appearance of both the sedimented paraffin phase and the overlying oil phase were determined and assessed visually. A small amount of sediment and a cloudy oil phase show a good paraffin dispersion.

In addition, the lower 20 vol% were isolated and the cloud point determined according to ISO 3015. Only a small deviation of the cloud point of the lower phase (CP _KS ) from the blank value of the oil shows a good paraffin dispersion.

For the following experiments, representative winter diesel fuels from German refineries were used. The middle distillates were added at room temperature with the specified amounts of the temperature-controlled to 60 ° C additives, heated for 15 minutes with occasional shaking at 40 ° C and then cooled to room temperature. The CFPP value of the thus-compounded middle distillate was determined according to EN 116.

The additized middle distillates were cooled to -13 ° C. in a cold cabinet at -2 ° C./hour in 200 ml graduated cylinders and stored at this temperature for 16 hours. Subsequently, the volume and appearance of both the sediment (paraffin phase) and the overlying oil phase were determined and assessed visually. A small amount of sediment and a cloudy oil phase show a good paraffin dispersion.

In addition, the lower 20 vol.% Were isolated and the cloud point determined. Only a small deviation of the cloud point of the lower phase (CP _KS ) from the blank value of the oil shows a good paraffin dispersion. Table 2: Activity as paraffin dispersant in test oil 1 Ex. FI Conc. PD Konz PN Konz CFPP sediment oil phase CP _KS ΔCP [Ppm] [Ppm] [Ppm] [° C] Vol .-% Vol .-% Appearance [° C] [° C] 1 A1 400 -24 51 49 clear -5.1 3.6 2 A1 400 B1 150 -23 0 100 cloudy -8.3 0.2 3 A1 400 B1 50 C1 100 -29 0 100 cloudy -8.3 0.2 4 A1 400 C1 150 -22 28 72 cloudy -0.5 8.0 5 A1 400 B2 75 C2 75 -25 47 53 clear with crystals -6.3 2.2 6 A1 400 B2 50 C2 100 -27 0 100 cloudy -8.3 0.2 7 A1 400 B3 150 -24 53 47 clear -5.0 3.5 8th A1 4001 83 75 C1 75 -27 37 63 clear -1.9 6.6 1, 4, 7, 8 = comparative examples Ex. FI Konz PD Konz PN Konz CFPP sediment oil phase CP _KS ΔCP [Ppm] [Ppm] [Ppm] [° C] Vol .-% Vol .-% Appearance [° C] [° C] 9 A1 400 -22 40 60 - clear -6.2 3.7 10 A1 600 -23 40 60 clear -6.0 3.9 11 A1 400 B1 200 -30 0 100 cloudy -7.3 2.6 12 A1 400 B1 67 C1 133 -32 0 100 cloudy -10.0 -0.1 13 A1 400 C1 150 -27 14 86 cloudy -6.0 3.9 14 A1 400 B1 30 C1 70 -32 0 100 cloudy -10.4 -0.5 15 A1 400 B2 50 C1 100 -32 0 100 cloudy -10.2 -0.3 16 A1 400 B4 67 C1 133 -33 0 100 cloudy -9.8 0.1 17 A1 400 B5 67 C1 133 -31 0 100 cloudy -10.2 -0.3 18 A1 400 B6 67 C1 133 -31 0 100 cloudy -9.7 -9.7 19 A1 400 B7 67 C1 133 -30 0 100 cloudy -9.0 0.9 9, 10, 13 = comparative examples Ex. FI Konz PD Konz PN Konz CFPP sediment oil phase CP _KS ΔCP [Ppm] [Ppm] [Ppm] [° C] Vol .-% Vol .-% Appearance [° C] [° C] 20 A2 200 -25 35 65 clear +4.0 9.6 21 A2 200 B1 150 -23 32 68 cloudy +1.0 6.6 22 A2 200 C1 150 -28 3 97 cloudy +3.0 8.6 23 A2 200 B1 50 C1 100 -29 0 100 cloudy -3.9 1.7 24 A2 200 B1 50 C2 100 -28 0 100 cloudy -3.5 2.1 25 A2 200 B1 50 C1 100 -29 9 91 clear 6.5 12.1 Ex. F1 Conc. PD Konz PN Konz CFPP sediment oil phase CP _KS ΔCP [Ppm] [Ppm] [Ppm] [° C] Vol .-% Vol .-% Appearance [° C] [° C] 26 A3 150 -21 25 75 clear +3.1 9.1 27 A3 300 -24 21 79 clear +3.4 9.4 28 A3 150 B1 150 -25 11 89 cloudy -2.5 3.5 29 A3 150 B1 100 C1 50 -24 0 100 cloudy -5.7 0.3 30 A3 150 B1 75 C1 75 -25 0 100 cloudy -5.0 1.0 31 A3 150 B1 50 C1 100 -27 0 100 cloudy -5.0 1.0 32 A3 150 C1 150 -25 22 88 cloudy -0.5 5.5 33 A3 150 B2 50 C1 100 -26 0 100 cloudy -5.5 0.5 20, 22, 26, 27, 32 = Comparative Examples Ex. FI Conc. PD Conc. PN Conc. CFPP sediment oil phase CP _KS ΔCP [Ppm] [Ppm] [Ppm] [° C] Vol .-% Vol .-% Appearance [° C] [° C] 34 A3 150 -19 31 75 cloudy +2.6 8.3 35 A3 300 -22 30 79 - cloudy +2.4 8.1 36 A3 150 B1 150 -21 15 89 cloudy -2.2 3.5 37 A3 150 B1 100 C1 50 -23 0 100 cloudy -4.8 0.9 38 A3 150 B1 75 C1 75 -25 0 100 cloudy -5.2 0.5 39 A3 150 B1 50 C1 100 -26 0 100 cloudy -4.9 0.8 40 A3 150 C1 150 -25 25 88 cloudy -0.5 6.2 41 A3 150 B2 50 C1 100 -25 1 99 cloudy -4.8 0.9 Ex. FI Konz PD Conc. PN Conc. CFPP sediment oil phase CP _KS ΔCP [Ppm] [Ppm] [Ppm] [° C] Vol .-% Vol .-% Appearance [° C] [° C] 42 A3 200 -18 25 75 clear +4.5 11.2 43 A3 350 -19 21 79 clear +3.9 10.6 44 A3 200 B1 150 -19 11 89 cloudy +1.0 7.7 45 A3 200 B1 100 C1 50 -20 0 100 cloudy -5.1 1.6 46 A3 200 B1 75 C1 75 -20 0 100 cloudy -4.8 -1.9 47 A3 200 B1 50 C1 100 -20 0 100 cloudy -5.0 1.7 48 A3 200 C1 150 -21 22 88 clear +3.2 9.9 49 A3 200 B2 50 C1 100 -20 0 100 cloudy -5.2 1.5 34, 35, 40, 42, 43 = Comparative Examples Ex. FI Conc. PD Conc. PN Conc. CFPP sediment oil phase CP _KS ΔCP [Ppm] [Ppm] [Ppm] [° C] Vol .-% Vol .-% Appearance [° C] [° C] 50 A3 200 -19 11 89 clear +4.2 10.7 51 A3 350 -20 12 88 clear +5.1 11.6 52 A3 200 B1 150 -19 35 65 cloudy +0.5 7 53 A3 200 B1 100 C1 50 -20 0 100 cloudy -4.6 1.9 54 A3 200 B1 75 C1 75 -20 0 100 cloudy -5.4 1.1 55 A3 200 B1 50 C1 100 -21 0 100 cloudy -5.0 1.5 56 A3 200 C1 150 -20 18 81 cloudy +3.1 8.6 57 A3 200 B2 50 C1 100 -20 0 100 cloudy -5.7 0.8 48, 50, 51, 56 = Comparative Examples Ex. FI Conc. PD Conc. PN Conc. CFPP sediment oil phase CP _KS ΔCP [Ppm] [Ppm] [Ppm] [° C] Vol .-% Vol .-% Appearance [° C] [° C] 58 A4 200 -21 15 85 clear +0.5 6.1 59 A4 200 B1 150 -24 0 100 cloudy -5.6 0 60 A4 200 B1 100 B1 50 -25 0 100 cloudy -5.5 0.1 61 A4 200 B1 75 B1 75 -27 0 100 cloudy -5.3 0.2 62 A4 200 B1 50 B1 100 -25 0 100 cloudy -5.0 0.6 63 A4 200 B1 30 B1 120 -26 0 100 cloudy -5.4 0.2 58 = comparative example

Efficacy as a solubilizer

1. A) Amide ammonium salt of a spirobislactone according to EP 0413279, 50% strength in solvent naphtha.
2. B) Reaction product of a terpolymer of C _14/16 α-olefin, maleic anhydride and allyl polyglycol with 2 equivalents of ditallow fatty amine, 50% in solvent naphtha (according to EP 0606055).
3. C) Nonylphenol-formaldehyde resin according to DE 3142955, prepared by acid-catalyzed condensation of p-nonylphenol and formaldehyde, 50% strength in solvent naphtha.

The active ingredients listed above are homogenized at 80 ° C with stirring. Subsequently, the stability of the solutions after 3 days of storage at room temperature or at 60 ° C is visually assessed. Table 10 components RT 60 ° C A (100%; comparison) - cloudy, crystalline
shares clear A (50%) C (50%) clear clear B (100%; comparison) - cloudy, crystalline
shares cloudy B (50%) C (50%) clear clear

List of used trade names

Solvent Naphtha®Shellsol AB® Solvesso 150

aromatic solvent mixtures with boiling range 180 to 210 ° C

® Solvesso 200

aromatic solvent mixture with boiling range 230 to 287 ° C

®Exxsol

Dearomatized solvents in various boiling ranges, for example ®Exxsol D60: 187 to 215 ° C

®ISOPAR (Exxon)

isoparaffinic solvent mixtures in various boiling ranges, for example ®ISOPAR L: 190 to 210 ° C

®Shellsol D

mainly aliphatic solvent mixtures in different boiling ranges

Claims (22)

1. Process for improving the flowability of paraffinic mineral oils and mineral oil distillates, characterized in that the paraffinic mineral oil or mineral oil distillate is admixed with

   A) at least one ethylene-vinyl ester co- or terpolymer, and

   B) at least one alkylphenol-aldehyde resin wherein the alkyl radicals of the alkylphenol possess 4 to 12 carbon atoms and the aldehyde possesses 1 to 4 carbon atoms, wherein the resin or resins contain not more than 10 mol% of alkylphenols which contain more than one alkyl group, and optionally also

   C) at least one non-B polar, low molecular weight or polymeric, oil-soluble nitrogen compound which

   - contains one or more ester, amide and/or imide groups substituted by at least one C₈-C₂₆-alkyl chain

   - and/or bears one or more ammonium groups derived from amines having one or two C₈-C₂₆ alkyl groups, raffin dispersant.
2. Process according to Claim 1, characterized in that the paraffinic mineral oil or mineral oil distillate is admixed with

   A) 10 - 5000 ppm and preferably 10 - 2000 ppm, based on the mineral oil or mineral oil distillate, of at least one ethylene-vinyl ester co- or terpolymer,

   B) 10 - 2000 ppm and preferably 10 - 1000 ppm, based on the mineral oil or mineral oil distillate, of at least one alkylphenol-aldehyde resin and optionally

   C) up to 2000 ppm and preferably up to 1000 ppm, based on the mineral oil or mineral oil distillate, of at least one non-B paraffin dispersant.
3. Process according to Claim 1 or 2, characterized in that the ethylene-vinyl ester co- or terpolymers A have an ethylene content of 60 - 90% by weight.
4. Process according to one or more of Claims 1 - 3, characterized in that it utilizes identical or different alkylphenol-aldehyde resins B wherein the alkyl radicals of the alkylphenol possess 6 to 12 carbon atoms and in particular constitute n- and iso-hexyl, n- and iso-octyl, n- and iso-nonyl, n-and iso-decyl, n- and iso-dodecyl and the aldehyde preferably constitutes formaldehyde, acetaldehyde and butyraldehyde, especially formaldehyde.
5. Process according to one or more of Claims 1 to 3, characterized in that it utilizes identical or different alkylphenol-aldehyde resins B wherein the alkyl radicals constitute n-, iso- and tert-butyl, n- and iso-pentyl.
6. Process according to one or more of Claims 1 - 5, characterized in that the ethylene-vinyl ester co- or terpolymers A and the alkylphenol-aldehyde resins B and also optionally the non-B paraffin dispersants C are added separately to the mineral oil or mineral oil distillate.
7. Process according to one or more of Claims 1 - 5, characterized in that the ethylene-vinyl ester co- or terpolymers A are added individually and the alkylphenol-aldehyde resins B and also the non-B paraffin dispersants C are added in a mixture which contains 10-90% by weight of at least one alkylphenol-aldehyde resin B and 90-10% by weight of at least one non-B paraffin dispersant, wherein the sum total of the additives B and C in the mixture is always 100% by weight.
8. Process according to one or more of Claims 1 - 5, characterized in that the mineral oil or mineral oil distillate is admixed with a mixture consisting of 5 - 90% by weight of at least one ethylene-vinyl ester co- or terpolymer A and 5 - 90% by weight of at least an alkylphenol-aldehyde resin B and also optionally 5 - 90% by weight of at least one non-B paraffin dispersant C, wherein the sum total of the additives A, B and C is always 100% by weight.
9. Process according to Claim 6, 7 or 8, characterized in that the individual additives A, B and optionally C or the corresponding mixtures of the additives B and C or A, B and optionally C are dissolved or dispersed in an organic solution or dispersion medium before being added to the mineral oil or mineral oil distillate.
10. Use of alkylphenol-aldehyde resins B wherein the alkyl radicals of the alkylphenol possess 4 to 12 carbon atoms and the aldehyde possesses 1 to 4 carbon atoms in combination with ethylene-vinyl ester co- or terpolymers A and optionally a non-B polar, low molecular weight or polymeric, oil-soluble nitrogen compound which

    - contains one or more ester, amide and/or imide groups substituted by at least one C₈-C₂₆-alkyl chain

    - and/or bears one or more ammonium groups derived from amines having one or two C₈-C₂₆ alkyl groups, as paraffin dispersants C,

    as flow improvers, especially paraffin dispersants in mineral oils and mineral oil distillates.
11. Mixture consisting of

    B) 10-90% by weight of at least one alkylphenol-aldehyde resin wherein the alkyl radicals of the alkyphenol possess 4 to 12 carbon atoms and the aldehyde possesses 1 to 4 carbon atoms and

    C) 90-10% by weight of at least one non-B polar, low molecular weight or polymeric, oil-soluble nitrogen compound which

    - contains one or more ester, amide and/or imide groups substituted by at least one C₈-C₂₆-alkyl chain

    - and/or bears one or more ammonium groups derived from amines having one or two C₈-C₂₆ alkyl groups, as a paraffin dispersant,

    wherein the sum total of the additives B and C is always 100% by weight, characterized in that it is dissolved or dispersed in an organic solution or dispersion medium, this solution or dispersion subsequently containing 5 - 90% and preferably 5 - 75% by weight of the mixture.
12. Mixture consisting of

    A) 5 - 90% by weight of at least one ethylene-vinyl ester co- or terpolymer and

    B) 5-90% by weight of at least one alkylphenol-aldehyde resin wherein the alkyl radicals of the alkylphenol possess 4 to 12 carbon atoms and the aldehyde possesses 1 to 4 carbon atoms, and optionally also

    C) 5-10% by weight of at least one non-B polar, low molecular weight or polymeric, oil-soluble nitrogen compound which

    - contains one or more ester, amide and/or imide groups substituted by at least one C₈-C₂₆-alkyl chain

    - and/or bears one or more ammonium groups derived from amines having one or two C₈-C₂₆ alkyl groups, as a paraffin dispersant,

    wherein the sum total of the additives B and C is always 100% by weight, characterized in that it is dissolved or dispersed in an organic solution or dispersion medium, this solution or dispersion subsequently containing 5 - 90% and preferably 5 - 75% by weight of the mixture.
13. Mineral oils or mineral oil distillates containing

    A) at least one ethylene-vinyl ester co- or terpolymer, and

    B) at least one alkylphenol-aldehyde resin wherein the alkyl radicals of the alkylphenol possess 4 to 12 carbon atoms and the aldehyde possesses 1 to 4 carbon atoms and also optionally

    C) at least one non-B polar, low molecular weight or polymeric, oil-soluble nitrogen compound which

    - contains one or more ester, amide and/or imide groups substituted by at least one C₈-C₂₆-alkyl chain

    - and/or bears one or more ammonium groups derived from amines having one or two C₈-C₂₆ alkyl groups, as a paraffin dispersant.
14. Mineral oils or mineral oil distillates according to Claim 13,
    characterized in that they contain

    A) 10 - 5000 ppm and preferably 10 - 2000 ppm, based on the mineral oil or mineral oil distillate, of at least one ethylene-vinyl ester co- or terpolymer,

    B) 10 - 2000 ppm and preferably 10 - 1000 ppm, based on the mineral oil or mineral oil distillate, of at least one alkylphenol-formaldehyde resin and optionally

    C) up to 2000 ppm and preferably up to 1000 ppm, based on the mineral oil or mineral oil distillate, of the non-B paraffin dispersant.
15. Additive mixtures for paraffin dispersion in paraffinic mineral oils and mineral oil distillates, containing at least one polar, low molecular weight or polymeric, oil-soluble nitrogen compound which

    - contains one or more ester, amide and/or imide groups substituted by at least one C₈-C₂₆-alkyl chain

    - and/or bears one or more ammonium groups derived from amines having one or two C₈-C₂₆ alkyl groups, as a paraffin dispersant

    and at least one aliphatic or aromatic, liquid hydrocarbon as a solvent, characterized in that at least one alkylphenol-aldehyde resin wherein the alkyl radicals of the alkylphenol possess 4 to 12 carbon atoms is used as a solubilizer.
16. Additive mixture according to Claim 15, characterized in that the alkylphenol-aldehyde resin derives from ortho- or para-alkylphenols.
17. Additive mixture according to one or more of Claims 15 and/or 16, characterized in that the alkyl radical of the alkylphenol-aldehyde resin has 6-12 carbon atoms.
18. Additive mixture according to one or more of Claims 15 to 17, characterized in that the alkyl radical is n-, iso- or tert-butyl, n- or iso-pentyl, n- or iso-hexyl, n- or iso-octyl, n- or iso-nonyl, n- or iso-decyl, n- or iso-dodecyl.
19. Additive mixture according to one or more of Claims 15 to 18, characterized in that the aldehyde of the alkylphenol-aldehyde resin has 1 to 4 carbon atoms.
20. Additive mixture according to Claim 19, characterized in that the aldehyde is formaldehyde, acetaldehyde or butyraldehyde.
21. Additive mixture according to one or more of Claims 15 to 20, characterized in that the molecular weight of the alkylphenol-aldehyde resins is between 400 and 10 000 and preferably between 400 to 5000 g/mol.
22. Additive mixture according to one or more of Claims 15 to 21, characterized in that it contains flow improvers which consist of co- and/or terpolymers of ethylene and vinyl esters.