DE19700159A1 - Increasing flow of mineral oil or distillate containing paraffin, especially at low temperature - Google Patents

Abstract

Improving the flow of mineral oils and mineral oil distillates containing paraffin comprises treatment with ethylene vinyl ester co- or terpolymer(s) (I), alkylphenol-aldehyde resin(s) (II) and optionally paraffin dispersant(s) (III) other than (II). Also claimed are the use of (II) and combinations of (II) with (I) and optionally (III) as flow enhancers, especially paraffin dispersants, in mineral oils and mineral oil distillates; and various compositions.

Description

The invention relates to a method for improving the Flowability of paraffinic mineral oils and refills crude oil distillates by adding flow improvers the basis of ethylene-vinyl ester copolymers and terpolymers, Alkylphenol-aldehyde resins and optionally others Paraffin dispersants.

Crude oils and co-products obtained by distilling crude oils contained distillates such as gas oil, diesel oil or heating oil different amounts depending on the origin of the crude oils n-paraffins, which when lowering the temperature than Crystallize platelet-shaped crystals and partially agglomerate with the inclusion of oil. Through this kri stallation and agglomeration there is a ver deterioration in the flow properties of the oils or distillate late, whereby during extraction, transport, storage and / or Use of mineral oils and mineral oil distillates disorders may occur. When transporting mineral oils through Pipelines can especially the crystallization phenomenon in winter to build up deposits on the pipe walls, individually cases, e.g. B. at a standstill of a pipeline, even to lead to complete constipation. During storage and Further processing of the mineral oils can also be done in the win ter be necessary, the mineral oils in heated tanks to store. With mineral oil distillates it happens as a result the crystallization may clog the Filters in diesel engines and combustion plants, whereby safe metering of the fuels is prevented  and possibly complete interruption of power material or heating medium supply occurs.

In addition to the classic methods of removing the crystallized paraffins (thermal, mechanical or with solvents) that only affect the distance of the already formed precipitates in recent years chemical additives (so-called Flow improver). Through physi calic interaction with the paraffin falling out crystals that their shape, size and adhesion are inherent be modified. The additives work as additional crystal nuclei and partially crystallize Identify with the paraffins, which means a larger number smaller paraffin crystals with changed crystal shape arises. The modified paraffin crystals tend less for agglomeration, so that they deal with these Pump additives with added oils at temperatures or have it processed, which was often more than 20 ° lower compared to non-additive oils.

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

Another task of flow improver additives is that Dispersion of paraffin crystals, d. H. the delay or prevention of sedimentation of the paraffin crystals and thus the formation of a paraffin-rich layer on Bottom of storage containers.

There are various paraffin dispersants both mono merer as well as polymeric structure known.

Examples of monomeric paraffin dispersants are from EP-A-0 413 279 reaction products of alkenylspi robis lactones known with amines. In EP-A-0 061 894 are also oil-soluble nitrogen-containing compounds such as  e.g. B. reaction products of phthalic anhydride with ami NEN described in a mixture with ethylene vinyl acetate Copolymers are used. Furthermore, from the EP-A-0 597 278 reaction products of aminoalkylene carbon known acids with primary or secondary amines.

Examples of polymeric paraffin dispersants are the following are described in the literature.

EP-A-0 688 796 describes copolymers based on α, β-unsaturated olefins with at least 3 carbon atoms and α, β-Unsaturated dicarboxylic anhydrides are known, where the dicarboxylic anhydride units by polymer analogs Reaction with polyetheramines or alkanolamines in Imide, amide or ammonium units are transferred.

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

EP-A-0 154 177 describes reaction products of old copolymers based on maleic anhydride and α, β-unsaturated compounds with primary monoal kylamines and aliphatic alcohols described. This Copolymers are particularly useful as paraffin inhibitors for petroleum products containing paraffin, for example crude oils and Distillation residues from petroleum processing, suitable.

From EP-A-0 436 151 there are reaction products of copolyme ren based on maleic anhydride and α, β-unsaturated known compounds with dialkylamines.  

EP-A-0 283 293 discloses copolymers based on aliphatic olefins and maleic anhydride, the Copolymer have both ester and amide groups , each of which has an alkyl group with at least 10 Contains carbon atoms, as well as copolymers by reacting a secondary amine with a polymer, which contains anhydride groups, from the anhydride groups Pen in equal parts amides or ammonium salts hen.

These paraffin dispersants are usually put together with other flow improvers, especially ethylene vi nyl ester copolymers used.

From WO 93/14178 it is also known that the cold flow properties of mineral oils and mineral oil distillates ten can be significantly improved by using Flow improvers known polyaddition products (e.g. Ethylene / vinyl ester copolymers) or polycondensation pro products in combination with so-called emulsion splitters starts.

These emulsion splitters have the ability to Oil / water emulsion forming separate oil and water break these phases. You must therefore be both hydrophobic as well as containing hydrophilic structural units on the one hand sufficient in the oil of the oil / water emul sion to split the latter, and focus on the other side after phase separation in the aqueous Enrich phase.

As an emulsion splitter with flow-improving / paraffinin The inhibitory effect is oxalkylated according to WO 93/14178 Suitable alkylphenol formaldehyde resins. Here contains the oxyalkyl component representing the hydrophilic structure Side chain up to 50 oxyalkyl units, each 2-6 Have carbon atoms.  

The above-described paraffin-dispersing effect of Known paraffin dispersants are not always sufficient chend, so that when the oils cool down sometimes large Paraffin crystals form because of their higher Sediment density over time and thus to bil formation of a paraffin-rich layer at the bottom of the warehouse lead. Problems occur especially with the Addi Activation of paraffin-rich narrow distillation cuts ten with boiling ranges of 20-90 vol% less than 110 ° C, ins especially less than 100 ° C. Also with distillates one of more than 20 ° C, especially more than 25 ° C Temperature difference between the end of boiling and the tempera tur at which 90 vol% are distilled can be the addition of known additives is often not sufficient Achieve paraffin dispersion.

There was therefore the task of fluidity, and in particular paraffin dispersion in mineral oil or mineral oil distillates by adding suitable ter improve additives.

The invention relates to a method for improving the flowability of paraffin-containing mineral oils and mineral oil distillates, which is characterized in that the paraffin-containing mineral oil or mineral oil distillate with

• A) at least one ethylene / vinyl ester co or ter poly meren,
• B) at least one alkylphenol-aldehyde resin and against if necessary
• C) at least one paraffin disperser different from B. gator offset.

The use of the alkylphenol-aldehyde resins B in combination nation with the ethylene / vinyl ester co - / - terpolymers A so such as the paraffin Dispersant C has a positive effect on parafindis dosing, d. H. the enrichment of the on cooling precipitating wax crystals, e.g. B. on the tank bottom or the fuel filter is delayed or prevented. As a result of the uniform dispersion of the paraf fine crystals a homogeneous cloudy phase is obtained. It there is also an improvement in cold flow dough the filterability of additi fourth paraffinic mineral oils and in particular Mineral oil distillates below the cloud point.

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

• A) with 10-5000 ppm, preferably 10-2000 ppm, based on the mineral oil or mineral oil distillate, at least an ethylene vinyl ester copolymer or terpolymer,
• B) 10-2000 ppm, preferably 10-1000 ppm, based on the mineral oil or mineral oil distillate, at least an alkylphenol-aldehyde resin and optionally
• C) up to 2000 ppm, preferably up to 1000 ppm, based at least on the mineral oil or mineral oil distillate one of B different paraffin dispersants, ver puts.

The additives A, B and optionally C can mineral oils or mineral oil distillates containing paraffin be added separately.  

Alternatively, additive A can be added individually and additives B and C in a mixture. Such Mi mixtures included

• B) 10-90% by weight of at least one alkylphenol aldehyde Resin and
• C) 90-10% by weight of at least one different from B. Paraffin dispersants,

the sum of additives B and C always be 100% by weight wearing.

It is also possible that the mineral oil or mineral oil distillate is mixed with a common mixture of additives A, B and, if appropriate, C. Such mixtures contain

• A) 5-90, preferably 10-90 wt .-% of at least one Ethylene / vinyl ester co- or terpolymers,
• B) 5-90, preferably 10-90% by weight of at least one Alkylphenol-aldehyde resin and optionally
• C) 5-90, preferably 10-90% by weight of at least one B different paraffin dispersants,

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

In a preferred embodiment, the individual Additives or the corresponding mixtures before Addition to mineral oils or mineral oil distillates in an organic solvent or dispersant or dispersed. In the case of mixing additives A, B and optionally C and the mixture of additive B  and C contains the solution or dispersion 5-90 before adds 5-75% by weight of the respective mixture.

Suitable solvents or dispersants are ali phatic and / or aromatic hydrocarbons or Hydrocarbon mixtures, e.g. B. gasoline fractions, Kero sin, decane, pentadecane, toluene, xylene, ethylbenzene or commercial solvent mixtures such as ®Solvent Naphtha, ®Shellsol AB, ®Solvesso 150, ®Solvesso 200, ®Solvesso 250, ®Exxsol, ®ISOPAR and Shellsol D types. If necessary, polar solubilizers such as 2-ethylhexanol, decanol, iso-decanol or iso-tridecanol be added.

The invention also relates to mineral oils or mineral oil distillates, which

• A) at least one ethylene / vinyl ester co or ter poly mer,
• B) at least one alkylphenol-aldehyde resin and given if
• C) at least one paraffin disperser different from B. gator included.

Mineral oils or mineral oil distillates are preferred

• A) 10-5000 ppm, preferably 10-2000 ppm at least one Ethylene / vinyl ester copolymers or terpolymers,
• B) 10-2000 ppm, preferably 10-1000 ppm at least one Alkylphenol aldehyde resin and optionally  
• C) up to 2000 ppm, preferably up to 1000 ppm at least one of B different paraffin dispersants ent hold.

The mineral oils or mineral oil distillates can also other common additives such as waxing auxiliary agents, corrosion inhibitors, antioxidants, Lubricity additives, sludge inhibitors, cetane number verbs serer, detergent additives, dehazer, conductivity verb serer or dyes included.

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

The alkyl radicals of the o- or p-alkylphenol can in the alkylphenol used in the process according to the invention Aldehyde resins B may be the same or different and possess zen 1-20, preferably 4-12 carbon atoms; preferably han it is n-, i- and tert. Butyl, n- and i-pentyl, n- and i-hexyl, n- and i-octyl, n- and i-nonyl, n- and i-decyl, n- and i-dodecyl. The aliphatic aldehyde in Alkylphenol-aldehyde resin B has 1-4 carbon atoms and is preferably formaldehyde. The molecular weight of the Alkylphenol aldehyde resins are 400-10,000, preferred 400-5000 g / mol. The prerequisite here is that the Resins are oil soluble.

The alkylphenol-aldehyde resins B are prepared in a known manner by basic catalysis, with condensates Resole type products arise, or by acid Catalysis, whereby condensation products of the novolak type ent stand.

The condensates obtained in both ways are as ad ditive B suitable in the inventive method. Before  condensation is present in the presence of acidic catalyst sators.

To produce the alkylphenol-aldehyde resins, a bifunctional o- or p-alkylphenol with 1 to 20 carbon atoms men, preferably 4 to 12 carbon atoms per alkyl group, or Mixtures thereof and an aliphatic aldehyde with 1 to 4 carbon atoms reacted with each other, per mol of alkylphe nol compound about 0.5-2 mol, preferably 0.7-1.3 mol of aldehyde can be used.

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

The alkylphenols to be used can be small amounts, expediently up to about 10% by weight of dialkylphenols contain.

Particularly suitable aldehydes are formaldehyde and acetalde hyd and butyraldehyde, formaldehyde is preferred.

The formaldehyde can be in the form of paraformaldehyde or in Form of a preferably 20-40 wt .-% aqueous forma lin solution can be used. It can also be appropriate Amounts of trioxane can be used.

The reaction of alkylphenol and aldehyde is usual usually in the presence of alkaline catalysts, for example alkali 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 halo genacetic acids, and in the presence of one with water Azeotropic organic solvent, for example  as toluene, xylene, higher aromatics or mixtures of this. The reaction mixture is brought to a temperature heated from 90 to 200 ° C, preferably 100-160 ° C, wherein the water of reaction formed during the reaction is removed by azeotropic distillation. Solutionmit tel that under the conditions of condensation none Protons can split off after the condensation reaction stay in the products. The resins can be directly or are used after neutralization of the catalyst, if necessary after further dilution of the solution with aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, e.g. B. gasoline fractions, Kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or solvents such as ®Solvent Naphtha, ®Shellsol AB, ®Solvesso 150, ®Solvesso 200, ®Solvesso 250, ®Exxsol, ®ISOPAR and Shellsol D types.

As ethylene / vinyl ester copolymers or terpolymers A, all known copolymers or terpolymers of this type can be used which, taken on their own, improve the cold flow properties of mineral oils or mineral oil distillates. Examples of suitable copolymers or terpolymers A are:
Ethylene-vinyl acetate copolymers with 10-40% by weight vinyl acetate and 60-90% by weight ethylene;
The ethylene vinyl acetate tat hexene terpolymers known from DE-OS 34 43 475;
The ethylene vinyl acetate tat diisobutylene terpolymers described in EP-B-0 203 554;
The mixture known from EP-B-0 254 284 of an ethylene-vinyl acetate-diisobutylene terpolymer and an ethylene / vinyl acetate copolymer;

The mixtures 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 / i-butyl 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 / neononanoic acid vinyl ester or neodecanoic acid vinyl ester terpolymers known from EP-B-0 493 769, which in addition to ethylene contain 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 the unpublished German patent application with the file number 196 20 118.7-44;
The terpolymers of ethylene, the vinyl ester of one or more aliphatic C ₂ -C ₂₀ monocarboxylic acids and bi cyclo [2.2.1] hept-2-enes disclosed in the unpublished German patent application with the file number 196 20 119.5-44.

Such ethylene-vinyl ester co- or terpo are preferred polymers with an ethylene content of 60-90% by weight.

Suitable as paraffin dispersants C other than B are, for example, polar, low molecular weight or polymeric, oil-soluble compounds which

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

Of the above-mentioned paraffin disperses are preferred polar nitrogen-containing compounds.

As monomeric polar nitrogen-containing compounds C can For example, the following substances are used will.

Suitable reaction products are described in EP-A-0 413 279 of alkenyl spirobis lactones with amines.

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

Furthermore, the implementations known from EP-A-0 597 278 tion products of aminoalkylene carboxylic acids with primary or secondary amines as monomeric nitrogen-containing Compounds C suitable.

As the polymeric polar nitrogen-containing compounds C, who preferably uses copolymers or terpolymers based on α, β-unsaturated compounds and maleic acid. For example:
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 known from EP-A-0 154 177 of alternating copolymers based on α, β-un saturated compounds and maleic anhydride with primary monoalkylamines and aliphatic alcohols;
The statistical copolymers and terpolymers described in the unpublished German patent application with the file number 196 45 603.7 on the basis of ethylene, α, β-unsaturated dicarboxylic acid anhydrides and, where appropriate, further α, β-unsaturated compounds, the dicarboxylic acid anhydride units becoming too high Share as imide units and to a lesser extent than amide / ammonium salt units;
The copolymers known from EP-A-0 688 796 based on α, β-unsaturated olefins with at least 3 C atoms and α, β-unsaturated dicarboxylic acid anhydrides, the dicarboxylic acid anhydride units being converted 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, the copolymer having both ester and amide groups, each of which contains an alkyl group of at least 10 carbon atoms.

The same applies to all three additives A, B and C: As Additive A can also be mixtures of different ethylene vinyl ester copolymers or terpolymers are used, wel different qualitative and / or quantitative tive composition and / or different (at 140 ° C measured) viscosities. As additive B are also mixtures of alkylphenol-aldehyde resins usable the various alkylphenols and / or alde hyde included as components. Likewise, Wed. of several paraffin disperga different from B. Cors can be used. In this way, the Customize the flow improver to meet individual requirements sen.

With the additives A, B and optionally C, he can Processes according to the invention Animal, vegetable oils or mineral origin.

Mineral oils and mineral oil distillates containing paraffin in The meaning of the invention is, for example, crude oils, distilla residues from oil processing or other paraf fin oils. (compare e.g. Compositions and Proper ties of petroleum, F. Enke Publishers, Stuttgart 1981, Page 1-37). Mineral oil products containing paraffin, esp special middle distillates such as jet fuel, Diesel, heating oil EL and heavy heating oil are one Boiling range of 120-500 ° C, preferably 150-400 ° C cha characterizes. The paraffins are ge wheel-chain or branched alkanes with about 10-50 Koh len atoms.

Examples Paraffin dispersion in middle distillates

As additives A, B and C in Examples 1-51 the following substances are used:  

• A) Ethylene vinyl acetate terpolymers
  • A1) Ethylene-vinyl acetate-versatic acid vinyl ester terpo lymer with about 31% by weight of vinyl acetate and a melt viscosity of 110 mPas, measured at 140 ° C., 50% in kerosene.
  • A2) Ethylene-vinyl acetate-versatic acid vinyl ester terpo lymer with about 31% by weight of vinyl acetate and a melt viscosity of 280 mPas, measured at 140 ° C., 50% in kerosene.
  • A3) Ethylene-vinyl acetate-versatic acid vinyl ester terpo lymer with approximately 31.5% by weight of vinyl acetate and a melt viscosity of 170 mPas, 55% in kerosene, measured at 140 ° C.
• B) Alkyphenol aldehyde resins
  • B1) Nonylphenol formaldehyde resin
    To produce 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, the reaction mixture by spinning out with a mixture of higher-boiling aromatic hydrocarbons (boiling range 185-215 ° C. ) freed from water and neutralized with potassium hydroxide. The red-brown resin was diluted in Solvent Naphtha to a solids content of 50%. The molecular weight determined by gel chromatography (calibration against polystyrene standards) is 2000 g / mol.
  • B2) Nonyl-butylphenol-formaldehyde resin
    Analogously to Example B1, equimolar amounts of nonylphenol and butylphenol were condensed with formaldehyde under acidic catalysis.
    The molecular weight of the red-brown resin is 1800 g / mol.
  • B3) With 5.5 mol of ethylene oxide under acid catalysis, converted nonylphenol-formaldehyde resin according to example B1, 50% in solvent naphtha.
• C) Paraffin dispersants other than B C
  • C1) Reaction product of a terpolymer from a C _14/16 α-olefin, maleic anhydride and allyl polyglycol with 2 equivalents of ditallow fatty amine, 50% strength in solvent naphtha (produced in accordance with EP-A-0606055)
  • C2) reaction product of a dodecenyl spirobislactone with a mixture of primary and secondary tallow fatty amine, 60% in solvent naphtha (prepared according to Example 1 from EP-A-0413279).

These additives A, B and C were added to reprä sentative winter diesel fuels from German Raffi series that are characterized in Table 1. The boil analyzes were performed according to ASTM D-86.  

Characterization of the test oils

Characterization of the test oils

The cold flow behavior was determined as follows:
The above-mentioned test oils were mixed at room temperature with the amounts of the additives temperature-controlled at 60 ° C., warmed to 40 ° C. for 15 minutes with occasional shaking and then cooled to room temperature. The CFPP value (Cold Filter Plugging Point) of the additive distilled in this way was determined in accordance with EN 116.

The paraffin dispersion in middle distillates was detected as follows in the short sediment test:
150 ml of the additive-containing medium end stills were cooled in 200 ml measuring cylinders in a refrigerator at -2 ° C / hour to -13 ° C and stored for 16 hours at this temperature. The volume and appearance of both the sedimented paraffin phase and the oil phase above it were then determined and assessed visually. A small amount of sediment and a cloudy oil phase show good paraffin dispersion.

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

Claims (16)

1. A process for improving the flowability of mineral oils containing paraffin and mineral oil distillates, characterized in that the mineral oil or mineral oil distillate containing paraffin is used

• A) at least one ethylene / vinyl ester copolymer or terpolymer
• B) at least one alkylphenol-aldehyde resin and optionally
• C) at least one paraffin dispersant different from B is added.

2. The method according to claim 1, characterized in that the paraffin-containing mineral oil or mineral oil with

• A) 10-5000 ppm, preferably 10-2000 ppm, based on the mineral oil or mineral oil distillate, at least one ethylene vinyl ester copolymer or terpolymer,
• B) 10-2000 ppm, preferably 10-1000 ppm, based on the mineral oil or mineral oil distillate, at least one alkylphenol-aldehyde resin and, if appropriate
• C) up to 2000 ppm, preferably up to 1000 ppm, based on the mineral oil or mineral oil distillate, at least one paraffin dispersant different from B is added.

3. The method according to claim 1 or 2, characterized in that the ethylene / vinyl ester co- or ter polymer A has an ethylene content of 60-90 wt .-%
exhibit. 4. The method according to one or more of claims 1-3, characterized in that alkylphenol alde uses hydric resins B, the alkyl radicals of the alkyl phenols are the same or different and 1-20, be preferably have 4-12 carbon atoms and esp special n, i and tert. Butyl, n- and i-pentyl, n- and i-hexyl, n- and i-octyl, n- and i-nonyl, n- and represent i-decyl, n- and i-dodecyl and the aldehyde Has 1-4 carbon atoms and preferably formaldehyde hyd, acetaldehyde and butyraldehyde, in particular Represents formaldehyde. 5. The method according to one or more of claims 1-4, characterized in that one uses as a different from B ver paraffin dispersants C polar, low molecular weight or polymeric, oil-soluble compounds which

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

6. The method according to one or more of claims 1-5, characterized in that the ethylene / vinyl ester copolymers or terpolymers A and the alkylphenol-Al dehyde resins B and optionally those of B ver  different paraffin dispersants C separately to the Add mineral oil or mineral oil distillate. 7. The method according to one or more of claims 1-5, characterized in that the ethylene / vinyl ester copolymers or terpolymers A individually and the alkyl phenol-aldehyde resins B and those different from B. Adding paraffin dispersants C in a mixture, the 10-90% by weight of at least one alkylphenol aldehyde Resin B and 90-10 wt .-% at least one of B ver contains various paraffin dispersants, the Sum of additives B and C in the mixture is always 100 % By weight. 8. The method according to one or more of claims 1-5, characterized in that the mineral oil or Mineral oil distillate mixed with a mixture of 5-90 wt .-% of at least one ethylene / vinyl ester co or -Terpolymers A and 5-90 wt .-% at least an alkylphenol-aldehyde resin B, and given if 5-90% by weight differs from at least one of B. those paraffin dispersants C, the sum of the Additives A, B and C are always 100% by weight. 9. The method according to claim 6, 7 or 8, characterized records that the individual additives A, B and given optionally C or the corresponding mixtures of Additives B and C or A, B and optionally C before the addition to the mineral oil or mineral oil distillate in an organic solvent or dispersant dissolves or disperses. 10. Use of the alkylphenol-aldehyde resins B as a flow improvers, especially paraffin dispersants in Mineral oils and mineral oil distillates.   11. Use according to claim 10, characterized in that that the alkylphenol-aldehyde resins B in combination with ethylene / vinyl ester copolymers or terpolymers A and possibly different from B Paraffindesperga Cors can be used. Mixture of

• B) 10-90% by weight of at least one alkylphenol-aldehyde resin and
• C) 90-10% by weight of at least one paraffin dispersant different from B,

the sum of additives B and C is always 100% by weight. 13. Mixture of

• A) 5-90% by weight of at least one ethylene / vinyl ester copolymer or terpolymer and
• B) 5-90 wt .-% of at least one alkylphenol-Alde hyd resin and optionally
• C) 5-10% by weight of at least one paraffin dispersant different from B,

the sum of additives A, B and C is always 100% by weight. 14. Mixture according to claim 12 or 13, characterized records that they are in an organic solution or Dispersant dissolves or disperses, whereby this solution or dispersion then 5-90, be preferably contains 5-75% by weight of the mixture. 15. Containing mineral oils or mineral oil distillates

• A) at least one ethylene-vinyl ester copolymer or terpolymer and
• B) at least one alkylphenol-aldehyde resin and optionally
• C) at least one paraffin dispersant different from B.

16. Mineral oils or mineral oil distillates according to claim 15, characterized in that they

• A) 10-5000 ppm, preferably 10-2000 ppm, based on the mineral oil or mineral oil distillate, at least one ethylene / vinyl ester copolymer or terpolymer,
• B) 10-2000 ppm, preferably 10-1000 ppm, based on the mineral oil or mineral oil distillate, at least one alkylphenol-formaldehyde resin and, if appropriate
• C) up to 2000 ppm, preferably up to 1000 ppm, based on the mineral oil or mineral oil distillate, contain at least one paraffin dispersant different from B.