EP0857776B1 - 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 method for improving the flowability of mineral oils and mineral oil distillates containing paraffin by adding Flow improver based on ethylene-vinyl ester copolymers and terpolymers, Alkylphenol aldehyde resins and optionally other paraffin dispersants.

Crude oils and middle distillates obtained by distilling crude oils such as gas oil, Diesel oil or heating oil contain different ones depending on the origin of the crude oils Amounts of n-paraffins, which as a platelet when the temperature is lowered Crystallize crystals and partially agglomerate with the inclusion of oil. This crystallization and agglomeration leads to a deterioration the flow properties of the oils or distillates, which means that during extraction, transport, Storage and / or use of mineral oils and mineral oil distillates may occur. This can happen when transporting mineral oils through pipes Crystallization phenomenon, especially in winter, to deposits on the Pipe walls, in individual cases, e.g. if a pipeline is at a standstill, even to it cause complete constipation. When storing and processing the Mineral oils may also be required in winter, the mineral oils in heated To store tanks. With mineral oil distillates, it occurs as a result of crystallization if necessary, clogging of the filters in diesel engines and Firing systems, which prevents safe metering of the fuels and possibly complete interruption of fuel or Heating medium supply occurs.

In addition to the classic methods for removing the crystallized paraffins (thermal, mechanical or with solvents) that only affect the Removal of the precipitates already formed have been made in the last Years of chemical additives (so-called flow improvers) have been developed. This effect through physical interaction with the failing Paraffin crystals that modify their shape, size and adhesive properties become. The additives act as additional crystal nuclei and crystallize partially with the paraffins, causing a larger number of smaller ones Paraffin crystals with a changed crystal shape are formed. The modified Paraffin crystals are less prone to agglomeration, so that they deal with them Additive-added oils can be pumped or processed at temperatures, which 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 task of flow improver additives is to disperse the Paraffin crystals, i.e. the delay or prevention of sedimentation of the Paraffin crystals and thus the formation of a paraffin-rich layer on the bottom of Storage tanks.

Different paraffin dispersants are both monomeric and polymeric Structure known.

The monomeric paraffin dispersants are, for example, from EP-A-0 413 279 Reaction products of alkenyl spirobis lactones with amines are known. In EP-A-0 061 894 are also oil-soluble nitrogen-containing compounds such as e.g. Reaction products of phthalic anhydride with amines described in Mixture with ethylene-vinyl acetate copolymers can be used. Furthermore are from EP-A-0 597 278 reaction products of aminoalkylene carboxylic acids with primary or secondary amines known.

The following are examples of polymeric paraffin dispersants in US Pat Literature described.

EP-A-0 688 796 discloses copolymers based on α, β-unsaturated Olefins with at least 3 carbon atoms and α, β-unsaturated Dicarboxylic acid anhydrides are known, the dicarboxylic acid anhydride units by polymer-analogous reaction with polyetheramines or alkanolamines in Imide, amide or ammonium units are transferred.

Furthermore, EP-A-0 606 055 discloses terpolymers based on α, β-unsaturated Dicarboxylic anhydrides, α, β-unsaturated compounds and Polyoxyalkylene ethers of lower, unsaturated alcohols, and their Use as paraffin inhibitors for petroleum products containing paraffin.

EP-A-0 154177 describes reaction products of alternating copolymers based on maleic anhydride and α, β-unsaturated compounds primary monoalkylamines and aliphatic alcohols described. This Copolymers are particularly useful as paraffin inhibitors for those containing paraffin Petroleum products, such as crude oils and distillation residues from Petroleum processing, suitable.

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

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

These paraffin dispersants are usually used with others Flow improver, in particular ethylene-vinyl ester copolymers, used.

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 polyaddition products known as flow improvers (e.g. ethylene / vinyl ester copolymers) or polycondensation products in combination with so-called Emulsion gap uses.

These emulsion splitters have the ability to take an oil / water emulsion Break formation of separate oil and water phases. You must therefore both Hydrophobic as well as hydrophilic structural units contain, on the one hand Side to dissolve sufficiently in the oil of the oil / water emulsion to the latter split, and on the other hand after the phase separation in the enrich aqueous phase.

As an emulsion splitter with a flow-improving / paraffin-inhibiting effect suitable according to WO93 / 14178 oxalkylated alkylphenol-formaldehyde resins. in this connection contains up to 50 of the oxyalkyl side chain that represents the hydrophilic structural part Oxalkyl units, each having 2 - 6 carbon atoms.

EP-A-0 311 452 discloses condensation products of at least 80 mol% difunctional, alkylated phenol and aldehydes containing 1 to 30 carbon atoms include, as a flow improver for mineral oils. The use of Condensation products of monoalkylated phenols with aldehydes as Flow improvers or paraffin dispersants are not disclosed.

The above-described paraffin-dispersing action of the known paraffin dispersants is not always sufficient, so that when the oils cool down partially form large wax crystals, which due to their higher density in the course sediment the time and thus to form a paraffin-rich layer on Guide the bottom of the storage container. Problems occur especially with the additives of paraffin-rich narrow distillation cuts with boiling ranges from 20-90 Vol% less than 110 ° C, especially less than 100 ° C. Even with distillates with one more than 20 ° C, in particular more than 25 ° C large temperature difference between The boiling point and the temperature at which 90% by volume are distilled can be determined by the Addition of known additives often does not provide sufficient paraffin dispersion achieve.

There was therefore the task of fluidity, especially the Paraffin dispersion for mineral oils or mineral oil distillates through the addition to improve suitable additives.

Furthermore, the solubility of paraffin-dispersing polar Often nitrogen compounds in the paraffinic or aromatic solvents unsatisfactory. The task was therefore also to be a broker between the polar nitrogen compounds and the paraffinic or to find aromatic solvents.

Surprisingly, it was found that alkylphenol-aldehyde resins themselves have a paraffin-dispersing effect, excellent solubilizers between these substances.

A) mindestens einem Ethylen/Vinylester-Co- oder -Terpolymeren,

B) mindestens einem Alkylphenol-Aldehyd-Harz, wobei das Harz oder die Harze höchstens 10 mol-% von Alkylphenolen enthalten, die mehr als eine Alkylgruppe enthalten, sowie gegebenenfalls

C) mindestens einem von B verschiedenen polaren Stickstoffverbindung als Paraffin-Dispergator versetzt.

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 copolymer or terpolymer,

B) at least one alkylphenol-aldehyde resin, the resin or the resins containing at most 10 mol% of alkylphenols which contain more than one alkyl group, and optionally

C) at least one polar nitrogen compound different from B is added as a paraffin dispersant.

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

The use of the alkylphenol-aldehyde resins B in combination with the Ethylene / vinyl ester co - / - terpolymers A and optionally that of B various paraffin dispersants C has a positive effect on the Paraffin dispersion from, i.e. the accumulation of those that fail when cooling Paraffin crystals, e.g. on the tank bottom or the fuel filter is delayed or prevented. As a result of the uniform dispersion of the wax crystals get a homogeneous cloudy phase. There is also an improvement in Cold flow properties, especially the filterability of the additive mineral oils containing paraffin and in particular mineral oil distillates below the Cloud points.

A) mit 10 - 5000 ppm, bevorzugt 10 - 2000 ppm, bezogen auf das Mineralöl bzw. Mineralöldestillat, mindestens eines Ethylenvinylester-Co- oder -Terpolymeren,

B) 10 - 2000 ppm, bevorzugt 10 - 1000 ppm, bezogen auf das Mineralöl bzw. Mineralöldestillat, mindestens eines Alkylphenol-Aldehyd-Harzes und gegebenenfalls

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

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,

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

C) up to 2000 ppm, preferably up to 1000 ppm, based on the mineral oil or mineral oil distillate, of at least one paraffin dispersant different from B, are added.

The additives A, B and optionally C can be the paraffinic Mineral oils or mineral oil distillates are added separately.

B) 10 - 90 Gew.-% mindestens eines Alkylphenol-Aldehyd-Harzes und

C) 90 - 10 Gew.-% mindestens eines von B verschiedenen Paraffin-Dispergators,

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

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. Additive B can also act as a solvent for additive C in organic solvents.

A) 5 - 90, vorzugsweise 10 - 90 Gew.-% mindestens eines Ethylen/Vinylester-Co- oder -Terpolymers,

B) 5 - 90, vorzugsweise 10 - 90 Gew.-% mindestens eines Alkylphenol-Aldehyd-Harzes sowie gegebenenfalls

C) 5 - 90, vorzugsweise 10 - 90 Gew.-% mindestens eines von B verschiedenen Paraffin-Dispergators,

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

A) 5-90, preferably 10-90% by weight of at least one ethylene / vinyl ester co- or terpolymer,

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 paraffin dispersant different from B,

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

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

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

A) mindestens ein EthylenNinylester-Co- oder -Terpolymer,

B) mindestens ein Alkylphenol-Aldehyd-Harz und gegebenenfalls

C) mindestens einen von B verschiedenen Paraffin-Dispergator enthalten.

The invention further relates to mineral oils or mineral oil distillates which

A) at least one ethylene / vinyl ester copolymer or terpolymer,

B) at least one alkylphenol-aldehyde resin and optionally

C) contain at least one paraffin dispersant different from B.

A) 10 - 5000 ppm, bevorzugt 10-2000 ppm mindestens eines EthylenNinylester-Co- oder -Terpolymeren,

B) 10 - 2000 ppm, bevorzugt 10-1000 ppm mindestens eines Alkylphenol-Aldehyd-Harzes und gegebenenfalls

C) bis zu 2000 ppm, bevorzugt bis zu 1000 ppm mindestens eines von B verschiedenen Paraffin-Dispergators enthalten.

Mineral oils or mineral oil distillates are preferred

A) 10 - 5000 ppm, preferably 10-2000 ppm of at least one ethylene / vinyl ester co- or terpolymer,

B) 10-2000 ppm, preferably 10-1000 ppm, of at least one alkylphenol-aldehyde resin and, if appropriate

C) up to 2000 ppm, preferably up to 1000 ppm, contain at least one paraffin dispersant different from B.

The mineral oils or mineral oil distillates can also be other common Additives such as dewaxing agents, corrosion inhibitors, Antioxidants, lubricity additives, sludge inhibitors, cetane number improvers, Detergent additives, dehazers, conductivity improvers or dyes.

Another object of the invention is an additive mixture for Paraffin dispersion in mineral oils and mineral oil distillates containing paraffin, 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 as Solubilizer is added.

Another object of the invention is a method for producing Solutions of paraffin dispersants in aliphatic or aromatic liquid Hydrocarbons by adding an alkylphenol-aldehyde resin to the mixture of these substances added.

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

The alkyl radicals of the o- or p-alkylphenol have 1-20, preferably 4-16, especially 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 can also contain up to 50 mol% Contain phenol units. For the alkylphenol-aldehyde resin, the same or different alkylphenols can be used. The aliphatic aldehyde in the Alkylphenol-aldehyde resin B has 1-4 carbon atoms and is preferred Formaldehyde. The molecular weight of the alkylphenol-aldehyde resins is 400 - 10,000, preferably 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, whereby condensation products of the resol type arise, or by acidic catalysis, producing condensation products of the novolak type.

The condensates obtained in both ways are as additives B in method according to the invention suitable. The condensation is preferred in Presence of acidic catalysts.

To produce the alkylphenol-aldehyde resins, a bifunctional o- or p-alkylphenol with 1 to 20 carbon atoms, preferably 4 to 16, in particular 6 to 12 C atoms per alkyl group, or mixtures thereof and an aliphatic aldehyde 1 to 4 carbon atoms reacted with each other, per mol of alkylphenol compound about 0.5-2 mol, preferably 0.7-1.3 mol, and in particular equimolar amounts Aldehyde can be used.

Suitable alkylphenols are, in particular, 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 can be small amounts, preferably up to about 10 mol%, in particular up to 7 mol% and especially up to 3 mol% Dialkylphenols included.

Particularly suitable aldehydes are formaldehyde, acetaldehyde and butyraldehyde, formaldehyde is preferred.

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

The reaction of alkylphenol and aldehyde usually takes place 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 haloacetic acids, and in the presence of one with water Azeotropic organic solvent, for example toluene, xylene, higher aromatics or mixtures thereof. The reaction mixture is on a Temperature of 90 to 200 ° C, preferably 100 - 160 ° C heated, which water of reaction formed during the reaction by azeotropic distillation Will get removed. Solvents that do not exist under the conditions of condensation Protons can split off after the condensation reaction in the products stay. The resins can be used directly or after neutralization of the catalyst are used, if necessary after further dilution of the solution with aliphatic and / or aromatic hydrocarbons or Hydrocarbon mixtures, e.g. Petrol 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.

All known copolymers or terpolymers of this type can be used as ethylene / vinyl ester copolymers or terpolymers A, which alone, by themselves, 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 of vinyl acetate and 60-90% by weight of ethylene;

The ethylene-vinyl acetate-hexene terpolymers known from DE-OS 34 43 475;

The ethylene-vinyl acetate-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 disclosed in EP-B-0 405 270 of an ethylene-vinyl acetate copolymer and an ethylene-vinyl acetate-N-vinylpyrrolidone terpolymer;

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 / 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 described in DE-A-196 20 118. of ethylene, the vinyl ester of one or more aliphatic C ₂ -C ₂₀ monocarboxylic acids and 4-methylpentene-1;

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-enes disclosed in DE-A-196 20 119.

Such ethylene-vinyl ester copolymers or terpolymers with a 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.

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

Of the above-mentioned paraffin dispersants, the polar ones are preferred nitrogenous compounds.

As monomeric polar nitrogen-containing compounds C, for example following substances are used.

EP-A-0 413 279 describes suitable reaction products of Alkenylspirobislactones with amines are described.

The oil-soluble reaction products of EP-A-0 061 894 Phthalic anhydride with amines can be mixed with ethylene-vinyl acetate copolymers be used.

Furthermore, the reaction products known from EP-A-0 597 278 of Aminoalkylene carboxylic acids with primary or secondary amines as monomers nitrogenous compounds C suitable.

Copolymers are preferred as polymeric polar nitrogen-containing compounds C. or terpolymers based on α, β-unsaturated compounds and Maleic acid used. For example, the following are suitable:

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

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

The in DE-A-196 45 603 described statistical copolymers and terpolymers the basis of ethylene, α, β-unsaturated dicarboxylic acid anhydrides as well optionally further α, β-unsaturated compounds, the Dicarboxylic anhydride units are present to a high extent as imide units and less than amide / ammonium salt units;

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

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

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

The same applies to all three additives A, B and C: Additive A can also Mixtures of various ethylene vinyl ester copolymers or terpolymers are used which have a different qualitative and / or quantitative Composition and / or different viscosities (measured at 140 ° C) exhibit. Mixtures of alkylphenol-aldehyde resins are also additive B. usable as the various alkylphenols and / or aldehydes Components included. Mixtures of several of B various paraffin dispersants C can be used. Leave this way the flow improvers adapt to individual requirements.

With additives A, B and optionally C in the invention Processes added oils of animal, vegetable or mineral origin become.

Mineral oils and mineral oil distillates containing paraffin are within the meaning of the invention for example crude oils, distillation residues from petroleum processing or others paraffinic oils. (compare e.g. Compositions and Properties of Petroleum, F. Enke Publishers, Stuttgart 1981, pages 1 - 37). Mineral oil products containing paraffin, in particular middle distillates such as jet fuel, diesel, heating oil EL and heavy heating oil is due to a boiling range of 120 - 500 ° C, preferably 150 - 400 ° C characterized. The paraffins are straight-chain or branched alkanes with about 10 - 50 carbon atoms.

Examples Paraffin dispersion in middle distillates

A) Ethylen-Vinylester-Terpolymere (Fl)

A1) Ethylen-Vinylacetat-Versaticsäurevinylester-Terpolymer mit ca. 31 Gew.-% Vinylacetat und einer bei 140°C gemessenen Schmelzviskosität von 110 mPas, 50%ig in Kerosin.

A2) Ethylen-Vinylacetat-Versaticsäurevinylester-Terpolymer mit ca. 31 Gew.-% Vinylacetat und einer bei 140°C gemessenen Schmelzviskosität von 280 mPas, 50%ig in Kerosin.

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.

A4) Mischung von 2 Teilen des Terpolymers gemäß Beispiel A1 und 1 Teil des Terpolymers gemäß Beispiel A2

B) Alkylphenol-Aldehyd-Harze (PD)

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.

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.

B3) (Vergleichsbeispiel)
Mit 5,5 mol Ethylenoxid unter saurer Katalyse umgesetztes Nonylphenol-Formaldehydharz gemäß Beispiel B1, 50%ig in Solvent Naphtha.

B4) Analog Beispiel B1 unter saurer Katalyse aus Dodecylphenol hergestelltes Harz

B5) Mit NaOH neutralisiertes Harz gemäß B4

B6) Analog Beispiel B1 unter saurer Katalyse aus equimolarer Mengen Phenol und Nonylphenol hergestelltes Harz.

B7) In Anlehnung an Beispiel B1 werden equimolare Mengen Nonylphenol und Formalinlösung in Gegenwart katalytischer Mengen KOH zur Reaktion gebracht.

C) Polare stickstoffhaltige Verbindungen (PN)

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).

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 1-63:

A) ethylene-vinyl ester terpolymers (Fl)

A1) Ethylene-vinyl acetate-versatic acid vinyl ester terpolymer with about 31% by weight of vinyl acetate and a melt viscosity of 110 mPas, measured at 140 ° C., 50% strength in kerosene.

A2) Ethylene-vinyl acetate-versatic acid vinyl ester terpolymer with about 31% by weight of vinyl acetate and a melt viscosity of 280 mPas, measured at 140 ° C., 50% strength in kerosene.

A3) Ethylene-vinyl acetate-versatic acid vinyl ester terpolymer with approximately 31.5% by weight of vinyl acetate and a melt viscosity of 170 mPas, 55% in kerosene, measured at 140 ° C.

A4) Mixture of 2 parts of the terpolymer according to Example A1 and 1 part of the terpolymer according to Example A2

B) alkylphenol aldehyde resins (PD)

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 to a solids content of 50% in ®Solvent Naphtha. 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 acid catalysis. The molecular weight of the red-brown resin is 1800 g / mol.

B3) (comparative example)
Nonylphenol-formaldehyde resin reacted with 5.5 mol of ethylene oxide under acid catalysis according to Example B1, 50% in solvent naphtha.

B4) Resin prepared from dodecylphenol analogously to Example B1 with acid catalysis

B5) Resin neutralized with NaOH according to B4

B6) Resin prepared from equimolar amounts of phenol and nonylphenol analogously to Example B1 with acid catalysis.

B7) Based on example B1, equimolar amounts of nonylphenol and formalin solution are reacted in the presence of catalytic amounts of KOH.

C) Polar nitrogen-containing compounds (PN)

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% 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 (produced according to EP-A-0413279).

These additives A, B and C were added to representative winter diesel fuels from German refineries, which are characterized in Table 1. The boiling analyzes were carried out in accordance with ASTM D-86. Characterization of the test oils test oil 1 2 3 4 5 6 7 8th Start of boiling ° 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 End of 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 above test oils were measured at room temperature using the table 2 specified amounts of the additives heated to 60 ° C, 15 minutes heated to 40 ° C with occasional shaking and then on Cooled to room temperature. The middle distillate so additized was according to EN 116 determines the CFPP value (Cold Filter Plugging Point).

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

150 ml of the middle distillates additized as described above were placed in 200 ml measuring cylinders cooled in a refrigerator at -2 ° C / hour to -13 ° C and 16 Stored at this temperature for hours. Subsequently, volume and Appearance of both the sedimented paraffin phase and the one above it standing oil phase determined and assessed. A small amount of sediment and one cloudy oil phase show good paraffin dispersion.

In addition, the lower 20% by volume was isolated and the cloud point determined in accordance with 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.

Representative winter diesel fuels were selected for the following tests German refineries used. The middle distillates were at room temperature mixed with the stated amounts of the additives tempered at 60 ° C., 15 Minunten heated to 40 ° C with occasional shaking and then on Cooled to room temperature. The middle distillate so additized was according to EN 116 determines the CFPP value.

The additive middle distillates were in 200 ml measuring cylinders in one Refrigerator cooled to -2 ° C / hour to -13 ° C and 16 hours at this Temperature stored. Subsequently, both volume and appearance were visual the sediment (paraffin phase) as well as the oil phase above it and judged. A small amount of sediment and a cloudy oil phase show one good paraffin dispersion.

In addition, the lower 20 vol.% Were isolated and the cloud point determined. A slight deviation of the cloud point of the lower phase (CP _KS ) from the blank value of the oil shows good paraffin dispersion.

Effectiveness as a solution mediator

A) Amide ammonium salt of a spirobislactone according to EP 0413279, 50% in Solvent naphtha.

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% strength in solvent naphtha (according to EP 0606055).

C) Nonylphenol-formaldehyde resin according to DE 3142955, produced by acid Catalyzed condensation of p-nonylphenol and formaldehyde, 50% in solvent Naphtha.

The active ingredients listed above are homogenized at 80 ° C. with stirring. The stability of the solutions is then assessed visually after storage for 3 days at room temperature or at 60 ° C. 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 trade names used

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 up to 287 ° C

®Exxsol

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

®ISOPAR (Exxon)

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

®Shellsol D

mainly aliphatic solvent mixtures in different boiling ranges

Claims (24)

1. A process for improving the flowability of paraffin-containing mineral oils and mineral oil distillates, which comprises adding

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

   B) at least one alkylphenol-aldehyde resin, where the resin or the resins contain at most 10 mol% of alkylphenols which contain more than one alkyl group, and, if appropriate,

   C) at least one polar nitogen compound different from B as paraffin dispersant

   to the paraffin-containing mineral oil or mineral oil distillate.
2. The process as claimed in claim 1, wherein

   A) 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,

   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, if appropriate,

   C) up to 2000 ppm, preferably up to 1000 ppm, based on the mineral oil or mineral oil distillate of at least one paraffin dispersant different from B,

   are added to the paraffin-containing mineral oil or mineral oil distillate.
3. The process as claimed in claim 1 or 2, wherein the ethylene/vinyl ester co- or terpolymers A have an ethylene content of 60 - 90% by weight.
4. The process as claimed in one or more of claims 1 - 3, wherein identical or different alkylphenol-aldehyde resins Bare used, the alkyl radicals of the alkylphenol having 1 - 20, preferably 4 - 16, in particular 6 - 12, carbon atoms and are in particular n-, tert- and isobutyl, n- and isopentyl, n- and isohexyl, n- and isooctyl, n-and isononyl, n- and isodecyl, n- and isododecyl, and the aldehyde has 1-4 carbon atoms and is preferably formaldehyde, acetaldehyde and butyraldehyde, in particular formaldehyde.
5. The process as claimed in one or more of claims 1 - 4, wherein, as paraffin dispersants C which are different from B, use is made of polar, low-molecular-weight or polymeric oil-soluble compounds which

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

   and/or bear one or more ammonium groups which are derived from amines having one or two C₈ - C₂₆ - alkyl groups.
6. The process as claimed in one or more of claims 1 - 5, wherein the ethylene/vinyl ester co- or terpolymers A and the alkylphenol-aldehyde resins B and, if appropriate, the paraffin dispersants C which are different from B are added separately to the mineral oil or mineral oil distillate.
7. The process as claimed in one or more of claims 1-5, wherein the ethylene/vinyl ester co- or terpolymers A are added individually and the alkylphenol-aldehyde resins B and the paraffin dispersants C which are different from B are added in a mixture which comprises 10-90% by weight of at least one alkylphenol-aldehyde resin B and 90-10% by weight of at least one paraffin dispersant different from B, the total of the additives B and C in the mixture always being 100% by weight.
8. The process as claimed in one or more of claims 1-5, wherein a mixture of 5-90% by weight of at least one ethylene/vinyl ester co- or terpolymer A and 5-90% by weight of at least one alkylphenol-aldehyde resin B, and, if appropriate, 5-90% by weight of at least one paraffin dispersant C which is different from B is added to the mineral oil or mineral oil distillate, the total of the additives A, B and C always being 100% by weight.
9. The process as claimed in claim 6, 7 or 8, wherein the individual additives A, B and, if appropriate, C, or the corresponding mixtures of the additives B and C or A, B and, if appropriate, C, are dissolved or dispersed in an organic solvent or dispersant prior to addition to the mineral oil or mineral oil distillate.
10. The use of the alkylphenol-aldehyde resins B in combination with ethylene/vinyl ester co- or terpolymer A and, if appropriate, polar nitrogen compounds which are different from B as paraffin dispersants C as flow improver, in particular the paraffin dispersants in mineral oils and mineral oil distillates.
11. A mixture of

    B) 10 - 90% by weight of at least one alkylphenol-aldehyde resin and

    C) 90 - 10% by weight of at least one polar nitrogen compound different from B as paraffin dispersant,

    the total of the additives B and C always being 100% by weight, wherein it is dissolved or dispersed in an organic solvent or dispersion medium, this solution or dispersion then containing 5 - 90, preferably 5 - 75, % by weight of the mixture.
12. A mixture 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 and, if appropriate,

    C) 5 - 10% by weight of at least one polar nitogen compound different from B as paraffin dispersant,

    the total of the additives A, B and C always being 100% by weight.
13. A mineral oil or mineral oil distillate comprising

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

    B) at least one alkylphenol-aldehyde resin and, if appropriate,

    C) at least one polar nitogen compound different from B as paraffin dispersant.
14. A mineral oil or mineral oil distillate as claimed in claim 13, wherein it comprises

    A) 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,

    B) 10 - 2000 ppm, preferably 10 - 1000 ppm, based on the mineral oil or mineral oil distillate, of 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, of at least one paraffin dispersant different from B.
15. An additive mixture for paraffin dispersion in paraffin-containing mineral oils and mineral oil distillates comprising at least one polar nitrogen compound as paraffin dispersant and at least one aliphatic or aromatic liquid hydrocarbon as solvent, wherein at least one alkylphenol-aldehyde resin is added as solubilizer.
16. An additive mixture as claimed in claim 15, wherein, as paraffin dispersants, use is made of polar low-molecular-weight or polymeric oil-soluble compounds which

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

    b) and/or bear one or more ammonium groups which are derived from amines having one or two C₈-C₂₆-alkyl groups,

    preferably polar nitrogen compounds.
17. An additive mixture as claimed in claim 15 and/or 16, wherein the alkylphenol-aldehyde resin is derived from ortho- or para-alkylphenols.
18. An additive mixture as claimed in one or more of claims 15 to 17, wherein the alkyl radical of the alkylphenol-aldehyde resin has 1 to 20, preferably 4 to 12, in particular 6-12, carbon atoms.
19. An additive mixture as claimed in one or more of claims 15 to 18, wherein the alkyl radical is n-, tert- or isobutyl, n- or isopentyl, n- or isohexyl, n- or isooctyl, n- or isononyl, n- or isodecyl, n- or isododecyl.
20. An additive mixture as claimed in one or more of claims 15 to 19, wherein the aldehyde of the alkylphenol-aldehyde resin has 1 to 4 carbon atoms.
21. An additive mixture as claimed in claim 20, wherein it relates to formaldehyde, acetaldehyde or butyraldehyde.
22. An additive mixture as claimed in one or more of claims 15 to 21, wherein the molecular weight of the alkylphenol-aldehyde resins is between 400 and 10,000, preferably between 400 and 5000, g/mol.
23. An additive mixture as claimed in one or more of claims 15 to 22, wherein it comprises flow improvers which consist of co- and/or terpolymers of ethylene and vinyl esters.
24. A process for preparing solutions of flow improvers and polar nitrogen compounds as paraffin dispersants in aliphatic or aromatic liquid hydrocarbons, which comprises adding to the mixture of these substances an alkylphenol-aldehyde resin.