EP1294832B1 - Additives for improving the cold flow properties and the storage stability of crude oil - Google Patents

Abstract

The invention relates to additives for improving the flowability of mineral oils, containing:A) 1-40 wt. % of at least one copolymer, which is oil-soluble and improves the cold flow properties of mineral oil, selected from A1) copolymers consisting of 80 to 96.5 mol % ethylene and 3.5-20 mol % vinyl esters of carboxylic acids with 1-20 C atoms and/or (meth)acrylic acid esters of alcohols with 1-8 C atoms, and A2) homopolymers or copolymers of esters, containing C10-C30 alkyl radicals, of ethylenically unsaturated carboxylic acids with up to 20 mol % of other olefinically unsaturated compounds,B) 20-80 wt. % of at least one poly-alpha-olefin with a molecular weight of 250-5000, derived from monoolefins with 3-5 C atoms, andC) 5-70 wt. % of at least one organic acid selected from C1) alkylphenol-aldehyde resins of formula (1),wherein R<1 >and R<2 >independently designate H or alkyl radicals with 1-30 C atoms, but both radicals do not at the same time signify H, n represents an integer of 3-50, and R<3 >represents H or an alkyl radical with 1-4 C atoms, and C2) aliphatic and/or aromatic sulfonic acids of formula R<18>-SO3H, wherein R<18 >stands for C6-C40-alkyl, C6-C40-alkenyl, or an alk(en)yl aryl radical which has 1, 2, 3 or 4 aromatic rings and 1, 2, 3 or 4 alkyl or aryl radicals with respectively 6-40 C-atoms.

Description

The present invention relates to an additive composition Flow improvers, poly-α-olefins and organic acids, and their Use to improve the cold flow and storage properties of Crude oils.

Crude oils, residual oils, oil distillates, e.g. Diesel fuel, mineral oils, Lubricating oils, hydraulic oils, etc. contain depending on their origin or the nature of their Processing more or less large amounts of n-paraffins and asphaltenes, which pose particular problems because they decrease in temperature crystallize out or agglomerate and thereby deteriorate the Flow properties of these oils can lead. This deterioration in The flow properties of the oils are known as "stagnation" of the oil. The Pour point is the standardized name for the temperature at which an oil, e.g. Mineral oil, diesel fuel or hydraulic fluid when cooling down just stops flowing. However, the pour point is not identical to the so-called pour point. The pour point is non-specific, not by Standard-covered term for the temperature at which a solid begins to flow under given measuring conditions. Through the The flow properties can then deteriorate, for example, when Transportation, storage and / or processing of these oils containers, Pipes, valves or pumps are blocked, especially if they contain paraffin Oils that are difficult to inhibit. Also require Paraffin precipitation increased pressures when restarting pipelines (Yield Point).

In practice, special difficulties arise when the wax Appearance Temperature (WAT) and in particular the intrinsic point of this Oils above ambient temperature, especially at 20 ° C or above lie. In view of the decreasing world oil reserves and increasing Development of deposits that deliver crude oils with high own stockpoints, the extraction and transportation of such problem oils always get one growing importance.

There is one to restore or maintain fluidity Series of measures of thermal or mechanical nature, e.g. the scraping of the crystallized paraffin from the inner tube wall by regular Newts, the heating of entire pipelines or flushing processes with solvents. The cause of the phenomenon is certainly more elegant Addition of flow improvers, which are also used as pour point depressants (pour point Depressants) or paraffin inhibitors. It is in generally a lowering of the pour point to values below the respective ambient temperature, in particular to values of approximately 10 ° C. and including advantageous.

The operation of these flow improvers is generally explained by that they inhibit the crystallization of paraffins and asphaltenes or with the Co-crystallize paraffins or paraffin-asphaltene adducts and thereby to Formation of smaller wax crystals that no longer aggregate and no longer Can build flow impairing network. The consequence is one Lowering the pour point and maintaining the fluidity of the Oil at low temperature. The effectiveness of the flow improver depends on it both of their chemical structure (composition) and of their Concentration.

US-3,567,597 describes mineral oil distillates containing crude oils, shale oils and residual oils which, as pour point depressants, contain a copolymer of ethylene and a vinyl ester of a saturated aliphatic C ₁ to C ₃₀ monocarboxylic acid, the copolymer having an average molecular weight of 4,000 to 60,000 and Contains 40 to 95 wt .-% ethylene.

DE-A-20 57 168 discloses a method for reducing the flow of friction in oily liquids flowing through lines and a small amount Concentrations of effective, shear-resistant additive with which the Reduce friction losses in oily liquids. This is the Liquids a small amount of at least one high molecular weight polymer added, which is derived from at least one α-olefin having 6 to 20 carbon atoms (Polyolefin).

EP-A-0 176 641 discloses that the properties of poly-α-olefins are known as This will improve flow accelerators for liquid hydrocarbons leave that the polymerization of the α-olefins by the Ziegler method in Presence of a dialkyl aluminum halide and one Trialkylaluminum compound performs.

GB-A-2 305 437 discloses pour point depressants for crude oils. These include a reaction product from an alkylphenol with an average of more than 30 carbon atoms in the alkyl radical, with an aldehyde with 1 to 12 carbon atoms. This pour point Depressants are suitable for treating crude oils that have a pour point above 4 ° C.

EP-A-0 311 452 discloses additives for improving the cold flow behavior of Fuel and lubricating oils. These additives include an alkylphenol aldehyde resin with a molecular weight of at least 3000, which has 6 to 50 carbon atoms in the alkyl radical and has a specified distribution of the carbon chain lengths the alkyl residue shows.

US 3,735,770 discloses a method for improving the flowability of Crude oils in the cold. This process involves the addition of copolymers Ethylene with unsaturated carboxylic acid esters, or from alkylphenols to oil.

EP-A-0 857 776 discloses mixtures of ethylene copolymers, alkylphenol-formaldehyde resins and optionally paraffin dispersants (polar nitrogenous compounds) to improve the cold properties of Mineral oils. These blends show up in paraffin-rich crude oils with long chain However, paraffins are not sufficiently effective.

A disadvantage of the known flow improvers for crude and residue oils in many cases still insufficient effectiveness and the resulting resulting high use concentrations, especially with oils with high Proportion of long-chain n-paraffins with more than 30 carbon atoms. The known flow improvers also favor by lowering the Viscosity of the additive oil the sedimentation of the failed, specific heavier wax crystals. High-molecular poly-α-olefins can do that To improve the flow behavior of oils, but they do not improve them Low-temperature behavior. The high intrinsic storey points of the Flow improvers that are used for dosing a warming and / or a very strong one Require dilution.

Additives are therefore sought which have improved properties as Pour point lower, i.e. which even with low doses have sufficient effectiveness and in comparison with pour point depressants of the prior art with a lower concentration Have their own pour point and with a variety of oils, especially at paraffinic oils are effective. The additive is supposed to lower the cloud point, reduce the viscosity and yield point of the oil in the cold, and the Delay or prevent sedimentation of the failed paraffin crystals.

Surprisingly, it has now been found that with a ternary mixture of Active ingredients the required properties of the additive can be achieved.

A) 1 bis 40 Gew.-% wenigstens eines Copolymers, welches öllöslich und ein Kaltfließverbesserer für Mineralöle ist, ausgewählt aus

A1) Copolymeren aus 80 bis 96,5 mol-% Ethylen und 3,5 bis 20 mol-% Vinylestern von Carbonsäuren mit 1 bis 20 C-Atomen und/oder (Meth)acrylsäureestern von Alkoholen mit 1 bis 8 C-Atomen, und

A2) Homo- oder Copolymeren von C₁₀-C₃₀-Alkylreste tragenden Estern ethylenisch ungesättigter Carbonsäuren mit bis zu 20 mol-% weiterer olefinisch ungesättigter Verbindungen,

B) 20 bis 80 Gew.-% mindestens eines Poly-α-Olefins mit einem Molekulargewicht von 250 bis 5000, das sich aus Monoolefinen mit 3 bis 5 C-Atomen ableitet, und

C) 5 bis 70 Gew.-% mindestens einer organischen Säure, ausgewählt aus

C1) Alkylphenol-Aldehydharzen der Formel 1

worin R¹ und R² unabhängig voneinander für H oder Alkylreste mit 1 bis 30 C-Atomen stehen, wobei aber nicht beide Reste zugleich H bedeuten, n eine ganze Zahl von 3 bis 50 bedeutet, und R³ für H oder einen Alkylrest mit 1 bis 4 C-Atomen steht, und

C2) aliphatischen und/oder aromatischen Sulfonsäuren der Formel R¹⁸-SO₃H, worin R¹⁸ für C₆- bis C₄₀-Alkyl, C₆- bis C₄₀-Alkenyl, oder einen Alk(en)ylarylrest steht, welcher 1, 2, 3 oder 4 aromatische Ringe und 1, 2, 3 oder 4 Alkyl- oder Alkenylreste mit jeweils 6 bis 40 C-Atomen aufweist.

The invention thus relates to additives for improving the flowability of mineral oils

A) 1 to 40% by weight of at least one copolymer which is oil-soluble and a cold flow improver for mineral oils is selected from

A1) copolymers of 80 to 96.5 mol% of ethylene and 3.5 to 20 mol% of vinyl esters of carboxylic acids with 1 to 20 C atoms and / or (meth) acrylic acid esters of alcohols with 1 to 8 C atoms, and

A2) homopolymers or copolymers of esters bearing C ₁₀ -C ₃₀ -alkyl radicals of ethylenically unsaturated carboxylic acids with up to 20 mol% of further olefinically unsaturated compounds,

B) 20 to 80 wt .-% of at least one poly-α-olefin with a molecular weight of 250 to 5000, which is derived from monoolefins having 3 to 5 carbon atoms, and

C) 5 to 70% by weight of at least one organic acid selected from

C1) Alkylphenol aldehyde resins of the formula 1

in which R ¹ and R ² independently of one another represent H or alkyl radicals having 1 to 30 C atoms, but not both radicals simultaneously being H, n being an integer from 3 to 50, and R ^{3 being} H or an alkyl radical having 1 is up to 4 carbon atoms, and

C2) aliphatic and / or aromatic sulfonic acids of the formula R ¹⁸ -SO ₃ H, in which R ^{18 represents} C ₆ - to C ₄₀ -alkyl, C ₆ - to C ₄₀ -alkenyl, or an alk (en) ylaryl radical which 1 , 2, 3 or 4 aromatic rings and 1, 2, 3 or 4 alkyl or alkenyl radicals each having 6 to 40 carbon atoms.

Another object of the invention are mineral oils that described Contain mixtures of the components A), B), and C).

Another object of the invention is the use of these Composition to improve cold flow properties and Storage stability of mineral oils.

The mixtures according to the invention preferably contain 2 to 30% by weight, especially 5 to 25% by weight of copolymer A), 25 to 70% by weight, especially 30 to 60 % By weight poly-α-olefin B) and 5 to 65% by weight, especially 10 to 50% by weight organic acid C).

The vinyl esters of component A1) are generally those of the formula 2 CH ₂ = CH - OCOR ⁴ wherein R ^{4 is} C ₁ -C ₂₀ alkyl, preferably C ₁ -C ₁₆ alkyl, especially C ₁ -C ₁₂ alkyl. In a further preferred embodiment, R ^{4 represents} a neoalkyl radical with 7 to 11 carbon atoms, in particular with 8, 9 or 10 carbon atoms. Suitable vinyl esters include vinyl acetate, vinyl propionate, 2-ethylhexyl vinyl ester, vinyl laurate, neononane, neodecanoic and neoundecanoic acid vinyl esters. Vinyl acetate and vinyl propionate are particularly preferred.

The acrylic esters of component A1) are preferably those of the formula 3 CH ₂ = CR ⁵ - COOR ⁶ wherein R ^{5 is} hydrogen or methyl and R ^{6 is} C ₁ -C ₈ alkyl, preferably C ₂ -C ₆ alkyl. Suitable acrylic esters include methyl acrylate, ethyl acrylate, n- and isopropyl acrylate, n-, iso- and tert-butyl acrylate and 2-ethylhexyl acrylate, as well as the corresponding esters of methacrylic acid.

In addition to vinyl and / or (meth) acrylic esters of the formulas 2 and 3, the copolymers of constituent A1) can also comprise up to 5 mol% of structural units of alkyl vinyl ethers and / or olefins.
The alkyl vinyl ethers are preferably compounds of the formula 4 CH ₂ = CH - OR ⁷ wherein R ^{7 is} C ₁ -C ₃₀ alkyl, preferably C ₁ -C ₁₆ alkyl, especially C ₁ -C ₁₂ alkyl.

The olefins are preferably alkenes with 3 to 30, especially with 3 to 10 carbon atoms. Suitable olefins are for example propene, butene, isobutene, pentene, hexene, isohexene, diisobutylene and norbornene.

The alkyl radicals R ⁴ , R ⁶ and R ⁷ can carry minor amounts of functional groups such as amino, amido, nitro, cyano, hydroxyl, keto, carbonyl, carboxy, ester, sulfo groups or halogen atoms, as long as these do not significantly impair the hydrocarbon character of the radicals mentioned.

The molecular weight of the copolymers of component A1) is preferably between 1000 and 100,000 units, which according to DIN 53735 at 190 ° C and a tracking force of 2.16 kg measured MFI values between 0.1 and Corresponds to 1000g / 10 min.

die aus DE-A-34 43 475 bekannten Ethylen-Vinylacetat-Hexen-Terpolymere;

die in EP-A-0 203 554 beschriebenen Ethylen-Vinylacetat-Diisobutylen-Terpolymere;

die aus EP-A-0 254 284 bekannte Mischung aus einem Ethylen-Vinylacetat-Diisobutylen-Terpolymerisat und einem Ethylen/Vinylacetat-Copolymer;

die in EP-A-0 405 270 offenbarten Mischungen aus einem Ethylen-Vinylacetat-Copolymer und einem Ethylen-Vinylacetat-N-Vinylpyrrolidon-Terpolymerisat;

die in EP-A-0 463 518 beschriebenen Ethylen/Vinylacetat/iso-Butylvinylether-Terpolymere;

die in EP-A-0 491 225 offenbarten Mischpolymerisate des Ethylens mit Alkylcarbonsäurevinylestern;

die aus EP-A-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-C-196 20 118 beschriebenen Terpolymere aus Ethylen, dem Vinylester einer oder mehrerer aliphatischer C₂-C₂₀-Monocarbonsäuren und 4-Methylpenten-1;

die in DE-C-196 20 119 offenbarten Terpolymere aus Ethylen, dem Vinylester einer oder mehrerer aliphatischer C₂-C₂₀-Monocarbonsäuren und Bicyclo[2.2.1]hepten.

The ethylene content in copolymer A1) is between 80 and 96.5, preferably between 84 and 95 mol%. Ingredient A1) is preferably a higher molecular weight variant of what is known as flow improver, which middle distillates are often added to improve the cold flow properties. In general, all known copolymers or terpolymers and mixtures thereof can be used as copolymer A) which, taken on their own, improve the cold flow properties of mineral oils or mineral oil distillates. Examples of suitable copolymers or terpolymers are:

the ethylene-vinyl acetate-hexene terpolymers known from DE-A-34 43 475;

the ethylene-vinyl acetate-diisobutylene terpolymers described in EP-A-0 203 554;

the mixture known from EP-A-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-A-0 405 270;

the ethylene / vinyl acetate / isobutyl vinyl ether terpolymers described in EP-A-0 463 518;

the copolymers of ethylene with alkylcarboxylic acid vinyl esters disclosed in EP-A-0 491 225;

the ethylene / vinyl acetate / neononanoic acid vinyl ester or neodecanoic acid vinyl ester terpolymers known from EP-A-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-C-196 20 118 made 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] disclosed in DE-C-196 20 119 hepten.

In particular, here are ethylene / vinyl acetate, ethylene / vinyl propionate, Ethylene / versatic acid vinyl ester, ethylene / vinyl acetate / versatic acid vinyl ester, Ethylene / vinyl acetate / diisobutylene, ethylene / vinyl acetate / 4-methylpentene and To name ethylene / vinyl acetate / isobutylene copolymers.

The copolymers A1) are prepared by known processes (see here e.g. Ullmann's Encyclopedia of Technical Chemistry, 5th edition, Vol. A 21, Pages 305 to 413). Polymerization in solution, in suspension, in the gas phase and high pressure bulk polymerization. Preferably turns the high-pressure bulk polymerization, which is carried out at pressures of 50 to 400 MPa, preferably 100 to 300 MPa and temperatures of 50 to 350 ° C, preferably 100 to 300 ° C, is carried out. The reaction of the comonomers is initiated by radical initiators (radical chain initiators). To this class of substances belongs e.g. Oxygen, hydroperoxides, peroxides and Azo compounds such as cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, Dibenzoyl peroxide, bis (2-ethylhexyl) peroxidicarbonate, t-butyl permaleinate, t-butyl perbenzoate, dicumyl peroxide, t-butylcumyl peroxide, di- (t-butyl) peroxide, 2,2'-azobis (2-methylpropanonitrile), 2,2'-azobis (2-methylbutyronitrile). The Initiators are used individually or as a mixture of two or more substances Amounts of 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the comonomer mixture used.

The desired melt viscosity of the copolymers A1) is given Composition of the comonomer mixture by varying the Reaction parameters pressure and temperature and optionally by adding Moderators hired. Hydrogen, saturated or unsaturated hydrocarbons, e.g. Propane, aldehydes, e.g. propionaldehyde, n-butyraldehyde or isobutyraldehyde, ketones, e.g. Acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone or alcohols, e.g. Butanol, proven. In Depending on the desired viscosity, the moderators in quantities up to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Comonomer mixture used.

High pressure bulk polymerization is carried out in known high pressure reactors, e.g.

Autoclaves or tube reactors are carried out batchwise or continuously, Tube reactors have proven particularly useful. Solvents such as aliphatic Hydrocarbons or hydrocarbon mixtures, benzene or toluene, can be contained in the reaction mixture, although the solvent-free working method has proven particularly successful. According to a preferred The embodiment of the polymerization is the mixture of the comonomers, the initiator and, if used, the moderator, a tubular reactor via the Reactor entrance and fed via one or more side branches. in this connection the comonomer streams can be composed differently (EP-B-0 271 738).

wobei R⁸ und R⁹ unabhängig voneinander für Wasserstoff, Phenyl oder eine Gruppe der Formel COOR¹¹ stehen, R¹⁰ für Wasserstoff, Methyl oder eine Gruppe der Formel -CH₂COOR¹¹ steht und R¹¹ für einen C₁₀- bis C₃₀-Alkyl- oder Alkylenrest, vorzugsweise für einen C₁₂ bis C₂₆-Alkyl- oder Alkylenrest steht, mit der Maßgabe, dass diese wiederkehrenden Struktureinheiten mindestens eine und höchstens zwei Carbonsäureestereinheiten in einem Strukturelement enthalten.Preferred copolymers A2) contain 80-100 mol% of the recurring structural element of the formula 5

where R ⁸ and R ⁹ independently of one another are hydrogen, phenyl or a group of the formula COOR ¹¹ , R ^{10 is} hydrogen, methyl or a group of the formula -CH ₂ COOR ¹¹ and R ^{11 is} a C ₁₀ - to C ₃₀ - Alkyl or alkylene radical, preferably a C ₁₂ to C ₂₆ alkyl or alkylene radical, with the proviso that these recurring structural units contain at least one and at most two carboxylic acid ester units in one structural element.

Copolymers in which R ⁸ and R ^{9 are} hydrogen or a group of the formula COOR ¹¹ and R ^{10 are} hydrogen or methyl are particularly suitable. These structural units are derived from esters of monocarboxylic acids such as, for example, acrylic acid, methacrylic acid, cinnamic acid, or from semi- or diesters of dicarboxylic acids, such as, for example, maleic acid, fumaric acid and itaconic acid.

The esters of acrylic acid are particularly preferred.

For the esterification of ethylenically unsaturated mono- and dicarboxylic acids Suitable alcohols are those with 10-30 carbon atoms, especially those with 12-26 carbon atoms such as 1-decanol, 1-dodecanol, 1-tridecanol, Isotridecanol, 1-tetradecanol, 1-hexadecanol, eicosanol, docosanol, Tetracosanol, hexacosanol and naturally occurring mixtures such as Coconut fatty alcohol, tallow fatty alcohol and behenyl alcohol. The alcohols can be of natural as well as synthetic origin.

In addition to C ₁₀ -C ₃₀ alkyl esters of unsaturated carboxylic acids, the copolymers of component A2) can contain up to 20 mol%, preferably up to 10 mol%, of comonomers such as vinyl esters of the formula 2, (meth) acrylic esters of the formula 3, alkyl vinyl ethers of the formula 4 and / or olefins. Furthermore, in particular heteroatoms bearing ethylenically unsaturated compounds such as allyl polyglycols, benzyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, dimethylaminoethyl acrylate, perfluoroalkyl acrylate, and the corresponding esters and amides of methacrylic acid, vinyl pyridine, vinyl pyrrolidone, acrylic acid, methacrylic acid, p-acetoxystyrene, and vinyl methoxyacetate as comonomers in Component A2) suitable.

worin

R¹²

für Wasserstoff oder Methyl steht,

Z

für C₁-C₃-Alkyl steht,

R¹³

für Wasserstoff, C₁-C₃₀-Alkyl, Cycloalkyl, Aryl oder -G(O)-R⁸ steht,

R¹⁴

für Wasserstoff, C₁-C₂₀-Alkyl steht,

R¹⁵

für C₁-C₃₀-Alkyl, C₃-C₃₀-Alkenyl, Cycloalkyl oder Aryl steht und

m

eine Zahl von 1 bis 50, vorzugsweise 1 bis 30 bedeutet.

In preferred embodiments of the invention, allyl polyglycols can comprise 1 to 50 EO or PO units and correspond to formula 6:

wherein

R ¹²

represents hydrogen or methyl,

Z

represents C ₁ -C ₃ alkyl,

R ¹³

represents hydrogen, C ₁ -C ₃₀ alkyl, cycloalkyl, aryl or -G (O) -R ⁸ ,

R ¹⁴

represents hydrogen, C ₁ -C ₂₀ alkyl,

R ¹⁵

represents C ₁ -C ₃₀ alkyl, C ₃ -C ₃₀ alkenyl, cycloalkyl or aryl and

m

is a number from 1 to 50, preferably 1 to 30.

Comonomers of the formula 6 in which R ¹² and R ^{14 are} hydrogen and R ^{13 are} hydrogen or C ₁ -C ₄ -alkyl groups and are particularly preferred.

The molecular weights or molecular weight distributions of the invention Copolymers have a K value (measured according to Fikentscher in 5% Solution in toluene) characterized from 10 to 100, preferably 15 to 80. The Molecular weights Mw can range from 2,000 to 500,000, preferred 5,000 to 300,000 and for example by means of gel permeation chromatography against polystyrene standards.

The copolymers A2) are prepared by (co) polymerizing esters ethylenically unsaturated carboxylic acids, especially (meth) acrylates, optionally with other comonomers according to conventional radicals Polymerization.

A suitable manufacturing process is to combine the monomers in one dissolve organic solvents and in the presence of a radical initiator Polymerize temperatures in the range of 30 to 150 ° C. As a solvent are aromatic hydrocarbons such. B. toluene, xylene, Trimethylbenzene, dimethylnaphthalene or mixtures of these aromatic Hydrocarbons. Commercially available mixtures of aromatic Hydrocarbons such as Solvent Naphtha or Shellsol AB® (manufacturer: Shell) are used. Aliphatic solvents are also suitable Suitable for hydrocarbons. Also alkoxylated aliphatic alcohols or their Esters such as Butyl glycol is used as a solvent, but is preferred as a mixture with aromatic hydrocarbons.

Commonly used starters such as azo-bisisobutyronitrile, Esters of peroxycarboxylic acids such as e.g. t-butyl perpivalate and t-Butyl-per-2-ethylhexanoate or dibenzoyl peroxide is used.

The polymers which form component B are poly-α-olefins which differ from Allow monoolefins with 3.4 or 5 carbon atoms to be derived. Especially preferred mono-olefins as the base of suitable polyolefins are propylene and isobutylene, of which polypropylene and polyisobutylene as polyolefins arise. You can also use minor amounts, preferably less than 10 mol% of longer-chain α-olefins with 6 to 50, preferably 12 to 40 Contain carbon atoms. Examples of suitable olefins are 1-dodecene, 1-tetradecene, 1-tridecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-Nonadecen, 1-Eicosen, 1-Hemicosen, 1-Docosen, 1-Tetracosen, 1-Hexacosen, 1-Octacoses etc. and their mixtures.

The polyolefins B) are accessible by ionic polymerization, and as Commercial products available (e.g. ®Ultravis, ®Napvis, ®Hyvis, ®Glissopal) (Polyisobutenes from BP, BASF with different alkyl vinylidene contents and Molecular weights).

zurückgehen, worin R¹⁶ oder R¹⁷ Methyl oder Ethyl bedeuten und die andere Gruppe ein Oligomeres des C₃-C₅-Olefins ist. Die Zahl der Kohlenstoffatome des Poly-α-olefins beträgt zwischen 35 und 350. In einer bevorzugten Ausführungsform der Erfindung beträgt die Zahl der Kohlenstoffatome zwischen 45 und 250.The distribution of the olefin isomers resulting from various polymerization processes is generally of minor importance for the use according to the invention, but in special cases poly-α-olefins with an increased alkylvinylidene content of more than 50 mol%, in particular more than 70 mol% proven to be advantageous.
Alkyl vinylidene content means the content of the polyolefins in structural units with terminal double bonds which are based on compounds of the formula 7

decrease in which R ¹⁶ or R ^{17 is} methyl or ethyl and the other group is an oligomer of the C ₃ -C ₅ olefin. The number of carbon atoms of the poly-α-olefin is between 35 and 350. In a preferred embodiment of the invention, the number of carbon atoms is between 45 and 250.

Component C1) is an alkylphenol-aldehyde resin. These are known in principle and for example in the Römpp Chemie Lexikon, 9th edition, Thieme Verlag 1988-92, Volume 4, pp. 3351 ff.

The alkyl radicals R ¹ and R ^{2 of} the alkylphenol can be the same or different in the alkylphenol-aldehyde resins C1) used in the additive according to the invention and have 1 to 30, preferably 4 to 20 carbon atoms; it is preferably 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, tripropenyl, tetrapropenyl and pentapropenyl. The phenol is preferably monoalkylated.

The aliphatic aldehyde in the alkylphenol-aldehyde resin C1) has 1 to 4 Carbon atoms and is preferably formaldehyde. The average molecular weight the alkylphenol-aldehyde resins are preferably 400-10,000, in particular 400 - 5000 g / mol. The prerequisite here is that the resins are oil-soluble.

The alkylphenol-aldehyde resins C1) are prepared in a known manner by basic catalysis, whereby condensation products of the resol type arise, or by acid catalysis, where novolak-type condensation products arise.

The condensates obtained according to both types are as additive component C1) suitable. The condensation in the presence of acidic catalysts is preferred. To produce the alkylphenol-aldehyde resins, a mono- and / or Dialkylphenol with 1 to 30 carbon atoms, preferably 4 to 20 carbon atoms each Alkyl group, or mixtures thereof and an aliphatic aldehyde with 1 to 4 carbon atoms reacted with each other, about per mole of alkylphenol compound 0.5-2 mol, preferably 0.7-1.3 mol, of aldehyde can be used.

Suitable alkylphenols are in particular C ₄ -C ₂₀ alkylphenols 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 1-dodecylphenol, tripropenylphenol, tetrapropenylphenol and pentapropenylphenol. The corresponding dialkylated phenols are likewise suitable, it being possible for the alkyl radicals to be the same or different.

Particularly suitable aldehydes are formaldehyde, acetaldehyde and Butyraldehyde, formaldehyde is preferred. The formaldehyde can take the form of Paraformaldehyde or in the form of a preferably 20 to 40 wt .-% aqueous formalin solution can be used. It can also be corresponding Amounts of trioxane can 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 acids, Sulfamido acids or haloacetic acids, and in the presence of one with water an 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 is removed. Solvents that are under the conditions of Condensation no protons can split off after the condensation reaction stay in the products. The resins can be used directly or after neutralization of the Catalyst are used, 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, ®Solvesso 250, ®Exxsol, ®ISOPAR and Shellsol D types.

Constituent C2) is organic, oil-soluble sulfonic acids or their metal or ammonium salts, preferably alkali metal salts. Aliphatic sulfonic acids such as alkane sulfonates having 8 to 30, particularly preferably 10 to 26, in particular 12 to 24, carbon atoms are preferred. The sulfone group can be terminal or attached to a methylene group on the hydrocarbon chain. Aromatic sulfonic acids with one or two C ₈ to C ₃₀ , in particular C ₁₂ to C ₂₄ alkyl or alkenyl radicals and 1 or 2 aromatic rings are further preferred. The alkyl or alkenyl radicals can be linear or branched and can be attached at any point on the aromatic system. They are preferably in the para position to the sulfone group in systems monosubstituted with alkyl or alkenyl radicals and in the ortho and para position to the sulfone group in systems disubstituted with alkyl or alkenyl radicals. Examples include: nonylbenzenesulfonic acid, dodecylbenzenesulfonic acid, nonylnaphthalenesulfonic acid, dinonylbenzenesulfonic acid and didodecylbenzenesulfonic acid.

Oil-soluble in the sense of the invention means that at least 10% by weight is preferred at least 1% by weight, in particular at least 0.1% by weight of the additive in addition additive middle distillate becomes clearly soluble. This definition is analogous apply if the term oil-soluble is used elsewhere. The additives according to the invention are particularly suitable, the flowability and paraffin sedimentation of crude oils and other paraffinic mineral oils to improve, whose paraffin sediments larger portions (preferably more than 20 area% according to GC, in particular 30 to 60 area%, especially 40 to 50 Area%) of n-paraffins with carbon chain lengths of 30 and more carbon atoms exhibit. These oils are usually dark due to asphaltenes and resins colored, but they are preferably transparent. Furthermore, the Additives according to the invention are able to determine the yield point of the additive oils lower and thus facilitate the restarting of pipelines.

The additive components according to the invention can be separated from the mineral oils or added in a mixture. Have to improve manageability solutions or dispersions containing 10 to 90 wt .-%, preferably 20 to 80 wt .-%, the additives or the additive combination contain, especially proven. Suitable solvents or dispersing agents 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 as well aliphatic or aromatic alcohols, ethers and / or esters. Through the Additive combination in its cold flow properties improved mineral oils contain between 0.001 and 1 wt .-%, preferably between 0.01 and 0.5% by weight of the additive combination based on the mineral oil. The additives according to the invention or the oils additized with them can contain other cold additives such as polar nitrogenous ones Compounds or polyoxyalkylene ethers. Furthermore, they can Corrosion inhibitors, detergent additives, defoamers, demulsifiers, Contain asphalt dispersants and other additives. The addition of this Additives to the oil can be used together with the invention Additive components or separately.

Examples 1. Characterization of the additives used

A1: Ethylen-Vinylacetat Copolymer mit 11,2 mol-% Vinylacetat und einem MFI von 7 g/10 min

A2: Acrylsäurestearylester-Allylpolyglykol-Copolymer aus 95 Gew.-% Acrylsäureester und 5 Gew.-% Allylpolyglykol (7 EO), K-Wert = 33, gemessen in 5 Gew.-% Lösung in Toluol.

A3: Ethylen-Vinylacetat-Copolymer mit 7,1 mol-% Vinylacetat, MFI 12 g/10 min

The following flow improvers were used as component A):

A1: Ethylene-vinyl acetate copolymer with 11.2 mol% of vinyl acetate and an MFI of 7 g / 10 min

A2: Stearyl acrylate-allyl polyglycol copolymer composed of 95% by weight acrylic ester and 5% by weight allyl polyglycol (7 EO), K value = 33, measured in 5% by weight solution in toluene.

A3: ethylene-vinyl acetate copolymer with 7.1 mol% of vinyl acetate, MFI 12 g / 10 min

B1: ®Glissopal 1000 (BASF), M = 1000 g/mol, Viskosität bei 100°C = 215 mPas Alkylvinylidengehalt 85 mol-%

B2: ®Hyvis 5 (BP), M = 780 g/mol, Viskosität bei 100°C = 103 mPas

B3: Hyvis 30 (BP), M = 1300 g/mol, Viskosität bei 100°C = 635 mPas

B4: Hyvis 200 (BP) M = 2600 g/mol, Viskosität bei 100°C = 4250 mPas

B5: Polyisobutylen M = 3000 g/mol, Viskosität bei 100°C = 600 - 670 mPas gemessen nach ASTM D445

The following polyolefins (polyisobutylene) were used as component B):

B1: ®Glissopal 1000 (BASF), M = 1000 g / mol, viscosity at 100 ° C = 215 mPas alkyl vinylidene content 85 mol%

B2: ®Hyvis 5 (BP), M = 780 g / mol, viscosity at 100 ° C = 103 mPas

B3: Hyvis 30 (BP), M = 1300 g / mol, viscosity at 100 ° C = 635 mPas

B4: Hyvis 200 (BP) M = 2600 g / mol, viscosity at 100 ° C = 4250 mPas

B5: polyisobutylene M = 3000 g / mol, viscosity at 100 ° C = 600 - 670 mPas measured according to ASTM D445

C1): Alkylphenol-Aldehydharr gemäß DE 3 142 955, Kondensationsprodukt aus p-n-Nonylphenol und Formaldehyd, hergestellt unter saurer Katalyse, mit 5 bis 8 p-n-Nonylphenoleinheiten

C2): Dodecylbenzolsulfonsäure

C3): Dodecylbenzolsulfonsäure-Natriumsalz

The following organic acids were used as component C):

C1): Alkylphenol-aldehyde resin according to DE 3 142 955, condensation product of pn-nonylphenol and formaldehyde, produced under acidic catalysis, with 5 to 8 pn-nonylphenol units

C2): Dodecylbenzenesulfonic acid

C3): Dodecylbenzenesulfonic acid sodium salt

The following additives were produced using components A, B and C defined above: additive compositions Example No. Weight fraction of the ingredients A B C D 1 1 (A1) 2 (B1) 2 (C1) - 2 1 (A1) 2 (B1) 1 (C1) 1 3 2 (A1) 1 (B1) 2 (C1) - 4 1 (A1) 1 (B1) 1 (C1) - 5 2 (A1) 1 (B1) 1 (C1) - 6 1 (A2) 2 (B1) 2 (C1) - 7 1 (A3) 2 (B1) 2 (C1) - 8th 1 (A1) 2 (B2) 2 (C1) - 9 1 (A1) 2 (B3) 2 (C1) - 10 1 (A1) 2 (B4) 2 (C1) - 11 1 (A1) 43 (B5) 10 (C2) - 12 1 (A1) 43 (B5) 10 (C3) -

2. Crude oil characteristics 2.1 oil

origin Kazakhstan Pour point <- 30 ° C W.A.T. / Cloud point + 39 ° C

2.2 sediment

Siedeverhalten des verwendeten Rohöls, in °C Siedebeginn 115,9 2 Gew.-% 119,7 5 Gew.-% 139,6 10 Gew.-% 172,4 50 Gew.-% 419,5 90 Gew.-% 599,5 95 Gew.-% 636,8 Siedeende 720,5 Iso / n paraffin ratio 1: 2.5 (see table 2) Softening point (SP) 62.5 ° C Oil content (% by weight) 31 D ₇₀ (kg / m ³ ) 799.2 n _D100 1.4370 V ₁₀₀ (mm ² / s) 3.1 Boiling range (° C) 115 - 720 (approx. 50% of the n - paraffins distill between 420 - 720 ° C, see table 3)

Boiling behavior of the crude oil used, in ° C Initial boiling point 115.9 2% by weight 119.7 5% by weight 139.6 10% by weight 172.4 50% by weight 419.5 90% by weight 599.5 95% by weight 636.8 Final boiling point 720.5

1.3 Reduction of the yield point

The yield point is a measure of the force that has to be exerted in order to bring the stocked crude oil back into the flowing state ("restartability"). In the case of the untreated oil, a force of approx. 2.2 Pa must be applied at -20 ° C, while only 0.6 - 0.7 Pa is required for the treated crude oil (500 ppm, example 1) at the same temperature. Yield point in Pa for untreated crude oil and for crude oil with 500 ppm additive according to Example 1, 3, 5 or 6 temperature Crude oil untreated example 1 Example 3 Example 5 Example 6 - 20th 2.2 0.7 0.95 0.9 0.6 - 15th 1.55 0.6 0.8 0.7 0.5 - 10th 1 0.25 0.3 0.3 0.2 - 5th 0.75 0.1 0.1 0.1 0.1 0 0.4 0.05 0.05 0.05 0.05

4. Reduction of viscosity (m Pas)

The viscosities were recorded in the temperature range between +50 and -20 ° C. This shows clear differences between the blank value and the crude oil sample treated with 500 ppm additive according to Example 1 or 6; Some viscosities are compared as examples: Viscosities in mPas sample temperature viscosity untreated crude oil 0 12 untreated crude oil -10 26 untreated crude oil -20 45 Crude oil + 500 ppm additive Ex. 1 0 6 Crude oil + 500 ppm additive Ex. 1 -10 23 Crude oil + 500 ppm additive Ex. 1 -20 34 Crude oil + 500 ppm additive Ex. 3 0 7 Crude oil + 500 ppm additive Ex. 3 -10 24 Crude oil + 500 ppm additive Ex. 3 -20 36 Crude oil + 500 ppm additive Ex. 5 0 6 Crude oil + 500 ppm additive Ex. 5 -10 22 Crude oil + 500 ppm additive Ex. 5 -20 32 Crude oil + 500 ppm additive Ex. 6 0 4 Crude oil + 500 ppm additive Ex. 6 -10 20 Crude oil + 500 ppm additive Ex. 6 -20 31

Not only the viscosity is determined by the addition of additive according to Example 1 or 6 reduced, but it also increases the location of the untreated crude recognizing plateaus shifted in an advantageous manner.

The viscosity plateau occurring when the crude oil cools down to the at a certain temperature, paraffin crystallization occurs increasingly due. The one with 500 ppm additive according to Example 1 or 6 treated sample appears that which occurs in the untreated sample Plateau significantly less pronounced, and only at -9 ° C instead of -5 ° C.

5. Sedimentation (laboratory tests)

Implementation: 50 ml each of the test crude oil are poured into a so-called torpedo glass, heated to 70 ° C. and mixed with 500 ppm of the additives (Examples 1 to 6). Then the oil samples on the shaker (250 strokes / min) for 5 min. shaken and then stored at 21 ° C or 0 ° C. The evaluation is carried out by visual assessment (ml sediment / appearance of the liquid phase etc .; see table) of the sample after or before centrifugation. sedimentation Sample example
No. sediment
(Ml) Appearance of the liquid phase Storage temp.
(° C) storage time
(H) dispersion
D (%) Remarks crude oil
(Blank) 7 cloudy 21 168 0 not centrifuged 4.5 opal 21 168 0 centrifuged
(2000 PM / min) 5 clear 0 24 0 not centrifuged Ex. 1 1 clear 21 168 86 not centrifuged 0.9 clear 21 168 80 centrifuged
(2000 RPM / 5min)
not centrifuged 1.2 cloudy 0 24 76 3.0 clear 21 168 33 20 h at 0 ° C then warm to 21 ° C Ex. 2 1.50 clear 21 168 67 centrifuged
(2000 RPM / 5min) Ex. 3 1.8 clear 21 168 60 centrifuged
(2000 RPM / 5min) Ex. 4 1.5 clear 21 168 67 centrifuged
(2000 RPM / 5min) Ex. 5 1.8 clear 21 168 60 centrifuged
(2000 RPM / 5min) Ex. 6 1.8 clear 21 168 60 centrifuged
(2000 RPM / 5min) Ex. 7 1.5 clear 21 168 79 centrifuged
(2000 RPM / 5min) Ex. 8 1.5 clear 21 168 79 centrifuged
(2000 RPM / 5min) Ex. 9 1.0 clear 21 168 86 centrifuged
(2000 RPM / 5min) Ex. 10 1.2 clear 21 168 83 centrifuged
(2000 RPM / 5min) Ex. 11 1.0 clear 21 168 80 Ex. 12 1.5 clear 21 168 70 Dispersion D = sediment (untreated) - sediment (treated) / sediment (untreated)

6. Comparative experiments

In order to demonstrate the superiority of the compositions according to the invention over the prior art, constituents A, B and C of the composition according to the invention were used alone or in combinations of two to improve the cold flow properties of crude oil. The following table shows the yield point (YP), viscosity (V) and dispersion (D) as previously described for the compositions given. The amount of additive was always 500 ppm. Comparative tests E.g. A B C YP (-10 ° C) V (-20 ° C) D (centrifuged) V1 500 (A1) - - 0.9 45 5 V2 - 500 (B1) - 0.95 43 5 V3 - - 500 0.92 45 7 V4 500 (A2) - - 0.88 42 9 V5 250 (A2) - 250 0.7 41 12 V6 250 (A2) 250 (B1) - 0.75 41 11 V7 - 250 (B1) 250 0.76 42 12

Claims (10)

1. An additive for improving the flowability of mineral oils comprising

   A) from 1 to 40% by weight of at least one copolymer which is oil-soluble and is a cold-flow improver for mineral oils selected from

   A1) copolymers of from 80 to 96.5 mol% of ethylene and from 3.5 to 20 mol% of vinyl esters of carboxylic acids having from 1 to 20 carbon atoms and/or (meth)acrylic esters of alcohols having from 1 to 8 carbon atoms, and

   A2) homo- or copolymers of esters which bear C₁₀-C₃₀-alkyl radicals and are esters of ethylenically unsaturated carboxylic acids comprising up to 20 mol% of further olefinically unsaturated compounds,

   B) from 20 to 80% by weight of at least one poly-α-olefin having a molecular weight of from 250 to 5000 which is derived from monoolefins having from 3 to 5 carbon atoms, and

   C) from 5 to 70% by weight of at least one organic acid selected from

   C1) alkylphenol-aldehyde resins of the formula 1

   

   where R¹ and R² are each independently H or alkyl radicals having from 1 to 30 carbon atoms, but where both radicals may not at the same time be H, n is an integer from 3 to 50 and R³ is H or an alkyl radical having from 1 to 4 carbon atoms, and

   C2) aliphatic and/or aromatic sulfonic acids of the formula R¹⁸-SO₃H, where R¹⁸ is C₆- to C₄₀-alkyl, C₆- to C₄₀-alkenyl or an alk(en)ylaryl radical which has 1, 2, 3 or 4 aromatic rings and 1, 2, 3 or 4 alkyl or alkenyl radicals each having from 6 to 40 carbon atoms.
2. The additive as claimed in claim 1, wherein component A1 is a copolymer of ethylene and vinyl acetate or vinyl propionate.
3. The additive as claimed in claim 1 and/or 2, wherein component A1 is a copolymer which comprises up. to 5 mol% of structural units which are derived from alkyl vinyl ethers and/or olefins.
4. The additive as claimed in one or more of claims 1 to 3, wherein from 80 to 100 mol% of component A2 consists of structural elements of the formula 5

   

   where R⁸ and R⁹ are each independently hydrogen, phenyl or a group of the formula COOR¹¹, R¹⁰ is hydrogen, methyl or a group of the formula -CH₂COOR¹¹ and R¹¹ is a C₁₀- to C₃₀-alkyl or alkylene radical, preferably a C₁₂-to C₂₆-alkyl or alkylene radical, with the proviso that these repeating structural units comprise at least one and at most two carboxylic ester units in one structural element.
5. The additive as claimed in one or more of claims 1 to 4, wherein component B is a polypropylene or polyisobutylene.
6. The additive as claimed in one or more of claims 1 to 5, wherein component C is derived from a monoalkylated phenol having from 4 to 20 carbon atoms in the alkyl chain.
7. The additive as claimed in one or more of claims 1 to 6, wherein component C has been condensed using formaldehyde.
8. The additive as claimed in one or more of claims 1 to 7, wherein component C) is an alk(en)ylaryl-sulfonic acid having one or two C₈- to C₃₀-alkyl or alkenyl radicals and 1 or 2 aromatic rings, or a salt thereof.
9. A mineral oil comprising from 0.001 to 1% by weight of an additive as claimed in one or more of claims 1 to 8.
10. The use of an additive as claimed in one or more of claims 1 to 8 for improving the cold flow properties and the storage stability of mineral oil