DE10247795A1 - Use of an additive mixture containing homopolymer of a hydrocarbylvinyl ether for improving the action of a cold flow improver for fuel oil compositions and for decreasing the Cold Filter Plugging Point with avoidance of aspiration - Google Patents

Abstract

Use of an additive mixture containing:(i) as component A at least one homopolymer of a hydrocarbylvinyl ether for improving the action of a cold flow improver for fuel oil compositions, (ii) as component B at least one conventional cold flow improver for decreasing the Cold Filter Plugging Point (CFPP) value of the fuel oil composition and optionally to decrease the CFPP2-value and/or avoid an aspiration value is new. Independent claims are included for: (1) a fuel oil composition containing a main quantity of a hydrocarbon fuel and an active amount of the additive mixture as defined above and optionally at least one other conventional additive; (2) a fuel oil composition where the fuel is diesel oil, fuel oil, or kerosene; (3) diesel fuel obtainable by refining, coal distillation, or gas liquefaction, or a mixture of diesel fuel and optionally regenerative fuel; (4) an additive concentrate containing an additive mixture as defined above and at least one diluting agent and optionally at least one further additive.

Description

The present invention relates to the use of hydrocarbyl vinyl ether homopolymers for improvement the effect of cold flow improvers for fuel oil compositions. The compound further relates to the use of an additive, which comprises such a polymer and a conventional cold flow improver, to reduce the CFPP value and possibly continue to reduce the CFPP2 value and / or the aspiration value a fuel oil composition.

Containing paraffinic waxes mineral oils and crude oils show a marked deterioration when the temperature drops the flow properties. The cause of this lies in the from the temperature of the cloud point (cloud point) occurring longer-chain crystallization Paraffins, the big one platelet-shaped wax crystals form. These wax crystals have a sponge-like structure and lead to include others Fuel components in the crystal composite.

The appearance of these crystals leads to Deterioration of flow properties of mineral oils and crude oils, which causes malfunctions in the extraction, transport, storage and / or use of the oils can. So it can occur when transporting the oils due to pipes, especially in winter, to deposits on the pipe walls and even complete Constipation come. Mineral oils can cause constipation and bonding of fuel filters in motor vehicle engines (fuel filters) and combustion plants come, which ensures a safe dosage of the Fuel is prevented and under certain circumstances a complete interruption of the fuel supply entry. At temperatures below the pour point (pour point, PP) finally does not find any Fuel flow more instead of.

To fix these problems continues one has been around for a long time the mineral oils and crude oils Additives in small concentrations too, often from a combination of nucleators with the actual cold flow improvers. nucleators are substances that generate crystal nuclei that prevent the formation of tiny crystals favor. cold flow improvers have similar ones Prevent crystallization properties such as the paraffins contained in mineral oil or crude oil however their growth. Furthermore, the crude and mineral oils are wax anti Settling additives (WASA) added to the sinking of the minute crystals in the oils prevent.

Such additive fuels pass through fuel filters at significantly lower temperatures as non-additive fuels. As a measure of the filterability of fuels the cold filter plugging point is used at low temperatures (CFPP; see EN 116, German version 1997). However, with certain fuel oils additional Effects that worsen the effect of cold flow improvers. This counts the occurrence of a so-called CFPP2 point during the determination of the CFPP Value according to the above EN116. This further CFPP point occurs when one flows back filtered fuel oil from the pipette of the analyzer on (see EN 116 German version 1997, point 4, penultimate sentence, 2nd half sentence) and is reached when the pipette reaches the next lower Test temperature (reduced by 1 degree) is not yet completely empty. Furthermore is for individual fuel oils a so-called aspiration value (a temperature value) can be determined, the in determining the CFPP value according to EN 116 in the temporary increase the filling time of the Pipette expresses that subsequently progressively again before reaching the actual CFPP value decreases (see EN 116, German version 1997, points 10.1.9 and 10.2.6, Annotation). Expresses itself in the case of fuels this in a significant decrease in the flow rate of the Fuel through the fuel filter in a certain temperature range. Both CFPP2 and aspiration value cause a decrease in Fuel oil quality.

Numerous cold flow improvers are known from the prior art. So describes the EP-A-0 360 419 Additives to improve the cold flow properties of fuel compositions which contain homo- or copolymers of alkyl vinyl ethers and, if appropriate, other conventional cold flow improvers.

The DE-A-2 047 448 describes an additive mixture of polyvinyl ethers with ethylene-vinyl acetate copolymers to improve the pumpability of crude oils. The use in fuel oils is not described.

A disadvantage of the additives of State of the art is that they sometimes have the CFPP value of fuel oils do not reduce or reduce it only slightly. The booth also describes no additives which have an effect on the CFPP2 and / or Aspiration value of the fuel oils have.

The object of the present invention was therefore to further improve the effect of conventional cold flow improvers. In particular, the additive should improve the effect of the cold flow improvers on reducing the CFPP of fuel oil compositions and, if necessary, reducing or Eliminate the CFPP2 values and / or avoid aspiration effects.

The task was solved by the use of a homopolymer of a hydrocarbyl vinyl ether for Improving the effect of cold flow improvers for fuel oil compositions.

In the context of the present invention, hydrocarbyl is understood as a hydrocarbon radical which is bonded via a carbon atom to the ether function of the vinyl ether. The hydrocarbon radical can be, for example, an aliphatic radical, such as alkyl and alkenyl, which is optionally substituted by at least one aromatic and / or alicyclic radical, an alicyclic radical, such as cycloalkyl or cycloalkenyl, which may optionally be substituted by at least one aromatic and / or aliphatic Radical is substituted, or an aromatic radical which is optionally substituted with at least one aliphatic and / or alicyclic radical. The aliphatic and alicyclic radicals can be interrupted by at least one group O, S, NR ⁵ , or CO. The hydrocarbon radical can furthermore be substituted by at least one radical such as OR ⁵ , SR ⁵ , NR ⁵ R ⁶ , COR ⁵ , COOR ⁵ or CONR ⁵ R ⁶ , the radicals R ⁵ and R ^{6 being} as defined below.

worin
R¹ für C₁-C₄₀-Alkyl, das gegebenenfalls durch eine oder mehrere Gruppierungen, die ausgewählt sind unter CO, NR⁵, O und S, unterbrochen, und/oder durch einen oder mehrere Reste, die ausgewählt sind unter NR⁵R⁶, OR⁵, SR⁵, COR⁵, COOR⁵, CONR⁵R⁶ und Aryl, substituiert ist, oder für Aryl steht,
R², R³ und R⁴ jeweils unabhängig voneinander für H oder C₁-C₄₀-Alkyl stehen,
R⁵ und R⁶ jeweils unabhängig voneinander für H oder für C₁-C₄-Alkyl stehen und
n für eine Zahl von 2 bis 3000 steht.The homopolymer of hydrocarbyl vinyl ether preferably has the following structural formula I:

wherein
R ¹ for C ₁ -C ₄₀ alkyl, which is optionally interrupted by one or more groupings which are selected from CO, NR ⁵ , O and S, and / or by one or more radicals which are selected from NR ⁵ R ⁶ , OR ⁵ , SR ⁵ , COR ⁵ , COOR ⁵ , CONR ⁵ R ⁶ and aryl, is substituted, or represents aryl,
R ² , R ³ and R ⁴ each independently represent H or C ₁ -C ₄₀ alkyl,
R ⁵ and R ⁶ each independently represent H or C ₁ -C ₄ alkyl and
n stands for a number from 2 to 3000.

In the above definition of the radicals R ¹ , R ² , R ³ and R ⁴ , C ₁ -C ₄₀ alkyl is in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, Pentyl, Hexyl, Heptyl, Octyl, 2-Ethylhexyl, Nonyl, Decyl, Undecyl, Dodecyl, Tridecyl, Tetradecyl, Pentadecyl, Hexadecyl, Heptadecyl, Octadecyl, Nonadecyl, Eicosyl, Docosyl, Tricosyl, Tetracosyl, Pentacosyl, Hexacosyl, Hexacosyl, Hexacosyl, Hexacosyl Nonacosyl, Squalyl and the higher homologues as well as the corresponding positional isomers.

In the definition of R ⁵ and R ⁶ , C ₁ -C ₄ alkyl is in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.

In the definition of R ¹ is aryl is preferably C ₆ -C ₁₄ aryl such as phenyl, naphthyl, anthracenyl and phenanthryl, wherein the aryl group is optionally substituted by one or more radicals selected from C ₁ -C ₄ 0-alkyl, OR ⁵ , SR ⁵ , NR ⁵ R ⁶ , COOR ⁵ , CONR ⁵ R ⁶ and aryl.

R ¹ preferably represents C ₁ -C ₄₀ alkyl, particularly preferably C ₁ -C ₃₀ alkyl and in particular C ₂ -C ₂₂ alkyl. The alkyl radical is preferably not very branched or linear, in particular linear. Furthermore, the alkyl radical is neither interrupted nor substituted by the groups listed above.

R ² , R ³ and R ⁴ are preferably H.

Preferred compounds of the formula I also point a number average molecular weight Mn in the range of about 1000 up to 20,000, in particular 2,000 to 20,000, preferably 3,000 to 15,000, on.

• a) Copolymeren von Ethylen mit wenigstens einem weiteren ethylenisch ungesättigten Monomer;
• b) Kammpolymeren;
• c) Polyoxyalkylenen;
• d) polaren Stickstoffverbindungen;
• e) Sulfocarbonsäuren oder Sulfonsäuren oder deren Derivaten; und
• f) Poly(meth)acrylsäureestern.

The cold flow improvers are preferably selected from

• a) copolymers of ethylene with at least one further ethylenically unsaturated monomer;
• b) comb polymers;
• c) polyoxyalkylenes;
• d) polar nitrogen compounds;
• e) sulfocarboxylic acids or sulfonic acids or their derivatives; and
• f) poly (meth) acrylic acid esters.

In the copolymers of ethylene with that is at least one further ethylenically unsaturated monomer a) Monomer preferably selected under alkenyl carboxylic acid esters, (Meth) Acrylsäureestern and olefins.

Suitable olefins are, for example, those with 3 to 10 carbon atoms and with 1 to 3, before preferably with 1 or 2, in particular with a, carbon-carbon double bond. In the latter case, the carbon-carbon double bond can be arranged both terminally (α-olefin) and internally. However, α-olefins are preferred, particularly preferably α-olefins having 3 to 6 carbon atoms, such as propene, 1-butene, 1-pentene and 1-hexene.

Suitable (meth) acrylic acid esters are, for example, esters of (meth) acrylic acid with C ₁ -C ₁₀ -alkanols, in particular with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol, hexanol, Heptanol, octanol, 2-ethylhexanol, nonanol and decanol.

Suitable alkenyl carboxylic acid esters are for example the vinyl and Propenyl ester of carboxylic acids with 2 to 20 carbon atoms, the hydrocarbon residue of which is linear or can be branched. Among these, the vinyl esters are preferred. Among the carboxylic acids with branched hydrocarbon radical are preferred those whose Branching in the α position to the carboxyl group, the α-carbon atom being particularly preferred tertiary is, d. H. the carboxylic acid a so-called neocarboxylic acid is. However, the hydrocarbon residue of the carboxylic acid is preferred linear.

Examples of suitable alkenyl carboxylic acid esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl neopentanoate, hexanoate, neononanoate, neodecanoate and the corresponding propenyl esters, the vinyl esters being preferred are. A particularly preferred alkenyl carboxylic acid ester is vinyl acetate.

This is particularly preferred ethylenically unsaturated Monomer selected among alkenyl carboxylic acid esters.

Copolymers which are also suitable two or more different alkenyl carboxylic acid esters contain in copolymerized form, these being in the alkenyl function and / or differentiate in the carboxylic acid group. Also suitable are copolymers which, in addition to the alkenyl carboxylic acid ester (s) at least one olefin and / or at least one (meth) acrylic acid ester polymerized included.

The ethylenically unsaturated monomer is in the copolymer in an amount of preferably 1 to 30 mol%, particularly preferably from 1 to 25 mol% and in particular from 5 to 20 mole%, based on the total copolymer, copolymerized.

The copolymer a) preferably has a number average molecular weight Mn of 500 to 20,000, especially preferably from 1000 to 15000.

worin
D für R⁷, COOR⁷, OCOR⁷, R⁸, COOR⁷ oder OR⁷ steht,
E für H, CH₃, D oder R⁸ steht,
G für H oder D steht,
J für H, R⁸, R⁸COOR⁷, Aryl oder Heterocyclyl steht,
K für H, COOR⁸, OCOR⁸, OR⁸ oder COOH steht,
L für H, R⁸ COOR⁸, OCOR⁸, COOH oder Aryl steht,
R⁷ für einen Kohlenwasserstoffrest mit wenigstens 10 Kohlenstoffatomen, vorzugsweise mit 10 bis 30 Kohlenstoffatomen, steht,
R⁸ für einen Kohlenwasserstoffrest mit wenigstens einem Kohlenstoffatom, vorzugsweise mit 1 bis 30 Kohlenstoffatomen, steht,
m für einen Molenbruch im Bereich von 1,0 bis 0,4 steht und
n für einen Molenbruch im Bereich von 0 bis 0,6 steht.Comb polymers b) are, for example, those described in "Comb-Like Polymers. Structure and Properties", NA Plate and VP Shibaev, J. Poly. Sci. Macromolecular Revs. 8, pages 117 to 253 (1974). Of the compounds described there, comb polymers of the formula II are suitable, for example

wherein
D represents R ⁷ , COOR ⁷ , OCOR ⁷ , R ⁸ , COOR ⁷ or OR ⁷ ,
E represents H, CH ₃ , D or R ⁸ ,
G represents H or D,
J represents H, R ⁸ , R ⁸ COOR ⁷ , aryl or heterocyclyl,
K represents H, COOR ⁸ , OCOR ⁸ , OR ⁸ or COOH,
L represents H, R ⁸ COOR ⁸ , OCOR ⁸ , COOH or aryl,
R ^{7 represents} a hydrocarbon radical with at least 10 carbon atoms, preferably with 10 to 30 carbon atoms,
R ^{8 represents} a hydrocarbon radical with at least one carbon atom, preferably with 1 to 30 carbon atoms,
m stands for a mole fraction in the range from 1.0 to 0.4 and
n stands for a mole fraction in the range from 0 to 0.6.

Preferred comb polymers can be obtained, for example, by copolymerizing maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an α-olefin or an unsaturated ester, such as vinyl acetate, and then esterifying the anhydride or acid function with an alcohol having at least 10 carbon atoms. Further preferred comb polymers are copolymers of α-olefins and esterified comonomers, for example esterified copolymers of Styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid. Mixtures of comb polymers are also suitable. Comb polymers can also be polyfumarates or polymaleates.

Suitable polyoxyalkylenes c) are, for example, polyoxyalkylene esters, ethers, esters / ethers and mixtures thereof. The polyoxyalkylene compounds preferably contain at least one, particularly preferably at least two linear alkyl groups with 10 to 30 carbon atoms and a polyoxyalkylene group with a molecular weight of up to 5000. The alkyl group of the polyoxyalkylene radical preferably contains 1 to 4 carbon atoms. Such polyoxyalkylene compounds are for example in the EP-A-0 061 895 as well as in the US 4,491,455 described, to which reference is hereby made in full. Preferred polyoxyalkylene esters, ethers and esters / ethers have the general formula III R ⁹ {-O- (CH ₂ ) _y } _x OR ¹⁰ (III) wherein
R ⁹ and R ¹⁰ each independently of one another for R ¹¹ , R ¹¹ -CO-,
R ¹¹ -O-CO (CH ₂ ) _z - or R ¹¹ -O-CO (CH ₂ ) _z -CO-,
R ^{11 represents} linear C ₁ -C ₃₀ alkyl,
y represents a number from 1 to 4,
x represents a number from 2 to 200, and
z represents a number from 1 to 4.

Preferred polyoxyalkylene compounds of the formula III, in which both R ⁹ and R ^{10 are} R ¹¹ , are polyethylene glycols and polypropylene glycols with a number average molecular weight of 100 to 5000. Preferred polyoxyalkylenes of the formula III, in which one of the radicals R ^{9 is} R ¹¹ and the other represents R ¹¹ -CO- are polyoxyalkylene esters of fatty acids with 10 to 30 carbon atoms, such as stearic acid or behenic acid. Preferred polyoxyalkylene compounds in which both R ⁹ and R ^{10 represent} a radical R ¹¹ -CO- are diesters of fatty acids having 10 to 30 carbon atoms, preferably stearic or behenic acid.

The polar nitrogen compounds d), which are suitably oil-soluble, can be both ionic and non-ionic and preferably have at least one, particularly preferably at least 2, substituents of the formula> NR ¹² , in which R ^{12 is} a C ₈ -C ₄₀ -hydrocarbon radical. The nitrogen substituents can also be quaternized, that is to say in cationic form. An example of such nitrogen compounds are ammonium salts and / or amides which can be obtained by reacting at least one amine substituted with at least one hydrocarbon radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof. The amines preferably contain at least one linear C ₈ -C ₄₀ alkyl radical. Suitable primary amines are, for example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologues. Suitable secondary amines are, for example, dioctadecylamine and methylbehenylamine. Also suitable are amine mixtures, in particular amine mixtures which are commercially available, such as fatty amines or hydrogenated tallamines, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, 2000 electronic release, chapter "Amines, aliphatic". Acids suitable for the reaction are, for example, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and succinic acids substituted with long-chain hydrocarbon radicals.

Another example of polar nitrogen compounds are ring systems which carry at least two substituents of the formula -A-NR ¹³ R ¹⁴ , in which A stands for a linear or branched aliphatic hydrocarbon group, which may be replaced by one or more groups selected from O, S , NR and CO, is interrupted, and R ¹³ and R ^{14 represent} a C ₉ -C ₄₀ hydrocarbon radical which is optionally interrupted and / or by one or more groups which are selected from O, S, NR ⁵ and CO is substituted by one or more substituents selected from OH, SH and NR ⁵ R ⁶ , where R ⁵ and R ^{6 are} as defined above. A is preferably a methylene or polymethylene group having 2 to 20 methylene units. Examples of suitable radicals R ¹³ and R ¹⁴ are 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-ketopropyl, ethoxyethyl and propoxypropyl. The cyclic system can be both homocyclic, heterocyclic, condensed polycyclic or uncondensed polycyclic systems. The ring system is preferably carbo- or heteroaromatic, in particular carboaromatic. Examples of such polycyclic ring systems are condensed benzoid structures, such as naphthalene, anthracene, phenanthrene and pyrene, condensed nonbenzoic structures, such as azulene, indene, hydrindens and fluorene, uncondensed polycycles, such as diphenyl, heterocycles, such as quinoline, indole, dihydroindole, benzofuran, Coumarin, isocoumarin, benzthiophene, carbazole, diphenylene oxide and diphenylene sulfide, non-aromatic or partially saturated ring systems, such as decalin, and three-dimensional structures, such as α-pinene, camphene, bornylene, norbonane, norbones, bicyclooctane and bicyclooctene.

Another example of suitable Polar nitrogen compounds are long-chain primary or condensates secondary Amines with polymers containing carboxyl groups.

The polar nitrogen compounds mentioned here are in WO 00/44857 and in the references mentioned therein described, to which reference is hereby made in full.

Suitable polar nitrogen compounds are, for example, also in the DE-A-198 48 621 the DE-A-196 22 052 or the EP-B-398 101 described, what is hereby incorporated by reference.

worin
Y für SO3^–(NR¹⁵ ₃R¹⁶)⁺, SO^3–(NHR¹⁵ ₂R¹⁶)⁺, SO^3–(NH₂R¹⁵R₁₆), SO^3–(NH₃R¹⁶) oder SO₂NR₁₅R¹⁶ steht,
X für Y, CONR¹⁵R¹⁷, CO₂–(NR¹⁵ ₃R¹⁷)⁺, C O₂-(NHR¹⁵ ₂R¹⁷)⁺, R¹⁸-COOR¹⁷, NR¹⁵COR¹⁷, R¹⁸OR¹⁷, R¹⁸OCOR¹⁷, R¹⁸R¹⁷, N(COR¹⁵)R¹⁷ od er Z-(NR¹⁵ ₃R¹⁷)⁺ steht,
worin
R¹⁵ für einen Kohlenwasserstoffrest steht,
R¹⁶ und R¹⁷ für Alkyl, Alkoxyalkyl oder Polyalkoxyalkyl mit wenigstens 10 Kohlenstoffatomen in der Hauptkette stehen,
R¹⁸ für C₀-C₅-Alkylen steht,
Z- für ein Anionenäquivalent steht und
A und B für Alkyl, Alkenyl oder zwei substituierte Kohlenwasserstoffreste stehen oder gemeinsam mit den Kohlenstoffatomen, an die sie gebunden sind, ein aromatisches oder cycloaliphatisches Ringsystem bilden.Suitable sulfocarboxylic acids / sulfonic acids or their derivatives e) are, for example, those of the general formula IV

wherein
Y for SO3^-(NO¹⁵ ₃R¹⁶)⁺, SO³(NHR¹⁵ ₂R¹⁶)⁺. SO³(NH₂R¹⁵R₁₆) SO³(NH₃R¹⁶) or so₂NO₁₅R¹⁶ stands,
X for Y, CONR¹⁵R¹⁷, CO₂-(NO¹⁵ ₃R¹⁷)⁺, C O₂- (NHR¹⁵ ₂R¹⁷)⁺, R¹⁸COOR¹⁷, NO¹⁵COR¹⁷, R¹⁸OR¹⁷, R¹⁸OCOR¹⁷, R¹⁸R¹⁷. N (COR¹⁵) R¹⁷ od he Z- (NO¹⁵ ₃R¹⁷)⁺ stands,
wherein
R¹⁵ For there is a hydrocarbon residue,
R¹⁶ and R¹⁷ For Alkyl, alkoxyalkyl or polyalkoxyalkyl having at least 10 carbon atoms stand in the main chain,
R¹⁸ for C₀-C₅-Alkylene stands,
Z- for a anion stands and
A and B for Alkyl, alkenyl or two substituted hydrocarbon radicals or together with the carbon atoms to which they are attached, form an aromatic or cycloaliphatic ring system.

Such sulfocarboxylic acids or sulfonic acids and their derivatives are in the EP-A-0 261 957 described, to which reference is hereby made in full.

Suitable poly (meth) acrylic acid esters f) are both homo- and copolymers of acrylic and methacrylic acid esters. Copolymers of at least two mutually different (meth) acrylic acid esters which differ with respect to the condensed alcohol are preferred. Optionally, the copolymer contains another, different olefinically unsaturated monomer copolymerized. The weight average molecular weight of the polymer is preferably 50,000 to 500,000. A particularly preferred polymer is a copolymer of methacrylic acid and methacrylic acid esters of saturated C ₁₄ and C ₁₅ alcohols, the acid groups being neutralized with hydrogenated tallamine. Suitable poly (meth) acrylic acid esters are described, for example, in WO 00/44857, to which reference is hereby made in full.

Preferably used as a cold flow improver Copolymers of ethylene with at least one other ethylenically unsaturated Monomer a). In terms of of preferred copolymers is based on the statements made above directed.

Mixtures of copolymers are also suitable a) with at least one of the cold flow improvers b) to f).

Under fuel oil compositions understood fuel is preferred. Suitable fuels are petrol and middle distillates, such as diesel fuels, heating oil or kerosene, being diesel fuel and heating oil are preferred.

The heating oils are, for example low-sulfur or high-sulfur petroleum refines or stone or Lignite distillates, which are usually have a boiling range of 150 to 400 ° C. Preferably it is the heating oils low-sulfur heating oils, for example those with a sulfur content of at most 0.1% by weight, preferably at most 0.05% by weight, particularly preferably of at most 0.005% by weight, and in particular of at most 0.001% by weight.

It deals with diesel fuels for example, oil refinements, the usual have a boiling range of 100 to 400 ° C. these are mostly distillates with a 95% point up to 360 ° C or also about that out. You can but also so-called "Ultra low sulfur diesel "or" city diesel " by a 95 ° point of, for example, a maximum of 345 ° C and a sulfur content of at most 0.005% by weight or by one 95% point of, for example, 285 ° C and a sulfur content of at most 0.001% by weight. In addition to those available through refining Diesel fuels are those produced by coal gasification or gas liquefaction ("gas to liquid" (GTL) fuels) available are suitable. Mixtures of the above are also suitable Diesel fuels with renewable fuels, such as biodiesel or bioethanol.

The additive mixture according to the invention is particularly preferred for the additization of diesel power substances with a low sulfur content, that is to say with a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, in particular less than 0.005% by weight and especially less than 0.001% by weight. % Sulfur or for the additive of heating oil with a low sulfur content, for example with a sulfur content of at most 0.1% by weight, preferably at most 0.05% by weight, particularly preferably at most 0.005% by weight, and in particular at most 0.001% by weight.

The hydrocarbyl vinyl ether homopolymer (Improver) is preferably obtained in a proportion on the total amount of fuel oil composition used the for seen essentially no influence on the cold flow properties of fuel oil compositions has. The effect improver is particularly preferred in one Amount from 0.0001 to 0.005% by weight, in particular from 0.0001 to 0.001 % By weight, based on the total amount of the fuel oil composition, is used.

The weight ratio of effectiveness improver for cold flow improvers is preferably 1: 1 to 1: 500, particularly preferably 1: 4 to 1: 500, still stronger preferably 1: 9 to 1: 500, in particular 1:19 to 1: 500 and especially 1:24 to 1: 200.

• i) als Komponente A wenigstens ein Homopolymer eines Hydrocarbylvinylethers und
• ii ) als Komponente B wenigstens einen üblichen Kaltfließverbesserer

zur Verringerung des CFPP-Werts einer Brennstoffölzusammensetzung und gegebenenfalls außerdem zur Verringerung des CFPP2-Werts und / oder zur Vermeidung von Aspirationseffekten.Another object of the present invention is the use of an additive mixture comprising

• i) as component A at least one homopolymer of a hydrocarbyl vinyl ether and
• ii) as component B at least one conventional cold flow improver

to reduce the CFPP of a fuel oil composition and possibly also to reduce the CFPP2 and / or to avoid aspiration effects.

The statements made above to the suitable and preferred hydrocarbyl vinyl ether homopolymers, cold flow improvers and fuel oil compositions apply here correspondingly.

• i) als Komponente A wenigstens ein Homopolymer eines Hydrocarbylvinylethers und
• ii ) als Komponente B wenigstens einen üblichen Kaltfließverbesserer

mit einem Gewichtsverhältnis von Komponente A zu Komponente B von 1:1 bis 1:500 zur Additivierung von Brennstoffölzusammensetzungen.Another object of the present invention is the use of an additive mixture comprising

• i) as component A at least one homopolymer of a hydrocarbyl vinyl ether and
• ii) as component B at least one conventional cold flow improver

with a weight ratio of component A to component B of 1: 1 to 1: 500 for the additive of fuel oil compositions.

Again, the above made executions to hydrocarbyl vinyl ether homopolymers, cold flow improvers and fuel oil compositions directed.

The ones used according to the invention are preferably used Additive mixtures to improve the cold flow properties of fuel oil compositions, such as lowering the cloud point, the pour point, the viscosity and especially the CFPP value.

• a) wenigstens eine Komponente A gemäß obiger Definition und
• b) wenigstens eine Komponente B gemäß obiger Definition,

wobei das Gewichtsverhältnis von Komponente A zu Komponente H 1:5 bis 1:500 beträgt.The present invention furthermore relates to an additive mixture comprising

• a) at least one component A as defined above and
• b) at least one component B as defined above,

wherein the weight ratio of component A to component H is 1: 5 to 1: 500.

The previous ones apply here as well versions to the suitable and preferred hydrocarbyl vinyl ether homopolymers and cold flow improvers.

The weight ratio is preferably from Component A to component B 1: 9 to 1: 500, particularly preferred 1:15 to 1: 500, even stronger preferably 1:20 to 1: 500 and especially 1:24 to 1: 200.

It is also the subject of the present Invention a fuel oil composition containing a major amount of a hydrocarbon fuel and an effective amount of an additive mixture as defined above and optionally at least one other customary additive.

On the statements made above to fuel oil compositions and additive mixtures are hereby referred.

Finally, the subject of the present Application for an additive concentrate containing one as defined above Additive mixture and at least one diluent and optionally at least one other additive.

Suitable diluents are, for example, fractions obtained in petroleum processing, such as kerosene, naphtha or brightstock. Aromatic and aliphatic hydrocarbons and alkoxyalkanols are also suitable. In the case of middle distillates, particularly preferred diluents for diesel fuels and heating oils, naphtha, kerosene, diesel fuels, aromatic hydrocarbons such as heavy solvent naphtha, Solvesso ^® or Shellsol ^® and mixtures of these solvents and diluents.

The additive mixture according to the invention is preferably present in the concentrates in an amount of 0.1 to 80% by weight, particularly preferably 1 to 70% by weight and in particular 20 to 60% by weight based on the total weight of the concentrate.

Suitable additives in the fuel according to the invention or concentrate in addition to the additive mixtures according to the invention could be, especially for Diesel fuels and heating oils, include detergents, corrosion inhibitors, dehazers, demulsifiers, Anti-foaming agents ("Antifoam"), antioxidants, Metal deactivators, multifunctional stabilizers, cetane number improvers, Combustion improvers, dyes, markers, solubilizers, antistatic agents, lubricity, different from those mentioned above improving the cold properties Additives such as flow improvers ("MDFI"), paraffin dispersants ("WASA") and the combination of the last two additives mentioned ("WAFI").

The use of hydrocarbyl vinyl ether homopolymers leads to an improved effect more common cold flow improvers on the cold flow properties of fuel oil compositions, in particular for a more effective reduction in CFPP. As a result, can the cold flow improvers are used in significantly smaller quantities than previously required.

The following examples illustrate the invention, but without restricting it.

Examples

To investigate the cold flow behavior of fuel oil compositions were six different middle distillates with different cold flow improvers added alone or as a mixture with hydrocarbyl vinyl ether homopolymers and the CFPP value is determined according to EN 116.

The following middle distillates were used
Middle distillate A (Q8): CP = 2.4 ° C; CFPP = -1 ° C; d = 855g / cm ³ ; n-paraffin content = 21%; Initial boiling point = 166 ° C, 20% point = 219 ° C; 90% point = 349 ° C; End of boiling = 380 ° C
Middle distillate B (Nerefco): CP = -4.2 ° C; CFPP = -5 ° C; 88% HOB; 12% LCO
Middle distillate C (Nerefco): CP = 2.0 ° C; CFPP = 1.0 ° C; 80% HOB; 10% HGO; 10 % LCO
Middle distillate D (Total Fina Elf France): CP = 2 ° C; CFPP = -6 ° C; d = 855g / cm ³ ; Initial boiling point = 155 ° C, 20% point = 202 ° C; 90% point = 350 ° C; End of boiling = 375 ° C
Middle distillate E (Nerefco): CFPP = 2 ° C; 8% HGO; 8% LCO
Middle distillate F (Total Fina Elf France): CFPP = 0 ° C
LCO = light cycle oil
HGO = heavy gas oil
HOB = Hearing oil blend

The following polymers were used as cold flow improvers (MDFI):
MDFI 1: ethylene-vinyl acetate-based polymer mixture (Keroflux 3283)
MDFI 2: ethylene-vinyl acetate-based polymer mixture (Keroflux ES 6103)
MDFI 3: ethylene-vinyl acetate-based polymer mixture (Keroflux ES 6305)
MDFI 4: ethylene-vinyl acetate-based polymer mixture (Keroflux ES 6309)
MDFI 5: ethylene-vinyl acetate-based polymer mixture (Keroflux ES 6100)
MDFI 6: ethylene-vinyl acetate-based polymer mixture (Keroflux ES 6204)
MDFI 7: ethylene-vinyl acetate-based polymer mixture (Keroflux ES 6203)
MDFI 8: ethylene-vinyl acetate-based polymer mixture (Keroflux ES 6205)
MDFI 9: ethylene-vinyl acetate-based polymer mixture (Keroflux ES 6310)

The following polyvinyl ethers (PVE) were used to improve the effect:
PVE 1: 40% by weight solution of polyoctadecyl vinyl ether (M _n = 3525; M _w = 12208) in Solvesso 150
PVE 2: 10% by weight solution of polyoctadecyl vinyl ether / polystearyl vinyl ether mixture (85/15) in Solvesso 150
PVE 3: 10% by weight solution of polyoctadecyl vinyl ether (M _n = 3525; M _w = 12208) in Solvesso 150
PVE 4: 10% by weight solution of polyoctadecyl vinyl ether (M _n = 10785; M _w = 43125) in Solvesso 150

The effect improvers PVE 1 to 4 were obtained in an amount of 1 to 4% by weight of pure substance on the amount of cold flow improver, used.

In the table below are the CFPP values of middle distillates listed, on the one hand only with cold flow improvers and on the other hand with the mixture of cold flow improvers according to the invention and polyvinyl ethers were added.

* CFPP2 value

"-": not determined

The CFPP values were determined in accordance with EN 116. For this purpose, a commercially available automati cal CFPP analyzer, such as available from WalterHerzog GmbH, Lauda-Koenigshofen, Germany, type MP842 used. Also compare the operating instructions for determining the CFPP 2 value.

Like the test results above show leads the addition of hydrocarbyl vinyl ether homopolymers to conventional ones Cold flow improvers contribute to a lowering of the CFPP value much lower doses of the cold flow improver. In addition, as the comparison of experiments 38 and 39 shows, no CFPP2 value observed more.

Claims (22)

Use of a homopolymer of a hydrocarbyl vinyl ether to improve the effect of a cold flow improver for fuel oil compositions. Use of an additive mixture comprising i) as component A at least one homopolymer of a hydrocarbyl vinyl ether and ii) as component B at least one conventional cold flow improver to Reducing the CFPP of a fuel oil composition and, if necessary Moreover to reduce CFPP2 and / or to avoid Aspiration value. Use of an additive mixture comprising i) as component A at least one homopolymer of a hydrocarbyl vinyl ether and ii) as component B at least one conventional cold flow improver With a weight ratio from component A to component B from 1: 1 to 1: 500 for additives of fuel oil compositions. Use according to one of the preceding claims, wherein the effect enhancer in a proportion based on the total quantity the fuel oil composition is used for have essentially no effect on the CFPP value of those with the cold flow improver additive fuel oil composition has. Use according to one of the preceding claims, wherein the fuel oil composition is selected under heating oils and diesel fuels. Use according to one of the preceding claims, wherein the fuel oil composition petroleum middle distillate includes. Use according to one of the preceding claims, wherein the fuel oil composition has a sulfur content of less than 500 ppm (0.05% by weight). Use according to one of the preceding claims, wherein the fuel oil composition has a share of renewable fuel. Use according to one of the preceding claims, wherein the homopolymer of the hydrocarbyl vinyl ether has the following structural formula:

wherein R ^{1 is} C ₁ -C ₄₀ alkyl, which is optionally interrupted by one or more groupings which are selected from CO, NR ⁵ , O and S, and / or by one or more radicals which are selected from NR ⁵ R ⁶ , OR ⁵ , SR ⁵ , COR ⁵ , COOR ⁵ , CONR ⁵ R ⁶ and aryl, or is aryl, R ² , R ³ and R ^{4 are} each independently of one another H or C ₁ -C ₄₀ - Stand alkyl, R ⁵ and R ⁶ each independently represent H or C ₁ -C ₄ alkyl and n represents a number from 2 to 3000. Use according to claim 9, wherein R ² , R ³ and R ^{4 are} H and R ^{1 is} C ₁ -C ₄₀ alkyl. Use according to one of the preceding claims, wherein the cold flow improver is selected under a) copolymers of ethylene with at least one other ethylenically unsaturated monomer; b) comb polymers other than hydrocarbyl vinyl ether; c) polyoxyalkylenes; d) polar nitrogen compounds; e) sulfocarboxylic or sulfonic acids or their derivatives; f) poly (meth) acrylic acid esters. Use according to claim 11, wherein the cold flow improver selected is among copolymers of ethylene and at least one other ethylenically unsaturated Monomers that selected is among alkenyl carboxylic acid esters, acrylsäureestern (meth) and olefins. Use according to claim 12, wherein the unsaturated monomer an alkenyl carboxylic acid ester is. Use according to claim 13, wherein the alkenyl carboxylic acid ester in an amount of 10 to 50 wt .-%, based on the total amount of the copolymerized monomers is copolymerized. Use according to one of claims 13 or 14, wherein the alkenyl carboxylic acid ester Is vinyl acetate. Use according to one of the preceding claims, for Improvement of the cold flow properties of fuel oil compositions. Additive mixture, comprising a) at least one Component A according to the above Definition and b) at least one component B according to the above Definition, where the weight ratio of component A to component B is about 1: 5 to 1: 500. Fuel oil composition, containing a major amount of a hydrocarbon fuel and an effective amount of an additive mixture as defined in any of the Expectations 1 to 15 or 17 and optionally at least one other usual Additive. Fuel oil composition of claim 18, wherein the fuel is diesel fuel, heating oil or kerosene. Fuel oil composition according to claim 19, wherein the diesel fuel by refining, Coal gasification or gas liquefaction available is, or is a mixture of such fuels and optionally with regenerative fuels is mixed. Fuel composition according to one of claims 19 or 20, the diesel fuel having a sulfur content of at most 500 ppm. Additive concentrate containing an additive mixture as defined in claim 17 and at least one diluent and optionally at least one other additive.