EP0405270A1 - Process to improve mineral oil and mineral oil distillate flowability - Google Patents

Process to improve mineral oil and mineral oil distillate flowability Download PDF

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EP0405270A1
EP0405270A1 EP90111397A EP90111397A EP0405270A1 EP 0405270 A1 EP0405270 A1 EP 0405270A1 EP 90111397 A EP90111397 A EP 90111397A EP 90111397 A EP90111397 A EP 90111397A EP 0405270 A1 EP0405270 A1 EP 0405270A1
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vinyl acetate
ethylene
mineral oil
flowability
mpa
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French (fr)
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EP0405270B1 (en
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Wolfgang Dr. Dipl.-Chem. Payer
Werner Dr. Dipl.-Chem. Reimann
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2368—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing heterocyclic compounds containing nitrogen in the ring

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Fats And Perfumes (AREA)

Abstract

The flow properties of mineral oils and mineral oil distillates are improved by addition of a mixture of an ethylene/vinyl acetate copolymer and an ethylene/vinyl acetate/N-vinylpyrrolidone terpolymer.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Ver­besserung der Fließfähigkeit von Mineralölen und Mineralöl­destillaten durch Zusatz von Mischungen aus Ethylen-Vinyl­acetat-Copolymerisaten und Ethylen-Vinylacetat-N-Vinyl­pyrrolidon-Terpolymerisaten.The present invention relates to a process for improving the flowability of mineral oils and mineral oil distillates by adding mixtures of ethylene-vinyl acetate copolymers and ethylene-vinyl acetate-N-vinylpyrrolidone terpolymers.

Mineralöle und Mineralöldestillate enthalten je nach Her­kunft unterschiedliche Mengen Paraffin gelöst, das sich bei tiefen Temperaturen in Form plättchenförmiger Kristalle, in denen noch Öl eingeschlossen ist, abscheidet. Hierdurch wird die Fließfähigkeit von Mineralölen und Mineralölde­stillaten erheblich beeinträchtigt. Dies führt z.B. im Fall von Dieselkraftstoff zur Verstopfung von Filtern mit der Folge, daß die Zufuhr des Kraftstoffs zu den Verbrennungs­aggregaten, wie Motoren oder Düsentriebwerken, ungleichmä­ßig erfolgt oder völlig unterbrochen wird. Ebenso können sich Störungen beim Transport von Heizölen in Verbrennungs­anlagen ergeben, wenn derartige Wachsausscheidungen, be­dingt durch tiefe Temperaturen, auftreten.Depending on their origin, mineral oils and mineral oil distillates contain different amounts of paraffin, which separates at low temperatures in the form of platelet-shaped crystals in which oil is still trapped. This significantly affects the flowability of mineral oils and mineral oil distillates. This leads e.g. in the case of diesel fuel for clogging of filters, with the result that the supply of fuel to the combustion units, such as engines or jet engines, takes place unevenly or is completely interrupted. Malfunctions can also occur during the transport of heating oils in incineration plants if such wax deposits occur due to low temperatures.

Auch das Fördern von Mitteldestillaten durch Rohrleitungen über größere Entfernungen kann im Winter durch das Ausfal­len von Paraffinkristallen beeinträchtigt werden.The pumping of middle distillates through pipelines over long distances can also be affected in winter by the precipitation of wax crystals.

Um die Abscheidung von Paraffinwachs zu kontrollieren, setzt man den Mineralölen und Mineralöldestillaten, insbe­sondere den sogenannten Mitteldestillaten Additive zu, die Größe und Form der Paraffinkristalle verändern, so daß die Mitteldestillate auch bei tiefen Temperaturen fließfähig bleiben. Die wirtschaftlich wichtigsten Stockpunkterniedri­ ger und Fließverbesserer für Mineralöle und Mineralöl­destillate sind Copolymerisate des Ethylens mit Estern des Vinylalkohols, insbesondere mit Vinylacetat. Derartige Mischpolymerisate und ihre Verwendung sind z.B. in der DE-C 19 14 756 und der DE-A 25 15 805 beschrieben. Aus der ver­öffentlichten japanischen Patentanmeldung 58 80 386, refe­riert in C.A. 99 (1983), 21 55 19, ist es bekannt, Terpoly­merisate aus Ethylen, Vinylacetat und N-Vinyl-2-Pyrrolidon als Fließverbesserer zu verwenden.In order to control the separation of paraffin wax, additives are added to the mineral oils and mineral oil distillates, in particular the so-called middle distillates, which change the size and shape of the paraffin crystals so that the middle distillates remain fluid even at low temperatures. The economically most important pour point lowers ger and flow improver for mineral oils and mineral oil distillates are copolymers of ethylene with esters of vinyl alcohol, especially with vinyl acetate. Such copolymers and their use are described, for example, in DE-C 19 14 756 and DE-A 25 15 805. From the published Japanese patent application 58 80 386, cited in CA 99 (1983), 21 55 19, it is known to use terpolymers of ethylene, vinyl acetate and N-vinyl-2-pyrrolidone as flow improvers.

In der Praxis hat sich gezeigt, daß die Wirksamkeit dieser Mischpolymerisate als Fließverbesserer abhängig ist von den Eigenschaften der Mineralöle und Mineralöldestillate, deren Fließfähigkeit erhöht werden soll. Bei Mitteldestillaten beispielsweise wird sie u.a. beeinflußt durch den Gesamtge­halt an n-Paraffinen und den Gehalt an n-Paraffinen be­stimmter Kettenlängen. Paraffingehalt und -verteilung wer­den bestimmt durch die Anteile leichter, mittelschwerer und schwerer Destillatfraktionen, aus denen das Mitteldestillat zusammengesetzt ist, sowie durch die Rohölprovenienz.It has been shown in practice that the effectiveness of these copolymers as flow improvers depends on the properties of the mineral oils and mineral oil distillates, the flowability of which is to be increased. In the case of middle distillates, for example, influenced by the total content of n-paraffins and the content of n-paraffins of certain chain lengths. Paraffin content and distribution are determined by the proportions of light, medium and heavy distillate fractions from which the middle distillate is composed, and by the crude oil provenance.

Es ist daher verständlich, daß die Ethylen-Vinylacetat-­Copolymerisate trotz ihrer hervorragenden Eignung die Fließfähigkeit zu erhöhen, nicht immer die erwünschte Wir­kung zeigen. In solchen Fällen behilft man sich dann da­durch, daß man sie in großen Mengen zusetzt oder daß man das Mineralöl oder das Mineralöldestillat mit niedrig sie­denden Kohlenwasserstoffen vermischt.It is therefore understandable that the ethylene-vinyl acetate copolymers, despite their outstanding suitability for increasing the flowability, do not always have the desired effect. In such cases, the remedy is to add them in large quantities or to mix the mineral oil or the mineral oil distillate with low-boiling hydrocarbons.

Eine andere Möglichkeit, die Wirksamkeit von Fließverbes­serern zu erhöhen besteht darin, Additivkombinationen ein­zusetzen. So werden in der DE-A-26 39 672 Mischungen aus Polymeren mit Ethylenskelett und Coplymeren von C₂- bis C₅₀-Olefinen beschrieben, die zu einer synergistischen Verbesserung der Fließeigenschaften von Destillatkohlenwas­serstoffölen in der Kälte führen können.Another way to increase the effectiveness of flow improvers is to use additive combinations. For example, DE-A-26 39 672 describes mixtures of polymers with an ethylene skeleton and copolymers of C₂- to C₅₀-olefins, which can lead to a synergistic improvement in the flow properties of distillate hydrocarbon oils in the cold.

Nach der US-A-36 60 057 setzt man Mischungen aus einem Ethylen-Vinylacetat-Copolymerisat und einem festen Kohlen­wasserstoff, der frei von n-Paraffinen ist, als Fließver­besserer ein.According to US-A-36 60 057, mixtures of an ethylene-vinyl acetate copolymer and a solid hydrocarbon which is free of n-paraffins are used as flow improvers.

Als Fließverbesserer für Erdölmitteldestillate werden in der US-A-40 19 878 Gemische offenbart, die aus einem Ethy­len enthaltenden Polymerisat, Bienenwachs, Ozokerit und/oder einem langkettigen alpha-Olefin bestehen.As a flow improver for petroleum middle distillates, US-A-40 19 878 discloses mixtures consisting of an ethylene-containing polymer, beeswax, ozokerite and / or a long-chain alpha-olefin.

Obgleich die bekannten Substanzen und Substanzgemische in vielen Fällen die Fließfähigkeit von Mineralölen und Mine­ralöldestillaten unterschiedlicher Herkunft und Zusammen­setzung bei niedrigen Temperaturen zum Teil sogar deutlich verbessert haben, fehlen dennoch Additive mit möglichst vielseitiger, im Idealfall universeller Anwendbarkeit.Although the known substances and substance mixtures have in many cases even significantly improved the flowability of mineral oils and mineral oil distillates of different origins and compositions at low temperatures, additives with the greatest possible versatility, ideally universal application, are still missing.

Es bestand daher die Aufgabe, Additive bereitzustellen, die gegenüber den bekannten Fließverbesserern eine noch größere Anwendungsbreite haben. Sie sollen die Fließfähigkeit auch solcher Öle erhöhen, bei denen die bekannten Additive keine oder nur geringe Wirkung zeigen.The object was therefore to provide additives which have an even greater range of uses than the known flow improvers. They are also intended to increase the flowability of oils in which the known additives have little or no effect.

Die Erfindung besteht in einem Verfahren zur Verbesserung der Fließfähigkeit von Mineralölen und Mineralöldestilla­ten. Es ist dadurch gekennzeichnet, daß man den Mineralölen bzw. Mineralöldestillaten Mischungen aus einem Ethylen-­Vinylacetat-Copolymerist und einem Ethylen-Vinylacetat-N-­Vinylpyrrolidon-Terpolymerisat zusetzt.The invention consists in a method for improving the flowability of mineral oils and mineral oil distillates. It is characterized in that mixtures of an ethylene-vinyl acetate copolymer and an ethylene-vinyl acetate-N-vinylpyrrolidone terpolymer are added to the mineral oils or mineral oil distillates.

Überraschenderweise hat sich gezeigt, daß das erfindungsge­mäße Verfahren die Ausscheidung von Paraffinen aus Mineral­ölen und Mineralöldestillaten wirksam unterdrückt und gege­benenfalls ausgeschiedene Paraffinkristalle in Schwebe hält. Die nach dem neuen Verfahren eingesetzten Additive wirken damit einem Ansteigen der Viskosität der Kohlenwas­serstoffgemische bei sinkenden Temperaturen entgegen und setzen den Stockpunkt herab. Die beanspruchte Arbeitsweise hat sich zur Verbesserung der Fließfähigkeit von Mineralö­len und deren Destillationsprodukten, unabhängig von ihrer qualitativen und quantitativen Zusammensetzung, bewährt. Von besonderer Bedeutung ist, daß sich die beiden Kompo­nenten synergistisch verstärken. Die Wirksamkeit des Poly­merisatgemisches ist also größer als die Summe der Wirk­samkeit seiner Bestandteile.Surprisingly, it has been shown that the process according to the invention effectively suppresses the separation of paraffins from mineral oils and mineral oil distillates and any paraffin crystals which have separated out in suspension holds. The additives used according to the new process thus counteract an increase in the viscosity of the hydrocarbon mixtures as temperatures drop and lower the pour point. The claimed working method has proven itself to improve the flowability of mineral oils and their distillation products, regardless of their qualitative and quantitative composition. It is particularly important that the two components reinforce each other synergistically. The effectiveness of the polymer mixture is therefore greater than the sum of the effectiveness of its components.

Die erfindungsgemäß eingesetzten Ethylen-Vinylacetat-Co­polymerisate enthalten 20 bis 40 Gew.-% Vinylacetat. Beson­ders bewährt haben sich Copolymerisate mit 25 bis 35 Gew.-% Vinylacetat. Ihre nach der deutschen Norm DIN 53 019 in einem Rotationsviskosimeter (Hersteller: Fa. Haake) bei 140°C gemessenen Viskosität beträgt 30 bis 1000 mPa.s, insbesondere 30 bis 250 mPa.s.The ethylene-vinyl acetate copolymers used according to the invention contain 20 to 40% by weight of vinyl acetate. Copolymers with 25 to 35% by weight of vinyl acetate have proven particularly useful. Its viscosity, measured according to the German standard DIN 53 019 in a rotary viscometer (manufacturer: Haake) at 140 ° C, is 30 to 1000 mPa.s, in particular 30 to 250 mPa.s.

Je 100 CH₂-Gruppen weisen sie 1 bis 10 und vorzugsweise 2 bis 7 CH₃-Gruppen in den Seitenketten auf, die nicht aus dem Acetatrest des Vinylacetats herrühren. Die Bestimmung der Anzahl CH₃-Gruppen erfolgt dabei durch H-NMR-Spektros­kopie.Each 100 CH₂ groups have 1 to 10 and preferably 2 to 7 CH₃ groups in the side chains, which do not result from the acetate residue of the vinyl acetate. The number of CH₃ groups is determined by H-NMR spectroscopy.

Die Herstellung der Ethylen-Vinylacetat-Copolymerisate ist bekannt. Sie kann z.B. durch Polymerisation des Monomerge­misches bei Drücken von 5 bis 15 MPa und Temperaturen von 70 bis 150°C in Gegenwart Radikale bildender Initiatoren erfolgen. Als Reaktionsmedium kann ein organisches Lösungs- oder Suspensionsmittel wie Toluol eingesetzt werden.The production of the ethylene-vinyl acetate copolymers is known. It can e.g. by polymerization of the monomer mixture at pressures of 5 to 15 MPa and temperatures of 70 to 150 ° C in the presence of free radical initiators. An organic solvent or suspension medium such as toluene can be used as the reaction medium.

Die als zweiter Bestandteil des Fließverbesserergemisches verwendeten Ethylen-Vinylacetat-N-Vinylpyrrolidon-Terpoly­ merisate enthalten 15 bis 50 Gew.-%, insbesondere 20 bis 35 Gew.-% Vinylacetat und 0,5 bis 10 Gew.-%, insbesondere 1,0 bis 5,0 Gew.-% N-Vinylpyrrolidon. Ihre in der gleichen Weise wie bei den Ethylen-Vinylacetat-Copolymerisaten ge­messene Viskosität beträgt 100 bis 5000 mPa.s und insbeson­dere 150 bis 1500 mPa.s.The ethylene-vinyl acetate-N-vinylpyrrolidone terpoly used as the second component of the flow improver mixture Merisates contain 15 to 50% by weight, in particular 20 to 35% by weight, of vinyl acetate and 0.5 to 10% by weight, in particular 1.0 to 5.0% by weight, of N-vinylpyrrolidone. Their viscosity, measured in the same way as for the ethylene-vinyl acetate copolymers, is 100 to 5000 mPa.s and in particular 150 to 1500 mPa.s.

Die Herstellung von Ethylen-Vinylacetat-N-Vinylpyrrolidon-­Terpolymerisaten ist bekannt. Sie erfolgt z.B. durch Poly­merisation des Monomerengemisches bei Drücken oberhalb von 5 MPa und Temperaturen oberhalb 60°C in Gegenwart Radikale bildender Initiatoren in Autoklaven. Als Reaktionsmedium wendet man organische Lösungsmittel an, die ≧ 5 Gew.-% Ethylen lösen. Geeignet sind Methanol, t-Butanol, Benzol, Dioxan (vgl. FR 1 392 354).The production of ethylene-vinyl acetate-N-vinylpyrrolidone terpolymers is known. It takes place e.g. by polymerization of the monomer mixture at pressures above 5 MPa and temperatures above 60 ° C in the presence of free radical initiators in autoclaves. Organic solvents which dissolve ≧ 5% by weight of ethylene are used as the reaction medium. Methanol, t-butanol, benzene, dioxane are suitable (cf. FR 1 392 354).

Das Gewichtsverhältnis der beiden Polymerisate im Additiv­gemisch kann innerhalb weiter Grenzen variiert werden. Es hat sich bewährt, Ethylen-Vinylacetat-Copolymerisat und Ethylen-Vinylacetat-N-Vinylpyrrolidon-Terpolymerisat im Gewichtsverhältnis von 1 : 1 bis 100 : 1 einzusetzen. Be­vorzugt werden Mischungen, die Copolymerisat und Terpolyme­risat im Gewichtsverhältnis von 3 : 1 bis 20 : 1 enthalten.The weight ratio of the two polymers in the additive mixture can be varied within wide limits. It has proven useful to use ethylene-vinyl acetate copolymer and ethylene-vinyl acetate-N-vinylpyrrolidone terpolymer in a weight ratio of 1: 1 to 100: 1. Mixtures which contain copolymer and terpolymer in a weight ratio of 3: 1 to 20: 1 are preferred.

Das erfindungsgemäße Verfahren verbessert sowohl die Fließ­fähigkeit von Mineralölen als auch von Mineralöldestilla­ten. Unter dem Begriff Mineralöle werden hierbei insbeson­dere Rohöle und Destillationsrückstände, wie schweres Heiz­öl, verstanden. Als Mineralöldestillate werden Kohlenwas­serstofffraktionen mit einer Siedetemperatur zwischen etwa 150 und 400°C bezeichnet. Hierzu gehören beispielsweise Petroleum, leichte Heizöle und Dieselkraftstoffe. Von be­sonderer Bedeutung sind die Mitteldestillate wie Heizöl EL und Dieselkraftstoff.The process according to the invention improves both the flowability of mineral oils and of mineral oil distillates. The term mineral oils is understood here to mean in particular crude oils and distillation residues, such as heavy fuel oil. Mineral oil distillates are hydrocarbon fractions with a boiling temperature between approximately 150 and 400 ° C. These include, for example, petroleum, light heating oils and diesel fuels. Middle distillates such as heating oil EL and diesel fuel are of particular importance.

Das Gemisch aus den beiden Polymerisaten wird Mineralölen bzw. den Mineralöldestillaten in Form von Lösungen, die 20 bis 70 Gew.-% (bezogen auf die Lösung) der Polymerisate enthalten, zugesetzt. Als Lösungsmittel geeignet sind ali­phatische oder aromatische Kohlenwasserstoffe oder Kohlen­wasserstoffgemische, z.B. Benzinfraktionen. Besonders ge­eignet ist Kerosin. Die Polymerisatmenge, bezogen auf Mine­ralöl bzw. Mineralölfraktionen, soll 0,001 bis 2, vorzugs­weise 0,005 bis 0,5 Gew.-% betragen.The mixture of the two polymers is added to mineral oils or the mineral oil distillates in the form of solutions which contain 20 to 70% by weight (based on the solution) of the polymers. Suitable solvents are aliphatic or aromatic hydrocarbons or hydrocarbon mixtures, e.g. Gasoline fractions. Kerosene is particularly suitable. The amount of polymer, based on mineral oil or mineral oil fractions, should be 0.001 to 2, preferably 0.005 to 0.5% by weight.

Die Polymerisatgemische können allein oder auch zusammen mit anderen Additiven verwendet werden, z.B. mit anderen Stockpunkterniedrigern oder Entwachsungshilfsmitteln, mit Korrosionsinhibitoren, Antioxidantien, Schlamminhibitoren und Zusätzen zur Erniedrigung des Cloud-Points.The polymer mixtures can be used alone or together with other additives, e.g. with other pour point depressants or dewaxing aids, with corrosion inhibitors, antioxidants, sludge inhibitors and additives to lower the cloud point.

Das erfindungsgemäße Verfahren wird durch die nachfolgenden Beispiele näher erläutert.The process according to the invention is explained in more detail by the following examples.

Die Beispiele 1 bis 4 betreffen das erfindungsgemäße Ver­fahren. In den Beispielen 5 bis 7 werden die Ergebnisse von Vergleichsversuchen wiedergegeben, die bei Einsatz von Ethylen-Vinylacetat-Copolymerisaten allein (Beispiele 5 und 6) und eines Ethylen-Vinylacetat-N-Vinylpyrrolidon-Terpoly­merisats allein (Beispiel 7) erhalten werden.Examples 1 to 4 relate to the process according to the invention. Examples 5 to 7 show the results of comparative experiments which are obtained using ethylene-vinyl acetate copolymers alone (Examples 5 and 6) and an ethylene-vinyl acetate-N-vinylpyrrolidone terpolymer alone (Example 7).

Die Wirksamkeit der untersuchten Verfahren zur Verbesserung der Fließfähigkeit wird an Hand des "Kalt-Filter-Verstop­fungspunkt-Test" (CFPP-Test) beschrieben. Die Durchführung des Tests erfolgt nach DIN 51428. Sie ist auch im J. of the Inst. of Petr. Bd. 52, Juni 1966, Seite 173 bis 185, publi­ziert.The effectiveness of the investigated methods for improving the flowability is described using the "cold filter plugging point test" (CFPP test). The test is carried out according to DIN 51428. It is also in the J. of the Inst. Of Petr. Vol. 52, June 1966, pages 173 to 185.

Zur Prüfung werden drei Mitteldestillate M1, M2 und M3 eingesetzt. Sie werden durch die in Tabelle 1 zusammenge­stellten Eigenschaftswerte gekennzeichnet.Three middle distillates M1, M2 and M3 are used for the test. They are characterized by the property values compiled in Table 1.

Beispiele 1 bis 8:Examples 1 to 8:

In den folgenden Beispielen werden die nachstehend charak­terisierten Polymerisate allein oder als Mischung einge­setzt.

  • A: ein Ethylen-Vinylactat-Copolymerisat mit einem Vinyl­acetat-Gehalt von 30,5 Gew.-% und einer Viskosität von 30 mPa.s bei 140°C.
  • B: ein Ethylen-Vinylacetat-Copolymerisat mit einem Vinyl­acetat-Gehalt von 29,8 Gew.-% und einer Viskosität von 80 mPa.s bei 140°C.
  • C: ein Ethylen-Vinylacetat-N-Vinylpyrrolidon-Terpolymerisat mit einem Vinylacetatgehalt von 23,2 Gew.-%, einem N-­Vinylpyrrolidongehalt von 1,4 Gew.-% und einer Viskosi­tät von 230 mPa.s bei 140°C.
In the following examples, the polymers characterized below are used alone or as a mixture.
  • A: an ethylene-vinyl lactate copolymer with a vinyl acetate content of 30.5% by weight and a viscosity of 30 mPa.s at 140 ° C.
  • B: an ethylene-vinyl acetate copolymer with a vinyl acetate content of 29.8% by weight and a viscosity of 80 mPa.s at 140 ° C.
  • C: an ethylene-vinyl acetate-N-vinylpyrrolidone terpolymer with a vinyl acetate content of 23.2% by weight, an N-vinylpyrrolidone content of 1.4% by weight and a viscosity of 230 mPa.s at 140 ° C.

Der Vinylacetatgehalt in den Polymerisaten wird nach der Pyrolysemethode bestimmt. Hierzu werden 200 mg des Polyme­risats mit 300 mg reinem Polyethylen in einem Pyrolysekol­ben 5 Minuten auf 450°C erhitzt und die Spaltgase in einem 250 ml-Rundkolben aufgefangen. Die entstandene Essigsäure wird mit einer NaJ/KJO₃-Lösung umgesetzt und das freiwer­dende Jod mit Na₂S₂O₃-Lösung titriert.The vinyl acetate content in the polymers is determined using the pyrolysis method. For this purpose, 200 mg of the polymer are heated with 300 mg of pure polyethylene in a pyrolysis flask to 450 ° C. for 5 minutes and the cracked gases are collected in a 250 ml round-bottom flask. The resulting acetic acid is reacted with a NaJ / KJO₃ solution and the iodine released is titrated with Na₂S₂O₃ solution.

Der N-Vinylpyrrolidongehalt im Polymerisat wird aus dem nach Dumas bestimmten Stickstoff-Gehalt des Polymers be­rechnet.The N-vinylpyrrolidone content in the polymer is calculated from the nitrogen content of the polymer determined according to Dumas.

Tabelle 2 enthält Angaben zur Wirksamkeit des erfindungs­gemäßen Verfahrens zur Verbesserung der Fließfähigkeit von Mineralölen und Mineralöldestillaten. Tabelle 1: Kennzeichnung der Prüföle M 1 M 2 M 3 Cloud Point (nach DIN 51 597) (°C) + 1 - 2,2 + 3 CFPP (°C) - 5 - 4 - 2 Pour Point (°C) - 6 - 15 - 9 Wax Appearance Temperature (°C) - 4,0 - 6,0 - 3,0 Gehalt an n-Paraffinen (%) 41 - 37 Siedeanalyse (°C) Siedeanfang 176 184 190 20 % - 217 234 90 % - 350 350 Siedeende 381 377 373

Figure imgb0001
Figure imgb0002
 Table 2 contains information on the effectiveness of the process according to the invention for improving the flowability of mineral oils and mineral oil distillates. Table 1: Identification of the test oils M 1 M 2 M 3 Cloud Point (according to DIN 51 597) (° C) + 1 - 2.2 + 3 CFPP (° C) - 5th - 4th - 2nd Pour point (° C) - 6th - 15th - 9 Wax Appearance Temperature (° C) - 4.0 - 6.0 - 3.0 N-paraffins content (%) 41 - 37 Boiling analysis (° C) Beginning of boiling 176 184 190 20% - 217 234 90% - 350 350 End of boiling 381 377 373
Figure imgb0001
Figure imgb0002

Claims (5)

1.) Verfahren zur Verbesserung der Fließfähigkeit von Mineralölen und Mineralöldestillaten, dadurch gekenn­zeichnet, daß man den Mineralölen bzw. Mineralöldestil­laten Mischungen aus einem Ethylen-Vinylacetat-Copoly­merisat und einem Ethylen-Vinylacetat-N-Vinylpyrroli­don-Terpolymerisat zusetzt.1.) Process for improving the flowability of mineral oils and mineral oil distillates, characterized in that mixtures of an ethylene-vinyl acetate copolymer and an ethylene-vinyl acetate-N-vinylpyrrolidone terpolymer are added to the mineral oils or mineral oil distillates. 2.) Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Ethylen-Vinylacetat-Copolymerisat 20 bis 40 Gew.-%, vorzugsweise 25 bis 35 Gew.-% Vinylacetat enthält, eine bei 140°C gemessene Viskosität von 30 bis 1000, vor­zugsweise 30 bis 250 mPa.s besitzt und je 100 CH₂-Grup­pen 1 bis 10, vorzugsweise 2 bis 7 CH₃-Gruppen in den Seitenketten aufweisen, die nicht aus dem Acetatrest des Vinylacetats herrühren.2.) Process according to claim 1, characterized in that the ethylene-vinyl acetate copolymer contains 20 to 40 wt .-%, preferably 25 to 35 wt .-% vinyl acetate, a viscosity measured at 140 ° C of 30 to 1000, preferably 30 to 250 mPa.s and each have 100 CH₂ groups 1 to 10, preferably 2 to 7 CH₃ groups in the side chains, which do not come from the acetate residue of the vinyl acetate. 3.) Verfahren nach Anspruch 1, dadurch gekennzeichnet, das das Ethylen-Vinylacetat-N-Vinylpyrrolidon-Terpolymeri­sat 15 bis 50 Gew.-%, vorzugsweise 20 bis 35 Gew.-% Vinylacetat, 0,5 bis 10 Gew.-%, vorzugsweise 1,0 bis 5,0 Gew.-% N-Vinylpyrrolidon enthält und eine bei 140°C gemessene Viskosität von 100 bis 5000 mPa.s, insbeson­dere 150 bis 1500 mPa.s besitzt.3.) Method according to claim 1, characterized in that the ethylene-vinyl acetate-N-vinylpyrrolidone terpolymer 15 to 50 wt .-%, preferably 20 to 35 wt .-% vinyl acetate, 0.5 to 10 wt .-%, preferably contains 1.0 to 5.0% by weight of N-vinylpyrrolidone and has a viscosity of 100 to 5000 mPa.s, in particular 150 to 1500 mPa.s, measured at 140 ° C. 4.) Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß Ethylen-Vinylacetat-Copolymerisat und Ethylen-Vinyl­acetat-N-Vinylpyrrolidon-Terpolymerisat im Gewichtsver­hältnis von 1 : 1 bis 100 : 1, vorzugsweise 3 : 1 bis 20 : 1 eingesetzt werden.4.) Process according to claim 1, characterized in that ethylene-vinyl acetate copolymer and ethylene-vinyl acetate-N-vinylpyrrolidone terpolymer are used in a weight ratio of 1: 1 to 100: 1, preferably 3: 1 to 20: 1. 5.) Mineralöl oder Mineralöldestillat mit verbessertem Fließverhalten, dadurch gekennzeichnet, daß es 0,001 bis 2, vorzugsweise 0,005 bis 0,5 Gew.-% einer Mischung aus einem Ethylen-Vinylacetat-Copolymerisat und einem Ethylen-Vinylacetat-N-Vinylpyrrolidon-Terpolymerisat enthält.5.) Mineral oil or mineral oil distillate with improved flow behavior, characterized in that it contains 0.001 to 2, preferably 0.005 to 0.5 wt .-% of a mixture of an ethylene-vinyl acetate copolymer and an ethylene-vinyl acetate-N-vinylpyrrolidone terpolymer .
EP90111397A 1989-06-29 1990-06-16 Process to improve mineral oil and mineral oil distillate flowability Expired - Lifetime EP0405270B1 (en)

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DE19816797A1 (en) * 1998-04-16 1999-10-21 Clariant Gmbh Process for improving lubricity of fuel oils
US5998530A (en) * 1997-01-07 1999-12-07 Clariant Gmbh Flowability of mineral oils and mineral oil distillates using alkylphenol-aldehyde resins
US6281292B1 (en) 1998-05-27 2001-08-28 Clariant Gmbh Mixtures of copolymers having an improved lubricating action
WO2001088066A1 (en) * 2000-05-19 2001-11-22 Nippon Mitsubishi Oil Corporation Fuel oil additive and fuel oil composition
US6821933B2 (en) 2000-06-15 2004-11-23 Clariant International Ltd. Additives for improving the cold flow properties and the storage stability of crude oil
US7041738B2 (en) 2002-07-09 2006-05-09 Clariant Gmbh Cold flow improvers for fuel oils of vegetable or animal origin

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DE19739271A1 (en) * 1997-09-08 1999-03-11 Clariant Gmbh Additive to improve the flowability of mineral oils and mineral oil distillates
DE10155774B4 (en) 2001-11-14 2020-07-02 Clariant Produkte (Deutschland) Gmbh Additives for low sulfur mineral oil distillates, comprising an ester of alkoxylated glycerin and a polar nitrogen-containing paraffin dispersant
DE10155748B4 (en) 2001-11-14 2009-04-23 Clariant Produkte (Deutschland) Gmbh Low-sulfur mineral oil distillates having improved cold properties, comprising an ester of an alkoxylated polyol and a copolymer of ethylene and unsaturated esters
DE50307929D1 (en) 2002-07-09 2007-09-27 Clariant Produkte Deutschland Oxidation-stabilized lubricating additives for highly desulphurised fuel oils
DE10349850C5 (en) 2003-10-25 2011-12-08 Clariant Produkte (Deutschland) Gmbh Cold flow improver for fuel oils of vegetable or animal origin
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DE10357878C5 (en) 2003-12-11 2013-07-25 Clariant Produkte (Deutschland) Gmbh Fuel oils from middle distillates and oils of vegetable or animal origin with improved cold properties
DE10357880B4 (en) 2003-12-11 2008-05-29 Clariant Produkte (Deutschland) Gmbh Fuel oils from middle distillates and oils of vegetable or animal origin with improved cold properties
EP2376609A1 (en) 2009-01-13 2011-10-19 Evonik RohMax Additives GmbH Fuel compositions having improved cloud point and improved storage properties
US20110192076A1 (en) 2010-02-05 2011-08-11 Evonik Rohmax Additives Gmbh Composition having improved filterability

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WO2001088066A1 (en) * 2000-05-19 2001-11-22 Nippon Mitsubishi Oil Corporation Fuel oil additive and fuel oil composition
JP4537642B2 (en) * 2000-05-19 2010-09-01 新日本石油株式会社 Fuel oil additive and fuel oil composition
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US7041738B2 (en) 2002-07-09 2006-05-09 Clariant Gmbh Cold flow improvers for fuel oils of vegetable or animal origin

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JPH0768505B2 (en) 1995-07-26

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