EP0254284B1 - Process to improve the flowability of mineral oils and mineral oil distillates - Google Patents

Process to improve the flowability of mineral oils and mineral oil distillates Download PDF

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Publication number
EP0254284B1
EP0254284B1 EP87110581A EP87110581A EP0254284B1 EP 0254284 B1 EP0254284 B1 EP 0254284B1 EP 87110581 A EP87110581 A EP 87110581A EP 87110581 A EP87110581 A EP 87110581A EP 0254284 B1 EP0254284 B1 EP 0254284B1
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vinyl acetate
ethylene
weight
parts
mineral oil
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French (fr)
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EP0254284A1 (en
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Wolfgang Dr. Dipl.-Chem. Payer
Ludger Dr. Dipl.-Chem. Bexten
John Dr. Dipl.-Chem. Hobes
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Hoechst AG
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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
    • C10L1/18—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

Definitions

  • the present invention relates to a process for improving the flowability of mineral oils and mineral oil distillates by adding mixtures of an ethylene-vinyl acetate-diisobutylene terpolymer and an ethylene-vinyl acetate copolymer.
  • Mineral oils such as crude oil, diesel fuel or heating oil contain dissolved paraffin, which crystallizes out at low temperatures. These solid deposits often lead to disruptions in the extraction and use of mineral oils. For example, the ability of crude oil production and transport facilities to function until their complete failure are impaired. In diesel engines and combustion plants, the filters can become clogged, which ultimately results in an interruption in the fuel or heating medium supply.
  • additives are added to mineral oils that counteract the formation of wax crystals. This prevents an increase in the viscosity of the oils and lowers their pour point.
  • Copolymers of ethylene and carboxylic acid esters of vinyl alcohol have become very important as pour point depressants and flow improvers for crude oils and middle distillates.
  • ethylene-vinyl acetate copolymers have proven particularly useful.
  • Such copolymers and their use are described, for example, in DE-PS 19 14 756. They are generally manufactured by copolymerization of the monomers in autoclaves at temperatures from 80 to 150 ° C and pressures from 5 to 15 MPa in the presence of peroxides as initiators and organic solvents as the reaction medium.
  • the remedy is to add large quantities or to mix the mineral oil or mineral oil distillate with low-boiling hydrocarbons.
  • DE 26 39 672 Al describes mixtures of polymers with an ethylene skeleton and copolymers of C2bis C50 olefins, which can lead to a synergistic improvement in the flow properties of distillate hydrocarbon oils in the cold.
  • the object was therefore to find 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.
  • the object described above is achieved by a method for improving the flowability of mineral oils and mineral oil distillates. It is characterized in that mixtures of an ethylene-vinyl acetate-diisobutylene terpolymer and an ethylene-vinyl acetate copolymer are added to the mineral oils or mineral oil distillates.
  • the ethylene-vinyl acetate-diisobutylene terpolymers used according to the invention contain 25 to 78 parts by weight of vinyl acetate and 0.5 to 45 parts by weight of diisobutylene per 100 parts by weight of ethylene. Terpolymers with 30 to 55 parts by weight of vinyl acetate and 1.0 to 27.5 parts by weight of diisobutylene per 100 parts by weight of ethylene have proven particularly useful.
  • the average molecular weight of the terpolymers measured by vapor pressure osmometry is 500 to 10 000 g.mol -1 , preferably 1000 to 5000.g mol -1 and in particular 1500 to 3500.g mol -1 .
  • Each 100 CH2 groups have 6 to 20 and preferably 7 to 15 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.
  • the production of the ethylene-vinyl acetate-diisobutylene terpolymers is known. It can e.g. by polymerization of the monomer mixture at pressures above 50 MPa and temperatures from 150 to 350 ° C. in the presence of oxygen or radical initiators in autoclaves or tubular reactors.
  • Diisobutylene is a mixture consisting essentially of 2,4,4-trimethylpentene (1) and 2,4,4-trimethylpentene (2). It is formed during the dimerization of isobutylene (2-methylpropene) with acidic catalysts (e.g. ion exchangers).
  • acidic catalysts e.g. ion exchangers
  • the ethylene-vinyl acetate copolymers used according to the invention contain 5 to 54 parts by weight of vinyl acetate per 100 parts by weight of ethylene. Copolymers with 11 to 33 parts by weight of vinyl acetate per 100 parts by weight of ethylene have proven particularly useful.
  • the average molecular weight of the copolymers which, like the average molecular weight of the terpolymers, is measured by vapor pressure osmometry, is 500 to 10 000 g.mo l-1 .
  • Copolymers with a molecular weight of 1,000 to 5,000 g.mol -1 have proven particularly useful.
  • Each l00 CH2 groups have the copolymers l to l0 and preferably 3 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.
  • 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.
  • the weight ratio of ethylene-vinyl acetate-diisobutylene terpolymer and ethylene-vinyl acetate copolymer in the mixtures is 100: 1 to 1: 1. Mixtures containing the terpolymer and copolymer in a weight ratio of 20: 1 to 3: 1 are preferred.
  • the process according to the invention improves both the flowability of mineral oils and of mineral oil distillates.
  • mineral oils is understood to mean crude oils and distillation residues such as heavy fuel oil.
  • Mineral oil distillates are hydrocarbon fractions with a boiling temperature between about 150 and 400 ° C. These include, for example, petroleum, light heating oils and diesel fuel. Middle distillates such as heating oil EL and diesel fuel are of particular importance.
  • the mixture of terpolymer and copolymer is added to mineral oils or 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 distillates should be 0.001 to 2, preferably 0.005 to 0.5% by weight.
  • 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.
  • additives e.g. with other pour point depressants or dewaxing aids, with corrosion inhibitors, antioxidants, sludge inhibitors and additives to lower the cloud point.
  • the vinyl acetate content in the polymer 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. The diisobutylene content in the polymer is determined by 13 C-NMR spectroscopy.
  • Table 2 summarizes the results which describe the effectiveness of the process according to the invention for improving the flowability of mineral oils and mineral oil distillates.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

The flowability is improved by adding mixtures of an ethylene/vinyl acetate/diisobutylene terpolymer and an ethylene/vinyl acetate copolymer.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Verbesserung der Fließfähigkeit von Mineralölen und Mineralöldestillaten durch Zusatz von Mischungen aus einem Ethylen-Vinylacetat-Diisobutylen-Terpolymerisat und einem Ethylen-Vinylacetat-Copolymerisat.The present invention relates to a process for improving the flowability of mineral oils and mineral oil distillates by adding mixtures of an ethylene-vinyl acetate-diisobutylene terpolymer and an ethylene-vinyl acetate copolymer.

Mineralöle wie Rohöl, Dieselkraftstoff oder Heizöl enthalten Paraffin gelöst, das bei niedrigen Temperaturen auskristallisiert. Diese Feststoffablagerungen führen häufig zu Störungen bei der Gewinnung und beim Einsatz von Mineralölen. So kann z.B. die Arbeitsfähigkeit von Förder- und Transporteinrichtungen für Rohöl bis zu deren völligem Ausfall beeinträchtigt werden. Bei Dieselmotoren und Feuerungsanlagen können Verstopfungen der Filter auftreten, die schließlich in einer Unterbrechung der Kraftstoff- bzw. Heizmittelzufuhr resultieren.Mineral oils such as crude oil, diesel fuel or heating oil contain dissolved paraffin, which crystallizes out at low temperatures. These solid deposits often lead to disruptions in the extraction and use of mineral oils. For example, the ability of crude oil production and transport facilities to function until their complete failure are impaired. In diesel engines and combustion plants, the filters can become clogged, which ultimately results in an interruption in the fuel or heating medium supply.

Um diese unerwünschte Feststoffbildung zu vermeiden, setzt man Mineralölen Additive zu, die der Entstehung von Paraffinkristallen entgegenwirken. Dadurch wird ein Anstieg der Viskosität der Öle verhindert und ihr Stockpunkt gesenkt.In order to avoid this undesirable solid formation, additives are added to mineral oils that counteract the formation of wax crystals. This prevents an increase in the viscosity of the oils and lowers their pour point.

Große Bedeutung als Stockpunktserniedriger und Fließverbesserer für Rohöle und Mitteldestillate haben Copolymerisate aus Ethylen und Carbonsäureestern des Vinylalkohols erlangt. Besonders bewährt haben sich unter ihnen Ethylen-Vinylacetat-Copolymerisate. Solche Mischpolymerisate und ihre Verwendung sind z.B. in der DE-PS l9 l4 756 beschrieben. Ihre Herstellung erfolgt im allgemeinen durch Copolymerisation der Monomeren in Autoklaven bei Temperaturen von 80 bis 150°C und Drücken von 5 bis l5 MPa in Gegenwart von Peroxiden als Initiatoren und organischen Lösungsmitteln als Reaktionsmedium.Copolymers of ethylene and carboxylic acid esters of vinyl alcohol have become very important as pour point depressants and flow improvers for crude oils and middle distillates. Among them, ethylene-vinyl acetate copolymers have proven particularly useful. Such copolymers and their use are described, for example, in DE-PS 19 14 756. They are generally manufactured by copolymerization of the monomers in autoclaves at temperatures from 80 to 150 ° C and pressures from 5 to 15 MPa in the presence of peroxides as initiators and organic solvents as the reaction medium.

In der Praxis hat sich gezeigt, daß die Wirksamkeit dieser Copolymerisate als Fließverbesserer abhängig ist von den Eigenschaften der Mineralöle und Mineralöldestillate, deren Fließfähigkeit erhöht werden soll. Bei Mitteldestillaten z.B. wird sie u.a. beeinflußt durch den Gesamtgehalt an n-Paraffinen und den Gehalt an n-Paraffinen bestimmter Kettenlängen.In practice it has been shown 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. With middle distillates e.g. among other things influenced by the total content of n-paraffins and the content of n-paraffins of certain chain lengths.

Es ist daher verständlich, daß die Ethylen-VinylacetatCopolymerisate 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 excellent suitability for increasing the flowability, do not always have the desired effect. In such cases, the remedy is to add large quantities or to mix the mineral oil or 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 26 39 672 Al Mischungen aus Polymeren mit Ethylenskelett und Copolymeren von C₂bis 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 26 39 672 Al describes mixtures of polymers with an ethylene skeleton and copolymers of C₂bis C₅₀ olefins, which can lead to a synergistic improvement in the flow properties of distillate hydrocarbon oils in the cold.

Nach der US 36 60 057 Cl setzt man Mischungen aus einem Ethylen-Vinylacetat-Copolymerisat und einem festen Kohlenwasserstoff, der frei von n-Paraffinen ist, als Fließverbesserer ein.According to US 36 60 057 Cl, 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 40 l9 878 Cl 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, mixtures are disclosed in US Pat Polymer containing ethylene, 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 Provenienz 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 provenance and composition at low temperatures, additives with the greatest possible versatility, ideally universal application, are still missing.

Es bestand daher die Aufgabe, Additive zu finden, 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 find 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 vorstehend beschriebene Aufgabe wird gelöst durch ein Verfahren zur Verbesserung der Fließfähigkeit von Mineralölen und Mineralöldestillaten. Es ist dadurch gekennzeichnet, daß man den Mineralölen bzw. Mineralöldestillaten Mischungen aus einem Ethylen-Vinylacetat-Diisobutylen-Terpolymerisat und einem Ethylen-Vinylacetat-Copolymerisat zusetzt.The object described above is achieved by a method for improving the flowability of mineral oils and mineral oil distillates. It is characterized in that mixtures of an ethylene-vinyl acetate-diisobutylene terpolymer and an ethylene-vinyl acetate copolymer are added to the mineral oils or mineral oil distillates.

Überraschenderweise hat sich gezeigt, daß die Kombination von Ethylen-Vinylacetat-Diisobutylen-Terpolymerisaten mit Ethylen-Vinylacetat-Copolymerisaten die Ausscheidung von Paraffinen aus Mineralölen und Mineralöldestillaten wirksam unterdrücken. Die aus bestimmten Polymerisaten bestehenden Additive wirken damit einem Ansteigen der Viskosität der Kohlenwasserstoffgemische bei sinkenden Temperaturen entgegen und setzen den Stockpunkt herab. Das neue Verfahren hat sich zur Verbesserung der Fließfähigkeit von Mineralölen und deren Destillationsprodukten, unabhängig von ihrer qualitativen und quantitativen Zusammensetzung, bewährt.Surprisingly, it has been shown that the combination of ethylene-vinyl acetate-diisobutylene terpolymers with ethylene-vinyl acetate copolymers effectively suppress the separation of paraffins from mineral oils and mineral oil distillates. The additives consisting of certain polymers thus counteract an increase in the viscosity of the hydrocarbon mixtures as temperatures drop and lower the pour point. The new process has proven itself to improve the flowability of mineral oils and their distillation products, regardless of their qualitative and quantitative composition.

Die erfindungsgemäß eingesetzten Ethylen-Vinylacetat-Diisobutylen-Terpolymerisate enthalten je l00 Gew.-Teile Ethylen 25 bis 78 Gew.-Teile Vinylacetat und 0,5 bis 45 Gew.-Teile Diisobutylen. Besonders bewährt haben sich Terpolymerisate mit 30 bis 55 Gew.-Teilen Vinylacetat und l,0 bis 27,5 Gew.-Teilen Diisobutylen je l00 Gew.-Teilen Ethylen.The ethylene-vinyl acetate-diisobutylene terpolymers used according to the invention contain 25 to 78 parts by weight of vinyl acetate and 0.5 to 45 parts by weight of diisobutylene per 100 parts by weight of ethylene. Terpolymers with 30 to 55 parts by weight of vinyl acetate and 1.0 to 27.5 parts by weight of diisobutylene per 100 parts by weight of ethylene have proven particularly useful.

Die durch Dampfdruckosmometrie gemessene mittlere Molmasse der Terpolymerisate beträgt 500 bis l0 000 g.mol-1, vorzugsweise l000 bis 5000.g mol-1 und insbesondere l500 bis 3500.g mol-1.The average molecular weight of the terpolymers measured by vapor pressure osmometry is 500 to 10 000 g.mol -1 , preferably 1000 to 5000.g mol -1 and in particular 1500 to 3500.g mol -1 .

Je l00 CH₂-Gruppen weisen sie 6 bis 20 und vorzugsweise 7 bis l5 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 6 to 20 and preferably 7 to 15 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-DiisobutylenTerpolymerisate ist bekannt. Sie kann z.B. durch Polymerisation des Monomerengemisches bei Drücken oberhalb von 50 MPa und Temperaturen von l50 bis 350°C in Gegenwart von Sauerstoff oder Radikale bildenden Initiatoren in Autoklaven oder Rohrreaktoren erfolgen.The production of the ethylene-vinyl acetate-diisobutylene terpolymers is known. It can e.g. by polymerization of the monomer mixture at pressures above 50 MPa and temperatures from 150 to 350 ° C. in the presence of oxygen or radical initiators in autoclaves or tubular reactors.

Diisobutylen ist ein im wesentlichen aus 2,4,4-Trimethylpenten-(l) und 2,4,4-Trimethylpenten-(2) bestehendes Gemisch. Es entsteht bei der Dimerisierung von Isobutylen (2-Methylpropen) mit sauren Katalysatoren (z.B. Ionenaustauscher).Diisobutylene is a mixture consisting essentially of 2,4,4-trimethylpentene (1) and 2,4,4-trimethylpentene (2). It is formed during the dimerization of isobutylene (2-methylpropene) with acidic catalysts (e.g. ion exchangers).

Die erfindungsgemäß eingesetzten Ethylen-Vinylacetat-Copolymerisate enthalten je l00 Gew.-Teile Ethylen 5 bis 54 Gew.-Teile Vinylacetat. Besonders bewährt haben sich Copolymerisate mit 11 bis 33 Gew.-Teilen Vinylacetat je l00 Gew.-Teilen Ethylen.The ethylene-vinyl acetate copolymers used according to the invention contain 5 to 54 parts by weight of vinyl acetate per 100 parts by weight of ethylene. Copolymers with 11 to 33 parts by weight of vinyl acetate per 100 parts by weight of ethylene have proven particularly useful.

Die mittlere Molmasse der Copolymerisate, die, ebenso wie die mittlere Molmasse der Terpolymerisate durch Dampfdruckosmometrie gemessen wird, beträgt 500 bis l0 000 g.mol-1. Besonders bewährt haben sich Copolymerisate mit einer Molmasse von l000 bis 5000 g.mol-1.The average molecular weight of the copolymers, which, like the average molecular weight of the terpolymers, is measured by vapor pressure osmometry, is 500 to 10 000 g.mo l-1 . Copolymers with a molecular weight of 1,000 to 5,000 g.mol -1 have proven particularly useful.

Je l00 CH₂-Gruppen weisen die Copolymerisate l bis l0 und vorzugsweise 3 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 l00 CH₂ groups have the copolymers l to l0 and preferably 3 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 Monomerengemisches bei Drücken von 5 bis l5 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.

Das Gewichtsverhältnis Ethylen-Vinylacetat-DiisobutylenTerpolymerisat und Ethylen-Vinylacetat-Copolymerisat in den Mischungen beträgt 100 : 1 bis 1 : 1. Bevorzugt werden Mischungen, die Terpolymerisat und Copolymerisat im Gewichtsverhältnis von 20 : 1 bis 3 : 1 enthalten.The weight ratio of ethylene-vinyl acetate-diisobutylene terpolymer and ethylene-vinyl acetate copolymer in the mixtures is 100: 1 to 1: 1. Mixtures containing the terpolymer and copolymer in a weight ratio of 20: 1 to 3: 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 Destillationsruckstände wie schweres Heizöl verstanden. Als Mineralöldestillate werden Kohlenwasserstofffraktionen mit einer Siedetemperatur zwischen etwa l50 und 400°C bezeichnet. Hierzu gehören beispielweise Petroleum, leichte Heizöle und Dieselkraftstoff. 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 to mean crude oils and distillation residues such as heavy fuel oil. Mineral oil distillates are hydrocarbon fractions with a boiling temperature between about 150 and 400 ° C. These include, for example, petroleum, light heating oils and diesel fuel. Middle distillates such as heating oil EL and diesel fuel are of particular importance.

Das Gemisch aus Terpolymerisat und Copolymerisat wird Mineralölen bzw. 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. Mineralöldestillate soll 0,00l bis 2, vorzugsweise 0,005 bis 0,5 Gew.-% betragen.The mixture of terpolymer and copolymer is added to mineral oils or 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 distillates 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:

Beispiele 1 bis 9:Examples 1 to 9:

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

  • A Ethylen-Vinylacetat-Diisobutylen-Terpolymerisat mit 38,1 Gew.-Teilen Vinylacetat und 5,6 Gew.-Teilen Diisobutylen je 100 Gew.-Teile Ethylen, mit einer Molmasse von 1 840 g.mol-1 und 8,2 CH-Gruppen in den Seitenketten, die nicht aus dem Acetatrest des Vinylacetats herrühren, je 100 CH₂-Gruppen.
  • B Ethylen-Vinylacetat-Copolymerisat mit 18,6 Gew.-Teilen Vinylacetat je 100 Gew.-Teilen Ethylen und mit einer Molmasse von 3l00 g.mol-1.
  • C Ethylen-Vinylacetat-Copolymerisat mit 25,0 Gew.-Teilen Vinylacetat je 100 Gew.-Teilen Ethylen und mit einer Molmasse von 3200 g.mol-1.
  • D Ethylen-Vinylacetat-Copolymerisat mit 18,9 Gew.-Teilen Vinylacetat je 100 Gew.-Teilen Ethylen und mit einer Molmasse von l800 g.mol-1.
  • E Ethylen-Vinylacetat-Copolymerisat mit 25,5 Gew.-Teilen Vinylacetat je 100 Gew.-Teilen Ethylen und mit einer Molmasse von 2000 g.mol-1.
  • F Ethylen-Vinylacetat-Copolymerisat mit 57,2 Gew.-Teilen Vinylacetat je 100 Gew.-Teilen Ethylen und mit einer Molmasse von 1950 g.mol-1.
In the following examples, the polymers characterized below are used alone or as a mixture.
  • A ethylene-vinyl acetate-diisobutylene terpolymer with 38.1 parts by weight of vinyl acetate and 5.6 parts by weight of diisobutylene per 100 parts by weight of ethylene, with a molar mass of 1 840 g.mol -1 and 8.2 CH -Groups in the side chains, which do not come from the acetate residue of the vinyl acetate, per 100 CH₂ groups.
  • B ethylene-vinyl acetate copolymer with 18.6 parts by weight of vinyl acetate per 100 parts by weight of ethylene and with a molar mass of 3 100 g.mol -1 .
  • C ethylene-vinyl acetate copolymer with 25.0 parts by weight of vinyl acetate per 100 parts by weight of ethylene and with a molar mass of 3200 g.mol -1 .
  • D ethylene-vinyl acetate copolymer with 18.9 parts by weight of vinyl acetate per 100 parts by weight of ethylene and with a molar mass of 1800 g.mol -1 .
  • E ethylene-vinyl acetate copolymer with 25.5 parts by weight of vinyl acetate per 100 parts by weight of ethylene and with a molar mass of 2000 g.mol -1 .
  • F ethylene-vinyl acetate copolymer with 57.2 parts by weight of vinyl acetate per 100 parts by weight of ethylene and with a molar mass of 1950 g.mol -1 .

Der Vinylacetatgehalt im Polymerisat 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. Die Bestimmung des Diisobutylengehaltes im Polymeren erfolgt durch 13 C-NMR-Spektroskopie.The vinyl acetate content in the polymer 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. The diisobutylene content in the polymer is determined by 13 C-NMR spectroscopy.

Die Beispiele 1 bis 5 betreffen das erfindungsgemäße Verfahren. In den Beispielen 6 bis 9 wird über Ergebnisse von Vergleichsversuchen berichtet, die bei Einsatz von

  • Ethylen-Vinylacetat-Diisobutylen-Terpolymerisat (Beispiel 6), von
  • Ethylen-Vinylacetat-Copolymerisaten (Beispiele 7 und 8) und
  • einer Mischung aus einem Terpolymerisat und einem Copolymerisat, dessen Zusammensetzung außerhalb des beanspruchten Bereiches liegt (Beispiel 9)

erhalten werden.Examples 1 to 5 relate to the process according to the invention. Examples 6 to 9 report the results of comparative experiments which were carried out using
  • Ethylene vinyl acetate diisobutylene terpolymer (Example 6), from
  • Ethylene-vinyl acetate copolymers (Examples 7 and 8) and
  • a mixture of a terpolymer and a copolymer, the composition of which lies outside the claimed range (Example 9)

be preserved.

Die Wirksamkeit des erfindungsgemäßen Verfahrens zur Verbesserung der Fließfähigkeit wird an Hand des "KaltFilter-Verstopfungspunkt-Tests" (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 method according to the invention for improving the flowability is described on the basis of the "cold filter clogging 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, die durch die in Tabelle 1 zusammengestellten Eigenschaftswerte gekennzeichnet sind.

Figure imgb0001
Three middle distillates M1, M2 and M3 are used for the test, which are characterized by the property values compiled in Table 1.
Figure imgb0001

In Tabelle 2 sind die Ergebnisse zusammengefaßt, die die Wirksamkeit des erfindungsgemäßen Verfahrens zur Verbesserung der Fließfähigkeit von Mineralölen und Mineralöldestillaten beschreiben.

Figure imgb0002
Figure imgb0003
 Table 2 summarizes the results which describe the effectiveness of the process according to the invention for improving the flowability of mineral oils and mineral oil distillates.
Figure imgb0002
Figure imgb0003

Claims (3)

  1. A process to improve the flowability of mineral oils and mineral oil distillates, characterised in that mixtures of an ethylene-vinyl acetate-diisobutylene terpolymer and an ethylene-vinyl acetate copolymer containing terpolymer and copolymer in a ratio of 100 to 1 to 1 to 1, preferably 20 to 1 to 3 to 1, are added to the mineral oils or mineral oil distillates, said ethylene-vinyl acetate-diisobutylene terpolymer containing 25 to 78, in particular 30 to 55 parts by weight of vinyl acetate and 0.5 to 45, in particular 1.0 to 27.5 parts by weight of diisobutylene per 100 parts by weight of ethylene, having an average molecular mass (measured by vapour pressure osmometry) of 500 to 10000, preferably 1000 to 5000, and in particular 1500 to 3500 g x mol-1 and exhibiting 6 to 20, preferably 7 to 15 CH₃ groups, which do not originate from the acetate radical of the vinyl acetate, in the side chains per 100 CH₂ groups, and said ethylene-vinyl acetate copolymer containing 5 to 54, in particular 11 to 33 parts by weight of vinyl acetate per 100 parts by weight of ethylene, having an average molecular mass (measured by vapour pressure osmometry) of 500 to 10000, in particular 1000 to 5000 g x mol-1 , and exhibiting 1 to 10, preferably 3 to 7 CH₃ groups, which do not originate from the acetate radical of the vinyl acetate,- in the side chains per 100 CH₂ groups.
  2. A mineral oil or mineral oil distillate with improved flowability, characterised in that it contains 0.001 to 2, preferably 0.005 to 0.5% by weight (related to the weight of the mineral oil or mineral oil distillate) of a mixture which consists of an ethylene-vinyl acetate-diisobutylene terpolymer and an ethylene-vinyl acetate copolymer in a weight ratio of 100 to 1 to 1 to 1, preferably 20 to 1 to 3 to 1.
  3. A mineral oil or mineral oil distillate according to claim 2, characterised in that
    - the ethylene-vinyl acetate-diisobutylene terpolymer contains 25 to 78, in particular 30 to 55 parts by weight of vinyl acetate and 0.5 to 45, in particular 1.0 to 27.5 parts by weight of diisobutylene per 100 parts by weight of ethylene, has an average molecular mass (measured by vapour pressure osmometry) of 500 to 10000, preferably 1000 to 5000 and in particular 1500 to 3500 g x mol -1, and exhibits 6 to 20, preferably 7 to 15 CH₃ groups, which do not originate from the acetate radical of the vinyl acetate, in the side chains per 100 CH₂ groups.
    - the ethylene-vinyl acetate copolymer contains 5 to 54, in particular 11 to 33 parts by weight of vinyl acetate per 100 parts by weight of ethylene, has an average molecular mass (measured by vapour pressure osmometry) of 500 to 10000, in particular 1000 to 5000 g x mol-1 , and exhibits 1 to 10, preferably 3 to 7 CH₃ groups, which do not originate from the acetate radical of the vinyl acetate, in the side chains per 100 CH₂ groups.
EP87110581A 1986-07-25 1987-07-22 Process to improve the flowability of mineral oils and mineral oil distillates Expired - Lifetime EP0254284B1 (en)

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EP0857776A1 (en) 1997-01-07 1998-08-12 Clariant GmbH Mineral oil and mineral oil distillate flowability improvemnt using alkylphenol-aldehyde resins
WO2010081634A1 (en) 2009-01-13 2010-07-22 Evonik Rohmax Additives Gmbh Fuel compositions having improved cloud point and improved storage properties
WO2011095249A1 (en) 2010-02-05 2011-08-11 Evonik Rohmax Additives Gmbh A composition having improved filterability
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

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DE19620118C1 (en) * 1996-05-18 1997-10-23 Hoechst Ag Terpolymers of ethylene, their preparation and their use as additives for mineral oil distillates
DE19620119C1 (en) * 1996-05-18 1997-10-23 Hoechst Ag Terpolymers of ethylene, their production and their use as additives for mineral oil distillates
US5681359A (en) * 1996-10-22 1997-10-28 Quantum Chemical Corporation Ethylene vinyl acetate and isobutylene terpolymer as a cold flow improver for distillate fuel compositions
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CA2412740A1 (en) 2000-06-15 2002-12-13 Clariant International Ltd Additives for improving the cold flow properties and the storage stability of crude oil
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US6673131B2 (en) 2002-01-17 2004-01-06 Equistar Chemicals, Lp Fuel additive compositions and distillate fuels containing same
ES2399626T3 (en) 2002-07-09 2013-04-02 Clariant Produkte (Deutschland) Gmbh Cold flow improving agent for combustible oils of vegetable or animal origin
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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
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WO2011095249A1 (en) 2010-02-05 2011-08-11 Evonik Rohmax Additives Gmbh A composition having improved filterability

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