EP0254284A1 - 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
EP0254284A1
EP0254284A1 EP87110581A EP87110581A EP0254284A1 EP 0254284 A1 EP0254284 A1 EP 0254284A1 EP 87110581 A EP87110581 A EP 87110581A EP 87110581 A EP87110581 A EP 87110581A EP 0254284 A1 EP0254284 A1 EP 0254284A1
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Prior art keywords
vinyl acetate
ethylene
weight
parts
mineral oil
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EP87110581A
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German (de)
French (fr)
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EP0254284B1 (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
Ruhrchemie AG
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/192Macromolecular compounds
    • C10L1/195Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197Macromolecular 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
    • C10L1/1973Macromolecular 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 blocked, 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 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.
  • 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 each contain 100 parts by weight of ethylene 25 to 78 parts by weight of vinyl acetate and 0.5 to 45 parts by weight of diisobutylene. 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 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.mol ⁇ 1. Copolymers with a molecular weight of 1000 to 5000 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 which contain the terpolymer and copolymer in a weight ratio of 20: 1 to 3: 1 are preferred.
  • mineral oils is understood here in particular to mean crude oils and distillation residues such as heavy heating 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 at 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 / KJ03 solution and the released iodine is titrated with Na2S2O3 solution. The diisobutylene content in the polymer is determined by 13 C-NMR spectroscopy.
  • 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.
  • 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.

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 fur 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 blocked, 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 l50°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-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 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 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 26 39 672 Al describes mixtures of polymers with 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 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 fur 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 are disclosed in US 40 l9 878 Cl mixtures consisting of a 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 most versatile and 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 each contain 100 parts by weight of ethylene 25 to 78 parts by weight of vinyl acetate and 0.5 to 45 parts by weight of diisobutylene. 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 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 is determined by H-NMR spectroscopy.

Die Herstellung der Ethylen-Vinylacetat-Diisobutylen-­Terpolymerisate 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 Katalysatiren (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 ll 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.mol⁻¹. Copolymers with a molecular weight of 1000 to 5000 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 l50°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-Diisobutylen-­Terpolymerisat und Ethylen-Vinylacetat-Copolymerisat in den Mischungen beträgt l00 : l bis l : l. Bevorzugt wer­den Mischungen, die Terpolymerisat und Copolymerisat im Gewichtsverhältnis von 20 : l bis 3 : l 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 which contain 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 here in particular to mean crude oils and distillation residues such as heavy heating 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. Mineralöldestillaten 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 l 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,l Gew.-Teilen Vinylacetat und 5,6 Gew.-Teilen Di­isobutylen je l00 Gew.-Teile Ethylen, mit einer Mol­masse von l 840 g.mol⁻¹ und 8,2 CH-Gruppen in den Seitenketten, die nicht aus dem Acetatrest des Vinyl­acetats herrühren, je l00 CH₂-Gruppen.
  • B Ethylen-Vinylacetat-Copolymerisat mit l8,6 Gew.-Teilen Vinylacetat je l00 Gew.-Teilen Ethylen und mit einer Molmasse von 3l00 g.mol⁻¹.
  • C Ethylen-Vinylacetat-Copolymerisat mit 25,0 Gew.-Teilen Vinylacetat je l00 Gew.-Teilen Ethylen und mit einer Molmasse von 3200 g.mol⁻¹.
  • D Ethylen-Vinylacetat-Copolymerisat mit l8,9 Gew.-Teilen Vinylacetat je l00 Gew.-Teilen Ethylen und mit einer Molmasse von l800 g.mol⁻¹.
  • E Ethylen-Vinylacetat-Copolymerisat mit 25,5 Gew.-Teilen Vinylacetat je l00 Gew.-Teilen Ethylen und mit einer Molmasse von 2000 g.mol⁻¹.
  • F Ethylen-Vinylacetat-Copolymerisat mit 57,2 Gew.-Teilen Vinylacetat je l00 Gew.-Teilen Ethylen und mit einer Molmasse von l950 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 molecular weight of l 840 g.mol⁻¹ and 8.2 CH -Groups in the side chains, which do not originate from the acetate residue of the vinyl acetate, per 100 CH₂ groups.
  • B ethylene-vinyl acetate copolymer with l8.6 parts by weight of vinyl acetate per 100 parts by weight of ethylene and with a molecular weight of 3 100 g.mol.m¹.
  • C ethylene-vinyl acetate copolymer with 25.0 parts by weight of vinyl acetate per 100 parts by weight of ethylene and with a molecular weight of 3200 g.mol⁻¹.
  • D ethylene-vinyl acetate copolymer with l8.9 parts by weight of vinyl acetate per 100 parts by weight of ethylene and with a molecular weight of l800 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 molecular weight 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 molecular weight of l950 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/KJ0₃-Lösung umgesetzt und das freiwerdende Jod mit Na₂S₂O₃-Lösung titriert. Die Bestimmung des Diisobutylengehaltes im Polymeren erfolgt durch l3 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 at 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 / KJ0₃ solution and the released iodine is titrated with Na₂S₂O₃ solution. The diisobutylene content in the polymer is determined by 13 C-NMR spectroscopy.

Die Beispiele l 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 "Kalt-­Filter-Verstopfungspunkt-Tests" (CFPP-Test) beschrieben. Die Durchführung des Tests erfolgt nach DIN 5l428. Sie ist auch im J. of the Inst. of Petr. Bd. 52, Juni l966, Seite l73 bis l85, 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 5l428. She is also in the J. of the Inst. Of Petr. Vol. 52, June l966, pages l73 to l85.

Zur Prüfung werden drei Mitteldestillate Ml, M2 und M3 eingesetzt, die durch die in Tabelle l zusammen­gestellten Eigenschaftswerte gekennzeichnet sind.

Figure imgb0001
Three middle distillates Ml, 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 (11)

1. Verfahren zur Verbesserung der Fließfähigkeit von Mineralölen und Mineralöldestillaten, dadurch gekenn­zeichnet, daß man den Mineralölen bzw. Mineralölde­stillaten Mischungen aus einem Ethylen-Vinylacetat-­Diisobutylen-Terpolymerisat und einem Ethylen-Vinyl­acetat-Copolymerisat zusetzt.1. A process for improving the flowability of mineral oils and mineral oil distillates, 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. 2. Verfahren nach Anspruch l, dadurch gekennzeichnet, daß das Ethylen-Vinylacetat-Diisobutylen-Terpolymerisat je l00 Gew.-Teile Ethylen, 25 bis 78, insbesondere 30 bis 55 Gew.-Teile Vinylacetat und 0,5 bis 45, insbesondere l,0 bis 27,5 Gew.-Teile Diisobutylen enthält.2. The method according to claim l, characterized in that the ethylene-vinyl acetate-diisobutylene terpolymer per 100 parts by weight of ethylene, 25 to 78, in particular 30 to 55 parts by weight of vinyl acetate and 0.5 to 45, in particular l, Contains 0 to 27.5 parts by weight of diisobutylene. 3. Verfahren nach Anspruch l oder 2, dadurch gekennzeich­net, daß die mittlere Molmasse des Terpolymerisats (gemessen durch Dampfdruckosmometrie) 500 bis l0000, vorzugsweise l000 bis 5000 und insbesondere l500 bis 3500 g.mol⁻¹ beträgt.3. The method according to claim l or 2, characterized in that the average molecular weight of the terpolymer (measured by vapor pressure osmometry) is 500 to 10000, preferably 1000 to 5000 and especially 1500 to 3500 g.mol⁻¹. 4. Verfahren nach einem oder mehreren der Ansprüche l bis 3, dadurch gekennzeichnet, daß das Terpolymerisat je l00 CH₂-Gruppen 6 bis 20, vorzugsweise 7 bis l5 CH₃-­Gruppen in den Seitenketten aufweist, die nicht aus dem Acetatrest des Vinylacetats herrühren.4. The method according to one or more of claims l to 3, characterized in that the terpolymer each has 100 CH₂ groups 6 to 20, preferably 7 to 15 CH₃ groups in the side chains which do not result from the acetate residue of the vinyl acetate. 5. Verfahren nach Anspruch l, dadurch gekennzeichnet, daß das Ethylen-Vinylacetat-Copolymerisat je l00 Gew.-­Teile Ethylen, 5 bis 54, insbesondere ll bis 33 Gew.-­Teile Vinylacetat enthält.5. The method according to claim l, characterized in that the ethylene-vinyl acetate copolymer contains 100 parts by weight of ethylene, 5 to 54, in particular 11 to 33 parts by weight of vinyl acetate. 6. Verfahren nach Anspruch l oder 5, dadurch gekennzeich­net, daß die mittlere Molmasse des Copolymerisats (ge­messen durch Dampfdruckosmometrie) 500 bis l0000, ins­besondere l000 bis 5000 g mol⁻¹ beträgt.6. The method according to claim l or 5, characterized in that the average molecular weight of the copolymer (measured by vapor pressure osmometry) is 500 to 10000, in particular 1000 to 5000 g mol⁻¹. 7. Verfahren nach einem oder mehreren der Ansprüche l, 5 oder 6, dadurch gekennzeichnet, daß das Copolymerisat je l00 CH₂ Gruppen l bis l0, vorzugsweise 3 bis 7 CH₃-­Gruppen in den Seitenketten aufweist, die nicht aus dem Acetatrest des Vinylacetats herrühren.7. The method according to one or more of claims l, 5 or 6, characterized in that the copolymer has l00 CH₂ groups l to l0, preferably 3 to 7 CH₃ groups in the side chains, which do not result from the acetate residue of the vinyl acetate. 8. Verfahren nach Anspruch l, dadurch gekennzeichnet, daß das Gewichtsverhältnis von Ethylen-Vinylacetat-Diiso­butylen-Terpolymerisat zu Ethylen-Vinylacetat-Copoly­merisat in der Mischung l00 : l bis l : l, vorzugsweise 20 : l bis 3 : l beträgt.8. The method according to claim l, characterized in that the weight ratio of ethylene-vinyl acetate-diisobutylene terpolymer to ethylene-vinyl acetate copolymer in the mixture is 100: 1 to 1: 1, preferably 20: 1 to 3: 1. 9. Mineralöl oder Mineralöldestillat mit verbessertem Fließverhalten dadurch gekennzeichnet, daß es 0,00l bis 2, vorzugsweise 0,005 bis 0,5 Gew.-% (bezogen auf das Gewicht des Mineralöls bzw. Mineralöldestillates) einer Mischung aus einem Ethylen-Vinylacetat-Diisobutylen-­Terpolymerisat und ein Ethylen-Vinylacetat-Copolymeri­sat enthält.9. Mineral oil or mineral oil distillate with improved flow behavior, characterized in that it 0.001 to 2, preferably 0.005 to 0.5 wt .-% (based on the weight of the mineral oil or mineral oil distillate) of a mixture of an ethylene-vinyl acetate-diisobutylene Terpolymer and an ethylene-vinyl acetate copolymer contains. l0. Mineralöl oder Mineralöldestillat nach Anspruch 9 da­durch gekennzeichnet, daß

- das Ethylen-Vinylacetat-Diisobutylen-Terpolymerisat je l00 Gew.-Teile Ethylen, 25 bis 78, insbesondere 30 bis 55 Gew.-Teile Vinylacetat und 0,5 bis 45 insbe­sondere l,0 bis 27,5 Gew.-Teile Diisobutylen enthält, eine mittlere Molmasse (gemessen durch Dampfdruck­osmometrie) von 500 bis l0000, vorzugsweise l000 bis 5000 und insbesondere l500 bis 3500 g.mol⁻¹ besitzt und je l00 CH₂-Gruppen 6 bis 20, vorzugsweise 7 bis l5 CH₃-Gruppen in den Seitenketten aufweist, die nicht aus dem Acetatrest des Vinylacetats herrühren.

- das Ethylen-Vinylacetat-Copolymerisat je l00 Gew.-­Teile Ethylen, 5 bis 54, insbesondere ll bis 33 Gew.-­Teile Vinylacetat enthält, eine mittlere Molmasse (gemessen durch Dampfdruckosmometrie) von 500 bis l0000, insbesondere l000 bis 5000 g.mol⁻¹ besitzt und je l00 CH₂-Gruppen l bis l0, vorzugsweise 3 bis 7 CH₃-Gruppen in den Seitenketten aufweist, die nicht aus dem Acetatrest des Vinylacetats herrühren.
l0. Mineral oil or mineral oil distillate according to claim 9, characterized in that

- The ethylene-vinyl acetate-diisobutylene terpolymer contains 100 parts by weight of ethylene, 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 , has an average molecular weight (measured by vapor pressure osmometry) of 500 to 10000, preferably 1000 to 5000 and in particular 1500 to 3500 g.mol⁻¹ and each 100 CH₂ groups 6 to 20, preferably 7 to l5 CH₃ groups in the side chains, which do not come from the acetate residue of the vinyl acetate.

- The ethylene-vinyl acetate copolymer contains 100 parts by weight of ethylene, 5 to 54, in particular 11 to 33 parts by weight of vinyl acetate, an average molar mass (measured by vapor pressure osmometry) of 500 to 10000, in particular 1000 to 5000 g.mol ⁻¹ has and each has 100 CH₂ groups l to l0, preferably 3 to 7 CH₃ groups in the side chains, which do not result from the acetate residue of the vinyl acetate.
11. Mineralöl- oder Mineralöldestillat nach Anspruch 9 oder l0, dadurch gekennzeichnet, daß das Gewichtsverhältnis von Ethylen-Vinylacetat-Diisobutylen-Terpolymerisat zu Ethylen-Vinylacetat-Copolymerisat l00 : l bis l : l, vorzugsweise 20 : l bis 3 : l beträgt.11. Mineral oil or mineral oil distillate according to claim 9 or 10, characterized in that the weight ratio of ethylene-vinyl acetate-diisobutylene terpolymer to ethylene-vinyl acetate copolymer is 100: 1 to 1: 1, preferably 20: 1 to 3: 1.
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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CN1035676C (en) * 1991-12-12 1997-08-20 中国石油化工总公司石油化工科学研究院 Process for diesel flow improving agent
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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US6010989A (en) * 1997-09-08 2000-01-04 Clariant Gmbh Additive for improving the flow properties of mineral oils and mineral oil distillates
US6110238A (en) * 1998-01-24 2000-08-29 Clariant Gmbh Process for improving the cold-flow properties of fuel oils
US6281292B1 (en) 1998-05-27 2001-08-28 Clariant Gmbh Mixtures of copolymers having an improved lubricating action
EP0649445B2 (en) 1992-06-30 2002-05-02 ExxonMobil Chemical Patents Inc. Oil additives and compositions
US6673131B2 (en) 2002-01-17 2004-01-06 Equistar Chemicals, Lp Fuel additive compositions and distillate fuels containing same
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
US7377949B2 (en) 2001-11-14 2008-05-27 Clariant Produkte (Deutschland) Gmbh Additives for sulphur-poor mineral oil distillates comprising an ester of an alkoxylated polyol and an alkylphenol-aldehye resin
US7473284B2 (en) 2003-12-11 2009-01-06 Clariant Produkte (Deutschland) Gmbh Fuel oils composed of middle distillates and oils of vegetable or animal origin and having improved cold flow properties
US7476264B2 (en) 2003-10-25 2009-01-13 Lariant Produkte (Deutshland) Gmbh Cold flow improvers for fuel oils of vegetable or animal origin
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CN1035676C (en) * 1991-12-12 1997-08-20 中国石油化工总公司石油化工科学研究院 Process for diesel flow improving agent
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EP0892012A2 (en) * 1997-07-08 1999-01-20 Clariant GmbH Flow improvers for mineral oils
EP0892012A3 (en) * 1997-07-08 2000-01-12 Clariant GmbH Flow improvers for mineral oils
US6010989A (en) * 1997-09-08 2000-01-04 Clariant Gmbh Additive for improving the flow properties of mineral oils and mineral oil distillates
US6110238A (en) * 1998-01-24 2000-08-29 Clariant Gmbh Process for improving the cold-flow properties of fuel oils
US6281292B1 (en) 1998-05-27 2001-08-28 Clariant Gmbh Mixtures of copolymers having an improved lubricating action
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
US7377949B2 (en) 2001-11-14 2008-05-27 Clariant Produkte (Deutschland) Gmbh Additives for sulphur-poor mineral oil distillates comprising an ester of an alkoxylated polyol and an alkylphenol-aldehye resin
US6673131B2 (en) 2002-01-17 2004-01-06 Equistar Chemicals, Lp Fuel additive compositions and distillate fuels containing same
US7041738B2 (en) 2002-07-09 2006-05-09 Clariant Gmbh Cold flow improvers for fuel oils of vegetable or animal origin
US7476264B2 (en) 2003-10-25 2009-01-13 Lariant Produkte (Deutshland) Gmbh Cold flow improvers for fuel oils of vegetable or animal origin
US7500996B2 (en) 2003-10-25 2009-03-10 Clariant International Ltd. Cold flow improvers for fuel oils of vegetable or animal origin
US7473284B2 (en) 2003-12-11 2009-01-06 Clariant Produkte (Deutschland) Gmbh Fuel oils composed of middle distillates and oils of vegetable or animal origin and having improved cold flow properties
US7815697B2 (en) 2003-12-11 2010-10-19 Clariant Finance (Bvi) Limited Fuel oils composed of middle distillates and oils of vegetable or animal origin and having improved cold flow properties
ITMI20132043A1 (en) * 2013-12-06 2015-06-07 Eni Spa COMPOSITIONS BASED ON ETHYLENE-VINYLACETATE COPOLYMERS AND THEIR USE AS ANTI-GELIFICATION ADDITIVES OF PARAFFIN-GRADE OIL WHEELS
WO2015083131A1 (en) * 2013-12-06 2015-06-11 Versalis S.P.A. Compositions based on ethylene-vinyl acetate copolymers and their use as anti-gelling additives of paraffinic crude oils
RU2675529C1 (en) * 2013-12-06 2018-12-19 ВЕРСАЛИС С.п.А. Compositions based on ethylene-vinyl acetate copolymers and their use as anti-gelling additives of paraffinic crude oils
US10370607B2 (en) 2013-12-06 2019-08-06 Versalis S.P.A. Compositions based on ethylene-vinyl acetate copolymers and their use as anti-gelling additives of paraffinic crude oils

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