EP0258572B1 - 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
EP0258572B1
EP0258572B1 EP87109734A EP87109734A EP0258572B1 EP 0258572 B1 EP0258572 B1 EP 0258572B1 EP 87109734 A EP87109734 A EP 87109734A EP 87109734 A EP87109734 A EP 87109734A EP 0258572 B1 EP0258572 B1 EP 0258572B1
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Prior art keywords
vinyl acetate
ethylene
mineral oil
weight
oxidised
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EP87109734A
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German (de)
French (fr)
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EP0258572A1 (en
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Wolfgang Dr. Dipl.-Chem. Payer
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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
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T137/00—Fluid handling
    • Y10T137/0318—Processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T137/00—Fluid handling
    • Y10T137/0318—Processes
    • Y10T137/0391—Affecting flow by the addition of material or energy

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 oxidized polyethylene wax and / or oxidized 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, for example, in the DE-PS 19 14 756 described. They are generally prepared 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 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 oxidized ethylene wax and / or an oxidized polyethylene-vinyl acetate copolymer are added to the mineral oils or mineral oil distillates.
  • ethylene-vinyl acetate-diisobutylene terpolymers in combination with oxidized polyethylene waxes and / or oxidized 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 processes have proven themselves to improve the flowability of mineral oils and their distillation products, regardless of their qualitative and quantitative composition.
  • 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 (eg ion exchangers).
  • oxidized polyethylene waxes is understood to mean products which are obtained when air is used to treat linear or branched polyethylene wax melts. These are waxes that contain oxygen functions such as carboxyl, carbonyl, hydroxyl groups in the molecule. They are characterized above all by their emulsifiability in aqueous media.
  • the wax oxidates used according to the invention have melting points of 85 to 135 ° C, dropping points of 95 to 135 ° C and densities of 0.94 to 1.00 g / cm3 determined according to DIN 51801 or ASTM D 566.
  • Oxidized ethylene-vinyl acetate copolymers are the products of the oxidation of molten ethylene-vinyl acetate copolymers with oxygen or gases containing oxygen. Their manufacture is e.g. described in DE 29 44 375 A1. According to the invention, oxidized ethylene-vinyl acetate copolymers are used which have dropping points of 80 to 110 ° C. and acid numbers of 5 to 200 mg KOH / g. The dropping point is determined, as in the case of the oxidized polyethylene waxes, in accordance with DIN 51801 or ASTM D 566. The acid number is measured in accordance with DIN 53402 or ASTM D 1386.
  • the mixtures added according to the invention to improve the flowability of mineral oils and mineral oil distillates consist of two or three components. They always contain ethylene-vinyl acetate-diisobutylene terpolymers and also oxidized polyethylene waxes or oxidized ethylene-vinyl acetate copolymers. In a further embodiment, according to the new procedure, ethylene-vinyl acetate-diisobutylene terpolymer is used together with oxidized polyethylene wax and oxidized ethylene-vinyl acetate copolymer.
  • the weight ratio of ethylene-vinyl acetate-diisobutylene terpolymer to oxidized polyethylene wax and / or oxidized ethylene-vinyl acetate copolymer is 1000: 1 to 1:10. Mixtures are preferred, the terpolymer to oxidized wax and / or oxidized copolymer in a weight ratio of 100: 1 to 1: 5 included.
  • the process according to the invention improves both the flowability of mineral oils and of mineral oil distillates.
  • 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 approximately 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 the various 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. Aliphatic or aromatic hydrocarbons or hydrocarbon mixtures, for example gasoline fractions, are suitable as solvents. 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.
  • 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.
  • Examples 1 to 5, 7 and 8 relate to the process according to the invention.
  • example 6 the results of comparative tests are reported which are obtained when an ethylene-vinyl acetate-diisobutylene terpolymer is used as a diluent improver.
  • 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. The diisobutylene content in the polymer is determined by 13 C-NMR spectroscopy.
  • Table 2 summarizes the results of the investigations, which show 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)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract

The flowability of mineral oils and mineral oil distillates is improved by the addition of mixtures of an ethylene-vinyl acetate-diisobutylene terpolymer, an oxidized polyethylene wax and/or an oxidized 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 oxidierten Polyethylenwachs und/oder oxidierten 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 oxidized polyethylene wax and / or oxidized 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 19 14 756 beschrieben. Ihre Herstellung erfolgt im allgemeinen durch Copolymerisation der Monomeren in Autoklaven bei Temperaturen von 80 bis 150°C und Drücken von 5 bis 15 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, for example, in the DE-PS 19 14 756 described. They are generally prepared 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 Mischpolymerisate 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.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. 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 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 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 19 878 Cl Gemische offenbart, die aus einem Ethylen enthaltenden Polymerisat, Bienenwachs, Ozokerit und/oder einem langkettigen alpha-Olefin bestehen.Mixtures which consist of an ethylene-containing polymer, beeswax, ozokerite and / or a long-chain alpha-olefin are disclosed as flow improvers for petroleum middle distillates in US Pat. No. 4,019,878 Cl.

Obgleich die bekannten Substanzen und Substanzgemische in vielen Fällen die Fließfähgkeit 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 in many cases the known substances and substance mixtures have in some cases significantly improved the fluidity of mineral oils and mineral oil distillates of different provenance and composition at low temperatures, additives with the most versatile, 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 oxidierten Ethylenwachs und/oder einem oxidierten Polyethylen-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 oxidized ethylene wax and / or an oxidized polyethylene-vinyl acetate copolymer are added to the mineral oils or mineral oil distillates.

Überraschenderweise hat sich gezeigt, daß Ethylen-Vinylacetat-Diisobutylen-Terpolymerisate in Kombination mit oxidierten Polyethylenwachsen und/oder oxidierten 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 ethylene-vinyl acetate-diisobutylene terpolymers in combination with oxidized polyethylene waxes and / or oxidized 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 processes have proven themselves 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 100 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 1,0 bis 27,5 Gew.-Teilen Diisobutylen je 100 Gew.-Teile 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 10.000 g.mol⁻¹, vorzugsweise 1000 bis 5000 g.mol⁻¹ und insbesondere 1500 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 100 CH₂-Gruppen weisen sie 6 bis 20 und vorzugsweise 7 bis 15 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-Diisobutylen-Terpolymerisate ist bekannt. Sie kann z.B. durch Polymerisation des Monomerengemisches bei Drücken oberhalb von 50 MPa und Temperaturen von 150 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-(1) 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 (eg ion exchangers).

Unter der Bezeichnung oxidierte Polyethylenwachse werden Produkte verstanden, die man bei der Behandlung von Schmelzen linearer oder verzweigter Polyethylenwachse mit Luft erhält. Es handelt sich hierbei um Wachse, die im Molekül Sauerstoff-Funktionen wie Carboxyl-, Carbonyl-, Hydroxyl-Gruppen enthalten. Sie zeichnen sich vor allem durch Emulgierbarkeit in wäßrigen Medien aus. Die erfindungsgemäß eingesetzten Wachsoxidate haben Schmelzpunkte von 85 bis 135°C, nach DIN 51801 oder ASTM D 566 bestimmte Tropfpunkte von 95 bis 135°C und Dichten von 0,94 bis 1,00 g/cm³. Ihre Säurezahl, gemessen nach DIN 53402 oder ASTM D 1386, beträgt 5 bis 60 mg KOH/g, die viskosimetrisch ermittelte Molmasse ist 500 bis 10.000 g.mol⁻¹. Bevorzugt werden oxidierte Polyethylenwachse mit Tropfpunkten von 100 bis 120°C und einer Säurezahl von 8 bis 30 mg KOH/g. Die genannten Polyethylenwachse sind handelsübliche Produkte. Sie gelangen z.B. unter der Bezeichnung "Hoechst-Wachs PED" (Hersteller: Hoechst AG) oder "Polyethylenwachs OA" (Hersteller: BASF AG) auf den Markt.The term oxidized polyethylene waxes is understood to mean products which are obtained when air is used to treat linear or branched polyethylene wax melts. These are waxes that contain oxygen functions such as carboxyl, carbonyl, hydroxyl groups in the molecule. They are characterized above all by their emulsifiability in aqueous media. The wax oxidates used according to the invention have melting points of 85 to 135 ° C, dropping points of 95 to 135 ° C and densities of 0.94 to 1.00 g / cm³ determined according to DIN 51801 or ASTM D 566. Their acid number, measured according to DIN 53402 or ASTM D 1386, is 5 to 60 mg KOH / g, the viscosimetrically determined molar mass is 500 to 10,000 g.mol⁻¹. Oxidized polyethylene waxes with dropping points of 100 to 120 ° C. and an acid number of 8 to 30 mg KOH / g are preferred. The polyethylene waxes mentioned are commercially available products. You get e.g. onto the market under the name "Hoechst-Wachs PED" (manufacturer: Hoechst AG) or "Polyethylenwachs OA" (manufacturer: BASF AG).

Oxidierte Ethylen-Vinylacetat-Copolymerisate sind die Produkte der Oxidation geschmolzener Ethylen-Vinylacetat-Copolymerisate mit Sauerstoff oder sauerstoffhaltigen Gasen. Ihre Herstellung ist z.B. in der DE 29 44 375 Al beschrieben. Erfindungsgemäß setzt man oxidierte Ethylen-Vinylacetat-Copolymerisate ein, die Tropfpunkte von 80 bis 110°C und Säurezahlen von 5 bis 200 mg KOH/g aufweisen. Die Bestimmung des Tropfpunktes erfolgt, wie im Falle der oxidierten Polyethylenwachse, nach DIN 51801 oder ASTM D 566. Die Säurezahl wird nach DIN 53402 oder ASTM D 1386 gemessen.Oxidized ethylene-vinyl acetate copolymers are the products of the oxidation of molten ethylene-vinyl acetate copolymers with oxygen or gases containing oxygen. Their manufacture is e.g. described in DE 29 44 375 A1. According to the invention, oxidized ethylene-vinyl acetate copolymers are used which have dropping points of 80 to 110 ° C. and acid numbers of 5 to 200 mg KOH / g. The dropping point is determined, as in the case of the oxidized polyethylene waxes, in accordance with DIN 51801 or ASTM D 566. The acid number is measured in accordance with DIN 53402 or ASTM D 1386.

Die erfindungsgemäß zur Verbesserung der Fließfähigkeit Mineralölen und Mineralöldestillaten zugesetzten Mischungen bestehen aus zwei oder drei Komponenten. Sie enthalten stets Ethylen-Vinylacetat-Diisobutylen-Terpolymerisate und ferner oxidierte Polyethylenwachse oder oxidierte Ethylen-Vinylacetat-Copolymerisate. In einer weiteren Ausgestaltung setzt man nach der neuen Arbeitsweise Ethylen-Vinylacetat-Diisobutylen-Terpolymerisat zusammen mit oxidiertem Polyethylenwachs und oxidiertem Ethylen-Vinylacetat-Copolymerisat ein.The mixtures added according to the invention to improve the flowability of mineral oils and mineral oil distillates consist of two or three components. They always contain ethylene-vinyl acetate-diisobutylene terpolymers and also oxidized polyethylene waxes or oxidized ethylene-vinyl acetate copolymers. In a further embodiment, according to the new procedure, ethylene-vinyl acetate-diisobutylene terpolymer is used together with oxidized polyethylene wax and oxidized ethylene-vinyl acetate copolymer.

Das Gewichtsverhältnis von Ethylen-Vinylacetat-Diisobutylen-Terpolymerisat zu oxidiertem Polyethylenwachs und/oder oxidiertem Ethylen-Vinylacetat-Copolymerisat beträgt 1000 : 1 bis 1 : 10. Bevorzugt werden Mischungen, die Terpolymerisat zu oxidiertes Wachs und/oder oxidiertes Copolymerisat im Gewichtsverhältnis von 100 : 1 bis 1 : 5 enthalten.The weight ratio of ethylene-vinyl acetate-diisobutylene terpolymer to oxidized polyethylene wax and / or oxidized ethylene-vinyl acetate copolymer is 1000: 1 to 1:10. Mixtures are preferred, the terpolymer to oxidized wax and / or oxidized copolymer in a weight ratio of 100: 1 to 1: 5 included.

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 Dieselkraftstoff. Von besonderer Bedeutung sind die Mitteldestillate wie Heizöl EL und Dieselkraftstoff. Das Gemisch aus den verschiedenen 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 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 approximately 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 the various 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. Aliphatic or aromatic hydrocarbons or hydrocarbon mixtures, for example gasoline fractions, are suitable as solvents. 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 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:Examples:

Die Beispiele 1 bis 5, 7 und 8 betreffen das erfindungsgemäße Verfahren. In Beispiel 6 wird über Ergebnisse von Vergleichsversuchen berichtet, die bei Einsatz eines Ethylen-Vinylacetat-Diisobutylen-Terpolymerisats als Fleißverbesserer erhalten werden.Examples 1 to 5, 7 and 8 relate to the process according to the invention. In example 6 the results of comparative tests are reported which are obtained when an ethylene-vinyl acetate-diisobutylene terpolymer is used as a diluent improver.

Die Wirksamkeit der untersuchten Verfahren zur Verbesserung der Fließfähigkeit wird an Hand des "Kalt-Filter-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 investigated methods for improving the flowability is described using 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 vier Mitteldestillate M1, M2, M3 und M4 eingesetzt, die durch die in Tabelle 1 zusammengestellten Eigenschaftswerte gekennzeichnet sind.

Figure imgb0001
Four middle distillates M1, M2, M3 and M4 are used for the test, which are characterized by the property values compiled in Table 1.
Figure imgb0001

In den Beispielen werden als Polymerisate eingesetzt:

  • A ein durch gemeinsame Polymerisation von Ethylen, Vinylacetat und Diisobutylen in einem Autoklaven bei 200°C und 150 MPa und in Gegenwart eines Peroxids als Initiator erhaltenes Produkt mit 38,2 Gew.-Teilen Vinylacetat und 5,6 Gew.-Teilen Diisobutylen je 100 Gew.-Teile Ethylen, einer Molmasse von 1840 g.mol⁻¹ und 8,2 CH₃-Gruppen in den Seitenketten, die nicht aus dem Acetatrest des Vinylacetats herrühren, je 100 CH₂-Gruppen,
  • B ein oxidiertes Polyethylenwachs mit einem Schmelzpunkt von 107°C, einem Tropfpunkt (nach DIN 51801) von 107°C, einer Dichte von 0,97 g/cm³, einer Säurezahl (nach DIN 53402) von 9 mg KOH/g, einer Verseifungszahl (nach DIN 53401) von 28 mg KOH/g und einer Molmasse von 2700 g.mol⁻¹,
  • C ein oxidiertes Ethylen-Vinylacetat-Copolymerisat mit einem Schmelzpunkt von 98°C, einem Tropfpunkt (nach DIN 51801) von 99°C, einer Säurezahl (nach DIN 53402) von 20 mg KOH/g, einer Verseifungszahl (nach DIN 53401) von 86 mg KOH/g und einer Molmasse von 1900 g.mol⁻¹.
In the examples, the following are used as polymers:
  • A is a product obtained by co-polymerizing ethylene, vinyl acetate and diisobutylene in an autoclave at 200 ° C. and 150 MPa and in the presence of a peroxide as initiator with 38.2 parts by weight of vinyl acetate and 5.6 parts by weight of diisobutylene per 100 Parts by weight of ethylene, a molar mass of 1840 g.mol⁻¹ and 8.2 CH₃ groups in the side chains, which do not result from the acetate residue of the vinyl acetate, 100 CH₂ groups,
  • B is an oxidized polyethylene wax with a melting point of 107 ° C, a dropping point (according to DIN 51801) of 107 ° C, a density of 0.97 g / cm³, an acid number (according to DIN 53402) of 9 mg KOH / g, a saponification number (according to DIN 53401) of 28 mg KOH / g and a molecular weight of 2700 g.mol⁻¹,
  • C is an oxidized ethylene-vinyl acetate copolymer with a melting point of 98 ° C, a dropping point (according to DIN 51801) of 99 ° C, an acid number (according to DIN 53402) of 20 mg KOH / g, a saponification number (according to DIN 53401) of 86 mg KOH / g and a molecular weight of 1900 g.mol⁻¹.

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

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

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

Claims (10)

  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 oxidised polyethylene wax and/or an oxidised ethylene-vinyl acetate copolymer are added to the mineral oils or mineral oil distillates.
  2. A process according to claim 1, 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.
  3. A process according to claim 1 or 2, characterised in that the average mol mass of the terpolymer (measured by vapour pressure osmometry) is 500 to 10,000, preferably 1,000 to 5,000 and in particular 1,500 to 3,500 gxmol⁻¹.
  4. A process according to one or several of the claims 1 to 3, characterised in that per 100 CH₂ groups the terpolymer exhibits 6 to 20, preferably 7 to 15 CH₃ groups in the side chains not originating from the acetate group of the vinyl acetate.
  5. A process according to claim 1, characterised in that the oxidised polyethylene wax has a melting point of 85 to 135°C, a dropping point of 95 to 135°C, in particular 100 to 120°C, a density of 0.94 to 1.00 g/cm³, an acid number of 5 to 60 in particular 8 to 30 mg KOH/g and an average mol mass of 500 to 10,000 gxmol⁻¹.
  6. A process according to claim 1, characterised in that the oxidised ethylene-vinyl acetate copolymer has a dropping point of 80 to 110°C and an acid number of 5 to 200 mg KOH/g.
  7. A process according to claim 1, characterised in that the weight ratio of ethylene-vinyl acetate-diisobutylene terpolymer to the oxidised polyethylene wax and/or the oxidised ethylene-vinyl acetate copolymer is 1000 : 1 to 1 : 10 and preferably 100 : 1 to 1 : 5.
  8. A mineral oil or mineral oil distillate with improved flow behaviour, 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 of an ethylene-vinyl acetate-diisobutylene terpolymer and an oxidised polyethylene wax and/or an oxidised ethylene-vinyl acetate copolymer.
  9. A mineral oil or mineral oil distillate according to claim 8, characterised in that
    - the ethylene-vinyl acetate-diisobutylene terpolymer contains 25 to 78, preferably 30 to 55 % 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 mol mass (measured by vapour pressure osmometry) of 500 to 10,000, preferably 1,000 to 5,000 and in particular 1,500 to 3,500 gxmol⁻¹ and exhibits per 100 CH₂ groups 6 to 20, preferably 7 to 15 CH₃ groups in the side chains not originating from the acetate group of the vinyl acetate,
    - the oxidised polyethylene wax has a melting point of 85 to 135°C, a dropping point of 95 to 135°C, preferably 100 to 120°C, a density of 0.94 to 1.00 g/cm³ and an acid number of 5 to 60, preferably 8 to 30 mg KOH/g and an average mol mass of 500 to 10,000 gxmol⁻¹
    and
    - the oxidised ethylene-vinyl acetate copolymer has a dropping point of 80 to 110°C and an acid number of 5 to 200 mg KOH/g.
  10. Mineral oil or mineral oil distillate according to claim 8 or 9, characterised in that the weight ratio of ethylene-vinyl acetate-diisobutylene terpolymer to the oxidised ethylene-vinyl acetate copolymer is 1000 : 1 to 1 : 10, preferably 100 : 1 to 1 : 5.
EP87109734A 1986-07-17 1987-07-07 Process to improve the flowability of mineral oils and mineral oil distillates Expired - Lifetime EP0258572B1 (en)

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