EP0251002B1 - 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
EP0251002B1
EP0251002B1 EP87108559A EP87108559A EP0251002B1 EP 0251002 B1 EP0251002 B1 EP 0251002B1 EP 87108559 A EP87108559 A EP 87108559A EP 87108559 A EP87108559 A EP 87108559A EP 0251002 B1 EP0251002 B1 EP 0251002B1
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Prior art keywords
vinyl acetate
ethylene
mineral oil
acetate copolymer
oxidised
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German (de)
French (fr)
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EP0251002A1 (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

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 copolymer and an oxidized polyethylene wax and / or an 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 working capacity of conveying and transport facilities for crude oil are impaired until their complete failure. 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 1 914 756. 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 2 639 672 A1 describes mixtures of polymers with an ethylene skeleton and copolymers of C 2 to Cso-olefins which lead to a synergistic improvement in the flow properties of Distillate hydrocarbon oils can lead in the cold.
  • 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 copolymer and an oxidized polyethylene wax and / or an oxidized ethylene-vinyl acetate copolymer are added to the mineral oils or mineral oil distillates.
  • the ethylene-vinyl acetate copolymers used according to the invention contain 17 to 70 parts by weight of vinyl acetate per 100 parts by weight of ethylene. Copolymers with 33 to 54 parts by weight of vinyl acetate per 100 parts by weight of ethylene have proven particularly useful.
  • Its viscosity measured in accordance with the German standard DIN 53019 in a rotary viscometer (manufacturer: Haake) at 140 ° C, is 100 to 5000 mPa s, in particular 200 to 1500 mPa s.
  • Each 100 CH 2 groups have 1 to 10 and preferably 2 to 7 CH 3 groups in the side chains, which do not result from the acetate residue of the vinyl acetate.
  • the number of CH 3 groups is determined by H-NMR spectroscopy.
  • the production of the ethylene-vinyl acetate copolymers is known. It can be carried out, for example, by polymerizing the monomer mixture at pressures of 5 to 15 MPa and temperatures of 70 to 150 ° C. in the presence of initiators which form free radicals.
  • An organic solvent or suspending agent such as toluene can be used as the reaction medium.
  • oxidized polyethylene waxes is understood to mean products which are obtained in the treatment of melts of linear or branched polyethylene waxes with air. 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 / cm 3 determined in accordance with 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 described, for example, in DE 2 944 375 AI. 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 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 copolymers and also oxidized polyethylene waxes or oxidized ethylene-vinyl acetate copolymers. In a further embodiment, according to the new procedure, ethylene-vinyl acetate copolymer is used together with oxidized polyethylene wax and oxidized ethylene-vinyl acetate copolymer.
  • the weight ratio of ethylene-vinyl acetate copolymer to oxidized polyethylene wax and / or oxidized ethylene-vinyl acetate copolymer is 1000: 1 to 1:10. Mixtures are preferred, the copolymer to oxidized wax and / or oxidized copolymer in a weight ratio of 100: 1 to 1: 5 included.
  • 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.
  • Suitable solvents are aliphatic or aromatic hydrocarbons or hydrocarbon mixtures, e.g. Gasoline fractions. Kerosene is particularly suitable.
  • the amount of polymer based on mineral oil or mineral oil fractions should be 0.001 to 2, preferably 0.005 to 0.5% by weight.
  • 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 14 relate to the process according to the invention.
  • Examples 15 and 16 report results of comparative experiments which are obtained using known flow improvers based on an ethylene-vinyl acetate copolymer alone and together with beeswax as the second component.
  • the vinyl acetate content in the polymers A 1 and A 2 is determined by 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 acetic acid formed is reacted with a NaJ / KJO 3 solution and the iodine released is titrated with Na 2 S 2 0a solution.
  • Table 2 shows the composition of the polymer mixtures which are used in the middle distillates Mi to M 4 as flow improvers.
  • the polymer mixtures are used as a solution in kerosene (50% by weight of polymer, based on the solution).
  • Table 3 contains information on 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)
  • Liquid Carbonaceous Fuels (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Lubricants (AREA)

Abstract

The flowability is improved by addition of a mixture of an ethylene/vinyl acetate copolymer, an oxidised polyethylene wax and/or an oxidised 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-Copolymerisat und einem oxidierten Polyethylenwachs und/oder einem 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 copolymer and an oxidized polyethylene wax and / or an 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 working capacity of conveying and transport facilities for crude oil are impaired until their complete failure. 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 1 914 756 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 described for example in DE-PS 1 914 756. 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 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 2 639 672 AI Mischungen aus Polymeren mit Ethylenskelett und Copolymeren von C2-bis Cso-Olefinen beschrieben, die zu einer synergistischen Verbesserung der Fließeigenschaften von Destillatkohlenwasserstoffölen in der Kälte führen können.Another way of increasing the effectiveness of flow improvers is to use additive combinations. DE 2 639 672 A1 describes mixtures of polymers with an ethylene skeleton and copolymers of C 2 to Cso-olefins which lead to a synergistic improvement in the flow properties of Distillate hydrocarbon oils can lead in the cold.

Nach der US 3 660 057 C1 setzt man Mischungen aus einem Ethylen-Vinylacetat-Copolymerisat und einem festen Kohlenwasserstoff, der frei von n-Paraffinen ist, als Fließverbesserer ein.According to US 3,660,057 C1, 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 4 019 878 C1 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 C1.

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 Awendungsbreite haben. Sie sollen die Fließfähigkeit auch solcher Öle erhöhen, bei denen die bekannten Additive keine oder nur geringe Wirkung zeigen.The task 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-Copolymerisat und einem oxidierten Polyethylenwachs und/oder einem oxidierten 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 copolymer and an oxidized polyethylene wax and / or an oxidized ethylene-vinyl acetate copolymer are added to the mineral oils or mineral oil distillates.

Überraschenderweise hat sich gezeigt, daß die Kombination von Ethylen-Vinylacetat-Copolymerisaten 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 Ansteigender 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 copolymers 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 at falling temperatures 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-Copolymerisate enthalten je 100 Gew.-Teile Ethylen 17 bis 70 Gew.-Teile Vinylacetat. Besonders bewährt haben sich Copolymerisate mit 33 bis 54 Gew.-Teilen Vinylacetat je 100 Gew.-Teilen Ethylen.The ethylene-vinyl acetate copolymers used according to the invention contain 17 to 70 parts by weight of vinyl acetate per 100 parts by weight of ethylene. Copolymers with 33 to 54 parts by weight of vinyl acetate per 100 parts by weight of ethylene have proven particularly useful.

Ihre nach der deutschen Norm DIN 53019 in einem Rotationsviskosimeter (Hersteller: Fa. Haake) bei 140°C gemessene Viskosität beträgt 100 bis 5000 mPa s, insbesondere 200 bis 1500 mPa s.Its viscosity, measured in accordance with the German standard DIN 53019 in a rotary viscometer (manufacturer: Haake) at 140 ° C, is 100 to 5000 mPa s, in particular 200 to 1500 mPa s.

Je 100 CH2-Gruppen weisen sie 1 bis 10 und vorzugsweise 2 bis 7 CH3-Gruppen in den Seitenketten auf, die nicht aus dem Acetatrest des Vinylacetats herrühren. Die Bestimmung der Anzahl CH3-Gruppen erfolgt dabei durch H-NMR-Spektroskopie.Each 100 CH 2 groups have 1 to 10 and preferably 2 to 7 CH 3 groups in the side chains, which do not result from the acetate residue of the vinyl acetate. The number of CH 3 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 15 MPa und Temperaturen von 70 bis 150°C in Gegenwart Radikale bildender Initiatoren erfolgen. Als Reaktionsmedium kann ein organisches Lösungs-oder Suspensionsmittel wie Toluol eingesetzt werden.The production of the ethylene-vinyl acetate copolymers is known. It can be carried out, for example, by polymerizing the monomer mixture at pressures of 5 to 15 MPa and temperatures of 70 to 150 ° C. in the presence of initiators which form free radicals. An organic solvent or suspending agent such as toluene can be used as the reaction medium.

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-, HydroxylGruppen 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 in the treatment of melts of linear or branched polyethylene waxes with air. 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 / cm 3 determined in accordance with 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. They are marketed, for example, 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 2 944 375 AI 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.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 described, for example, in DE 2 944 375 AI. 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.

Die erfindungsgemäß zur Verbesserung der Fließfähigkeit Mineralölen und Mineralöldestillaten zugesetzten Mischungen bestehen aus zwei oder drei Komponenten. Sie enthalten stets Ethylen-Vinylacetat-Copolymerisate und ferner oxidierte Polyethylenwachse oder oxidierte Ethylen-Vinylacetat-Copolymerisate. In einer weiteren Ausgestaltung setzt man nach der neuen Arbeitsweise Ethylen-Vinylacetat-Copolymerisat 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 copolymers and also oxidized polyethylene waxes or oxidized ethylene-vinyl acetate copolymers. In a further embodiment, according to the new procedure, ethylene-vinyl acetate copolymer is used together with oxidized polyethylene wax and oxidized ethylene-vinyl acetate copolymer.

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

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 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. Suitable solvents are aliphatic or aromatic hydrocarbons or hydrocarbon mixtures, e.g. Gasoline fractions. Kerosene is particularly suitable. The amount of polymer based on mineral oil or mineral oil fractions should be 0.001 to 2, preferably 0.005 to 0.5% by weight.

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

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

Die Beispiele 1 bis 14 betreffen das erfindungsgemäße Verfahren. In den Beispielen 15 und 16 wird über Ergebnisse von Vergleichsversuchen berichtet, die bei Einsatz bekannter Fließverbesserer auf Basis eines Ethylen-Vinylacetat-Copolymerisates allein und zusammen mit Bienenwachs als zweiter Komponente erhalten werden.Examples 1 to 14 relate to the process according to the invention. Examples 15 and 16 report results of comparative experiments which are obtained using known flow improvers based on an ethylene-vinyl acetate copolymer alone and together with beeswax as the second component.

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

Beispiele 1 - 16Examples 1-16

In den folgenden Beispielen werden als Polymere eingesetzt:

  • A1 ein nach dem Hochdruckverfahren synthetisiertes Ethylen-Vinylacetat-Copolymerisat mit 40 Gew.-Teilen Vinylacetat je 100 Gew.-Teile Ethylen und einer osmometrisch bestimmten Molmasse von 1900 g·mol-1,
  • A2 ein nach dem Hochdruckverfahren synthetisiertes Ethylen-Vinylacetat-Copolymerisat mit 57,2 Gew.-Teilen Vinylacetat je 100 Gew.-Teile Ethylen und einer Molmasse von 2000 g·mol-1,
  • 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 DIM 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 gomol-1,
  • D ein Bienenwachs.
The following examples use as polymers:
  • A 1 is an ethylene-vinyl acetate copolymer synthesized by the high-pressure process with 40 parts by weight of vinyl acetate per 100 parts by weight of ethylene and an osmometrically determined molar mass of 1900 gmol -1 ,
  • A 2 is an ethylene-vinyl acetate copolymer synthesized by the high-pressure process with 57.2 parts by weight of vinyl acetate per 100 parts by weight of ethylene and a molar mass of 2000 gmol -1 ,
  • B 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 / cm 3 , an acid number (according to DIN 53402) of 9 mg KOH / g, one Saponification number (according to DIM 53401) of 28 mg KOH / g and a molecular weight of 2700 gmol -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 gomol-1,
  • DA beeswax.

Der Vinylacetatgehalt in den Polymeren A1 und A2 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 Na2S20a-Lösung titriert.The vinyl acetate content in the polymers A 1 and A 2 is determined by 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 acetic acid formed is reacted with a NaJ / KJO 3 solution and the iodine released is titrated with Na 2 S 2 0a solution.

Tabelle 2 ist die Zusammensetzung der Polymergemische zu entnehmen, die in den Mitteldestillaten Mi, bis M4 als Fließverbesserer Anwendung finden. Die Polymergemische werden als Lösung in Kerosin (50 Gew.-% Polymere, bezogen auf die Lösung) eingesetzt.Table 2 shows the composition of the polymer mixtures which are used in the middle distillates Mi to M 4 as flow improvers. The polymer mixtures are used as a solution in kerosene (50% by weight of polymer, based on the solution).

Tabelle 3 schließlich enthält Angaben zur Wirksamkeit des erfindungsgemäßen Verfahrens zur Verbesserung der Fließfähigkeit von Mineralölen und Mineralöldestillaten.

Figure imgb0002
Figure imgb0003
 Finally, Table 3 contains information on 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 (8)

1. A process to improve the flowability of mineral oils and mineral oil distillates, characterised in that mixtures of an ethylene-vinyl acetate copolymer 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 copolymer contains 17 to 70, preferably 33 to 54 parts by weight of vinyl acetate per 100 parts by weight of ethylene, has a viscosity of 100 to 5000, preferably 200 to 1500 mPa x sec., measured at 140°C and per 100 CH2 groups exhibits 1 to 10, preferably 2 to 7 CH3 groups in the side chains not originating from the acetate group of the vinyl acetate.
3. A process according to claim 1, characterised in that the oxidised polyethylene wax has a mol mass of 500 to 10 000 g x mol-1, 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.
4. 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.
5. A process according to claim 1, characterised in that the weight ratio of ethylene-vinyl acetate copolymer 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.
6. 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 copolymer and an oxidised polyethylene wax and/or an oxidised ethylene-vinyl acetate copolymer.
7. A mineral oil or mineral oil distillate according to claim 6, characterised in that
- the ethylene-vinyl acetate copolymer contains 17 to 70, preferably 33 to 54% by weight vinyl acetate per 100 parts by weight ethylene, has a viscosity of 100 to 5000, preferably 200 to 1500 mPa x s, measured at 140°C and exhibits per 100 CH2 groups 1 to 10, preferably 2 to 7 CH3 groups in the side chains not originating from the acetate group of the vinyl acetate.
- the oxidised polyethylene wax has a mol mass of 500 to 10 000 g x mol-1, 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
- 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.
8. Mineral oil or mineral oil distillate according to claim 6 or 7, characterised in that the weight ratio of ethylene-vinyl acetate copolymer to the oxidised polyethylene wax and/or the oxidised ethylene-vinyl acetate copolymer is 1000:1 to 1:10, preferably 100:1 to 1:5.
EP87108559A 1986-06-26 1987-06-13 Process to improve the flowability of mineral oils and mineral oil distillates Expired - Lifetime EP0251002B1 (en)

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DE3921279A1 (en) * 1989-06-29 1991-01-03 Hoechst Ag METHOD FOR IMPROVING THE FLOWABILITY OF MINERAL OILS AND MINERAL OIL DISTILLATES
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US2875029A (en) * 1953-05-21 1959-02-24 Phillips Petroleum Co Stabilized liquid fuel
US3250599A (en) * 1962-12-03 1966-05-10 Sinclair Research Inc Fuels of improved low temperature pumpability
US3374073A (en) * 1964-06-23 1968-03-19 Lubrizol Corp Oxidized, degraded interpolymer of ethylene and propylene and fuel composition containing the same
US3454379A (en) * 1964-10-23 1969-07-08 Sinclair Research Inc Hydrocarbon oil composition having improved low temperature pumpability
NO121523B (en) * 1964-12-11 1971-03-08 Exxon Co
US3388977A (en) * 1965-01-06 1968-06-18 Exxon Research Engineering Co Pour point depressant for middle distillates
DE1914756C3 (en) * 1968-04-01 1985-05-15 Exxon Research and Engineering Co., Linden, N.J. Use of ethylene-vinyl acetate copolymers for petroleum distillates
US3961916A (en) * 1972-02-08 1976-06-08 Exxon Research And Engineering Company Middle distillate compositions with improved filterability and process therefor
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DE3501384A1 (en) * 1985-01-17 1986-07-17 Ruhrchemie Ag, 4200 Oberhausen METHOD FOR IMPROVING THE FLOWABILITY OF MINERAL OILS AND MINERAL OIL DISTILLATES

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