EP0251002A1 - 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

Info

Publication number
EP0251002A1
EP0251002A1 EP87108559A EP87108559A EP0251002A1 EP 0251002 A1 EP0251002 A1 EP 0251002A1 EP 87108559 A EP87108559 A EP 87108559A EP 87108559 A EP87108559 A EP 87108559A EP 0251002 A1 EP0251002 A1 EP 0251002A1
Authority
EP
European Patent Office
Prior art keywords
vinyl acetate
ethylene
mineral oil
acetate copolymer
oxidized
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP87108559A
Other languages
German (de)
French (fr)
Other versions
EP0251002B1 (en
Inventor
Wolfgang Dr. Dipl.-Chem. Payer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
Ruhrchemie AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst AG, Ruhrchemie AG filed Critical Hoechst AG
Priority to AT87108559T priority Critical patent/ATE58749T1/en
Publication of EP0251002A1 publication Critical patent/EP0251002A1/en
Application granted granted Critical
Publication of EP0251002B1 publication Critical patent/EP0251002B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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 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 are of great importance as pour point depressants and flow improvers for crude oils and middle distillates obtained alcohol.
  • 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 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.
  • 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 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 according to 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 CH2 groups have 1 to 10 and preferably 2 to 7 CH3 groups in the side chains, which do not result from the acetate residue of the vinyl acetate.
  • the number of CH3 groups is determined by H-NMR spectroscopy.
  • 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 suspension medium 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 / 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 Al. 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 oxi dated 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.
  • 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 14 relate to the process according to the invention.
  • Examples 15 and 16 report the 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.
  • A1 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
  • A2 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 ⁇
  • 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 DIM 53401) of 28 mg KOH / g and a molecular weight of 2700 g ⁇ mol ⁇ 1,
  • C is an oxidized ethylene-vinylene-
  • the vinyl acetate content in the polymers A1 and A2 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 resulting acetic acid is reacted with a NaJ / KJO3 solution and the iodine released is titrated with Na2S2O3 solution.
  • Table 2 shows the composition of the polymer mixtures which are used in the middle distillates M1 to M4 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.

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 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 Vinyl­ alkohols 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 are of great importance as pour point depressants and flow improvers for crude oils and middle distillates obtained alcohol. 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 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 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. DE 26 39 672 Al describes mixtures of polymers with ethylene skeleton and copolymers of C₂ to C₅₀ olefins, which lead to a synergistic improvement in the flow properties of distillate hydrocarbon oils can lead in the cold.

Nach der US 36 60 057 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 36 60 057 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 40 19 878 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 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 Awendungsbreite 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-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 according to 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 CH₂ groups have 1 to 10 and preferably 2 to 7 CH₃ groups in the side chains, which do not result from the acetate residue of the vinyl acetate. The number of CH₃ groups is determined by H-NMR spectroscopy.

Die Herstellung der Ethylen-Vinylacetat-Copolymerisate ist bekannt. Sie kann z.B. durch Polymerisation des 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 suspension medium 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-, 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 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 / 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 molecular weight 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.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 Al. 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 oxi­ dierte 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 oxi dated 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. 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 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 the 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 g·mol⁻¹,
D ein Bienenwachs.The following examples use as polymers:
A₁ 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,
A₂ 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 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 DIM 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 gmol⁻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 Na₂S₂O₃-Lösung titriert.The vinyl acetate content in the polymers A₁ and A₂ 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 resulting acetic acid is reacted with a NaJ / KJO₃ solution and the iodine released is titrated with Na₂S₂O₃ solution.

Tabelle 2 ist die Zusammensetzung der Polymergemische zu entnehmen, die in den Mitteldestillaten M₁, 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 M₁ to M₄ 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.) Verfahren zur Verbesserung der Fließfähigkeit von Mineralölen und Mineralöldestillaten, dadurch gekenn­zeichnet, daß man den Mineralölen bzw. Mineralöldestilla­ten Mischungen aus einem Ethylen-Vinylacetat-Copolymeri­sat und einem oxidierten Polyethylenwachs und/oder einem oxidierten Ethylen-Vinylacetat-Copolymerisat zusetzt.1.) Process for improving the flowability of mineral oils and mineral oil distillates, characterized in that mixtures of an ethylene-vinyl acetate copolymer and an oxidized polyethylene wax and / or an oxidized ethylene-vinyl acetate copolymer are added to the mineral oils or mineral oil distillates. 2.) Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Ethylen-Vinylacetat-Copolymerisat 17 bis 70, vorzugsweise 33 bis 54 Gew.-Teile Vinylacetat je 100 Gew.-Teile Ethylen enthält, eine bei 140°C gemessene Viskosität von 100 bis 5000, vorzugsweise 200 bis 1500 mPa.s besitzt und je 100 CH₂-Gruppen 1 bis 10, vorzugs­weise 2 bis 7 CH₃-Gruppen in den Seitenketten aufweist, die nicht aus dem Acetatrest des Vinylacetats herrühren.2.) The method according to claim 1, characterized 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, a viscosity measured at 140 ° C from 100 to 5000, preferably 200 to 1500 mPa.s and has 100 CH₂ groups 1 to 10, preferably 2 to 7 CH₃ groups in the side chains, which do not come from the acetate residue of the vinyl acetate. 3.) Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das oxidierte Polyethylenwachs eine Molmasse von 500 bis 10000 g · mol⁻¹ besitzt, einen Schmelzpunkt von 85 bis 135°C, einen Tropfpunkt von 95 bis 135°C, vorzugswei­se 100 bis 120°C, eine Dichte von 0,94 bis 1,00 g/cm³ und eine Säurezahl von 5 bis 60, vorzugsweise 8 bis 30 mg KOH/g aufweist.3.) Process according to claim 1, characterized in that the oxidized polyethylene wax has a molecular weight of 500 to 10,000 g · 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.) Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das oxidierte Ethylen-Vinylacetat-Copolymerisat einen Tropfpunkt von 80 bis 110°C und eine Säurezahl von 5 bis 200 mg KOH/g besitzt.4.) Process according to claim 1, characterized in that the oxidized 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.) Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Gewichtsverhältnis von Ethylen-Vinylacetat-­Copolymerisat zu dem oxidierten Polyethylenwachs und/oder dem oxidierten Ethylen-Vinylacetat-Copolymerisat 1000 : 1 bis 1 : 10 und vorzugsweise 100 : 1 bis 1 : 5 beträgt.5.) Process according to claim 1, characterized in that the weight ratio of ethylene-vinyl acetate copolymer to the oxidized polyethylene wax and / or the oxidized ethylene-vinyl acetate copolymer 1000: 1 to 1:10 and preferably 100: 1 to 1: 5 is. 6.) Mineralöl oder Mineralöldestillat mit verbessertem Fließverhalten, dadurch gekennzeichnet, daß es 0,001 bis 2, vorzugsweise 0,005 bis 0,5 Gew.-% (bezogen auf das Gewicht des Mineralöls bzw. Mineralöldestillates) einer Mischung aus einem Ethylen-Vinylacetat-Copolymerisat und einem oxidierten Polyethylenwachs und/oder einem oxidier­ten Ethylen-Vinylacetat-Copolymerisat enthält.6.) Mineral oil or mineral oil distillate with improved flow behavior, characterized in that it is 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 copolymer and contains an oxidized polyethylene wax and / or an oxidized ethylene-vinyl acetate copolymer. 7.) Mineralöl oder Mineralöldestillat nach Anspruch 6, da­durch gekennzeichnet, daß
- das Ethylen-Vinylacetat-Copolymerisat 17 bis 70, vor­zugsweise 33 bis 54 Gew.-% Vinylacetat je 100 Gew.-Teile Ethylen enthält, eine bei 140°C gemessene Viskosität von 100 bis 5000, vorzugsweise 200 bis 1500 mPa · s besitzt und je 100 CH₂-Gruppen 1 bis 10, vorzugsweise 2 bis 7 CH₃-Gruppen in den Seitenketten aufweist, die nicht aus dem Acetatrest des Vinylacetats herrühren,
- das oxidierte Polyethylenwachs eine Molmasse von 500 bis 10 000 g · mol⁻¹ besitzt, einen Schmelzpunkt von 85 bis 135°C, einen Tropfpunkt von 95 bis 135°C, vorzugs­weise 100 bis 120°C, eine Dichte von 0,94 bis 1,00 g/cm³ und eine Säurezahl von 5 bis 60, vorzugsweise 8 bis 30 mg KOH/g aufweist
und
- das oxidierte Ethylen-Vinylacetat-Copolymerisat einen Tropfpunkt von 80 bis 110°C und eine Säurezahl von 5 200 mg KOH/g besitzt.7.) Mineral oil or mineral oil distillate according to claim 6, characterized in that
- The ethylene-vinyl acetate copolymer contains 17 to 70, preferably 33 to 54% by weight of vinyl acetate per 100 parts by weight of ethylene, has a viscosity of 100 to 5000, preferably 200 to 1500 mPa · s measured at 140 ° C. and per 100 CH₂ groups has 1 to 10, preferably 2 to 7 CH₃ groups in the side chains which do not result from the acetate residue of the vinyl acetate,
- The oxidized polyethylene wax has a molecular weight of 500 to 10,000 g · 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 having
and
- The oxidized ethylene-vinyl acetate copolymer has a dropping point of 80 to 110 ° C and an acid number of 5 200 mg KOH / g. 8.) Mineralöl oder Mineralöldestillat nach Anspruch 6 oder 7, dadurch gekennzeichnet, daß das Gewichtsverhält­nis von Ethylen-Vinylacetat-Copolymerisat zu dem oxidier­ten Polyethylenwachs und/oder dem oxidierten Ethylen-­Vinylacetat-Copolymerisat 1000 : 1 bis 1 : 10, vorzugs­weise 100 : 1 bis 1 : 5 beträgt.8.) Mineral oil or mineral oil distillate according to claim 6 or 7, characterized in that the weight ratio of ethylene-vinyl acetate copolymer to the oxidized polyethylene wax and / or the oxidized ethylene-vinyl acetate copolymer 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)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87108559T ATE58749T1 (en) 1986-06-26 1987-06-13 METHOD OF IMPROVING THE FLOWABILITY OF MINERAL OILS AND MINERAL OIL DISTILLATES.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863621395 DE3621395A1 (en) 1986-06-26 1986-06-26 METHOD FOR IMPROVING THE FLOWABILITY OF MINERAL OILS AND MINERAL OIL DISTILLATES
DE3621395 1986-06-26

Publications (2)

Publication Number Publication Date
EP0251002A1 true EP0251002A1 (en) 1988-01-07
EP0251002B1 EP0251002B1 (en) 1990-11-28

Family

ID=6303741

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87108559A Expired - Lifetime EP0251002B1 (en) 1986-06-26 1987-06-13 Process to improve the flowability of mineral oils and mineral oil distillates

Country Status (4)

Country Link
EP (1) EP0251002B1 (en)
AT (1) ATE58749T1 (en)
DE (2) DE3621395A1 (en)
ES (1) ES2019901B3 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0405270A1 (en) * 1989-06-29 1991-01-02 Hoechst Aktiengesellschaft Process to improve mineral oil and mineral oil distillate flowability
WO2005040315A1 (en) * 2003-10-22 2005-05-06 Leuna Polymer Gmbh Additive mixture as component of a mineral oil composition

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
GB1101039A (en) * 1964-12-11 1968-01-31 Exxon Research Engineering Co Improved process for manufacturing potent pour depressants
US3388977A (en) * 1965-01-06 1968-06-18 Exxon Research Engineering Co Pour point depressant for middle distillates
US3454379A (en) * 1964-10-23 1969-07-08 Sinclair Research Inc Hydrocarbon oil composition having improved low temperature pumpability
DE1914756A1 (en) * 1968-04-01 1969-11-06 Exxon Research Engineering Co Process for the production of copolymers and their use in distillation units
DE1570884A1 (en) * 1964-06-23 1970-03-19 Lubrizol Corp Fuel oil preparations
US3961916A (en) * 1972-02-08 1976-06-08 Exxon Research And Engineering Company Middle distillate compositions with improved filterability and process therefor
US4019878A (en) * 1974-12-17 1977-04-26 Exxon Research And Engineering Company Additive combination for cold flow improvement of middle distillate fuel oil
DE2944375A1 (en) * 1979-11-02 1981-05-14 Hoechst Ag, 6000 Frankfurt Hard workable polar wax prepn. - by oxidn. of ethylene! copolymer with oxygen gp.-contg. co-monomer esp. vinyl acetate
EP0190553A1 (en) * 1985-01-17 1986-08-13 Ruhrchemie Aktiengesellschaft Process to improve the viscosity of mineral oils and of the distillates of mineral oils

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
DE1570884A1 (en) * 1964-06-23 1970-03-19 Lubrizol Corp Fuel oil preparations
US3454379A (en) * 1964-10-23 1969-07-08 Sinclair Research Inc Hydrocarbon oil composition having improved low temperature pumpability
GB1101039A (en) * 1964-12-11 1968-01-31 Exxon Research Engineering Co Improved process for manufacturing potent pour depressants
US3388977A (en) * 1965-01-06 1968-06-18 Exxon Research Engineering Co Pour point depressant for middle distillates
DE1914756A1 (en) * 1968-04-01 1969-11-06 Exxon Research Engineering Co Process for the production of copolymers and their use in distillation units
US3961916A (en) * 1972-02-08 1976-06-08 Exxon Research And Engineering Company Middle distillate compositions with improved filterability and process therefor
US4019878A (en) * 1974-12-17 1977-04-26 Exxon Research And Engineering Company Additive combination for cold flow improvement of middle distillate fuel oil
DE2944375A1 (en) * 1979-11-02 1981-05-14 Hoechst Ag, 6000 Frankfurt Hard workable polar wax prepn. - by oxidn. of ethylene! copolymer with oxygen gp.-contg. co-monomer esp. vinyl acetate
EP0190553A1 (en) * 1985-01-17 1986-08-13 Ruhrchemie Aktiengesellschaft Process to improve the viscosity of mineral oils and of the distillates of mineral oils

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0405270A1 (en) * 1989-06-29 1991-01-02 Hoechst Aktiengesellschaft Process to improve mineral oil and mineral oil distillate flowability
JPH0339385A (en) * 1989-06-29 1991-02-20 Hoechst Ag Method for improving the fluidity of mineral oil or mineral oil distillate
WO2005040315A1 (en) * 2003-10-22 2005-05-06 Leuna Polymer Gmbh Additive mixture as component of a mineral oil composition
EA011358B1 (en) * 2003-10-22 2009-02-27 Лейна Полимер Гмбх Mineral oil composition comprising additive mixture, additive mixture as components of mineral oil composition, a method for producing thereof and use thereof

Also Published As

Publication number Publication date
ES2019901B3 (en) 1991-07-16
DE3621395A1 (en) 1988-01-28
ATE58749T1 (en) 1990-12-15
DE3766426D1 (en) 1991-01-10
EP0251002B1 (en) 1990-11-28

Similar Documents

Publication Publication Date Title
EP0254284B1 (en) Process to improve the flowability of mineral oils and mineral oil distillates
EP0493769B1 (en) Terpolymers of ethylene, their preparation and their use as additives for mineral oil distillates
EP0203554B1 (en) Use of ethylene terpolymers as additives for mineral distillates oils and mineral oil
DE19757830C2 (en) Fuel oils with improved lubrication
EP0807642B1 (en) Ethylene terpolymers, their preparation and their use as additives for mineral oil distillates
EP0258572B1 (en) Process to improve the flowability of mineral oils and mineral oil distillates
EP0922716B1 (en) Process for the manufacture of terpolymers of ethylene and their use as additives to mineral oil and mineral oil distillates
EP0463518B1 (en) Terpolymers of ethylene, their preparation and their use for mineral oil distillates
DE3640613A1 (en) METHOD FOR THE PRODUCTION OF ETHYLENE MIXED POLYMERISATES AND THE USE THEREOF AS AN ADDITION TO MINERAL OIL AND MINERAL OIL FRACTIONS
EP0405270B1 (en) Process to improve mineral oil and mineral oil distillate flowability
DE10260714A1 (en) Fuel oils with improved cold properties
DE2519577C2 (en) ADDITIVES AND THE FUELS AND FUELS CONTAINING THEM
DE2331041A1 (en) HEATING OIL FORMULATION
DE2446829A1 (en) FUEL OIL
EP1200539B1 (en) Use of hydroxyl group-containing copolymers for producing fuel oils with improved lubricity
DE19823565A1 (en) Mixtures of copolymers with improved lubrication
DE19729057A1 (en) Copolymers based on ethylene and unsaturated carboxylic acid esters and their use as mineral oil additives
EP0190553B1 (en) Process to improve the viscosity of mineral oils and of the distillates of mineral oils
EP0251002B1 (en) Process to improve the flowability of mineral oils and mineral oil distillates
EP0111883B1 (en) Use of ethylene copolymers as mineral oil additives
EP0309897B1 (en) Copolymers of ethylene and methoxy acetic acid vinyl ester and their use as additives for mineral oil distillates
DE19816797C2 (en) Use of nitrogen-containing ethylene copolymers for the production of fuel oils with improved lubrication

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FR GB IT LI LU NL SE

17P Request for examination filed

Effective date: 19880123

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: HOECHST AKTIENGESELLSCHAFT

17Q First examination report despatched

Effective date: 19890830

ITF It: translation for a ep patent filed

Owner name: STUDIO MASSARI S.R.L.

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB IT LI LU NL SE

REF Corresponds to:

Ref document number: 58749

Country of ref document: AT

Date of ref document: 19901215

Kind code of ref document: T

ET Fr: translation filed
REF Corresponds to:

Ref document number: 3766426

Country of ref document: DE

Date of ref document: 19910110

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19910522

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19910527

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19910528

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19910531

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19910607

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19910613

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19910621

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19910628

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19910630

Year of fee payment: 5

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

EPTA Lu: last paid annual fee
26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19920613

Ref country code: GB

Effective date: 19920613

Ref country code: AT

Effective date: 19920613

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19920614

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 19920615

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19920630

Ref country code: CH

Effective date: 19920630

Ref country code: BE

Effective date: 19920630

BERE Be: lapsed

Owner name: HOECHST A.G.

Effective date: 19920630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19930101

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19920613

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19930226

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19940719

Year of fee payment: 8

EUG Se: european patent has lapsed

Ref document number: 87108559.3

Effective date: 19930109

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19960301

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 19990601

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050613