EP0186009B1 - Use of ethylene copolymers as crude-oil additives - Google Patents

Use of ethylene copolymers as crude-oil additives Download PDF

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Publication number
EP0186009B1
EP0186009B1 EP85115541A EP85115541A EP0186009B1 EP 0186009 B1 EP0186009 B1 EP 0186009B1 EP 85115541 A EP85115541 A EP 85115541A EP 85115541 A EP85115541 A EP 85115541A EP 0186009 B1 EP0186009 B1 EP 0186009B1
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Prior art keywords
crude oil
crude
weight
ethylene
ethylene copolymers
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German (de)
French (fr)
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EP0186009A2 (en
EP0186009A3 (en
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John Dr. Dipl.-Chem. Hobes
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Hoechst AG
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • 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
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • 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
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
    • C10L1/1832—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy
    • 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
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
    • 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
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2406—Organic compounds containing sulfur, selenium and/or tellurium mercaptans; hydrocarbon sulfides
    • C10L1/2412—Organic compounds containing sulfur, selenium and/or tellurium mercaptans; hydrocarbon sulfides sulfur bond to an aromatic radical
    • 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
    • C10L1/26—Organic compounds containing phosphorus
    • C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
    • C10L1/2641—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) oxygen bonds only

Definitions

  • the present invention relates to additives for improving the flow behavior of crude oil. These additives remain effective even under high shear loads.
  • Crude oil is the crude oil that comes directly from the earth. Crude oil consists essentially of hydrocarbons, namely alkanes, cycloalkanes and alkylbenzene. In addition, it contains oxygen and sulfur-containing compounds such as naphthenic acids, phenols, aldehydes, thioethers and various heterocyclic compounds.
  • the alkanes are a mixture of straight-chain unbranched paraffins having 1 to about 30 carbon atoms, the gaseous and the solid hydrocarbons being dissolved in the liquid.
  • the separation of the paraffins is promoted by lowering the temperature and reducing the pressure. Both measures reduce the solubility of the solid in the liquid hydrocarbons. The result is a supersaturated solution from which the paraffin eventually crystallizes.
  • This process changes the rheological behavior of the crude oil. Its viscosity increases and its fluidity in the conveyor systems and lines is impaired accordingly. The increase in viscosity can lead to the crude oil stalling.
  • the pour point (according to DIN 51 583) or the pour point (yield point; according to DIN ISO 3016) is determined. They are determined in conventional test equipment.
  • paraffin inhibitors are also used, which influence the rheological properties of the extracted or transported oil and prevent the formation of paraffin crystals by incorporating them into the resulting structures or by their absorption. In both cases, crystal growth is counteracted, so that small particles are formed which do not allow the formation of networks.
  • the addition of paraffin inhibitors therefore enables crude oil to be extracted and transported below the pour point temperature.
  • Paraffin inhibitors or flow improvers predominantly have a paraffin-like structure and generally have polar groups in the side chains.
  • these branches have the task of counteracting the crystal formation of the inhibitor. Chemically, they belong to the group of polyethylenes, polymethacrylates and ethylene-vinyl acetate copolymers.
  • the dosage of paraffin inhibitors to crude oil is not always without side effects. For example, they can adversely affect the viscosity and pour point of the crude oil in plant parts such as orifices or centrifugal pumps that are subject to high shear stress.
  • This object is achieved by using 0.005 to 0.5% by weight (based on the crude oil) of a copolymer which consists of 65 to 80% by weight of ethylene units and 35 to 20% by weight of vinyl acetate units, together with 0 , 01 to 1.0 wt .-% (based on the crude oil) of an antioxidant and 0.001 to 1.0 wt .-% (based on the crude oil) of an amine as a flow improver for crude oil.
  • the preparation of the copolymers used according to the invention is known. It is carried out by polymerizing the monomer mixture at temperatures from 100 to 350 ° C. and pressures from 1000 to 8000 bar in the presence of free radical initiators. The polymerization does not require the presence of a solvent as the reaction medium.
  • the ethylene used as comonomer is used in the purity customary for polymerization reactions of at least 99%.
  • the polymerization takes place in the presence of catalytic amounts of free radical initiators, for example oxygen, in amounts of 2 to 250 mol.ppm, based on the ethylene to be polymerized.
  • free radical initiators for example oxygen
  • peroxides such as tert-butyl perbenzoate, dilauroyl peroxide, di-tert-butyl peroxide or azo-butyrononitrile in amounts of 2 to 200 mol.ppm, based on the ethylene, can also be used as initiators.
  • the molecular weight is adjusted using moderators, such as aliphatic alcohols and / or carbonyl compounds, saturated, unsaturated or chlorinated hydrocarbons or hydrogen.
  • copolymers used according to the invention have molecular weights of 500 to 25,000, determined according to K. Rast. Ber. 550, 1922.
  • Antioxidants in the sense of the invention are understood to mean substances which prevent or inhibit undesirable processes caused by the action of oxygen in plastics. These are organic compounds of very different structures. They essentially belong to the group of amines and phenols and also include sulfur and phosphorus compounds. What they have in common is that they intervene in the antioxidant mechanism in different ways. They are mainly used as free radical scavengers, as peroxide decomposers, as metal ion deactivators and as UV absorbers. 2,6-Di-tert.-buty!
  • Suitable amines correspond to the general formula R-NH 2 , where R represents saturated or monounsaturated, straight-chain or branched hydrocarbon radicals having 8 to 18 carbon atoms.
  • the copolymer, antioxidant and optionally amine can be added to the crude oil separately, in the form of the dissolved or undissolved substances. You can also dissolve the components in a solvent and add this solution to the crude oil.
  • Aromatic hydrocarbons are preferred as solvents, for example aromatic mixtures which are commercially available under the name solvent naphtha or heavy benzene.
  • the pour point of Montrose and Beatrice North Sea crude is determined before and after shear stress. The measurement is carried out according to DIN ISO 3016.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Lubricants (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)

Description

Die vorliegende Erfindung betrifft Additive zur Verbesserung des Fließverhaltens von Rohöl. Diese Additive behalten auch bei hoher Scherbelastung ihre Wirksamkeit.The present invention relates to additives for improving the flow behavior of crude oil. These additives remain effective even under high shear loads.

Als Rohöl wird das unmittelbar aus der Erde kommende ungereinigteerdöl bezeichnet. Rohöl bestehtim wesentlichen aus Kohlenwasserstoffen, nämlich Alkanen, Cycloalkanen und Alkylbenzol. Daneben enthältes sauerstoff- und schwefelhaltige Verbindungen wie Naphthensäuren, Phenole, Aldehyde, Thioether und verschiedene heterocyclische Verbindungen. Die Alkane stellen ein Gemisch aus geradkettigen unverzweigten Paraffinen mit 1 bis etwa 30 Kohlenstoffatomen dar, wobei die gasförmigen und die festen Kohlenwasserstoffe in den flüssigen gelöst sind.Crude oil is the crude oil that comes directly from the earth. Crude oil consists essentially of hydrocarbons, namely alkanes, cycloalkanes and alkylbenzene. In addition, it contains oxygen and sulfur-containing compounds such as naphthenic acids, phenols, aldehydes, thioethers and various heterocyclic compounds. The alkanes are a mixture of straight-chain unbranched paraffins having 1 to about 30 carbon atoms, the gaseous and the solid hydrocarbons being dissolved in the liquid.

Sowohl die Förderung als auch der Transport von Rohöl erfolgt unter wechselnden Temperatur- und Druckbedingungen. Bei Rohölen, die höhermolekulare Kohlenwasserstoffe in größeren Mengen enthalten, kann es zur Auskristallisation von Paraffinen kommen. Die Kristalle bilden normalerweise dünne Plättchen oder Nadeln, unter Umständen kann sich aber auch ein dreidimensionales Netzwerk ausbilden.Both the extraction and the transportation of crude oil take place under changing temperature and pressure conditions. In the case of crude oils that contain higher molecular weight hydrocarbons in large quantities, paraffins can crystallize. The crystals usually form thin platelets or needles, but under certain circumstances a three-dimensional network can also form.

Die Abscheidung der Paraffine wird durch Herabsetzung der Temperatur und Verminderung des Druckes begünstigt. Beide Maßnahmen bewirken eine Abnahme der Löslichkeit der festen in den flüssigen Kohlenwasserstoffen. Es entsteht eine übersättigte Lösung, aus der schließlich das Paraffin auskristallisiert.The separation of the paraffins is promoted by lowering the temperature and reducing the pressure. Both measures reduce the solubility of the solid in the liquid hydrocarbons. The result is a supersaturated solution from which the paraffin eventually crystallizes.

Durch diesen Vorgang wird das rheologische Verhalten des Rohöls verändert. Seine Viskosität steigt an und seine Fließfähigkeit in den Fördereinrichtungen und Leitungen wird entsprechend beeinträchtigt. Die Zunahme der Viskosität kann bis zum Stocken des Rohöls führen.This process changes the rheological behavior of the crude oil. Its viscosity increases and its fluidity in the conveyor systems and lines is impaired accordingly. The increase in viscosity can lead to the crude oil stalling.

Zur Beschreibung des Kaltverhaltens von Rohöl ermittelt man den Stockpunkt (nach DIN 51 583) oder den Pourpoint (Fließgrenze; nach DIN ISO 3016). Ihre Bestimmung erfolgt in konventionellen Testapparaturen.To describe the cold behavior of crude oil, the pour point (according to DIN 51 583) or the pour point (yield point; according to DIN ISO 3016) is determined. They are determined in conventional test equipment.

Der Ablagerung von Paraffinen bei der Förderung und dem Transport von Rohöl begegnet man auf verschiedenen Wegen. So entfernt man Paraffinablagerungen mechanisch mit Hilfe von Kratzern oder Molchen. Auch Spülungen mit erhitztem Öl, Behandlung mit Dampf oder elektrische Beheizung werden zur Verhinderung oder Beseitigung von Paraffinabscheidungen angewandt. Weiterhin setzt man auch Paraffininhibitoren ein, die die rheologischen Eigenschaften des geförderten oder transportierten Öls beeinflussen und die Entstehung von Paraffinkristallen dadurch verhindern, daß sie in die entstehenden Strukturen eingebaut oder von ihnen absorbiert werden. In beiden Fällen wird dem Kristallwachstum entgegengewirkt, so daß kleine Partikel entstehen, die keine Bildung von Netzwerken zulassen. Der Zusatz von Paraffininhibitoren ermöglicht es daher, Rohöl auch unterhalb der Stockpunkttemperatur zu fördern und zu transportieren.The deposition of paraffins during the production and transportation of crude oil is encountered in various ways. How to remove paraffin deposits mechanically with the help of scratches or newts. Heated oil rinsing, steam treatment, or electrical heating are also used to prevent or remove paraffin deposits. Furthermore, paraffin inhibitors are also used, which influence the rheological properties of the extracted or transported oil and prevent the formation of paraffin crystals by incorporating them into the resulting structures or by their absorption. In both cases, crystal growth is counteracted, so that small particles are formed which do not allow the formation of networks. The addition of paraffin inhibitors therefore enables crude oil to be extracted and transported below the pour point temperature.

Paraffininhibitoren oder Fließverbesserer (Cold-Flow-Improver) besitzen überwiegend paraffinähnlichen Aufbau und weisen in den Seitenketten im allgemeinen polare Gruppen auf. Diese Verzweigungen haben unter anderem die Aufgabe, der Kristallbildung des Inhibitors entgegenzuwirken. Chemisch gehören sie zu den Polyethylenen, den Polymethacrylaten und den Ethylen-Vinylacetat-Copolymeren.Paraffin inhibitors or flow improvers (cold flow improvers) predominantly have a paraffin-like structure and generally have polar groups in the side chains. Among other things, these branches have the task of counteracting the crystal formation of the inhibitor. Chemically, they belong to the group of polyethylenes, polymethacrylates and ethylene-vinyl acetate copolymers.

Aus der GB-A-1 473155 ist es bekannt, wachshaltigem Rohöl Mischungen aus einem Ethylen/Vinylacetatcopolymerisat und einem Antioxidans als Fließverbesserer zuzusetzen. Diese Mischungen werden in Form einer Lösung in einer solchen Menge verwendet, daß die Konzentration des Copolymerisats im Rohöl 5 bis 10.000 ppm beträgt. Die Konzentration des Antioxidans ist ähnlich der des Copolymerisats.From GB-A-1 473155 it is known to add mixtures of an ethylene / vinyl acetate copolymer and an antioxidant as a flow improver to wax-containing crude oil. These mixtures are used in the form of a solution in such an amount that the concentration of the copolymer in the crude oil is 5 to 10,000 ppm. The concentration of the antioxidant is similar to that of the copolymer.

Die Dosierung von Paraffininhibitoren zu Rohöl ist nicht immer ohne Nebenwirkungen. So können sie in stark scherbeanspruchten Anlagenteilen wie Blenden oder Kreiselpumpen die Viskosität und den Stockpunkt des Rohöls nachteilig beeinflussen.The dosage of paraffin inhibitors to crude oil is not always without side effects. For example, they can adversely affect the viscosity and pour point of the crude oil in plant parts such as orifices or centrifugal pumps that are subject to high shear stress.

Es bestand daher die Aufgabe, Additive zur Verbesserung des Fließverhaltens von Rohöl zu entwikkein, die gegen Scherbeanspruchung beständig sind.It was therefore the task to develop additives to improve the flow behavior of crude oil which are resistant to shear stress.

Diese Aufgabe wird gelöst durch die Verwendung von 0,005 bis 0,5 Gew.-% (bezogen auf das Rohöl) eines Copolymerisats, das aus 65 bis 80 Gew.-% Ethyleneinheiten und 35 bis 20 Gew.-% Vinylacetateinheiten besteht, zusammen mit 0,01 bis 1,0 Gew.-% (bezogen auf das Rohöl) eines Antioxidans und 0,001 bis 1,0 Gew.-% (bezogen auf das Rohöl) eines Amins als Fließverbesserer für Rohöl.This object is achieved by using 0.005 to 0.5% by weight (based on the crude oil) of a copolymer which consists of 65 to 80% by weight of ethylene units and 35 to 20% by weight of vinyl acetate units, together with 0 , 01 to 1.0 wt .-% (based on the crude oil) of an antioxidant and 0.001 to 1.0 wt .-% (based on the crude oil) of an amine as a flow improver for crude oil.

Überraschenderweise wird durch die gemeinsame Verwendung von Ethylen-Vinylacetat-Copolymerisat, Antioxidans und Amin die Fließfähigkeit von Rohöl auch unter der Einwirkung von Scherkräften weitgehend aufrechterhalten.Surprisingly, the flowability of crude oil is largely maintained even under the action of shear forces due to the joint use of ethylene-vinyl acetate copolymer, antioxidant and amine.

Die Herstellung der erfindungsgemäß verwendeten Copolymerisate ist bekannt. Sie erfolgt durch Polymerisation des Monomerengemisches bei Temperaturen von 100 bis 350 °C und Drücken von 1000 bis 8000 bar in Gegenwart von Radikale bildenden Initiatoren. Die Polymerisation erfordert nicht die Anwesenheit eines Lösungsmittels als Reaktionsmedium.The preparation of the copolymers used according to the invention is known. It is carried out by polymerizing the monomer mixture at temperatures from 100 to 350 ° C. and pressures from 1000 to 8000 bar in the presence of free radical initiators. The polymerization does not require the presence of a solvent as the reaction medium.

Das als Comonomer verwendete Ethylen wird in der für Polymerisationsreaktionen üblichen Reinheit von mindestens 99% eingesetzt.The ethylene used as comonomer is used in the purity customary for polymerization reactions of at least 99%.

Die Polymerisation läuft in Gegenwart katalytischer Mengen Radikale bildender Initiatoren, zum Beispiel Sauerstoff, in Mengen von 2 bis 250 Mol.-ppm, bezogen auf das zu polymerisierende Ethylen, ab. Neben Sauerstoff können als Initiatoren auch Peroxide, wie tert.-Butylperbenzoat, Dilauroylperoxid, Di-tert.-Butylperoxid oder Azo-buttersäuredinitril in Mengen von 2 bis 200 Mol.-ppm, bezogen auf das Ethylen, verwendet werden. Die Einstellung der Molekulargewicht erfolgt mit Moderatoren, wie aliphatischen Alkoholen und/oder Carbonylverbindungen, gesättigten, ungesättigten oder chlorierten Kohlenwasserstoffen oder Wasserstoff. In Abhängigkeit vom gewünschten Molekulargewicht werden sie in Konzentrationen zwischen 2 bis 25 Vol.-%, bezogen auf Ethylen, angewandt. Die erfindungsgemäß eingesetzten Copolymerisate haben Molekulargewichte von 500 bis 25 000, bestimmt nach K. Rast. Ber. 550, 1922.The polymerization takes place in the presence of catalytic amounts of free radical initiators, for example oxygen, in amounts of 2 to 250 mol.ppm, based on the ethylene to be polymerized. In addition to oxygen, peroxides such as tert-butyl perbenzoate, dilauroyl peroxide, di-tert-butyl peroxide or azo-butyrononitrile in amounts of 2 to 200 mol.ppm, based on the ethylene, can also be used as initiators. The molecular weight is adjusted using moderators, such as aliphatic alcohols and / or carbonyl compounds, saturated, unsaturated or chlorinated hydrocarbons or hydrogen. Depending on the desired molecular weight, they are used in concentrations of between 2 and 25% by volume, based on ethylene. The copolymers used according to the invention have molecular weights of 500 to 25,000, determined according to K. Rast. Ber. 550, 1922.

Unter Antioxidantien im Sinne der Erfindung werden Substanzen verstanden, die unerwünschte, durch Sauerstoffeinwirkung bedingte Vorgänge bei Kunststoffen verhindern oder hemmen. Es handelt sich hierbei um organische Verbindungen von sehr verschiedener Struktur. Sie gehören im wesentlichen zur Gruppe der Amine und Phenole und umfassen auch Schwefel- und Phosphorverbindungen. Ihnen ist gemeinsam, dass sie auf unterschiedliche Weise in den Antioxidationsmechanismus eingreifen. In der Hauptsache werden sie dabei als Radikalfänger, als Peroxidzersetzer, als Metallionen-Desaktivatoren und als UV-Absorber wirksam. Als besonders geeignete Antioxidantien erwiesen sich 2,6-Di-tert.-buty!-4-methylphenol, 4,4'-Thio-bis-(-methyi-6-tert.-butyi- phenol), Bis-(3,3-bis(4'hydroxy-3'-tert.-butylphenyl)-butansäure)-glykolester und Tri(3,4-di-tert.-butyl- phenylphosphit). Eine allgemeine Übersicht findet sich in Ullmanns Encyclopädie der technischen Chemie, 4. Auflage, Band 8, Seiten 19 ff (1974); über Antioxidantien für Kunststoffe in demselben Werk, Band 15, Seite 253 ff (1978).Antioxidants in the sense of the invention are understood to mean substances which prevent or inhibit undesirable processes caused by the action of oxygen in plastics. These are organic compounds of very different structures. They essentially belong to the group of amines and phenols and also include sulfur and phosphorus compounds. What they have in common is that they intervene in the antioxidant mechanism in different ways. They are mainly used as free radical scavengers, as peroxide decomposers, as metal ion deactivators and as UV absorbers. 2,6-Di-tert.-buty! -4-methylphenol, 4,4'-thio-bis - (- methyl-6-tert.-butyi-phenol), bis- (3, 3-bis (4'hydroxy-3'-tert-butylphenyl) butanoic acid) glycol ester and tri (3,4-di-tert-butylphenyl phosphite). A general overview can be found in Ullmann's Encyclopedia of Technical Chemistry, 4th edition, volume 8, pages 19 ff (1974); on antioxidants for plastics in the same work, volume 15, page 253 ff (1978).

Geeignete Amine entsprechen der allgemeinen Formel R-NH2, wobei R für gesättigte oder einfach ungesättigte, geradkettige oder verzweigte Kohlenwasserstoffreste mit 8 bis 18 Kohlenstoffatomen steht.Suitable amines correspond to the general formula R-NH 2 , where R represents saturated or monounsaturated, straight-chain or branched hydrocarbon radicals having 8 to 18 carbon atoms.

Mit Erfolg wurden auch Fettamin-Oxethylate eingesetzt, die durch Umsetzung von Aminen R-NH2 (wobei R die vorstehende Bedeutung hat) mit Ethylenoxid erhalten werden. Sie entsprechen der allgemeinen Formel: wobei x + y = n die Zahl der angelagerten Ethylenoxidmoleküle ist, n ist eine ganze Zahl zwischen 5 und 25. Fettamin-Oxethylate der genannten Zusammensetzung sind unter dem Namen RGenamin im Handel (Hersteller: Hoechst AG).Fatty amine oxethylates were also successfully used, which are obtained by reacting amines R-NH 2 (where R has the above meaning) with ethylene oxide. They correspond to the general formula: where x + y = n is the number of attached ethylene oxide molecules, n is an integer between 5 and 25. Fatty amine oxethylates of the composition mentioned are commercially available under the name R Genamin (manufacturer: Hoechst AG).

Besonders bewährt hat es sich, die Konzentration des Antioxidans auf Werte von 0,025 bis 0,1 Gew.-% und die Konzentration des Amins auf Werte von 0,005 bis 0,5 Gew.-% einzustellen. Die vorstehenden Prozentangaben beziehen sich jeweils auf das Rohöl.It has proven particularly useful to adjust the concentration of the antioxidant to values from 0.025 to 0.1% by weight and the concentration of the amine to values from 0.005 to 0.5% by weight. The above percentages relate to the crude oil.

Die Zugabe von Copolymerisat, Antioxidans und gegebenenfalls Amin zum Rohöl kann getrennt, in Form der gelösten oder ungelösten Substanzen erfolgen. Man kann die Komponenten aber auch in einem Lösungsmittel auflösen und diese Lösung dem Rohöl zudosieren. Als Lösungsmittel werden aromatische Kohlenwasserstoffe bevorzugt, zum Beispiel Aromatengemische, die unter dem Namen Solventnaphtha oder Schwerbenzol im Handel sind.The copolymer, antioxidant and optionally amine can be added to the crude oil separately, in the form of the dissolved or undissolved substances. You can also dissolve the components in a solvent and add this solution to the crude oil. Aromatic hydrocarbons are preferred as solvents, for example aromatic mixtures which are commercially available under the name solvent naphtha or heavy benzene.

Im folgenden wird die Erfindung durch eine Reihe Beispiele näher erläutert, ohne sie in ihrem Schutzumfang zu beschränken.The invention is explained in more detail below by means of a number of examples, without restricting its scope.

BeispieleExamples

Zur Prüfung der Wirksamkeit der erfindungsgemäßen Additive wird der Pour Point von Montrose-und Beatrice-Nordsee-Rohöl vor und nach Scherbelastung ermittelt. Die Messung erfolgt nach DIN ISO 3016.To test the effectiveness of the additives according to the invention, the pour point of Montrose and Beatrice North Sea crude is determined before and after shear stress. The measurement is carried out according to DIN ISO 3016.

100 ml Rohöl werden mit 0,02 Gew.-% (bezogen auf das Rohöl) eines Ethylen/Vinylacetat-Copolymerisats mit 26 bis 30 Gew.-% Vinylacetat (als 28 bis 30 Gew.-%ige Lösung in Solventnaphtha) versetzt. Die Scherung des jeweiligen Prüföls erfolgt durch Rühren mit 10000 Umdrehungen/min über einen Zeitraum von 6 Stunden bei Raumtemperatur (Ultra Turrax T 45 der Firma Janke & Kunkel).100 ml of crude oil are mixed with 0.02% by weight (based on the crude oil) of an ethylene / vinyl acetate copolymer with 26 to 30% by weight of vinyl acetate (as a 28 to 30% by weight solution in solvent naphtha). The respective test oil is sheared by stirring at 10,000 revolutions / min over a period of 6 hours at room temperature (Ultra Turrax T 45 from Janke & Kunkel).

Die Ergebnisse der Untersuchungen sind in der folgenden Tabelle zusammengestellt.

Figure imgb0001
The results of the tests are summarized in the following table.
Figure imgb0001

Claims (1)

  1. The use of 0.005 to 0.5% by weight (related to the crude oil) of a copolymer consisting of 65 to 80% by weight of ethylene and 35 to 20% by weight of vinyl acetate, together with 0.01 to 1.0% by weight (related to the crude oil) of an antioxidant and 0.001 to 1.0% by weight (related to the crude oil) of an amine as a flow improver for crude oil.
EP85115541A 1984-12-15 1985-12-06 Use of ethylene copolymers as crude-oil additives Expired EP0186009B1 (en)

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DE3445811 1984-12-15
DE19843445811 DE3445811A1 (en) 1984-12-15 1984-12-15 USE OF ETHYLENE COPOLYMERISATES AS A RAW OIL ADDITIVE

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GB9200694D0 (en) * 1992-01-14 1992-03-11 Exxon Chemical Patents Inc Additives and fuel compositions

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US2696427A (en) * 1951-01-26 1954-12-07 Du Pont Stabilized fuel oil compositions
NL134313C (en) * 1966-06-01
FR2067558A5 (en) * 1969-11-07 1971-08-20 Universal Oil Prod Co N-substituted alkoxyamines in resin-curing - catalyst systems
GB1413323A (en) * 1972-07-06 1975-11-12 United Lubricants Ltd Diesel fuel additives
US3850587A (en) * 1973-11-29 1974-11-26 Chevron Res Low-temperature flow improves in fuels
GB1473155A (en) * 1974-09-04 1977-05-11
US3955940A (en) * 1975-01-06 1976-05-11 Exxon Research And Engineering Company Middle distillate petroleum oils containing cold flow improving additives
DE2862158D1 (en) * 1977-12-20 1983-02-17 Ici Plc Crude oil having improved cold flow properties
US4405825A (en) * 1981-10-30 1983-09-20 Union Oil Company Of California Pour point reduction of syncrude
US4564460A (en) * 1982-08-09 1986-01-14 The Lubrizol Corporation Hydrocarbyl-substituted carboxylic acylating agent derivative containing combinations, and fuels containing same

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