EP0045342B1 - Fuel composition with particular fluidity at low temperatures - Google Patents

Fuel composition with particular fluidity at low temperatures Download PDF

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Publication number
EP0045342B1
EP0045342B1 EP80890087A EP80890087A EP0045342B1 EP 0045342 B1 EP0045342 B1 EP 0045342B1 EP 80890087 A EP80890087 A EP 80890087A EP 80890087 A EP80890087 A EP 80890087A EP 0045342 B1 EP0045342 B1 EP 0045342B1
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Prior art keywords
fuel composition
ethylene
vinyl acetate
weight
copolymer
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EP80890087A
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German (de)
French (fr)
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EP0045342A1 (en
Inventor
Wolfgang Dr. Nette
Hiltrud Dr. Täubert
Leo Dipl. Chem. Schlemmer
Manfred Dipl. Chem. Gebauer
Gerhard Uhlig
Jürgen Dr. Welker
Lutz Dipl. Chem. Döscher
Konrad Dr. Bormann
Günter Dipl. Ing. Stirnal
Heinz Dipl. Chem. Limmer
Annelies Dipl. Chem. Gerstmeyer
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Leuna Werke GmbH
Leuna Werke Walter Ulbright Germany VEB
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Leuna Werke GmbH
Leuna Werke Walter Ulbright Germany VEB
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Application filed by Leuna Werke GmbH, Leuna Werke Walter Ulbright Germany VEB filed Critical Leuna Werke GmbH
Priority to EP80890087A priority Critical patent/EP0045342B1/en
Priority to DE8080890087T priority patent/DE3065883D1/en
Priority to AT80890087T priority patent/ATE5599T1/en
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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

Abstract

1. Fuel composition with improved flow at low temperatures, consisting of heating fuels or engine fuels with a boiling range of above 453 K and of ethylene copolymers, characterized in that the fuel composition contains 0.001 to 0.5 % by weight of an ethylene copolymer having a number-average means molecular weight of 500 to 5,000, preferably 1,000 to 3,500, and a comonomer content of 25 to 60 % by weight, which copolymer has 3 to 10 long-chain branches per 10**4 C atoms.

Description

Die vorliegende Erfindung bezieht sich auf Heiz-oder Treibstoffmischungen, insbesondere Mitteldestillate, mit einem Zusatz an Polymeren, der das Fliessvermögen der Mischung bei tiefen Temperaturen verbessert.The present invention relates to heating or fuel mixtures, in particular middle distillates, with an addition of polymers which improves the fluidity of the mixture at low temperatures.

Die in den Mitteldestillaten (Siedebereich 453-673 K bzw. 180 bis 400° C) enthaltenen Paraffine sind kirstallisationsfähig und fallen bei tiefen Temperaturen aus, agglomerieren allmählich zu grösseren Gebilden und setzen schliesslich die Fliess-und Pumpfähigkeit sowie die Filtrierbarkeit herab, so dass die Verwendung der Öle eingeschränkt wird.The paraffins contained in the middle distillates (boiling range 453-673 K or 180 to 400 ° C) are suitable for installation and precipitate at low temperatures, gradually agglomerate into larger structures and ultimately reduce the flow and pumpability as well as the filterability, so that the Use of the oils is restricted.

Es ist seit langem bekannt, dass eine Reihe von Polymeren, wie chlorierte Polyäthylene, Äthylen/ Propylen- Mischpolymere, Copolymere aus Äthylen mit Akrylestern oder Vinylestern, flüssige Kondensationsprodukte aus mehrfach ungesättigten Monoestern und aromatischen Kohlenwasserstoffen, Polyolefine, Polyestergemische, Polymethacrylate, Säureamide, akylierte Napthene allein oder im Gemisch, das Kälteverhalten von Mitteldestillaten und damit den Gebrauchswert erfiohen (H. Gondermann und H.H. Giere, "Chemiker Zeitung", 97 [1973] 9 S.462-469).It has long been known that a number of polymers, such as chlorinated polyethylene, ethylene / propylene mixed polymers, copolymers of ethylene with acrylic esters or vinyl esters, liquid condensation products from polyunsaturated monoesters and aromatic hydrocarbons, polyolefins, polyester mixtures, polymethacrylates, acid amides, acylated naphthenes alone or in a mixture, the low-temperature behavior of middle distillates and thus the utility value (H. Gondermann and HH Giere, " Chemiker Zeitung", 97 [1973] 9 pp. 462-469).

Der Einsatz von Äthylencopolymeren, speziell Äthylen/Vinylacetat-Copolymeren, als Fliessverbesserer für Mitteldestillate in dem Konzentrationsbereich 0,001 bis 1 Masse-%, der mittleren Molekularmasse von 500 bis 50040 und dem Comonomerengehalt von 1 bis 60 Masse-% ist allgemein bekannt (DE-C Nr. 1147799, DE-A Nr. 1162630, DE-B Nr. 1645873, DE-A Nr.2227786).The use of ethylene copolymers, especially ethylene / vinyl acetate copolymers, as flow improvers for middle distillates in the concentration range 0.001 to 1 mass%, the average molecular mass from 500 to 50040 and the comonomer content from 1 to 60 mass% is generally known (DE-C No. 1147799, DE-A No. 1162630, DE-B No. 1645873, DE-A No. 2227786).

Es ist auch bekannt (DE-B Nr. 1914756), als Fliessverbesserer Copolymere zu benutzen, in denen bei der Herstellung durch die Begrenzung der Polymerisationstemperatur der Grad der Verzweigungen eingestellt wird. Bei diesen Ver-' zweigungen handelt es sich um sogenannte Kurzkettenverzweigungen oder Äthylenseitenketten. Diese bilden sich an dem Hauptkettenmolekül nach dem sogenannten backbiting- Mechanismus und enthalten 4 bis 6 C-Atome.It is also known (DE-B No. 1914756) to use copolymers as flow improvers in which the degree of branching is set during production by limiting the polymerization temperature. Two conditions for these encryption 'is so-called short-chain branches or Äthylenseitenketten. These form on the main chain molecule according to the so-called backbiting mechanism and contain 4 to 6 carbon atoms.

Diese Art von Verzweigungen beeinträchtigt die Wirksamkeit von Fliessverbessern, da sie zum einen den Einbau des Polymeren in die Störstellen des Wachskristallgitters erschweren und zum anderen das weitere Anwachsen von Wachskristallen (Abschirmeffekt) nicht genügend verhindern.This type of branching affects the effectiveness of flow improvers because, on the one hand, they make it more difficult for the polymer to be incorporated into the impurities in the wax crystal lattice and, on the other hand, they do not sufficiently prevent wax crystals from growing further (shielding effect).

Es ist weiterhin bekannt, dass man Mitteldestillate mit verbessertem Tieftemperaturverhalten erhalten kann, wenn man sie mit einer Kombination von

  • a) 1 bis 20 Gew.-Teilen einer als Kristallisationsverbesserer oder Impfkeime wirksamen polymeren Verbindung, und
  • b) 1 bis 99 Gew.-Teilen einer als Wachskristallisationnhemmer wirksamen polymeren Verbindung
    versetzt (DE-A Nr. 2206719).
It is also known that middle distillates with improved low-temperature behavior can be obtained by combining them with
  • a) 1 to 20 parts by weight of a polymeric compound effective as a crystallization improver or seed, and
  • b) 1 to 99 parts by weight of a polymeric compound effective as a wax crystallization inhibitor
    offset (DE-A No. 2206719).

Im allgemeinen weisen die als Impfkeime eingesetzten Verbindungen ein Molekulargewicht von 500 bis 30000 und vorzugsweise 500 bis 10000 und die als Kristallisationshemmer eingesetzten Verbindungen ein Molekulargewicht von 1200 bis 20000 und vorzugsweise 1200 bis 6000 auf. In den bevorzugten Ausführungsformen werden verschiedene Copolymere aus Äthylen und Vinylacetat eingesetzt, wobei das Verhältnis zwischen der Konzentration des Vinylacetates und dem Molekulargewicht des Copolymeren besonders wichtig ist.In general, the compounds used as inoculants have a molecular weight of 500 to 30,000 and preferably 500 to 10,000 and the compounds used as crystallization inhibitors have a molecular weight of 1200 to 20,000 and preferably 1200 to 6000. In the preferred embodiments, various copolymers of ethylene and vinyl acetate are used, the ratio between the concentration of the vinyl acetate and the molecular weight of the copolymer being particularly important.

Aufgabe der Erfindung ist die Verbesserung des Kälteverhaltens von Heiz- oder Treibstoffmischungen durch Zusatz spezieller Polymerer, durch deren Gegenwart das Fliessvermögen und die Pumpfähigkeit bei tiefen Temperaturen verbessert werden.The object of the invention is to improve the low-temperature behavior of heating or fuel mixtures by adding special polymers, the presence of which improves the fluidity and pumpability at low temperatures.

Zur Lösung der Aufgabe wird erfindungsgemäss bei einer Kraftstoffzusammensetzung mit verbessertem Fliessvermögen bei tiefen Temperaturen bestehend aus Heiz- oder Treibstoffen mit einem Siedebereich oberhalb von 453 K und aus Äthylencopolymeren vorgeschlagen, dass die Kraftstoffzusammensetzung 0,001 bis 0,5 Gew.-% eines Äthylencopolymeren mit einer mittleren Molekularmasse (Zahlenmittel) von 500 bis 5000, vorzugsweise 1000 bis 3500, und einem Comonomerengehalt von 25 bis 60 Gew.-% enthält, 3 bis 10 Langkettenverzweigungen pro 104 C-Atome besitzt.To achieve the object, it is proposed according to the invention for a fuel composition with improved fluidity at low temperatures consisting of heating or propellants with a boiling range above 453 K and of ethylene copolymers that the fuel composition has 0.001 to 0.5% by weight of an ethylene copolymer with a medium Molecular mass (number average) of 500 to 5000, preferably 1000 to 3500, and a comonomer content of 25 to 60 wt .-% contains, has 3 to 10 long chain branches per 10 4 carbon atoms.

Die Langkettenverzweigungen besitzen eine Kettenlänge von mindestens 100 C-Atomen und sind teilweise beträchtlich länger. Damit unterscheiden sie sich deutlich von den Kurzkettenverzweigungen, die bei anderen Fliessverbesserern bekannt sind und vorzugsweise aus Methylgruppen bestehen. Es haben sich besonders ÄthylenVinylacetat-Copolymere mit einer mittleren Molekularmasse (Zahlenmittel) von 1000 bis 3500, einem Vinylacetatgehalt von 35 bis 50 Gew.-% und 4 bis 8 Langkettenverzweigungen pro 104 C-Atome als geeignet erwiesen. Diese Copolymeren zeigen ein gutes Lösungsverhalten in den meisten aromatischen Lösungsmitteln, so dass die Zusatzstoffe sowohl in Form eines Konzentrates in einem aromatischen Lösungsmittel bzw. Lösungsmittelgemisch als auch direkt in den Kraftstoff gegeben werden können.The long chain branches have a chain length of at least 100 carbon atoms and are sometimes considerably longer. This clearly distinguishes them from the short chain branches known from other flow improvers, which preferably consist of methyl groups. Ethylene-vinyl acetate copolymers with an average molecular weight (number average) of 1000 to 3500, a vinyl acetate content of 35 to 50% by weight and 4 to 8 long-chain branches per 10 4 carbon atoms have proven to be particularly suitable. These copolymers show good dissolution behavior in most aromatic solvents, so that the additives can be added both in the form of a concentrate in an aromatic solvent or solvent mixture and directly in the fuel.

Besonders vorteilhaft ist, dass diese Copolymeren durch wiederholtes Abkühlen und Erwärmen kaum eine Beeinträchtigung der Wirkung zeigen, da sie ein gutes Lösungsverhalten zeigen.It is particularly advantageous that these copolymers show hardly any impairment of the action due to repeated cooling and heating, since they show good dissolution behavior.

Aufgrund ihres Aufbaus und ihrer Zusammensetzung verfügen die erfindungsgemäss eingesetzten Äthylen/Vinylacetat-Copolymeren sowohl über die notwendigen Polymethylensegmente, die von den Vinylacetateinheiten unterbrochen werden, sich aber an den Störstellen in das Gitter der Wachskristalle einbauen können, als auch über voluminöse Gruppen aufgrund der Langkettenverzweigungen, die den weiteren Einbau der in den Mitteldestillaten enthaltenen Paraffine an den Störstellen der Gitter erschweren und damit das weitere Kristallwachstum vermindern.Due to their structure and composition, the ethylene / vinyl acetate copolymers used according to the invention have both the necessary polymethylene segments which are interrupted by the vinyl acetate units but can be incorporated into the lattice of the wax crystals at the defects, and also have voluminous groups due to the long chain branches, the further installation of the paraf contained in the middle distillates fine at the defects of the lattice and thus reduce further crystal growth.

Mikrofotografien von unter extremen Bedingungen abgeschiedenen Wachskristallen des unbeschnittenen Ausgangsdieselkraftstoffes und des mit den erfindungsgemässen Äthylen/Vinylacetat-Copolymeren versetzten Dieselkraftstoffes zeigten, dass durch den Zusatz des Äthylen/Vinylacetat-Copolymeren die Abscheidung der Wachse als schwammartige Masse oder plättchenförmige Kristalle wesentlich verschoben wird, so dass die Grösse der sich bildenden Wachskristalle um 40 bis 60% verkleinert wird.Photomicrographs of wax crystals deposited under extreme conditions of the untrimmed starting diesel fuel and of the diesel fuel mixed with the ethylene / vinyl acetate copolymers according to the invention showed that the addition of the ethylene / vinyl acetate copolymer significantly displaced the deposition of the waxes as a sponge-like mass or platelet-shaped crystals, so that the size of the wax crystals that form is reduced by 40 to 60%.

Nach einer besonderen Ausführungsform der Erfindung kann das verwendete Äthylen/Vinylacetat-Copolymere durch Veresterung mit 2- Äthylhexylacryl-, Isobutylacryl-, Laurylacryl- und Phthalsäure, mit weiteren grossen, raumfüllenden Substituenten versehen sein.According to a particular embodiment of the invention, the ethylene / vinyl acetate copolymer used can be provided with further large, space-filling substituents by esterification with 2-ethylhexyl acrylic, isobutyl acrylic, lauryl acrylic and phthalic acid.

Beispiel 1example 1

Es wurde ein Dieselkraftstoff mit einem Siedebereich von 473 bis 628 K, einem Stockpunkt von 261 K und einem CFPP von 266 K eingesetzt. Diesem Kraftstoff wurde ein Äthylen/Vinylacetat-Copolymeres mit einem Vinylacetatgehalt von 38 Masse-% einer zahlenmittleren Molekularmassevon 2650 und 5 Langkettenverzweigungen pro 104 C-Atomen in Form einer Lösung zugegeben. Dabei wurden folgende Ergebnisse erhalten:

Figure imgb0001
A diesel fuel with a boiling range of 473 to 628 K, a pour point of 261 K and a CFPP of 266 K was used. To this fuel, an ethylene / vinyl acetate copolymer having a vinyl acetate content of 38 mass% of a number average molecular weight of 2650 and 5 long chain branches per 10 4 C atoms was added in the form of a solution. The following results were obtained:
Figure imgb0001

Beispiel 2Example 2

Es wurde ein Dieselkraftstoff mit einem Siedebereich von 471 bis 615 K, einem Stockpunkt von 269 K und einem CFPP von 267 K eingesetzt. Diesem Kraftstoff wurde ein Äthylen/Vinylacetat-Copolymeres mit einem Vinylacetatgehalt von 44 Masse-%, einer zahlenmittleren Molukularmasse von 1870 und 8 Langkettenverzweigungen pro 104 C-Atomen in Form einer Lösung zugegeben. Dabei wurden folgende Ergebnisse erhalten:

Figure imgb0002
A diesel fuel with a boiling range of 471 to 615 K, a pour point of 269 K and a CFPP of 267 K was used. An ethylene / vinyl acetate copolymer with a vinyl acetate content of 44% by mass, a number average molecular weight of 1870 and 8 long chain branches per 10 4 C atoms was added to this fuel in the form of a solution. The following results were obtained:
Figure imgb0002

Beispiel 3Example 3

Einem Heizöl HE-D (nach TGL 3667) mit einem Stockpunkt von 286 K wurde ein Äthylen/Vinylacetat-Copolymeres mit einem Vinylacetatgehalt von 44 Masse-%, einer zahlenmittleren Molekularmasse von 1870 und 8 Langkettenverzweigungen pro 104 C-Atomen zugesetzt. Es wurden dabei folgende Ergebnisse erhalten:

Figure imgb0003
A heating oil HE-D (according to TGL 3667) with a pour point of 286 K was added an ethylene / vinyl acetate copolymer with a vinyl acetate content of 44 mass%, a number average molecular mass of 1870 and 8 long chain branches per 10 4 C atoms. The following results were obtained:
Figure imgb0003

Claims (4)

1. Fuel composition with improved flow at low temperatures, consisting of heating fuels or engine fuels with a boiling range of above 453 K and of ethylene copolymers, characterized in that the fuel composition contains 0.001 to 0.5% by weight of an ethylene copolymer having a number-average mean molecular weight of 500 to 5,000, preferably 1,000 to 3,500, and a comonomer content of 25 to 60% by weight, which copolymer has 3 to 10 long- chain branches per 104 C atoms.
2. Fuel composition according to claim 1, characterized in that it contains vinyl esters, preferably vinyl acetate, as comonomers.
3. Fuel composition according to claims 1 and 2, characterized in that the ethylene/vinyl acetate copolymer is provided with additional large, bulky substituents by esterification with 2-ethyl- hexylacrylic acid, isobutylacrylic acid, laurylacrylic acid and phthalic acid.
4. Fuel composition according to claims 1, 2 and 3, characterized in that there may be added to the mixture further compounds which act as cold-
Figure imgb0004
filter plugging point improvers, antioxidants, residual inhibitors or sludge inhibitors, and sludge dispersants.
EP80890087A 1980-07-31 1980-07-31 Fuel composition with particular fluidity at low temperatures Expired EP0045342B1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP80890087A EP0045342B1 (en) 1980-07-31 1980-07-31 Fuel composition with particular fluidity at low temperatures
DE8080890087T DE3065883D1 (en) 1980-07-31 1980-07-31 Fuel composition with particular fluidity at low temperatures
AT80890087T ATE5599T1 (en) 1980-07-31 1980-07-31 FUEL COMPOSITION WITH IMPROVED FLUIDITY AT LOW TEMPERATURES.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP80890087A EP0045342B1 (en) 1980-07-31 1980-07-31 Fuel composition with particular fluidity at low temperatures

Publications (2)

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EP0045342A1 EP0045342A1 (en) 1982-02-10
EP0045342B1 true EP0045342B1 (en) 1983-12-14

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Families Citing this family (10)

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Publication number Priority date Publication date Assignee Title
CA1263663A (en) * 1984-12-06 1989-12-05 Joseph Fischer Terpolymers of ethylene, vinyl acetate and isobutylene useful as pour point depressants in distillate oils
JPS6270488A (en) * 1985-09-24 1987-03-31 Mitsubishi Petrochem Co Ltd Additive of fuel oil and fuel oil improved in flowability
GB9213827D0 (en) * 1992-06-30 1992-08-12 Exxon Chemical Patents Inc Oil additives and compositions
GB9213909D0 (en) * 1992-06-30 1992-08-12 Exxon Chemical Patents Inc Oil additives and compositions
GB9213904D0 (en) * 1992-06-30 1992-08-12 Exxon Chemical Patents Inc Oil additives and compositions
GB9213870D0 (en) 1992-06-30 1992-08-12 Exxon Chemical Patents Inc Oil additives and compositions
GB9417667D0 (en) * 1994-09-02 1994-10-19 Exxon Chemical Patents Inc Oil additives, compositions and polymers for use therein
GB9417670D0 (en) * 1994-09-02 1994-10-19 Exxon Chemical Patents Inc Oil additives, compositions and polymers for use therein
US5681359A (en) * 1996-10-22 1997-10-28 Quantum Chemical Corporation Ethylene vinyl acetate and isobutylene terpolymer as a cold flow improver for distillate fuel compositions
US6495495B1 (en) 1999-08-20 2002-12-17 The Lubrizol Corporation Filterability improver

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GB968462A (en) * 1961-12-21 1964-09-02 Monsanto Chemicals Reactive resins containing unsaturated groups
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
GB1314855A (en) * 1970-06-17 1973-04-26 Monsanto Chemicals Lubricating oil compositions containing viscosity index improvers
US3887610A (en) * 1971-12-09 1975-06-03 Exxon Research Engineering Co Emulsion polymerization of ethylene with chain transfer agents to form copolymers
EP0003489B1 (en) * 1977-12-20 1983-01-12 Imperial Chemical Industries Plc Crude oil having improved cold flow properties

Non-Patent Citations (1)

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Title
Brauer et al.:"Untersuchung zur Charakterisierung von Äthylen-Vinylazetat-Kopolymeren durch Gelchromatographie, Viskosimetrie und osmotisch Messungen", Plaste und Kautschuk 24, Seiten 630-635 (1977) *

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EP0045342A1 (en) 1982-02-10
ATE5599T1 (en) 1983-12-15

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