EP1444312B1 - Additives for low-sulfur fuels - Google Patents

Additives for low-sulfur fuels Download PDF

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Publication number
EP1444312B1
EP1444312B1 EP02795062A EP02795062A EP1444312B1 EP 1444312 B1 EP1444312 B1 EP 1444312B1 EP 02795062 A EP02795062 A EP 02795062A EP 02795062 A EP02795062 A EP 02795062A EP 1444312 B1 EP1444312 B1 EP 1444312B1
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Prior art keywords
fuel composition
fuel
diesel
additives
formula
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German (de)
French (fr)
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EP1444312A2 (en
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Frank Bongardt
Jürgen Röder
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Cognis IP Management GmbH
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Cognis Deutschland GmbH and Co KG
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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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • 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
    • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols

Definitions

  • the present application relates to low sulfur fuel compositions containing certain alkoxylated esters as additives.
  • Fuels based on crude oil or crude oil products usually contain small amounts of sulfur.
  • crude oils usually contain between 2 and 0.5% by weight of sulfur.
  • sulfur dioxide which is oxidized in the air to sulfuric acid and then as acid rain can cause significant environmental damage.
  • the sulfur not only has adverse effects, but also serves as a lubricant improver in the small amounts in which it is usually present, which is quite desirable in many industrial applications, for example as a fuel for internal combustion engines. Therefore, the use of low-sulfur fuels often leads to problems with the friction of the corresponding fired engine parts.
  • additives are usually added to the fuels.
  • low-sulfur propellants preferably diesel fuels
  • esters of carboxylic acids and alcohols containing more than 1 carbon atom are added to adjust the corresponding coefficients of friction.
  • esters of carboxylic acids having 2 to 50 carbon atoms and polyols are used.
  • the present application therefore relates to fuel compositions containing more than 50% by weight of diesel, gasoline, kerosene or other hydrocarbons which are liquid at room temperature, these fuel compositions being an additive of the formula (I) R-COO- (C n H 2n -O) k -H in which R is a mono- or polyunsaturated alkylene radical having 17 carbon atoms and n is 2 and k is a number between 0.5 and 3, in amounts of 0.001 to 0.1 wt .-%, containing Provided that the fuel composition has a sulfur content of at most 0.2 wt .-%.
  • the fuel compositions according to the invention are further distinguished by the fact that the sulfur content max. 0.2 wt .-% based on the fuel composition.
  • fuels are understood to mean all energy-supply operating materials whose free combustion energy is converted into mechanical work. These include all types of liquid at room temperature and normal pressure motor and aviation fuels.
  • Motor fuels eg for car or truck engines, usually contain hydrocarbons, for example gasoline or higher-boiling petroleum fractions.
  • Diesel fuels are flame retardant mixtures of liquid hydrocarbons which are used as fuels for constant pressure or burner engines (diesel engines) and consist predominantly of paraffins with admixtures of olefins, naphthenes and aromatic hydrocarbons. Their composition is inconsistent and depends especially on the manufacturing method. Diesel is obtained, for example, from gas oil by cracking or from tars obtained from the carbonization of lignite or coal.
  • Typical products have a density between 0.83 and 0.88 g / cm 3 , a boiling point between 170 and 360 ° C and flash points between 70 and 100 ° C.
  • Diesel fuels Diesel oils for stationary installations and for marine engines have a similar composition as heavy fuel oil, which is used for cars, buses and the like. Lorries correspond to the fuel oil EL.
  • a key factor in the usability of diesel is its ignitability, for the quantitative indication of which the cetane number (CZ) was introduced.
  • CZ cetane number
  • Zündwillmaschine the property of a motor fuel is called lighter od in a working on the diesel engine engine or harder to ignite.
  • pressure u. Temp. A treatment period (ignition delay) to detectable combustion required.
  • Quality Ignition of a fuel means favorable starting behavior u. smooth running of the diesel engine as a result of a short preparation period or small ignition delay; at large ignition delay occurs the well-known "nailing" ohrentechnisch in appearance.
  • the requirements for diesel are CZ 20-40 for low-speed engines, CZ> 45 for small and high-speed engines. Also desirable are a low pour point, low levels of non-combustible and sooty substances, and low sulfur content.
  • the fuel compositions of the present invention include diesel, gasoline, kerosene or other room temperature liquid hydrocarbons, such as hexane or pentane. Particularly preferred are those fuel compositions containing diesel fuel. In principle, it is also possible to provide fuel compositions according to the present invention containing mixtures of, for example, gasoline and kerosene in any proportions.
  • the additives of formula (I) are known per se alkoxylated carboxylic acid ester. It is one of the essential knowledge of the present invention that it must be unsaturated carboxylic acids having 19 to 17 carbon atoms in the alkyl chain. Particular preference is given to a compound of the formula (I) in which R is an unsaturated radical having 17 carbon atoms, the oleic acid being particularly preferred according to the invention.
  • the alkoxylation ie the reaction of the acid with ethylene oxide and / or propylene oxide, is carried out in a manner known per se. Reference may be made, for example, to US Pat. No. 5,326,891 or US Pat. No.
  • a peculiarity of the present additives according to formula (I) is that the number of alkoxide units per molecule is strictly limited and preferably 1, ie a part of acid and a part of the alkoxide have come to the reaction. Since no uniform products are obtained even by the use of modern catalysts, there are regularly mixtures of various alkoxylated compounds, which is expressed in the partially fractional number k of the present formula (I). Particular preference is given to those compounds of the formula (I) in which n is 2, ie ethoxylated fatty acids. The number k should preferably be in the range from 0.5 to 1.5, very particular preference is given to those compounds of the formula (I) in which k is 1.
  • Fuel compositions contain the additives of formula (I), preferably in amounts of from 0.001 to 0.01% by weight, and preferably from 0.001 to 0.005% by weight. Particular preference is given to oil esters with 1 part of ethylene oxide.
  • an extremely low sulfur content ie. H. a sulfur content in the range of 0.005 to max. 0.05% by weight.
  • Very particularly preferred is the use in fuel compositions whose sulfur content is less than 0.005 wt .-%.
  • the aromatic content of the claimed fuel composition should be less than 25% by volume, and preferably less than 20% by volume.
  • Particularly preferred are those fuel compositions which are free of aromatics.
  • diesel If diesel is selected as the actual fuel, it should have a cetane index of less than 50 and preferably less than 45.
  • the cetane number of the diesel should be less than 50.
  • the addition of the compounds of the formula (I) leads to good broad-spectrum action of the corresponding fuels, the HFRR value at 60 ° C. preferably being 600 ⁇ m, preferably not more than 500 ⁇ m and in particular 400 ⁇ m or less.
  • the HFRR method High Frequency Reciprocating Rig is known to measure the friction of fuels in use. A description of the details can be found in ISO / TC22 / SC7 / WG6 / N188.
  • the fuels of the present invention may contain other conventional additives, e.g. Cetane number improvers (nitric or nitric acid esters), corrosion inhibitors, flow improvers, surfactants (keep the injectors clean), defoamers, or smoke reducers are added as.
  • Cetane number improvers nitric or nitric acid esters
  • corrosion inhibitors e.g., corrosion inhibitors, flow improvers, surfactants (keep the injectors clean), defoamers, or smoke reducers are added as.
  • the concomitant use for example of fatty alcohols and / or alkoxylated fatty alcohols and / or alkanolamides and / or derivatives thereof is preferably excluded.
  • Very particular preference is given to those fuel compositions which contain only additives according to formula (I) for reducing the stimulus.
  • the HFRR value of the non-added diesel was 591 .mu.m, for the additive added with GMO diesel, a value of 529 .mu.m was measured, while the additive according to the invention reached an HFRR value of 500 .mu.m.

Description

Die vorliegende Anmeldung betrifft schwefelarme Treibstoffzusammensetzungen, die bestimmte alkoxylierte Ester als Additive enthalten.The present application relates to low sulfur fuel compositions containing certain alkoxylated esters as additives.

Treibstoffe auf Basis von Erdöl bzw. Erdölfolgeprodukten enthalten in aller Regel geringe Anteile von Schwefel. Üblicherweise enthalten Rohöle zwischen 2 und 0,5 Gew.-% an Schwefel. Bei der Verbrennung von derartig schwefelhaltigen Treibstoffen entsteht als Verbrennungsprodukt Schwefeldioxid, welches in der Luft bis zur Schwefelsäure oxidiert wird und danach als saurer Regen erhebliche Umweltschäden verursachen kann. Es besteht daher seit langem ein Bedarf, den Schwefelgehalt in Erdölprodukten, insbesondere in Treibstoffen zu reduzieren. Allerdings hat der Schwefel nicht nur nachteilige Wirkungen, sondern dient auch in den geringen Mengen, in denen er üblicherweise vorliegt, als Schmierstoffverbesserer, was bei vielen technischen Anwendungen, beispielsweise als Treibstoff für Verbrennungsmotoren, durchaus erwünscht ist. Daher führt der Einsatz von schwefelarmen Treibstoffen häufig zu Problemen mit der Reibung der entsprechend gefeuerten Maschinenteile. Um die Anforderungen an den Umweltschutz und geringe Emission auf der einen Seite und die Anforderung an die entsprechenden Reibwerte auf der anderen Seite zu erfüllen, werden den Treibstoffen üblicherweise Additive zugesetzt. Aus der WO 94/17160 ist bekannt, dass schwefelarme Treibstoffe, vorzugsweise Dieseltreibstoffe, mit Estern aus Carbonsäuren und Alkoholen, die mehr als 1 Kohlenstoffatom enthalten, versetzt werden, um die entsprechenden Reibwerte einzustellen. Vorzugsweise werden Ester von Carbonsäuren mit 2 bis 50 Kohlenstoffatomen und Polyolen eingesetzt. Dabei stellt sich allerdings das Problem, dass bei geringem Zusatz von teuren Additiven die Schmierwirkung der so erhaltenen Treibstoffe nicht immer den Anforderungen genügt. Es war daher die Aufgabe der vorliegenden Erfindung, ein Additiv für schwefelarme Treibstoffe zu finden, welches bereits in geringen Mengen eine ausreichende Verbesserung der Schmierwirkung von Treibstoffen ermöglicht.Fuels based on crude oil or crude oil products usually contain small amounts of sulfur. Usually, crude oils contain between 2 and 0.5% by weight of sulfur. In the combustion of such sulfur-containing fuels is produced as a combustion product sulfur dioxide, which is oxidized in the air to sulfuric acid and then as acid rain can cause significant environmental damage. There has therefore long been a need to reduce the sulfur content in petroleum products, especially in fuels. However, the sulfur not only has adverse effects, but also serves as a lubricant improver in the small amounts in which it is usually present, which is quite desirable in many industrial applications, for example as a fuel for internal combustion engines. Therefore, the use of low-sulfur fuels often leads to problems with the friction of the corresponding fired engine parts. In order to meet the requirements of environmental protection and low emissions on the one hand and the requirement for the corresponding coefficients of friction on the other hand, additives are usually added to the fuels. From WO 94/17160 it is known that low-sulfur propellants, preferably diesel fuels, with esters of carboxylic acids and alcohols containing more than 1 carbon atom, are added to adjust the corresponding coefficients of friction. Preferably, esters of carboxylic acids having 2 to 50 carbon atoms and polyols are used. However, there is the problem that with little addition of expensive additives, the lubricating effect of the fuels thus obtained does not always meet the requirements. It was therefore the object of the present invention to find an additive for low-sulfur propellants, which enables a sufficient improvement in the lubricity of fuels even in small amounts.

Gegenstand der vorliegenden Anmeldung sind daher Treibstoffzusammensetzungen, enthaltend mehr als 50 Gew.-% Diesel, Benzin, Kerosin oder andere bei Raumtemperatur flüssige Kohlenwasserstoffe, wobei diese Treibstoffzusammensetzungen ein Additiv der Formel (I)

        R-COO-(CnH2n-O)k-H

in der R für einen ein- oder mehrfach ungesättigten Alkylenrest mit 17 C-Atomen steht und n für 2 und k einen Zahl zwischen 0,5 und 3 steht, in Mengen von 0,001 bis 0,1 Gew.-% enthält, mit der Maßgabe, daß die Treibstoffzusammensetzung einen Schwefelgehalt von maximal 0,2 Gew.-% aufweist.The present application therefore relates to fuel compositions containing more than 50% by weight of diesel, gasoline, kerosene or other hydrocarbons which are liquid at room temperature, these fuel compositions being an additive of the formula (I)

R-COO- (C n H 2n -O) k -H

in which R is a mono- or polyunsaturated alkylene radical having 17 carbon atoms and n is 2 and k is a number between 0.5 and 3, in amounts of 0.001 to 0.1 wt .-%, containing Provided that the fuel composition has a sulfur content of at most 0.2 wt .-%.

Die erfindungsgemäßen Treibstoffzusammensetzungen zeichnen sich weiterhin dadurch aus, dass der Schwefelgehalt max. 0,2 Gew.-% bezogen auf die Treibstoffzusammensetzung beträgt.The fuel compositions according to the invention are further distinguished by the fact that the sulfur content max. 0.2 wt .-% based on the fuel composition.

Unter Treibstoffen werden im Rahmen dieser Anmeldung alle energieliefemden Betriebsstoffe, deren freie Verbrennungsenergie in mechanische Arbeit umgesetzt wird, verstanden. Dazu zählen alle Arten von bei Raumtemperatur und Normaldruck flüssigen Motor- und Flugkraftstoffe. Motorkraftstoffe, z.B. für PKW- oder LKW-Motoren, enthalten in der Regel Kohlenwasserstoffe, z.B. Benzin- oder höhersiedende Erdöl-Fraktionen.
Dieseltreibstoffe sind schwer entflammbare Gemische von flüssigen Kohlenwasserstoffen, die als Kraftstoffe für Gleichdruck- od. Brennermotoren (Dieselmotoren) verwendet werden und überwiegend aus Paraffinen mit Beimengungen von Olefinen, Naphthenen und aromatischen Kohlenwasserstoffen bestehen. Ihre Zusammensetzung ist uneinheitlich und hängt besonders von der Herstellungs-Methode ab. Diesel wird beispielsweise aus Gasöl durch Cracken oder aus Teeren, die bei der Schwelung von Braun- oder Steinkohle gewonnen werden, erhalten. Übliche Produkte haben eine Dichte zwischen 0,83 und 0,88 g/cm3, einen Siedepunkt zwischen 170 und 360 °C und Flammpunkte zwischen 70 und 100 °C. Dieselkraftstoffe. Dieselöle für stationäre Anlagen und für Schiffsmotoren haben eine ähnliche Zusammensetzung wie schweres Heizöl, die für PKW, Autobusse u. Lastkraftwagen entsprechen dem Heizöl EL.For the purposes of this application, fuels are understood to mean all energy-supply operating materials whose free combustion energy is converted into mechanical work. These include all types of liquid at room temperature and normal pressure motor and aviation fuels. Motor fuels, eg for car or truck engines, usually contain hydrocarbons, for example gasoline or higher-boiling petroleum fractions.
Diesel fuels are flame retardant mixtures of liquid hydrocarbons which are used as fuels for constant pressure or burner engines (diesel engines) and consist predominantly of paraffins with admixtures of olefins, naphthenes and aromatic hydrocarbons. Their composition is inconsistent and depends especially on the manufacturing method. Diesel is obtained, for example, from gas oil by cracking or from tars obtained from the carbonization of lignite or coal. Typical products have a density between 0.83 and 0.88 g / cm 3 , a boiling point between 170 and 360 ° C and flash points between 70 and 100 ° C. Diesel fuels. Diesel oils for stationary installations and for marine engines have a similar composition as heavy fuel oil, which is used for cars, buses and the like. Lorries correspond to the fuel oil EL.

Bei der Verbrennung im Dieselmotor wird Luft in den Zylinder gesogen, durch starke Verdichtung (Verdichtungsgrad 14:1 bis 25:1) auf 550-900 °C erhitzt, wodurch sich ein Strahl von eingespritztem Diesel von selbst entzündet und bei einer Verbrennungstemperatur von 1500-2200 °C einen Verbrennungsdruck von 50-80 bar erreicht, durch den der Kolben bewegt und Arbeit geleistet wird. Man verbraucht zur Verbrennung von 1 l Diesel im Dieselmotor 13 m3 Luft; die freiwerdende Verbrennungsenergie beträgt etwa 42 000 kJ/kg.During combustion in the diesel engine, air is drawn into the cylinder, heated to 550-900 ° C by heavy compression (degree of compaction 14: 1 to 25: 1), whereby a jet of injected diesel ignites spontaneously and at a combustion temperature of 1500 2200 ° C reaches a combustion pressure of 50-80 bar, through which the piston moves and work is done. It consumes 13 m3 of air to burn 1 l of diesel in the diesel engine; the released combustion energy is about 42 000 kJ / kg.

Ein wesentlicher Faktor für die Verwendbarkeit von Diesel ist ihre Zündwilligkeit, für deren quantitative Angabe die Cetan-Zahl (CZ) eingeführt wurde. Als Zündwilligkeit wird die Eigenschaft eines Motorkraftstoffs bezeichnet, in einem nach dem Dieselprinzip arbeitenden Motor leichter od. schwerer zu zünden. Hierzu ist bei jedem Kraftstoff außer Zerstäubung, Druck u. Temp. eine Aufbereitungszeitspanne (Zündverzug) bis zur feststellbaren Verbrennung erforderlich. Gute Zündwilligkeit eines Kraftstoffs bedeutet günstiges Startverhalten u. ruhigen Lauf des Dieselmotors infolge kurzer Aufbereitungszeitspanne bzw. kleinen Zündverzugs; bei großem Zündverzug tritt das bekannte "Nageln" ohrenfällig in Erscheinung. Die Anforderungen an Diesel sind bei langsamlaufenden Motoren CZ 20-40, bei kleinen und schnellaufenden CZ >45. Erwünscht sind ferner ein niedriger Stockpunkt, geringer Gehalt an nicht verbrennbaren und rußenden Substanzen und ein niedriger Schwefel-Gehalt.A key factor in the usability of diesel is its ignitability, for the quantitative indication of which the cetane number (CZ) was introduced. As Zündwilligkeit the property of a motor fuel is called lighter od in a working on the diesel engine engine or harder to ignite. For each fuel except atomization, pressure u. Temp. A treatment period (ignition delay) to detectable combustion required. Quality Ignition of a fuel means favorable starting behavior u. smooth running of the diesel engine as a result of a short preparation period or small ignition delay; at large ignition delay occurs the well-known "nailing" ohrenfällig in appearance. The requirements for diesel are CZ 20-40 for low-speed engines, CZ> 45 for small and high-speed engines. Also desirable are a low pour point, low levels of non-combustible and sooty substances, and low sulfur content.

Die erfindungsgemäßen Treibstoffzusammensetzungen enthalten Diesel, Benzin, Kerosin oder andere bei Raumtemperatur flüssige Kohlenwasserstoffe, beispielsweise Hexan oder Pentan. Besonders bevorzugt sind solche Treibstoffzusammensetzungen, die als Treibstoff Diesel enthalten. Prinzipiell ist es auch möglich, Treibstoffzusammensetzungen gemäß der vorliegenden Erfindung bereitzustellen, die Mischungen aus beispielsweise Benzin und Kerosin in beliebigen Verhältnissen enthalten.The fuel compositions of the present invention include diesel, gasoline, kerosene or other room temperature liquid hydrocarbons, such as hexane or pentane. Particularly preferred are those fuel compositions containing diesel fuel. In principle, it is also possible to provide fuel compositions according to the present invention containing mixtures of, for example, gasoline and kerosene in any proportions.

Die Additive gemäß Formel (I) stellen an sich bekannte alkoxylierte Carbonsäureester dar. Es ist eine der wesentlichen Kenntnisse der vorliegenden Erfindung, dass es sich dabei um ungesättigte Carbonsäuren mit 19 bis 17 C-Atomen in der Alkylkette handeln muß. Besonders bevorzugt ist eine Verbindungen der Formel (I) in der R für ein ungesättigter Rest mit 17 C-Atomen steht, besonders bevorzugt ist erfindungsgemäß die Ölsäure. Die Alkoxylierung, also die Umsetzung der Säure mit Ethylenoxid und/oder Propylenoxid, erfolgt in an sich bekannter Art und Weise. Hier sei beispielsweise auf die US 5,326,891 oder die US 5,292,910 verwiesen, die die Synthese derartiger Verbindungen beschreibt, wobei die Säuren in Gegenwart ausgewählter Hydrotalcidkatalysatoren mit den Alkoxiden zu den gewünschten alkoxylierten Verbindungen umgesetzt werden. Einschlägig ist hierbei auch die Offenbarung der WO 98/25878, die ein Verfahren zur Synthese dieser kurzethoxylierten Fettsäuren durch Umsetzung der Fettsäuren in Gegenwart von Alkanolaminen beschreibt.The additives of formula (I) are known per se alkoxylated carboxylic acid ester. It is one of the essential knowledge of the present invention that it must be unsaturated carboxylic acids having 19 to 17 carbon atoms in the alkyl chain. Particular preference is given to a compound of the formula (I) in which R is an unsaturated radical having 17 carbon atoms, the oleic acid being particularly preferred according to the invention. The alkoxylation, ie the reaction of the acid with ethylene oxide and / or propylene oxide, is carried out in a manner known per se. Reference may be made, for example, to US Pat. No. 5,326,891 or US Pat. No. 5,292,910, which describes the synthesis of such compounds, wherein the acids are reacted with the alkoxides in the presence of selected hydrotalcite catalysts to give the desired alkoxylated compounds. Also relevant here is the disclosure of WO 98/25878, which describes a process for the synthesis of these short-ethoxylated fatty acids by reacting the fatty acids in the presence of alkanolamines.

Eine Besonderheit der vorliegenden Additive gemäß Formel (I) ist darin zu sehen, dass die Anzahl der Alkoxideinheiten pro Molekül streng begrenzt ist und vorzugsweise 1 beträgt, d. h. ein Teil Säure und ein Teil des Alkoxids sind zur Reaktion gelangt. Da auch durch Einsatz moderner Katalysatoren keine einheitlichen Produkte erhalten werden, liegen regelmäßig Mischungen verschiedener alkoxylierter Verbindungen vor, was sich in der teilweise gebrochenen Zahl k der vorliegenden Formel (I) ausdrückt. Besonders bevorzugt sind solche Verbindungen der Formel (I), in denen n für 2 steht, also ethoxylierte Fettsäuren. Die Zahl k sollte vorzugsweise im Bereich von 0,5 bis 1,5 liegen, ganz besonders bevorzugt sind solche Verbindungen der Formel (I), in denen k für 1 steht. Die erfindungsgemäßen Treibstoffzusammensetzungen enthalten die Additive der Formel (I), vorzugsweise in Mengen von 0,001 bis 0,01 Gew.-% und vorzugsweise 0,001 bis 0,005 Gew.-%. Als besonders bevorzugt sind Ölsäureester mit 1 Teil Ethylenoxid anzusehen.A peculiarity of the present additives according to formula (I) is that the number of alkoxide units per molecule is strictly limited and preferably 1, ie a part of acid and a part of the alkoxide have come to the reaction. Since no uniform products are obtained even by the use of modern catalysts, there are regularly mixtures of various alkoxylated compounds, which is expressed in the partially fractional number k of the present formula (I). Particular preference is given to those compounds of the formula (I) in which n is 2, ie ethoxylated fatty acids. The number k should preferably be in the range from 0.5 to 1.5, very particular preference is given to those compounds of the formula (I) in which k is 1. The invention Fuel compositions contain the additives of formula (I), preferably in amounts of from 0.001 to 0.01% by weight, and preferably from 0.001 to 0.005% by weight. Particular preference is given to oil esters with 1 part of ethylene oxide.

Besonders bevorzugt ist der Einsatz der erfindungsgemäßen Additive gemäß Formel (I) in solchen Treibstoffzusammensetzungen, die einen extrem niedrigen Schwefelgehalt, d. h. ein Schwefelgehalt im Bereich von 0,005 bis max. 0,05 Gew.% enthalten. Ganz besonders bevorzugt ist der Einsatz in Treibstoffzusammensetzungen, deren Schwefelgehalt unter 0,005 Gew.-% liegt. Der Aromatengehalt der beanspruchten Treibstoffzusammensetzung sollte kleiner als 25 Vol.-% und vorzugsweise weniger als 20 Vol.-% betragen. Ganz besonders bevorzugt sind Treibstoffzusammensetzungen, die weniger als 5 Vol.% an Aromaten enthalten. Insbesondere bevorzugt sind solche Treibstoffzusammensetzungen, die frei von Aromaten sind.Particularly preferred is the use of the additives according to the invention according to formula (I) in such fuel compositions which have an extremely low sulfur content, ie. H. a sulfur content in the range of 0.005 to max. 0.05% by weight. Very particularly preferred is the use in fuel compositions whose sulfur content is less than 0.005 wt .-%. The aromatic content of the claimed fuel composition should be less than 25% by volume, and preferably less than 20% by volume. Very particular preference is given to fuel compositions which contain less than 5% by volume of aromatics. Particularly preferred are those fuel compositions which are free of aromatics.

Sofern Diesel als eigentlicher Treibstoff ausgewählt ist, sollte dieser einen Cetan-Index von kleiner als 50 und vorzugsweise kleiner als 45 aufweisen. Die Cetan-Nummer des Diesels sollte kleiner als 50 sein.If diesel is selected as the actual fuel, it should have a cetane index of less than 50 and preferably less than 45. The cetane number of the diesel should be less than 50.

Der Zusatz der Verbindungen gemäß Formel (I) führt zu einer guten Breitwirkung der entsprechenden Treibstoffe, wobei der HFRR-Wert bei 60 °C vorzugsweise 600 µm, bevorzugt höchstens 500 µm und insbesondere 400 µm oder weniger beträgt. Die HFRR-Methode (High Frequency Reciprocating Rig) dient bekanntermaßen der Messung der Reibung von Treibstoffen im Gebrauch. Eine Beschreibung der Einzelheiten findet sich in der ISO/TC22/SC7/WG6/N188.The addition of the compounds of the formula (I) leads to good broad-spectrum action of the corresponding fuels, the HFRR value at 60 ° C. preferably being 600 μm, preferably not more than 500 μm and in particular 400 μm or less. The HFRR method (High Frequency Reciprocating Rig) is known to measure the friction of fuels in use. A description of the details can be found in ISO / TC22 / SC7 / WG6 / N188.

Den erfindungsgemäßen Treibstoffen können weitere übliche Additive, z.B. Cetan-Zahlverbesserer (Salpeter- od. Salpetrigsäureester), Korrosionsinhibitoren, Fließverbesserer, Tenside (halten die Einspritzdüsen sauber), Entschäumer, oder Qualmverminderer als zugesetzt werden.The fuels of the present invention may contain other conventional additives, e.g. Cetane number improvers (nitric or nitric acid esters), corrosion inhibitors, flow improvers, surfactants (keep the injectors clean), defoamers, or smoke reducers are added as.

Bei der Auswahl der Additive für die erfindungsgemäßen Treibstoffzusammensetzungen ist zu beachten, dass die Mitverwendung, beispielsweise von Fettalkoholen und/oder alkoxylierten Fettalkoholen und/oder Alkanolamiden und/oder deren Derivaten vorzugsweise ausgeschlossen ist. Ganz besonders bevorzugt sind solche Treibstoffzusammensetzungen, die zur Reizverminderung nur Additive gemäß Formel (I) enthalten.When selecting the additives for the fuel compositions according to the invention, it should be noted that the concomitant use, for example of fatty alcohols and / or alkoxylated fatty alcohols and / or alkanolamides and / or derivatives thereof is preferably excluded. Very particular preference is given to those fuel compositions which contain only additives according to formula (I) for reducing the stimulus.

Die Verwendung der oben definierten Verbindungen der Formel (I) in Treibstoffen, insbesondere in Dieseltreibstoffen, führt zum einen zu einem ausreichenden Schmierverhalten der Treibstoffe, ohne dass dadurch die nachteiligen ökologischen Konsequenzen wie bei schwefelhaltigen Treibstoffen üblich, in Kauf genommen werden müssen. Weiterhin zeigt sich, dass die erfindungsgemäß additiwierten Treibstoffe ein hervorragendes Kälteverhalten aufweisen und auch bei niedrigen Temperaturen keine Ausflockungen auftreten.The use of the above-defined compounds of formula (I) in fuels, especially in diesel fuels, on the one hand leads to a sufficient lubrication behavior of the fuels, without thereby the adverse environmental consequences as usual in sulfur-containing fuels, must be taken into account. Furthermore, it is found that the propellants added according to the invention have an excellent low-temperature behavior and that no flocculation occurs even at low temperatures.

BeispieleExamples

Es wurde ein erfindungsgemäßer Ölsäureester mit 1 Mol Ethylenoxid pro Mol Fettsäure in seiner Wirkung zur Reibwertverminderung (HFRR) von Diesel geprüft, wobei als Vergleich ein handelsüblicher Glycerinmonoölsäureester (GMO) verwendet wurde. Die Einsatzmenge betrug jeweils 50 ppm des Additivs. Als Referenz wurde der nicht-additiwierte Diesel vermessen.An inventive oleic acid ester with 1 mole of ethylene oxide per mole of fatty acid was tested in its effect for reducing friction (HFRR) of diesel, using as a comparison a commercial Glycerinmonoölsäureester (GMO) was used. The amount used was in each case 50 ppm of the additive. For reference, the non-additive diesel was measured.

Der HFRR-Wert des nicht-additiwierten Diesels betrug 591 µm, für den mit GMO additiwierten Diesel wurde ein Wert von 529 µm gemessen, während das erfindungsgemäße Additiv einen HFRR-Wert von 500 µm erreichte.The HFRR value of the non-added diesel was 591 .mu.m, for the additive added with GMO diesel, a value of 529 .mu.m was measured, while the additive according to the invention reached an HFRR value of 500 .mu.m.

Claims (14)

  1. A fuel composition containing more than 50% by weight of diesel, gasoline, kerosene or other hydrocarbons liquid at room temperature, characterized in that the compositions contain an additive corresponding to formula (I):

            R-COO-(CnH2n-O)k-H     (I)

    where R is a mono- or polyunsaturated alkylene group containing 10 to 17 carbon atoms, n has a value of 2 and k has a value of 0.5 to 3,
    in quantities of 0.001 to 0.1 % by weight, with the proviso that the fuel composition has a sulfur content of at most 0.2% by weight.
  2. A fuel composition as claimed in claim 1, characterized in that it contains compounds of formula (I) where k has a value of 0.5 to 1.5 as additives.
  3. A fuel composition as claimed in claims 1 to 2, characterized in that it contains compounds of formula (I) where k has a value of 1 as additives.
  4. A fuel composition as claimed in claims 1 to 3, characterized in that it contains compounds of formula (I) where R is an unsaturated group containing 17 carbon atoms as additives.
  5. A fuel composition as claimed in claims 1 to 4, characterized in that it contains the additives of formula (I) in quantities of 0.001 to 0.01 % by weight and preferably in quantities of 0.001 to 0.005% by weight.
  6. A fuel composition as claimed in claims 1 to 5, characterized in that the sulfur content of the fuel is in the range from 0.005 to 0.05.
  7. A fuel composition as claimed in claims 1 to 6, characterized in that the sulfur content of the fuel is below 0.005% by weight.
  8. A fuel composition as claimed in claims 1 to 7, characterized in that the content of aromatics is below 25% by volume, preferably below 20% by volume and more particularly below 5% by volume.
  9. A fuel composition as claimed in claims 1 to 8, characterized in that the fuel does not contain any aromatics.
  10. A fuel composition as claimed in claims 1 to 9, characterized in that diesel is selected as the fuel.
  11. A fuel composition as claimed in claim 10, characterized in that the cetane index of the diesel is below 50 and preferably below 45.
  12. A fuel composition as claimed in claims 10 and 11, characterized in that the cetane number of the diesel is below 50.
  13. A fuel composition as claimed in claims 1 to 12, characterized in that the HFRR friction coefficient at 60°C is at most 500 µm.
  14. A fuel composition as claimed in claims 1 to 13, characterized in that the composition is free from fatty alcohols and/or alkoxylated fatty alcohols and/or alkanolamides and/or derivatives thereof.
EP02795062A 2001-11-15 2002-11-06 Additives for low-sulfur fuels Expired - Fee Related EP1444312B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10156024A DE10156024A1 (en) 2001-11-15 2001-11-15 Additives for low sulfur fuels
DE10156024 2001-11-15
PCT/EP2002/012371 WO2003042335A2 (en) 2001-11-15 2002-11-06 Additives for low-sulfur fuels

Publications (2)

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EP1444312A2 EP1444312A2 (en) 2004-08-11
EP1444312B1 true EP1444312B1 (en) 2006-01-18

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US (2) US20040255510A1 (en)
EP (1) EP1444312B1 (en)
CA (1) CA2467394A1 (en)
DE (2) DE10156024A1 (en)
WO (1) WO2003042335A2 (en)

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CN102286299B (en) * 2010-06-21 2016-01-13 周向进 A kind of gasoline products of clean and effective environmental protection

Family Cites Families (11)

* Cited by examiner, † Cited by third party
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DE4010606A1 (en) * 1990-04-02 1991-10-10 Henkel Kgaa USE OF HYDROPHOBIC HYDROTALCITES AS CATALYSTS FOR THE ETHOXYLATION OR PROPOXYLATION
DE4034305A1 (en) * 1990-10-29 1992-04-30 Henkel Kgaa HYDROPHOBIC DOUBLE LAYER HYDROXIDE COMPOUNDS, METHOD FOR THE PRODUCTION AND USE THEREOF AS ALCOXYLATION CATALYSTS
GB2307247B (en) * 1995-11-13 1999-12-29 Ethyl Petroleum Additives Ltd Fuel additive
FR2752850A1 (en) * 1996-08-27 1998-03-06 Inst Francais Du Petrole COMPOSITIONS OF ADDITIVES IMPROVING THE LUBRICATING POWER OF FUELS AND FUELS CONTAINING THEM
US5936107A (en) * 1996-12-09 1999-08-10 Henkel Kommanditgesellschaft Auf Aktien Process for the production of fatty acid polyethylene glycol esters
US6074445A (en) * 1997-10-20 2000-06-13 Pure Energy Corporation Polymeric fuel additive and method of making the same, and fuel containing the additive
FR2772784B1 (en) * 1997-12-24 2004-09-10 Elf Antar France ONCTUOSITY ADDITIVE FOR FUEL
AU1741100A (en) * 1998-11-23 2000-06-13 Pure Energy Corporation Diesel fuel composition
US6017369A (en) * 1998-11-23 2000-01-25 Pure Energy Corporation Diesel fuel composition
US6222082B1 (en) * 1999-09-08 2001-04-24 Leonard Bloom Diesel fuel for use in diesel engine-powered vehicles
AU2002223789B2 (en) * 2000-11-08 2007-03-01 O2 Diesel Europe Limited Fuel composition

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Publication number Publication date
US20040255510A1 (en) 2004-12-23
EP1444312A2 (en) 2004-08-11
US20070144061A1 (en) 2007-06-28
DE10156024A1 (en) 2003-05-28
WO2003042335A2 (en) 2003-05-22
WO2003042335A3 (en) 2003-09-25
CA2467394A1 (en) 2003-05-22
DE50205670D1 (en) 2006-04-06

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