EP0087073B1 - Process for improving fuels for diesel engines - Google Patents

Process for improving fuels for diesel engines Download PDF

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Publication number
EP0087073B1
EP0087073B1 EP83101271A EP83101271A EP0087073B1 EP 0087073 B1 EP0087073 B1 EP 0087073B1 EP 83101271 A EP83101271 A EP 83101271A EP 83101271 A EP83101271 A EP 83101271A EP 0087073 B1 EP0087073 B1 EP 0087073B1
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EP
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Prior art keywords
process according
salts
fuel
carboxylic acids
acids
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EP83101271A
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German (de)
French (fr)
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EP0087073A2 (en
EP0087073A3 (en
Inventor
Manfred Dr. Wildersohn
Werner Dipl.-Chem. Dewin
Bela Dr. Dipl.-Chem. Tihanyi
Jürgen Dr. Dipl.-Chem. Weber
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Wenzel and Weidmann GmbH
Ruhrchemie AG
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Wenzel and Weidmann GmbH
Ruhrchemie AG
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Priority to AT83101271T priority Critical patent/ATE14748T1/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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
    • 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
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00—Engines characterised by air compression and subsequent fuel addition
    • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition

Definitions

  • the present invention relates to a method for improving the combustion of fuels for diesel engines by adding mixtures of salts of organic acids of the lanthanoids and free carboxylic acids.
  • Diesel fuels are more susceptible to soot when burning in engines than petrol.
  • the soot indicates that the combustion process in the engine is incomplete, i. H. the generation of energy from the fuel is not fully used.
  • diesel smoke which u. a. Containing hydrocarbons and carbon monoxide is a major environmental burden. For this reason, efforts have long been made to suppress the formation of soot during the combustion of diesel fuels by adding additives and to ensure that the combustion is as complete as possible.
  • cerium soaps in which an atom of the trivalent cerium is essentially connected to three molecules of a fatty acid, by the action of a carboxylic acid with more than 8 carbon atoms on cerium hydroxide. These compounds are used as drying agents in the field of paints or varnishes and varnishes and, moreover, as combustion aids.
  • organic radical u. a. also as a combustion aid.
  • their main area of application is that of drying agents for paints and varnishes.
  • the invention consists in a method for improving the combustion of fuels for diesel engines with the aid of salts of organic acids. It is characterized in that a mixture of neutral salts of carboxylic acids and metals of atomic number 57 to 71 and free carboxylic acids is added to the fuels.
  • the process according to the invention ie the addition of neutral salts of organic acids of certain metals in combination with free carboxylic acids, leads to a perfect combustion of the diesel fuels without deposits occurring.
  • the soot number which is a measure of the completeness of the combustion of the fuel, is significantly reduced compared to fuels which have not been treated by the method according to the invention. It is particularly important that the carbon monoxide concentration and the nitrogen oxide concentration are considerably reduced by the process according to the invention.
  • the method according to the invention brings a considerable saving in fuel, depending on the speed, of at least 2%.
  • the acceleration time is reduced in the high speed range compared to fuel not provided with additives according to the invention.
  • neutral salts of carboxylic acids are understood to be those salts in which all valences of the metal are saturated by carboxylic acid residues. It is possible to use salts of a wide variety of carboxylic acids. Both aliphatic and aromatic carboxylic acids are suitable. Salts of aliphatic monocarboxylic acids, in particular aliphatic monocarboxylic acids with 4 to 10 carbon atoms, have proven successful.
  • carboxylic acids can be branched one or more times, in addition to isooctanoic acid, particular importance is attached to the carboxylic acids which have the branching in the a position, such as 2-ethylbutyric acid and 2-ethylhexanoic acid.
  • the above-mentioned isooctanoic acid means the Cg-carboxylic acid mixture containing predominantly isomeric dimethylhexanoic acid. It is obtained by hydroformylation of an industrial heptene mixture and subsequent oxidation of the hydroformylation product.
  • Carboxylic acids obtained by the addition of carbon monoxide and water to olefins after the cooking process have also proven successful. These include e.g. B. pivalic acid, 2,2-dimethylvaleric acid and neohexanoic acid.
  • Uniform salts can be used in the process according to the invention, ie salts which contain only one cation. It is also possible to use salts which contain different metals, or else mixtures of different salts. This includes mixtures of salts of the same metals and different acids from salts of different metals and the same acids and of salts of different metals and different acids. It is particularly expedient to use salts which are derived from the naturally occurring cerium earths. Cerite earths are minerals that contain the elements of atomic number 57 to 71, ie lanthanum and the so-called lanthanoids varying amounts included. Salts derived from the mineral bastnäsite, which is available in large quantities, have proven particularly useful.
  • the salts are prepared in a known manner. So one can start from the solutions of the nitrates of metals, which are reacted with the stoichiometric amount of the sodium salts of the carboxylic acids.
  • the sodium salts of the carboxylic acids are advantageously used as a solution in an organic solvent in which the reaction product, ie. H. the lanthanoid salts, is soluble. They are obtained from the solution by distilling off the solvent, further cleaning operations are not necessary.
  • the nitrates of the metals are obtained directly by digestion with nitric acid.
  • free carboxylic acids are used as a further component of the mixtures added to the diesel fuel.
  • all carboxylic acids that are soluble in the fuel for diesel engines can be used. It has proven very useful to use as carboxylic acids those acids that are present as acid residues in the salts that are part of the mixture.
  • the mixture contains 0.1 to 2 moles and in particular 0.2 to 1.5 moles of free carboxylic acids. It is particularly useful to use 0.5 to 1.0 mol of free carboxylic acid.
  • the mixtures of organic acid salts of lanthanides and free carboxylic acids used in the process according to the invention for improving combustion are added to the fuels for diesel engines in amounts such that their concentration is 5 to 200 mg of lanthanide metal or metal mixture per kg of fuel. Concentrations of 10 to 50 and based on native oils concentrations of 10 to 100 mg lanthanide metal or metal mixture per kg fuel have proven particularly useful in fuels based on mineral oil.
  • the diesel fuel used in the experiments below contains 15 mg Ce per kg as Ce (III) -2-ethylhexanoate / 2-ethylhexanoic acid mixture.
  • the basis for the tests is the ECE-15 driving cycle, which is used for exhaust gas tests in accordance with European regulations and for fuel consumption measurements in accordance with DIN 70 030.
  • the following engine is used:
  • Fuel consumption measurements are carried out at 50 km / h, 90 km / h and 120 km / h, whereby 20 measured values are averaged and the standard deviation is taken into account.
  • the measurement series is carried out with diesel fuel plus additive compared to diesel fuel without additive. With diesel fuel with additive, there is a minimum consumption of at least achieved. The maximum savings are well over 2%.
  • the influence of the additive on the acceleration time can be seen in the higher speed range as a decrease in the acceleration times, starting at 1,000 revolutions / min with a full throttle. up to 4,500 revolutions. Here, too, an average of 20 measured values is used.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Output Control And Ontrol Of Special Type Engine (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

In order to improve the combustion of diesel engine fuels, mixtures of neutral salts of carboxylic acids and metals of Atomic Nos. 57 to 71 and free carboxylic acids are added thereto.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Verbesserung der Verbrennung von Kraftstoffen für Dieselmotoren durch Zusatz von Gemischen aus Salzen organischer Säuren der Lanthanoide und freier Carbonsäuren.The present invention relates to a method for improving the combustion of fuels for diesel engines by adding mixtures of salts of organic acids of the lanthanoids and free carboxylic acids.

Dieselkraftstoffe neigen bei der Verbrennung in Motoren stärker zur Rußbildung als Ottokraftstoffe. Der Ruß zeigt an, daß der Verbrennungsprozeß im Motor nur unvollständig abläuft, d. h. die Energiegewinnung aus dem Kraftstoff nicht voll genutzt wird. Abgesehen von der schlechten Ausnutzung des Kraftstoffes stellt Dieselqualm, der u. a. Kohlenwasserstoffe und Kohlenmonoxid enthält, eine starke Umweltbelastung dar. Aus diesem Grunde bemüht man sich schon seit langem, durch Zusatz von Additiven die Rußbildung bei der Verbrennung von Dieselkraftstoffen zu unterdrücken und eine möglichst vollständige Verbrennung sicherzustellen.Diesel fuels are more susceptible to soot when burning in engines than petrol. The soot indicates that the combustion process in the engine is incomplete, i. H. the generation of energy from the fuel is not fully used. Apart from the poor use of the fuel, diesel smoke, which u. a. Containing hydrocarbons and carbon monoxide is a major environmental burden. For this reason, efforts have long been made to suppress the formation of soot during the combustion of diesel fuels by adding additives and to ensure that the combustion is as complete as possible.

Es ist bereits bekannt, Cerseifen, in welchen ein Atom des dreiwertigen Cers im wesentlichen mit drei Molekülen einer Fettsäure verbunden ist, durch Einwirkung einer Carbonsäure mit mehr als 8 Kohlenstoffatomen auf Cerhydroxid herzustellen. Diese Verbindungen werden als Trockenstoffe auf dem Gebiet der Farben bzw. Lacke und Firnisse und darüber hinaus als Verbrennungshilfsmittel eingesetzt.It is already known to manufacture cerium soaps, in which an atom of the trivalent cerium is essentially connected to three molecules of a fatty acid, by the action of a carboxylic acid with more than 8 carbon atoms on cerium hydroxide. These compounds are used as drying agents in the field of paints or varnishes and varnishes and, moreover, as combustion aids.

Nach der DE-A-27 29 365 verwendet man Cersalze von organischen Säuren, von Sulfonsäuren oder von Phosphorsäuren, die durch ein organisches Radikal substituiert sind, u. a. auch als Verbrennungshilfsmittel. Ihr Hauptanwendungsgebiet ist jedoch das der Trockenstoffe für Farben und Lacke.According to DE-A-27 29 365 cerium salts of organic acids, of sulfonic acids or of phosphoric acids, which are substituted by an organic radical, u. a. also as a combustion aid. However, their main area of application is that of drying agents for paints and varnishes.

Die vorgenannten Verbindungen erfüllen nicht alle Voraussetzungen, die man an ein gutes Verbrennungshilfsmittel für Dieselkraftstoffe stellt. Insbesondere ihre Löslichkeit im Dieselkraftstoff befriedigt in keiner Weise. Daher ist es unmöglich, die für eine weitgehende Verbrennung des Kraftstoffes erforderliche katalytische Wirkung sicherzustellen, so daß schädliche Ablagerungen in wesentlichen Teilen des Motors, insbesondere im Verbrennungsraum, auftreten. Schwefel und phosphorhaltige Salze bilden darüber hinaus unerwünschte Verbrennungsprodukte, die zu Emissionsproblemen führen. Schließlich sind die bekannten Verbrennungshilfsmittel mit anderen, dem Kraftstoff zugefügten Additiven nicht oder nur in begrenztem Maße verträglich, so daß zusätzliche Ablagerungen begünstigt werden.The aforementioned compounds do not meet all the requirements that are placed on a good combustion aid for diesel fuels. In particular, their solubility in diesel fuel is in no way satisfactory. It is therefore impossible to ensure the catalytic effect required for extensive combustion of the fuel, so that harmful deposits occur in essential parts of the engine, particularly in the combustion chamber. Sulfur and phosphorus-containing salts also form undesirable combustion products that lead to emission problems. Finally, the known combustion aids are incompatible or only to a limited extent compatible with other additives added to the fuel, so that additional deposits are favored.

Es bestand daher die Aufgabe, für die Verbesserung der Verbrennung von Dieselkraftstoffen solche Zusätze zu entwickeln, die die aufgezeigten Nachteile nicht besitzen.It was therefore the task of developing additives for the improvement of the combustion of diesel fuels which do not have the disadvantages shown.

Die Erfindung besteht in einem Verfahren zur Verbesserung der Verbrennung von Kraftstoffen für Dieselmotoren mit Hilfe von Salzen organischer Säuren. Es ist dadurch gekennzeichnet, daß den Kraftstoffen ein Gemisch aus Neutralsalzen von Carbonsäuren und Metallen der Ordnungszahl 57 bis 71 und freien Carbonsäuren zugesetzt wird.The invention consists in a method for improving the combustion of fuels for diesel engines with the aid of salts of organic acids. It is characterized in that a mixture of neutral salts of carboxylic acids and metals of atomic number 57 to 71 and free carboxylic acids is added to the fuels.

Es hat sich gezeigt, daß das erfindungsgemäße Verfahren, also der Zusatz von Neutralsalzen organischer Säuren bestimmter Metalle in Verbindung mit freien Carbonsäuren, zu einer einwandfreien Verbrennung der Dieselkraftstoffe führt, ohne daß Ablagerungen auftreten. Überdies wird die Rußzahl, die ein Maß für die Vollständigkeit der Verbrennung des Kraftstoffes ist, gegenüber Kraftstoffen, die nicht nach dem erfindungsgemäßen Verfahren behandelt wurden, deutlich reduziert. Von besonderer Bedeutung ist, daß die Kohlenmonoxidkonzentration und die Stickoxidkonzentration durch das erfindungsgemäße Verfahren erheblich herabgesetzt wird. Schließlich hat sich gezeigt, daß gegenüber Maßnahmen, die zur Verbesserung der Verbrennung von Dieselkraftstoffen nach dem Stand der Technik angewandt werden, das erfindungsgemäße Verfahren eine erhebliche Einsparung von Kraftstoff, je nach Geschwindigkeit, von mindestens 2 % bringt. Außerdem wird die Beschleunigungszeit im Vergleich zu nicht entsprechend der Erfindung mit Additiv versehenem Kraftstoff, im hohen Drehzahlbereich erniedrigt.It has been shown that the process according to the invention, ie the addition of neutral salts of organic acids of certain metals in combination with free carboxylic acids, leads to a perfect combustion of the diesel fuels without deposits occurring. In addition, the soot number, which is a measure of the completeness of the combustion of the fuel, is significantly reduced compared to fuels which have not been treated by the method according to the invention. It is particularly important that the carbon monoxide concentration and the nitrogen oxide concentration are considerably reduced by the process according to the invention. Finally, it has been shown that compared to measures which are used to improve the combustion of diesel fuels according to the prior art, the method according to the invention brings a considerable saving in fuel, depending on the speed, of at least 2%. In addition, the acceleration time is reduced in the high speed range compared to fuel not provided with additives according to the invention.

Eine Komponente des Gemisches, das entsprechend der Erfindung Dieselkraftstoffen zugesetzt wird, sind Neutralsalze von Carbonsäuren. Unter Neutralsalzen im Sinne der Erfindung werden solche Salze verstanden, in denen alle Valenzen des metalls durch Carbonsäurereste abgesättigt sind. Es ist möglich, Salze der verschiedensten Carbonsäuren einzusetzen. Geeignet sind sowohl aliphatische als auch aromatische Carbonsäuren. Bewährt haben sich Salze aliphatischer Monocarbonsäuren, insbesondere aliphatischer Monocarbonsäuren mit 4 bis 10 Kohlenstoffatomen. Diese Carbonsäuren können ein- oder mehrfach verzweigt sein, wobei neben Isooctansäure besonders den Carbonsäuren Bedeutung zukommt, die die Verzweigung in a-Stellung aufweisen, wie 2-Ethylbuttersäure und 2-Ethylhexansäure. Unter der vorstehend genannten Isooctansäure versteht man das vorwiegend isomere Dimethylhexansäure enthaltende Cg-Carbonsäuregemisch. Es wird durch Hydroformylierung eines technischen Heptengemisches und anschließende Oxidation des Hydroformylierungsproduktes erhalten. Bewährt haben sich auch solche Carbonsäuren, die durch Anlagerung von Kohlenmonoxid und Wasser an Olefine nach dem Kochverfahren erhalten werden. Hierzu gehören z. B. Pivalinsäure, 2,2-Dimethylvaleriansäure und Neohexansäure.One component of the mixture that is added to diesel fuels in accordance with the invention are neutral salts of carboxylic acids. For the purposes of the invention, neutral salts are understood to be those salts in which all valences of the metal are saturated by carboxylic acid residues. It is possible to use salts of a wide variety of carboxylic acids. Both aliphatic and aromatic carboxylic acids are suitable. Salts of aliphatic monocarboxylic acids, in particular aliphatic monocarboxylic acids with 4 to 10 carbon atoms, have proven successful. These carboxylic acids can be branched one or more times, in addition to isooctanoic acid, particular importance is attached to the carboxylic acids which have the branching in the a position, such as 2-ethylbutyric acid and 2-ethylhexanoic acid. The above-mentioned isooctanoic acid means the Cg-carboxylic acid mixture containing predominantly isomeric dimethylhexanoic acid. It is obtained by hydroformylation of an industrial heptene mixture and subsequent oxidation of the hydroformylation product. Carboxylic acids obtained by the addition of carbon monoxide and water to olefins after the cooking process have also proven successful. These include e.g. B. pivalic acid, 2,2-dimethylvaleric acid and neohexanoic acid.

Nach dem erfindungsgemäßen Verfahren können einheitliche Salze eingesetzt werden, d. h. Salze, die nur ein Kation enthalten. Es ist ferner möglich, Salze zu verwenden, die verschiedene Metalle enthalten, oder aber auch Gemische verschiedener Salze. Dazu gehören Gemische aus Salzen gleicher Metalle und verschiedener Säuren aus Salzen verschiedener Metalle und gleicher Säuren und aus Salzen verschiedener Metalle und verschiedener Säuren. Besonders zweckmäßig ist es, solche Salze zu verwenden, die sich von den natürlich vorkommenden Ceriterden ableiten. Ceriterden sind Mineralien, die die Elemente der Ordnungszahl 57 bis 71, d. h. Lanthan und die sogenannten Lanthanoiden in wechselnden Mengen enthalten. Besonders bewährt haben sich Salze, die sich von dem Mineral Bastnäsit, das in großen Mengen zur Verfügung steht, ableiten.Uniform salts can be used in the process according to the invention, ie salts which contain only one cation. It is also possible to use salts which contain different metals, or else mixtures of different salts. This includes mixtures of salts of the same metals and different acids from salts of different metals and the same acids and of salts of different metals and different acids. It is particularly expedient to use salts which are derived from the naturally occurring cerium earths. Cerite earths are minerals that contain the elements of atomic number 57 to 71, ie lanthanum and the so-called lanthanoids varying amounts included. Salts derived from the mineral bastnäsite, which is available in large quantities, have proven particularly useful.

Die Herstellung der Salze erfolgt in bekannter Weise. So kann man von den Lösungen der Nitrate der Metalle ausgehen, die mit der stöchiometrischen Menge der Natriumsalze der Carbonsäuren umgesetzt werden. Die Natriumsalze der Carbonsäuren gelangen zweckmäßig als Lösung in einem organischen Lösungsmittel zur Anwendung, in dem auch das Reaktionsprodukt, d. h. die Lanthanoidensalze, löslich ist. Sie werden aus der Lösung durch Abdestillieren des Lösungsmittels gewonnen, weitere Reinigungsoperationen entfallen. Die Nitrate der Metalle erhält man bei Einsatz von Mineralien als Ausgangsmaterial direkt durch Aufschluß mit Salpetersäure.The salts are prepared in a known manner. So one can start from the solutions of the nitrates of metals, which are reacted with the stoichiometric amount of the sodium salts of the carboxylic acids. The sodium salts of the carboxylic acids are advantageously used as a solution in an organic solvent in which the reaction product, ie. H. the lanthanoid salts, is soluble. They are obtained from the solution by distilling off the solvent, further cleaning operations are not necessary. When using minerals as the starting material, the nitrates of the metals are obtained directly by digestion with nitric acid.

Als weiterer Bestandteil der dem Dieselkraftstoff zugesetzten Gemische verwendet man erfindungsgemäß freie Carbonsäuren. Grundsätzlich lassen sich alle Carbonsäuren einsetzen, die in dem Kraftstoff für Dieselmotoren löslich sind. Sehr bewährt hat es sich, als Carbonsäuren jene Säuren anzuwenden, die als Säurereste in den Salzen, die Bestandteil des Gemisches sind, vorkommen.According to the invention, free carboxylic acids are used as a further component of the mixtures added to the diesel fuel. Basically, all carboxylic acids that are soluble in the fuel for diesel engines can be used. It has proven very useful to use as carboxylic acids those acids that are present as acid residues in the salts that are part of the mixture.

Bezogen auf ein Mol Salz enthält das Gemisch 0,1 bis 2 Mol und insbesondere 0,2 bis 1,5 Mol freie Carbonsäuren. Ganz besonders zweckmäßig ist es, 0,5 bis 1,0 Mol freie Carbonsäure anzuwenden.Based on one mole of salt, the mixture contains 0.1 to 2 moles and in particular 0.2 to 1.5 moles of free carboxylic acids. It is particularly useful to use 0.5 to 1.0 mol of free carboxylic acid.

Als Kraftstoffe für Dieselmotoren, die nach dem erfindungsgemäßen Verfahren verbessert werden können, kommen nicht nur Mineralöl-Mitteldestillate in Betracht. Mit besonderem Erfolg kann das erfindungsgemäße Verfahren auch auf native Öle angewandt werden, die als Dieselkraftstoffe Verwendung finden. Hierunter werden Pflanzenöle verstanden, zu denen z. B. Olivenöl, Erdnußöl, Sesamöl, Sonnenblumenöl und Rapsöl gehören. Es ist besonders überraschend, daß die neue Arbeitsweise auch auf diese Öle angewendet werden kann, da sie sich in ihrer physikalischen Beschaffenheit und in ihrem chemischen Verhalten grundlegend von Mineralölen unterscheiden. Die Anwendung pflanzlicher Öle im Dieselmotor führt zu erheblichen Problemen, die ihre Ursache in der Lackbildung und in der gegenüber Mineralölen wesentlich höheren Rußbildung haben. Beide Erscheinungen sind darauf zurückzuführen, daß es sich bei den natürlichen Produkten um ungesättigte Verbindungen handelt. Es ist überraschend, daß die neue Arbeitsweise den Einsatz nativer Öle als Kraftstoff für Dieselmotoren erheblich erleichtert.Not only mineral oil middle distillates come into consideration as fuels for diesel engines, which can be improved by the method according to the invention. The method according to the invention can also be applied with particular success to native oils which are used as diesel fuels. Vegetable oils are understood to include z. B. include olive oil, peanut oil, sesame oil, sunflower oil and rapeseed oil. It is particularly surprising that the new way of working can also be applied to these oils since they differ fundamentally from mineral oils in their physical properties and chemical behavior. The use of vegetable oils in the diesel engine leads to considerable problems, which have their cause in the formation of lacquer and in the soot formation, which is much higher than in mineral oils. Both phenomena are due to the fact that the natural products are unsaturated compounds. It is surprising that the new way of working considerably facilitates the use of native oils as fuel for diesel engines.

Die nach dem erfindungsgemäßen Verfahren zur Verbesserung der Verbrennung verwendeten Gemische aus Salzen organischer Säuren der Lanthanoide und freien Carbonsäuren setzt man den Kraftstoffen für Dieselmotoren in solchen Mengen zu, daß ihre Konzentration 5 bis 200 mg Lanthanoidmetall bzw. -Metallgemisch je kg Kraftstoff beträgt. Besonders bewährt haben sich in Kraftstoffen auf Mineralölbasis Konzentrationen von 10 bis 50 und auf Basis nativer Öle Konzentrationen von 10 bis 100 mg Lanthanoidmetall bzw. -Metallgemisch je kg Kraftstoff.The mixtures of organic acid salts of lanthanides and free carboxylic acids used in the process according to the invention for improving combustion are added to the fuels for diesel engines in amounts such that their concentration is 5 to 200 mg of lanthanide metal or metal mixture per kg of fuel. Concentrations of 10 to 50 and based on native oils concentrations of 10 to 100 mg lanthanide metal or metal mixture per kg fuel have proven particularly useful in fuels based on mineral oil.

Versuchetries

Der in den nachstehenden Versuchen eingesetzte Dieselkraftstoff enthält je kg 15 mg Ce als Ce(III)-2-ethylhexanoat/2-Ethylhexansäure-Gemisch.The diesel fuel used in the experiments below contains 15 mg Ce per kg as Ce (III) -2-ethylhexanoate / 2-ethylhexanoic acid mixture.

Basis für die Untersuchungen ist der ECE-15 Fahrzyklus, der für die Abgasuntersuchungen gemäß den euroäischen Vorschriften und für Kraftstoffverbrauchsmessungen gemäß DIN 70 030 eingesetzt wird. Folgender Motor wird verwendet :

Figure imgb0001
The basis for the tests is the ECE-15 driving cycle, which is used for exhaust gas tests in accordance with European regulations and for fuel consumption measurements in accordance with DIN 70 030. The following engine is used:
Figure imgb0001

Kraftstoffverbrauchsmessungen werden bei 50 km/h, 90 km/h und 120 km/h vorgenommen, wobei jeweils 20 Messwerte gemittelt und die Standardabweichung berücksichtigt wird. Die Messreihe wird mit Dieselkraftstoff plus Additiv im Vergleich zu Dieselkraftstoff ohne Additiv durchgeführt. Beim Dieselkraftstoff mit Additiv wird ein Minderverbrauch von mindestens

Figure imgb0002
erzielt. Die maximalwerte der Einsparung liegen deutlich über 2 %.Fuel consumption measurements are carried out at 50 km / h, 90 km / h and 120 km / h, whereby 20 measured values are averaged and the standard deviation is taken into account. The measurement series is carried out with diesel fuel plus additive compared to diesel fuel without additive. With diesel fuel with additive, there is a minimum consumption of at least
Figure imgb0002
 achieved. The maximum savings are well over 2%.

Der Einfluß der Additivierung auf die Beschleunigungszeit zeigt sich im höheren Drehzahlbereich als Abnahme der Beschleunigungszeiten, die bei voller Drossel, ausgehend von 1 000 Umdrehungen/Min. bis 4 500 Umdrehungen, gemessen werden. Hier wird ebenfalls aus 20 Messwerten gemittelt.The influence of the additive on the acceleration time can be seen in the higher speed range as a decrease in the acceleration times, starting at 1,000 revolutions / min with a full throttle. up to 4,500 revolutions. Here, too, an average of 20 measured values is used.

Bei den Abgasmessungen werden Kohlenmonoxid, Kohlendioxid, Kohlenwasserstoffe und Stickoxide in Abhängigkeit von der Drehzahl bestimmt. Die erhaltenen Werte sind auf Menge in der Zeiteinheit (g/h) und Menge je Leistung (g/kWh) berechnet. Sowohl bei Straßenvollast (Tabellen 1 und 2), als auch bei Straßenteillast (Tabellen 3 und 4), ist der Vorteil des inhibierten Dieselkraftstoffs zu erkennen.

Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
 In the exhaust gas measurements, carbon monoxide, carbon dioxide, hydrocarbons and nitrogen oxides are determined as a function of the engine speed. The values obtained are calculated in terms of quantity in the time unit (g / h) and quantity per output (g / kWh). The advantage of the inhibited diesel fuel can be seen both at full road load (Tables 1 and 2) and at partial road load (Tables 3 and 4).
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006

Claims (18)

1. Process for improving the combustion of diesel engine fuels by means of salts of organic acids, characterised in that a mixture of neutral salts of carboxylic acids and metals of the atomic Nos. 57 to 71 and free carboxylic acids is added to the fuels.
2. Process according to claim 1, characterised in that the salts are derived from aliphatic monocarboxylic acids.
3. Process according to claim 2, characterised in that the aliphatic monocarboxylic acids contain 4 to 10 carbon atoms.
4. Process according to claims 2 and 3, characterised in that the aliphatic monocarboxylic acids are singly or multiply branched.
5. Process according to claim 4, characterised in that the aliphatic monocarboxylic acids are branched in the a-position.
6. Process according to claims 1 to 4, characterised in that the aliphatic monocarboxylic acids are 2-ethylbutyric acid, 2-ethylhexanoic acid or isooctanoic acid.
7. Process according to claims 1 to 6, characterised in that the salts contain the metais individually or in the form of mixtures thereof.
8. Process according to claim 7, characterised in that the salt mixtures are derived from the naturally occurring cerite earths.
9. Process according to claim 8, characterised in that the salt mixtures are derived from the mineral bastnasite.
10. Process according to claims 1 to 9, characterised in that the carboxylic acids on which the salts are based are used as free carboxylic acids.
11. Process according to claims 1 to 10, characterised in that 0.1 to 1 mole of free carboxylic acids is used per mole of salt.
12. Process according to claim 10, characterised in that 0.2 to 0.4 mole of free carboxylic acid is used per mole of salt.
13. Process according to claims 1 to 12, characterised in that the fuel is a natural oil.
14. Process according to claim 13, characterised in that the natural oil is sunflower oil and/or rapeseed oil.
15. Process according to claims 1 to 14, characterised in that the fuel is a mixture of mineral oil and natural oil.
16. Process according to claims 1 to 15, characterised in that 5 to 200 mg of lanthanoid metal or lanthanoid metal mixture is added per kg of fuel.
17. Process according to claims 1 to 16, characterised in that 10 to 50 mg lanthanoid metal or metal mixture is added per kg of mineral oil-based fuel.
18. Process according to claims 1 to 16, characterised in that 10 to 100 mg lanthanoid metal or metal mixture is added per kg of natural oil-based fuel.
EP83101271A 1982-02-18 1983-02-10 Process for improving fuels for diesel engines Expired EP0087073B1 (en)

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AT83101271T ATE14748T1 (en) 1982-02-18 1983-02-10 PROCESS FOR IMPROVING FUELS FOR DIESEL ENGINES.

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DE19823205732 DE3205732A1 (en) 1982-02-18 1982-02-18 METHOD FOR IMPROVING THE COMBUSTION OF FUELS FOR DIESEL ENGINES
DE3205732 1982-02-18

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EP0087073A3 EP0087073A3 (en) 1984-04-25
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US4474579A (en) 1984-10-02
DE3205732A1 (en) 1983-08-25
DE3360492D1 (en) 1985-09-12
EP0087073A2 (en) 1983-08-31
IN159185B (en) 1987-04-04
BR8300717A (en) 1983-11-16
EP0087073A3 (en) 1984-04-25
ATE14748T1 (en) 1985-08-15
ZA83961B (en) 1983-11-30

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