EP0501097B1 - Fuel for internal combustion engines and application of methylformate - Google Patents

Fuel for internal combustion engines and application of methylformate Download PDF

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Publication number
EP0501097B1
EP0501097B1 EP91890292A EP91890292A EP0501097B1 EP 0501097 B1 EP0501097 B1 EP 0501097B1 EP 91890292 A EP91890292 A EP 91890292A EP 91890292 A EP91890292 A EP 91890292A EP 0501097 B1 EP0501097 B1 EP 0501097B1
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volume
fuel
methyl
methyl formate
moz
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German (de)
French (fr)
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EP0501097A1 (en
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Peter Dr. Klezl
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OMV AG
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OMV AG
OEMV AG
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition

Definitions

  • the invention relates to the use of methyl formate as an additive to fuels and to a fuel for internal combustion engines with electrical ignition.
  • the efficiency of heat engines increases the greater the temperature difference between the entering and leaving medium. In the case of internal combustion engines, this has the consequence that at the same time it is necessary to work with ever higher pressures in order to achieve a higher working temperature. In internal combustion engines with forced ignition of the mixture, the mixture must not ignite on its own.
  • the octane number was introduced as a measure of this ability. Depending on the different determination methods, the research octane number (RON), the motor octane number (MOZ), the street octane number (SOZ) and the front octane number (FOZ) are spoken of.
  • the front octane number is used in such a way that a fraction is drawn from the fuel that distills up to 100 ° C, and the research octane number is then determined from this.
  • the FOZ is therefore a measure of the knock resistance of the fuel components that initially boil.
  • iron or manganese compounds can also be used as anti-knock agents, for example.
  • These compounds have a high toxicity, whereby oxides remain in the combustion chamber, which, if no further additives are provided in the fuel, can on the one hand lead to premature wear of the piston and cylinder and on the other hand can also cause premature ignition of the mixture due to glowing residues.
  • This phenomenon is known in the literature under the designation "post-diesel". In the case of an engine that is subject to higher loads, however, this phenomenon can lead to the pistons melting.
  • methyl tert-butyl ether As an anti-knock agent that has been used particularly recently, methyl tert-butyl ether should be mentioned. This compound has a boiling point of 55.3 ° C and a density at 15 ° C of 0.7458 g / cm3. With the addition of methyl tert-butyl ether (MTBE) an RON between 115 and 135 and an MOZ between 98 and 120 can be achieved depending on the composition of the base gasoline. MTBE is added in a range between 3.0% by volume and 15.0% by volume. A disadvantage of the addition of MTBE is that the increase in the number that is important for the normal operation of an engine, u. between the MOZ, not as much as desired with the ROZ.
  • MTBE methyl tert-butyl ether
  • Additives are known to avoid contamination of the carburetor. Additives to keep the gasoline from oxidizing so that no resinous sticky residues form. Additives to prevent gasoline from corroding metals. Additives that form a copper complex to prevent oxidation of the fuel and also additives to prevent carburetor icing. Under this group to prevent carburetor icing, either surface-active substances or compounds that lower the freezing point of the water are used.
  • amines, diamines, amides, ammonium salts of diesters are the Phosphoric acid, glycerols, alcohols, glycols, ketones, dimethylformamide and dimethylacetamide are mentioned in the literature.
  • DE-A1 2 447 345 discloses artificial fuel mixtures made from methanol, formaldehyde dimethyl acetal and methyl formate, which are intended to serve as artificial fuel mixtures.
  • additions of iron carbonyl and organic manganese compounds are provided.
  • GB-A-1,411,947 discloses a mixture of hydrocarbons with 1% by weight to 10% by weight of water and 12.5% by weight of methyl formate. According to this literature reference, methyl, ethyl or propyl formates are unsuitable as additives for fuels.
  • Another object of the present invention is to lower the cloud point of gasolines and to reduce the risk of icing in both carburetor and injection engines.
  • the invention consists in the use of methyl formate as an octane-increasing, in particular MOZ-increasing additive to a manganese, lead and iron-free fuel for internal combustion engines with electrical ignition with carburetor and / or fuel injection with a boiling fraction of 30 ° C to 200 ° C, in particular 30 ° C to 180 ° C, with paraffinic and / or olefinic and / or naphthenic and / or aromatic hydrocarbons, in particular in an amount of 1.0 vol.% to 50.0 vol.%, optionally 1.0 vol.% to 30.0 vol. -%. preferably 3.5% by volume to 10.0% by volume, based on the total solution of the fuel.
  • methyl formate was already known as a fuel component, it was only used because of its good properties as a fuel because of its calorific value and as a solubilizer. In addition to the methyl formate, metallic compounds that increase the octane number have been provided. Although methyl formate has a lower RON than various other additives that increase the knock number, it has an identical RON and MOZ, which makes the suitability for practice particularly clear. Methyl formate already has an increase in small vol.% Limits, for example 1.0 vol.% Or 3.5 vol.% RON, although in addition to these properties, the properties for lowering the cloud point of the fuel as well as Separation of sediments from the fuel can be highlighted. The starting behavior of injection engines at low temperature is also improved.
  • By volume to 10.0% by volume of methyl formate essentially consists in the fact that it contains an additional content of methyl tert-butyl ether, in particular in the same volume as that of methyl formate.
  • the fuel can also contain alcohols, in particular methyl alcohol and / or ethyl alcohol, instead of methyl tert-butyl ether.
  • Methyl formate is a large-scale chemical that meets all the requirements placed on an octane number improver.
  • the starting product is synthesis gas, which is converted to methanol in a known manner and which also gives methyl formate by carbonylation using a known method.
  • the toxicity has also been extensively investigated: there is no carcinogenic effect, the MAK value is the same as that of higher aromatics (ethylbenzene, xylenes), and it is even harmless in animal experiments; LCL0 values; Inhalation guinea pig: Xylene mixture 450 ppm toluene 1,600 ppm MF 10,000 ppm.
  • Methyl formate has a boiling point of 31.5 ° C, so that it can also be used in larger quantities as an ingredient in gasoline. It was now quite surprising that additions of methyl formate, for example the addition of other knocking agents, such as lead compounds, can replace the properties of the carburetor and injection systems, and also prevent the aging by oxygen in the fuel to a lesser extent can. Despite the higher density of methyl formate compared to MTBE, it can already increase the FOZ. It is not necessary to add organometallic compounds to increase the number of knocks.
  • the fuel contains 10.0% by volume to 60.0% by volume, in particular 30.0% by volume to 50.0% by volume, of a mixture of methyl formate and methyl tert-butyl ether, one becomes Get fuel that has a particularly high percentage of Products that distill up to 100 ° C, so that in addition to increasing the RON, a particularly favorable acceleration behavior of vehicles is achieved.
  • a particularly significant increase in the practice-oriented properties of the fuel is obtained when about 30.0% by volume to 50.0% by volume of this mixture is present in the fuel.
  • the fuel additionally has alcohols, in particular methyl alcohol and / or ethyl alcohol
  • alcohols in particular methyl alcohol and / or ethyl alcohol
  • an additional increase in both the RON and the MOZ can be achieved, the solubility of hydrophilic substances in the fuel being able to be increased at the same time, so that particularly trouble-free operation in the carburetor or in the injection system can be achieved.
  • These properties are achieved in particular by the low alcohols, such as methyl alcohol or ethyl alcohol, and there is also a particularly good availability of these two chemicals.
  • the fuel has 10.0% by volume to 60.0% by volume of a mixture of methyl formate, methyl tert-butyl ether and methyl alcohol, in particular in equal volumes, then trouble-free operation is possible even under difficult climatic conditions Conditions guaranteed.
  • a boiling fraction of a petroleum base stock from 30 ° C to 180 ° C had a density of 0.740 g / cm3. After storing the mixture at - 22 ° C, turbidity occurred after 5 hours, since the water content of 250 ppm at this temperature could no longer be kept in solution. After 3 days of storage at room temperature, sedimentation in the gasoline was observed.
  • the RON and MOZ were determined on the boiling fraction according to Example 1 without addition.
  • the RON and MOZ were determined on pure methyl formate.
  • Example 2 A boiling fraction according to Example 2 was mixed with 10.0% by volume of methyl tert-butyl ether and the RON and MOZ were determined.
  • a boiling fraction according to Example 2 was mixed with 20.0% by volume of methyl tert-butyl ether and the RON and MOZ were determined.
  • a boiling fraction according to Example 2 was mixed with 30.0% by volume of methyl tert-butyl ether and the RON and MOZ were determined.
  • a mixture of one part by volume of methyl formate and one part by volume of methyl tert-butyl ether was prepared and a mixture with the boiling fraction according to Example 2 of 10.0% by volume of this mixture was prepared.
  • the RON and MOZ were determined.
  • a mixture was prepared analogously to Example 13, but with 20.0% by volume of the mixture of methyl formate and methyl tert-butyl ether. The RON and MOZ were determined.
  • a fuel was prepared according to Example 14, 30.0% by volume of the mixture of methyl alcohol, methyl formate and methyl tert-butyl ether being present.
  • a boiling fraction of a petroleum base stock from 30 ° C to 185 ° C had a density of 0.745 g / cm3. After storage The mixture at - 22 ° C. became cloudy after 5 hours, since the water content of 200 ppm was no longer kept in solution at this temperature. After the mixture had been stored for 3 days, sedimentation in the gasoline was observed.
  • the RON and MOZ were determined on the boiling fraction according to Example 17 without addition.
  • the RON and MOZ were determined on pure methyl formate.
  • Example 18 A boiling fraction according to Example 18 was mixed with 10.0% by volume of methyl tert-butyl ether and the RON and MOZ were determined.
  • a boiling fraction according to Example 18 was mixed with 20.0% by volume of methyl tert-butyl ether and the RON and MOZ were determined.
  • a boiling fraction according to Example 18 was mixed with 30.0% by volume of methyl tert-butyl ether and the RON and MOZ were determined.
  • a mixture of one part by volume of methyl formate and one part by volume of methyl tert-butyl ether was prepared and a mixture with the boiling fraction according to Example 18 of 10.0% by volume of this mixture was prepared and the RON and MOZ were determined.
  • a mixture was prepared analogously to Example 18, but with 20.0% by volume of the mixture of methyl formate and methyl tert-butyl ether, and the RON and MOZ were determined.
  • Example 18 A fuel was produced according to Example 18, 30.0% by volume of the mixture of methyl alcohol, methyl formate and methyl tert-butyl ether being present, and the RON and MOZ were determined.
  • Table I REGULAR GASOLINE RON MOZ
  • Example 2 90.3 81.6
  • Example 3 91.1 82.3
  • Example 4 91.8 83.0
  • Example 5 93.1 84.2
  • Example 6 94.2 85.1
  • Example 7 95.2 86.1
  • Example 8 96.1 87.0
  • Example 10 91.9 82.4
  • Example 11 93.1 84.0 Example 12 94.3 84.8
  • Example 13 92.0 83.3
  • Example 14 94.5 84.9
  • Example 15 92.1 83.6
  • Example 16 94.4 85.0 EUROSUPER RON MOZ
  • Example 18 96.0 84.5
  • Example 19 96.6 85.1
  • Example 20 97.1 85.6
  • Example 21 98.1 86.9
  • Example 22 99.0 88.1
  • Example 23 99.9 89.0
  • Example 24 101.0 89

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Description

Die Erfindung bezieht sich auf die Verwendung von Methylformiat als Zusatz zu Treibstoffen und auf einen Treibstoff für Verbrennungsmotoren mit elektrischer Zündung.The invention relates to the use of methyl formate as an additive to fuels and to a fuel for internal combustion engines with electrical ignition.

Wie allgemein bekannt, steigert sich der Wirkungsgrad von Wärmekraftmaschinen, je größer der Temperaturunterschied zwischen dem eintretenden und dem austretenden Medium ist. Bei Verbrennungsmotoren hat das zur Folge, daß gleichzeitig mit immer höheren Drücken gearbeitet werden muß, um eine höhere Arbeitstemperatur zu erreichen. Bei Verbrennungsmotoren mit zwangsweise eingeleiteter Entzündung des Gemisches darf sich das Gemisch nicht von selbst entzünden. Als Maßstab für diese Fähigkeit, wurde die Oktanzahl eingeführt. Je nach unterschiedlichen Bestimmungsmethoden wird von der Research-Oktanzahl (ROZ), von der Motor-Oktanzahl (MOZ), der Straßen-Oktanzahl (SOZ) und der Front-Oktanzahl (FOZ) gesprochen. Da die ROZ sowohl unter mechanisch als auch thermisch geringeren Beanspruchungen bestimmt wird als die MOZ, weisen viele Treibstoffe eine höhere ROZ denn MOZ auf. Die MOZ stellt allerdings einen Wert dar, der auf Grund der härteren Bedingungen eher praxisbezogen ist. Bei der Frontoktanzahl wird so vorgegangen, daß vom Kraftstoff eine Fraktion gezogen wird, die bis 100° C überdestilliert, und von dieser wird sodann die ResearchOktanzahl bestimmt. Die FOZ ist somit ein Maßstab über die Klopffestigkeit der am Anfang siedenden Treibstoffbestandteile.As is generally known, the efficiency of heat engines increases the greater the temperature difference between the entering and leaving medium. In the case of internal combustion engines, this has the consequence that at the same time it is necessary to work with ever higher pressures in order to achieve a higher working temperature. In internal combustion engines with forced ignition of the mixture, the mixture must not ignite on its own. The octane number was introduced as a measure of this ability. Depending on the different determination methods, the research octane number (RON), the motor octane number (MOZ), the street octane number (SOZ) and the front octane number (FOZ) are spoken of. Since the RON is determined under both mechanically and thermally lower loads than the MOZ, many fuels have a higher RON than MOZ. However, the MOZ represents a value that is more practical due to the tougher conditions. The front octane number is used in such a way that a fraction is drawn from the fuel that distills up to 100 ° C, and the research octane number is then determined from this. The FOZ is therefore a measure of the knock resistance of the fuel components that initially boil.

Da sich ein Unterschied, insbesondere bei der Zugabe von Antiklopfmitteln, zwischen dem realen Verhalten des Treibstoffes in einem Motor und den bestimmten Werten, wie MOZ, ROZ und FOZ, ergeben, werden zusätzlich auch Straßentests durchgeführt, die mit serienmäßigen Motoren durchgeführt werden, wobei hier von der SOZ gesprochen wird. Diese Versuche sind insoferne von besonderer Bedeutung, als sich ergeben hat, daß sich beispielsweise der Zusatz von Tetraethylblei bei Straßentests besser bewährt als bei den Versuchsmotoren, mit welchen die ROZ oder MOZ oder FOZ bestimmt werden. Man spricht in diesem Zusammenhang von einem Bleibonus.Because there is a difference, especially when adding Anti-knock agents, between the real behavior of the fuel in an engine and the specific values such as MOZ, RON and FOZ, are also carried out on road tests that are carried out with standard engines, which is referred to as the SOZ. These tests are of particular importance insofar as it has been found that the addition of tetraethyl lead, for example, has proven itself better in road tests than in the test engines with which the RON or MOZ or FOZ are determined. In this context one speaks of a lead bonus.

Mit dem Einsatz von Katalysatoren zur weiteren katalytischen chemischen Umsetzung der Abgase, wie sie in U.S.A. begonnen wurden, mußten klopffeste bleifreie Treibstoffe entwickelt werden, da das Blei als Katalysatorgift wirkt und eine dementsprechende Unwirksamkeit der Katalysatoren verursachen würde.With the use of catalysts for the further catalytic chemical conversion of the exhaust gases, as started in the U.S.A., anti-knock lead-free fuels had to be developed, since the lead acts as a catalyst poison and would cause the catalysts to be ineffective accordingly.

Anstelle der Bleiverbindungen können beispielsweise auch andere Eisen- oder Manganverbindungen als Antiklopfmittel verwendet werden. Diese Verbindungen weisen eine hohe Toxizität auf, wobei weiters im Verbrennungsraum Oxide zurückbleiben, die, so nicht weitere Zusätze im Treibstoff vorgesehen werden, einerseits zum vorzeitigen Verschleiß von Kolben und Zylinder führen können und anderseits auch ein vorzeitiges Zünden des Gemisches durch glühende Rückstände verursachen können. Dieses Phänomen ist unter der Bezeichnung "Nachdieseln" literaturbekannt. Bei einem Motor, der unter höherer Beanspruchung liegt, kann dieses Phänomen allerdings bis zum Durchschmelzen der Kolben führen.Instead of the lead compounds, other iron or manganese compounds can also be used as anti-knock agents, for example. These compounds have a high toxicity, whereby oxides remain in the combustion chamber, which, if no further additives are provided in the fuel, can on the one hand lead to premature wear of the piston and cylinder and on the other hand can also cause premature ignition of the mixture due to glowing residues. This phenomenon is known in the literature under the designation "post-diesel". In the case of an engine that is subject to higher loads, however, this phenomenon can lead to the pistons melting.

Da auf Grund des Einsatzes der Katalysatoren ein bleifreier Benzin angestrebt werden muß und auf der anderen Seite aus gesundheitlichen Gründen versucht wird, die Bleiemissionen so gering wie möglich zu halten, wird der Bleigehalt in den Benzinen stufenweise gesenkt bzw. gänzlich reduziert, und es kommen andere Antiklopfmittel zum Einsatz. Als Antiklopfmittel, das in letzter Zeit einen besonders breiten Einsatz gefunden hat, ist der Methyl-tert.-butylether zu nennen. Diese Verbindung weist einen Siedepunkt von 55,3° C und eine Dichte bei 15° C von 0,7458 g/cm³ auf. Mit einem Zusatz von Methyl-tert.-butylether (MTBE) kann je nach der Zusammensetzung des Grundbenzins eine ROZ zwischen 115 und 135 und eine MOZ zwischen 98 und 120 erreicht werden. Der Zusatz von MTBE erfolgt in Grenzen zwischen 3,0 Vol.-% und 15,0 Vol.-%. Nachteilig ist bei der Zugabe von MTBE, daß die Steigerung jener Maßzahl, welche für den Normalbetrieb eines Motors von Bedeutung ist, u. zw. die MOZ, nicht in so erwünschtem Maße wie bei der ROZ erfolgt.Because of the use of catalysts unleaded gasoline must be aimed for and on the other hand for health reasons an attempt is made to keep the lead emissions as low as possible, the lead content in the gasolines is gradually reduced or completely reduced, and other anti-knock agents are used. As an anti-knock agent that has been used particularly recently, methyl tert-butyl ether should be mentioned. This compound has a boiling point of 55.3 ° C and a density at 15 ° C of 0.7458 g / cm³. With the addition of methyl tert-butyl ether (MTBE) an RON between 115 and 135 and an MOZ between 98 and 120 can be achieved depending on the composition of the base gasoline. MTBE is added in a range between 3.0% by volume and 15.0% by volume. A disadvantage of the addition of MTBE is that the increase in the number that is important for the normal operation of an engine, u. between the MOZ, not as much as desired with the ROZ.

Neben dem Zusatz von Antiklopfmitteln werden Benzinen eine hohe Anzahl von weiteren Stoffen zugesetzt um ein bestimmtes Eigenschaftsniveau zu erreichen. So sind Zusätze bekannt, um eine Vergaserverschmutzung zu vermeiden. Zusätze, um die Oxidation der Benzine hintanzuhalten, so daß sich keine harzartigen klebrigen Rückstände bilden. Zusätze, die die Korrosion von Benzin an Metallen verhindern sollen. Zusätze, die Kupferkomplex bilden, um eine Oxidation des Treibstoffes zu vermeiden und auch Zusätze, um eine Vergaservereisung zu verhindern. Unter dieser Gruppe zur Verhinderung der Vergaservereisung werden entweder oberflächenaktive Stoffe oder Verbindungen, die den Gefrierpunkt des Wassers erniedrigen, eingesetzt. In der Vielfalt von Verbindungen sind Amine, Diamine, Amide, Ammoniumsalze von Diestern der Phosphorsäure, Glyzerine, Alkohole, Glykole, Ketone, Dimethylformamid und Dimethylacetamid in der Literatur genannt.In addition to the addition of anti-knock agents, a large number of other substances are added to petrol in order to achieve a certain level of properties. Additives are known to avoid contamination of the carburetor. Additives to keep the gasoline from oxidizing so that no resinous sticky residues form. Additives to prevent gasoline from corroding metals. Additives that form a copper complex to prevent oxidation of the fuel and also additives to prevent carburetor icing. Under this group to prevent carburetor icing, either surface-active substances or compounds that lower the freezing point of the water are used. In the variety of compounds, amines, diamines, amides, ammonium salts of diesters are the Phosphoric acid, glycerols, alcohols, glycols, ketones, dimethylformamide and dimethylacetamide are mentioned in the literature.

Aus der DE-A1 2 447 345 werden künstliche Treibstoffmischungen aus Methanol, Formaldehyddimethylacetal und Ameisensäuremethylester bekannt, welche als künstliche Treibstoffmischungen dienen sollen. Um eine entsprechende Oktanzahl zu erhalten, werden Zusätze von Eisenkarbonyl und organischen Manganverbindungen vorgesehen.DE-A1 2 447 345 discloses artificial fuel mixtures made from methanol, formaldehyde dimethyl acetal and methyl formate, which are intended to serve as artificial fuel mixtures. In order to obtain an appropriate octane number, additions of iron carbonyl and organic manganese compounds are provided.

Aus der GB-A-1,411.947 wird eine Mischung von Kohlenwasserstoffen mit 1 Gew.-% bis 10 Gew.-% Wasser und 12,5 Gew.-% Methylformiat bekannt. Methyl-, Ethyl- oder Propylformiate sind gemäß dieser Literaturstelle als Zusatz für Treibstoffe ungeeignet.GB-A-1,411,947 discloses a mixture of hydrocarbons with 1% by weight to 10% by weight of water and 12.5% by weight of methyl formate. According to this literature reference, methyl, ethyl or propyl formates are unsuitable as additives for fuels.

Die vorliegende Erfindung hat sich zum Ziel gesetzt, einen Treibstoff für Verbrennungsmotoren mit elektrischer Zündung zu schaffen, der einen möglichst geringen Unterschied zwischen den ROZ- und MOZ-Werten aufweist, welcher besonders klopffest ist. Eine weitere Aufgabe der vorliegenden Erfindung besteht darin, einen Treibstoff zu schaffen, der mit den Katalysatoren, wie sie zur chemischen Nachbehandlung der Abgase eingesetzt werden, verträglich ist, und welcher weiters die Alterungsbeständigkeit des Benzins wesentlich verbessert.The present invention has set itself the goal of creating a fuel for internal combustion engines with electrical ignition, which has the smallest possible difference between the RON and MOZ values, which is particularly knock-resistant. Another object of the present invention is to provide a fuel which is compatible with the catalysts as are used for the chemical aftertreatment of the exhaust gases and which further improves the aging resistance of the gasoline significantly.

Eine weitere Aufgabe der vorliegenden Erfindung besteht darin, den Trübungspunkt von Benzinen herabzusetzen und die Vereisungsgefahr sowohl bei Vergaser- als auch bei Einspritzmotoren herabzusetzen.Another object of the present invention is to lower the cloud point of gasolines and to reduce the risk of icing in both carburetor and injection engines.

Die Erfindung besteht in der Verwendung von Methylformiat als oktanzahlerhöhender, insbesondere MOZ erhöhender Zusatz zu einem mangan-, blei- und eisenfreien Treibstoff für Verbrennungsmotoren mit elektrischer Zündung mit Vergaser und/oder Treibstoffeinspritzung mit einer Siedefraktion von 30° C bis 200° C, insbesondere 30° C bis 180° C, mit paraffinischen und/oder olefinischen und/oder naphtenischen und/oder aromatischen Kohlenwasserstoffen, insbesondere in einer Menge von 1,0 Vol.-% bis 50,0 Vol.-%, gegebenenfalls 1,0 Vol.-% bis 30,0 Vol.-%. vorzugsweise 3,5 Vol.-% bis 10,0 Vol.-%, bezogen auf die Gesamtlösung des Treibstoffes.The invention consists in the use of methyl formate as an octane-increasing, in particular MOZ-increasing additive to a manganese, lead and iron-free fuel for internal combustion engines with electrical ignition with carburetor and / or fuel injection with a boiling fraction of 30 ° C to 200 ° C, in particular 30 ° C to 180 ° C, with paraffinic and / or olefinic and / or naphthenic and / or aromatic hydrocarbons, in particular in an amount of 1.0 vol.% to 50.0 vol.%, optionally 1.0 vol.% to 30.0 vol. -%. preferably 3.5% by volume to 10.0% by volume, based on the total solution of the fuel.

Obwohl Methylformiat bereits als Treibstoffkomponente bekannt war, ist es lediglich auf Grund seiner guten Eigenschaften als Treibstoff wegen seines kalorischen Wertes und als Lösungsvermittler zum Einsatz gekommen. Zusätzlich zu dem Methylformiat wurden metallische Verbindungen vorgesehen, welche die Oktanzahl erhöhen. Obwohl Methylformiat eine geringere ROZ als verschiedene andere die Klopfzahl erhöhende Zusätze aufweist, weist es eine idente ROZ und MOZ auf, wodurch die Praxiseignung besonders deutlich zum Ausdruck kommt. Methylformiat wirkt bereits in geringen Vol.-%-Grenzen, wie beispielsweise 1,0 Vol.-% bzw. 3,5 Vol.-% ROZ erhöhend, wobei allerdings neben diesen Eigenschaften besonders die Eigenschaften zur Herabsetzung des Trübungspunktes des Treibstoffes als auch die Abscheidung von Sedimenten aus dem Treibstoff hervorgehoben werden kann. Weiters wird das Startverhalten bei Einspritzmotoren bei niedriger Temperatur verbessert. Beim Einspritzen von Treibstoff besteht bei niedrigen Temperaturen die Gefahr, daß der nach der Düse beim Einspritzvorgang expandierende Treibstoff zu einer Vereisung der Düse führt, wobei neben einem Zuwachsen der Einspritzöffnung auch ein asymmetrisches Verlegen der Einspritzdüsen erfolgen kann, wodurch die Längsorientierung des eingespritzten Brennstoffstrahles wesentlich verändert werden kann, so daß beispielsweise Olfilme im kalten Motor von der Zylinderwandung durch den desorientierten Treibstoffstrahl abgewaschen werden können, sodaß irreversible, vorzeitige Motorabnützungen bedingt werden können.Although methyl formate was already known as a fuel component, it was only used because of its good properties as a fuel because of its calorific value and as a solubilizer. In addition to the methyl formate, metallic compounds that increase the octane number have been provided. Although methyl formate has a lower RON than various other additives that increase the knock number, it has an identical RON and MOZ, which makes the suitability for practice particularly clear. Methyl formate already has an increase in small vol.% Limits, for example 1.0 vol.% Or 3.5 vol.% RON, although in addition to these properties, the properties for lowering the cloud point of the fuel as well as Separation of sediments from the fuel can be highlighted. The starting behavior of injection engines at low temperature is also improved. When fuel is injected at low temperatures, there is a risk that the fuel expanding after the nozzle during the injection process will lead to icing of the nozzle, and in addition to an increase in the opening of the injection, there is also an asymmetrical laying of the nozzle Injection nozzles can take place, whereby the longitudinal orientation of the injected fuel jet can be changed significantly, so that, for example, oil films in the cold engine can be washed off the cylinder wall by the disoriented fuel jet, so that irreversible, premature engine wear can be caused.

Der erfindungsgemäße Treibstoff für Verbrennungsmotoren mit elektrischer Zündung mit Vergaser und/oder Treibstoffeinspritzung mit einer Siedefraktion von 30° C bis 200° C, insbesondere von 30°C bis 180° C, mit paraffinischen und/oder olefinischen und/oder naphtenischen und/oder aromatischen Kohlenwasserstoffen, welcher mangan-, blei- und eisenfrei ist und insbesondere 1,0 Vol.-% bis 50,0 Vol.-%, gegebenenfalls 1,0 Vol.-% bis 30,0 Vol.-%, vorzugsweise 3,5 Vol.-% bis 10,0 Vol.-%, Methylformiat enthält, besteht im wesentlichen darin, daß er einen zusätzlichen Gehalt an Methyl-tert.-butylether, insbesondere in gleichen Volumsmengen, wie an Methylformiat enthält.The fuel according to the invention for internal combustion engines with electric ignition with carburetor and / or fuel injection with a boiling fraction of 30 ° C to 200 ° C, in particular from 30 ° C to 180 ° C, with paraffinic and / or olefinic and / or naphthenic and / or aromatic Hydrocarbons, which are manganese, lead and iron-free and in particular 1.0 vol.% To 50.0 vol.%, Optionally 1.0 vol.% To 30.0 vol.%, Preferably 3.5 % By volume to 10.0% by volume of methyl formate essentially consists in the fact that it contains an additional content of methyl tert-butyl ether, in particular in the same volume as that of methyl formate.

Der Treibstoff kann auch anstelle von Methyl-tert.-buthylether Alkohole, insbesondere Methylalkohol und/oder Ethylalkohol enthalten.The fuel can also contain alcohols, in particular methyl alcohol and / or ethyl alcohol, instead of methyl tert-butyl ether.

Methylformiat ist eine großtechnische Chemikalie, die alle Anforderungen, die an einen Oktanzahlverbesserer gestellt werden, erfüllt. Ausgangsprodukt ist Synthesegas, das in bekannter Weise zu Methanol umgesetzt wird und dieses durch Carbonylierung ebenfalls nach bekanntem Verfahren Methylformiat ergibt.Methyl formate is a large-scale chemical that meets all the requirements placed on an octane number improver. The starting product is synthesis gas, which is converted to methanol in a known manner and which also gives methyl formate by carbonylation using a known method.

Ein weiterer Vorteil ist, daß diese Verbindung, so wie andere sauerstoffhältige Komponenten (z. B. Furane), keinen negativen Einfluß auf die Stabilität des Vergaserkraftstoffes (Induktionsperiode, Existent Gum) besitzt.Another advantage is that this connection, like other oxygen-containing components (e.g. furans), has no negative influence on the stability of the gasoline (induction period, existent gum).

Auch die Toxizität ist hinlänglich untersucht: Es besteht keine cancerogene Wirkung, der MAK-Wert ist dem höherer Aromaten (Ethylbenzol, Xylole) gleich, und im Tierversuch ist es sogar harmloser als diese; LCL₀-Werte; Inhalation Meerschwein: Xylolgemisch 450 ppm Toluol 1.600 ppm MF 10.000 ppm. The toxicity has also been extensively investigated: there is no carcinogenic effect, the MAK value is the same as that of higher aromatics (ethylbenzene, xylenes), and it is even harmless in animal experiments; LCL₀ values; Inhalation guinea pig: Xylene mixture 450 ppm toluene 1,600 ppm MF 10,000 ppm.

Methylformiat (MF) weist einen Siedepunkt von 31,5° C auf, so daß es auch in größeren Mengen als Bestandteil für Benzin Verwendung finden kann. Es war nun durchaus überraschend, daS Zusätze von Methylformiat, beispielsweise die Zusätze von anderen Klopfmitteln, wie Bleiverbindungen, ersetzen können, wobei neben der Eigenschaft die Vereisung von Vergasern und Einspritzanlagen verhindert wird, und auch bereits in geringeren Prozentgrenzen die Alterung durch Sauerstoff im Treibstoff verhindern kann. Trotz der höheren Dichte des Methylformiates im Vergleich zu MTBE kann es bereits auch die FOZ erhöhen. Auf einen Zusatz von metallorganischen Verbindungen zur Erhöhung der Klopfzahl kann verzichtet werden.Methyl formate (MF) has a boiling point of 31.5 ° C, so that it can also be used in larger quantities as an ingredient in gasoline. It was now quite surprising that additions of methyl formate, for example the addition of other knocking agents, such as lead compounds, can replace the properties of the carburetor and injection systems, and also prevent the aging by oxygen in the fuel to a lesser extent can. Despite the higher density of methyl formate compared to MTBE, it can already increase the FOZ. It is not necessary to add organometallic compounds to increase the number of knocks.

Enthält der Treibstoff 10,0 Vol.-% bis 60,0 Vol.-%, insbesondere 30,0 Vol.-% bis 50,0 Vol.-% einer Mischung von Methylformiat und Methyl-tert.-butylether, so wird ein Treibstoff erhalten, der einen besonders hohen Anteil an Produkten aufweist, die bis 100° C überdestillieren, so daß neben der Steigerung der ROZ auch ein besonders günstiges Beschleunigungsverhalten von Fahrzeugen erreicht wird. Eine besonders deutliche Steigerung der praxisorientierten Eigenschaften des Treibstoffes ergibt sich dann, wenn ca. 30,0 Vol.-% bis 50,0 Vol.-% dieser Mischung im Treibstoff vorliegen.If the fuel contains 10.0% by volume to 60.0% by volume, in particular 30.0% by volume to 50.0% by volume, of a mixture of methyl formate and methyl tert-butyl ether, one becomes Get fuel that has a particularly high percentage of Products that distill up to 100 ° C, so that in addition to increasing the RON, a particularly favorable acceleration behavior of vehicles is achieved. A particularly significant increase in the practice-oriented properties of the fuel is obtained when about 30.0% by volume to 50.0% by volume of this mixture is present in the fuel.

Weist der Treibstoff zusätzlich Alkohole, insbesondere Methylalkohol und/oder Ethylalkohol, auf, so kann in Einzelfällen, so erwünscht, noch eine zusätzliche Erhöhung sowohl der ROZ als auch der MOZ erreicht werden, wobei gleichzeitig die Löslichkeit von hydrophilen Substanzen im Treibstoff erhöht werden kann, so daß ein besonders störungsfreier Betrieb im Vergaser oder auch im Einspritzsystem erreicht werden kann. Diese Eigenschaften werden besonders durch die niedrigen Alkohole, wie Methylalkohol oder Ethylalkohol erreicht, wobei weiters eine besonders gute Verfügbarkeit dieser beiden Chemikalien gegeben ist.If the fuel additionally has alcohols, in particular methyl alcohol and / or ethyl alcohol, then in individual cases, if desired, an additional increase in both the RON and the MOZ can be achieved, the solubility of hydrophilic substances in the fuel being able to be increased at the same time, so that particularly trouble-free operation in the carburetor or in the injection system can be achieved. These properties are achieved in particular by the low alcohols, such as methyl alcohol or ethyl alcohol, and there is also a particularly good availability of these two chemicals.

Weist der Treibstoff 10,0-Vol.-% bis 60,0-Vol.-% einer Mischung aus Methylformiat, Methyl-tert.-butylether und Methylalkohol, insbesondere in gleichen Volumsmengen, auf, so ist ein störungsfreier Betrieb auch unter schwierigen klimatischen Bedingungen gewährleistet.If the fuel has 10.0% by volume to 60.0% by volume of a mixture of methyl formate, methyl tert-butyl ether and methyl alcohol, in particular in equal volumes, then trouble-free operation is possible even under difficult climatic conditions Conditions guaranteed.

Liegen 30,0 Vol.-% bis 50,0 Vol.-% dieser Mischung im Treibstoff vor, so liegen extrem beanspruchbare Treibstoffmischungen vor.If 30.0% by volume to 50.0% by volume of this mixture is present in the fuel, then fuel mixtures which can be used under extreme conditions are present.

Im folgenden wird die Erfindung anhand der Beispiele näher erläutert.The invention is explained in more detail below with reference to the examples.

Beispiel 1: (REGULARBENZIN)Example 1: (REGULAR GASOLINE)

Eine Siedefraktion eines Erdöl-Base-stocks von 30° C bis 180° C wies eine Dichte von 0,740 g/cm³ auf. Nach Lagerung der Mischung bei - 22° C trat nach 5 Stunden eine Trübung auf, da der Wassergehalt von 250 ppm bei dieser Temperatur nicht mehr in Lösung gehalten werden konnte. Nach 3 Tagen Lagerung bei Raumtemperatur war eine Sedimentation im Benzin zu beobachten.A boiling fraction of a petroleum base stock from 30 ° C to 180 ° C had a density of 0.740 g / cm³. After storing the mixture at - 22 ° C, turbidity occurred after 5 hours, since the water content of 250 ppm at this temperature could no longer be kept in solution. After 3 days of storage at room temperature, sedimentation in the gasoline was observed.

Bei derselben Siedefraktion unter Zusatz von 2,0 Vol.-% Methylformiat trat erst bei fünfstündiger Lagerung bei - 60° C eine Trübung auf. Nach dreitägiger Lagerung bei Raumtemperatur trat keine Sedimentation auf.With the same boiling fraction with the addition of 2.0% by volume of methyl formate, turbidity only occurred after storage for five hours at -60 ° C. After three days of storage at room temperature, no sedimentation occurred.

Beispiel 2:Example 2:

An der Siedefraktion gemäß Beispiel 1 wurden ohne Zusatz die ROZ und MOZ bestimmt.The RON and MOZ were determined on the boiling fraction according to Example 1 without addition.

Beispiel 3:Example 3:

Der Siedefraktion gemäß Beispiel 2 wurden 5,0 Vol.-% Methylformiat zugesetzt und die ROZ und MOZ bestimmt.5.0% by volume of methyl formate were added to the boiling fraction according to Example 2 and the RON and MOZ were determined.

Beispiel 4:Example 4:

Zusatz von 10 Vol.-% Methylformiat zu der Siedefraktion gemäß Beispiel 2. Es wurden die ROZ und MOZ bestimmt.Addition of 10% by volume of methyl formate to the boiling fraction according to Example 2. The RON and MOZ were determined.

Beispiel 5:Example 5:

Zusatz von 20 Vol.-% Methylformiat zu der Siedefraktion gemäß Beispiel 2. Es wurden die ROZ und MOZ bestimmt.Addition of 20% by volume of methyl formate to the boiling fraction according to Example 2. The RON and MOZ were determined.

Beispiel 6:Example 6:

Zusatz von 30 Vol.-% Methylformiat zu der Siedefraktion gemäß Beispiel 2. Es wurden die ROZ und MOZ bestimmt.Addition of 30% by volume of methyl formate to the boiling fraction according to Example 2. The RON and MOZ were determined.

Beispiel 7:Example 7:

Zusatz von 40 Vol.-% Methylformiat zu der Siedefraktion gemäß Beispiel 2. Es wurden die ROZ und MOZ bestimmt.Addition of 40% by volume of methyl formate to the boiling fraction according to Example 2. The RON and MOZ were determined.

Beispiel 8:Example 8:

Zusatz von 50 Vol.-% Methylformiat zu der Siedefraktion gemäß Beispiel 2. Es wurden die ROZ und MOZ bestimmt.Addition of 50% by volume of methyl formate to the boiling fraction according to Example 2. The RON and MOZ were determined.

Beispiel 9:Example 9:

Es wurden am reinen Methylformiat die ROZ und MOZ bestimmt.The RON and MOZ were determined on pure methyl formate.

Beispiel 10:Example 10:

Eine Siedefraktion gemäß Beispiel 2 wurde mit 10,0 Vol.-% Methyl-tert.-butylether versetzt und es wurden die ROZ und MOZ bestimmt.A boiling fraction according to Example 2 was mixed with 10.0% by volume of methyl tert-butyl ether and the RON and MOZ were determined.

Beispiel 11:Example 11:

Eine Siedefraktion gemäß Beispiel 2 wurde mit 20,0 Vol.-% Methyl-tert.-butylether versetzt und es wurden die ROZ und MOZ bestimmt.A boiling fraction according to Example 2 was mixed with 20.0% by volume of methyl tert-butyl ether and the RON and MOZ were determined.

Beispiel 12:Example 12:

Eine Siedefraktion gemäß Beispiel 2 wurde mit 30,0 Vol.-% Methyl-tert.-butylether versetzt und es wurden die ROZ und MOZ bestimmt.A boiling fraction according to Example 2 was mixed with 30.0% by volume of methyl tert-butyl ether and the RON and MOZ were determined.

Beispiel 13:Example 13:

Es wurde eine Mischung aus einem Volumsteil Methylformiat und einem Volumsteil Methyl-tert.-butylether hergestellt und eine Mischung mit der Siedefraktion gemäß Beispiel 2 von 10,0 Vol.-% dieser Mischung hergestellt. Es wurden die ROZ und MOZ bestimmt.A mixture of one part by volume of methyl formate and one part by volume of methyl tert-butyl ether was prepared and a mixture with the boiling fraction according to Example 2 of 10.0% by volume of this mixture was prepared. The RON and MOZ were determined.

Beispiel 14:Example 14:

Es wurde eine Mischung analog Beispiel 13, jedoch mit 20,0 Vol.-% der Mischung Methylformiat und Methyl-tert.-butylether hergestellt. Es wurden die ROZ und MOZ bestimmt.A mixture was prepared analogously to Example 13, but with 20.0% by volume of the mixture of methyl formate and methyl tert-butyl ether. The RON and MOZ were determined.

Beispiel 15:Example 15:

Es wurde eine Mischung aus gleichen Teilen Methylformiat, Methylalkohol und Methyl-tert.-butylether angefertigt und der Siedefraktion gemaß Beispiel 2 diese Mischung zugefügt, so daß ein Treibstoff mit 15,0 Vol.-% dieser Mischung erhalten wurde. Es wurden die ROZ und MOZ bestimmt.A mixture of equal parts of methyl formate, methyl alcohol and methyl tert-butyl ether was prepared and this mixture was added to the boiling fraction according to Example 2, so that a fuel with 15.0% by volume of this mixture was obtained. The RON and MOZ were determined.

Beispiel 16:Example 16:

Es wurde ein Treibstoff gemäß Beispiel 14 angefertigt, wobei 30,0 Vol.-% der Mischung aus Methylalkohol, Methylformiat und Methyl-tert.-butylether vorgelegen sind.A fuel was prepared according to Example 14, 30.0% by volume of the mixture of methyl alcohol, methyl formate and methyl tert-butyl ether being present.

Beispiel 17: (EUROSUPER)Example 17: (EUROSUPER)

Eine Siedefraktion eines Erdöl-Base-stocks von 30° C bis 185° C wies eine Dichte von 0,745 g/cm³ auf. Nach Lagerung der Mischung bei - 22° C trat nach 5 Stunden eine Trübung auf, da der Wassergehalt von 200 ppm bei dieser Temperatur nicht mehr in Lösung gehalten wurde. Nach 3 Tagen Lagerung der Mischung war eine Sedimentation im Benzin zu beobachten.A boiling fraction of a petroleum base stock from 30 ° C to 185 ° C had a density of 0.745 g / cm³. After storage The mixture at - 22 ° C. became cloudy after 5 hours, since the water content of 200 ppm was no longer kept in solution at this temperature. After the mixture had been stored for 3 days, sedimentation in the gasoline was observed.

Bei derselben Siedefraktion unter Zusatz von 2,0 Vol.-% Methylformiat trat erst bei fünfstündiger Lagerung bei - 62° C eine Trübung auf. Bei dreitägiger Lagerung bei Raumtemperatur trat keine Sedimentation auf.In the same boiling fraction with the addition of 2.0% by volume of methyl formate, turbidity only occurred after storage for five hours at -62 ° C. When stored at room temperature for three days, no sedimentation occurred.

Beispiel 18:Example 18:

An der Siedefraktion gemäß Beispiel 17 wurden ohne Zusatz die ROZ und MOZ bestimmt.The RON and MOZ were determined on the boiling fraction according to Example 17 without addition.

Beispiel 19:Example 19:

Der Siedefraktion gemäß Beispiel 18 wurden 5,0 Vol.-% Methylformiat zugesetzt und die ROZ und MOZ bestimmt.5.0% by volume of methyl formate was added to the boiling fraction according to Example 18 and the RON and MOZ were determined.

Beispiel 20:Example 20:

Zusatz von 10 Vol.-% Methylformiat zur Siedefraktion gemäß Beispiel 18. Es wurden die ROZ und MOZ bestimmt.Addition of 10% by volume of methyl formate to the boiling fraction according to Example 18. The RON and MOZ were determined.

Beispiel 21:Example 21:

Zusatz von 20 Vol.-% Methylformiat zur Siedefraktion gemäß Beispiel 18. Es wurden die ROZ und MOZ bestimmt.Addition of 20% by volume of methyl formate to the boiling fraction according to Example 18. The RON and MOZ were determined.

Beispiel 22:Example 22:

Zusatz von 30 Vol.-% Methylformiat zur Siedefraktion gemäß Beispiel 18. Es wurden die ROZ und MOZ bestimmt.Add 30% by volume of methyl formate to the boiling fraction according to Example 18. The RON and MOZ were determined.

Beispiel 23:Example 23:

Zusatz von 40 Vol.-% Methylformiat zur Siedefraktion gemäß Beispiel 18. Es wurden die ROZ und MOZ bestimmt.Addition of 40% by volume of methyl formate to the boiling fraction according to Example 18. The RON and MOZ were determined.

Beispiel 24:Example 24:

Zusatz von 50 Vol.-% Methylformiat zur Siedefraktion gemäß Beispiel 18. Es wurden die ROZ und MOZ bestimmt.Addition of 50% by volume of methyl formate to the boiling fraction according to Example 18. The RON and MOZ were determined.

Beispiel 25:Example 25:

Es wurden am reinen Methylformiat die ROZ und MOZ bestimmt.The RON and MOZ were determined on pure methyl formate.

Beispiel 26:Example 26:

Eine Siedefraktion gemäß Beispiel 18 wurde mit 10,0 Vol.-% Methyl-tert.-butylether versetzt und es wurden die ROZ und MOZ bestimmt.A boiling fraction according to Example 18 was mixed with 10.0% by volume of methyl tert-butyl ether and the RON and MOZ were determined.

Beispiel 27:Example 27:

Eine Siedefraktion gemäß Beispiel 18 wurde mit 20,0 Vol.-% Methyl-tert.-butylether versetzt und es wurden die ROZ und MOZ bestimmt.A boiling fraction according to Example 18 was mixed with 20.0% by volume of methyl tert-butyl ether and the RON and MOZ were determined.

Beispiel 28:Example 28:

Eine Siedefraktion gemäß Beispiel 18 wurde mit 30,0 Vol.-% Methyl-tert.-butylether versetzt und es wurden die ROZ und MOZ bestimmt.A boiling fraction according to Example 18 was mixed with 30.0% by volume of methyl tert-butyl ether and the RON and MOZ were determined.

Beispiel 29:Example 29:

Es wurde eine Mischung aus einem Volumsteil Methylformiat und einem Volumsteil Methyl-tert.-butylether hergestellt und eine Mischung mit der Siedefraktion gemäß Beispiel 18 von 10,0 Vol.-% dieser Mischung hergestellt und es wurden die ROZ und MOZ bestimmt.A mixture of one part by volume of methyl formate and one part by volume of methyl tert-butyl ether was prepared and a mixture with the boiling fraction according to Example 18 of 10.0% by volume of this mixture was prepared and the RON and MOZ were determined.

Beispiel 30:Example 30:

Es wurde eine Mischung analog Beispiel 18, jedoch mit 20,0 Vol.-% der Mischung Methylformiat und Methyl-tert.-butylether hergestellt und es wurden die ROZ und MOZ bestimmt.A mixture was prepared analogously to Example 18, but with 20.0% by volume of the mixture of methyl formate and methyl tert-butyl ether, and the RON and MOZ were determined.

Beispiel 31:Example 31:

Es wurde eine Mischung aus gleichen Teilen Methylformiat, Methylalkohol und Methyl-tert.-butylether angefertigt und der Siedefraktion gemäß Beispiel 18 diese Mischung zugefügt, so daß ein Treibstoff mit 15,0 Vol.-% dieser Mischung erhalten wurde und es wurden die ROZ und MOZ bestimmt.A mixture of equal parts of methyl formate, methyl alcohol and methyl tert-butyl ether was prepared and this mixture was added to the boiling fraction according to Example 18, so that a fuel with 15.0% by volume of this mixture was obtained and the RON and MOZ determined.

Beispiel 32:Example 32:

Es wurde ein Treibstoff gemäß Beispiel 18 angefertigt, wobei 30,0 Vol.-% der Mischung aus Methylalkohol, Methylformiat und Methyl-tert.-butylether vorgelegen sind und es wurden die ROZ und MOZ bestimmt. Tabelle I REGULARBENZIN ROZ MOZ Beispiel 2 90,3 81,6 Beispiel 3 91,1 82,3 Beispiel 4 91,8 83,0 Beispiel 5 93,1 84,2 Beispiel 6 94,2 85,1 Beispiel 7 95,2 86,1 Beispiel 8 96,1 87,0 Beispiel 9 115,0 114,8 Beispiel 10 91,9 82,4 Beispiel 11 93,1 84,0 Beispiel 12 94,3 84,8 Beispiel 13 92,0 83,3 Beispiel 14 94,5 84,9 Beispiel 15 92,1 83,6 Beispiel 16 94,4 85,0 Tabelle II EUROSUPER ROZ MOZ Beispiel 18 96,0 84,5 Beispiel 19 96,6 85,1 Beispiel 20 97,1 85,6 Beispiel 21 98,1 86,9 Beispiel 22 99,0 88,1 Beispiel 23 99,9 89,0 Beispiel 24 101,0 89,9 Beispiel 25 115,0 114,8 Beispiel 26 97,0 85,9 Beispiel 27 98,2 86,2 Beispiel 28 99,1 87,7 Beispiel 29 98,0 86,2 Beispiel 30 98,7 86,7 Beispiel 31 98,0 86,6 Beispiel 32 99,3 87,9 A fuel was produced according to Example 18, 30.0% by volume of the mixture of methyl alcohol, methyl formate and methyl tert-butyl ether being present, and the RON and MOZ were determined. Table I REGULAR GASOLINE RON MOZ Example 2 90.3 81.6 Example 3 91.1 82.3 Example 4 91.8 83.0 Example 5 93.1 84.2 Example 6 94.2 85.1 Example 7 95.2 86.1 Example 8 96.1 87.0 Example 9 115.0 114.8 Example 10 91.9 82.4 Example 11 93.1 84.0 Example 12 94.3 84.8 Example 13 92.0 83.3 Example 14 94.5 84.9 Example 15 92.1 83.6 Example 16 94.4 85.0 EUROSUPER RON MOZ Example 18 96.0 84.5 Example 19 96.6 85.1 Example 20 97.1 85.6 Example 21 98.1 86.9 Example 22 99.0 88.1 Example 23 99.9 89.0 Example 24 101.0 89.9 Example 25 115.0 114.8 Example 26 97.0 85.9 Example 27 98.2 86.2 Example 28 99.1 87.7 Example 29 98.0 86.2 Example 30 98.7 86.7 Example 31 98.0 86.6 Example 32 99.3 87.9

Claims (7)

  1. Use of methyl formate as an additive for increasing the octane number, in particular the motor octane number, in a manganese-, lead- and iron-free fuel for internal combustion engines having electrical ignition and having a carburettor and/or fuel injection, having a boiling fraction from 30°C to 200°C, in particular from 30°C to 180°C, containing paraffinic and/or olefinic and/or naphthenic and/or aromatic hydrocarbons, in particular in an amount of 1.0% by volume to 50.0% by volume, optionally 1.0% by volume to 30.0% by volume, preferably 3.5% by volume to 10.0% by volume, relative to the total solution of the fuel.
  2. Fuel for internal combustion engines having electrical ignition and having a carburettor and/or fuel injection, having a boiling fraction of from 30°C to 200°C, in particular from 30°C to 180°C, containing paraffinic and/or olefinic and/or naphthenic and/or aromatic hydrocarbons, which fuel is free of manganese, of lead and of iron and contains in particular 1.0% by volume to 50.0% by volume, optionally 1.0% by volume to 30.0% by volume, preferably 3.5% by volume to 10.0% by volume of methyl formate, characterized in that it additionally contains methyl tert-butyl ether, in particular in amounts by volume which are equal to those of methyl formate.
  3. Fuel according to Claim 2, characterized in that it contains 10.0% by volume to 60.0% by volume, in particular 30.0% by volume to 50.0% by volume, of a mixture of methyl formate and methyl tert-butyl ether.
  4. Fuel according to Claim 2 or 3, characterized in that it additionally contains alcohols, in particular methyl alcohol and/or ethyl alcohol.
  5. Fuel according to one of Claims 2, 3 or 4, characterized in that it contains 10.0% by volume to 60.0% by volume, in particular 30.0% by volume to 50.0% by volume, of a mixture of methyl tert-butyl ether, methyl formate and methyl alcohol, in particular in equal parts by volume.
  6. Fuel for internal combustion engines having electrical ignition and having a carburettor and/or fuel injection, having a boiling fraction of from 30°C to 200°C, in particular from 30°C to 180°C, containing paraffinic and/or olefinic and/or naphthenic and/or aromatic hydrocarbons, which fuel is free of manganese, of lead and of iron and contains in particular 1.0% by volume to 50.0% by volume, optionally 1.0% by volume to 30.0% by volume, preferably 3.5% by volume to 10.0% by volume, of methyl formate, characterized in that it additionally contains alcohols, in particular methyl alcohol and/or ethyl alcohol.
  7. Fuel according to Claim 2 for internal combustion engines having electrical ignition and having a carburettor and/or fuel injection, having a boiling fraction of from 30°C to 200°C, in particular from 30°C to 180°C, containing paraffinic and/or olefinic and/or naphthenic and/or aromatic hydrocarbons, which fuel is free of manganese, of lead and of iron and contains in particular 1.0% by volume to 50.0% by volume, optionally 1.0% by volume to 30.0% by volume, preferably 3.5% by volume to 10.0% by volume, of methyl formate, characterized in that it contains 10.0% by volume to 60.0% by volume, in particular 30.0% by volume to 50.0% by volume, of a mixture of methyl tert-butyl ether, methyl formate and methyl alcohol, in particular in equal parts by volume.
EP91890292A 1991-02-26 1992-01-01 Fuel for internal combustion engines and application of methylformate Expired - Lifetime EP0501097B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT401/91 1991-02-26
AT0040191A AT404596B (en) 1991-02-26 1991-02-26 FUEL FOR COMBUSTION ENGINES AND USE OF METHYL FORMATE

Publications (2)

Publication Number Publication Date
EP0501097A1 EP0501097A1 (en) 1992-09-02
EP0501097B1 true EP0501097B1 (en) 1995-08-30

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Application Number Title Priority Date Filing Date
EP91890292A Expired - Lifetime EP0501097B1 (en) 1991-02-26 1992-01-01 Fuel for internal combustion engines and application of methylformate

Country Status (7)

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US (1) US5232464A (en)
EP (1) EP0501097B1 (en)
AT (1) AT404596B (en)
CS (1) CS53792A3 (en)
DE (1) DE59203411D1 (en)
HU (1) HU210759B (en)
YU (1) YU16892A (en)

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EP3636910A1 (en) 2018-10-08 2020-04-15 OxFA GmbH Use of a formic acid alkylester and/or an oxymethylene dimethyl ether or polyoxymethylene dimethyl ether

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US5236467A (en) * 1992-06-12 1993-08-17 Excellene Limited Double fortified hydrocarbon and process for making and using the same
US5380346A (en) * 1992-06-12 1995-01-10 Fritz; James E. Fortified hydrocarbon and process for making and using the same
US6923839B2 (en) * 2001-06-26 2005-08-02 Cooper Cameron Fuel blend for an internal combustion engine
GB0126990D0 (en) * 2001-11-09 2002-01-02 Carroll Robert Method and composition for improving fuel consumption
WO2011053650A2 (en) * 2009-10-30 2011-05-05 Chevron U.S.A. Inc. A fuel composition
WO2012058280A2 (en) * 2010-10-26 2012-05-03 Delphi Technologies, Inc. High-efficiency internal combustion engine and method for operating employing full-time low-temperature partially-premixed compression ignition with low emissions
US10577549B2 (en) * 2016-08-24 2020-03-03 Sabic Global Technologies B.V. N,N-dimethylacetamide as wash-oil for dilution steam systems
EP3399008B1 (en) * 2017-05-02 2020-03-18 ASG Analytik-Service Gesellschaft mbH Potentially co2-neutral and ecological gasoline based on c1-chemistry

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GB1411947A (en) * 1972-02-01 1975-10-29 British Petroleum Co Gasoline composition
DE2447345A1 (en) * 1974-10-04 1976-04-15 Kuehn Martin Prof Dr Phil Nat Anti-knock motor fuels contg. alcohols - with addn. of acetals, esters, iron carbonyl and soluble manganese cpds.
US4182913A (en) * 1976-11-22 1980-01-08 Nippon Oil Company Ltd. Method for producing methyl tert-butyl ether and fuel composition containing the same
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Cited By (1)

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Publication number Priority date Publication date Assignee Title
EP3636910A1 (en) 2018-10-08 2020-04-15 OxFA GmbH Use of a formic acid alkylester and/or an oxymethylene dimethyl ether or polyoxymethylene dimethyl ether

Also Published As

Publication number Publication date
EP0501097A1 (en) 1992-09-02
HU9200619D0 (en) 1992-05-28
CS53792A3 (en) 1992-09-16
DE59203411D1 (en) 1995-10-05
US5232464A (en) 1993-08-03
ATA40191A (en) 1998-05-15
YU16892A (en) 1994-06-10
AT404596B (en) 1998-12-28
HU210759B (en) 1995-07-28
HUT60319A (en) 1992-08-28

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