EP0014992A1 - Application of polyethers and acetals based on methanol and/or ethanol as fuels for Diesel engines and fuels for Diesel engines comprising these compounds - Google Patents

Application of polyethers and acetals based on methanol and/or ethanol as fuels for Diesel engines and fuels for Diesel engines comprising these compounds Download PDF

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Publication number
EP0014992A1
EP0014992A1 EP80100827A EP80100827A EP0014992A1 EP 0014992 A1 EP0014992 A1 EP 0014992A1 EP 80100827 A EP80100827 A EP 80100827A EP 80100827 A EP80100827 A EP 80100827A EP 0014992 A1 EP0014992 A1 EP 0014992A1
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Prior art keywords
fuels
methanol
ethanol
polyethers
diesel engines
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EP80100827A
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German (de)
French (fr)
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EP0014992B1 (en
Inventor
Knut Dr. Oppenlaender
Franz Dr. Merger
Rainer Dr. Strickler
Friedrich Dr. Hovemann
Helmut Schmidt
Klaus Starke
Karl Dr. Stork
Wolfgang Dr. Vodrazka
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BASF SE
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BASF SE
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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
    • 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
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • 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 the use of polyethers and acetals based on methanol and / or ethanol as diesel fuels, and to diesel fuels containing these components.
  • alcohols including methanol and ethanol
  • these alcohols are not suitable for diesel engines, since they only produce cetane numbers of around 8-10, and trouble-free driving is only guaranteed with cetane numbers from around 20.
  • these auxiliaries are either expensive or have considerable disadvantages.
  • Alkyl and cycloalkyl nitrates which are mainly used for this purpose, are not toxicologically harmless or technically difficult to manufacture and, since they tend to explode, are not safe to handle. Above all, however, they can hydrolyze due to the water still contained in the alcohols to form the corrosive nitric acid.
  • the 'degree of polyetherification n is to be understood in each case as the mean degree of polyetherification.
  • the monomethyl and monoethyl ether of ethylene glycol and of prcpylene glycol as compounds (I) are less suitable in their own right than diesel fuels, but as components in amounts of around 85% by volume in mixtures with the higher molecular weight compounds (I) and (II) .
  • polyethers (I) preference is given to those in which A represents ethylene units, since most of these can be prepared from ethanol as a raw material by dehydrating ethanol to form ethylene, which is then oxidatively converted into ethylene oxide, which is then added to methanol in a polyaddition reaction .
  • the quality of the acetals (II) increases with increasing degree of etherification m and increasing C content of the radicals R 3 and R 4 .
  • formaldehyde and acetaldehyde dimethyl acetal is preferred for economic reasons, since these acetals can be obtained entirely from methanol and ethanol.
  • this also applies to those aldehydes which can be obtained via the aldol condensation of acetaldehyde, such as crotonaldehyde.
  • the relatively inexpensive ethyl hexanal should also be emphasized here.
  • the alkyl radicals can be branched or unbranched, but preference is given to the compounds (II) with branched straight-chain radicals.
  • polyethers (I) and the acetals (II) are known or are easily accessible by known, large-scale processes.
  • the engine power is surprisingly not reduced by the relatively high water content.
  • the absolute energy content in water-containing mixtures is lower in accordance with their water content, the efficiency of the motors is increased by the water because the heat losses are reduced.
  • the diesel fuels according to the invention to which the auxiliaries customary for mineral diesel fuels can be added, but as a rule do not need to be added, are not only suitable for their purpose in terms of engine performance and driving behavior, but are also particularly environmentally friendly since they are practical Burn completely to carbon dioxide and water and because the exhaust gases therefore contain very little carbon monoxide, hydrocarbons, nitrous gases and soot.
  • the energy content of the diesel fuels according to the invention is 60-90% of the conventional mineral oil-based fuels per unit weight.
  • cetane number (CZ) of various diesel fuels according to the invention was measured under practical conditions, ie in each case with a full air filling.

Abstract

1. Use of a) polyethers of the general formula I R**1 -O-(A-O-)n -R**2 where A is an ethylene or 1,2-propylene group, R**1 is C1 -C8 -alkyl and R**2 is hydrogen or C1 -C4 -alkyl, and n is from 1 to 5, and/or b) acetals of the general formula II see diagramm : EP0014992,P13,F1 where R**3 is hydrogen or C1 -C12 -alkyl and R**4 is methyl or ethyl, and m is from 0 to 5, used individually or mixed with c) up to 45% by volume of ethanol (III) and/or methanol (IV) and/or d) up to 30% by volume of water (V) and/or e) up to 85% by volume of petroleum-based diesel fuels (VI) as fuels for diesel engines.

Description

Die vorliegende Erfindung betrifft die Verwendung von Polyäthern und Acetalen auf der Basis von Methanol und/oder Äthanol als Dieselkraftstoffe sowie diese Komponenten enthaltende Dieselkraftstoffe.The present invention relates to the use of polyethers and acetals based on methanol and / or ethanol as diesel fuels, and to diesel fuels containing these components.

Es ist allgemein bekannt, daß sich Alkohole, darunter Methanol und Äthanol, als Kraftstoffe für Ottomotoren eignen. Für Dieselmotoren sind diese Alkohole jedoch nicht brauchbar, da sie hier nur Cetanzahlen von ungefähr 8 - 10 erbringen, ein störungsfreier Fahrbetrieb aber erst mit Cetanzahlen ab etwa 20 gewährleistet ist. Zwar kann man die Wirkung derartiger Mischungen zur Verbesserung des Zündverhaltens durch Zugabe von Zündwilligkeitsverbesserern oder Zündbeschleunigern erhöhen, jedoch sind diese Hilfsmittel entweder teuer oder sie weisen erhebliche Nachteile auf. Alkyl- und Cycloalkylnitrate, die hauptsächlich für diesen Zweck verwendet werden, sind toxikologisch nicht unbedenklich oder technisch nur aufwendig herzustellen und, da sie zu Explosionen neigen, nicht gefahrlos zu handhaben. Vor allem aber können sie infolge des in den Alkoholen stets noch enthaltenen Wassers unter Bildung der korrosiven Salpetersäure hydrolysieren.It is well known that alcohols, including methanol and ethanol, are useful fuels for gasoline engines. However, these alcohols are not suitable for diesel engines, since they only produce cetane numbers of around 8-10, and trouble-free driving is only guaranteed with cetane numbers from around 20. Although the effect of such mixtures for improving the ignition behavior can be increased by adding ignition enhancers or ignition accelerators, these auxiliaries are either expensive or have considerable disadvantages. Alkyl and cycloalkyl nitrates, which are mainly used for this purpose, are not toxicologically harmless or technically difficult to manufacture and, since they tend to explode, are not safe to handle. Above all, however, they can hydrolyze due to the water still contained in the alcohols to form the corrosive nitric acid.

Da sich einerseits Kraftstoffe auf Basis von Mineralöl zunehmend verteuern und die ausreichende Versorgung mit Rohöl bekanntermaßen gefährdet ist, andererseits aber Methanol, wenn auch in begrenztem Umfang, zunehmend konkurrenzfähiger wird und Äthanol pflanzlicher Provenienz in zahlreichen Ländern in großen Mengen zur Verfügung gestellt werden kann, lag der Erfindung die allgemeine Aufgabe zugrunde, die Mineralöl-Dieselkarftstoffe durch wirtschaftliche und umweltfreundliche Kraftstoffe auf der Basis dieser Alkohole zu ersetzen.Because on the one hand fuels based on mineral oil are becoming increasingly expensive and the sufficient supply of crude oil is known to be at risk, but on the other hand methanol is becoming increasingly competitive, albeit to a limited extent, and ethanol of plant origin can be made available in large quantities in numerous countries the invention is based on the general task of the mine Replacing ralöl diesel car fuels with economical and environmentally friendly fuels based on these alcohols.

Aus der DE-OS 27 53 027 ist es bekannt, Mischungen aus überwiegenden Mengen Methanol und Polyalkylenglykoläthern als Dieselkraftstoffe zu verwenden. Methanol ist jedoch im wesentlichen preiswert nur erhältlich, wo auch Erdgas oder Kohle verfügbar ist, so daß das Problem der größeren Unabhängigkeit von Erdgas oder Erdöl produzierenden Ländern mit diesem Vorschlag nicht zufriedenstellend gelöst wird. Außerdem ist es ein Nachteil dieser Gemische, daß sie mit herkömmlichen Dieselkraftstoffen nicht mischbar sind.From DE-OS 27 53 027 it is known to use mixtures of predominant amounts of methanol and polyalkylene glycol ethers as diesel fuels. However, methanol is essentially only available cheaply where natural gas or coal is available, so this proposal does not satisfactorily solve the problem of greater independence from natural gas or oil producing countries. It is also a disadvantage of these blends that they are immiscible with conventional diesel fuels.

Demgemäß war es Aufgabe der Erfindung, herkömmliche Dieselkraftstoffe gänzlich oder zum Teil durch Dieselkraftstoffe auf der Basis von Methanol und vor allem Äthanol zu ersetzen.Accordingly, it was an object of the invention to replace conventional diesel fuels entirely or in part with diesel fuels based on methanol and, above all, ethanol.

Es wurde gefunden, daß sich

  • a) Polyäther der allgemeinen Formel I
    Figure imgb0001
    in der A eine Äthylen- oder 1,2-Propylengruppe bedeutet, R1 für einen C1-C8-Alkylrest und R2 für Wasserstoff oder einen C1-C4-Alkylrest steht und n einen Wert von 1-5 hat, und/oder
  • b) Acetale. der allgemeinen Formel II
    Figure imgb0002
    in der R3 Wasserstoff oder eine C1-C12-ALKYLgrup- pe und R4 für die Methylgruppe cder die Äthylgruppe steht und m einen Wert von 0-5 hat, allein oder in Mischung mit
  • c) bis zu 45 Vol.% Äthanol (III) und/oder Methanol (IV) und/oder
  • d) bis zu 30 Vol.-% Wasser (V) und/oder
  • e) bis zu 85 Vol.-% von Dieselkraftstoffen auf Mineralölbasis (VI)

hervorragend als Dieselkraftstoffe eignen.It has been found that
  • a) polyether of the general formula I.
    Figure imgb0001
     in which A represents an ethylene or 1,2-propylene group, R 1 represents a C 1 -C 8 alkyl radical and R 2 represents hydrogen or a C 1 -C 4 alkyl radical and n has a value of 1-5, and or
  • b) acetals. of the general formula II
    Figure imgb0002
     in which R 3 is hydrogen or a C 1 -C 12 -ALKYL group and R 4 represents the methyl group or the ethyl group and m has a value of 0-5, alone or in a mixture with
  • c) up to 45% by volume of ethanol (III) and / or methanol (IV) and / or
  • d) up to 30 vol .-% water (V) and / or
  • e) up to 85 vol .-% of diesel fuels based on mineral oil (VI)

excellent as diesel fuels.

Gut geeignete Kraftstoffe dieser Art sind durch folgende Zusammensetzung gekennzeichnet:

  • i) 15-90 Vol.-% eines Polyäthers (I) oder Mischungen solcher Polyäther und/oder 15-90 Vol.-% eines Acetals (II) oder Mischungen solcher Acetale
  • ii) bis zu 45 Vol.-% Äthanol (III) und/oder Methanol (IV)
  • iii) bis zu 30 Vol.-%'Wasser (V) und
  • iv) bis zu 85 Vol.-% von Dieselkraftstoffen auf Mineralölbasis (VI).
Well-suited fuels of this type are characterized by the following composition:
  • i) 15-90% by volume of a polyether (I) or mixtures of such polyethers and / or 15-90% by volume of an acetal (II) or mixtures of such acetals
  • ii) up to 45% by volume of ethanol (III) and / or methanol (IV)
  • iii) up to 30% by volume of water (V) and
  • iv) up to 85% by volume of mineral oil-based diesel fuels (VI).

Hierbei gilt die Regel, daß die durch die Cetanzahl definierte Qualität des Polyäthers (I) und des Acetals (II) mit steigendem Polyverätherungsgrad zunimmt, wodurch sich der Anteil der Komponenten (III) bis (V) entsprechend erhöhen läßt.The rule here is that the quality of the polyether (I) and the acetal (II) defined by the cetane number increases with increasing degree of polyetherification, which means that the proportion of components (III) to (V) can be increased accordingly.

Unter dem' Polyverätherungsgrad n ist jeweils der mittlere Polyverätherungsgrad zu verstehen.The 'degree of polyetherification n is to be understood in each case as the mean degree of polyetherification.

Da die Polyäther (I) und die Acetale (II) mit steigendem Verätherungsgrad einerseits teurer werden, andererseits aber mit umso größeren Mengen der wesentlich billigeren Alkohole (III) und (IV) verschnitten werden können, richtet sich das wirtschaftliche Mischungsoptimum nach dem Preis dieser Komponenten. Der Monomethyl- und Monoäthyläther des Äthylenglykols und des Prcpylenglykols als Verbindungen (I) eignen sich für sich allein weniger als Dieselkraftstoffe, hingegen jedoch als Komponenten in Mengen bei zu etwa 85 Vol.% in Mischungen mit den höhermolekularen Verbindungen (I) und (II).As the polyether (I) and acetals (II) on the one hand more expensive with increasing degree of etherification, on the other hand with even larger amounts of the substantially cheaper alcohols (III) and (I V) can be blended, the economic mixture optimum depends on the value of these Components. The monomethyl and monoethyl ether of ethylene glycol and of prcpylene glycol as compounds (I) are less suitable in their own right than diesel fuels, but as components in amounts of around 85% by volume in mixtures with the higher molecular weight compounds (I) and (II) .

Unter den Polyäthern (I) werden diejenigen bevorzugt, in denen A für Äthyleneinheiten steht, da diese größtenteils aus Äthanol als Rohstoff hergestellt werden können, indem man Äthanol zum Äthylen dehydratisiert, dieses oxidativ in Äthylenoxid überführt, welches sodann in einer Polyadditionsreaktion an Methanol angelagert wird.Among the polyethers (I), preference is given to those in which A represents ethylene units, since most of these can be prepared from ethanol as a raw material by dehydrating ethanol to form ethylene, which is then oxidatively converted into ethylene oxide, which is then added to methanol in a polyaddition reaction .

Die Qualität der Acetale (II) nimmt zwar mit steigendem Verätherungsgrad m und steigendem C-Gehalt der Reste R3 und R4. zu, jedoch bevorzugt man aus wirtschaftlichen Gründen Formaldehyd- und Acetaldehyddimethylacetal, da diese Acetale gänzlich aus Methanol und Äthanol gewonnen werden können. In abgeschwächter Form gilt dies auch für solche Aldehyde, die über die Aldolkondensation von Acetaldehyd erhältlich sind, wie beispielsweise Crotonaldehyd. Auch das relativ preiswerte Äthylhexanal ist hier hervorzuheben. Allgemein können die Alkylreste verzweigt oder unverzweigt sein, wobei jedoch den Verbindungen (II) mit Verzweigt geradkettigem Resten der Vorzug zu geben ist.The quality of the acetals (II) increases with increasing degree of etherification m and increasing C content of the radicals R 3 and R 4 . to, however, formaldehyde and acetaldehyde dimethyl acetal is preferred for economic reasons, since these acetals can be obtained entirely from methanol and ethanol. To a lesser extent, this also applies to those aldehydes which can be obtained via the aldol condensation of acetaldehyde, such as crotonaldehyde. The relatively inexpensive ethyl hexanal should also be emphasized here. In general, the alkyl radicals can be branched or unbranched, but preference is given to the compounds (II) with branched straight-chain radicals.

Die Acetale (II) bieten den Vorteil, daß sie mit Dieselkraftstoff auf Basis von Mineralöl in jedem Verhältnis gemischt und in Form dieser Mischungen verwendet werden können. Dies gilt auch für Polyäther (I), in denen R2 ‡ H ist. Für die übrigen Polyäther (R2 = H) sind die Mischungsverhältnisse unschwer zu ermitteln.The acetals (II) offer the advantage that they can be mixed with diesel fuel based on mineral oil in any ratio and used in the form of these mixtures. This also applies to polyethers (I) in which R 2 ‡ H. The mixing ratios for the other polyethers (R 2 = H) are easy to determine.

Die Polyäther (I) und die Acetale (II) sind bekannt oder nach bekannten, großtechnisch ausgeübten Verfahren leicht zugänglich.The polyethers (I) and the acetals (II) are known or are easily accessible by known, large-scale processes.

Durch die verhältnismäßig hohen Wasseranteile wird die Motorleistung überraschenderweise nicht herabgesetzt. Zwar ist der absolute Energieinhalt in wasserhaltigen Mischungen entsprechend ihrem Wasseranteil geringer, jedoch wird der Wirkungsgrad der Motoren durch das Wasser erhöht, weil die Wärmeverluste vermindert werden.The engine power is surprisingly not reduced by the relatively high water content. Although the absolute energy content in water-containing mixtures is lower in accordance with their water content, the efficiency of the motors is increased by the water because the heat losses are reduced.

Die erfindungsgemäßen Dieselkraftstoffe, denen man die für mineralische Dieselkraftstoffe üblichen Hilfsmittel zusetzen kann, in aller Regel aber nicht zuzusetzen braucht, eignen sich nicht nur im Hinblick auf die Motorleistung und das Fahrverhalten hervorragend für ihren Zweck, sondern sind außerdem noch besonders umweltfreundlich, da sie praktisch restlos zu Kohlendioxid und Wasser verbrennen und da die Abgase deshalb nur noch sehr wenig Kohlenmonoxid, Kohlenwasserstoffe, nitrose Gase und Ruß enthalten. Ein zusätzlicher Vorteil der erfindungsgemäßen Dieselkraftstoffe liegt darin, daß sie mit steigendem Gehalt an den Polyäthern (I) und den Acetalen (II) kältestabiler als die herkömmlichen Kraftstoffe werden. Besonders sind hier die Polyäther mit R2 = H hervorzuheben, die in reiner Form bis zu (-50°C) betriebsfähig bleiben.The diesel fuels according to the invention, to which the auxiliaries customary for mineral diesel fuels can be added, but as a rule do not need to be added, are not only suitable for their purpose in terms of engine performance and driving behavior, but are also particularly environmentally friendly since they are practical Burn completely to carbon dioxide and water and because the exhaust gases therefore contain very little carbon monoxide, hydrocarbons, nitrous gases and soot. An additional advantage of the diesel fuels according to the invention is that they become more stable to cold than the conventional fuels with increasing content of the polyethers (I) and the acetals (II). Particularly noteworthy here are the polyethers with R2 = H , which in pure form remain operational down to (-50 ° C).

Der Energieinhalt der erfindungsgemäßen Dieselkraftstoffe liegt pro Gewichtseinheit bei 60 - 90% der herkömmlichen Kraftstoffe auf Mineralölbasis. Hierdurch werden an den Dieselmotoren üblicher Bauart einige technische Veränderungen, wie die Vergrößerung der Pumpenelemente in der Kraftstoffeinspritzpumpe, bedingt. Diese Änderungen lassen sich bei der Fertigung der Motoren ohne weiteres berücksichtigen sowie an herkömmlichen Motoren nachträglich anbringen. Im übrigen bestehen keine Unterschiede zu den herkömmlichen Motoren, weder im Hinblick auf die Bauart noch auf das Fahrverhalten.The energy content of the diesel fuels according to the invention is 60-90% of the conventional mineral oil-based fuels per unit weight. As a result, some technical changes, such as the enlargement of the pump elements in the fuel injection pump, are caused on the diesel engines of conventional design. These changes can easily be taken into account in the manufacture of the motors and can be retrofitted to conventional motors. Otherwise, there are no differences to conventional engines, neither in terms of design nor in terms of driving behavior.

BeispieleExamples

Mittels eines Prüfmotors mit dem Verdichtungsverhältnis ε = 22 wurde unter praktischen Bedingungen, d.h. jeweils mit voller Luftfüllung, die Cetanzahl (CZ) verschiedener erfindungsgemäßer Dieselkraftstoffe gemessen. Als Bezugskraftstoffe dienten α-Methylnaphthalin (CZ = 0) und Cetan (Hexadecan) (CZ = 100). Die Ergebnisse sind den folgenden Tabellen zu entnehmen.

Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
 Using a test engine with the compression ratio ε = 22, the cetane number (CZ) of various diesel fuels according to the invention was measured under practical conditions, ie in each case with a full air filling. The reference fuels were α-methylnaphthalene (CZ = 0) and cetane (hexadecane) (CZ = 100). The results are shown in the following tables.
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014

Claims (2)

1. Verwendung von a) Polyäthern der allgemeinen Formel I
Figure imgb0015
in der A eine Äthylen- oder 1,2-Propylengruppe bedeutet, R1 für einen C1-C8-Alkylrest und R2 für Wasserstoff oder einen C1-C4-Alkylrest steht und n einen Wert von 1-5 hat, und/oder b) Acetalen der allgemeinen Formel II
Figure imgb0016
in der R3 Wasserstoff oder eine C1-C12-Alkylgruppe und R4 für die Methylgruppe oder die Äthyl- .gruppe steht und m einen Wert von 0-5 hat, allein oder in Mischung mit c) bis zu 45 Vol.-% Äthanol (III) und/oder Methanol (IV) und/oder d) bis zu 30 Vol.-% Wasser (V) und/oder e) bis zu 85 Vol.-% von Dieselkraftstoffen auf Mineralölbasis (VI)als Dieselkraftstoffe.1. Use of a) Polyethers of the general formula I
Figure imgb0015
 in which A represents an ethylene or 1,2-propylene group, R 1 represents a C 1 -C 8 alkyl radical and R 2 represents hydrogen or a C 1 -C 4 alkyl radical and n has a value of 1-5, and or b) acetals of the general formula II
Figure imgb0016
 in which R 3 is hydrogen or a C 1 -C 12 alkyl group and R 4 is the methyl group or the ethyl group and m has a value of 0-5, alone or in a mixture with c) up to 45 vol .-% ethanol (III) and / or methanol (IV) and / or d) up to 30 vol .-% water (V) and / or e) up to 85 vol .-% of diesel fuels based on mineral oil (VI) than diesel fuels. 2. Dieselkraftstoffe, gekennzeichnet durch folgende Zus-ammensetzung: i) 15-90 Vol.-% eines Polyäthers (I) oder Mischungen solcher Polyäther und/oder 15-90 Vol.-% eines Acetals (II) oder Mischungen solcher Acetale ii) bis zu 45 Vol.-% Äthanol (III) und/oder Methanol (IV) iii) bis zu 30 Vol.-% Wasser (V) und iv) bis zu 85 Vol.-% von Dieselkraftstoffen auf Mineralölbasis (VI). 2. Diesel fuels, characterized by the following composition: i) 15-90% by volume of a polyether (I) or mixtures of such polyethers and / or 15-90% by volume of an acetal (II) or mixtures of such acetals ii) up to 45% by volume of ethanol (III) and / or methanol (IV) iii) up to 30 vol .-% water (V) and iv) up to 85% by volume of mineral oil-based diesel fuels (VI).
EP80100827A 1979-02-21 1980-02-20 Application of polyethers and acetals based on methanol and/or ethanol as fuels for diesel engines and fuels for diesel engines comprising these compounds Expired EP0014992B1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE2906604 1979-02-21
DE19792906604 DE2906604A1 (en) 1979-02-21 1979-02-21 Synthetic diesel fuel compsns. - contg. poly:ol ether and/or acetal cpds.
DE2937487 1979-09-17
DE2937487 1979-09-17

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EP0014992A1 true EP0014992A1 (en) 1980-09-03
EP0014992B1 EP0014992B1 (en) 1983-05-25

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AU (1) AU5573180A (en)
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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2949118A1 (en) * 1979-12-06 1981-06-11 Basf Ag, 6700 Ludwigshafen Easily ignitable diesel fuels - contg. diesel oil cut, ethanol and higher alcohol(s) as solvents
DE2949535A1 (en) * 1979-12-08 1981-06-11 Basf Ag, 6700 Ludwigshafen Easily ignitable diesel fuels - contg. diesel oil cut, methanol, and higher alcohol(s) as solvents
WO1986003511A1 (en) * 1984-12-11 1986-06-19 Snamprogetti S.P.A. Extenders for gasoil for automotive use
US4723963A (en) * 1984-12-18 1988-02-09 Exxon Research And Engineering Company Fuel having improved cetane
EP0289785A1 (en) * 1987-04-09 1988-11-09 RWE-DEA Aktiengesellschaft für Mineraloel und Chemie Process to prevent or reduce scales in mixture preparation devices of engines
WO1989007637A1 (en) * 1988-02-22 1989-08-24 Berol Nobel Stenungsund Ab Ethanol fuel and its use as a diesel fuel
US5268008A (en) * 1982-12-27 1993-12-07 Union Oil Company Of California Hydrocarbon fuel composition
US5308365A (en) * 1993-08-31 1994-05-03 Arco Chemical Technology, L.P. Diesel fuel
US5314511A (en) * 1992-12-23 1994-05-24 Arco Chemical Technology, L.P. Diesel fuel
US5425790A (en) * 1992-12-23 1995-06-20 Arco Chemical Technology, L.P. Diesel fuel
FR2764301A1 (en) * 1997-06-09 1998-12-11 Elf Antar France FUEL COMPOSITION COMPRISING OXYGEN COMPOUNDS FOR DIESEL ENGINES
EP0903395A1 (en) * 1997-09-23 1999-03-24 Air Products And Chemicals, Inc. Diesel fuel composition comprising dialkoxy alkanes for increased cetane number
WO2001018154A1 (en) * 1999-09-06 2001-03-15 Agrofuel Ab Motor fuel for diesel engines
WO2003078552A2 (en) * 2002-03-14 2003-09-25 The Lubrizol Corporation Ethanol-diesel fuel composition and methods thereof
EP1422285A1 (en) * 2002-11-22 2004-05-26 Eni S.P.A. Use of an oxygenated product as a substitute of gas oil in diesel engines
EP2143778A3 (en) * 2008-07-09 2010-09-08 Man Nutzfahrzeuge Ag Low-soot diesel fuel containing a fuel additive, its use and the use of the fuel additive to create low-soot diesel fuel
WO2011012339A1 (en) * 2009-07-31 2011-02-03 Man Nutzfahrzeuge Aktiengesellschaft Use of polyoxymethylene (alkyl polyglycol) ethers as an additive to diesel fuels for lowering the soot emission in spontaneous combustion engines
US9447724B2 (en) 2010-11-25 2016-09-20 Gane Energy & Resources Pty Ltd. Fuel and process for powering a compression ignition engine
RU2674168C2 (en) * 2012-03-21 2018-12-05 МЭЙМАН РИСЕРЧ, ЭлЭлСи Internal combustion engine using a mixture based on water as a fuel, and the way it works
US10436108B2 (en) 2013-09-25 2019-10-08 MayMaan Research, LLC Internal combustion engine using a water-based mixture as fuel and method for operating the same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2842432A (en) * 1953-12-07 1958-07-08 Texas Co Supplementary fuel mixture for cold starting diesel engines
FR2372224A1 (en) * 1976-11-29 1978-06-23 Berol Kemi Ab

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2842432A (en) * 1953-12-07 1958-07-08 Texas Co Supplementary fuel mixture for cold starting diesel engines
FR2372224A1 (en) * 1976-11-29 1978-06-23 Berol Kemi Ab
DE2753027A1 (en) * 1976-11-29 1978-07-20 Berol Kemi Ab USE OF A COMPOSITION BASED ON METHANOL AS DIESEL FUEL

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2949118A1 (en) * 1979-12-06 1981-06-11 Basf Ag, 6700 Ludwigshafen Easily ignitable diesel fuels - contg. diesel oil cut, ethanol and higher alcohol(s) as solvents
DE2949535A1 (en) * 1979-12-08 1981-06-11 Basf Ag, 6700 Ludwigshafen Easily ignitable diesel fuels - contg. diesel oil cut, methanol, and higher alcohol(s) as solvents
US5268008A (en) * 1982-12-27 1993-12-07 Union Oil Company Of California Hydrocarbon fuel composition
WO1986003511A1 (en) * 1984-12-11 1986-06-19 Snamprogetti S.P.A. Extenders for gasoil for automotive use
US4723963A (en) * 1984-12-18 1988-02-09 Exxon Research And Engineering Company Fuel having improved cetane
EP0289785A1 (en) * 1987-04-09 1988-11-09 RWE-DEA Aktiengesellschaft für Mineraloel und Chemie Process to prevent or reduce scales in mixture preparation devices of engines
WO1989007637A1 (en) * 1988-02-22 1989-08-24 Berol Nobel Stenungsund Ab Ethanol fuel and its use as a diesel fuel
US5183476A (en) * 1988-02-22 1993-02-02 Berol Nobel Stenungsund Ab Ethanol fuel and its use as a diesel fuel
US5425790A (en) * 1992-12-23 1995-06-20 Arco Chemical Technology, L.P. Diesel fuel
US5314511A (en) * 1992-12-23 1994-05-24 Arco Chemical Technology, L.P. Diesel fuel
US5308365A (en) * 1993-08-31 1994-05-03 Arco Chemical Technology, L.P. Diesel fuel
FR2764301A1 (en) * 1997-06-09 1998-12-11 Elf Antar France FUEL COMPOSITION COMPRISING OXYGEN COMPOUNDS FOR DIESEL ENGINES
WO1998056879A1 (en) * 1997-06-09 1998-12-17 Elf Antar France Fuel composition for diesel engines containing oxygenated compounds
US6113661A (en) * 1997-06-09 2000-09-05 Elf Antar France Fuel composition for diesel engines containing oxygenated compounds
EP0903395A1 (en) * 1997-09-23 1999-03-24 Air Products And Chemicals, Inc. Diesel fuel composition comprising dialkoxy alkanes for increased cetane number
WO2001018154A1 (en) * 1999-09-06 2001-03-15 Agrofuel Ab Motor fuel for diesel engines
US7014668B2 (en) 1999-09-06 2006-03-21 Agrofuel Ab Motor fuel for diesel, gas-turbine and turbojet engines
BG65624B1 (en) * 1999-09-06 2009-03-31 Agrofuel Ab Motor fuel for diesel, gas-turbine and turbojet engines, comprising at least four different oxygen-containing functional groups selected from alcohol, ether, aldehyde, ketone, ester, inorganic ester, acetal, epoxide and peroxide
WO2003078552A2 (en) * 2002-03-14 2003-09-25 The Lubrizol Corporation Ethanol-diesel fuel composition and methods thereof
US7208022B2 (en) 2002-03-14 2007-04-24 The Lubrizol Corporation Ethanol-diesel fuel composition and methods thereof
WO2003078552A3 (en) * 2002-03-14 2004-03-25 Lubrizol Corp Ethanol-diesel fuel composition and methods thereof
EP1422285A1 (en) * 2002-11-22 2004-05-26 Eni S.P.A. Use of an oxygenated product as a substitute of gas oil in diesel engines
US7235113B2 (en) 2002-11-22 2007-06-26 Eni S.P.A. Use of an oxygenated product as a substitute of gas oil in diesel engines
EP2143778A3 (en) * 2008-07-09 2010-09-08 Man Nutzfahrzeuge Ag Low-soot diesel fuel containing a fuel additive, its use and the use of the fuel additive to create low-soot diesel fuel
DE102009035503A1 (en) 2009-07-31 2011-02-10 Man Nutzfahrzeuge Ag Use of polyoxymethylene di (alkylpolyglycol) ethers as an additive to diesel fuels to reduce soot emissions in compression ignition engines
WO2011012339A1 (en) * 2009-07-31 2011-02-03 Man Nutzfahrzeuge Aktiengesellschaft Use of polyoxymethylene (alkyl polyglycol) ethers as an additive to diesel fuels for lowering the soot emission in spontaneous combustion engines
US8298303B2 (en) 2009-07-31 2012-10-30 Man Nutzfahrzeuge Ag Use of polyoxymethylene di (alkyl polyglycol) ethers as additives to diesel fuels to reduce the particulate emission in self-ignition engines
RU2485170C2 (en) * 2009-07-31 2013-06-20 Ман Трак Унд Бас Аг Using dialkylpolyglycol ethers of polyoxymethylene as diesel fuel additive for reducing emission of solid particles with exhaust gases in self-ignition engines
US9447724B2 (en) 2010-11-25 2016-09-20 Gane Energy & Resources Pty Ltd. Fuel and process for powering a compression ignition engine
US10815441B2 (en) 2010-11-25 2020-10-27 Gane Energy & Resources Pty Ltd. Fuel and process for powering a compression ignition engine
RU2674168C2 (en) * 2012-03-21 2018-12-05 МЭЙМАН РИСЕРЧ, ЭлЭлСи Internal combustion engine using a mixture based on water as a fuel, and the way it works
US10436108B2 (en) 2013-09-25 2019-10-08 MayMaan Research, LLC Internal combustion engine using a water-based mixture as fuel and method for operating the same

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BR8000889A (en) 1980-10-21

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