EP0157268A2 - Injection improver for a fuel mixture - Google Patents

Injection improver for a fuel mixture Download PDF

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Publication number
EP0157268A2
EP0157268A2 EP85103095A EP85103095A EP0157268A2 EP 0157268 A2 EP0157268 A2 EP 0157268A2 EP 85103095 A EP85103095 A EP 85103095A EP 85103095 A EP85103095 A EP 85103095A EP 0157268 A2 EP0157268 A2 EP 0157268A2
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EP
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Prior art keywords
nitrocellulose
parts
ethylene oxide
fuel
fuel mixture
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Granted
Application number
EP85103095A
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German (de)
French (fr)
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EP0157268B1 (en
EP0157268A3 (en
Inventor
Christian Dr. Wegner
Helmut Dr. Waniczek
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Bayer AG
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Bayer AG
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Priority to AT85103095T priority Critical patent/ATE30737T1/en
Publication of EP0157268A2 publication Critical patent/EP0157268A2/en
Publication of EP0157268A3 publication Critical patent/EP0157268A3/en
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Classifications

    • 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
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
    • C10L1/231—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites nitro compounds; nitrates; nitrites
    • 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
    • F02B2275/00—Other engines, components or details, not provided for in other groups of this subclass
    • F02B2275/14—Direct injection into combustion chamber

Definitions

  • the invention relates to ignition improvers for alcoholic fuels and alcoholic fuel mixtures which can be used for the operation of diesel engines.
  • Methanol and ethanol cannot be used in place of the mineral hydrocarbons in conventional diesel engines because the cetane number of ethanol and methanol is only 8 and 3, respectively.
  • diesel engines require a fuel with a cetane number of at least 45 (DIN 51 601; Winnacker-Küchler, Chemische Technologie, Band 3 / I, 326 (1971)).
  • Ignition improvers are therefore required to increase the cetane number.
  • alkyl and cycloalkyl nitrates are known (DE-OS 2 701 588, DE-OS 20 39 609, Mineralogietechnik 80, 25 (4), 1 to 12), but their production is based on is agile and which can hydrolyze in the presence of water. This creates nitric acid, which destroys the motors through corrosion.
  • Nitric acid salts of primary, secondary and tertiary amines such as mono-, di- and triethylammonium nitrate, are also known as ignition improvers for methanol and ethanol (DE-OS 29 09 565), but they also have corrosive properties.
  • ignition improvers for alcoholic fuels which contain nitric acid esters of mono- and / or polysaccharides, e.g. Nitrocellulose included.
  • nitric acid esters of mono- and / or polysaccharides e.g. Nitrocellulose included.
  • films of nitrocellulose form on the walls, which can lead to solid, constipating residues. This disadvantage cannot be solved satisfactorily by adding further solvents.
  • Ignition improvers for alcoholic fuels for internal combustion engines have been found which contain nitrocellulose with a nitrogen content of 9 to 14% and polyether with at least three ethylene oxide units.
  • the ignition improvers according to the invention do not leave any residues which lead to blockages. They are completely compatible with petroleum-based fuels.
  • Nitrocellulose with a nitrogen content of 9 to 14%, preferably 10 to 13%, can be used for the ignition improvers according to the invention.
  • Nitrocelluloses which increase the viscosity of the alcoholic fuel as little as possible are particularly preferred. Therefore, according to the invention, nitrocelluloses with an intrinsic viscosity k of less than 1000, preferably from 800 to 200, are used particularly advantageously.
  • the intrinsic viscosity of nitrocellulose can be determined in a manner known per se (Fikentscher, Cellulosechemie 13, 58 (1932)).
  • nitrocellulose for the ignition improvers is known per se (K. Fabel, nitrocellulose production and properties, Enke Verlag, Stuttgart (1950)). It can be produced, for example, by mixing it with nitric acid or its anhydride in a homogeneous and / or heterogeneous phase Presence of water-drawing agents such as sulfuric acid, phosphoric acid, phosphorus pentoxide or acetic anhydride is implemented. The degree of nitration can be controlled as desired by the amount and concentration of the nitric acid or the dehydrating additives.
  • Polyethers having at least three ethylene oxide units, preferably 4 to 100 ethylene oxide units, are used for the ignition improvers according to the invention. According to the invention, preference is given to polyethers which are prepared in a manner known per se by reacting compounds which have at least one OH and / or NH group with ethylene oxide. It is of course possible and possibly also technically expedient to use polyethers with different degrees of ethoxylation and different OH and NH compounds.
  • the polyethers can also contain alkylene oxide units, preferably 0.1 to 0.5 propylene oxide units, based on an ethylene oxide unit.
  • Alkyl here generally represents a straight-chain or branched hydrocarbon radical having 1 to 6 carbon atoms.
  • the following alkyl radicals may be mentioned, for example: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl and isohexyl.
  • the compounds having at least one OH or NH group are substituted by further hydroxyamino groups, compounds having 1 to 5, preferably 1 or 2, hydroxyl and / or amino groups are preferred.
  • Examples of compounds with an OH and / or NH group are water, mono- and polyols such as methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol, Propylene glycol, glycerin, trimethylolpropane, pentaerythritol, and nitrogen-containing compounds such as ammonia, ethanolamine, triethanolamine and dimethylethanolamine. Mixtures of these compounds can also be used as starter molecules for the addition of ethylene oxide. Water and lower mono- and polyols are particularly preferred as starters.
  • the concentrates generally contain 15 to 60 parts by weight of nitrocellulose and 20 to 70 parts by weight of polyether.
  • the ignition improvers according to the invention preferably contain 20 to 50 parts by weight of nitrocellulose and 30 to 60 parts by weight of polyether.
  • the ignition improvers according to the invention can of course also contain other additives known per se.
  • other, known ignition improvers as well as the addition of components that are suitable for diesel engine combustion, such as.
  • the addition of detergents and starting aids is also possible.
  • the fuels containing the ignition improvers according to the invention can be obtained directly from the individual components, i.e. H. Nitrocellulose, polyether and alcohol can be produced. However, it is preferred to prepare a concentrate consisting of these components, which is then to be diluted with alcohol to such an extent that the concentration of the ignition improver according to the invention ensures that an engine runs properly.
  • the ignition improvers according to the invention can be used as an additive to alcoholic fuels.
  • the present invention also relates to fuel mixtures which contain alcohol and an ignition improver which contains nitrocellulose with a nitrogen content of 9 to 14% and a polyether with at least three ethylene oxide units.
  • the fuel mixtures according to the invention are suitable for the operation of diesel engines, in particular vehicle diesel engines and those which place similar demands on the fuel.
  • alcohol is a lower aliphatic alcohol with 1 to 6 carbon atoms. Methanol and / or ethanol is particularly preferred here.
  • the alcohols can optionally contain up to 10% by weight of water.
  • ethanol can be used, which is obtained by fermentation and is produced as an azeotrope with 4.5% water.
  • concentration of the nitrocellulose in the fuel mixtures according to the invention depends on the cetane number to be achieved. Concentrations of 2 to 12% by weight, preferably 4 to 8% by weight, are preferred for trouble-free operation in a conventional diesel engine.
  • the concentration of the polyether in the fuel mixtures according to the invention depends on the concentration of the nitrocellulose, its k value and the desired consistency of the residue after volatilization of alcohol.
  • the ratio of nitrocellulose to polyether should be from 1: 0.2 to 1: 2.0. It is preferably 1: 0.5 to 1: 1.5, particularly preferably 1: 0.8 to 1: 1.2.
  • polyethers with at least three ethylene oxide units are particularly advantageous since these products also serve as desensitizing agents for the nitrocellulose.
  • the nitrocellulose can be mixed with the polyethers immediately after production, and it is therefore excluded that deflagrations or explosions occur during the transport of the nitrocellulose to be used as an ignition improver or after the alcohol component has evaporated.
  • Another advantageous aspect of the use of ethylene oxide polyethers is their lubricating effect, which is particularly important since, in contrast to conventional diesel oil, lower alcohols have no self-lubricating effect.
  • ethylene oxide polyethers with at least three ethylene oxide units can advantageously be used in ignition improvers, since lower homologs of this class of compounds, such as ethylene glycol or diethylene glycol, which are likewise not volatile at room temperature, are not suitable if they are used comparably.
  • the propylene oxide polyethers which are structurally closely related to the ethylene oxide polyethers, do not suppress the film formation tendency when used in terms of weight, even if they have three or more propylene oxide units.
  • the plasticizers used for the nitrocelluloses in the paint sector such as phthalic acid esters of butanol and 2-ethylhexanol, also show poor effectiveness.
  • Example 1 The fuel mixture described in Example 1 is used in a diesel engine with direct injection, with 1.4 times the amount being injected in accordance with the lower calorific value of the mixture compared to conventional diesel fuel.
  • the diesel engine runs well with an ignition delay identical to that of conventional diesel fuel. The engine will still run if the concentration of nitrocellulose is reduced to 6%.
  • Example 2 The fuel mixture described in Example 2 is used in a prechamber diesel engine, double the amount of fuel being injected in accordance with the lower calorific value of the mixture.
  • the diesel engine runs well with an ignition delay identical to that of conventional diesel fuel. The engine will still run if the concentration of nitrocellulose is reduced to 5%.
  • a fuel mixture consisting of 6 parts of a nitrocellulose with a k value of 460, 6 parts of a homologue mixture of an ethylene oxide polyether started on water with an average of 8 ethylene oxide units and 88 parts of methanol are used in a direct-injection diesel engine, with twice the amount corresponding to the lower calorific value of the mixture Fuel compared to petroleum-based diesel fuel is used. Good runnability is obtained in all speed ranges, the ignition delay of the mixture according to the invention being identical to that of a conventional diesel fuel with a cetane number of 51.
  • Equal parts of the fuel mixture described in Example 1 and of conventional diesel fuel are converted into an emulsion under the action of shear forces.
  • the emulsion separates within 1 hour with the formation of the initial phases. Cloudiness or precipitation are not observed.

Abstract

Mixtures of nitrocellulose and polyether are used as ignition improvers for alcoholic propellants.

Description

Die Erfindung betrifft Zündverbesserer für alkoholische Treibstoffe und alkoholische Kraftstoffgemische, die für den Betrieb von Dieselmotoren verwendet werden können.The invention relates to ignition improvers for alcoholic fuels and alcoholic fuel mixtures which can be used for the operation of diesel engines.

Methanol und Ethanol können nicht anstelle der mineralischen Kohlenwasserstoffe in Dieselmotoren üblicher Bauart verwendet werden, da die Cetanzahl von Ethanol und Methanol nur 8 bzw. 3 beträgt. Dieselmotoren benötigen jedoch für den störungsfreien Betrieb einen Treibstoff mit einer Cetanzahl von mindestens 45 (DIN 51 601; Winnacker-Küchler, Chemische Technologie, Band 3/I, 326 (1971)).Methanol and ethanol cannot be used in place of the mineral hydrocarbons in conventional diesel engines because the cetane number of ethanol and methanol is only 8 and 3, respectively. For trouble-free operation, however, diesel engines require a fuel with a cetane number of at least 45 (DIN 51 601; Winnacker-Küchler, Chemische Technologie, Band 3 / I, 326 (1971)).

Zur Anhebung der Cetanzahl sind daher Zündverbesserer erforderlich. Für Treibstoffe auf Basis von Methanol und Ethanol sind Alkyl- und Cycloalkylnitrate bekannt (DE-OS 2 701 588, DE-OS 20 39 609, Mineralogie Technik 80, 25 (4), 1 bis 12), deren Herstellung jedoch aufwendig ist und die in Anwesenheit von Wasser hydrolysieren können. Hierbei entsteht Salpetersäure, welche die Motoren durch Korrosion zerstört. Auch Salpetersäuresalze von primären, sekundären und tertiären Aminen, wie z.B. Mono-, Di- und Triethylammoniumnitrat sind als Zündverbesserer für Methanol und Ethanol bekannt (DE-OS 29 09 565), jedoch weisen auch sie korrosive Eigenschaften auf.Ignition improvers are therefore required to increase the cetane number. For fuels based on methanol and ethanol, alkyl and cycloalkyl nitrates are known (DE-OS 2 701 588, DE-OS 20 39 609, Mineralogie Technik 80, 25 (4), 1 to 12), but their production is based on is agile and which can hydrolyze in the presence of water. This creates nitric acid, which destroys the motors through corrosion. Nitric acid salts of primary, secondary and tertiary amines, such as mono-, di- and triethylammonium nitrate, are also known as ignition improvers for methanol and ethanol (DE-OS 29 09 565), but they also have corrosive properties.

Aus der EP-A 0071134 sind Zündverbesserer für alkoholische Treibstoffe bekannt, die Salpetersäureester von Mono-und/oder Polysacchariden, z.B. Nitrocellulose, enthalten. Bei der Anwendung dieser Zündverbesserer in den kraftstofführenden Teilen der Motoren bilden sich jedoch Filme aus Nitrocellulose an den Wandungen, die zu festen, verstopfend wirkenden Rückständen führen können. Dieser Nachteil läßt sich durch den Zusatz von weiteren Lösungsmitteln nicht befriedigend lösen.From EP-A 0071134 ignition improvers for alcoholic fuels are known which contain nitric acid esters of mono- and / or polysaccharides, e.g. Nitrocellulose included. When these ignition improvers are used in the fuel-carrying parts of the engines, however, films of nitrocellulose form on the walls, which can lead to solid, constipating residues. This disadvantage cannot be solved satisfactorily by adding further solvents.

Bei der Verwendung von Treibstoffen auf Alkoholbasis mit den in der EP-A 007 1134 offenbarten Zündverbesserern treten außerdem Probleme auf, wenn sie mit konventionellen Treibstoffen auf Mineralölbasis in Kontakt kommen. Durch die schlechtere Löslichkeit dieser Zündverbesserer in Mineralöl bedingt, treten Ausfällungen des Zündverbesserers auf, die ebenfalls zu einer Verstopfung des Motors führen.Problems also arise when using alcohol-based fuels with the ignition improvers disclosed in EP-A 007 1134 when they come into contact with conventional petroleum-based fuels. Due to the poorer solubility of these ignition improvers in mineral oil, malfunctions of the ignition improver occur, which likewise lead to a blockage of the engine.

Für die Anwendung in der Praxis ist die Kompatibilität von Treibstoffen auf Mineralölbasis und Alkoholbasis jedoch besonders wichtig.However, the compatibility of petroleum-based and alcohol-based fuels is particularly important for practical use.

Es wurden Zündverbesserer für alkoholische Treibstoffe für Verbrennungskraftmaschinen gefunden, die Nitrocellulose mit einem Stickstoffgehalt von 9 bis 14 % und Polyether mit mindestens drei Ethylenoxideinheiten enthalten.Ignition improvers for alcoholic fuels for internal combustion engines have been found which contain nitrocellulose with a nitrogen content of 9 to 14% and polyether with at least three ethylene oxide units.

Die erfindungsgemäßen Zündverbesserer hinterlassen bei der Anwendung in den Motoren keine Rückstände, die zu Verstopfungen führen. Sie sind völlig kompatibel gegenüber Treibstoffen auf Mineralölbasis.When used in the engines, the ignition improvers according to the invention do not leave any residues which lead to blockages. They are completely compatible with petroleum-based fuels.

Für die erfindungsgemäßen Zündverbesserer kann Nitrocellulose mit einem Stickstoffgehalt von 9 bis 14 %, bevorzugt von 10 bis 13 %, verwendet werden.Nitrocellulose with a nitrogen content of 9 to 14%, preferably 10 to 13%, can be used for the ignition improvers according to the invention.

Besonders bevorzugt sind Nitrocellulosen, welche die Viskosität des alkoholischen Treibstoffes in möglichst geringem Maße erhöhen. Es werden daher erfindungsgemäß Nitrocellulosen mit einer Eigenviskosität k von kleiner als 1000, bevorzugt von 800 bis 200, besonders vorteilhaft eingesetzt. Die Eigenviskosität der Nitrocellulose kann in an sich bekannter Weise bestimmt werden (Fikentscher, Cellulosechemie 13, 58 (1932)).Nitrocelluloses which increase the viscosity of the alcoholic fuel as little as possible are particularly preferred. Therefore, according to the invention, nitrocelluloses with an intrinsic viscosity k of less than 1000, preferably from 800 to 200, are used particularly advantageously. The intrinsic viscosity of nitrocellulose can be determined in a manner known per se (Fikentscher, Cellulosechemie 13, 58 (1932)).

Die Herstellung der Nitrocellulose für die erfindungsgemäßen Zündverbesserer ist an sich bekannt (K. Fabel, Nitrocellulose - Herstellung und Eigenschaften, Enke Verlag, Stuttgart (1950)). Sie kann beispielsweise hergestellt werden, indem sie in homogener und/oder heterogener Phase mit Salpetersäure oder dessen Anhydrid in Anwesenheit von wasserziehenden Mitteln wie Schwefelsäure, Phosphorsäure, Phosphorpentoxid oder Essigsäureanhydrid umgesetzt wird. Der Nitrierungsgrad kann durch die Menge und Konzentration der Salpetersäure bzw. der wasserentziehenden Zusätze beliebig gesteuert werden.The production of the nitrocellulose for the ignition improvers according to the invention is known per se (K. Fabel, nitrocellulose production and properties, Enke Verlag, Stuttgart (1950)). It can be produced, for example, by mixing it with nitric acid or its anhydride in a homogeneous and / or heterogeneous phase Presence of water-drawing agents such as sulfuric acid, phosphoric acid, phosphorus pentoxide or acetic anhydride is implemented. The degree of nitration can be controlled as desired by the amount and concentration of the nitric acid or the dehydrating additives.

Für die erfindungsgemäßen Zündverbesserer werden Polyether mit mindestens drei Ethylenoxideinheiten, bevorzugt 4 bis 100 Ethylenoxideinheiten, eingesetzt. Erfindungsgemäß werden Polyether bevorzugt, die durch Umsetzung von Verbindungen, die mindestens eine OH-und/oder NH-Gruppe aufweisen, mit Ethylenoxid in an sich bekannter Weise hergestellt werden. Es ist selbstverständlich möglich und gegebenenfalls auch technisch zweckmäßig Polyether mit verschiedenen Ethoxylierungsgraden und verschiedenen OH- und NH-Verbindungen einzusetzen. Die Polyether können außer den erfindungsgemäßen Ethylenoxideinheiten auch weiter Alkylenoxideinheiten, bevorzugt 0,1 bis 0,5 Propylenoxideinheiten, bezogen auf eine Ethylenoxideinheit, enthalten.Polyethers having at least three ethylene oxide units, preferably 4 to 100 ethylene oxide units, are used for the ignition improvers according to the invention. According to the invention, preference is given to polyethers which are prepared in a manner known per se by reacting compounds which have at least one OH and / or NH group with ethylene oxide. It is of course possible and possibly also technically expedient to use polyethers with different degrees of ethoxylation and different OH and NH compounds. In addition to the ethylene oxide units according to the invention, the polyethers can also contain alkylene oxide units, preferably 0.1 to 0.5 propylene oxide units, based on an ethylene oxide unit.

Als Verbindungen, die eine OH-Gruppe aufweisen, seien bevorzugt Verbindungen der Formel

Figure imgb0001
in der

  • R 1 Wasserstoff oder gegebenenfalls durch Hydroxy oder Amino substituiertes Alkyl bedeutet

genannt.Compounds of the formula are preferred as compounds which have an OH group
Figure imgb0001
 in the
  • R 1 is hydrogen or alkyl which is optionally substituted by hydroxyl or amino

called.

Als Verbindungen, die eine NH-Gruppe aufweisen, seien bevorzugt Verbindungen der Formel

Figure imgb0002
in der

  • R2 und R3 gleich oder verschieden sind und Wasserstoff oder gegebenenfalls durch Hydroxy oder Amino substituiertes Alkyl bedeuten

genannt.Compounds of the formula are preferred as compounds which have an NH group
Figure imgb0002
 in the
  • R 2 and R 3 are the same or different and are hydrogen or alkyl which is optionally substituted by hydroxy or amino

called.

Alkyl steht hierbei im allgemeinen für einen geradkettigen oder verzweigten Kohlenwasserstoffrest mit 1 bis 6 Kohlenstoffatomen. Beispielsweise seien die folgenden Alkylreste genannt: Methyl, Ethyl, Propyl, Isopropyl, Butyl, Isobutyl, Pentyl, Isopentyl, Hexyl und Isohexyl.Alkyl here generally represents a straight-chain or branched hydrocarbon radical having 1 to 6 carbon atoms. The following alkyl radicals may be mentioned, for example: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl and isohexyl.

Für den Fall, daß die Verbindungen mit mindestens einer OH- oder NH-Gruppe durch weitere Hydroxyaminogruppen substituiert sind, werden Verbindungen mit 1 bis 5, bevorzugt 1 oder 2, Hydroxy und/oder Aminogruppen bevorzugt.In the event that the compounds having at least one OH or NH group are substituted by further hydroxyamino groups, compounds having 1 to 5, preferably 1 or 2, hydroxyl and / or amino groups are preferred.

Beispiele für Verbindungen mit einer OH- und/oder NH-Gruppe sind Wasser, Mono- und Polyole wie Methanol, Ethanol, Propanol, Butanol, Amylalkohol, Ethylenglykol, Propylenglykol, Glycerin, Trimethylolpropan, Pentaerythrit, und stickstoffhaltige Verbindungen wie Ammoniak, Ethanolamin, Triethanolamin und Dimethylethanolamin. Als Startermoleküle für die Ethylenoxidanlagerung sind auch Gemische dieser Verbindungen einsetzbar. Besonders bevorzugt als Starter sind Wasser und niedere Mono- und Polyole.Examples of compounds with an OH and / or NH group are water, mono- and polyols such as methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol, Propylene glycol, glycerin, trimethylolpropane, pentaerythritol, and nitrogen-containing compounds such as ammonia, ethanolamine, triethanolamine and dimethylethanolamine. Mixtures of these compounds can also be used as starter molecules for the addition of ethylene oxide. Water and lower mono- and polyols are particularly preferred as starters.

Die Konzentrate enthalten im allgemeinen 15 bis 60 Gew.-Teile an Nitrocellulose und 20 bis 70 Gew.-Teile an Polyether. Bevorzugt enthalten die erfindungsgemäßen Zündverbesserer 20 bis 50 Gew.-Teile an Nitrocellulose und 30 bis 60 Gew.-Teile an Polyether.The concentrates generally contain 15 to 60 parts by weight of nitrocellulose and 20 to 70 parts by weight of polyether. The ignition improvers according to the invention preferably contain 20 to 50 parts by weight of nitrocellulose and 30 to 60 parts by weight of polyether.

Selbstverständlich können die erfindungsgemäßen Zündverbesserer noch andere, an sich bekannte Zusätze enthalten. Insbesondere zu nennen ist hier die Mitverwendung von weiteren, an sich bekannten Zündverbesserern, sowie der Zusatz von Komponenten, die für eine dieselmotorische Verbrennung geeignet sind, wie z. B. Propylenoxidpolyether, Fettalkohole, Fettsäureester, Dieselöl und pflanzliche öle wie Soja-, Rizinus- oder Tallöl. Der Zusatz von Detergentien und Starthilfen ist ebenfalls möglich.The ignition improvers according to the invention can of course also contain other additives known per se. In particular, the use of other, known ignition improvers, as well as the addition of components that are suitable for diesel engine combustion, such as. B. propylene oxide polyethers, fatty alcohols, fatty acid esters, diesel oil and vegetable oils such as soybean, castor or tall oil. The addition of detergents and starting aids is also possible.

Die die erfindungsgemäßen Zündverbesserer enthaltenden Treibstoffe können direkt aus den Einzelkomponenten, d. h. Nitrocellulose, Polyether und Alkohol hergestellt werden. Bevorzugt ist jedoch die Herstellung eines aus diesen Komponenten bestehenden Konzentrates, welches dann mit Alkohol soweit zu verdünnen ist, daß die Konzentration des erfindungsgemäßen Zündverbesserers die einwandfreie Lauffähigkeit eines Motors gewährleistet.The fuels containing the ignition improvers according to the invention can be obtained directly from the individual components, i.e. H. Nitrocellulose, polyether and alcohol can be produced. However, it is preferred to prepare a concentrate consisting of these components, which is then to be diluted with alcohol to such an extent that the concentration of the ignition improver according to the invention ensures that an engine runs properly.

Die erfindungsgemäßen Zündverbesserer können als Zusatz zu alkoholischen Kraftstoffen verwendet werden.The ignition improvers according to the invention can be used as an additive to alcoholic fuels.

Gegenstand der vorliegenden Erfindung sind auch Kraftstoffgemische, die Alkohol und einen Zündverbesserer, der Nitrocellulose mit einem Stickstoffgehalt von 9 bis 14 % und einen Polyether mit mindestens drei Ethylenoxideinheiten enthält, enthalten. Die erfindungsgemäßen Kraftstoffgemische sind geeignet für den Betrieb von Dieselmotoren, insbesondere Fahrzeugdieselmotoren und solchen, die ähnliche Anforderungen an den Kraftstoff stellen.The present invention also relates to fuel mixtures which contain alcohol and an ignition improver which contains nitrocellulose with a nitrogen content of 9 to 14% and a polyether with at least three ethylene oxide units. The fuel mixtures according to the invention are suitable for the operation of diesel engines, in particular vehicle diesel engines and those which place similar demands on the fuel.

Alkohol ist erfindungsgemäß ein niederer aliphatischer Alkohol mit 1 bis 6 Kohlenstoffatomen. Insbesondere bevorzugt ist hier Methanol und/oder Ethanol. Die Alkohole können gegebenenfalls bis zu 10 Gew.-% Wasser enthalten. So kann beispielsweise Ethanol verwendet werden, das durch Gärung gewonnen wird, und dabei als Azeotrop mit 4,5 % Wasser anfällt.According to the invention, alcohol is a lower aliphatic alcohol with 1 to 6 carbon atoms. Methanol and / or ethanol is particularly preferred here. The alcohols can optionally contain up to 10% by weight of water. For example, ethanol can be used, which is obtained by fermentation and is produced as an azeotrope with 4.5% water.

Die Konzentration der Nitrocellulose in den erfindungsgemäßen Treibstoffgemischen ist abhängig von der zu erreichenden Cetanzahl. Für einen störungsfreien Betrieb in einem konventionellen Dieselmotor sind Konzentrationen von 2 bis 12 Gew.-%, bevorzugt 4 bis 8 Gew.-% bevorzugt.The concentration of the nitrocellulose in the fuel mixtures according to the invention depends on the cetane number to be achieved. Concentrations of 2 to 12% by weight, preferably 4 to 8% by weight, are preferred for trouble-free operation in a conventional diesel engine.

Die Konzentration des Polyethers in den erfindungsgemäßen Kraftstoffgemischen richtet sich nach der Konzentration der Nitrocellulose, ihrem k-Wert und der gewünschten Konsistenz des Rückstandes nach Verflüchtigung des Alkohols. Bei den erfindungsgemäßen Kraftstoffgemischen soll das Verhältnis von Nitrocellulose zu Polyether von 1:0,2 bis 1:2,0 betragen. Vorzugsweise beträgt es 1:0,5 bis 1:1,5, besonders bevorzugt 1:0,8 bis 1:1,2.The concentration of the polyether in the fuel mixtures according to the invention depends on the concentration of the nitrocellulose, its k value and the desired consistency of the residue after volatilization of alcohol. In the fuel mixtures according to the invention, the ratio of nitrocellulose to polyether should be from 1: 0.2 to 1: 2.0. It is preferably 1: 0.5 to 1: 1.5, particularly preferably 1: 0.8 to 1: 1.2.

Man setzt im allgemeinen 3 bis 20 Gew.-Teile, bevorzugt 6 bis 15 Gew.-Teile des erfindungsgemäßen Zündverbesserers bezogen auf den Alkohol ein.In general, 3 to 20 parts by weight, preferably 6 to 15 parts by weight, of the ignition improver according to the invention, based on the alcohol, are used.

Die Verwendung von Polyethern mit mindestens drei Ethylenoxideinheiten ist besonders vorteilhaft, da diese Produkte gleichzeitig auch als Phlegmatisierungsmittel für die Nitrocellulose dienen. So kann die Nitrocellulose sofort nach der Herstellung mit den Polyethern vermischt werden und es ist somit ausgeschlossen, daß es während des Transportes der als Zündverbesserer einzusetzenden Nitrocellulose oder nach Verdunsten der Alkoholkomponente zu Verpuffungen oder Explosionen kommt. Ein weiterer vorteilhafter Aspekt der Mitverwendung von Ethylenoxidpolyethern ist ihre Schmierwirkung, die besonders wichtig ist, da niedere Alkohole im Gegensatz zu konventionellem Dieselöl keine selbstschmierende Wirkung besitzen.The use of polyethers with at least three ethylene oxide units is particularly advantageous since these products also serve as desensitizing agents for the nitrocellulose. Thus, the nitrocellulose can be mixed with the polyethers immediately after production, and it is therefore excluded that deflagrations or explosions occur during the transport of the nitrocellulose to be used as an ignition improver or after the alcohol component has evaporated. Another advantageous aspect of the use of ethylene oxide polyethers is their lubricating effect, which is particularly important since, in contrast to conventional diesel oil, lower alcohols have no self-lubricating effect.

Es ist besonders überraschend, daß nur Ethylenoxidpolyether mit mindestens drei Ethylenoxideinheiten vorteilhaft in Zündverbesserern eingesetzt werden können, da niedere, ebenfalls bei Raumtemperatur nicht flüchtige Homologe dieser Verbindungsklasse, wie z.B. Ethylenglykol oder Diethylenglykol, nicht geeignet sind, wenn sie vergleichbar angewendet werden. Überraschend ist auch die Tatsache, daß die mit den Ethylenoxidpolyethern strukturell eng verwandten Propylenoxidpolyether die Filmbildungstendenz bei gewichtsmäßig äquivalentem Einsatz nicht unterdrücken, auch wenn sie drei oder mehr Propylenoxideinheiten aufweisen. Auch die für die Nitrocellulosen im Lackbereich verwendeten Weichmacher, wie z.B. Phthalsäureester von Butanol und 2-Ethylhexanol zeigen ebenfalls eine schlechte Wirksamkeit.It is particularly surprising that only ethylene oxide polyethers with at least three ethylene oxide units can advantageously be used in ignition improvers, since lower homologs of this class of compounds, such as ethylene glycol or diethylene glycol, which are likewise not volatile at room temperature, are not suitable if they are used comparably. Is surprising also the fact that the propylene oxide polyethers, which are structurally closely related to the ethylene oxide polyethers, do not suppress the film formation tendency when used in terms of weight, even if they have three or more propylene oxide units. The plasticizers used for the nitrocelluloses in the paint sector, such as phthalic acid esters of butanol and 2-ethylhexanol, also show poor effectiveness.

Beispiel 1example 1 Herstellung einer Treibstoffmischung auf Basis EthanolProduction of a fuel mixture based on ethanol Ausführungsform A - Direkte HerstellungEmbodiment A - Direct Manufacturing

8 Teile einer handelsüblichen Nitrocellulose (Stickstoffgehalt zwischen 10,0 und 11,5, k-Wert = 400) und 12,5 Teile eines Homologengemisches eines auf Wasser gestarteten Ethylenoxidpolyethers mit 4 bis 13 Ethylenoxideinheiten werden mit 80 Teilen 96 %igem Ethanol 15 Min. bei Raumtemperatur gerührt. Man erhält eine klare farblose Lösung.8 parts of a commercially available nitrocellulose (nitrogen content between 10.0 and 11.5, k value = 400) and 12.5 parts of a homologue mixture of a water-started ethylene oxide polyether with 4 to 13 ethylene oxide units are mixed with 80 parts of 96% ethanol for 15 minutes. stirred at room temperature. A clear, colorless solution is obtained.

Ausführungsform B - Herstellung eines KonzentratsEmbodiment B - Preparation of a concentrate

24 Teile der Nitrocellulose und 37,5 Teile des Polyethers aus Ausführungsform A werden mit 38 Teilen 96 %igem Ethanols bis zum Erhalt einer klaren, gelblichen Lösung gerührt. Das Konzentrat weist bei 25°C eine Viskosität von 4000 cp auf. Um die in Ausführungsform A beschriebene Mischung zu erhalten, muß ein Teil des Konzentrats mit zwei Teilen Ethanol verdünnt werden. Ein Konzentrat, welches mit drei Teilen Ethanol verdünnt werden muß, um zu dem Gemisch der Ausführungsform A zu gelangen, wird hergestellt aus 32 Teilen Nitrocellulose, 50 Teilen Polyether und 18 Teilen Ethanol. Es weist bei 25°C eine Viskosität von 60 000 cp auf.24 parts of the nitrocellulose and 37.5 parts of the polyether from embodiment A are stirred with 38 parts of 96% ethanol until a clear, yellowish solution is obtained. The concentrate has a viscosity of 4000 cp at 25 ° C. To obtain the mixture described in embodiment A, one part of the concentrate must be diluted with two parts of ethanol. A concentrate, which must be diluted with three parts of ethanol to arrive at the mixture of embodiment A, is made from 32 parts of nitrocellulose, 50 parts of polyether and 18 parts of ethanol. It has a viscosity of 60,000 cp at 25 ° C.

Beispiel 2Example 2 Herstellung einer Treibstoffmischung auf Basis MethanolProduction of a fuel mixture based on methanol

8 Teile einer handelsüblichen Nitrocellulose (Stickstoffgehalt zwischen 10,0 und 11,5 %, k-Wert 450) werden mit 12 Teilen eines auf Trimethylolpropan gestarteten Ethylenoxidpolyethers eines Molekulargewichts von 700 und 80 Teilen Methanol 15 Minuten bei Raumtemperatur gerührt. Man erhält eine klare, farblose Lösung.8 parts of a commercially available nitrocellulose (nitrogen content between 10.0 and 11.5%, k value 450) are stirred for 15 minutes at room temperature with 12 parts of an ethylene oxide polyether started on trimethylolpropane with a molecular weight of 700 and 80 parts of methanol. A clear, colorless solution is obtained.

Beispiel 3Example 3 Prüfung auf RückstandbildungCheck for residue formation

Eine alkoholische Lösung, bei der das Verhältnis von der in Beispiel 1 verwendeten Nitrocellulose zu eingesetztem Hilfsstoff 1:1,5 beträgt, wird auf einer Glasplatte verstrichen. Man läßt den Alkohol vollständig verdampfen und prüft den Rückstand in seiner Konsistenz.

Figure imgb0003
An alcoholic solution in which the ratio of the nitrocellulose used in Example 1 to the auxiliary used is 1: 1.5 is spread on a glass plate. The alcohol is allowed to evaporate completely and the consistency of the residue is checked.
Figure imgb0003

Die Beispiele zeigen, daß nur bei Verwendung der erfindungsgemäß einzusetzenden Ethylenoxidpolyether mit mindestens drei Ethylenoxideinheiten die verbleibenden Rückstände den Charakter einer hochviskosen Flüssigkeit mit z.T. noch schmierender Wirkung aufweisen. Alle anderen Substanzen bewirken bei gewichtsmäßig äquivalentem Einsatz Rückstände, welche nach Verdunsten des Treibstoffs bei beweglichen Teilen, z.B. in der Einspritzpumpe, Störungen hervorrufen würden.The examples show that only when the ethylene oxide polyethers to be used according to the invention with at least three ethylene oxide units are used, the remaining residues have the character of a highly viscous liquid with some. still have a lubricating effect. All other substances, when used in terms of weight, cause residues, which after evaporation of the fuel evaporate from moving parts, e.g. in the injection pump would cause malfunctions.

Beispiel 4Example 4 überprüfung der Lauffähigkeit einer Treibstoffmischung auf Basis 96 %igem EthanolsChecking the operability of a fuel mixture based on 96% ethanol

In einem Dieselmotor mit Direkteinspritzung wird die in Beispiel 1 beschriebene Treibstoffmischung eingesetzt, wobei entsprechend dem geringeren Heizwert der Mischung gegenüber konventionellen Dieseltreibstoff die 1,4-fache Menge eingespritzt wird. Man erhält eine gute Lauffähigkeit des Dieselmotors mit einem dem konventionellen Dieseltreibstoff identischen Zündverzug. Die Lauffähigkeit des Motors ist auch dann noch gegeben, wenn die Konzentration der Nitrocellulose auf 6 % herabgesetzt wird.The fuel mixture described in Example 1 is used in a diesel engine with direct injection, with 1.4 times the amount being injected in accordance with the lower calorific value of the mixture compared to conventional diesel fuel. The diesel engine runs well with an ignition delay identical to that of conventional diesel fuel. The engine will still run if the concentration of nitrocellulose is reduced to 6%.

Beispiel 5Example 5 überprüfung der Lauffähigkeit einer Treibstoffmischung auf Basis Methanolchecking the operability of a fuel mixture based on methanol

In einem Vorkammerdieselmotor wird die in Beispiel 2 beschriebene Treibstoffmischung eingesetzt, wobei entsprechend des geringeren Heizwertes der Mischung die doppelte Menge Treibstoff eingespritzt wird. Man erhält eine gute Lauffähigkeit des Dieselmotors mit einem dem konventionellen Dieseltreibstoff identischen Zündverzug. Die Lauffähigkeit des Motors ist auch dann noch gegeben, wenn die Konzentration der Nitrocellulose auf 5 % herabgesetzt wird.The fuel mixture described in Example 2 is used in a prechamber diesel engine, double the amount of fuel being injected in accordance with the lower calorific value of the mixture. The diesel engine runs well with an ignition delay identical to that of conventional diesel fuel. The engine will still run if the concentration of nitrocellulose is reduced to 5%.

Beispiel 6Example 6 Überprüfung der Lauffähigkeit einer Treibstoffmischung auf Basis MethanolChecking the operability of a fuel mixture based on methanol

Eine Treibstoffmischung bestehend aus 6 Teilen einer Nitrocellulose eines k-Wertes von 460, 6 Teilen eines Homologengemisches eines auf Wasser gestarteten Ethylenoxidpolyethers mit durchschnittlich 8 Ethylenoxideinheiten und 88 Teilen Methanol werden in einem direkt einspritzenden Dieselmotor eingesetzt, wobei entsprechend dem geringerem Heizwert der Mischung die doppelte Menge Treibstoff im Vergleich zu Dieselkraftstoff auf Mineralölbasis eingesetzt wird. Man erhält in allen Drehzahlbereichen eine gute Lauffähigkeit, wobei der Zündverzug der erfindungsgemäßen Mischung mit dem eines konventionellen Dieseltreibstoffes einer Cetanzahl von 51 identisch ist.A fuel mixture consisting of 6 parts of a nitrocellulose with a k value of 460, 6 parts of a homologue mixture of an ethylene oxide polyether started on water with an average of 8 ethylene oxide units and 88 parts of methanol are used in a direct-injection diesel engine, with twice the amount corresponding to the lower calorific value of the mixture Fuel compared to petroleum-based diesel fuel is used. Good runnability is obtained in all speed ranges, the ignition delay of the mixture according to the invention being identical to that of a conventional diesel fuel with a cetane number of 51.

Beispiel 7Example 7 Kompatibilität einer Treibstoffmischung mit konventionellem DieseltreibstoffCompatibility of a fuel mixture with conventional diesel fuel

Gleiche Teile der in Beispiel 1 beschriebenen Treibstoffmischung und von konventionellem Dieseltreibstoff werden unter Einwirkung von Scherkräften in eine Emulsion umgewandelt. Die Emulsion trennt sich innerhalb von 1 Stunde unter Ausbildung der Ausgangsphasen. Trübungen oder Ausfällungen werden nicht beobachtet.Equal parts of the fuel mixture described in Example 1 and of conventional diesel fuel are converted into an emulsion under the action of shear forces. The emulsion separates within 1 hour with the formation of the initial phases. Cloudiness or precipitation are not observed.

Claims (9)

1. Zündverbesserer für alkoholische Treibstoffe für Verbrennungskraftmaschinen, enthaltend Nitrocellulose mit einem Stickstoffgehalt von 9 bis 14 % und Polyether mit mindestens drei Ethylenoxideinheiten.1. Z ündverbesserer for alcoholic fuels for internal combustion engines, containing nitrocellulose with a nitrogen content of 9 to 14% and polyethers with at least three ethylene oxide units. 2. Zündverbesserer nach Anspruch 1, dadurch gekennzeichnet, daß die Nitrocellulose eine Eigenviskosität k von< 1000 aufweist.2. Ignition improver according to claim 1, characterized in that the nitrocellulose has an intrinsic viscosity k of <1000. 3. Zündverbesserer nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß die Nitrocellulose eine Eigenviskosität im Bereich von 800 bis 200 aufweist.3. Ignition improver according to claims 1 and 2, characterized in that the nitrocellulose has an intrinsic viscosity in the range from 800 to 200. 4. Zündverbesserer nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß die Polyether 4 bis 100 Ethylenoxideinheiten aufweisen.4. Ignition improver according to claims 1 to 3, characterized in that the polyethers have 4 to 100 ethylene oxide units. 5. Zündverbesserer nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß er als Konzentrat mit 15 bis 60 Gew.-Teilen Nitrocellulose und 20 bis 70 Gew.-Teilen an Polyether eingesetzt wird.5. Ignition improver according to claims 1 to 4, characterized in that it is used as a concentrate with 15 to 60 parts by weight of nitrocellulose and 20 to 70 parts by weight of polyether. 6. Verwendung eines Zündverbesserers, der Nitrocellulose mit einem Stickstoffgehalt von 9 bis 14 % und Polyether mit mindestens 3 Ethylenoxideinheiten enthält, als Zusatz zu alkoholischen Treibstoffen.6. Use of an ignition improver which contains nitrocellulose with a nitrogen content of 9 to 14% and polyether with at least 3 ethylene oxide units, as an additive to alcoholic fuels. 7. Kraftstoffgemisch, dadurch gekennzeichnet, daß es Alkohol und einen Zündverbesserer, der aus Nitrocellulose mit einem Stickstoffgehalt von 9 bis 14 % und Polyether mit mindestens drei Ethylenoxideinheiten besteht, enthält.7. Fuel mixture, characterized in that it contains alcohol and an ignition improver, which consists of nitrocellulose with a nitrogen content of 9 to 14% and polyether with at least three ethylene oxide units. 8. Kraftstoffgemisch nach Anspruch 7, dadurch gekennzeichnet, daß es 3 bis 20 Gew.-Teile des Zündverbesserers bezogen auf Alkohol enthält.8. Fuel mixture according to claim 7, characterized in that it contains 3 to 20 parts by weight of the ignition improver based on alcohol. 9. Verwendung eines Kraftstoffgemisches nach Ansprüchen 7 und 8 für den Betrieb von Dieselmotoren.9. Use of a fuel mixture according to claims 7 and 8 for the operation of diesel engines.
EP85103095A 1984-03-31 1985-03-18 Injection improver for a fuel mixture Expired EP0157268B1 (en)

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JPS60219296A (en) 1985-11-01
DK144785A (en) 1985-10-01
DE3560951D1 (en) 1987-12-17
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ZA852392B (en) 1985-11-27
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