EP0289785A1 - Process to prevent or reduce scales in mixture preparation devices of engines - Google Patents

Process to prevent or reduce scales in mixture preparation devices of engines Download PDF

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Publication number
EP0289785A1
EP0289785A1 EP88105287A EP88105287A EP0289785A1 EP 0289785 A1 EP0289785 A1 EP 0289785A1 EP 88105287 A EP88105287 A EP 88105287A EP 88105287 A EP88105287 A EP 88105287A EP 0289785 A1 EP0289785 A1 EP 0289785A1
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Prior art keywords
groups
alkyl
unsubstituted
fuels
hydrocarbons
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EP88105287A
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German (de)
French (fr)
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EP0289785B1 (en
Inventor
Dagmar Dr. Mertens-Gottselig
Hartmut Dr. Hammer
Heinrich Dr. Müller
Manfred Dr. Wildersohn
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Wintershall Dea International AG
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RWE Dea AG fuer Mineraloel und Chemie
Union Rheinische Braunkohlen Kraftstoff AG
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Priority to AT88105287T priority Critical patent/ATE64948T1/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
    • C10L1/18—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
    • C10L1/224—Amides; Imides carboxylic acid amides, imides
    • 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
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2462—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds
    • C10L1/2475—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon to carbon bonds
    • C10L1/2487—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon to carbon bonds polyoxyalkylene thioethers (O + S 3=)
    • 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
    • C10L1/26—Organic compounds containing phosphorus
    • C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
    • C10L1/2641—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) oxygen bonds 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal

Definitions

  • the invention relates to a method for preventing or reducing deposits in mixture preparation systems of engines, in which alcohol fuels are used in conjunction with lubricants which are suitable for engines operated with hydrocarbon fuels, by adding polyol ether (s) to the alcohol fuels.
  • Alcohols especially methanol and ethanol, have been intensively investigated as alternative fuels or fuel components for several years (see, for example, EP-A-0 166 096).
  • R 1 H, C 1 -C 8 alkyl, unsubstituted or substituted aryl;
  • R 2 H, C 1 -C 8 alkyl, unsubstituted or substituted aryl and,
  • the effect according to the invention was surprising and unpredictable in particular because the polyol ether is only present in the fuel in a small amount and is mixed with it in a very fine distribution in the interior, for example of a carburetor or an injection device.
  • the polyol ethers are used in amounts of 15 ppm to 1% by weight, based on the total fuel, preferably from 15 ppm to ⁇ 2000 ppm and particularly preferably from 30 ppm to ⁇ 2000 ppm.
  • the 'substituents R 1 and R 2 are preferably H and / or CH 3 , but can also be higher alkyl groups from C 2 to C 8 and aryl groups.
  • R and R 3 were mentioned above.
  • the groups H, alkyl, aryl and carboxy groups are preferred for R.
  • the polyol ether groups are selected so that the polyol ethers are soluble in the respective alcohol or mixture.
  • Preferred fuels for the use mentioned above are fuels which contain 0.1 to 25 vol.%, Preferably 1 to 25 vol.% And particularly preferably 2 to 25 vol.% Hydrocarbons and 75 to 99.9 vol.%, Preferably 75 to 99 % By volume and particularly preferably 75 to 98% by volume of methanol and / or ethanol and / or any mixtures of methanol and ethanol, the hydrocarbons added preferably being C 4 to C x hydrocarbons, where x is the number of carbon atoms in the hydrocarbons at the upper limit of gasoline hydrocarbons.
  • the alcohols can also be hydrocarbon-free.
  • the lubricating oils used are generally in a separate lubricating oil circuit, but can also be added to the fuels. Very good results are obtained, for example, with fuels based on methanol or ethanol or their mixtures which contain 0.1 to 15% by weight, preferably 2 to 15% by weight, of C 4 / C 5 or C 4 to Cs -Carbons contain, in the case of methanol up to 15 wt .-% water and in the case of ethanol up to 25 wt .-% water in the fuel and the C4iCs or the C 4 . : C s / C 6 ratio 1: 500 parts by weight to 3: 1 parts by weight, preferably 1: 1 to 1:20.
  • C 4 -C 7 hydrocarbons 0.1 to 18% by weight, preferably 2 to 18% by weight, of hydrocarbons being contained in the fuel and the C 4 .
  • Cs-C 7 ratio 1: 500 parts by weight to 3: 1 parts by weight, preferably 1: 1 to 1:20.
  • hydrocarbon additives which contain, for example, little or no C 4 hydrocarbons, such as, for example, summer gasoline, light gasoline cuts, platinum cuts, pyrolysis gasoline cuts, Merox gasoline cuts, alkylation and polymer gasoline cuts, and others
  • the alcohols can be pure or raw alcohols.
  • pure as well as raw methanol or topped methanol can be used, as well as distilled, anhydrous or azeotropic ethanol or ethanol, which can contain even more water and impurities, such as e.g. arises in the production of bioethanol.
  • the fuels used can also contain additional aromatics, for example C 6 -C 8 aromatics or so-called platformat, and additions of ethers such as dimethyl ether, tert-alkyl ether, for example methyl tert-butyl or amyl ether, and also ketones, for example acetone and other oxygen-containing compounds .
  • additional aromatics for example C 6 -C 8 aromatics or so-called platformat
  • ethers such as dimethyl ether, tert-alkyl ether, for example methyl tert-butyl or amyl ether
  • ketones for example acetone and other oxygen-containing compounds
  • Additional alcohols such as all isomers of the C 3 -C 10 alcohols, in particular C 3 and C4 alcohols, can also be present. Refinery cuts in the corresponding boiling range are very suitable as added hydrocarbons, so C 4 -, Cs -, C 6 -, C 7 -hydrocarbons as well as gasolines and their combinations can be used.
  • additives such as additional emulsifiers, ignition control additives, anti-rust additives, wear additives etc. can also be used in the fuels. be included.
  • a VW Jetta with a 90 HP engine was operated with a fuel in normal driving as well as in extreme driving with very high summer and very low winter temperatures (approx. 35 ° C + or - 30 ° C) as well as in cold and short distance operation , which contained 90% by weight of methanol and 10% by weight of C 4 -hydrocarbons + light petrol, and a corrosion inhibitor which contained an amphoteric nitrogen-containing condensation product and, according to the invention, 200 ppm and 500 ppm of the polyol ether.
  • a commercial product of class SAE 15 W 40 was used as the lubricant.
  • the carburetor was checked for deposits every 2500 km. Even after a total of 25,000 km the carburetor was completely clean. No deposits were found.
  • the same fuel without polyol ether was used for comparison. Deposits in the throttle valve area were found in the carburetor after the test was completed.
  • Experiment 1 was repeated, except that conventional lead-free gasoline was added to the methanol in an amount of 15% by weight as the hydrocarbon.
  • the gasifier was perfectly clean after the test was completed.
  • Experiment 1 was repeated, but an alcohol mixture of 3 parts of methanol and 1 part of ethanol was used.
  • hydrocarbon 10 wt.% C4 + hydrocarbons a refinery fraction containing 7 hydrocarbons substantially Cs-C, are used.
  • a polyol ether of ethylene oxide with n 4, a terminal isooctyl ether group and a terminal hydroxyl group was used. After completing the test, the carburetor and injection system were found to be perfectly clean.
  • Experiment 1 was repeated, but using methanol, with 5% by weight of water and 5% by weight of light petrol, and the polyol ether used in an amount of 800 ppm.
  • the carburetor was perfectly clean after the test.
  • the present invention represents an important improvement in the field of alcohol fuels.
  • the experiments show that by adding the polyol ethers according to the invention, conventional, commercially available lubricants can be used in engines operated with alcohol fuels instead of lubricants specially produced for such engines.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Combustion & Propulsion (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Lubricants (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Lubrication Details And Ventilation Of Internal Combustion Engines (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Superconductive Dynamoelectric Machines (AREA)
  • Preliminary Treatment Of Fibers (AREA)
  • Combustion Methods Of Internal-Combustion Engines (AREA)
  • Grinding-Machine Dressing And Accessory Apparatuses (AREA)
  • Cephalosporin Compounds (AREA)
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Abstract

In engines in which alcohol fuels are used together with lubricants, these contain a small quantity of one or more compounds based on polyol ethers and are suitable for engines run with hydrocarbon fuels.

Description

Die Erfindung bertifft ein Verfahren zur Verhinderung oder Verminderung von Ablagerungen in Gemischaufbereitungssystemen von Motoren, in welche Alkoholkraftstoffe in Verbindung mit Schmiermitteln eingesetzt werden, die für mit Kohlenwasserstoff-Kraftstoffen betriebene Motoren geeignet sind, durch Zusatz von Polyolether(n) zu den Alkoholkraftstoffen.The invention relates to a method for preventing or reducing deposits in mixture preparation systems of engines, in which alcohol fuels are used in conjunction with lubricants which are suitable for engines operated with hydrocarbon fuels, by adding polyol ether (s) to the alcohol fuels.

Alkohole, insbesondere Methanol und Ethanol werden als alternative Kraftstoffe bzw. Kraftstoff-Komponenten seit einigen Jahren intensiv untersucht (s. beispielsweise EP-A-0 166 096).Alcohols, especially methanol and ethanol, have been intensively investigated as alternative fuels or fuel components for several years (see, for example, EP-A-0 166 096).

Bei diesen Kraftstoffen ist bereits ein hoher technischer Entwicklungsgrad erreicht worden. Dies gilt in ähnlichem Umfang auch für mit diesen Kraftstoffen betriebene Kraftfahrzeuge. Problematisch ist jedoch noch immer die Bildung von Ablagerungen in den Gemischaufbereitungssystemen, insbesondere in den Vergasern und Injektionsvorrichtungen der Kraftfahrzeuge, wenn Schmiermittel eingesetzt werden, die für mit Kohlenwasserstoff-Kraftstoffen, wie z.B. Benzin und Dieselöl, betriebene Motoren geeignet sind. Mit hoher Wahrscheinlichkeit stammen diese Ablagerungen aus den Bestandteilen dieser Schmiermittel.A high level of technical development has already been achieved with these fuels. This applies to a similar extent to motor vehicles operated with these fuels. However, the formation of deposits in the mixture preparation systems, in particular in the carburetors and injection devices of the motor vehicles, is still problematic when using lubricants which are suitable for use with hydrocarbon fuels, such as e.g. Petrol and diesel, powered engines are suitable. These deposits are very likely to come from the components of these lubricants.

Bisher wurden daher für mit Alkoholkraftstoffen betriebene Kraftfahrzeuge, insbesondere wenn die Kraftstoffe Alkoholkonzentrationen von über 75 Vol.-% enthalten, Spezialschmierstoffe eingesetzt.To date, special lubricants have therefore been used for motor vehicles operated with alcohol fuels, especially if the fuels contain alcohol concentrations of more than 75% by volume.

Die Untersuchungen der Anmelderin haben nunmehr überraschend ergeben, daß diese Ablagerungen bei Einsatz üblicher kommerzieller Schmiermittel vermieden bzw. vermindert werden können durch ein Verfahren zur Verhinderung oder Verminderung von Ablagerungen in Gemischaufbereitungssystemen von Motoren, in welche Kraftstoffe auf Methanol-und/oder Ethanolbasis eingesetzt werden, die ggfs. Zusätze an Wasser und/oder C3-C10-Alkoholen und/oder andere Sauerstoff enthaltende Verbindungen und/oder Kohlenwasserstoffen und wenigstens einen Korrosionsinhibitor enthalten, dadurch gekennzeichnet, daß den Kraftstoffen ein oder mehrere Polyolether in einer Menge von 15 ppm bis zu 1 Gew.-%, vorzugsweise von 15 bis < 2000 ppm und besonders bevorzugt von 30 bis < 2000 ppm zugesetzt werden, wobei der (die) Polyolether die allgemeine Formel

Figure imgb0001
besitzt(en) worin R eine der folgenden Gruppen sein kann: H, unverzweigtes und verzweigtes C1-C2o-Alkyl, C1-C20-Alkenyl, mehrfach ungesättigtes C1-C2o-Alkyl, C1-C2o-Cycloalkyl, mono-und bicyclisches C6-C14-Aryl mit und ohne funktionelle Gruppen wie OH, OR4, NH2, Alkylamingruppen, SH, SR4, C ≡ N, (wobei R4. jeweils aliphatische gesättigte und ungesättigte Alkylgruppen sein können sowie unsubstituierte und substituierte Arylgruppen), eine 0-, S-und P-haltige Gruppe wie z.B. Carboxygruppe aliphatischer gesättigter und ungesättigter Carbonsäuren, insbeson dere von Fettsäuren von aromatischen substituierten und unsubstituierten Carbonsäuren, Phosphorsäureestergruppen, Thiophosphorsäureestergruppen, Acetalgruppen; R1 = H, C1-C8-Alkyl, unsubstituiertes oder substituiertes Aryl; R2 = H, C1-C8-Alkyl, unsubstituiertes oder substituiertes Aryl und, R3 = ORs, SRs,
Figure imgb0002
N(Rs)2 wobei R5 = H, unverzweigtes und verzweigtes C1-C20 Alkyl, C1-C20 Alkenyl, mehrfach ungesättigtes C1-C2o-Alkyl, C1-C20-Cycloalkyl, mono-und bicyclisches C6-C14 Aryl mit und ohne funktionelle Gruppen wie OH, OR4, NH2, Alkylamingruppen, SH, SR4, C ≡ N,(wobei R4 jeweils aliphatische gesättigte und ungesättigte Alkylgruppen sein können sowie unsubstitutierte und substituierte Arylgruppen:
Figure imgb0003
wobei R6 = H, eine geradkettige, verzweigte, gesättigte und ungesättigte C1-C20-Alkyl und Mono-und Bicycloalkylgruppe sowie substituierte und unsubstituierte Mono-und Bicycloarylgruppe, unsubstituierte und substituierte Aminogruppe, unsubstituierte und substituierte Alkoxygruppe, unsubstituierte und substituierte Thioethergruppe sein kann, wobei R7 = geradkettige, verzweigte, gesättigte und ungesättigte Alkylgruppen sein können,
Figure imgb0004
wobei R8 = R6 sein kann sowie die C = O-Gruppen durch unsubstituierte, substituierte, gesättigte und ungesättigte Methylenbrücken aus 2 - 5 Methylengruppen verbunden sein können Phosphorsäure-und Thiophosphorsäureestergruppen, Alkylethylendiamintetraessigsäureester, -amid oder -imid sein kann und m = 2 - 4, wobei m im Polyolether-Molekül ausschließlich aus 2 oder 3 oder 4 oder aus Kombinationen derselben besteht und n = 1 - 200, bevorzugt 2 - 100 und besonders bevorzugt 2 - 75 ist. Die erfindungsgemäße Wirkung war insbesondere deshalb überraschend und unvorhersehbar, da der Polyolether nur in einer kleinen Menge im Kraftstoff enthalten ist und sich mit diesem im Gemisch mit Luft in sehr feiner Verteilung im Inneren, beispielsweise eines Vergasers oder einer Einspritz-Vorrichtung befindet. Erfindungsgemäß werden die Polyolether in Mengen von 15 ppm bis zu 1 Gew.-% bezogen auf den Gesamtkraftstoff, bevorzugt von 15 ppm bis < 2000 ppm und besonders bevorzugt von 30 ppm bis < 2000 ppm eingesetzt.The investigations of the applicant have now surprisingly shown that these deposits can be avoided or reduced when using conventional commercial lubricants by a method for preventing or reducing deposits in engine mixture preparation systems in which fuels based on methanol and / or ethanol are used. which optionally contains water and / or C 3 -C 10 alcohols and / or other oxygen-containing compounds and / or hydrocarbons and at least one corrosion inhibitor, characterized in that the fuels contain one or more polyol ethers in an amount of 15 ppm to 1% by weight, preferably from 15 to <2000 ppm and particularly preferably from 30 to <2000 ppm, the polyol ether (s) having the general formula
Figure imgb0001
 has (s) in which R can be one of the following groups: H, unbranched and branched C 1 -C 2 o -alkyl, C 1 -C 20 alkenyl, polyunsaturated C 1 -C 2 o -alkyl, C 1 -C 2 o-cycloalkyl, mono- and bicyclic C 6 -C 14 aryl with and without functional groups such as OH, OR 4 , NH 2 , alkylamine groups, SH, SR 4 , C ≡ N, (where R 4. Each aliphatic saturated and can be unsaturated alkyl groups and unsubstituted and substituted aryl groups), a 0-, S- and P-containing group such as, for example, carboxy group of aliphatic saturated and unsaturated carboxylic acids, in particular of fatty acids of aromatic substituted and unsubstituted carboxylic acids, phosphoric acid ester groups, thiophosphoric acid ester groups, acetal groups; R 1 = H, C 1 -C 8 alkyl, unsubstituted or substituted aryl; R 2 = H, C 1 -C 8 alkyl, unsubstituted or substituted aryl and, R 3 = ORs, SRs,
Figure imgb0002
 N (Rs) 2 where R 5 = H, unbranched and branched C 1 -C 20 alkyl, C 1 -C 20 alkenyl, polyunsaturated C 1 -C 2 o-alkyl, C 1 -C 20 cycloalkyl, mono- and bicyclic C 6 -C 14 aryl with and without functional groups such as OH, OR 4 , NH 2 , alkylamine groups, SH, SR 4 , C ≡ N, (where R 4 can each be aliphatic saturated and unsaturated alkyl groups and unsubstituted and substituted aryl groups:
Figure imgb0003
 where R 6 = H, a straight-chain, branched, saturated and unsaturated C 1 -C 20 -alkyl and mono- and bicycloalkyl group and substituted and unsubstituted mono- and bicycloaryl group, unsubstituted and substituted amino group, unsubstituted and substituted alkoxy group, unsubstituted and substituted thio where R 7 can be straight-chain, branched, saturated and unsaturated alkyl groups,
Figure imgb0004
 where R 8 = R 6 and the C = O groups can be connected by unsubstituted, substituted, saturated and unsaturated methylene bridges from 2-5 methylene groups, phosphoric acid and thiophosphoric acid ester groups, alkyl ethylenediaminetetraacetic acid ester, amide or imide and m = 2 - 4, where m in the polyol ether molecule consists exclusively of 2 or 3 or 4 or combinations thereof and n = 1 - 200, preferably 2 - 100 and particularly preferably 2 - 75. The effect according to the invention was surprising and unpredictable in particular because the polyol ether is only present in the fuel in a small amount and is mixed with it in a very fine distribution in the interior, for example of a carburetor or an injection device. According to the invention, the polyol ethers are used in amounts of 15 ppm to 1% by weight, based on the total fuel, preferably from 15 ppm to <2000 ppm and particularly preferably from 30 ppm to <2000 ppm.

Bevorzugt werden Polyolether aus Ethylenoxid oder Propylenoxideinheiten oder Gemische derselben verwendet, wobei die Anzahl n der Polyoleinheiten = 1 bis 200, bevorzugt = 2 - 100 und besonders bevorzugt 2 - 75 ist, wobei bekanntlich bei höheren Polymerisaten n eine Durchschnittszahl ist. Die' Substituenten R1 und R2 sind bevorzugt H und/oder CH3, können jedoch auch höhere Alkylgruppen von C2 bis C8 sein und Arylgruppen sein.Polyol ethers are preferably of ethylene oxide or propylene oxide units or mixtures thereof are used, wherein the number n of the polyol is from 1 to 200, preferably = 2 - 1 00 and more preferably 2 - 75, wherein known, at higher polymers n is an average number. The 'substituents R 1 and R 2 are preferably H and / or CH 3 , but can also be higher alkyl groups from C 2 to C 8 and aryl groups.

Geeignete Polyolether können jedoch auch durch Polymerisation von Tetrahydrofuran bzw. Derivaten (m = 4) oder Trimethylenoxid bzw. Derivaten (m = 3) hergestellt sein bzw. Mischpolymerisate mit Di-, Tri-und Tetramethyleneinheiten bzw. deren Derivaten sein.Suitable polyol ethers can, however, also be prepared by polymerizing tetrahydrofuran or derivatives (m = 4) or trimethylene oxide or derivatives (m = 3) or copolymers with di-, tri- and tetramethylene units or their derivatives.

Die Gruppen R und R3 wurden oben genannt. Bevorzugt sind für R die Gruppen H, Alkyl, Aryl und Carboxygruppen. Bevorzugt werden für R3 die Gruppen H, ORs, SRs,

Figure imgb0005
N(Rs)2,
Figure imgb0006
 The groups R and R 3 were mentioned above. The groups H, alkyl, aryl and carboxy groups are preferred for R. Are preferred for R 3 the groups H, ORs, SRs,
Figure imgb0005
 N (Rs) 2 ,
Figure imgb0006

Die Polyolethergruppen werden so ausgewählt, daß die Polyolether im jeweiligen Alkohol bzw. Gemisch löslich sind. Bevorzugte Kraftstoffe zur oben genannten Verwendung sind Kraftstoffe, die 0,1 bis 25 Vol.%, vorzugsweise 1 bis 25 Vol.% und besonders bevorzugt 2 bis 25 Vol.% Kohlenwasserstoffe und 75 bis 99,9 Vol.%, vorzugsweise 75 bis 99 Vol.% und besonders bevorzugt 75 bis 98 Vol.% Methanol und/oder Ethanol und/oder beliebige Gemische aus Methanol und Ethanol enthalten, wobei die zugesetzten Kohlenwasserstoffe bevorzugt C4 bis Cx-Kohlenwasserstoffe sind, wobei x der Kohlenstoffanzahl der Kohlenwasserstoffe an der oberen Grenze der Benzinkraftstoff-Kohlenwasserstoffe entspricht. Die Alkohole können jedoch auch Kohlenwasserstoff-frei sein. Durch die erfindungsgemäße Verwendung der Polyolether werden Ablagerungen jedoch auch dann vermieden, wenn die Alkoholkonzentration geringer ist, wie z.B. nur 50 Vol.% oder noch geringer.The polyol ether groups are selected so that the polyol ethers are soluble in the respective alcohol or mixture. Preferred fuels for the use mentioned above are fuels which contain 0.1 to 25 vol.%, Preferably 1 to 25 vol.% And particularly preferably 2 to 25 vol.% Hydrocarbons and 75 to 99.9 vol.%, Preferably 75 to 99 % By volume and particularly preferably 75 to 98% by volume of methanol and / or ethanol and / or any mixtures of methanol and ethanol, the hydrocarbons added preferably being C 4 to C x hydrocarbons, where x is the number of carbon atoms in the hydrocarbons at the upper limit of gasoline hydrocarbons. However, the alcohols can also be hydrocarbon-free. By using the polyol ethers according to the invention, however, deposits are avoided even if the alcohol concentration is lower, for example only 50% by volume or even less.

Die verwendeten Schmieröle befinden sich im allgemeinen in einem gesonderten Schmierölkreislauf, können jedoch auch den Kraftstoffen zugesetzt sein. Sehr gute Ergebnisse werden beispielsweise erhalten mit Kraftstoffen auf Methanol-oder Ethanolbasis bzw. deren Gemischen die 0,1 bis 15 Gew.-%, bevorzugt 2 bis 15 Gew.-% an C4/C5 bzw. an C4-bis Cs-Kohlenwasserstoffen enthalten, wobei im Falle von Methanol bis zu 15 Gew.-% an Wasser und im Falle von Ethanol bis zu 25 Gew.-% an Wasser im Kraftstoff enthalten sein können und das C4iCs bzw das C4. : Cs/C6-Verhältnis 1:500 Gewichtsteile bis 3:1 Gewichtsteile, bevorzugt 1:1 bis 1:20 ist.The lubricating oils used are generally in a separate lubricating oil circuit, but can also be added to the fuels. Very good results are obtained, for example, with fuels based on methanol or ethanol or their mixtures which contain 0.1 to 15% by weight, preferably 2 to 15% by weight, of C 4 / C 5 or C 4 to Cs -Carbons contain, in the case of methanol up to 15 wt .-% water and in the case of ethanol up to 25 wt .-% water in the fuel and the C4iCs or the C 4 . : C s / C 6 ratio 1: 500 parts by weight to 3: 1 parts by weight, preferably 1: 1 to 1:20.

Ebenso werden beispielsweise sehr gute Ergebnisse mit C4-C7-Kohlenwasserstoffen erhalten, wobei 0,1 bis 18 Gew.-%, bevorzugt 2 bis 18 Gew.-% an Kohlenwasserstoffen im Kraftstoff enthalten sind und das C4. Cs-C7-Verhältnis 1:500 Gew. Teile bis 3:1 Gew. Teile, bevorzugt 1:1 bis 1:20 ist.Very good results are also obtained, for example, with C 4 -C 7 hydrocarbons, 0.1 to 18% by weight, preferably 2 to 18% by weight, of hydrocarbons being contained in the fuel and the C 4 . Cs-C 7 ratio 1: 500 parts by weight to 3: 1 parts by weight, preferably 1: 1 to 1:20.

Auch bei Zusatz von C4-Kohlenwasserstoffen und Kohlenwasserstoffen im Benzinsiedebereich bzw. bei Zusatz von Benzin zu den genannten Alkoholen werden sehr gute Ergebnisse erhalten. Hierbei werden 0,1 bis 25 Gew.-%, bevorzugt 2 bis 25 Gew.-% zugesetzt, bei einem Verhältnis von C4 : Benzin von 1:500 bis 3:1 Gewichtsteilen, bevorzugt von 1:1 bis 1:20.Very good results are also obtained when C4 hydrocarbons and hydrocarbons are added in the gasoline boiling range or when gasoline is added to the alcohols mentioned. Here, 0.1 to 25% by weight, preferably 2 to 25% by weight, are added, at a ratio of C 4 : gasoline of 1: 500 to 3: 1 parts by weight, preferably 1: 1 to 1:20.

Sehr gute Ergebnisse werden jedoch auch mit Kohlenwasserstoffzusätzen erhalten, die beispielsweise nur wenig oder keine C4-Kohlenwasserstoffe enthalten, wie z.B. Sommerbenzin, Leichtbenzinschnitten, Platformatschnitten, Pyrolysebenzinschnitten, Merox-Benzinschnitten, Alkylierungs-und Polymerbenzinschnitten u.a.However, very good results are also obtained with hydrocarbon additives which contain, for example, little or no C 4 hydrocarbons, such as, for example, summer gasoline, light gasoline cuts, platinum cuts, pyrolysis gasoline cuts, Merox gasoline cuts, alkylation and polymer gasoline cuts, and others

Die Alkohole können Rein-oder Rohalkohole sein. So kann beispielsweise sowohl Rein-als auch Rohmethanol oder abgetopptes Methanol eingesetzt werden, sowie destilliertes, wasserfreies oder azeotropes Ethanol oder Ethanol das noch mehr Wasser und Verunreinigungen enthalten kann, wie es z.B. bei der Bioethanolerzeugung anfällt.The alcohols can be pure or raw alcohols. For example, pure as well as raw methanol or topped methanol can be used, as well as distilled, anhydrous or azeotropic ethanol or ethanol, which can contain even more water and impurities, such as e.g. arises in the production of bioethanol.

Die eingesetzten Kraftstoffe können auch zusätzliche Aromaten enthalten z.B. C6-C8-Aromaten oder sog. Platformat sowie Zu sätze an Ethern wie Dimethylether, tert.-Alkylether beispielsweise Methyltert.- butyl-oder amylether, ferner Ketone wie beispielsweise Aceton und andere Sauerstoff enthaltende Verbindungen.The fuels used can also contain additional aromatics, for example C 6 -C 8 aromatics or so-called platformat, and additions of ethers such as dimethyl ether, tert-alkyl ether, for example methyl tert-butyl or amyl ether, and also ketones, for example acetone and other oxygen-containing compounds .

Zusätzliche Alkohole wie sämtliche Isomeren der C3-C10-Alkohole, insbesondere C3-und C4--Alkohole können ebenfalls enthalten sein. Als zugesetzte Kohlenwasserstoffe sind Raffinerieschnitte im entsprechenden Siedebereich sehr gut geeignet, so können C4-, Cs-, C6-, C7-Kohlenwasserstoffe sowie Benzine und deren Kombinationen eingesetzt werden.Additional alcohols, such as all isomers of the C 3 -C 10 alcohols, in particular C 3 and C4 alcohols, can also be present. Refinery cuts in the corresponding boiling range are very suitable as added hydrocarbons, so C 4 -, Cs -, C 6 -, C 7 -hydrocarbons as well as gasolines and their combinations can be used.

Die Ablagerungen in den Gemischaufbereitungssystemen werden auch dann erfindungsgemäß vermieden, wenn im eingesetzten Kraftstoff Korrosionsinhibitoren und sonstige übliche Additive enthalten sind. Korrosionsinhibitoren können beispielsweise folgende Verbindungen und ihre Derivate bzw. Gemische derselben sein bzw. Gemische, welche die folgenden Verbindungen, ihre Derivate bzw. Gemische derselben enthalten, wobei die genannten Verbindungen als beispielhaft zu verstehen sind, ohne daß die Nennung derselben eine Einschränkung darstellt:

  • Imidazolinderivate, Glycylamide, aliphatische Mono-, Di-und Polyamine und ihre N-substituierten Derivate, Ethylendiamin, Succinsäure, Alkenylsuccinsäure und Polymere derselben, Alkanolamine, Monomere und Polymerisate ungesättigter aliphatischer Carbonsäuren, wie beispielsweise von Ölsäure und Linolsäure, aliphatische Dicarbonsäuren, Oxalsäure bis C2o-Dicarbonsäuren, Polyalkylenpolyamine, Triazole, Aminotriazole, Triazoline, Aminotriazoline, Benzoesäure und ihre Salze, Morpholine, organische Phosphorsäurederivate, Salze organischer gesättigter und ungesättigter Carbonsäuren, Carbonsäureanhydride, Alkoxyalkylamine, Stickstoff enthaltende Kondensate, Borverbindungen, amphotere N-Verbindungen, Aryltriazolverbindungen u.a.
According to the invention, the deposits in the mixture preparation systems are also avoided if the fuel used contains corrosion inhibitors and other customary additives. Corrosion inhibitors can be, for example, the following compounds and their derivatives or mixtures thereof or mixtures which contain the following compounds, their derivatives or mixtures thereof, the compounds mentioned being to be understood as examples without the naming of them being a limitation:
  • Imidazoline derivatives, glycylamides, aliphatic mono-, di- and polyamines and their N-substituted derivatives, ethylenediamine, succinic acid, alkenylsuccinic acid and polymers thereof, alkanolamines, monomers and polymers of unsaturated aliphatic carboxylic acids, such as, for example, of oleic acid and linoleic acid, aliphatic dicarboxylic acids, oxalic acids 2 o-dicarboxylic acids, polyalkylene polyamines, triazoles, aminotriazoles, triazolines, aminotriazolines, benzoic acid and their salts, morpholines, organic phosphoric acid derivatives, salts of organic saturated and unsaturated carboxylic acids, carboxylic acid anhydrides, alkoxyalkylamines, nitrogen-containing condensates, boron compounds, amphoteric niazole compounds, and other aryl compounds

Gemäß der erfindungsgemäßen Verwendung können in den Kraftstoffen auch andere Additive wie zusätzliche Emulgatoren, Zündkontrolladditive, Rostschutzadditive, Verschleißadditive u.a. enthalten sein.According to the use according to the invention, other additives such as additional emulsifiers, ignition control additives, anti-rust additives, wear additives etc. can also be used in the fuels. be included.

An folgenden Versuchen wird die erfindungsgemäße Verwendung zusätzlich erläutert.The use according to the invention is additionally explained in the following experiments.

Versuch 1Trial 1

Ein VW-Jetta mit einem 90 PS Motor wurde im üblichen Fahrbetrieb sowie bei extremer Fahrweise bei sehr hohen sommerlichen und sehr tiefen winterlichen Temperaturen (ca. 35 °C + bzw. - 30 °C) sowie im Kalt-und Kurzstreckenbetrieb mit einem Kraftstoff betrieben, der 90 Gew.-% Methanol und 10 Gew.-% C4-Kohlenwasserstoffe + Leichtbenzin enthielt sowie einen Korrosionsinhibitor, der ein amphoteres stickstoffhaltiges Kondensationsprodukt enthielt und erfindungsgemäß 200 ppm und 500 ppm des Polyolethers.

Figure imgb0007
A VW Jetta with a 90 HP engine was operated with a fuel in normal driving as well as in extreme driving with very high summer and very low winter temperatures (approx. 35 ° C + or - 30 ° C) as well as in cold and short distance operation , which contained 90% by weight of methanol and 10% by weight of C 4 -hydrocarbons + light petrol, and a corrosion inhibitor which contained an amphoteric nitrogen-containing condensation product and, according to the invention, 200 ppm and 500 ppm of the polyol ether.
Figure imgb0007

Als Schmiermittel wurde ein kommerzielles Produkt der Klasse SAE 15 W 40 eingesetzt. Der Vergaser wurde alle 2500 km auf Ablagerungen untersucht. Auch nach insgesamt 25.000 km war der Vergaser völlig sauber. Ablagerungen wurden nicht gefunden. Zum Vergleich wurde der gleiche Kraftstoff ohne Polyolether eingesetzt. Im Vergaser wurden nach Beendigung des Tests Ablagerungen im Drosselklappenbereich gefunden.A commercial product of class SAE 15 W 40 was used as the lubricant. The carburetor was checked for deposits every 2500 km. Even after a total of 25,000 km the carburetor was completely clean. No deposits were found. The same fuel without polyol ether was used for comparison. Deposits in the throttle valve area were found in the carburetor after the test was completed.

Versuch 2Trial 2

Versuch 1 wurde wiederholt mit dem Polyolether

Figure imgb0008
als Zusatz in einer Menge von 100 ppm. Der Vergaser erwies sich nach Beendigung des Tests als einwandfrei sauber.Experiment 1 was repeated with the polyol ether
Figure imgb0008
 as an additive in an amount of 100 ppm. The carburetor was found to be perfectly clean after the test.

Versuch 3Trial 3

Versuch 1 wurde wiederholt mit dem Polyolether

Figure imgb0009
als Zusatz in einer Menge von 1500 ppm. Der Vergaser war nach Beendigung des Tests einwandfrei sauber.Experiment 1 was repeated with the polyol ether
Figure imgb0009
 as an additive in an amount of 1500 ppm. The carburetor was perfectly clean after the test.

Versuch 4Trial 4

Versuch 1 wurde wiederholt, jedoch als Kohlenwasserstoff übliches bleifreies Benzin in einer Menge von 15 Gew.% dem Methanol zugesetzt. Als Polyolether wurde ein Mischpolyolether aus Propylenoxid und Ethylenoxid eingesetzt mit endständigen Methylethergruppen und n = 10 sowie mit einer endständigen p-Kresolgruppe (R), einer endständigen Succinimidgruppe und n = 75. Der Vergaser war nach Beendigung des Tests einwandfrei sauber.Experiment 1 was repeated, except that conventional lead-free gasoline was added to the methanol in an amount of 15% by weight as the hydrocarbon. A mixed polyol ether of propylene oxide and ethylene oxide with terminal methyl ether groups and n = 10 and with a terminal p-cresol group (R), a terminal succinimide group and n = 75 was used as the polyol ether. The gasifier was perfectly clean after the test was completed.

Ein Vergleichsversuch ohne Polyoletherzusatz ergab Ablagerungen an Einspritzsystem und Vergaser.A comparison test without addition of polyol ether showed deposits on the injection system and carburetor.

Versuch 5Trial 5

Versuch 1 wurde wiederholt, jedoch ein Alkoholgemisch von 3 Teilen Methanol und 1 Teil Ethanol eingesetzt. Als Kohlenwasserstoff wurden 10 Gew.% C4-Kohlenwasserstoffe + eine Raffineriefraktion, die im wesentlichen Cs-C7 Kohlenwasserstoffe enthielt, eingesetzt. Es wurde ein Polyolether aus Ethylenoxid mit n = 4, einer endständigen Isooctylethergruppe und einer endständigen Hydroxylgruppe eingesetzt. Nach Beendigung des Tests erwiesen sich Vergaser und Einspritzsystem als einwandfrei sauber.Experiment 1 was repeated, but an alcohol mixture of 3 parts of methanol and 1 part of ethanol was used. As the hydrocarbon, 10 wt.% C4 + hydrocarbons a refinery fraction containing 7 hydrocarbons substantially Cs-C, are used. A polyol ether of ethylene oxide with n = 4, a terminal isooctyl ether group and a terminal hydroxyl group was used. After completing the test, the carburetor and injection system were found to be perfectly clean.

Versuch 6Trial 6

Versuch 1 wurde wiederholt,jedoch Superbenzin in einer Menge von 20 Gew.% dem Methanol zugesetzt. Als Polyolether wurde

Figure imgb0010
in einer Menge von 1700 ppm zugesetzt. Der Vergaser war nach Beendigung des Test einwandfrei sauber.Experiment 1 was repeated, but super gasoline was added to the methanol in an amount of 20% by weight. As a polyol ether
Figure imgb0010
 added in an amount of 1700 ppm. The carburetor was perfectly clean after the test.

Versuch 7Trial 7

Versuch 1 wurde wiederholt, jedoch Methanol,mit 5 Gew.% Wasser,und 5 Gew.% Leichtbenzin verwendet und der Polyolether

Figure imgb0011
in einer Menge von 800 ppm eingesetzt. Der Vergaser war nach Beendigung des Test einwandfrei sauber.Experiment 1 was repeated, but using methanol, with 5% by weight of water and 5% by weight of light petrol, and the polyol ether
Figure imgb0011
 used in an amount of 800 ppm. The carburetor was perfectly clean after the test.

Versuch 8Trial 8

Versuch 1 wurde wiederholt, jedoch azeotropes Ethanol anstelle von Methanol verwendet. Der Vergaser war nach Beendigung des Tests einwandfrei sauber.Experiment 1 was repeated, but using azeotropic ethanol instead of methanol. The carburetor was perfectly clean after the test.

Ein Vergleichsversuch ohne Polyolether ergab Ablagerungen im Vergaser.A comparison test without polyol ether showed deposits in the gasifier.

Versuch 9Trial 9

Versuch 1 wurde wiederholt mit einem Mercedes-Benz 200 E. Als Polyolether wurde

Figure imgb0012
eingesetzt.Experiment 1 was repeated with a Mercedes-Benz 200 E. As a polyol ether
Figure imgb0012
 used.

Nach Beendigung des Tests erwies sich das Einspritzsystem als einwandfrei sauber. Im Vergleichstest ohne Polyolether befanden sich Ablagerungen am Einspritzsystem.At the end of the test, the injection system was found to be perfectly clean. In the comparison test without polyol ether, there were deposits on the injection system.

Ähnliche Ergebnisse wurden mit anderen erfindungsgemäßen Polyolethern mit und ohne Korrosionsinhibitoren und anderen Additiven erhalten.Similar results were obtained with other polyol ethers according to the invention with and without corrosion inhibitors and other additives.

Die vorliegende Erfindung stellt eine wichtige Verbesserung auf dem Gebiet der Alkoholkraftstoffe dar. Die Versuche zeigen, daß durch den erfindungsgemäßen Zusatz der Polyolether, konventionelle, käufliche Schmiermittel in mit Alkoholkraftstoffen betriebenen Motoren eingesetzt werden können, anstelle speziell für solche Motoren hergestellten Schmiermitteln.The present invention represents an important improvement in the field of alcohol fuels. The experiments show that by adding the polyol ethers according to the invention, conventional, commercially available lubricants can be used in engines operated with alcohol fuels instead of lubricants specially produced for such engines.

Claims (18)

1. Verfahren zur Verhinderung oder Verminderung von Ablagerungen in Gemischaufbereitungssystemen von Motoren, in welche Kraftstoffe auf Methanol-und/oder Ethanolbasis, die ggfs. Zusätze an Wasser und/oder C3-C10-Alkoholen und/oder andere Sauerstoff enthaltende Verbindungen, und/oder Kohlenwasser stoffen und wenigstens einen Korrosionsinhibitor enthalten, in Verbindung mit Schmiermitteln eingesetzt werden, die für mit Kohlenwasserstoff-Kraftstoffen betriebene Motoren geeignet sind, dadurch gekennzeichnet, daß den Kraftstoffen ein oder mehrere Polyolether in einer Menge von 15 ppm bis zu 1 Gew.-%, vorzugsweise von 15 bis < 2000 ppm und besonders bevorzugt von 30 bis < 2000 ppm zugesetzt werden, wobei der (die) Polyolether die allgemeine Formel
Figure imgb0013
besitzt(en) worin R eine der folgenden Gruppen sein kann: H, unverzweigtes und verzweigtes C1-C20 Alkyl, C1-C20-Alkenyl, mehrfach ungesättigtes C1-C20-Alkyl, C1-C20-Cycloalkyl, mono-und bicyclisches C5-C14-Aryl mit und ohne funktionelle Gruppen wie OH, OR4, NH2, Alkylamingruppen, SH, SR4, C * N, (wobei R4 jeweils aliphatische gesättigte und ungesättigte Alkylgruppen sein können sowie unsubstituierte und substituierte Arylgruppen), eine 0-, S-und P-haltige Gruppe wie z.B. Carboxygruppe aliphatischer gesättigter und ungesättigter Carbonsäuren, insbesondere von Fettsäuren, von aromatischen substituierten und unsubstituierten Carbonsäuren, Phosphorsäureestergruppen, Thiophosphorsäureestergruppen, Acetalgruppen; Ri = H, C1-C8-Alkyl, unsubstituiertes oder substituiertes Aryl; R2 = H, C1-C8-Alkyl, unsubstituiertes oder substituiertes Aryl und R3 =OR5, SR5,
Figure imgb0014
N(Rs)2 wobei Rs = H, unverzweigtes undverzweigtes C1-C20-Alkyl, C1-C20-Alkenyl, mehrfach ungesättigtes C1-C20-Alkyl, C1-C20-Cycloalkyl, mono-und bicyclisches C6-C14 Aryl mit und ohne funktionelle Gruppen wie OH, OR4-, NH2, Alkylamingruppen, SH, SRa., C = N,(wobei R4. jeweils aliphatische gesättigte und ungesättigte Alkylgruppen sein können sowie unsubstitutierte und substituierte Arylgruppen);
Figure imgb0015
wobei R6 = H, eine geradkettige, verzweigte, gesättigte und ungesättigte C1-C2o-Alkyl und Mono-und Bicycloalkylgruppe sowie eine substituierte und unsubstituierte Mono-und Bicycloarylgruppe, unsubstituierte und substituierte Aminogruppe, unsubstituierte und substituierte Alkoxygruppe, unsubstituierte und substituierte Thioethergruppe sein kann, wobei R7 = geradkettige, verzweigte, gesättigte und ungesättigte Alkylgruppen sein können,
Figure imgb0016
wobei R8 = R6 sein kann sowie die C = 0-Gruppen durch unsubstituierte, substituierte, gesättigte und ungesättigte Methylenbrücken aus 2 - 5 Methylengruppen verbunden sein können, = Phosphorsäure-und Thiophosphorsäureestergruppen, = Alkylethylendiamintetraessigsäureester, -amid oder -imid und m = 2 - 4, wobei m im Polyolether-Molekül ausschließlich aus 2 oder 3 oder 4 oder aus Kombinationen derselben besteht und n = 1 - 200, bevorzugt 2 - 100 und besonders bevorzugt 2 - 75 ist.1. A method for preventing or reducing deposits in mixture preparation systems of engines, in which fuels based on methanol and / or ethanol, possibly the additions of water and / or C 3 -C 10 alcohols and / or other oxygen-containing compounds, and / or hydrocarbons and contain at least one corrosion inhibitor, are used in conjunction with lubricants which are suitable for engines operated with hydrocarbon fuels, characterized in that the fuels contain one or more polyol ethers in an amount of 15 ppm up to 1% by weight. %, preferably from 15 to <2000 ppm and particularly preferably from 30 to <2000 ppm, the polyol ether (s) having the general formula
Figure imgb0013
 has (s) wherein R can be one of the following groups: H, unbranched and branched C 1 -C 20 alkyl, C 1 -C 20 alkenyl, polyunsaturated C 1 -C 20 alkyl, C 1 -C 20 cycloalkyl , mono- and bicyclic C 5 -C 14 aryl with and without functional groups such as OH, OR 4 , NH 2 , alkylamine groups, SH, SR 4 , C * N, (where R 4 can each be aliphatic saturated and unsaturated alkyl groups and unsubstituted and substituted aryl groups), a 0-, S- and P-containing group such as, for example, carboxy group of aliphatic saturated and unsaturated carboxylic acids, in particular of fatty acids, of aromatic substituted and unsubstituted carboxylic acids, phosphoric acid ester groups, thiophosphoric acid ester groups, acetal groups; Ri = H, C 1 -C 8 alkyl, unsubstituted or substituted aryl; R 2 = H, C 1 -C 8 alkyl, unsubstituted or substituted aryl and R 3 = OR 5 , SR 5 ,
Figure imgb0014
 N (Rs) 2 where Rs = H, unbranched and branched C 1 -C 20 alkyl, C 1 -C 20 alkenyl, polyunsaturated C 1 -C 20 alkyl, C 1 -C 20 cycloalkyl, mono- and bicyclic C 6 -C 14 aryl with and without functional groups such as OH, OR 4 -, NH 2 , alkylamine groups, SH, SRa., C = N, (where R 4. can each be aliphatic saturated and unsaturated alkyl groups and unsubstituted and substituted aryl groups);
Figure imgb0015
 where R 6 = H, a straight-chain, branched, saturated and unsaturated C 1 -C 2 o -alkyl and mono- and bicycloalkyl group and a substituted and unsubstituted mono- and bicycloaryl group, unsubstituted and substituted amino group, unsubstituted and substituted alkoxy group, unsubstituted and substituted Can be thioether group, where R 7 = straight-chain, branched, saturated and unsaturated alkyl groups,
Figure imgb0016
 where R 8 = R 6 and the C = 0 groups can be connected by unsubstituted, substituted, saturated and unsaturated methylene bridges from 2-5 methylene groups, = phosphoric acid and thiophosphoric acid ester groups, = alkyl ethylenediaminetetraacetic acid ester, amide or imide and m = 2-4, where m in the polyol ether molecule consists exclusively of 2 or 3 or 4 or combinations thereof and n = 1-200, preferably 2-100 and particularly preferably 2-75. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß R1 und R2 H und/oder CH3 sind.2. The method according to claim 1, characterized in that R 1 and R 2 are H and / or CH 3 . 3. Verfahren nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß die Kraftstoffe 0,1 bis 25 Vol.%, vorzugsweise 1 bis 25 Vol.% und besonders bevorzugt 2 bis 25 Vol.% Kohlenwasserstoffe und 75 bis 99,9 Vol.%, vorzugsweise 75 bis 99 Vol.% und besonders bevorzugt 75 bis 98 Vol.% Methanol undioder Ethanol und/oder beliebige Gemische aus Methanol und Ethanol enthalten.3. Process according to claims 1 and 2, characterized in that the fuels 0.1 to 25 vol.%, Preferably 1 to 25 vol.% And particularly preferably 2 to 25 vol.% Hydrocarbons and 75 to 99.9 vol. %, preferably 75 to 99% by volume and particularly preferably 75 to 98% by volume of methanol and / or ethanol and / or any mixtures of methanol and ethanol. 4. Verfahren nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß die Kohlenwasserstoffe C4-bis Cx-Kohlenwasserstoffe sind, wobei x der Kohlenstoffanzahl der Kohlenwasserstoffe an der oberen Grenze der Benzinkraftstoff-Kohlenwasserstoffe entspricht.4. The method according to claims 1 to 3, characterized in that the hydrocarbons are C 4 to C x hydrocarbons, where x corresponds to the carbon number of the hydrocarbons at the upper limit of the gasoline-hydrocarbons. 5. Verfahren nach den Ansprüchen 1 - 4, dadurch gekennzeichnet, daß das eingesetzte Ethanol zumindest teilweise wasserhaltiges Ethanol ist.5. Process according to claims 1-4, characterized in that the ethanol used is at least partially water-containing ethanol. 6. Verfahren nach den Ansprüchen 1 - 5, dadurch gekennzeichnet, daß das eingesetzte Methanol zumindest teilweise undestilliertes technisches Methanol und/oder abgetopptes technisches Methanol ist.6. Process according to claims 1-5, characterized in that the methanol used is at least partially undistilled technical methanol and / or topped technical methanol. 7. Verfahren nach den Ansprüchen 1 - 6, dadurch gekennzeichnet, daß in den Kraftstoffen zusätzlich aromatische Kohlenwasserstoffe enthalten sind.7. Process according to claims 1-6, characterized in that aromatic hydrocarbons are additionally contained in the fuels. 8. Verfahren nach den Ansprüchen 1 - 7, dadurch gekennzeichnet, daß R ein Rest aus der Gruppe H, Alkyl, Aryl und Carboxy ist.8. The method according to claims 1-7, characterized in that R is a radical from the group H, alkyl, aryl and carboxy. 9. Verfahren nach den Ansprüchen 1 - 8, dadurch gekennzeichnet, daß R3 ein Rest aus der Gruppe H, ORs, SRs,
Figure imgb0017
und
Figure imgb0018
ist.9. The method according to claims 1-8, characterized in that R 3 is a radical from the group H, ORs, SRs,
Figure imgb0017
 and
Figure imgb0018
 is. 10. Kraftstoffe auf Methanol-und/oder Ethanolbasis, die in Verbindung mit Schmiermitteln eingesetzt werden, die für mit Kohlenwasserstoff-Kraftstoffen betriebene Motoren geeignet sind, wobei die Kraftstoffe ggfs. Zusätze an Wasser und/oder C3-Cio-Alkoholen und/oder Kohlenwasserstoffen und/oder anderen Sauerstoff enthaltenden Verbindungen und wenigstens einen Korrosionsinhibitor enthalten, dadurch gekennzeichnet, daß die Kraftstoffe einen oder mehrere Polyolether in einer Menge von 15 ppm bis zu 1 Gew.-%, vorzugsweise von 15 bis < 2000 ppm und besonders bevorzugt von 30 bis < 2000 ppm enthalten und daß der (die) Polyolether die allgemeine Formel
Figure imgb0019
besitzt(en) worin R eine der folgenden Gruppen sein kann: H, unverzweigtes und verzweigtes C1-C20 Alkyl, C1-C2o-Alkenyl, mehrfach ungesättigtes C1-C20-Alkyl, C1-C20-Cycloalkyl, mono-und bicyclisches C6-C14-Aryl mit und ohne funktionelle Gruppen wie OH, OR4, NH2, Alkylamingruppen, SH, SR4, C ≡ N, (wobei R4 jeweils aliphatische gesättigte und ungesättigte Alkylgruppen sein können sowie unsubstituierte und substituierte Arylgruppen), eine 0-, S-und P-haltige Gruppe wie z.B. Carboxygruppe aliphatischer gesättigter und ungesättigter Carbonsäuren, insbesondere von Fettsäuren, von aromatischen substituierten und unsubstituierten Carbonsäuren, Phosphorsäureestergruppen, Thiophosphorsäureestergruppen, Acetalgruppen; R1 = H, C1-C8-Alkyl, unsubstituiertes oder substituiertes Aryl; R2 = H, C1-C8-Alkyl, unsubstituiertes oder substituiertes Aryl und Ra = ORs, SRs,
Figure imgb0020
V(R5)2 wobei R5 = H, unverzweigtes undverzweigtes C1-C20-Alkyl, C1-C20-Alkenyl, mehrfach ungesättigtes C1-C20-Alkyl, C1-C20-Cycloalkyl, mono-und bicyclisches C6-C14-Aryl mit und ohne funktionelle Gruppen wie OH, OR4, NH2, Alkylamingruppen, SH, SR4, C = N,(wobei R4. jeweils aliphatische gesättigte und ungesättigte Alkylgrup pen sein können sowie unsubstitutierte und substituierte Arylgruppen);
Figure imgb0021
wobei R6 = H, eine geradkettige, verzweigte, gesättigte und ungesättigte C1-C20-Alkyl und Mono-und Bicycloalkylgruppe sowie eine substituierte und unsubstituierte Mono-und Bicycloarylgruppe, unsubstituierte und substituierte Aminogruppe, unsubstituierte und substituierte Alkoxygruppe, unsubstituierte und substituierte Thioethergruppe sein kann, wobei R7 = geradkettige, verzweigte, gesättigte und ungesättigte Alkylgruppen sein können,
Figure imgb0022
wobei R8 = R6 sein kann sowie die C = O-Gruppen durch unsubstituierte, substituierte, gesättigte und ungesättigte Methylenbrücken aus 2 - 5 Methylengruppen verbunden sein können, = Phosphorsäure-und Thiophosphorsäureestergruppen, = Alkylethylendiamintetraessigsäureester, -amid oder -imid und m = 2 - 4, wobei m im Polyolether-Molekül ausschließlich aus 2 oder 3 oder 4 oder aus Kombinationen derselben besteht und n = 1 - 200, bevorzugt 2 - 100 und besonders bevorzugt 2 - 75 ist.10. Fuels based on methanol and / or ethanol which are used in conjunction with lubricants which are suitable for engines operated with hydrocarbon fuels, the fuels possibly adding water and / or C3-Cio alcohols and / or hydrocarbons and / or other oxygen-containing compounds and at least one corrosion inhibitor, characterized in that the fuels contain one or more polyol ethers in an amount of from 15 ppm to 1% by weight, preferably from 15 to <2000 ppm and particularly preferably from 30 to Contain <2000 ppm and that the polyol ether (s) has the general formula
Figure imgb0019
 has (s) in which R can be one of the following groups: H, unbranched and branched C 1 -C 20 alkyl, C 1 -C 2 o-alkenyl, polyunsaturated C 1 -C 20 alkyl, C 1 -C 20 - Cycloalkyl, mono- and bicyclic C 6 -C 14 aryl with and without functional groups such as OH, OR 4 , NH 2 , alkylamine groups, SH, SR 4 , C ≡ N, (where R 4 can each be aliphatic saturated and unsaturated alkyl groups as well as unsubstituted and substituted aryl groups), a 0-, S- and P-containing group such as, for example, carboxy group of aliphatic saturated and unsaturated carboxylic acids, in particular of fatty acids, of aromatic substituted and unsubstituted carboxylic acids, phosphoric acid ester groups, thiophosphoric acid ester groups, acetal groups; R 1 = H, C 1 -C 8 alkyl, unsubstituted or substituted aryl; R 2 = H, C 1 -C 8 alkyl, unsubstituted or substituted aryl and Ra = ORs, SRs,
Figure imgb0020
 V (R 5 ) 2 where R 5 = H, unbranched and branched C 1 -C 20 alkyl, C 1 -C 20 alkenyl, polyunsaturated C 1 -C 20 alkyl, C 1 -C 20 cycloalkyl, mono- and bicyclic C 6 -C 14 aryl with and without functional Groups such as OH, OR 4 , NH 2 , alkylamine groups, SH, SR 4 , C = N, (where R 4. Can each be aliphatic saturated and unsaturated alkyl groups and unsubstituted and substituted aryl groups);
Figure imgb0021
 where R 6 = H, a straight-chain, branched, saturated and unsaturated C 1 -C 20 alkyl and mono- and bicycloalkyl group and a substituted and unsubstituted mono and bicycloaryl group, unsubstituted and substituted amino group, unsubstituted and substituted alkoxy group, unsubstituted and substituted thio where R 7 can be straight-chain, branched, saturated and unsaturated alkyl groups,
Figure imgb0022
 where R 8 = R 6 and the C = O groups can be connected by unsubstituted, substituted, saturated and unsaturated methylene bridges from 2-5 methylene groups, = phosphoric acid and thiophosphoric acid ester groups, = alkyl ethylenediaminetetraacetic acid ester, amide or imide and m = 2-4, where m in the polyol ether molecule consists exclusively of 2 or 3 or 4 or combinations thereof and n = 1-200, preferably 2-100 and particularly preferably 2-75. 11. Kraftstoffe nach Anspruch 10, dadurch gekennzeichnet, daß R1 und R2 H und/oder CH3 sind.11. Fuels according to claim 10, characterized in that R 1 and R 2 are H and / or CH 3 . 12. Kraftstoffe nach den Ansprüchen 10 und 11, dadurch gekennzeichnet, daß die Kraftstoffe 0,1 bis 25 Vol.-%, vorzugsweise 1 bis 25 Vol: % und besonders bevorzugt 2 bis 25 Vol.-% Kohlenwasserstoffe und 75 bis 99,9 Vol.-%, vorzugsweise 75 bis 99 Vol.-% und besonders bevorzugt 75 bis 98 Vol.-% Methanol und/oder Ethanol und/oder beliebige Gemische aus Methanol und Ethanol enthalten.12. Fuels according to claims 10 and 11, characterized in that the fuels 0.1 to 25 vol .-%, preferably 1 to 25 vol:% and particularly preferably 2 to 25 vol .-% hydrocarbons and 75 to 99.9 Vol .-%, preferably 75 to 99 vol .-% and particularly preferably 75 to 98 vol .-% contain methanol and / or ethanol and / or any mixtures of methanol and ethanol. 13. Kraftstoffe nach den Ansprüchen 10 - 12, dadurch gekennzeichnet, daß die Kohlenwasserstoffe C4- bis Cx-Kohlenwasserstoffe sind, wobei x der Kohlenstoffanzahl der Kohlenwasserstoffe an der oberen Grenze der BeniinkraftstoffKohlenwasserstoffe entspricht.13. Fuels according to claims 10 - 12, characterized in that the hydrocarbons are C4 to C x hydrocarbons, where x corresponds to the number of carbon atoms in the hydrocarbons at the upper limit of the gasoline hydrocarbons. 14. Kraftstoffe nach den Ansprüchen 10 - 13, dadurch gekennzeichnet, daß das eingesetzte Ethanol zumindest teilweise wasserhaltiges Ethanol ist.14. Fuels according to claims 10-13, characterized in that the ethanol used is at least partially water-containing ethanol. 15. Kraftstoffe nach den Ansprüchen 10 - 14, dadurch gekennzeichnet, daß das eingesetzte Methanol zumindest teilweise undestilliertes technisches Methanol und/oder abgetopptes technisches Methanol ist.15. Fuels according to claims 10-14, characterized in that the methanol used is at least partially undistilled technical methanol and / or topped technical methanol. 16. Kraftstoffe nach den Ansprüchen 10 - 15, dadurch gekennzeichnet, daß in den Kraftstoffen zusätzlich aromatische Kohlenwasserstoffe enthalten sind.16. Fuels according to claims 10-15, characterized in that the fuels additionally contain aromatic hydrocarbons. 17. Kraftstoffe nach den Ansprüchen 10 - 16, dadurch gekennzeichnet, daß R ein Rest aus der Gruppe H, Alkyl, Aryl und Carboxy ist.17. Fuels according to claims 10-16, characterized in that R is a radical from the group H, alkyl, aryl and carboxy. 18. Kraftstoffe nach den Ansprüchen 10 - 17, dadurch gekennzeichnet, daß R3 ein Rest aus der Gruppe H, ORs, SRs,
Figure imgb0023
und
Figure imgb0024
 18. Fuels according to claims 10-17, characterized in that R 3 is a radical from the group H, ORs, SRs,
Figure imgb0023
 and
Figure imgb0024
EP88105287A 1987-04-09 1988-03-31 Process to prevent or reduce scales in mixture preparation devices of engines Expired - Lifetime EP0289785B1 (en)

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