EP0548617B1 - Kraftstoffe für Ottomotoren - Google Patents
Kraftstoffe für Ottomotoren Download PDFInfo
- Publication number
- EP0548617B1 EP0548617B1 EP92120622A EP92120622A EP0548617B1 EP 0548617 B1 EP0548617 B1 EP 0548617B1 EP 92120622 A EP92120622 A EP 92120622A EP 92120622 A EP92120622 A EP 92120622A EP 0548617 B1 EP0548617 B1 EP 0548617B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fuel
- fuels
- weight
- detergent component
- additives
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000000446 fuel Substances 0.000 title claims abstract description 18
- 239000003599 detergent Substances 0.000 claims abstract description 24
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012141 concentrate Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 239000002199 base oil Substances 0.000 abstract description 18
- 239000000654 additive Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002816 fuel additive Substances 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 0 *CCC=CC(O*)=C(*)C=N Chemical compound *CCC=CC(O*)=C(*)C=N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- JKTAIYGNOFSMCE-UHFFFAOYSA-N 2,3-di(nonyl)phenol Chemical compound CCCCCCCCCC1=CC=CC(O)=C1CCCCCCCCC JKTAIYGNOFSMCE-UHFFFAOYSA-N 0.000 description 1
- KGBURRFUTVSDKX-UHFFFAOYSA-N 2-[(2-amino-2-oxoethyl)-[2-[bis(2-amino-2-oxoethyl)amino]ethyl]amino]acetamide Chemical class NC(=O)CN(CC(N)=O)CCN(CC(N)=O)CC(N)=O KGBURRFUTVSDKX-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000005521 carbonamide group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006280 diesel fuel additive Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005652 polyisobutylene succinic anhydride Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
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- 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
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- C10L1/16—Hydrocarbons
- C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
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- C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
- C10L1/233—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring containing nitrogen and oxygen in the ring, e.g. oxazoles
- C10L1/2335—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring containing nitrogen and oxygen in the ring, e.g. oxazoles morpholino, and derivatives thereof
-
- 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
- C10L1/234—Macromolecular compounds
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
-
- 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
- C10L1/234—Macromolecular compounds
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
- C10L1/2387—Polyoxyalkyleneamines (poly)oxyalkylene amines and derivatives thereof (substituted by a macromolecular group containing 30C)
-
- 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
- F02B1/00—Engines characterised by fuel-air mixture compression
- F02B1/02—Engines characterised by fuel-air mixture compression with positive ignition
- F02B1/04—Engines characterised by fuel-air mixture compression with positive ignition with fuel-air mixture admission into cylinder
Definitions
- the invention relates to fuels for gasoline engines which contain small amounts of a combination of a nitrogen-containing detergent component and a carrier oil component, the carrier oil component comprising dialkylphenol-started propoxylates.
- Carburetor and intake system of gasoline engines are increasingly contaminated by contaminants that are caused by dust particles from the air, unburned hydrocarbon residues from the combustion chamber and the crankcase ventilation gases passed into the carburetor.
- the first generation of additives could only prevent the formation of deposits in the intake system, but not remove existing deposits, whereas the modern additives of the second generation can do both ("keep-clean” and "clean-up effect") and because of changed thermal properties, in particular also at zones of higher temperatures, namely at the inlet valves.
- carrier oils in particular play a central role here.
- the addition of carrier oil can have a positive effect on engine areas which are normally not reached by the conventional additives, which mainly act in the intake system.
- US Pat. No. 4,877,416 discloses fuel mixtures which, in addition to an amine as detergent component, contain a carrier oil.
- a carrier oil Poly (oxyalkylene) monools with hydrocarbon end groups are mentioned as carrier oil.
- a large number of possible radicals are mentioned as hydrocarbon end groups, including in particular C7-C30-alkylphenyl.
- a carrier oil is described which was obtained by butoxylation of dodecylphenol.
- the compatibility with one another must also be taken into account when selecting additives.
- the detergents and carrier oils if present in a concentrate, must not lead to deposition or phase separation. This is according to US 4,877,416 for the alkylphenol-started carrier oils e.g. achieved in that butylene oxide is used as the alkylene oxide, which, however, is relatively expensive to produce and its use is cost-intensive.
- the alkoxylates according to the invention although no butylene oxide is used for their preparation, have good compatibility with the nitrogen-containing detergent component and also prevent the deposits mentioned in the inlet system and in the combustion chamber.
- the alkoxylates of the formula I according to the invention also provide compatibility with the detergent when a monoalkyl-substituted propoxylate is present as an additional component of the carrier oil component, although this propoxylate is not readily compatible with the Nitrogen-containing detergent component is compatible.
- the carrier oil component can therefore also comprise 10 to 5000 ppm (based on the fuel) of a monoalkylphenol-started propoxylate, the structure given in formula I applying to this propoxylate, with the proviso that R 1 is omitted, and in particular, the amount of the monoalkylphenol started propoxylate is not greater than the amount of the dialkylphenol started propoxylate according to formula I.
- the fuels preferably contain 20 to 2,000 ppm, in particular 50 to 1,000 ppm (all ppm data are in each case based on the weight) of the detergent component a) or of the alkoxylate b).
- nitrogen-containing detergent component in the mixture with the carrier oils according to the invention it is possible in principle to use any known of the products suitable for this purpose, such as those e.g. with J. Falbe, U. Hasserodt, catalysts, surfactants and mineral oil additives, G. Thieme Verlag Stuttgart 1978, p. 221 f. or in K. Owen, Gasoline and Diesel Fuel Additives, John Wiley & Sons 1989, pp. 23 ff.
- Amides or imides of polyisobutylene succinic anhydride, polybutene polyamines and long-chain carbonamides and imides are suitable as further detergents or additional dispersants.
- dialkylphenols used as starters are prepared in a customary manner by Friedel-Crafts alkylation of phenols with the corresponding olefins or olefin mixtures.
- the propoxylates according to the invention have excellent compatibility, particularly with the polyisobutylamines already mentioned in the respective formulations.
- Leaded and especially unleaded regular and premium gasoline are considered as fuels for gasoline engines.
- the gasolines can also contain components other than hydrocarbons, e.g. Alcohols for methanol, ethanol, tert-butanol and ethers, e.g. Contain methyl tertiary butyl ether.
- the fuels generally also contain further additives such as corrosion inhibitors, stabilizers, antioxidants and / or further detergents.
- Corrosion inhibitors are mostly ammonium salts org. Carboxylic acids which tend to form films due to the corresponding structure of the starting compounds. Amines to lower the pH are also often found in corrosion inhibitors. Heterocyclic aromatics are mostly used as non-ferrous metal corrosion protection.
- Antioxidants or stabilizers include, in particular, amines such as para-phenylenediamine, dicyclohexylamine, morpholine or derivatives of these amines.
- Phenolic antioxidants such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxiphenylpropionic acid and their derivatives are also added to fuels and lubricants.
- thermogravimetric analyzes as a measure of the effectiveness with regard to combustion chamber deposits, since a general engine test for this does not yet exist.
- thermogravimetric analyzes provide information about the thermal load capacity of a sample, eg a thermo-oxidative condition.
- thermo-oxidative condition e.g. a thermo-oxidative condition.
- they allow conclusions to be drawn about the formation of deposits or residual amounts after such a thermo-oxidative treatment.
- the high thermal load-bearing capacity combined with the least possible to vanishing residue formation is favorable for use as carrier oil in the sense of this invention.
- alkoxylates of longer-chain dialkylphenols according to the invention meet all of these requirements (synergism with detergents, demonstrated in the engine test; excellent thermooxidative properties, verified by thermogravimetric analysis) to a high degree.
- the additive combination of nitrogen-containing detergent component and alkoxylate as carrier oil component is preferably provided as a concentrate which contains 10 to 80% by weight, in particular 30 to 60% by weight, of the detergent component and 5 to 70% by weight .-%, in particular 20 to 60 wt .-% of the carrier oil component, ie of the propoxylate.
- the concentrate contains a suitable solvent, e.g. aromatic and / or aliphatic hydrocarbons, especially heavy naphtha (Solvesso®).
- thermogravimetry curve shown in the figure shows the relative mass decrease m / m o as a function of the temperature at a heating rate of 2 ° C. per minute and in the presence of air.
- the half-life temperature of 260 to 270 ° C indicates sufficient thermo-oxidative stability; at higher temperatures the product disintegrates almost without residue (m is the mass measured in each case, m o the initial mass).
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- General Chemical & Material Sciences (AREA)
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- Solid Fuels And Fuel-Associated Substances (AREA)
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- Liquid Carbonaceous Fuels (AREA)
Description
- Die Erfindung betrifft Kraftstoffe für Ottomotoren, die geringe Mengen einer Kombination einer Stickstoff-haltigen Detergens-Komponente und einer Trägeröl-Komponente enthalten, wobei die Trägeröl-Komponente Dialkylphenol-gestartete Propoxylate umfaßt.
- Vergaser und Einlaßsystem von Ottomotoren, aber auch Einspritzsysteme für die Kraftstoffdosierung in Otto- und Dieselmotoren werden in zunehmendem Maße durch Verunreinigungen belastet, die durch Staubteilchen aus der Luft, unverbrannte Kohlenwasserstoffreste aus dem Brennraum und die in den Vergaser geleiteten Kurbelwellengehäuseentlüftungsgase verursacht werden.
- Diese Rückstände verschieben das Luft-Kraftstoffverhältnis im Leerlauf und im unteren Teillastbereich, so daß das Gemisch fetter, die Verbrennung unvollständiger und wiederum die Anteile unverbrannter oder teilverbrannter Kohlenwasserstoffe im Abgas größer werden und der Benzinverbrauch steigt.
- Es ist bekannt, daß zur Vermeidung dieser Nachteile Kraftstoffadditive zur Reinhaltung von Ventilen und Vergaser bzw. Einspritzsystemen verwendet werden (vgl. z.B.: M. Rossenbeck in Katalysatoren, Tenside, Mineralöladditive, Hrsg. J. Falbe, U. Hasserodt, S. 223 f., G. Thieme Verlag, Stuttgart 1978).
- Je nach Wirkungsweise, aber auch nach dem bevorzugten Wirkort solcher Detergens-Additive unterscheidet man heute zwei Generationen.
- Die erste Additiv-Generation konnte nur die Bildung von Ablagerungen im Ansaugsystem verhindern, nicht aber bereits vorhandene Ablagerungen wieder entfernen, wohingegen die modernen Additive der zweiten Generation beides bewirken können ("keep-clean-" und "clean-up-Effekt") und zwar, aufgrund veränderter thermischer Eigenschaften, insbesondere auch an Zonen höherer Temperaturen, nämlich an den Einlaßventilen.
- Auch die Frage nach der Zunahme des Oktanzahlbedarfs eines Ottomotors, bedingt durch Ablagerungen im Brennraum über eine gewisse Laufzeit, und die Möglichkeit, hier durch gezielte Additivierung des Kraftstoffes positiv einzugreifen, geraten immer mehr in den Blickpunkt des Interesses bei der Entwicklung neuer Additive.
- Durch geschickte Kombination solcher das Einlaßsystem reinhaltender Detergentien mit weiteren Komponenten kann ein breiteres Wirkungsspektrum solcher Formulierungen erzielt werden.
- Insbesondere den sogenannten Trägerölen kommt hierbei eine zentrale Aufgabe zu.
- So gelingt es zum einen, mit speziellen, meist synthetischen Trägerölkomponenten aufgrund synergistischer Effekte den Wirkungsgrad der Detergentien im Vergaser oder Einlaßsystem zu erhöhen. Bestimmte Additive entfalten diese Wirkung überhaupt erst in Kombination mit einem Öl.
- Zum anderen können durch Trägerölzugaben Motorbereiche positiv beeinflußt werden, die von den herkömmlichen, vorwiegend im Einlaßsystem wirkenden Additiven normalerweise nicht erreicht werden.
- Hierzu sind vor allem die bereits angesprochenen Brennraumablagerungen (ORI-Problem) zu nennen.
- Aus der US 4,877,416 sind Kraftstoffgemische bekannt, die neben einem Amin als Detergens-Komponente ein Trägeröl enthalten. Als Trägeröl werden Poly(oxyalkylen)monoole mit Kohlenwasserstoff-Endgruppen genannt. Als Kohlenwasserstoff-Endgruppen sind eine große Zahl von möglichen Resten erwähnt, darunter insbesondere C₇-C₃₀-Alkylphenyl. Beispielhaft wird ein Trägeröl beschrieben, das durch Butoxilierung von Dodecylphenol erhalten wurde.
- Neben den Effekten bezüglich der Reinhaltung von Ventilen und Einlaßsystem und der Verhinderung von Brennraumablagerungen ist bei der Auswahl der Additive jedoch auch noch die Verträglichkeit untereinander zu berücksichtigen. So dürfen die Detergentien und Trägeröle, wenn sie in einem Konzentrat vorliegen, nicht zu Abscheidungen oder Phasentrennung führen. Dies wird gemäß der US 4,877,416 bei den Alkylphenol-gestarteten Trägerölen z.B. dadurch erreicht, daß als Alkylenoxid Butylenoxid verwendet wird, das jedoch verhältnisgemäß aufwendig herzustellen und dessen Einsatz kostenintensiv ist.
- Es bestand daher die Aufgabe, Kombinationen von Additiven für Kraftstoffe zu finden, die zum einen synergistische Wirkung im Hinblick auf Einlaßsystemreinhaltung in Ottomotoren entfalten, andererseits den Anstieg des Oktanzahlbedarfs eines Motors möglichst gering halten bzw. sogar verhindern und die in konzentrierter Lösung gut miteinander verträglich sind, d.h. sich nicht entmischen. Die Additive sollen sich zudem aus möglichst leicht zugänglichen Stoffen herstellen lassen und thermostabil sein.
- Diese Aufgabe wird gelöst durch Kraftstoffe für Ottomotoren, die enthalten eine Kombination aus
- a) 10 bis 5 000 ppm einer Stickstoff-haltigen Detergens-Komponente und
- b) 10 bis 5 000 ppm eines Alkoxylats der folgenden Formel I
- R¹ und R
- unabhängig voneinander einen verzweigten oder unverzweigten C₆-C₃₀-Alkylrest,
einer der beiden Reste R³ Methyl und der andere Wasserstoff
und - n=
- 1 bis 100.
- Überraschenderweise hat sich gezeigt, daß die erfindungsgemäßen Alkoxylate, obwohl zu ihrer Herstellung kein Butylenoxid verwendet wird, eine gute Verträglichkeit mit der Stickstoff-haltigen Detergens-Komponente aufweisen und außerdem die genannten Ablagerungen im Einlaßsystem und im Brennraum verhindern.
- Als besonders vorteilhaft hat sich herausgestellt, daß durch die erfindungsgemäßen Alkoxylate der Formel I eine Verträglichkeit mit dem Detergens auch dann noch gegeben ist, wenn als zusätzlicher Bestandteil der Trägeröl-Komponente ein monoalkylsubstituiertes Propoxylat vorhanden ist, obwohl dieses Propoxylat für sich nicht ohne weiteres mit der Stickstoff-haltigen Detergens-Komponente verträglich ist.
- Die Trägeröl-Komponente kann daher neben dem Bestandteil b) noch 10 bis 5 000 ppm (bez. auf den Kraftstoff) eines Monoalkylphenol-gestarteten Propoxylats umfassen, wobei für dieses Propoxylats die in Formel I angegebene Struktur mit der Maßgabe gilt, daß R¹ wegfällt, und insbesondere gilt, daß die Menge des Monoalkylphenol-gestarteten Propoxylats nicht größer ist als die Menge des Dialkylphenol-gestarteten Propoxylats nach Formel I.
- Es ist auch möglich, zu der erfindungsgemäßen Additiv-Kombination noch andere Trägeröl-Komponenten zuzugeben, z.B. Ester aus Monocarbonsäuren oder Polycarbonsäuren und Alkanolen oder Polyolen, wie sie in der DE 38 38 918 A1 beschrieben sind.
- Als bevorzugte Alkoxylate werden Verbindungen eingesetzt, in denen R¹ und/oder R einen verzweigten oder unverzweigten C₇-C₁₈-Alkylrest bedeuten und n = 5 bis 50, insbesondere n = 7 bis 30, ist.
- Bevorzugt enthalten die Kraftstoffe 20 bis 2 000 ppm, insbesondere 50 bis 1 000 ppm (alle ppm-Angaben sind jeweils bezogen auf das Gewicht) der Detergens-Komponente a) bzw. des Alkoxylats b).
- Als Stickstoff-haltige Detergens-Komponente in der Mischung mit den erfindungsgemäßen Trägerölen kann prinzipiell jedes bekannte der hierfür geeigneten Produkte eingesetzt werden, wie sie z.B. bei J. Falbe, U. Hasserodt, Katalysatoren, Tenside und Mineralöladditive, G. Thieme Verlag Stuttgart 1978, S. 221 f. oder bei K. Owen, Gasoline und Diesel Fuel Additives, John Wiley & Sons 1989, S. 23 ff. beschrieben sind.
- Vorzugsweise verwendet man Verbindungen mit einer Amin-, Amid- oder Imid-Gruppe, insbesondere Polyisobutylamine gemäß EP 0 244 616, Ethylendiamintetraessigsäureamide und/oder -imide gemäß EP 0 188 786 oder Polyetheramine gemäß EP 0 356 725, wobei auf die Definitionen in diesen Literaturstellen hiermit Bezug genommen wird.
- Auch Mischungen derartiger Detergentien können eingesetzt werden.
- Als weitere Detergentien bzw. zusätzliche Dispergatoren sind Amide oder Imide des Polyisobutylenbernsteinsäureanhydrids, Polybutenpolyamine sowie langkettige Carbonamide und -imide geeignet.
- Die Herstellung der Alkoxylate ist allgemein bekannt und z.B. in der EP 376 236 Al beschrieben.
- Die als Starter eingesetzten Dialkylphenole werden in üblicher Weise durch Friedel-Crafts-Alkylierung von Phenolen mit den entsprechenden Olefinen oder Olefingemischen hergestellt.
- Die erfindungsgemäßen Propoxylate weisen ausgezeichnete Verträglichkeit besonders mit den bereits genannten Polyisobutylaminen in den jeweiligen Formulierungen auf.
- Sie unterstützen deren Wirkung als Einlaßsystemreiniger unter anderem auch im Sinne einer Detergens-Einsparung.
- Als Kraftstoffe für Ottomotoren kommen verbleites und insbesondere unverbleites Normal- und Superbenzin in Betracht. Die Benzine können auch andere Komponenten als Kohlenwasserstoffe, z.B. Alkohole für Methanol, Ethanol, tert.-Butanol sowie Ether, z.B. Methyltertiärbutylether enthalten. Neben den erfindungsgemäß zu verwendenden alkoxylierten Polyetheraminen enthalten die Kraftstoffe in der Regel noch weitere Zusätze wie Korrosionsinhibitoren, Stabilisatoren, Antioxidantien und/oder weitere Detergentien.
- Korrosionsinhibitoren sind meist Ammoniumsalze org. Carbonsäuren, die durch entsprechende Struktur der Ausgangsverbindungen zur Filmbildung neigen. Auch Amine zur Absenkung des pH-Wertes finden sich häufig in Korrosionsinhibitoren. Als Buntmetallkorrosionsschutz werden meist heterocyclische Aromaten eingesetzt.
- Als Antioxidantien oder Stabilisatoren sind insbesondere Amine wie para-Phenylendiamin, Dicyclohexylamin, Morpholin oder Derivate dieser Amine zu nennen. Auch phenolische Antioxidantien wie 2,4-Di-tert.-Butylphenol oder 3,5-Di-tert.-Butyl-4-hydroxiphenylpropionsäure und deren Derivate werden Kraft- und Schmierstoffen zugesetzt.
- Als Maß für die Wirksamkeit im Hinblick auf Brennraumablagerungen werden von verschiedenen Autoren (s. z.B. US 4,877,416) die Ergebnisse thermogravimetrischer Analysen herangezogen, da ein genereller Motortest hierfür noch nicht existiert.
- Thermogravimetrische Analysen liefern zum einen Aussagen über die thermische Belastbarkeit einer Probe, z.B. einer thermooxidativen Bedingungen. Andererseits lassen sie Rückschlüsse auf die Bildung von Ablagerungen bzw. Restmengen nach einer solchen thermooxodativen Behandlung zu. Erfahrungsgemäß günstig für den Einsatz als Trägeröl im Sinne dieser Erfindung ist die hohe thermische Belastbarkeit verbunden mit möglichst geringer bis verschwindender Rückstandbildung.
- Die erfindungsgemäßen Alkoxylate längerkettiger Dialkylphenole erfüllen alle diese Forderungen (Synergismus mit Detergentien, belegt im Motortest; ausgezeichnete thermooxidative Eigenschaften, belegt durch thermogravimetrische Analyse) in hohem Maße.
- Die Additiv-Kombination aus Stickstoff-haltiger Detergens-Komponente und Alkoxylat als Trägerölkomponente wird bevorzugt als Konzentrat zur Verfügung gestellt, das 10 bis 80 Gew.-%, insbesondere 30 bis 60 Gew.-%, der Detergens-Komponente und 5 bis 70 Gew.-%, insbesondere 20 bis 60 Gew.-% der Trägerölkomponente, d.h. des Propoxylats, enthält. Zur Vervollständigung auf 100 Gew.-% enthält das Konzentrat ein geeignetes Lösungsmittel, z.B. aromatische und/oder aliphatische Kohlenwasserstoffe, insbesondere Schwernaphtha (Solvesso®).
- Die Prüfung der Produkte auf ihre Eignung als Kraftstoffadditive erfolgt mittels Motorentest:
- Nach CEC-F-02-T-79 wird die Wirkung als Ventilreiniger getestet.
- 300 Gew.-Teile eines Gemisches aus 55 Gew.-% Dinonylphenol und 45 Gew.-% Nonylphenol werden mit 0,8 Gew.-Teilen K-tert.-butylat in Autoklaven vorgelegt und mit 620 Gew.-Teilen Propylenoxid bei 120 bis 125°C umgesetzt. Nach beendeter Reaktion wird das so erhaltene Propoxylat mit Magnesiumsilikat solange behandelt, bis der Kalium-Gehalt unter 1 ppm liegt.
-
- Die in der Figur abgebildete Thermogravimetrie-Kurve zeigt die relative Massenabnahme m/mo in Abhängigkeit von der Temperatur bei einer Aufheizrate von 2°C pro Minute und in Anwesenheit von Luft. Die Halbwertstemperatur von 260 bis 270°C zeigt eine ausreichende thermooxidative Stabilität an; bei höheren Temperaturen zerfällt das Produkt nahezu rückstandsfrei (m ist dabei die jeweils gemessene Masse, mo die Anfangsmasse).
Claims (6)
- Kraftstoffe für Ottomotoren, enthaltend eine Kombination ausa) 10 bis 5 000 ppm einer Stickstoff-haltigen Detergens-Komponente und
- Kraftstoffe nach Anspruch 1, dadurch gekennzeichnet, daß die Detergens-Komponente a) mindestens eine Verbindung mit einer Amin-, Amid- oder Imid-Gruppe ist.
- Kraftstoffe nach Anspruch 2, dadurch gekennzeichnet, daß die Detergens-Komponente a) ein Polyisobutylamin ist oder enthält.
- Kraftstoffe nach Anspruch 1, dadurch gekennzeichnet, daß R¹ und/oder R einen verzweigten oder unverzweigten C₇-C₁₈-Alkylrest bedeuten.
- Kraftstoffe nach Anspruch 1, dadurch gekennzeichnet, daß n = 5 bis 50, insbesondere 7 bis 30 ist.
- Konzentrat der Komponenten a) und b) nach Anspruch 1 in einem Lösungsmittel, enthaltend 10 bis 80 Gew.-% der Stickstoff-haltigen Detergens-Komponente a) und 5 bis 70 Gew.-% des Alkoxylats b) der Formel I sowie eine zur Vervollständigung auf 100 Gew.-% erforderliche Menge an Lösungsmittel.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4142241A DE4142241A1 (de) | 1991-12-20 | 1991-12-20 | Kraftstoffe fuer ottomotoren |
DE4142241 | 1991-12-20 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0548617A2 EP0548617A2 (de) | 1993-06-30 |
EP0548617A3 EP0548617A3 (de) | 1993-07-21 |
EP0548617B1 true EP0548617B1 (de) | 1996-03-13 |
Family
ID=6447659
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92120622A Expired - Lifetime EP0548617B1 (de) | 1991-12-20 | 1992-12-03 | Kraftstoffe für Ottomotoren |
Country Status (6)
Country | Link |
---|---|
US (1) | US5298039A (de) |
EP (1) | EP0548617B1 (de) |
AT (1) | ATE135394T1 (de) |
CA (1) | CA2082435C (de) |
DE (2) | DE4142241A1 (de) |
ES (1) | ES2084255T3 (de) |
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US7850744B2 (en) | 2004-08-05 | 2010-12-14 | Basf Aktiengesellschaft | Heterocyclic compounds containing nitrogen as a fuel additive in order to reduce abrasion |
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US5366517A (en) * | 1992-12-18 | 1994-11-22 | Chevron Research And Technology Company | Fuel additive compositions containing poly(oxyalkylene) hydroxyaromatic ethers and poly(oxyalkylene) amines |
US5405418A (en) † | 1994-05-02 | 1995-04-11 | Chevron Chemical Company | Fuel additive compositions containing an aliphatic amine, a polyolefin and an aromatic ester |
US5405419A (en) * | 1994-05-02 | 1995-04-11 | Chevron Chemical Company | Fuel additive compositions containing an aliphatic amine, a polyolefin and a poly(oxyalkylene) monool |
DE4425834A1 (de) | 1994-07-21 | 1996-01-25 | Basf Ag | Umsetzungsprodukte aus Polyisobutenen und Stickoxiden oder Gemischen aus Stickoxiden und Sauerstoff und ihre Verwendung als Kraft- und Schmierstoffadditive |
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-
1991
- 1991-12-20 DE DE4142241A patent/DE4142241A1/de not_active Withdrawn
-
1992
- 1992-11-09 CA CA002082435A patent/CA2082435C/en not_active Expired - Fee Related
- 1992-12-03 DE DE59205692T patent/DE59205692D1/de not_active Expired - Lifetime
- 1992-12-03 AT AT92120622T patent/ATE135394T1/de not_active IP Right Cessation
- 1992-12-03 EP EP92120622A patent/EP0548617B1/de not_active Expired - Lifetime
- 1992-12-03 ES ES92120622T patent/ES2084255T3/es not_active Expired - Lifetime
- 1992-12-18 US US07/993,054 patent/US5298039A/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US7850744B2 (en) | 2004-08-05 | 2010-12-14 | Basf Aktiengesellschaft | Heterocyclic compounds containing nitrogen as a fuel additive in order to reduce abrasion |
US8814957B2 (en) | 2004-08-05 | 2014-08-26 | Basf Aktiengesellschaft | Heterocyclic compounds containing nitrogen as a fuel additive in order to reduce abrasion |
Also Published As
Publication number | Publication date |
---|---|
DE4142241A1 (de) | 1993-06-24 |
EP0548617A2 (de) | 1993-06-30 |
DE59205692D1 (de) | 1996-04-18 |
ES2084255T3 (es) | 1996-05-01 |
ATE135394T1 (de) | 1996-03-15 |
CA2082435C (en) | 2000-11-07 |
CA2082435A1 (en) | 1993-06-21 |
EP0548617A3 (de) | 1993-07-21 |
US5298039A (en) | 1994-03-29 |
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