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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
  • C10L1/1905—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polycarboxylic acids
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
  • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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)
• • 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 internal combustion engines, which contain small amounts of additives consisting of known amino or amide groups containing detergents for cleaning or keeping the fuel inlet system clean and as a carrier oil of a mixture of polyethers and alkanol or polyol esters.
• detergents as active ingredients for fuel additives for cleaning and keeping the mixture formation and intake system of gasoline engines (carburettors, injection nozzles, intake valves, mixture distribution system) clean is known.
• the detergents with a wide variety of chemical compositions are usually combined with so-called carrier oils.
• the carrier oils have a solvent or washing function in combination with the detergents.
• the carrier oils are usually high-boiling, viscous, thermostable liquids. They coat the hot metal surface (e.g. the inlet valves) with a thin liquid film and thereby prevent or delay the formation or deposition of decomposition products on the metal surfaces.
• high-boiling, refined mineral oil fractions mostly vacuum distillates
• a particularly good carrier oil is Brightstock in combination with low-boiling, highly refined lubricating oil fractions.
• Synthetic components have also been used as carrier oils. Esters in particular have been described as suitable carrier oils (e.g. DE 10 62 484, DE 21 29 461 and DE 23 04 086).
• polyethers have already been used as fuel additives or as a component of fuel additive mixtures.
• Valve plug Since the valves no longer close under these conditions in extreme cases, such an engine can no longer be started.
• All known detergents are high-boiling or difficult to evaporate substances. Due to the unavoidable dilution of petrol in the engine oil during daily driving, the detergents are also enriched in significant concentrations in the engine oil during an oil change interval. While the gasoline components gradually evaporate from the oil, especially when the engine is warm, the detergents remain in the oil sump. In the course of an oil change interval, this leads to oil thickening, the motor oil viscosity increases, the motor oil is increasingly loaded with foreign substances and the oil's dispersing effect for solids is no longer sufficient. Deposits and oil silting occur before the end of the oil change interval.
• the amount of mixture (b) contained in the fuel is generally 50 to 5000 ppm, preferably 100 to 2000 ppm, that of (a) generally 50 to 1000 ppm, preferably 50 to 400 ppm.
• Fuels for internal combustion engines are organic, mostly hydrocarbon-containing liquids that are suitable for the operation of Otto, Wankel and diesel engines.
• hydrocarbons from coal hydrogenation hydrocarbons from coal hydrogenation, alcohols of various origins and compositions and ethers such as Methyl tertiary butyl ether contained therein.
• the admissible mixtures are mostly nationally defined worldwide.
• Polybutenamines produced by other processes e.g. by chlorination of polyisobutylene with a molecular weight of 1000 and subsequent reaction with mono- or diamines or oligoamines such as diethylenetriamine, triethylenetetramine and alkanolamines such as aminoethylethanolamine are equally suitable.
• polycarboxamides e.g. phthalamides or imides
• amides and / or imides of nitrilotriacetic acid are obtained by reacting the acids (possibly the anhydrides) with long-chain mono- or polyamines (C8 to C18) or fatty amines e.g. Coconut fatty amine or dicocosamine but also e.g. To name oleic acid diethylenetriamine diamide.
• Polyalkylene oxides are generally suitable as polyethers (ba).
• the polyethers In order to be effective as carrier oils, the polyethers must have at least molecular weights above 500. The viscosity of these polyethers is usually significantly higher than that of the esters described below. In most cases, polyalkylene oxides have high viscosity indices. This makes them, especially in combination with esters according to the invention, suitable carrier oils for formulating additive packages which do not tend to "valve sticking".
• suitable starting molecules for the polyalkylene oxides are aliphatic and aromatic mono-, di- or polyalcohols, but also amines or amides and alkylphenols.
• Preferred olefin oxides for suitable polyethers are propylene oxide and butene oxides and mixtures thereof.
• pentene oxide and higher oxides are also suitable for polyethers which can be combined according to the invention.
• the following polyethers may be mentioned: Starter molecule Butene oxide [mol] Propene oxide [mol] 1 hexanediol 0 30th 2 iso-tridecanol 15 22 3 iso-tridecanol 8th 0 4 iso-nonylphenol 8th 0 5 iso-dodecylphenol 0 12 6 iso-tridecylamine 24th 0 7 bisphenol A 24th 0
• Esters according to bb) are e.g. Esters of aliphatic or aromatic mono- or polycarboxylic acids with long-chain alcohols; they are more or less viscous liquids. However, only those esters with a minimum viscosity of 2 mm2 / s at 100 ° C are suitable as carrier oils for fuel additives.
• polyol esters e.g. based on neopentyl glycol, pentaerythritol or trimethylol propane with corresponding monocarboxylic acids
• oligomer esters or polymer esters e.g. those based on dicarboxylic acid, polyol and monoalcohol.
• Esters of aromatic di-, tri- and tetracarboxylic acid with long-chain aliphatic alcohols containing only carbon, hydrogen and oxygen are also suitable, the total carbon number of the esters being at least 22 carbon atoms and the molecular weight 370 to 1500, preferably 414 to 1200.
• adipates, phthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanols, iso-decanols and iso-tridekanols and mixtures thereof may be mentioned in particular as esters.
• the test results of the systematic testing of detergents in combination with different carrier oil systems are summarized in the attached Table 1.
• the Opel Kadett test (CEC-F-02-T-79) was used as the test method.
• the formation of deposits in the Opel Kadett test engine fluctuates very strongly under the standardized test conditions with the quality of the test gasoline used.
• a test gasoline with deposits between 300 and 450 mg per intake valve was selected.
• the results in the table show that when the Pure detergent dosages of 600 to 800 ppm are required to reduce deposits to below 10 mg per valve. At doses of 300 to 400 ppm, the deposits are on average less than 50 mg per valve and if only 150 ppm of the detergents are used, residual deposits in the range of approx. 110 - 180 mg per valve can still be expected.
• esters When only esters were used as fuel additives without the presence of detergents, residual deposits in the range of 110 to 200 mg per valve were still found in the dose range of the esters from 500 to 800 ppm in the Opel Kadett Test. The effect of the esters decreases significantly with a total number of carbon atoms below C36.
• polyethers based on aliphatic alcohols alkoxylated with butylene oxide
• polyethers with propylene oxide / butylene oxide / mixed oxide which have been started in the same way.
• the average residual deposits were 68 to 82 mg per valve, in the second case even with higher ether doses 84 - 93 mg per valve.
• Alkylphenol-started polyethers based on butylene oxide show a better effectiveness when combined alone with the known detergents compared to the polyethers started with aliphatic alcohols. Average residual deposits of 30 - 45 mg per valve were found here.
• esters and polyethers have now been used in a mixture with the known detergents. It was shown that the synergistic effect increases with increasing molecular weight of the polyethers and in all cases investigated average residual deposits of less than 20 mg per valve were found.
• Carrier oil mixtures based on phthalic acid and trimellitic acid esters in combination with polyethers based on butylene oxide have proven to be particularly effective if the detergent component was based on polybutene chemistry.
• butene oxide-based polyethers offer fewer advantages than mixed oxide or pure propene oxide. Table 1 Keeping various detergents clean in the Opel-Kadett engine (comparison tests) Current No.
• the fuels according to the invention based on detergent doses of only 100 to 200 ppm in combination with the polyether / ester / carrier oil mixtures made it possible to solve the undesirable phenomenon of valve sticking in a very satisfactory manner.
• a Volkswagen van with a 1.9 l (44 kW) boxer engine (water-cooled) is subjected to a road driving program.
• the road driving program runs under the following conditions: 10 km driving distance at a speed of 50 km / h 10 minutes standstill 10 km driving distance at a speed of 60 km / h 10 minutes standstill
• the cycle is repeated until approximately 130 km of driving have been completed in one day.
• the valve stems of the intake valves are visually assessed with the aid of a motoscope.
• a compression diagram is created with the exhaust manifold removed. After complete assembly of the engine again, start attempts are made. The starting behavior and engine running immediately after starting are described.
• Table 5 shows results from the Volkswagen valve adhesive test described above. The advantages when using the ester / polyether-carrier oil mixtures according to the invention are obvious.
• non-volatile, non-evaporable additive components accumulate in the oil sump of an engine during the course of an oil change interval. Due to the so-called “blow-by gases" circulating over the oil pan, which contain partially burned hydrocarbons and nitrogen oxides (NOX), chemical secondary reactions occur at the high oil sump temperatures of 120 to 150 ° C. Gasoline components containing olefins and high-boiling aromatic gasoline fractions, but also the lubricating oil additives in the oil sump are subjected to the nitriding reaction. As a result, polymerizations and resinification occur, which ultimately can no longer be carried by the dispersants in the motor oil. Oil thickening, precipitation and oil sludge are the result.
• Polyisobutylamines are not critical with regard to sludge formation in motor oil.
• polyisobutene residue when linked to a dispersing polyamine group, such polyisobutene amines even contribute to an improvement in the sludge behavior in motor oils.
• Detergents with a different chemical structure, in particular those with amide or imide groups, can only be regarded as non-critical with regard to the sludge formation in the motor oil if the dosage is correspondingly low.
• Table 5 Valve sticking test in a 1.9 liter VW transporter (44 kW) with a water-cooled boxer engine Current No.
• Type Additive dose (ppm) Test temperature (° C) Deposits on the valve stems 1) Loss of compression Starting behavior 2) Engine run after start 3) Remark kung Yes No in cylinders 9 A 600 -1 ++ Yes 4th b) ⁇ ⁇ Comparative tests 52 A *) 600 -3 +++ Yes 1 - 4 c) - 6 B 400 -5 ++ Yes 1 c) - 10th B 800 -3 +++ Yes 1 - 4 c) - 53 A **) 400 -3 +++ Yes 1 - 4 c) - 43 A, I, K 200/100/500 -5 - No - a) ⁇ Experiments according to the invention 45 A, F, K 200/400/200 -2 + No - b) ⁇ 48 D, G, L 200/400/200 -6 - No - a) ⁇ 50 A, B, G, K 200/100/400/100 -3 - No - a) ⁇ 51 A, D, H, L 150/100/400/150
• Footnote table 3 **) Medium molecular weight polybutenamine 1250 1) Rating: +++ strong ++ medium + low - no 2) Evaluation: a) Engine starts within 4 seconds b) Engine starts after 5 to 10 seconds c) Engine does not start 3) Evaluation: ⁇ Motor runs smoothly ⁇ ⁇ Motor runs out of round / stutters

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

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Cited By (17)

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• 1988
  • 1988-11-17 DE DE3838918A patent/DE3838918A1/de not_active Withdrawn
• 1989
  • 1989-10-31 US US07/429,814 patent/US5004478A/en not_active Expired - Lifetime
  • 1989-11-08 CA CA002002675A patent/CA2002675C/fr not_active Expired - Fee Related
  • 1989-11-10 DE DE8989120840T patent/DE58901419D1/de not_active Expired - Lifetime
  • 1989-11-10 EP EP89120840A patent/EP0374461B1/fr not_active Expired - Lifetime
  • 1989-11-10 ES ES198989120840T patent/ES2033067T3/es not_active Expired - Lifetime
  • 1989-11-17 JP JP1299478A patent/JP2803732B2/ja not_active Expired - Lifetime

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