EP1278814B1 - Compositions d'additifs pour essence de moteurs, presentant des proprietes de viscosite ameliorees et de bonnes proprietes detergentes pour le systeme d'admission - Google Patents

Compositions d'additifs pour essence de moteurs, presentant des proprietes de viscosite ameliorees et de bonnes proprietes detergentes pour le systeme d'admission Download PDF

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Publication number
EP1278814B1
EP1278814B1 EP01943321A EP01943321A EP1278814B1 EP 1278814 B1 EP1278814 B1 EP 1278814B1 EP 01943321 A EP01943321 A EP 01943321A EP 01943321 A EP01943321 A EP 01943321A EP 1278814 B1 EP1278814 B1 EP 1278814B1
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Prior art keywords
fuel
additive
composition according
fuel additive
carrier oil
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German (de)
English (en)
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EP1278814A2 (fr
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Harald Schwahn
Dietmar Posselt
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • 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
    • 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
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
    • 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
    • C10L1/19—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, 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
    • 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
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
    • 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
    • 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)

Definitions

  • the invention relates to gasoline fuel additive compositions and additives for these fuels for gasoline engines, wherein the gasoline additive packages according to the invention in addition to a very good performance in the intake system purity improved viscosity properties, especially at low temperatures have.
  • Carburettors and intake systems of gasoline engines, but also injection systems for fuel metering are increasingly burdened by impurities caused by dust particles from the air, unburned hydrocarbon residues from the combustion chamber and the guided into the carburetor crankcase vent gases.
  • the first additive generation could only prevent the formation of deposits in the intake system, but not remove already existing deposits, whereas the modern additives of the second generation can cause both (keep-clean and clean-up effect) and especially because of their excellent thermal stability at higher temperature zones, namely at the inlet valves.
  • Such detergents which can come from a variety of chemical classes of substances, such as polyalkeneamines, polyetheramines, polybutene Mannich bases or Polybutensuccinimide, are generally used in combination with carrier oils and sometimes other additive components, such as corrosion inhibitors and demulsifiers, for use.
  • the carrier oils perform a solvent or wash function in combination with the detergents.
  • Carrier oils are typically high boiling, viscous, thermostable liquids which coat the hot metal surface thereby preventing the build-up of impurities on the metal surface.
  • Such semisynthetic additive formulations according to the invention showed that on the one hand they ensure very good performance with regard to their purity-retaining properties and, moreover, they are distinguished by surprisingly significantly lower viscosities at lower temperatures.
  • Lower viscosities of additive formulations provide advantages in processing since less solvent must be used to set the desired viscosity.
  • a first aspect of the invention therefore relates to fuel additive compositions according to claim 1.
  • Preferred fuel additive compositions are those whose mineral carrier oil component has a viscosity of 350 to a maximum of 410 mm 2 / s, determined at + 20 ° C. according to DIN 51562, part 1.
  • compositions according to the invention are those whose synthetic carrier oil component (polyether) has a viscosity of 140 to 240 mm 2 / s, determined at + 20 ° C. according to DIN 51562, part 1.
  • Particularly preferred fuel additive compositions contain mineral carrier oil component and synthetic carrier oil component in a weight ratio of 10: 1 to 1:10, especially 5: 1 to 1: 5, preferably 4: 1 to 1: 4.
  • the weight ratio of detergent additive component to carrier oil component is in the range from 1:20 to 20: 1, in particular 1:10 to 10: 1, preferably 1: 5 to 5: 1 or 2: 3 to 4: 1.
  • Fuel additive compositions preferred according to the invention comprise as detergent additive component (component a) a detergent additive selected from polyalkene mono- and polyamines, polyetheramines and mixtures thereof.
  • a detergent additive selected from polyalkene mono- and polyamines, polyetheramines and mixtures thereof.
  • useful polyetheramines are poly-C 2 -C 6 -alkylenoxideamines
  • polyalkeneamines are poly-C 2 -C 6 -alkeneamines, and functional derivatives thereof, each having a preferred Mn of 150 to 5000, preferably 500 to 2000, in particular 700 to 1500 g.
  • Amines in this context include both mono- and polyamines, preferably having up to 6 nitrogen atoms.
  • Useful polyalkene mono- or polyalkene polyamines or functional derivatives thereof according to the invention are in particular poly-C 2 -C 6 -alkeneamines or functional derivatives thereof, for example based on polypropene, polybutene or polyisobutene.
  • Examples of functional derivatives of the above additives are compounds which, for example in the amine part, carry one or more polar substituents, in particular hydroxyl groups.
  • Such additives based on highly reactive polyisobutene, which of polyisobutene, which may contain up to 20 wt .-% of n-butene units, by hydroformylation and reductive amination with ammonia, monoamines or polyamines, such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or Tetraethylenepentamine, are particularly known from EP-A-244 616 or EP-A-0 578 323.
  • monoamino-containing additives are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in DE-A 196 20 262.
  • polyalkenamine-type detergent additives are sold by BASF AG, Ludwigshafen under the tradename Kerocom PIBA. These contain polyisobuteneamines dissolved in aliphatic C 10 -C 14 hydrocarbons and can be used as such in the additive packages according to the invention.
  • useful carrier oils or carrier oil liquids include combinations of mineral carrier oil (s) and synthetic carrier oil (s) which are compatible with the additive (s) used and the fuel.
  • Suitable mineral carrier oils which fulfill the above viscosity criterion according to the invention, are fractions obtained in petroleum processing, such as bright stock or base oils with viscosities such as, for example, from the class SN 500-2000; but also aromatic hydrocarbons and paraffinic hydrocarbons Also useful is one known as "hydrocrack oil” and in refining mineral oil fraction (vacuum distillate section having a boiling range of 360 to 500 ° C, available from high pressure catalytically hydrogenated and isomerized and deparaffinized natural mineral oil). Also suitable are mixtures of the abovementioned mineral carrier oils.
  • Synthetic carrier oils which can be used according to the invention and which meet the above viscosity criterion according to the invention are selected from polyethers.
  • suitable polyethers are preferably compounds containing polyoxy-C 2 -C 4 -alkylene groups which are prepared by reacting C 2 -C 60 -alkanols, C 6 -C 30 -alkanediols, mono- or di-C 2 -C 30 -alkylamines , C 1 -C 30 -alkylcyclohexanols or C 1 -C 30 -alkylphenols with 1 to 30 moles of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group are obtainable.
  • Such products are described in particular in EP-A-310 875 EP-A-356 725, EP-A-700 985 and US-A-4,877,416. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobutenolbutoxylate and propoxylates.
  • suitable synthetic carrier oils are alcohol-started polyethers having 5 to 35, such as 5 to 30, C 3 -C 6 alkylene oxide units, for example selected from propylene oxide, n-butylene oxide and i-butylene oxide units, or mixtures thereof.
  • suitable starter alcohols are long-chain alkanols or long-chain alkyl-substituted phenols, where the long-chain alkyl radical is in particular a straight-chain or branched C 6 -C 18 -alkyl radical, especially C 8 -C 15 -alkyl radical.
  • Preferred examples are tridecanol and nonylphenol.
  • the hydrophobic hydrocarbon radical in these detergent additives which provides sufficient solubility in the fuel, has a number average molecular weight (Mn) of 85 to 20,000, in particular from 113 to 10,000, especially from 300 to 5000.
  • Mn number average molecular weight
  • Carboxyl groups or their alkali metal or alkaline earth metal salts containing additives (ad) are preferably copolymers of C 2 -C 40 olefins with maleic anhydride having a total molecular weight of 500 to 20,000, their carboxyl groups wholly or partially to the alkali metal or alkaline earth metal salts and a remainder the carboxyl groups reacted with alcohols or amines are.
  • additives are known in particular from EP-A 307 815.
  • Such additives are mainly used to prevent valve seat wear and, as described in WO-A 87/01126, can be advantageously used in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.
  • Sulfonic acid groups or their alkali metal or alkaline earth metal salts containing additives (ae) are preferably alkali metal or alkaline earth metal salts of a Sulfobernsteinklaklalesters, as described in particular in EP-A-639 632.
  • additives are primarily used to prevent valve seat wear and can be used to advantage in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.
  • derivatives with aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine.
  • Such gasoline additives are described in particular in US-A-4,849,572.
  • Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated moieties containing additives (ag) are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or di-methylamino-propylamine ,
  • Such "polyisobutene-Mannich bases" are described in particular in EP-A 831 141.
  • customary additives are corrosion inhibitors, for example based on film-forming ammonium salts of organic carboxylic acids or heterocyclic aromatics in non-ferrous metal corrosion protection, dyes, antioxidants or stabilizers, for example based on amines such as p-phenylenediamine, dicyclohexylamine or derivatives thereof or phenols such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid, demulsifiers, antistatic agents, metallocenes such as ferrocene or methylcyclopentadienyl manganese tricarbonyl, other lubricity improvers (lubricity additives) such as certain fatty acids , Alkenylbernsteinklander, bis (hydroxyalkyl) fatty amines or hydroxyacetamides and dyes (markers).
  • amines are added to lower the pH of the fuel.
  • novel fuel additive combinations optionally in combination with one or more of the above-mentioned further fuel additives with the polar groups, as well as the other components mentioned, are added to the fuel and unfold their effect there.
  • the components or additives can be added to the fuel individually or as a previously prepared concentrate ("additive package").
  • solvent or diluent when providing additive packages are aliphatic and aromatic hydrocarbons, e.g. Solvent naphtha or kerosene, into consideration.
  • the fuel additive mixtures according to the invention are added to the fuel, for example, in an amount in the range of 10 to 5000 ppm (mg / kg fuel), preferably 20 to 1500 ppm (mg / kg fuel).
  • the optionally used further fuel additives with the polar groups are added to the fuel usually in an amount of 10 to 5000 ppm, in particular 50 to 1000 ppm, and the other components and additives mentioned, if desired, in customary amounts.
  • the fuel to which the fuel additive mixtures of the present invention are added is not particularly limited in itself. It can be e.g. to trade a petrol according to DIN EN 228.
  • the fuel may be, for example, a gasoline having an aromatics content of at most 42% by volume, e.g. 20 to 42% by volume and a maximum sulfur content of 150 ppm, e.g. 0.5 to 150 ppm.
  • the gasoline may also have an olefin content of not more than 21% by volume, e.g. from 6 to 21 vol.%.
  • the benzene content may be a maximum of 1.0% by volume, e.g. 0.5 to 1.0 vol .-%, amount; the oxygen content may e.g. in the range of 0.1 to 2.7 wt .-% are.
  • the content of alcohols and ethers in gasoline is usually relatively low. Typical maximum contents for methanol are 3% by volume, for ethanol 5% by volume, for isopropanol 10% by volume, for tert-butanol 7% by volume, for isobutanol 10% by volume and for ethers 5 or more C atoms in the molecule 15 vol .-%.
  • the summer vapor pressure of the gasoline is usually not more than 70 kPa, in particular 60 kPa (each at 37 ° C).
  • the research octane number ("RON") of the gasoline is typically 90 to 100.
  • a common range for the corresponding engine octane number (“MOZ”) is 80 to 90.
  • the specified specifications are determined by conventional methods (DIN EN 228).
  • 38% of a mineral base oil viscosity at + 20 ° C: 407
  • Example A mixture is prepared analogously to Example A, wherein only the mineral carrier oil is replaced by a non-inventive base oil having a viscosity at + 20 ° C of 432 mm 2 / s.
  • composition according to the invention surprisingly shows a clearly advantageous IVD performance.
  • 20 wt .-% of a base oil vis
  • Production Example C is repeated, the mineral carrier oil being replaced by a non-inventive base oil having viscosity at +20 ° C. of 432 mm 2 / s.
  • 20 wt .-% of a base oil vis
  • Production Example E is repeated, the mineral carrier oil being replaced by a non-inventive base oil with viscosity at + 20 ° C. of 432 mm 2 / s.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Claims (11)

  1. Composition d'additif pour carburant, caractérisée en ce qu'elle contient
    a) au moins un additif détergent,
    b) un mélange d'huiles de support, comprenant
    i) au moins une huile de support synthétique choisie parmi des polyéthers ayant une viscosité de 120 à 270 mm2/s, déterminée à +20°C selon la norme DIN 51562, partie 1, et
    ii) au moins une huile de support minérale ayant une viscosité de 250 à 410 mm2/s, déterminée à +20°C selon la norme DIN 51562, partie 1, et
    c) éventuellement d'autres composants d'additifs pour carburant courants.
  2. Composition d'additif pour carburant suivant la revendication 1, caractérisée en ce que le composant d'huile de support minérale est une huile de support choisie parmi du bright stock, des huiles de base ayant des viscosités de la classe SN 500-2000, des hydrocarbures aromatiques, des hydrocarbures paraffiniques et de l' "huile d'hydrocraquage", ou leurs mélanges.
  3. Composition d'additif pour carburant suivant l'une des revendications précédentes, caractérisée en ce que des composants d'huile de support minérale et des composants d'huile de support synthétiques sont contenus dans un rapport pondéral de 10/1 à 1/10.
  4. Composition d'additif pour carburant suivant l'une des revendications précédentes, caractérisée en ce que le composant d'additif détergent comporte un additif détergent choisi parmi des polyalcènemonoamines et des polyalcènepolyamines, des polyétheramines et leurs mélanges.
  5. Composition d'additif pour carburant suivant la revendication 4, caractérisée en ce que l'additif détergent comporte une polyalcèneamine en C2-C6 ou une polyalkylèneoxydeamine en C2-C6.
  6. Composition d'additif pour carburant suivant la revendication 5, caractérisée en ce que l'additif détergent comporte une polyalcèneamine en C2-C6 ou une polyalkylèneoxydeamine en C2-C6 présentant un Mn=150 à 5000.
  7. Composition d'additif pour carburant suivant l'une des revendications précédentes, caractérisée en ce qu'elle contient
    a) 10 à 80 % en poids d'additif(s) détergent(s),
    b) 20 à 90 % en poids d'un mélange d'huiles de support, et
    c) éventuellement 0 à 30 % en poids d'autres composants d'additif pour carburant courants.
  8. Composition de carburant, caractérisée en ce que, à côté d'une quantité principale d'un carburant à base d'hydrocarbure, elle comporte une quantité active du point de vue détergent, diminuant les dépôts dans les soupapes d'admission, d'une composition d'additif suivant l'une des revendications précédentes.
  9. Composition de carburant suivant la revendication 8, caractérisée en ce que la composition d'additif est contenue en une fraction de 10 à 5000 mg/kg de carburant.
  10. Utilisation d'une composition d'additif pour carburant suivant l'une des revendications 1 à 7, pour la diminution des dépôts dans les soupapes d'admission de moteurs à combustion.
  11. Concentré d'additif pour carburant, comprenant une composition d'additif pour carburant suivant l'une des revendications 1 à 7.
EP01943321A 2000-05-05 2001-05-04 Compositions d'additifs pour essence de moteurs, presentant des proprietes de viscosite ameliorees et de bonnes proprietes detergentes pour le systeme d'admission Expired - Lifetime EP1278814B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10021936A DE10021936A1 (de) 2000-05-05 2000-05-05 Kraftstoffadditivpakete für Ottokraftstoffe mit verbesserten Viskositätseigenschaften und guter IVD Performance
DE10021936 2000-05-05
PCT/EP2001/005039 WO2001085874A2 (fr) 2000-05-05 2001-05-04 Compositions d'additifs pour essence de moteurs, presentant des proprietes de viscosite ameliorees et de bonnes proprietes detergentes pour le systeme d'admission

Publications (2)

Publication Number Publication Date
EP1278814A2 EP1278814A2 (fr) 2003-01-29
EP1278814B1 true EP1278814B1 (fr) 2006-05-31

Family

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EP01943321A Expired - Lifetime EP1278814B1 (fr) 2000-05-05 2001-05-04 Compositions d'additifs pour essence de moteurs, presentant des proprietes de viscosite ameliorees et de bonnes proprietes detergentes pour le systeme d'admission

Country Status (22)

Country Link
US (1) US6840970B2 (fr)
EP (1) EP1278814B1 (fr)
JP (1) JP5192627B2 (fr)
KR (1) KR100727363B1 (fr)
AR (1) AR033821A1 (fr)
AT (1) ATE328053T1 (fr)
AU (2) AU6592501A (fr)
BR (1) BR0110543A (fr)
CA (1) CA2406762C (fr)
CZ (1) CZ20023608A3 (fr)
DE (2) DE10021936A1 (fr)
EE (1) EE200200624A (fr)
HR (1) HRP20020957A2 (fr)
HU (1) HUP0301874A2 (fr)
IL (1) IL152357A (fr)
MX (1) MXPA02010048A (fr)
MY (1) MY127143A (fr)
NO (1) NO20025285L (fr)
NZ (1) NZ521875A (fr)
PL (1) PL198793B1 (fr)
SK (1) SK15502002A3 (fr)
WO (1) WO2001085874A2 (fr)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7204863B2 (en) 2001-12-11 2007-04-17 Exxonmobil Research And Engineering Company Gasoline additives for reducing the amount of internal combustion engine intake valve deposits and combustion chamber deposits
DE10209830A1 (de) 2002-03-06 2003-09-18 Basf Ag Kraftstoffadditivgemische für Ottokraftstoffe mit synergistischer IVD-Performance
DE10256161A1 (de) 2002-12-02 2004-06-09 Basf Ag Verwendung von Aminen und/oder Mannich-Addukten in Kraft- und Schmierstoffzusammensetzungen für direkteinspritzende Ottomotoren
DE10314809A1 (de) 2003-04-01 2004-10-14 Basf Ag Polyalkenamine mit verbesserten Anwendungseigenschaften
DE10316871A1 (de) 2003-04-11 2004-10-21 Basf Ag Kraftstoffzusammensetzung
EP1705234A1 (fr) * 2005-03-24 2006-09-27 Basf Aktiengesellschaft Utilisation d'additifs détergents afin d'empêcher ou de réduire la formation des dépôts dans les systèmes d'injection pour moteurs diesel à injection directe
US20060277820A1 (en) * 2005-06-13 2006-12-14 Puri Suresh K Synergistic deposit control additive composition for gasoline fuel and process thereof
US20060277819A1 (en) * 2005-06-13 2006-12-14 Puri Suresh K Synergistic deposit control additive composition for diesel fuel and process thereof
US8222180B2 (en) * 2005-08-01 2012-07-17 Indian Oil Corporation Limited Adsorbent composition for removal of refractory sulphur compounds from refinery streams and process thereof
US8231695B2 (en) * 2006-08-09 2012-07-31 Afton Chemical Corporation Fuel compositions comprising hydrocarbon oil carriers and methods for using the same
US8778034B2 (en) * 2006-09-14 2014-07-15 Afton Chemical Corporation Biodegradable fuel performance additives
US20080168708A1 (en) * 2007-01-11 2008-07-17 Cunningham Lawrence J Method and compositions for reducing deposits in engines combusting ethanol-containing fuels and a corrosion inhibitor
GB201001920D0 (en) * 2010-02-05 2010-03-24 Innospec Ltd Fuel compostions
GB201007756D0 (en) 2010-05-10 2010-06-23 Innospec Ltd Composition, method and use
KR101241387B1 (ko) * 2010-11-08 2013-03-11 석종호 연료 첨가제 조성물 및 이를 포함하는 연료 조성물
KR101287026B1 (ko) * 2011-01-11 2013-07-17 주식회사 재윤 연료 첨가제 조성물 및 이를 포함하는 연료 조성물
US8641788B2 (en) 2011-12-07 2014-02-04 Igp Energy, Inc. Fuels and fuel additives comprising butanol and pentanol
CN112410131B (zh) * 2020-11-09 2022-04-12 3M中国有限公司 发动机进气阀沉积物清洗组合物及其制备方法，以及清洗发动机进气阀沉积物的方法

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3732908A1 (de) * 1987-09-30 1989-04-13 Basf Ag Polyetheramine enthaltende kraftstoffe fuer ottomotoren
DE3826608A1 (de) 1988-08-05 1990-02-08 Basf Ag Polyetheramine oder polyetheraminderivate enthaltende kraftstoffe fuer ottomotoren
DE3838918A1 (de) 1988-11-17 1990-05-23 Basf Ag Kraftstoffe fuer verbrennungsmaschinen
NZ231731A (en) * 1988-12-30 1991-03-26 Mobil Oil Corp Additive for fuels of internal combustion engines comprising a polyalkylene succinimide
US5006130A (en) 1989-06-28 1991-04-09 Shell Oil Company Gasoline composition for reducing intake valve deposits in port fuel injected engines
ES2081472T3 (es) * 1990-03-05 1996-03-16 Polar Molecular Corp Composicion de aditivo para combustibles de motores y metodo para su preparacion.
JPH0488089A (ja) * 1990-07-30 1992-03-19 Tonen Corp ガソリン添加用組成物
US5242469A (en) * 1990-06-07 1993-09-07 Tonen Corporation Gasoline additive composition
US5089028A (en) * 1990-08-09 1992-02-18 Mobil Oil Corporation Deposit control additives and fuel compositions containing the same
DE4142241A1 (de) 1991-12-20 1993-06-24 Basf Ag Kraftstoffe fuer ottomotoren
AU668151B2 (en) * 1992-05-06 1996-04-26 Afton Chemical Corporation Composition for control of induction system deposits
EP0587250B1 (fr) 1992-09-11 1997-05-14 Shell Internationale Researchmaatschappij B.V. Compositions d'essence
DE4309074A1 (de) 1993-03-20 1994-09-22 Basf Ag Als Kraftstoffadditiv geeignete Mischungen
GB2279965A (en) * 1993-07-12 1995-01-18 Ethyl Petroleum Additives Ltd Additive compositions for control of deposits, exhaust emissions and/or fuel consumption in internal combustion engines
DE4434603A1 (de) 1994-09-28 1996-04-04 Basf Ag Als Kraft- und Schmierstoffadditiv geeignete Mischung aus Aminen, Kohlenwasserstoffpolymeren und Trägerölen
CA2180498C (fr) 1995-07-06 2008-03-25 Richard E. Cherpeck Methode et composition pour la reduction des depots a l'interieur d'une chambre de combustion
AU4355997A (en) 1996-09-23 1998-04-14 Petrokleen, Ltd. Method of synthesizing pure additives and the improved compositions thereby produced

Also Published As

Publication number Publication date
EE200200624A (et) 2004-06-15
HRP20020957A2 (en) 2005-02-28
MY127143A (en) 2006-11-30
US20030140552A1 (en) 2003-07-31
CZ20023608A3 (cs) 2003-06-18
AU2001265925B2 (en) 2006-02-16
IL152357A0 (en) 2003-05-29
PL198793B1 (pl) 2008-07-31
SK15502002A3 (sk) 2003-05-02
WO2001085874A2 (fr) 2001-11-15
EP1278814A2 (fr) 2003-01-29
MXPA02010048A (es) 2003-03-10
NO20025285D0 (no) 2002-11-04
ATE328053T1 (de) 2006-06-15
CA2406762C (fr) 2009-11-03
AR033821A1 (es) 2004-01-07
AU6592501A (en) 2001-11-20
JP5192627B2 (ja) 2013-05-08
DE10021936A1 (de) 2001-11-08
BR0110543A (pt) 2003-04-01
KR100727363B1 (ko) 2007-06-13
PL358461A1 (en) 2004-08-09
HUP0301874A2 (hu) 2003-08-28
NZ521875A (en) 2004-05-28
US6840970B2 (en) 2005-01-11
CA2406762A1 (fr) 2002-10-17
IL152357A (en) 2005-07-25
JP2003532783A (ja) 2003-11-05
NO20025285L (no) 2002-11-04
DE50109967D1 (de) 2006-07-06
KR20020093128A (ko) 2002-12-12
WO2001085874A3 (fr) 2002-04-04

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