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EP4163353A1 - Method for reducing deposits on intake valves - Google Patents

Method for reducing deposits on intake valves Download PDF

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Publication number
EP4163353A1
EP4163353A1 EP21201213.2A EP21201213A EP4163353A1 EP 4163353 A1 EP4163353 A1 EP 4163353A1 EP 21201213 A EP21201213 A EP 21201213A EP 4163353 A1 EP4163353 A1 EP 4163353A1
Authority
EP
European Patent Office
Prior art keywords
fuel
carbon atoms
volume
carrier oil
deposits
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.)
Withdrawn
Application number
EP21201213.2A
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German (de)
French (fr)
Inventor
Jochen Mezger
Markus Hansch
Marc Walter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP21201213.2A priority Critical patent/EP4163353A1/en
Publication of EP4163353A1 publication Critical patent/EP4163353A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G 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
    • C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
    • C10L1/1832—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy
    • 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
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0415—Light distillates, e.g. LPG, naphtha
    • C10L2200/0423—Gasoline
    • 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
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines

Definitions

  • diarylamines to reduce and/or eliminate deposits on intake valves of spark ignition engines, a method of operating them and methods of reducing intake valve deposits.
  • Diarylamines have long been known as fuel additives.
  • WO 2018/041710 A1 describes the use of diarylamines in direct-injection gasoline engines to reduce combustion chamber deposits or the injection nozzle. Thus, only the reduction of coking on components that are in contact with combustion gases is described.
  • the present invention relates to the reduction and/or elimination of deposits that are on the intake valves of indirect injection gasoline engines, so-called intake valve deposits (IVD): These deposits are on the inside of the intake valves on the intake manifold side Area of the intake valve that comes into contact with a fuel-air mixture.
  • the valves are thermally connected to the combustion chamber, so that they have a higher wall temperature than when stored in the tank or conveyed in the fuel system, to which the fuel-air mixture is exposed.
  • the insides of the valves are not exposed to the combustion process, so that the problem of deposits is different here than according to the WO 2018/041710 A1 .
  • the object of the present invention was to provide gasoline additives with which the deposits on the intake valves of indirect-injection Otto engines can be reduced or eliminated.
  • the object was achieved by using at least one diarylamine in a fuel or fuel additive to reduce and/or eliminate deposits on the intake valves (IVD) in Otto engines with indirect injection.
  • Another object of the present invention is a method for operating a gasoline engine with indirect injection using a gasoline containing at least one diarylamine to reduce and/or eliminate deposits on the intake valves (IVD).
  • Diarylamines are generally those amines in which the amine nitrogen atom is directly attached to two aromatic rings. The aromatic rings can be unsubstituted or substituted with one or more substituents.
  • alkyl radical having 1 to 20 carbon atoms for example methyl, ethyl, isopropyl , n-propyl, n-butyl, isobutyl , sec-butyl, tert-butyl, n-hexyl, n-heptyl, n-octyl, 2- ethylhexyl, n-decyl, 2-propylheptyl n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl or n-eicosyl.
  • Methyl, ethyl, iso -propyl, iso -butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-decyl, 2-propylheptyl, n-dodecyl, n-tetradecyl or n-hexadecyl are particularly preferred methyl, isopropyl , tert-butyl and 2-ethylhexyl are preferred.
  • Alkenyl radicals having 2 to 20 carbon atoms are vinyl, allyl, isopropenyl, octenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl and octadecenyl.
  • hydroxyalkyl radicals having 1 to 4 carbon atoms are hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 2-hydroxypropyl and 2-hydroxyprop-2-yl.
  • R 1 and R 2 are preferably, independently of one another, hydrogen, methyl, isopropyl, tert. butyl, 2-ethylhexyl, hydroxymethyl or 2-hydroxyprop-2-yl.
  • R 1 and R 2 are the same.
  • Preferred diphenylamines are diphenylamine, dinaphthylamine, 4,4'-di(dimethylbenzyl)diphenylamine ( CAS 10081-67-1 ), 4-hydroxydiphenylamine ( CAS 122-37-2 ), 4-Methoxy-2-methyldiphenylamine ( CAS 41317-15-1 ), alkylated diphenylamines, reaction product of diphenylamine with 2,4,4-trimethylpentene ( CAS 68411-46-1 , Irganox ® L57), reaction product of styrene with diphenylmethane ( CAS 68442-68-2 ), p-aminodiphenylamine ( CAS 101-54 -), 4-isopropylaminodiphenylamine ( CAS 101-72-4 ), bis(nonyl)diphenylamine (reaction product of diphenylamine with nonene, bis(4-(1,1,3,3-tetramethylbuty
  • diphenylamine or N-phenyl-naphthylamine can be reacted with isobutene, diisobutene, nonene, styrene, ⁇ -methylstyrene or propylene tetramer using suitable catalysts to give mixtures of mono- and disubstituted products as particularly preferred dipjenylamines.
  • Reaction products from the reaction of diphenylamine with mixtures of the olefins mentioned can also be used.
  • reaction product of diphenylamine with 2,4,4-trimethylpentene (CAS 68411-46-1 , Irganox ® L57) and butylated, octylated diphenylamine (Naugalube ® 640).
  • the above identified diphenylamine is used in a fuel additive package together with at least one sterically hindered phenol and/or aminophenol, preferably at least one sterically hindered phenol.
  • Preferred sterically hindered phenols have the formula
  • alkyl radicals having 1 to 20 carbon atoms alkenyl radicals having 2 to 20 carbon atoms and alkyl radicals having 4 to 16 carbon atoms correspond to the definitions and individuals given for the diphenylamines.
  • Preferred radicals R 10 , R 11 and R 12 are, independently of one another, methyl, ethyl, isopropyl , isobutyl , tert -butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-decyl, 2-propylheptyl n- Dodecyl, n-tetradecyl or n-hexadecyl, particular preference is given to methyl, isopropyl , tert -butyl and 2-ethylhexyl and very particular preference to methyl and tert. butyl.
  • R 12 can additionally preferably be hydrogen, 2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)ethyl, 2-(n-butyloxycarbonyl)ethyl, 2-(tert-butyloxycarbonyl)ethyl, 2-(n-octyloxycarbonyl)ethyl or 2- (2'-ethylhexyloxycarbonyl)ethyl.
  • Preferred sterically hindered phenols are 2,6-di tert. butyl phenol, 2-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-dimethyl-phenol, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butylphenol, 4- tert-butylphenol, 2,4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 4-tert-butyl-2,6-dimethylphenol, 2-tert-butyl-6-methylphenol, 2,4,6-Tris-tert-butylphenol, 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2,6-dimethylphenol, 2,6-di-tert-butyl- p-cresol, 3-(3',5'-di- tert -butyl-4'-hydroxyphenyl)propionic acid octadec
  • the amino and the phenolic hydroxy group can be in the ortho, meta or para position to one another, preferably ortho or para.
  • the amino group can be unsubstituted in the form of an -NH 2 group, or mono. or disubstituted, preferably disubstituted.
  • the substituents can be the same or different, and are preferably C 1 -C 4 -alkyl or hydroxy-C 1 -C 4 -alkyl.
  • the preparation route by hydroformylation and subsequent amination under reductive (hydrogenating) conditions is an option.
  • Amines such as ammonia, monoamines or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine can be used for the amination.
  • Corresponding additives based on polypropylene are in particular in the WO-A-94/24231 described.
  • additives containing monoamino groups are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as they are particularly DE-A-196 20 262 are described.
  • Additives containing groups produced by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or especially dimethylaminopropylamine.
  • Such "polyisobutene Mannich bases" are particularly in the EP-A-831 141 described.
  • the anion can have multiple negative charges, for example in the case of anions of dicarboxylic acids.
  • the stoichiometric ratio of ammonium ions to anions corresponds to the ratio of the respective positive and negative charges.
  • the detergent additives mentioned are usually added to the fuel in an amount of 10 to 5000 ppm by weight, in particular 50 to 1000 ppm by weight.
  • the other components and additives mentioned are added, if desired, in amounts customary for this purpose.
  • the diphenylamine described above is used in a fuel additive package which additionally contains at least one carrier oil, preferably a polyalkoxylate.
  • Carrier oils do not normally exhibit pronounced detergency.
  • Suitable mineral carrier oils are fractions obtained during petroleum processing, such as bright stock or base oils with viscosities such as those from the class SN 500-2000; but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. Also usable is a fraction known as "hydrocrack oil” and obtained in the refining of mineral oil (vacuum distillate cut having a boiling range of about 360 to 500°C, obtainable from natural mineral oil which has been catalytically hydrogenated and isomerized and dewaxed under high pressure). Mixtures of the mineral carrier oils mentioned above are also suitable.
  • Examples of synthetic carrier oils that can be used according to the invention are selected from: polyolefins (polyalphaolefins or polyinternal olefins), (poly)esters, (poly)alkoxylates, polyethers, alkanol- or alkylphenol-started polyethers (polyalkoxylates), alkylphenol- or alkanol-started polyetheramines (polyethers, in in which at least one hydroxy group is replaced by an amino group) and carboxylic acid esters of long-chain alkanols.
  • polyolefins polyalphaolefins or polyinternal olefins
  • (poly)esters poly)alkoxylates
  • polyethers alkanol- or alkylphenol-started polyethers (polyalkoxylates)
  • alkylphenol- or alkanol-started polyetheramines polyethers, in in which at least one hydroxy group is replaced by
  • polyethers or polyetheramines are preferably compounds containing polyoxy-C 2 -C 4 -alkylene groups, which are obtained 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 mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia , monoamines or polyamines are available.
  • poly-C 2 -C 6 -alkylene oxide amines or functional derivatives thereof can be used as polyetheramines.
  • Preferred examples of polyalkoxylates are tridecanol or isotridecanol butoxylates, isoheptadecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates and the corresponding reaction products with ammonia.
  • carboxylic acid esters of long-chain alkanols are, in particular, esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, such as those in particular DE-A-38 38 918 are described.
  • Aliphatic or aromatic acids can be used as mono-, di- or tricarboxylic acids, and long-chain representatives having, for example, 6 to 24 carbon atoms are particularly suitable as ester alcohols or ester polyols.
  • esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol, such as di-(n- or isotridecyl)phthalate.
  • suitable synthetic carrier oils are alcohol-started polyethers having about 5 to 35, such as about 5 to 30, C 3 -C 6 -alkylene oxide units, such as selected from propylene oxide, n-butylene oxide and i-butylene oxide units, or mixtures of that.
  • suitable starter alcohols are long-chain alkanols or phenols substituted with long-chain alkyl, where the long-chain alkyl radical is in particular a straight-chain or branched C 6 -C 18 -alkyl radical.
  • Preferred examples are tridecanol, heptadecanol and nonylphenol.
  • the additive packages according to the invention often contain at least one solvent to reduce the viscosity and/or improve formulatability.
  • Suitable are, for example, non-polar organic solvents such as aromatic and aliphatic hydrocarbons, for example toluene, xylenes, "white spirit” and products sold under the trade names SHELLSOL (Royal Dutch/Shell Group) and EXXSOL (ExxonMobil), as well as polar organic solvents, for example Alcohols such as 2-ethylhexanol, decanol and isotridecanol.
  • solvents usually get into the fuel together with the aforementioned additives and co-additives, which they are supposed to dissolve or dilute for better handling.
  • customary additives are corrosion inhibitors, for example based on film-forming ammonium salts of organic carboxylic acids or on heterocyclic aromatics in the case of non-ferrous metal corrosion protection;
  • Antioxidants or stabilizers for example based on amines such as p-phenylenediamine, dicyclohexylamine or derivatives thereof, or on phenols such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid; demulsifiers; antistatic agents; lubricity improvers, such as certain fatty acids, alkenyl succinic acid esters, bis(hydroxyalkyl) fatty amines, hydroxyacetamides or castor oil; and dyes (markers). If necessary, amines are also added to lower the pH of the fuel.
  • the components or additives can be added to the fuel individually or as a previously prepared concentrate (additive package) together with the diphenylamine according to the invention.
  • Such additive packages contain at least one diphenylamine and optionally at least one of the other additives specified above.
  • preferred additive packages also contain at least one sterically hindered phenol and optionally at least one of the other additives specified above.
  • At least one diphenylamine, at least one sterically hindered phenol, and the at least one detergent particularly preferred additive packages also contain at least one carrier oil, preferably selected from the group consisting of polyalkoxylates and polyetheramines, particularly preferably at least one polyalkoxylate, and optionally at least one of the above other additives.
  • the additive packages are usually added to the gasoline in amounts of 100 to 3000 ppm by weight, preferably in amounts of 200 to 2500, particularly preferably 500 to 2000 ppm by weight.
  • Another object of the present invention is the use of such additive packages in a fuel to reduce and/or eliminate deposits on the intake valves (IVD) in indirect injection spark-ignition engines.
  • IVD intake valves
  • a further object of the present invention is a method for operating a gasoline engine with indirect injection with a gasoline containing at least one such additive package for reducing and/or eliminating deposits on the intake valves (IVD).
  • additive compositions listed can be used in all conventional gasoline fuels, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition 1990, Volume A16, p. 719 et seq.
  • a gasoline with an aromatics content of no more than 60 such as no more than 42 or no more than 35% by volume and/or a sulfur content of no more than 2000, such as no more than 150 or no more than 10 ppm by weight, is possible.
  • the aromatics content of petrol is, for example, 10 to 50% by volume, such as 30 to 42% by volume, in particular 32 to 40% by volume, or a maximum of 35% by volume.
  • the sulfur content of petrol is, for example, 2 to 500, such as 5 to 100 ppm by weight, or a maximum of 10 ppm by weight.
  • the gasoline can, for example, have an olefin content of up to 50% by volume, such as from 6 to 21% by volume, in particular 7 to 18% by volume; a benzene content of up to 5% by volume, such as 0.5 to 1.0% by volume, in particular 0.6 to 0.9% by volume, and/or an oxygen content of up to 25% by volume , such as up to 10% by weight or 1.0 to 2.7% by weight, in particular from 1.2 to 2.0% by weight.
  • an olefin content of up to 50% by volume, such as from 6 to 21% by volume, in particular 7 to 18% by volume
  • a benzene content of up to 5% by volume, such as 0.5 to 1.0% by volume, in particular 0.6 to 0.9% by volume
  • an oxygen content of up to 25% by volume such as up to 10% by weight or 1.0 to 2.7% by weight, in particular from 1.2 to 2.0% by weight.
  • petrol fuels that can be mentioned by way of example have an aromatic content of no more than 38 or 35% by volume, an olefin content of no more than 21% by volume, a sulfur content of no more than 50 or 10 ppm by weight, a benzene content of no more than 1, 0% by volume and an oxygen content of 1.0 to 2.7% by weight.
  • the gasoline can contain up to 85% by volume, preferably up to 65% by volume, particularly preferably up to 50% by volume, very particularly preferably up to 25% by volume and in particular up to 10% by volume of at least one C 1 -C 4 alkanol contain methanol, ethanol or n-butanol, particularly preferably methanol or ethanol and very particularly preferably ethanol.
  • the content of alcohols and ethers in petrol can vary over a wide range. Examples of typical maximum contents are 15% by volume for methanol, 85% by volume for ethanol, 20% by volume for isopropanol, 15% by volume for tert-butanol, 20% by volume for isobutanol and ether with 5 or more carbon atoms in the molecule, 30% by volume. Pure alkanols, especially pure methanol or ethanol, are also conceivable.
  • the summer vapor pressure of petrol is usually a maximum of 70 kPa, in particular 60 kPa (each at 37° C.).
  • the RON of petrol is usually 75 to 105.
  • a typical range for the corresponding MON is 65 to 95.
  • the subject of the present invention is a method for operating a vehicle with a spark-ignition engine, in which the spark-ignition fuel used for operation contains at least one diphenylamine to reduce and/or eliminate deposits on the intake valves (IVD).

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Die vorliegende Schrift beschreibt die Verwendung von Diarylaminen zur Verringerung und/oder Beseitigung von Ablagerungen auf Einlaßventilen von Ottomotoren, ein Verfahren zu deren Betrieb und Verfahren zur Verringerung von Ablagerungen auf Einlaßventilen.The present specification describes the use of diarylamines to reduce and/or eliminate deposits on intake valves of spark ignition engines, a method of operating them and methods of reducing intake valve deposits.

Description

Die vorliegende Schrift beschreibt die Verwendung von Diarylaminen zur Verringerung und/oder Beseitigung von Ablagerungen auf Einlaßventilen von Ottomotoren, ein Verfahren zu deren Betrieb und Verfahren zur Verringerung von Ablagerungen auf Einlaßventilen.The present specification describes the use of diarylamines to reduce and/or eliminate deposits on intake valves of spark ignition engines, a method of operating them and methods of reducing intake valve deposits.

Diarylamine sind bereits seit langem als Zusätze zu Kraftstoffen bekannt.Diarylamines have long been known as fuel additives.

So beschreibt US 2107147 A den Einsatz von Diarylaminen als Zusatz zu Benzinen, um die Bildung von harzigen Polymeren aus der Oxidation von Diolefinen zu unterdrücken, die sich bei der Lagerung der Kraftstoffe bilden.So describes US2107147A the use of diarylamines as an additive to gasoline to suppress the formation of resinous polymers from the oxidation of diolefins formed during fuel storage.

WO 2018/041710 A1 beschreibt den Einsatz von Diarylaminen in direkteinspritzenden Benzinmotoren zur Verringerung von Brennraumablagerungen oder der Einspritzdüse. Beschrieben wird mithin lediglich die Verringerung von Verkokungen an Bauteilen, die mit Verbrennungsgasen in Kontakt stehen. WO 2018/041710 A1 describes the use of diarylamines in direct-injection gasoline engines to reduce combustion chamber deposits or the injection nozzle. Thus, only the reduction of coking on components that are in contact with combustion gases is described.

Im Gegensatz dazu bezieht sich die vorliegende Erfindung auf die Verringerung und/oder Beseitigung von Ablagerungen, die sich an Einlaßventilen von indirekt einspritzenden Ottomotoren befinden, sogenannte Intake Valve Deposits (IVD): Diese Ablagerungen befinden sich auf der Innenseite der Einlaßventile auf der Saugrohr-seitigen Fläche der Einlaßventile, die mit einem Kraftstoff-Luft-Gemisch in Kontakt kommt. Die Ventile sind wärmeleitend mit dem Brennraum verbunden, so daß sie eine gegenüber der Lagerung im Tank oder der Förderung im Kraftstoffsystem erhöhte Wandtemperatur aufweisen, der das Kraftstoff-Luft-Gemisch ausgesetzt ist. Andererseits sind die Ventilinnenseiten nicht dem Verbrennungsprozeß ausgesetzt, so daß die Ablagerungsproblematik hier ein andere ist als gemäß der WO 2018/041710 A1 .In contrast, the present invention relates to the reduction and/or elimination of deposits that are on the intake valves of indirect injection gasoline engines, so-called intake valve deposits (IVD): These deposits are on the inside of the intake valves on the intake manifold side Area of the intake valve that comes into contact with a fuel-air mixture. The valves are thermally connected to the combustion chamber, so that they have a higher wall temperature than when stored in the tank or conveyed in the fuel system, to which the fuel-air mixture is exposed. On the other hand, the insides of the valves are not exposed to the combustion process, so that the problem of deposits is different here than according to the WO 2018/041710 A1 .

Aufgabe der vorliegenden Erfindung war es, Benzinadditive zur Verfügung zu stellen, mit denen die Ablagerungen auf Einlaßventilen von indirekt einspritzenden Ottomotoren verringert oder beseitigt werden können.The object of the present invention was to provide gasoline additives with which the deposits on the intake valves of indirect-injection Otto engines can be reduced or eliminated.

Die Aufgabe wurde gelöst durch die Verwendung mindestens eines Diarylamins in einem Kraftstoff oder Kraftstoffadditiv zur Verringerung und/oder Beseitigung von Ablagerungen auf den Einlaßventilen (IVD) in Ottomotoren mit indirekter Einspritzung.The object was achieved by using at least one diarylamine in a fuel or fuel additive to reduce and/or eliminate deposits on the intake valves (IVD) in Otto engines with indirect injection.

Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zum Betreiben eines Ottomotors mit indirekter Einspritzung mit einem Ottokraftstoff, enthaltend mindestens ein Diarylamin zur Verringerung und/oder Beseitigung von Ablagerungen auf den Einlaßventilen (IVD). Diarylamine sind allgemein solche Amine, in denen das aminische Stickstoffatom direkt mit zwei aromatischen Ringen verbunden ist. Die aromatischen Ringe können dabei unsubstituiert oder mit einem oder mehreren Substituenten substituiert sein.Another object of the present invention is a method for operating a gasoline engine with indirect injection using a gasoline containing at least one diarylamine to reduce and/or eliminate deposits on the intake valves (IVD). Diarylamines are generally those amines in which the amine nitrogen atom is directly attached to two aromatic rings. The aromatic rings can be unsubstituted or substituted with one or more substituents.

In einer bevorzugten Ausführungsform handelt es sich bei dem Diarylamin um eines der Formel

         R1-Ar1-NH-Ar2-R2 ,

worin

  • Ar1 und Ar2 unabhängig voneinander einen 6 bis 12 Kohlenstoffatome aufweisenden, aromatischen Ring, bevorzugt mit R1 bzw. R2 substituiertes Phenyl oder Naphthyl, besonders bevorzugt mit R1 bzw. R2 substituiertes Phenyl und
  • R1 und R2 unabhängig voneinander Wasserstoff, einen 1 bis 20 Kohlenstoffatome aufweisenden Alkylrest, einen 2 bis 20 Kohlenstoffatome aufweisenden Alkenylrest oder einen 1 bis 4 Kohlenstoffatome aufweisenden Hydroxyalkylrest, bevorzugt einen 4 bis 16 Kohlenstoffatome aufweisenden Alkylrest
bedeuten.In a preferred embodiment, the diarylamine is one of the formula

R 1 -Ar 1 -NH-Ar 2 -R 2 ,

wherein
  • Ar 1 and Ar 2 are, independently of one another, an aromatic ring containing 6 to 12 carbon atoms, preferably phenyl or naphthyl substituted by R 1 or R 2 , particularly preferably phenyl substituted by R 1 or R 2 , and
  • R 1 and R 2 are independently hydrogen, an alkyl radical having 1 to 20 carbon atoms, an alkenyl radical having 2 to 20 carbon atoms or a hydroxyalkyl radical having 1 to 4 carbon atoms, preferably an alkyl radical having 4 to 16 carbon atoms
mean.

Darin bedeutenmean therein

ein 1 bis 20 Kohlenstoffatome aufweisender Alkylrest beispielsweise Methyl, Ethyl, iso-Propyl, n-Propyl, n-Butyl, iso-Butyl, sek-Butyl, tert-Butyl, n-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Decyl, 2-Propylheptyl n-Dodecyl, n-Tetradecyl, n-Hexadecyl, n-Octadecyl oder n-Eicosyl.an alkyl radical having 1 to 20 carbon atoms, for example methyl, ethyl, isopropyl , n-propyl, n-butyl, isobutyl , sec-butyl, tert-butyl, n-hexyl, n-heptyl, n-octyl, 2- ethylhexyl, n-decyl, 2-propylheptyl n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl or n-eicosyl.

Bevorzugt handelt es sich um einen 4 bis 16 Kohlenstoffatome aufweisenden Alkylrest. Beispiele dafür sind die oben aufgeführten 4 bis 16 Kohlenstoffatome aufweisenden Individuen.It is preferably an alkyl radical having 4 to 16 carbon atoms. Examples are the 4 to 16 carbon atom individuals listed above.

Bevorzugt sind Methyl, Ethyl, iso-Propyl, iso-Butyl, tert-Butyl, n-Hexyl, n-Octyl, 2-Ethylhexyl, n-Decyl, 2-Propylheptyl n-Dodecyl, n-Tetradecyl oder n-Hexadecyl, besonders bevorzugt sind Methyl, iso-Propyl, tert-Butyl, und 2-Ethylhexyl.Methyl, ethyl, iso -propyl, iso -butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-decyl, 2-propylheptyl, n-dodecyl, n-tetradecyl or n-hexadecyl are particularly preferred methyl, isopropyl , tert-butyl and 2-ethylhexyl are preferred.

2 bis 20 Kohlenstoffatome aufweisende Alkenylreste sind Vinyl, Allyl, Isopropenyl, Octenyl, Decenyl, Dodecenyl, Tetradecenyl, Hexadecenyl und Octadecenyl.Alkenyl radicals having 2 to 20 carbon atoms are vinyl, allyl, isopropenyl, octenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl and octadecenyl.

1 bis 4 Kohlenstoffatome aufweisende Hydroxyalkylreste sind beispielsweise Hydroxymethyl, 1-Hydroxyethyl, 2-Hydroxyethyl, 2-Hydroxypropyl und 2-Hydroxyprop-2-yl.Examples of hydroxyalkyl radicals having 1 to 4 carbon atoms are hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 2-hydroxypropyl and 2-hydroxyprop-2-yl.

Bevorzugt handelt es sich bei R1 und R2 unabhängig voneinander um Wasserstoff, Methyl, iso Propyl, tert. Butyl, 2-Ethylhexyl, Hydroxymethyl oder 2-Hydroxyprop-2-yl.R 1 and R 2 are preferably, independently of one another, hydrogen, methyl, isopropyl, tert. butyl, 2-ethylhexyl, hydroxymethyl or 2-hydroxyprop-2-yl.

In einer bevorzugten Ausführungsform sind R1 und R2 gleich.In a preferred embodiment, R 1 and R 2 are the same.

Bevorzugte Diphenylamine sind Diphenylamin, Dinaphthylamin, 4,4'-Di(dimethylbenzyl)diphenylamin ( CAS 10081-67-1 ), 4-Hydroxydiphenylamin ( CAS 122-37-2 ), 4-Methoxy-2-methyldiphenylamin ( CAS 41317-15-1 ), alkylierte Diphenylamine, Reaktionsprodukt von Diphenylamin mit 2,4,4-Trimethylpenten ( CAS 68411-46-1 , Irganox® L57), Reaktionsprodukt von Styrol mit Diphenylmethan ( CAS 68442-68-2 ), p-Aminodiphenylamin ( CAS 101-54 -), 4-Isopropylaminodiphenylamin ( CAS 101-72-4 ), Bis(nonyl)diphenylamin (Reaktionsprodukt von Diphenylamin mit Nonen, Bis(4-(1,1,3,3-tetramethylbutyl)phenyl)amin ( CAS 15721-78-5 ), 4-(Dimethylbutylamino)diphenylamin ( CAS 793-24-8 ), 4-[3-(1-Naphthylamino)propyl]morpholin ( CAS 5235-82-5 ), N-1,3-Dimethylbutyl-N'-phenyl-p-phenylenediamin ( CAS 793-24-8 ), Alpha-Methylstyrol umgesetzt mit Diphenylamin (Naugalube® AMS), Phenyl-alpha-naphthylamine (Additin® 7130), Styrol umgesetzt mit Diphenylamin (Additin® 7135 oder Naugalube® 635), butyliertes, octyliertes Diphenylamin (Naugalube® 640), octyliertes, styryliertes Diphenylamin (Naugalube® 680), Phenyl-alpha-naphthylamin (Naugard® PANA).Preferred diphenylamines are diphenylamine, dinaphthylamine, 4,4'-di(dimethylbenzyl)diphenylamine ( CAS 10081-67-1 ), 4-hydroxydiphenylamine ( CAS 122-37-2 ), 4-Methoxy-2-methyldiphenylamine ( CAS 41317-15-1 ), alkylated diphenylamines, reaction product of diphenylamine with 2,4,4-trimethylpentene ( CAS 68411-46-1 , Irganox ® L57), reaction product of styrene with diphenylmethane ( CAS 68442-68-2 ), p-aminodiphenylamine ( CAS 101-54 -), 4-isopropylaminodiphenylamine ( CAS 101-72-4 ), bis(nonyl)diphenylamine (reaction product of diphenylamine with nonene, bis(4-(1,1,3,3-tetramethylbutyl)phenyl)amine ( CAS 15721-78-5 ), 4-(dimethylbutylamino)diphenylamine ( CAS 793-24-8 ), 4-[3-(1-Naphthylamino)propyl]morpholine ( CAS 5235-82-5 ), N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine ( CAS 793-24-8 ), alpha-methylstyrene reacted with diphenylamine (Naugalube ® AMS), phenyl-alpha-naphthylamine (Additin ® 7130), styrene reacted with diphenylamine (Additin ® 7135 or Naugalube ® 635), butylated, octylated diphenylamine (Naugalube ® 640), octylated , styrylated diphenylamine (Naugard ® 680), phenyl-alpha-naphthylamine (Naugard ® PANA).

Die Herstellung der alkylierten Diphenylamine ist allgemein beschrieben in Lubricant Additives, Chemistry and Applications, second edition, edited by L. R. Rudnick, CRC Press 2009, International Standard Book Number-13:978-1-4200-5964-9 (Hardcover), Part 1, Chapter 1. Die hier genannten aminischen Antioxidanzien, insbesondere Derivate von Diphenylaminen und N-Phenyl-naphthylaminen sind ebenfalls bevorzugt. Im Allgemeinen kann Diphenylamin oder N-Phenyl-naphthylamin mit Isobuten, Diisobuten, Nonen, Styrol, α-Methylstyrol oder Propylentetramer unter Verwendung geeigneter Katalysatoren umgesetzt werden, wobei Gemische mono-und disubstituierter Produkte als besonders bevorzugte Dipjenylamine erhalten werden. Es können auch Reaktionsprodukte aus der Umsetzung von Diphenylamin mit Gemischen der genannten Olefine eingesetzt werden.The preparation of the alkylated diphenylamines is generally described in Lubricant Additives, Chemistry and Applications, second edition, edited by L. R. Rudnick, CRC Press 2009, International Standard Book Number-13:978-1-4200-5964-9 (Hardcover), Part 1 , Chapter 1. The aminic antioxidants mentioned here, in particular derivatives of diphenylamines and N-phenyl-naphthylamines, are also preferred. In general, diphenylamine or N-phenyl-naphthylamine can be reacted with isobutene, diisobutene, nonene, styrene, α-methylstyrene or propylene tetramer using suitable catalysts to give mixtures of mono- and disubstituted products as particularly preferred dipjenylamines. Reaction products from the reaction of diphenylamine with mixtures of the olefins mentioned can also be used.

Besonders bevorzugt ist das Reaktionsprodukt von Diphenylamin mit 2,4,4-Trimethylpenten ( CAS 68411-46-1 , Irganox® L57) sowie butyliertes, octyliertes Diphenylamin (Naugalube® 640).Particularly preferred is the reaction product of diphenylamine with 2,4,4-trimethylpentene ( CAS 68411-46-1 , Irganox ® L57) and butylated, octylated diphenylamine (Naugalube ® 640).

In einer bevorzugten Ausführungsform wird das oben bezeichnete Diphenylamin in einem Kraftstoffadditivpaket zusammen mit mindestens einem sterisch gehinderten Phenol und/oder Aminophenol, bevorzugt mindestens einem sterisch gehinderten Phenol verwendet.In a preferred embodiment, the above identified diphenylamine is used in a fuel additive package together with at least one sterically hindered phenol and/or aminophenol, preferably at least one sterically hindered phenol.

Bevorzugte sterisch gehinderte Phenol weisen die FormelPreferred sterically hindered phenols have the formula

Figure imgb0001
auf, worin

  • R10, R11 und R12 unabhängig voneinander einen 1 bis 20 Kohlenstoffatome aufweisenden Alkylrest oder einen 2 bis 20 Kohlenstoffatome aufweisenden Alkenylrest, wobei einer der beiden Reste R10 und R11 auch Wasserstoff sein kann, bevorzugt einen 4 bis 16 Kohlenstoffatome aufweisenden Alkylrest und
  • R12 zusätzlich Wasserstoff oder eine C1-C10-Alkyloxycarbonyl-C1-C4-alkylgruppe
bedeuten.
Figure imgb0001
 on what
  • R 10 , R 11 and R 12 are independently an alkyl radical having 1 to 20 carbon atoms or an alkenyl radical having 2 to 20 carbon atoms, where one of the two radicals R 10 and R 11 can also be hydrogen, preferably an alkyl radical having 4 to 16 carbon atoms and
  • R 12 is additionally hydrogen or a C 1 -C 10 -alkyloxycarbonyl-C 1 -C 4 -alkyl group
mean.

Darin entsprechen die Bedeutungen für 1 bis 20 Kohlenstoffatome aufweisende Alkylreste, 2 bis 20 Kohlenstoffatome aufweisende Alkenylreste und 4 bis 16 Kohlenstoffatome aufweisende Alkylreste den bei den Diphenylaminen aufgeführten Definitionen und Individuen.The meanings therein for alkyl radicals having 1 to 20 carbon atoms, alkenyl radicals having 2 to 20 carbon atoms and alkyl radicals having 4 to 16 carbon atoms correspond to the definitions and individuals given for the diphenylamines.

Bevorzugte Reste R10, R11 und R12 sind unabhängig voneinander Methyl, Ethyl, iso-Propyl, iso-Butyl, tert-Butyl, n-Hexyl, n-Octyl, 2-Ethylhexyl, n-Decyl, 2-Propylheptyl n-Dodecyl, n-Tetradecyl oder n-Hexadecyl, besonders bevorzugt sind Methyl, iso-Propyl, tert-Butyl, und 2-Ethylhexyl und ganz besonders bevorzugt Methyl und tert. Butyl.Preferred radicals R 10 , R 11 and R 12 are, independently of one another, methyl, ethyl, isopropyl , isobutyl , tert -butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-decyl, 2-propylheptyl n- Dodecyl, n-tetradecyl or n-hexadecyl, particular preference is given to methyl, isopropyl , tert -butyl and 2-ethylhexyl and very particular preference to methyl and tert. butyl.

R12 kann zusätzlich bevorzugt Wasserstoff, 2-(Methoxycarbonyl)ethyl, 2-(Ethoxycarbonyl)ethyl, 2-(n-Butyloxycarbonyl)ethyl, 2-(tert-Butyloxycarbonyl)ethyl, 2-(n-Octyloxycarbonyl)ethyl oder 2-(2'-Ethylhexyl oxycarbonyl)ethyl bedeuten.R 12 can additionally preferably be hydrogen, 2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)ethyl, 2-(n-butyloxycarbonyl)ethyl, 2-(tert-butyloxycarbonyl)ethyl, 2-(n-octyloxycarbonyl)ethyl or 2- (2'-ethylhexyloxycarbonyl)ethyl.

Bevorzugte sterisch gehinderte Phenole sind 2,6-Di tert. Butyl phenol,
2-tert.-Butyl-4-methylphenol, 6-tert.-Butyl-2,4-dimethyl-phenol, 2,6-Di-tert.-Butyl-4-methylphenol, 2-tert.-Butylphenol, 4-tert.-Butylphenol, 2,4-di-tert.-Butylphenol, 2-Methyl-4-tert.-Butylphenol, 4-tert.-Butyl-2,6-dimethylphenol, 2-tert-Butyl-6-methylphenol, 2,4,6-Tris-tert-Butylphenol, 2,6-Di-tert.-butylphenol, 2,4-Di-tert.-butylphenol, 2,6-Dimethylphenol, 2,6-Di-tert-Butyl-p-kresol, 3-(3',5'-Di-tert.-butyl-4'-hydroxyphenyl)propionsäureoctadecylester, 3-(3',5'-Di-tert.-butyl-4'-hydroxyphenyl)propionsäurehexadecylester, 3-(3',5'-Di-tert.-butyl-4'-hydroxyphenyl)propionsäureoctylester, 3-(3',5'-Di-tert.-butyl-4'-hydroxyphenyl)propionsäure 2-ethylhexylester oder 3-(3',5'-Di-tert.-butyl-4'-hydroxyphenyl)propionsäuremethylester.Preferred sterically hindered phenols are 2,6-di tert. butyl phenol,
2-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-dimethyl-phenol, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butylphenol, 4- tert-butylphenol, 2,4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 4-tert-butyl-2,6-dimethylphenol, 2-tert-butyl-6-methylphenol, 2,4,6-Tris-tert-butylphenol, 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2,6-dimethylphenol, 2,6-di-tert-butyl- p-cresol, 3-(3',5'-di- tert -butyl-4'-hydroxyphenyl)propionic acid octadecyl ester, 3-(3',5'-di- tert -butyl-4'-hydroxyphenyl)propionic acid hexadecyl ester, 3-(3',5'-Di- tert -butyl-4'-hydroxyphenyl)propionic acid octyl ester, 3-(3',5'-Di- tert -butyl-4'-hydroxyphenyl)propionic acid 2-ethylhexyl ester or 3 -(3',5'-Di- tert -butyl-4'-hydroxyphenyl)propionic acid methyl ester.

In den Aminophenolen können die Amino- und die phenolische Hydroxygruppe zueinander in ortho-, meta- oder para-Position stehen, bevorzugt ortho oder para.In the aminophenols, the amino and the phenolic hydroxy group can be in the ortho, meta or para position to one another, preferably ortho or para.

Die Aminogruppe kann unsubstituiert in Form einer -NH2-Gruppe vorliegen, oder mono. oder disubstituiert, bevorzugt disubstituiert. Die Substituenten können gleich oder verschieden sein, bevorzugt handelt es sich um C1- bis C4-Alkyl oder Hydroxy-Ci- bis C4-Alkyl.The amino group can be unsubstituted in the form of an -NH 2 group, or mono. or disubstituted, preferably disubstituted. The substituents can be the same or different, and are preferably C 1 -C 4 -alkyl or hydroxy-C 1 -C 4 -alkyl.

Beispiele für Aminophenole sind 2-Aminophenol, 3-Aminophenol, 4-Aminophenol, 3-Diethylaminophenol, 3-Methyl-4-aminophenol, 2-Methyl-5-hydroxyethylaminophenol, 6-Methyl-3-aminophenol, Ethyl p-aminophenol, 4-Methyl-2-Aminophenol, 3-phenylaminophenol
In einer weiteren Ausführungsform wird das oben bezeichnete Diphenylamin in einem Kraftstoffadditivpaket zusammen mit mindestens einem Detergens verwendet, bevorzugt ausgewählt aus der Gruppe bestehend aus

  • Polyalkenmono- oder -Polyamine mit einem zahlenmittleren Molekulargewicht von 300 bis 5000 g/mol,
  • Mannich Addukten und
  • quaternären Ammoniumverbindungen.
Examples of aminophenols are 2-aminophenol, 3-aminophenol, 4-aminophenol, 3-diethylaminophenol, 3-methyl-4-aminophenol, 2-methyl-5-hydroxyethylaminophenol, 6-methyl-3-aminophenol, ethyl p-aminophenol, 4 -Methyl-2-aminophenol, 3-phenylaminophenol
In another embodiment, the diphenylamine identified above is used in a fuel additive package along with at least one detergent, preferably selected from the group consisting of
  • Polyalkene mono- or polyamines with a number-average molecular weight of 300 to 5000 g/mol,
  • Mannich adducts and
  • quaternary ammonium compounds.

Mono- oder Polyaminogruppen enthaltende Additive sind vorzugsweise Polyalkenmono- oder Polyalkenpolyamine auf Basis von Polypropen oder hochreaktivem oder konventionellem (d.h. mit überwiegend mittenständigen Doppelbindungen) Polybuten oder Polyisobuten mit Mn = 300 bis 5000. Geht man bei der Herstellung der Additive von Polybuten oder Polyisobuten mit überwiegend mittenständigen Doppelbindungen (meist in der beta-und gamma-Position) aus, bietet sich der Herstellweg durch Chlorierung und anschließende Aminierung oder durch Oxidation der Doppelbindung mit Luft oder Ozon zur Carbonyl- oder Carboxylverbindung und anschließende Aminierung unter reduktiven (hydrierenden) Bedingungen an. In einer besonderen Ausführungsform ausgehend von hochreaktivem Polyisobuten mit Mn = 300 bis 5000 mit überwiegend endständigen Doppelbindungen (meist in der alpha-Position), bietet sich der Herstellweg durch Hydroformylierung und anschließende Aminierung unter reduktiven (hydrierenden) Bedingungen an. Zur Aminierung können hier Amine, wie z.B. Ammoniak, Monoamine oder Polyamine, wie Dimethylaminopropylamin, Ethylendiamin, Diethylentriamin, Triethylentetramin oder Tetraethylenpentamin, eingesetzt werden. Entsprechende Additive auf Basis von Polypropen sind insbesondere in der WO-A-94/24231 beschrieben.Additives containing mono- or polyamino groups are preferably polyalkenemono- or polyalkenepolyamines based on polypropylene or highly reactive or conventional (ie with predominantly central double bonds) polybutene or polyisobutene with Mn=300 to 5000 double bonds in the middle (usually in the beta and gamma position), the production route is through chlorination and subsequent amination or through oxidation of the double bond with air or ozone to form the carbonyl or carboxyl compound and subsequent amination under reductive (hydrogenating) conditions. In a particular embodiment, starting from highly reactive polyisobutene with Mn=300 to 5000 with predominantly terminal double bonds (usually in the alpha position), the preparation route by hydroformylation and subsequent amination under reductive (hydrogenating) conditions is an option. Amines such as ammonia, monoamines or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine can be used for the amination. Corresponding additives based on polypropylene are in particular in the WO-A-94/24231 described.

Weitere bevorzugte Monoaminogruppen enthaltende Additive sind die Hydrierungsprodukte der Umsetzungsprodukte aus Polyisobutenen mit einem mittleren Polymerisationsgrad P = 5 bis 100 mit Stickoxiden oder Gemischen aus Stickoxiden und Sauerstoff, wie sie insbesondere in WO-A-97/03946 beschrieben sind.Other preferred additives containing monoamino groups are the hydrogenation products of the reaction products of polyisobutenes with an average degree of polymerization P=5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as are found in particular in WO-A-97/03946 are described.

Weitere bevorzugte Monoaminogruppen enthaltende Additive sind die aus Polyisobutenepoxiden durch Umsetzung mit Aminen und nachfolgender Dehydratisierung und Reduktion der Aminoalkohole erhältlichen Verbindungen, wie sie insbesondere in DE-A-196 20 262 beschrieben sind.Other preferred additives containing monoamino groups are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as they are particularly DE-A-196 20 262 are described.

Durch Mannich-Umsetzung von substituierten Phenolen mit Aldehyden und Mono- oder Polyaminen erzeugte Gruppierungen enthaltende Additive sind vorzugsweise Umsetzungsprodukte von polyisobutensubstituierten Phenolen mit Formaldehyd und Mono- oder Polyaminen wie Ethylendiamin, Diethylentriamin, Triethylentetramin, Tetraethylenpentamin oder besonders Dimethylaminopropylamin. Die polyisobutenylsubstituierten Phenole können aus konventionellem oder hochreaktivem Polyisobuten mit Mn = 300 bis 5000 stammen. Derartige "Polyisobuten-Mannichbasen" sind insbesondere in der EP-A-831 141 beschrieben.Additives containing groups produced by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or especially dimethylaminopropylamine. The polyisobutenyl substituted phenols can be derived from conventional or highly reactive polyisobutene having Mn = 300 to 5000. Such "polyisobutene Mannich bases" are particularly in the EP-A-831 141 described.

Quaternäre Ammoniumverbindungen erfüllen bevorzugt die Formel

         +NR3R4R5R6     A-

worin

  • A- für ein Anion, bevorzugt ein Carboxylat R7COO- oder Carbonat R7O-COO- stehen,
    und
  • R3, R4, R5, R6, und R7 unabhängig voneinander ein organischer Rest mit 1 bis 100 Kohlenstoffatomen, substituiertes oder unsubstituiertes, bevorzugt unsubstituiertes, lineare oder verzweigte Alkyl, Alkenyl oder Hydroxyalkyl mit 1 bis 100, bevorzugt 1 bis 75, besonders bevorzugt 1 bis 30, ganz besonders bevorzugt 1 bis 25 und insbesondere 1 bis 20 Kohlenstoffatomen,
  • R7 zusätzlich für substituierte oder unsubstituierte Cycloalkyl- oder Arylreste mit 5 bis 20, bevorzugt 5 bis 12 Kohlenstoffatomen.
Quaternary ammonium compounds preferably satisfy the formula

+NR 3 R 4 R 5 R 6 A -

wherein
  • A - for an anion, preferably a carboxylate R 7 COO - or carbonate R 7 O-COO - stand,
    and
  • R 3 , R 4 , R 5 , R 6 , and R 7 are independently an organic radical having 1 to 100 carbon atoms, substituted or unsubstituted, preferably unsubstituted, linear or branched alkyl, alkenyl or hydroxyalkyl having 1 to 100, preferably 1 to 75 , particularly preferably 1 to 30, very particularly preferably 1 to 25 and in particular 1 to 20 carbon atoms,
  • R 7 additionally represents substituted or unsubstituted cycloalkyl or aryl radicals having 5 to 20, preferably 5 to 12, carbon atoms.

Es ist ebenso möglich, daß das Anion mehrfach negativ geladen sein kann, beispielsweise bei Anionen von Dicarbonsäuren. In diesem Fall entspricht das stöchiometrische Verhältnis von Ammoniumionen zu Anionen dem Verhältnis der jeweiligen positiven und negativen Ladungen.It is also possible that the anion can have multiple negative charges, for example in the case of anions of dicarboxylic acids. In this case, the stoichiometric ratio of ammonium ions to anions corresponds to the ratio of the respective positive and negative charges.

Das gleiche gilt für Verbindungen, in denen das Kation mehr als ein Ammoniumion aufweist, z.B. wenn die Substituenten zwei oder mehr Ammoniumionen verbinden.The same applies to compounds in which the cation has more than one ammonium ion, for example when the substituents link two or more ammonium ions.

Bevorzugte quaternären Ammoniumverbindungen als Detergentien sind beschrieben in

  • WO 2006/135881 A1 , Seite 5, Zeile 13 bis Seite 12, Zeile 14;
  • WO 10/132259 A1 , Seite 3, Zeile 28 bis Seite 10, Zeile 25;
  • WO 2008/060888 A2 , Seite 6, Zeile 15 bis Seite 14, Zeile 29;
  • WO 2011/095819 A1 , Seite 4, Zeile 5 bis Seite 9, Zeile 29;
  • GB 2496514 A , Absatz [00012] bis Absatz [00041];
  • WO 2013/117616 A1 , Seite 3, Zeile 34 bis Seite 11, Zeile 2;
  • WO 14/202425 A2 , Seite 3, Zeile 14 bis Seite 5, Zeile 9;
  • WO 14/195464 A1 , Seite 15, Zeile 31 bis Seite 45, Zeile 26 und Seite 75, Zeile 1 bis 4;
  • WO 15/040147 A1 , Seite 4, Zeile 34 bis Seite 5, Zeile 18 und Seite 19, Zeile 11 bis Seite 50, Zeile 10;
  • WO 14/064151 A1 , Seite 5, Zeile 14 bis Seite 6, Zeile 17 und Seite 16, Zeile 10 bis Seite 18, Zeile 12;
  • WO 2013/064689 A1 , Seite 18, Zeile 16 bis Seite 29, Zeile 8,
  • WO 2013/087701 A1 , Seite 13, Zeile 25 bis Seite 19, Zeile 30,
  • WO 13/000997 A1 , Seite 17, Zeile 4 bis Seite 25, Zeile 3, sowie
  • WO 12/004300 , Seite 5, Zeiles 20 bis 30, Seite 8, Zeile 1 bis Seite 10, Zeile 10, and Seite 19,
Preferred quaternary ammonium compounds as detergents are described in
  • WO 2006/135881 A1 , page 5, line 13 to page 12, line 14;
  • WO 10/132259 A1 , page 3, line 28 to page 10, line 25;
  • WO 2008/060888 A2 , page 6, line 15 to page 14, line 29;
  • WO 2011/095819 A1 , page 4, line 5 to page 9, line 29;
  • GB 2496514A , paragraph [00012] to paragraph [00041];
  • WO 2013/117616 A1 , page 3, line 34 to page 11, line 2;
  • WO 14/202425 A2 , page 3, line 14 to page 5, line 9;
  • WO 14/195464 A1 , page 15, line 31 to page 45, line 26 and page 75, line 1 to 4;
  • WO 15/040147 A1 , page 4, line 34 to page 5, line 18 and page 19, line 11 to page 50, line 10;
  • WO 14/064151 A1 , page 5, line 14 to page 6, line 17 and page 16, line 10 to page 18, line 12;
  • WO 2013/064689 A1 , page 18, line 16 to page 29, line 8,
  • WO 2013/087701 A1 , page 13, line 25 to page 19, line 30,
  • WO 13/000997 A1 , page 17, line 4 to page 25, line 3, as well as
  • WO 12/004300 , page 5, lines 20 to 30, page 8, line 1 to page 10, line 10, and page 19,

Zeile 29 bis Seite 28, Zeile 3,
die jeweils durch Bezugnahme Bestandteil der vorliegenden Offenbarung seien.Line 29 to page 28, line 3,
each of which is incorporated herein by reference.

Die genannten Detergensadditive werden dem Kraftstoff üblicherweise in einer Menge von 10 bis 5000 Gew.-ppm, insbesondere 50 bis 1000 Gew.-ppm, zugegeben. Die sonstigen erwähnten Komponenten und Additive werden, wenn gewünscht, in hierfür üblichen Mengen zugesetzt.The detergent additives mentioned are usually added to the fuel in an amount of 10 to 5000 ppm by weight, in particular 50 to 1000 ppm by weight. The other components and additives mentioned are added, if desired, in amounts customary for this purpose.

Erfindungsgemäß wird das oben bezeichnete Diphenylamin in einem Kraftstoffadditivpaket verwendet, das zusätzlich mindestens ein Trägeröl enthält, bevorzugt ein Polyalkoxylat. Trägeröle zeigen normalerweise keine ausgeprägte Detergenswirkung.According to the invention, the diphenylamine described above is used in a fuel additive package which additionally contains at least one carrier oil, preferably a polyalkoxylate. Carrier oils do not normally exhibit pronounced detergency.

Geeignete mineralische Trägeröle sind bei der Erdölverarbeitung anfallende Fraktionen, wie Brightstock oder Grundöle mit Viskositäten wie beispielsweise aus der Klasse SN 500 - 2000; aber auch aromatische Kohlenwasserstoffe, paraffinische Kohlenwasserstoffe und Alkoxyalkanole. Brauchbar ist ebenfalls eine als "hydrocrack oil" bekannte und bei der Raffination von Mineralöl anfallende Fraktion (Vakuumdestillatschnitt mit einem Siedebereich von etwa 360 bis 500°C, erhältlich aus unter Hochdruck katalytisch hydriertem und isomerisiertem sowie entparaffiniertem natürlichen Mineralöl). Ebenfalls geeignet sind Mischungen oben genannter mineralischer Trägeröle.Suitable mineral carrier oils are fractions obtained during petroleum processing, such as bright stock or base oils with viscosities such as those from the class SN 500-2000; but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. Also usable is a fraction known as "hydrocrack oil" and obtained in the refining of mineral oil (vacuum distillate cut having a boiling range of about 360 to 500°C, obtainable from natural mineral oil which has been catalytically hydrogenated and isomerized and dewaxed under high pressure). Mixtures of the mineral carrier oils mentioned above are also suitable.

Beispiele für erfindungsgemäß verwendbare synthetische Trägeröle sind ausgewählt unter: Polyolefinen (Polyalphaolefine oder Poly interne-olefine), (Poly)estern, (Poly)alkoxylaten, Polyethern, alkanol- oder alkylphenolgestarteten Polyethern (Polyalkoxylate), alkylphenol- oder alkanolgestarteten Polyetheraminen (Polyether, in denen mindestens eine Hydroxygruppe durch eine Aminogruppe ersetzt ist) und Carbonsäureester langkettiger Alkanole. Unter diesen sind Polyalkoxylate und Polyetheramine bevorzugt besonders bevorzugt sind Polyalkoxylate.Examples of synthetic carrier oils that can be used according to the invention are selected from: polyolefins (polyalphaolefins or polyinternal olefins), (poly)esters, (poly)alkoxylates, polyethers, alkanol- or alkylphenol-started polyethers (polyalkoxylates), alkylphenol- or alkanol-started polyetheramines (polyethers, in in which at least one hydroxy group is replaced by an amino group) and carboxylic acid esters of long-chain alkanols. Among these, preferred are polyalkoxylates and polyetheramines, particularly preferred are polyalkoxylates.

Beispiele für geeignete Polyolefine sind Olefinpolymerisate mit Mn = 400 bis 1800, vor allem auf Polybuten- oder Polyisobuten-Basis (hydriert oder nicht hydriert).Examples of suitable polyolefins are olefin polymers with Mn=400 to 1800, primarily based on polybutene or polyisobutene (hydrogenated or non-hydrogenated).

Beispiele für besonders geeignete Polyether oder Polyetheramine sind vorzugsweise Polyoxy-C2-C4-alkylengruppierungen enthaltende Verbindungen, welche durch Umsetzung von C2-C60-Alkanolen, C6-C30-Alkandiolen, Mono- oder Di-C2-C30-alkylaminen, C1-C30-Alkylcyclohexanolen oder C1-C30-Alkylphenolen mit 1 bis 30 mol Ethylenoxid und/ oder Propylenoxid und/oder Butylenoxid pro Hydroxylgruppe oder Aminogruppe und, im Falle der Polyetheramine, durch anschließende reduktive Aminierung mit Ammoniak, Monoaminen oder Polyaminen erhältlich sind. Derartige Produkte werden insbesondere in EPA-310 875, EP-A-356 725 , EP-A-700 985 und US-A-4,877,416 beschrieben. Beispielsweise können als Polyetheramine Poly-C2-C6-Alkylenoxidamine oder funktionelle Derivate davon verwendet werden. Bevorzugte Beispiele für Polyalkoxylate sind Tridecanol- oder Isotridecanolbutoxylate, Isoheptadecanolbutoxylate, Isononylphenolbutoxylate sowie Polyisobutenolbutoxylate und -propoxylate sowie die entsprechenden Umsetzungsprodukte mit Ammoniak.Examples of particularly suitable polyethers or polyetheramines are preferably compounds containing polyoxy-C 2 -C 4 -alkylene groups, which are obtained 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 mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia , monoamines or polyamines are available. Such products are discussed in particular in EPA-310 875, EP-A-356 725 , EP-A-700 985 and US-A-4,877,416 described. For example, poly-C 2 -C 6 -alkylene oxide amines or functional derivatives thereof can be used as polyetheramines. Preferred examples of polyalkoxylates are tridecanol or isotridecanol butoxylates, isoheptadecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates and the corresponding reaction products with ammonia.

Beispiele für Carbonsäureester langkettiger Alkanole sind insbesondere Ester aus Mono-, Di-oder Tricarbonsäuren mit langkettigen Alkanolen oder Polyolen , wie sie insbesondere in der DE-A-38 38 918 beschrieben sind. Als Mono-, Di- oder Tricarbonsäuren können aliphatische oder aromatische Säuren eingesetzt werden, als Esteralkohole bzw. -polyole eignen sich vor allem langkettige Vertreter mit beispielsweise 6 bis 24 C-Atomen. Typische Vertreter der Ester sind Adipate, Phthalate, iso-Phthalate, Terephthalate und Trimellitate des Isooctanols, Isononanols, Isodecanols und des Isotridecanols, wie z.B. Di-(n- oder Iso-tridecyl)-phthalat.Examples of carboxylic acid esters of long-chain alkanols are, in particular, esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, such as those in particular DE-A-38 38 918 are described. Aliphatic or aromatic acids can be used as mono-, di- or tricarboxylic acids, and long-chain representatives having, for example, 6 to 24 carbon atoms are particularly suitable as ester alcohols or ester polyols. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol, such as di-(n- or isotridecyl)phthalate.

Weitere geeignete Trägerölsysteme sind beispielsweise beschrieben in DE-A-38 26 608 , DE-A-41 42 241 , DE-A-43 09 074 , EP-A-0 452 328 und EP-A-0 548 617 , worauf hiermit ausdrücklich Bezug genommen wird.Other suitable carrier oil systems are described, for example, in DE-A-38 26 608 , DE-A-41 42 241 , DE-A-43 09 074 , EP-A-0 452 328 and EP-A-0 548 617 , which is hereby expressly referred to.

Beispiele für besonders geeignete synthetische Trägeröle sind alkoholgestartete Polyether mit etwa 5 bis 35, wie z.B. etwa 5 bis 30, C3-C6-Alkylenoxideinheiten, wie z.B. ausgewählt unter Propylenoxid-, n-Butylenoxid- und i-Butylenoxid-Einheiten, oder Gemischen davon. Nichtlimitierende Beispiele für geeignete Starteralkohole sind langkettige Alkanole oder mit langkettigem Alkyl substituierte Phenole, wobei der langkettige Alkylrest insbesondere für einen geradkettigen oder verzweigten C6-C18-Alkylrest steht. Als bevorzugte Beispiele sind zu nennen Tridecanol, Heptadecanol und Nonylphenol.Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers having about 5 to 35, such as about 5 to 30, C 3 -C 6 -alkylene oxide units, such as selected from propylene oxide, n-butylene oxide and i-butylene oxide units, or mixtures of that. Non-limiting examples of suitable starter alcohols are long-chain alkanols or phenols substituted with long-chain alkyl, where the long-chain alkyl radical is in particular a straight-chain or branched C 6 -C 18 -alkyl radical. Preferred examples are tridecanol, heptadecanol and nonylphenol.

Weitere geeignete synthetische Trägeröle sind alkoxylierte Alkylphenole, wie sie in der DE-A-10 102 913 beschrieben sindOther suitable synthetic carrier oils are alkoxylated alkyl phenols, as in the DE-A-10 102 913 are described

Oftmals enthalten die erfindungsgemäßen Additivpakete mindestens ein Lösungsmittel zur Verringerung der Viskosität und/oder besseren Formulierbarkeit.The additive packages according to the invention often contain at least one solvent to reduce the viscosity and/or improve formulatability.

Geeignete sind z.B. unpolare organische Lösungsmittel wie aromatische und aliphatische Kohlenwasserstoffe, beispielsweise Toluol, Xylole, "white spirit" und Produkte, die unter dem Handelsnamen SHELLSOL (Royal Dutch/Shell Group) und EXXSOL (ExxonMobil) vertrieben werden, sowie polare organische Lösungsmittel, beispielsweise Alkohole wie 2-Ethylhexanol, Decanol und Isotridecanol. Derartige Lösungsmittel gelangen meist zusammen mit den vorgenannten Additiven und Co-Additiven, die sie zur besseren Handhabung lösen oder verdünnen sollen, in den Kraftstoff.Suitable are, for example, non-polar organic solvents such as aromatic and aliphatic hydrocarbons, for example toluene, xylenes, "white spirit" and products sold under the trade names SHELLSOL (Royal Dutch/Shell Group) and EXXSOL (ExxonMobil), as well as polar organic solvents, for example Alcohols such as 2-ethylhexanol, decanol and isotridecanol. Such solvents usually get into the fuel together with the aforementioned additives and co-additives, which they are supposed to dissolve or dilute for better handling.

Weitere Co-AdditiveOther co-additives

Weitere übliche Additive sind Korrosionsinhibitoren, beispielsweise auf Basis von zur Filmbildung neigenden Ammoniumsalzen organischer Carbonsäuren oder von heterocyclischen Aromaten im Falle von Buntmetallkorrosionsschutz; Antioxidantien oder Stabilisatoren, beispielsweise auf Basis von Aminen wie p-Phenylendiamin, Dicyclohexylamin oder Derivaten hiervon oder von Phenolen wie 2,4-Di-tert.-butylphenol oder 3,5-Di-tert.-butyl-4-hydroxyphenylpropionsäure; Demulgatoren; Antistatikmittel; Schmierfähigkeitsverbesserer, wie bestimmte Fettsäuren, Alkenylbernsteinsäureester, Bis(hydroxyalkyl)fettamine, Hydroxyacetamide oder Ricinusöl; sowie Farbstoffe (Marker). Gegebenenfalls werden auch Amine zur Absenkung des pH-Wertes des Kraftstoffes zugesetzt.Other customary additives are corrosion inhibitors, for example based on film-forming ammonium salts of organic carboxylic acids or on heterocyclic aromatics in the case of non-ferrous metal corrosion protection; Antioxidants or stabilizers, for example based on amines such as p-phenylenediamine, dicyclohexylamine or derivatives thereof, or on phenols such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid; demulsifiers; antistatic agents; lubricity improvers, such as certain fatty acids, alkenyl succinic acid esters, bis(hydroxyalkyl) fatty amines, hydroxyacetamides or castor oil; and dyes (markers). If necessary, amines are also added to lower the pH of the fuel.

Die Komponenten bzw. Additive können dem Kraftstoff einzeln oder als vorher zubereitetes Konzentrat (Additivpaket) zusammen mit dem erfindungsgemäßen Diphenylamin zugegeben werden.The components or additives can be added to the fuel individually or as a previously prepared concentrate (additive package) together with the diphenylamine according to the invention.

Derartige Additivpakete enthalten mindestens ein Diphenylamin, sowie optional mindestens eines der oben bezeichneten weiteren Additive.Such additive packages contain at least one diphenylamine and optionally at least one of the other additives specified above.

Bevorzugte Additivpakete enthalten neben dem mindestens einen Diphenylamin noch mindestens ein sterisch gehindertes Phenol, sowie optional mindestens eines der oben bezeichneten weiteren Additive.In addition to the at least one diphenylamine, preferred additive packages also contain at least one sterically hindered phenol and optionally at least one of the other additives specified above.

Bevorzugte Additivpakete enthalten neben dem mindestens einen Diphenylamin und mindestens einem sterisch gehinderten Phenol zusätzlich mindestens ein Detergens, bevorzugt ausgewählt aus der Gruppe bestehend aus

  • Polyalkenmono- oder -Polyamine mit einem zahlenmittleren Molekulargewicht von 300 bis 5000 g/mol,
  • Mannich Addukten und
  • quaternären Ammoniumverbindungen,
sowie optional mindestens eines der oben bezeichneten weiteren Additive.In addition to the at least one diphenylamine and at least one sterically hindered phenol, preferred additive packages also contain at least one detergent, preferably selected from the group consisting of
  • Polyalkene mono- or polyamines with a number-average molecular weight of 300 to 5000 g/mol,
  • Mannich adducts and
  • quaternary ammonium compounds,
and optionally at least one of the other additives specified above.

Besonders bevorzugte Additivpakete enthalten neben dem mindestens einen Diphenylamin, mindestens einem sterisch gehinderten Phenol, und dem mindestens einen Detergens noch mindestens ein Trägeröl, bevorzugt ausgewählt aus der Gruppe bestehend aus Polyalkoxylaten und Polyetheraminen, besonders bevorzugt mindestens einem Polyalkoxylat, sowie optional mindestens eines der oben bezeichneten weiteren Additive.In addition to the at least one diphenylamine, at least one sterically hindered phenol, and the at least one detergent, particularly preferred additive packages also contain at least one carrier oil, preferably selected from the group consisting of polyalkoxylates and polyetheramines, particularly preferably at least one polyalkoxylate, and optionally at least one of the above other additives.

Die Additivpakete werden dem Ottokraftstoff üblicherweise in Mengen von 100 bis 3000 Gew.ppm zugegeben, bevorzugt in Mengen von 200 bis 2500, besonders bevorzugt 500 bis 2000 Gew.ppm.The additive packages are usually added to the gasoline in amounts of 100 to 3000 ppm by weight, preferably in amounts of 200 to 2500, particularly preferably 500 to 2000 ppm by weight.

Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung solcher Additivpakete in einem Kraftstoff zur Verringerung und/oder Beseitigung von Ablagerungen auf den Einlaßventilen (IVD) in Ottomotoren mit indirekter Einspritzung.Another object of the present invention is the use of such additive packages in a fuel to reduce and/or eliminate deposits on the intake valves (IVD) in indirect injection spark-ignition engines.

Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zum Betreiben eines Ottomotors mit indirekter Einspritzung mit einem Ottokraftstoff, enthaltend mindestens ein solches Additivpaket zur Verringerung und/oder Beseitigung von Ablagerungen auf den Einlaßventilen (IVD).A further object of the present invention is a method for operating a gasoline engine with indirect injection with a gasoline containing at least one such additive package for reducing and/or eliminating deposits on the intake valves (IVD).

Kraftstoffefuels

Die aufgeführten Additivzusammensetzungen sind in allen herkömmlichen Ottokraftstoffen, wie sie beispielsweise in Ullmann's Encyclopedia of Industrial Chemistry, 5. Aufl. 1990, Band A16, S. 719 ff. beschrieben sind, verwendbar.The additive compositions listed can be used in all conventional gasoline fuels, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition 1990, Volume A16, p. 719 et seq.

Zum Beispiel ist die Verwendung in einem Ottokraftstoff mit einem Aromatengehalt von maximal 60, wie z.B. maximal 42 oder maximal 35 Vol.-% und/oder einem Schwefelgehalt von maximal 2000, wie z.B. maximal 150 oder maximal 10 Gew.-ppm möglich.For example, use in a gasoline with an aromatics content of no more than 60, such as no more than 42 or no more than 35% by volume and/or a sulfur content of no more than 2000, such as no more than 150 or no more than 10 ppm by weight, is possible.

Der Aromatengehalt des Ottokraftstoffes beträgt beispielsweise10 bis 50, wie z.B. 30 bis 42 Vol.-%, insbesondere 32 bis 40 Vol.-%, oder maximal 35 Vol.-%. Der Schwefelgehalt des Ottokraftstoffes beträgt beispielsweise 2 bis 500, wie z.B. 5 bis 100Gew.-ppm, oder maximal10 Gew.-ppm.The aromatics content of petrol is, for example, 10 to 50% by volume, such as 30 to 42% by volume, in particular 32 to 40% by volume, or a maximum of 35% by volume. The sulfur content of petrol is, for example, 2 to 500, such as 5 to 100 ppm by weight, or a maximum of 10 ppm by weight.

Weiterhin kann der Ottokraftstoff beispielsweise einen Olefingehalt bis zu 50 Vol.-%, wie z.B. von 6 bis 21 Vol.-%, insbesondere 7 bis 18 Vol.-%; einen Benzolgehalt von bis zu 5 Vol.-%, wie z.B. 0,5 bis 1,0 Vol.-%, insbesondere 0,6 bis 0,9 Vol.-% und/oder einen Sauerstoffgehalt von bis zu 25 Vol.-%, wie z.B. bis zu 10 Gew.-% oder 1,0 bis 2,7 Gew.-%, insbesondere von 1,2 bis 2,0 Gew.-%, aufweisen.Furthermore, the gasoline can, for example, have an olefin content of up to 50% by volume, such as from 6 to 21% by volume, in particular 7 to 18% by volume; a benzene content of up to 5% by volume, such as 0.5 to 1.0% by volume, in particular 0.6 to 0.9% by volume, and/or an oxygen content of up to 25% by volume , such as up to 10% by weight or 1.0 to 2.7% by weight, in particular from 1.2 to 2.0% by weight.

Insbesondere können solche Ottokraftstoffe beispielhaft genannt werden, welche gleichzeitig einen Aromatengehalt von maximal 38 oder 35 Vol.-%, einen Olefingehalt von maximal 21 Vol.-%, einen Schwefelgehalt von maximal 50 oder 10 Gew.-ppm, eine Benzolgehalt von maximal 1,0 Vol.-% und eine Sauerstoffgehalt von 1,0 bis 2,7 Gew.-% aufweisen.In particular, petrol fuels that can be mentioned by way of example have an aromatic content of no more than 38 or 35% by volume, an olefin content of no more than 21% by volume, a sulfur content of no more than 50 or 10 ppm by weight, a benzene content of no more than 1, 0% by volume and an oxygen content of 1.0 to 2.7% by weight.

Der Ottokraftstoff kann bis zu 85 Vol%, bevorzugt bis zu 65 Vol%, besonders bevorzugt bis zu 50 Vol%, ganz besonders bevorzugt bis zu 25 Vol% und insbesondere bis zu 10 Vol% mindestens eines C1-C4-Alkanols, bevorzugt Methanol, Ethanol oder n-Butanol, besonders bevorzugt Methanol oder Ethanol und ganz besonders bevorzugt Ethanol enthalten.The gasoline can contain up to 85% by volume, preferably up to 65% by volume, particularly preferably up to 50% by volume, very particularly preferably up to 25% by volume and in particular up to 10% by volume of at least one C 1 -C 4 alkanol contain methanol, ethanol or n-butanol, particularly preferably methanol or ethanol and very particularly preferably ethanol.

Der Gehalt an Alkoholen und Ethern im Ottokraftstoff kann über einem weiten Bereich variieren. Beispiele typischer maximaler Gehalte sind für Methanol 15 Vol.-%, für Ethanol 85 Vol.-%, für Isopropanol 20 Vol.-%, für tert.-Butanol 15 Vol.-%, für Isobutanol 20 Vol.-% und für Ether mit 5 oder mehr C-Atomen im Molekül 30 Vol.-%. Denkbar sind auch reine Alkanole, besonders reines Methanol oder Ethanol.The content of alcohols and ethers in petrol can vary over a wide range. Examples of typical maximum contents are 15% by volume for methanol, 85% by volume for ethanol, 20% by volume for isopropanol, 15% by volume for tert-butanol, 20% by volume for isobutanol and ether with 5 or more carbon atoms in the molecule, 30% by volume. Pure alkanols, especially pure methanol or ethanol, are also conceivable.

Der Sommer-Dampfdruck des Ottokraftstoffes beträgt üblicherweise maximal 70 kPa, insbesondere 60 kPa (jeweils bei 37°C).The summer vapor pressure of petrol is usually a maximum of 70 kPa, in particular 60 kPa (each at 37° C.).

Die ROZ des Ottokraftstoffes beträgt in der Regel 75 bis 105. Ein üblicher Bereich für die entsprechende MOZ liegt bei 65 bis 95.The RON of petrol is usually 75 to 105. A typical range for the corresponding MON is 65 to 95.

Die genannten Spezifikationen werden nach üblichen Methoden bestimmt (DIN EN 228).The specifications mentioned are determined using standard methods (DIN EN 228).

Demzufolge ist ein Verfahren zum Betreiben eines Fahrzeuges mit einem Ottomotor Gegenstand der vorliegenden Erfindung, in dem der zum Betrieb eingesetzte Ottokraftstoff mindestens ein Diphenylamin zur Verringerung und/oder Beseitigung von Ablagerungen auf den Einlaßventilen (IVD) enthält.Accordingly, the subject of the present invention is a method for operating a vehicle with a spark-ignition engine, in which the spark-ignition fuel used for operation contains at least one diphenylamine to reduce and/or eliminate deposits on the intake valves (IVD).

Derartige Ottokraftstoffzusammensetzungen enthalten neben der Hauptmenge an Ottokraftstoff noch

  • 100 bis 3000 Gew.ppm mindestens eines Diphenylamins, bevorzugt 200 bis 2500 und besonders bevorzugt 500 bis 2000 Gew.ppm,
  • 0 bis 1000 Gew.ppm mindestens eines sterisch gehinderten Phenols, bevorzugt 50 bis 750 und besonders bevorzugt 100 bis 500 Gew.ppm,
  • 0 bis 1000 Gew.ppm mindestens eines Trägeröls, bevorzugt 50 bis 750 und besonders bevorzugt 100 bis 500 Gew.ppm,
  • 10 bis 5000 Gew.ppm mindestens eines Detergens, bevorzugt 50 bis 1000 und besonders bevorzugt 100 bis 500 Gew.ppm,
  • sowie optional noch jeweils bis zu 200 Gew.ppm mindestens eines der anderen oben genannten Additive,
mit der Maßgabe, daß die Summe aller Bestandteile stets 100 Gew% ergibt.Gasoline fuel compositions of this type also contain, in addition to the main amount of gasoline
  • 100 to 3000 ppm by weight of at least one diphenylamine, preferably 200 to 2500 and particularly preferably 500 to 2000 ppm by weight,
  • 0 to 1000 ppm by weight of at least one sterically hindered phenol, preferably 50 to 750 and particularly preferably 100 to 500 ppm by weight,
  • 0 to 1000 ppm by weight of at least one carrier oil, preferably 50 to 750 and particularly preferably 100 to 500 ppm by weight,
  • 10 to 5000 ppm by weight of at least one detergent, preferably 50 to 1000 and particularly preferably 100 to 500 ppm by weight,
  • and optionally also up to 200 ppm by weight of at least one of the other additives mentioned above,
with the proviso that the sum of all components is always 100% by weight.

Die Erfindung wird nun anhand der folgenden Ausführungsbeispiele näher beschrieben:The invention will now be described in more detail using the following exemplary embodiments:

Experimenteller Teilexperimental part

Eingesetzte Verbindungen

  • Diphenylamin 1: Reaktionsprodukt von Diphenylamin mit 2,4,4-Trimethylpenten (Irganox® L57 von BASF SE)
  • Phenol 1: 3-[3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-phenyl] propionsäure C7-C9 (verzweigt) alkyl ester
  • Phenol 2: 2,6-Di-tert-butylphenol
  • Trägeröl 1: 15fach propoxyliertes Tridecanol, erhältlich aus Trimerbuten durch Hydroformylierung und Hydrierung
  • Trägeröl 2: Polyetheramin, aminiertes 22fach butoxyliertes Tridecanol
  • Trägeröl 3: 23fach propoxyliertes Tridecanol
Deployed Connections
  • Diphenylamine 1: Reaction product of diphenylamine with 2,4,4-trimethylpentene (Irganox ® L57 from BASF SE)
  • Phenol 1: 3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]propionic acid C 7 -C 9 (branched) alkyl ester
  • Phenol 2: 2,6-di-tert-butylphenol
  • Carrier Oil 1: 15-fold propoxylated tridecanol obtainable from trimerbutene by hydroformylation and hydrogenation
  • Carrier Oil 2: Polyetheramine, aminated 22-butoxylated tridecanol
  • Carrier Oil 3: 23xpropoxylated tridecanol

Formulierungenformulations

  • Formulierung 1: Diphenylamin 1, Phenol 1, Trägeröl 1 und Phenol 2 im Gewichtsverhältnis 45 : 3:3:8Formulation 1: Diphenylamine 1, phenol 1, carrier oil 1 and phenol 2 in a weight ratio of 45:3:3:8
  • Formulierung 2: Diphenylamin 1, Phenol 1, Trägeröl 2 und Phenol 2 im Gewichtsverhältnis 45 : 3:3:8Formulation 2: Diphenylamine 1, phenol 1, carrier oil 2 and phenol 2 in a weight ratio of 45:3:3:8
  • Formulierung 3: Diphenylamin 1, Phenol 1, Trägeröl 3 und Phenol 2 im Gewichtsverhältnis 45 : 3:3:8Formulation 3: Diphenylamine 1, phenol 1, carrier oil 3 and phenol 2 in a weight ratio of 45:3:3:8
  • Formulierung 4: Diphenylamin 1 und Phenol 1 im Gewichtsverhältnis 46 : 3Formulation 4: Diphenylamine 1 and phenol 1 in a weight ratio of 46:3
  • Formulierung 5: Trägeröl 2Formulation 5: Carrier Oil 2
Anwendungstest 1Application test 1

Reduktion von Ablagerungen in einem M111 (PFI) Motor:
E10 Kraftstoff, 95 Oktan; Test nach CEC F-020-98 Dosierung [mg/kg] IVD1) [mg] Grundwert 0 159 Formulierung 1 1200 122,5 Formulierung 2 1200 81,75 Formulierung 3 1200 110 Formulierung 4 1200 175 Formulierung 5 61 142 1) intake valve deposits (Durchschnittswert der Einlaßventile aller 4 Zylinder) Reduction of deposits in an M111 (PFI) engine:
E10 fuel, 95 octane; Test according to CEC F-020-98 Dosage [mg/kg] IVD 1) [mg] core value 0 159 Formulation 1 1200 122.5 Formulation 2 1200 81.75 Formulation 3 1200 110 Formulation 4 1200 175 Formulation 5 61 142 1) intake valve deposits (average value of the intake valves of all 4 cylinders)

Anwendungstest 2application test 2

Reduktion von Ablagerungen in einem M111 (PFI) Motor:
E10 Kraftstoff, 95 Oktan; Test nach CEC F-020-98 Dosierung [mg/kg] IVD1) [mg] Grundwert 0 137 Grundwert (Wiederholung) 0 195 Diphenylamin 1, Phenol 1 im Gewichtsverhältnis 46 : 3 1500 162 Trägeröl 1 102 53 Trägeröl 1 61 79 Diphenylamin 1 915 195 Diphenylamin 1 + Trägeröl 2 915 + 61 61 1) intake valve deposits (Durchschnittswert der Einlaßventile aller 4 Zylinder) Reduction of deposits in an M111 (PFI) engine:
E10 fuel, 95 octane; Test according to CEC F-020-98 Dosage [mg/kg] IVD 1) [mg] core value 0 137 Base Value (Repeat) 0 195 Diphenylamine 1, phenol 1 in a 46:3 weight ratio 1500 162 carrier oil 1 102 53 carrier oil 1 61 79 diphenylamine 1 915 195 Diphenylamine 1 + carrier oil 2 915 + 61 61 1) intake valve deposits (average value of the intake valves of all 4 cylinders)

Claims (15)

Verwendung mindestens eines Diarylamins zusammen mit mindestens einem Trägeröl in einem Kraftstoff oder Kraftstoffadditivpaket zur Verringerung und/oder Beseitigung von Ablagerungen auf den Einlaßventilen (IVD) in Ottomotoren mit indirekter Einspritzung.Use of at least one diarylamine together with at least one carrier oil in a fuel or fuel additive package for reducing and/or eliminating intake valve (IVD) deposits in indirect injection spark ignition engines. Verwendung gemäß Anspruch 1 in einem Kraftstoff oder Kraftstoffadditivpaket, das zusätzlich mindestens ein Detergens enthält, bevorzugt ausgewählt aus der Gruppe bestehend aus - Polyalkenmono- oder -Polyamine mit einem zahlenmittleren Molekulargewicht von 300 bis 5000 g/mol, - Mannich Addukten und - quaternären Ammoniumverbindungen. Use according to claim 1 in a fuel or fuel additive package which additionally contains at least one detergent, preferably selected from the group consisting of - Polyalkene mono- or polyamines with a number-average molecular weight of 300 to 5000 g/mol, - Mannich adducts and - quaternary ammonium compounds. Verwendung gemäß Anspruch 1 oder 2, in einem Kraftstoff oder Kraftstoffadditivpaket, wobei das mindestens eine Trägeröl mindestens ein Polyalkoxylat umfaßt.Use according to claim 1 or 2 in a fuel or fuel additive package wherein the at least one carrier oil comprises at least one polyalkoxylate. Verwendung gemäß einem der vorstehenden Ansprüche in einem Kraftstoff oder Kraftstoffadditivpaket, das zusätzlich mindestens ein sterisch gehindertes Phenol und/oder Aminophenol enthält.Use according to any one of the preceding claims in a fuel or fuel additive package which additionally contains at least one sterically hindered phenol and/or aminophenol. Verwendung gemäß Anspruch 4, dadurch gekennzeichnet, daß das sterisch gehinderte Phenol die Formel
Figure imgb0002
 aufweist, worin R10, R11 und R12 unabhängig voneinander einen 1 bis 20 Kohlenstoffatome aufweisenden Alkylrest oder einen 2 bis 20 Kohlenstoffatome aufweisenden Alkenylrest, wobei einer der beiden Reste R10 und R11 auch Wasserstoff sein kann, bevorzugt einen 4 bis 16 Kohlenstoffatome aufweisenden Alkylrest und R12 zusätzlich Wasserstoff oder eine C1-C10-Alkyloxycarbonyl-C1-C4-alkylgruppe bedeuten.Use according to Claim 4, characterized in that the sterically hindered phenol has the formula
Figure imgb0002
 has, wherein R 10 , R 11 and R 12 are independently an alkyl radical having 1 to 20 carbon atoms or an alkenyl radical having 2 to 20 carbon atoms, where one of the two radicals R 10 and R 11 can also be hydrogen, preferably an alkyl radical having 4 to 16 carbon atoms and R 12 is additionally hydrogen or a C 1 -C 10 -alkyloxycarbonyl-C 1 -C 4 -alkyl group mean. Verwendung gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß es sich bei dem Diarylamin um eines der Formel

         R1-Ar1-NH-Ar2-R2

handelt, worin Ar1 und Ar2 unabhängig voneinander einen 6 bis 12 Kohlenstoffatome aufweisenden, aromatischen Ring, bevorzugt mit R1 bzw. R2 substituiertes Phenyl oder Naphthyl, besonders bevorzugt mit R1 bzw. R2 substituiertes Phenyl und R1 und R2 unabhängig voneinander Wasserstoff, einen 1 bis 20 Kohlenstoffatome aufweisenden Alkylrest, einen 2 bis 20 Kohlenstoffatome aufweisenden Alkenylrest oder einen 1 bis 4 Kohlenstoffatome aufweisenden Hydroxyalkylrest, bevorzugt einen 4 bis 16 Kohlenstoffatome aufweisenden Alkylrest bedeuten.Use according to any one of the preceding claims, characterized in that the diarylamine is one of the formula

R 1 -Ar 1 -NH-Ar 2 -R 2

acts in which Ar 1 and Ar 2 are, independently of one another, an aromatic ring containing 6 to 12 carbon atoms, preferably phenyl or naphthyl substituted by R 1 or R 2 , particularly preferably phenyl substituted by R 1 or R 2 , and R 1 and R 2 are independently hydrogen, an alkyl radical having 1 to 20 carbon atoms, an alkenyl radical having 2 to 20 carbon atoms or a hydroxyalkyl radical having 1 to 4 carbon atoms, preferably an alkyl radical having 4 to 16 carbon atoms mean. Verfahren zum Betreiben eines Ottomotors mit indirekter Einspritzung mit einem Ottokraftstoff, enthaltend mindestens ein Diarylamin zusammen mit mindestens einem Trägeröl, zur Verringerung und/oder Beseitigung von Ablagerungen auf den Einlaßventilen (IVD).Method for operating a spark-ignition engine with indirect injection with a spark-ignition fuel containing at least one diarylamine together with at least one carrier oil to reduce and/or eliminate deposits on the intake valves (IVD). Verfahren zur Verringerung und/oder Beseitigung von Ablagerungen auf den Einlaßventilen (IVD) von Ottomotoren mit indirekter Einspritzung, dadurch gekennzeichnet, daß man den Ottomotor mit einem Ottokraftstoff enthaltend mindestens ein Diarylamin zusammen mit mindestens einem Trägeröl betreibt.Process for reducing and/or eliminating deposits on the intake valves (IVD) of Otto engines with indirect injection, characterized in that the Otto engine is operated with a gasoline containing at least one diarylamine together with at least one carrier oil. Verfahren gemäß Anspruch 7 oder 8, dadurch gekennzeichnet, daß der Ottokraftstoff bis zu 85 Vol%, bevorzugt bis zu 65 Vol%, besonders bevorzugt bis zu 50 Vol%, ganz besonders bevorzugt bis zu 25 Vol% und insbesondere bis zu 10 Vol% mindestens eines C1-C4-Alkanols, bevorzugt Methanol, Ethanol oder n-Butanol, besonders bevorzugt Methanol oder Ethanol und ganz besonders bevorzugt Ethanol enthält.Process according to Claim 7 or 8, characterized in that the petrol contains up to 85% by volume, preferably up to 65% by volume, particularly preferably up to 50% by volume, very particularly preferably up to 25% by volume and in particular up to 10% by volume a C 1 -C 4 alkanol, preferably methanol, ethanol or n-butanol, particularly preferably methanol or ethanol and very particularly preferably ethanol. Verfahren gemäß einem der Ansprüche 7 bis 9, dadurch gekennzeichnet, daß der Kraftstoff zusätzlich noch mindestens ein Detergens enthält, bevorzugt ausgewählt aus der Gruppe bestehend aus - Polyalkenmono- oder -Polyamine mit einem zahlenmittleren Molekulargewicht von 300 bis 5000 g/mol, - Mannich Addukten und - quaternären Ammoniumverbindungen. Process according to one of Claims 7 to 9, characterized in that the fuel additionally contains at least one detergent, preferably selected from the group consisting of - Polyalkene mono- or polyamines with a number-average molecular weight of 300 to 5000 g/mol, - Mannich adducts and - quaternary ammonium compounds. Verfahren gemäß einem der Ansprüche 7 bis 10, dadurch gekennzeichnet, daß das mindestens eine Trägeröl mindestens ein Polyalkoxylat umfaßt.Process according to one of Claims 7 to 10, characterized in that the at least one carrier oil comprises at least one polyalkoxylate. Verfahren gemäß einem der Ansprüche 7 bis 11, dadurch gekennzeichnet, daß der Kraftstoff zusätzlich noch mindestens ein sterisch gehindertes Phenol enthält, bevorzugt wie definiert in Anspruch 5.Process according to one of Claims 7 to 11, characterized in that the fuel additionally contains at least one sterically hindered phenol, preferably as defined in Claim 5. Verfahren gemäß einem der Ansprüche 7 bis 12, dadurch gekennzeichnet, daß das Diarylamin definiert ist wie in Anspruch 6.Process according to any one of Claims 7 to 12, characterized in that the diarylamine is as defined in Claim 6. Verwendung von Additivpaketen, enthaltend mindestens ein Diphenylamin zusammen mit mindestens einem Trägeröl, in einem Kraftstoff zur Verringerung und/oder Beseitigung von Ablagerungen auf den Einlaßventilen (IVD) in Ottomotoren mit indirekter Einspritzung.Use of additive packages containing at least one diphenylamine together with at least one carrier oil in a fuel for reducing and/or eliminating intake valve deposits (IVD) in indirect injection spark ignition engines. Verfahren zum Betreiben eines Ottomotors mit indirekter Einspritzung mit einem Ottokraftstoff, enthaltend mindestens ein Additivpaket, enthaltend mindestens ein Diphenylamin zusammen mit mindestens einem Trägeröl, zur Verringerung und/oder Beseitigung von Ablagerungen auf den Einlaßventilen (IVD).A method of operating an indirect-injection spark ignition engine with a spark-ignition fuel containing at least one additive package containing at least one diphenylamine together with at least one carrier oil to reduce and/or eliminate intake valve deposits (IVD).
EP21201213.2A 2021-10-06 2021-10-06 Method for reducing deposits on intake valves Withdrawn EP4163353A1 (en)

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