EP1705234A1 - Use of detergent additives to inhibit or reduce the formation of injection system deposits in direct injection diesel engines - Google Patents

Use of detergent additives to inhibit or reduce the formation of injection system deposits in direct injection diesel engines Download PDF

Info

Publication number
EP1705234A1
EP1705234A1 EP05006599A EP05006599A EP1705234A1 EP 1705234 A1 EP1705234 A1 EP 1705234A1 EP 05006599 A EP05006599 A EP 05006599A EP 05006599 A EP05006599 A EP 05006599A EP 1705234 A1 EP1705234 A1 EP 1705234A1
Authority
EP
European Patent Office
Prior art keywords
detergent additives
injection
additives
diesel engines
formation
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Withdrawn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
EP05006599A
Other languages
German (de)
French (fr)
Inventor
Jörn KARL
Georg Schäper
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 EP05006599A priority Critical patent/EP1705234A1/en
Priority to AR20060101031A priority patent/AR054240A1/en
Priority to MX2007010950A priority patent/MX2007010950A/en
Priority to JP2008502332A priority patent/JP2008534699A/en
Priority to US11/909,183 priority patent/US20080196586A1/en
Priority to AU2006226517A priority patent/AU2006226517B2/en
Priority to CNA2006800094515A priority patent/CN101146897A/en
Priority to BRPI0609694-8A priority patent/BRPI0609694A2/en
Priority to EP06723673A priority patent/EP1866396A1/en
Priority to KR1020077024495A priority patent/KR20070116149A/en
Priority to PCT/EP2006/002686 priority patent/WO2006100083A1/en
Priority to CA002602275A priority patent/CA2602275A1/en
Publication of EP1705234A1 publication Critical patent/EP1705234A1/en
Priority to NO20074587A priority patent/NO20074587L/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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
    • 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
    • C10L1/16—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
    • C10L1/18—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
    • C10L1/1983—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 polyesters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
    • 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
    • C10L1/1905—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-carboxylic
    • 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
    • C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
    • C10L1/231—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites nitro compounds; nitrates; nitrites
    • 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
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
    • C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters

Definitions

  • the present invention relates to the use of detergent additives to reduce or prevent the formation of deposits in the injection systems of direct injection diesel engines, and more particularly in common rail injection systems.
  • direct-injection diesel engines the fuel is injected through a directly into the combustion chamber-reaching multi-hole injection nozzle of the engine and finely distributed (nebulized), instead of being introduced as in the classic (chamber) diesel engine in a vortex or vortex chamber.
  • the advantage of direct-injection diesel engines lies in their high performance for diesel engines and yet low consumption. In addition, these engines achieve a very high torque even at low speeds.
  • the diesel fuel is pumped by a pump with pressures up to 2000 bar into a high-pressure line, the common rail (literally "common line").
  • spur lines run to the various injectors, which inject the fuel directly into the combustion chamber.
  • the full pressure is always applied to the common rail, which allows a multiple injection or a special injection form.
  • only one injection is possible.
  • Injection in the common rail is essentially subdivided into three groups: (1) preinjection, which substantially achieves softer combustion, so that hard combustion noises ("nails") are reduced and engine running appears quiet; (2.) main injection, which is responsible in particular for a good torque curve; and (3.) post-injection, which provides in particular for a low NO x value.
  • preinjection which substantially achieves softer combustion, so that hard combustion noises ("nails") are reduced and engine running appears quiet
  • main injection which is responsible in particular for a good torque curve
  • post-injection which provides in particular for a low NO x value.
  • the fuel is not burned in the rule, but evaporated by residual heat in the cylinder.
  • the resulting exhaust gas / fuel mixture is transported to the exhaust system, where the fuel in the presence of suitable catalysts acts as a reducing agent for the nitrogen oxides NO x .
  • the Euro 4 emission standard (EU 4), which should lead to improved air purity in Europe, requires compliance with certain limit values, which must be complied with not only at the factory setting but also after the engine has run for 100,000 km and are measured under certain test conditions become.
  • the diesel particulate emissions limit is 0.025 g / km.
  • the object is achieved by the use of detergent additives to reduce or prevent the formation of deposits in the injection systems of direct-injection diesel engines.
  • the formation of deposits reduced or prevented in common rail injection systems and especially in the injectors.
  • the hydrophobic hydrocarbon residue in the above detergent additives which provides sufficient solubility in the fuel, has a number average molecular weight (Mn) of 85 to 20,000, especially 113 to 10,000, especially 300 to 5000.
  • Mn number average molecular weight
  • ammonia monoamines or polyamines, such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, are used.
  • Corresponding additives based on polypropene are especially in the WO 94/24231 described.
  • monoamino groups (a) 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 DE-A-196 20 262 are described.
  • Carboxyl groups or their alkali metal or alkaline earth metal salts (d) containing additives 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 are reacted with alcohols or amines.
  • Such additives are in particular from the EP-A-307,815 known.
  • Such additives are primarily for preventing valve seat wear and can, as in the WO-A-87/01126 described, be used with advantage 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 (e) containing additives are preferably alkali metal or alkaline earth metal salts of a Sulfobernsteinklaklalesters, as described in particular in EP-A-639 632 is described.
  • Such 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.
  • Polyoxy-C 2 -C 4 alkylene groupings (f) containing additives are preferably polyethers or polyetheramines, which by reaction of 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 used in particular EP-A-310 875 .
  • polyethers such products also meet carrier oil properties. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.
  • Carboxylic ester groups (g) containing additives are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, in particular those having a minimum viscosity of 2 mm 2 / s at 100 ° C, as in particular DE-A-38 38 918 are described.
  • mono-, di- or tricarboxylic acids can aliphatic or aromatic acids are used, especially suitable as ester alcohols or polyols are long-chain representatives with, for example, 6 to 24 carbon atoms.
  • esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and of isotridecanol. Such products also meet carrier oil properties.
  • derivatives with aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine.
  • the groups having hydroxyl and / or amino and / or amido and / or imido groups are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of diamines or polyamines which, in addition to the amide function, still have free amine groups, succinic acid derivatives with a Acid and an amide, Carbon Textreimide with monoamines, Carbonklareimide with di- or polyamines, which still have free amine groups in addition to the imide function, or diimides, which are formed by the reaction of di- or polyamines with two succinic acid derivatives.
  • Such fuel additives are particularly in U.S. Patent 4,849,572 described.
  • Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated groupings (i) containing additives are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine.
  • Such "polyisobutene-Mannich bases" are particularly in the EP-A-831 141 described.
  • detergent additives from group (h) are preferably the reaction products of alkyl- or alkenyl-substituted succinic anhydrides, in particular of polyisobutenylsuccinic anhydrides, with amines. It goes without saying that these reaction products are obtainable not only when substituted succinic anhydride is used, but also when substituted succinic acid or suitable acid derivatives such as succinic acid halides or esters are used.
  • Particularly preferred detergent additives are polyisobutenyl-substituted succinimides, especially the imides with aliphatic polyamines.
  • Particularly preferred polyamines are diethylenetriamine, tetraethylenepentamine and pentaethylenehexamine, with tetraethylenepentamine being particularly preferred.
  • the polyisobutenyl radical has a number average molecular weight M n of preferably 500 to 5000, particularly preferably 500 to 2000 and in particular about 1000.
  • detergent additives can be used alone or in combination with at least one of the aforementioned detergent additives.
  • the detergent additive is used in combination with at least one carrier oil.
  • Suitable mineral carrier oils are fractions obtained in petroleum processing, such as bright stock or base oils with viscosities such as from class SN 500-2000; but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. It is also useful as a "hydrocrack oil” known and obtained in the refining of mineral oil fraction (Vakuumdestillatites with a boiling range of about 360 to 500 ° C, available from high pressure catalytically hydrogenated and isomerized and dewaxed natural mineral oil). Also suitable are mixtures of the abovementioned mineral carrier oils.
  • Examples of synthetic carrier oils which can be used according to the invention are selected from: polyolefins (polyalphaolefins or polyinternalolefins), (poly) esters, (poly) alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-initiated polyethers, alkylphenol-initiated polyetheramines and carboxylic esters of long-chain alkanols.
  • suitable polyethers or polyetheramines are preferably polyoxy-C 2 -C 4 -alkylene group-containing compounds 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.
  • EP-A-310 875 Such products are used in particular EP-A-310 875 .
  • EP-A-356 725 EP-A-700 985 and US-A-4,877,416 described.
  • polyetheramines poly-C 2 -C 6 alkylene oxide amines or functional derivatives thereof can be used. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobutenolbutoxylate 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, as are described in particular in US Pat DE-A-38 38 918 are described.
  • mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 C atoms.
  • esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and Isotridecanols, such as. As di (n- or iso-tridecyl) phthalate.
  • suitable synthetic carrier oils are alcohol-started polyethers with about 5 to 35, such as. B. about 5 to 30, C 3 -C 6 alkylene oxide, such as. B. 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.
  • Preferred examples are tridecanol and nonylphenol.
  • Suitable synthetic carrier oils are alkoxylated alkylphenols, as described in the DE-A-10 102 913.6 are described.
  • Preferred carrier oils are synthetic carrier oils, with polyethers being particularly preferred.
  • the detergent additive is preferably supplied to the injection system with the diesel fuel.
  • the diesel fuel, the detergent additive or the mixture of various detergent additives in an amount of preferably 10 to 2000 ppm by weight, more preferably from 20 to 1000 ppm by weight, more preferably from 50 to 500 ppm by weight and in particular from 50 to 200 ppm by weight, eg from 70 to 150 ppm by weight, added.
  • a carrier oil When a carrier oil is used, it is added to the diesel fuel in an amount of preferably from 1 to 1000 ppm by weight, more preferably from 10 to 500 ppm by weight, and more preferably from 20 to 100 ppm by weight.
  • the diesel fuel may contain other conventional co-additives, such as cold flow improvers, corrosion inhibitors, demulsifiers, dehazers, defoamers, cetane improvers, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, dyes, and the like.
  • cold flow improvers corrosion inhibitors, demulsifiers, dehazers, defoamers, cetane improvers, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, dyes, and the like.
  • the diesel fuels are, for example, petroleum raffinates, which usually have a boiling range of 100 to 400 ° C. These are mostly distillates with a 95% point up to 360 ° C or even beyond. However, these may also be so-called “Ultra Low Sulfur Diesel” or “City Diesel", characterized by a 95% point of, for example, a maximum of 345 ° C and a maximum sulfur content of 0.005 wt .-% or by a 95% point of for example, 285 ° C and a maximum sulfur content of 0.001 wt .-%.
  • those obtainable by coal gasification or gas liquefaction (“gas to liquid” (GTL) fuels) are suitable.
  • GTL gas to liquid
  • mixtures of the abovementioned diesel fuels with regenerative fuels such as biodiesel or bioethanol.
  • the diesel fuels are particularly preferably those with a low sulfur content, ie with a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, in particular less than 0.005% by weight. % and especially less than 0.001% by weight of sulfur.
  • the inventive use of detergent additives ensures that in the exhaust emissions of direct-injection diesel engines, especially diesel engines with a common rail injection system, after 100000 km engine operation preferably at most 2.5 times the amount, more preferably at most 2, 2 times the amount and in particular at most 2 times the amount of particles compared to the factory setting is included.
  • the quantities of particulates contained in the output remain well below the limit of the Euro 4 standard.
  • the values given refer to the exhaust emissions taken directly after the engine ("engine out"), ie. H. in front of a possibly installed particle filter, which would reduce the amount of particles in the output.
  • factory setting is meant that state of the direct injection diesel engine or the injection system, as it is at the factory, d. H.
  • detergent additives not only ensures compliance with the limit values for particle emissions in accordance with the Euro 4 standard, but also without an additional particle filter over an engine running time of 100,000 km, but also for significantly longer operating times.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Treating Waste Gases (AREA)
  • Fuel-Injection Apparatus (AREA)

Abstract

Use of detergent additives (I) for decreasing or preventing the formation of deposits in the injection systems of direct injecting diesel engines.

Description

Die vorliegende Erfindung betrifft die Verwendung von Detergens-Additiven zur Verringerung oder Verhinderung der Bildung von Ablagerungen in den Einspritzsystemen von direkteinspritzenden Dieselmotoren und insbesondere in Common-Rail-Einspritzsystemen.The present invention relates to the use of detergent additives to reduce or prevent the formation of deposits in the injection systems of direct injection diesel engines, and more particularly in common rail injection systems.

Bei in direkteinspritzenden Dieselmotoren wird der Kraftstoff durch eine direkt in den Brennraum reichende Mehrloch-Einspritzdüse des Motors eingespritzt und feinst verteilt (vernebelt), anstatt wie beim klassischen (Kammer-)Dieselmotor in eine Vor- oder Wirbelkammer eingeführt zu werden. Der Vorteil der direkteinspritzenden Dieselmotoren liegt in ihrer für Dieselmotoren hohen Leistung und einem dennoch geringen Verbrauch. Außerdem erreichen diese Motoren ein sehr hohes Drehmoment schon bei niedrigen Drehzahlen.In direct-injection diesel engines, the fuel is injected through a directly into the combustion chamber-reaching multi-hole injection nozzle of the engine and finely distributed (nebulized), instead of being introduced as in the classic (chamber) diesel engine in a vortex or vortex chamber. The advantage of direct-injection diesel engines lies in their high performance for diesel engines and yet low consumption. In addition, these engines achieve a very high torque even at low speeds.

Zur Zeit werden im Wesentlichen drei Verfahren eingesetzt, um den Kraftstoff direkt in den Brennraum einzuspritzen: Die konventionelle Verteilereinspritzpumpe, das PumpeDüse-System (Unit-Injector-System bzw. Unit-Pump-System) und das Common-Rail-System.Essentially, three methods are currently used to inject the fuel directly into the combustion chamber: the conventional distributor injection pump, the unit injector system and the common rail system.

Beim Common-Rail-System wird der Dieselkraftstoff von einer Pumpe mit Drücken bis zu 2000 bar in eine Hochdruckleitung, der Common-Rail (wörtlich "gemeinsame Leitung") gefördert. Ausgehend von der Common-Rail laufen Stichleitungen zu den verschiedenen Injektoren, die den Kraftstoff direkt in den Brennraum injizieren. Dabei liegt auf der Common-Rail stets der volle Druck an, was eine Mehrfacheinspritzung oder eine spezielle Einspritzform ermöglicht. Bei den anderen Injektionssystemen ist dagegen nur eine Einspritzung möglich. Die Einspritzung beim Common-Rail wird im Wesentlichen in drei Gruppen unterteilt: (1.) Voreinspritzung, durch die im Wesentlichen eine weichere Verbrennung erreicht wird, so dass harte Verbrennungsgeräusche ("Nageln") vermindert werden und der Motorlauf ruhig erscheint; (2.) Haupteinspritzung, die insbesondere für einen guten Drehmomentverlauf verantwortlich ist; und (3.) Nacheinspritzung, die insbesondere für einen geringen NOx-Wert sorgt. Bei dieser Nacheinspritzung wird der Kraftstoff in der Regel nicht verbrannt, sondern durch Restwärme im Zylinder verdampft. Das dabei gebildete Abgas/Kraftstoffgemisch wird zur Abgasanlage transportiert, wo der Kraftstoff in Gegenwart geeigneter Katalysatoren als Reduktionsmittel für die Stickoxide NOx wirkt.In the common-rail system, the diesel fuel is pumped by a pump with pressures up to 2000 bar into a high-pressure line, the common rail (literally "common line"). Starting from the common rail, spur lines run to the various injectors, which inject the fuel directly into the combustion chamber. In this case, the full pressure is always applied to the common rail, which allows a multiple injection or a special injection form. For the other injection systems, however, only one injection is possible. Injection in the common rail is essentially subdivided into three groups: (1) preinjection, which substantially achieves softer combustion, so that hard combustion noises ("nails") are reduced and engine running appears quiet; (2.) main injection, which is responsible in particular for a good torque curve; and (3.) post-injection, which provides in particular for a low NO x value. In this post injection, the fuel is not burned in the rule, but evaporated by residual heat in the cylinder. The resulting exhaust gas / fuel mixture is transported to the exhaust system, where the fuel in the presence of suitable catalysts acts as a reducing agent for the nitrogen oxides NO x .

Durch die variable, zylinderindividuelle Einspritzung kann beim Common-Rail-Einspritzsystem der Schadstoffausstoß des Motors, z.B. der Ausstoß von Stickoxiden (NOx), Kohlenmonoxid (CO) und insbesondere von Partikeln (Ruß) positiv beeinflusst werden. Dies ermöglicht beispielsweise, dass mit Common-Rail-Einspritzsystemen ausgerüstete Motoren der Euro 4 Norm theoretisch auch ohne zusätzlichen Partikelfilter genügen können.Due to the variable, cylinder-specific injection of the common rail injection system of the pollutant emissions of the engine, such as the emission of nitrogen oxides (NO x ), carbon monoxide (CO) and in particular of particles (soot) can be positively influenced. This makes it possible, for example, that engines equipped with common-rail injection systems can theoretically meet the Euro 4 standard even without an additional particle filter.

Die Abgasvorschriften der Euro 4 Norm (EU 4), die zu einer verbesserten Luftreinheit in Europa führen sollen, verlangen die Einhaltung bestimmter Grenzwerte, die nicht nur bei Werkeinstellung, sondern auch nach 100000 km Laufzeit des Motors noch eingehalten werden müssen und unter bestimmten Prüfbedingungen gemessen werden. So beträgt der Grenzwert für den Partikelausstoß von Dieselmotoren 0,025 g/km.The Euro 4 emission standard (EU 4), which should lead to improved air purity in Europe, requires compliance with certain limit values, which must be complied with not only at the factory setting but also after the engine has run for 100,000 km and are measured under certain test conditions become. For example, the diesel particulate emissions limit is 0.025 g / km.

Versuche der Anmelderin haben festgestellt, dass es im Laufe des Motorenbetriebs von direkteinspritzenden Dieselmotoren und insbesondere von solchen mit einem Common-Rail-Einspritzsystem zur Bildung von Ablagerungen im Einspritzsystem kommt. Beispielsweise können sich Verkokungsablagerungen an der Einspritzdüse bilden; es kommt aber auch zu Ablagerungen an anderen Teilen des Einspritzsystems. Insbesondere kommt es zur Bildung von Ablagerungen in den Injektoren, was bewirkt, dass diese ein verändertes Ansprechverhalten zeigen, wodurch der Kraftstoff nicht mehr in der richtigen Dosierung eingespritzt wird, d.h. die eingespritzte Menge weicht nach oben oder unten von der ursprünglichen Einstellung ab. Die Ablagerungen können auch bewirken, dass der Kraftstoff nicht mehr ausreichend fein, d. h. nicht mehr mit einer ausreichend kleinen Tröpfchengröße, und/oder nicht mehr mit der richtigen Geometrie vernebelt wird. Insgesamt führt die Bildung von Ablagerungen dazu, dass mit zunehmender Kilometerzahl die Verbrennung immer suboptimaler, insbesondere immer unvollständiger und damit unter Verkokung/Rußbildung verläuft, wodurch die Partikelmenge in den Abgasemissionen des Motors zunimmt und letzten Endes die Grenzwerte der Euro 4 Norm nicht über längere Zeiträume oder nur mit Hilfe aufwendiger Partikelfilter einzuhalten sind.Applicant's experiments have found that in the course of engine operation direct injection diesel engines, and in particular those with a common rail injection system, form deposits in the injection system. For example, coking deposits may form on the injection nozzle; but it also comes to deposits on other parts of the injection system. In particular, deposits are formed in the injectors, causing them to exhibit a different response, thereby no longer injecting the fuel at the correct dosage, i. the injected amount deviates up or down from the original setting. The deposits can also cause the fuel to be insufficiently fine, d. H. no longer with a sufficiently small droplet size, and / or is no longer fogged with the right geometry. Overall, the formation of deposits leads to the fact that with increasing mileage, the combustion is increasingly suboptimal, especially incomplete and thus under coking / soot formation, whereby the amount of particulates in the exhaust emissions of the engine increases and ultimately the limits of the Euro 4 norm not longer periods or can be adhered to only with the help of elaborate particulate filter.

Aufgabe der vorliegenden Erfindung war es daher, Additive bereitzustellen, welche die Bildung von Ablagerungen in den Einspritzsystemen von direkteinspritzenden Dieselmotoren, speziell in Common-Rail-Einspritzsystemen, verringern oder verhindern sollen.It is an object of the present invention to provide additives which are intended to reduce or prevent the formation of deposits in the injection systems of direct injection diesel engines, especially in common rail injection systems.

Die Aufgabe wird gelöst durch die Verwendung von Detergens-Additiven zur Verringerung oder Verhinderung der Bildung von Ablagerungen in den Einspritzsystemen von direkteinspritzenden Dieselmotoren. Insbesondere wird die Bildung von Ablagerungen in Common Rail Einspritzsystemen und dort vor allem in den Injektoren verringert oder verhindert.The object is achieved by the use of detergent additives to reduce or prevent the formation of deposits in the injection systems of direct-injection diesel engines. In particular, the formation of deposits reduced or prevented in common rail injection systems and especially in the injectors.

Im Rahmen der vorliegenden Erfindung hat der Begriff "Partikel" die gleiche Bedeutung wie in der Euro 4 Norm. Detergens-AdditiveIn the context of the present invention, the term "particle" has the same meaning as in the Euro 4 standard. Detergent additives

Vorzugsweise handelt es sich bei den Detergens-Additiven um amphiphile Substanzen, die mindestens einen hydrophoben Kohlenwasserstoffrest mit einem zahlengemittelten Molekulargewicht (Mn) von 85 bis 20000 und mindestens eine polare Gruppierung besitzen, die ausgewählt ist unter:

  • (a) Mono- oder Polyaminogruppen mit bis zu 6 Stickstoffatomen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat;
  • (b) Nitrogruppen, gegebenenfalls in Kombination mit Hydroxylgruppen;
  • (c) Hydroxylgruppen in Kombination mit Mono- oder Polyaminogruppen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat;
  • (d) Carboxylgruppen oder deren Alkalimetall- oder Erdalkalimetallsalzen;
  • (e) Sulfonsäuregruppen oder deren Alkalimetall- oder Erdalkalimetallsalzen;
  • (f) Polyoxy-C2-C4-alkylengruppierungen, die durch Hydroxylgruppen, Mono- oder Polyaminogruppen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat, oder durch Carbamatgruppen terminiert sind;
  • (g) Carbonsäureestergruppen;
  • (h) aus Bernsteinsäureanhydrid abgeleiteten Gruppierungen mit Hydroxy- und/oder Amino- und/oder Amido- und/oder Imidogruppen; und/oder
  • (i) durch Mannich-Umsetzung von substituierten Phenolen mit Aldehyden und Mono- oder Polyaminen erzeugten Gruppierungen;
Preferably, the detergent additives are amphiphilic substances having at least one hydrophobic hydrocarbon radical having a number average molecular weight (M n ) of from 85 to 20,000 and at least one polar moiety selected from:
  • (a) mono- or polyamino groups having up to 6 nitrogen atoms, at least one nitrogen atom having basic properties;
  • (b) nitro groups, optionally in combination with hydroxyl groups;
  • (c) hydroxyl groups in combination with mono- or polyamino groups, wherein at least one nitrogen atom has basic properties;
  • (d) carboxyl groups or their alkali metal or alkaline earth metal salts;
  • (e) sulfonic acid groups or their alkali metal or alkaline earth metal salts;
  • (f) polyoxy-C 2 -C 4 alkylene moieties terminated by hydroxyl groups, mono- or polyamino groups wherein at least one nitrogen atom has basic properties, or by carbamate groups;
  • (g) carboxylic acid ester groups;
  • (h) succinic anhydride-derived moieties having hydroxy and / or amino and / or amido and / or imido groups; and or
  • (i) moieties generated by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines;

Der hydrophobe Kohlenwasserstoffrest in den obigen Detergens-Additiven, welcher für die ausreichende Löslichkeit im Kraftstoff sorgt, hat ein zahlengemitteltes Molekulargewicht (Mn) von 85 bis 20000, insbesondere von 113 bis 10000, vor allem von 300 bis 5000. Als typischer hydrophober Kohlenwasserstoffrest, insbesondere in Verbindung mit den polaren Gruppierungen (a), (c), (h) und (i), kommen längerkettige Alkyl- oder Alkenylgruppen, insbesondere der Polypropenyl-, Polybutenyl- und Polyisobutenylrest mit jeweils Mn = 300 bis 5000, insbesondere 500 bis 2500, vor allem 700 bis 2300, in Betracht.The hydrophobic hydrocarbon residue in the above detergent additives, which provides sufficient solubility in the fuel, has a number average molecular weight (Mn) of 85 to 20,000, especially 113 to 10,000, especially 300 to 5000. As a typical hydrophobic hydrocarbon radical, in particular in conjunction with the polar groups (a), (c), (h) and (i), come longer-chain alkyl or alkenyl groups, in particular the polypropenyl, polybutenyl and polyisobutenyl radical each having Mn = 300 to 5000, especially 500 to 2500, especially 700 to 2300, into consideration.

Als Beispiele für obige Gruppen von Detergens-Additiven seien die folgenden genannt:As examples of the above groups of detergent additives, the following are mentioned:

Mono- oder Polyaminogruppen (a) enthaltende Additive sind vorzugsweise Polyalkenmono- oder Polyalkenpolyamine auf Basis von Polypropen 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. 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.Mono- or polyamino (a) -containing additives are preferably polyalkene mono- or polyalkene polyamines based on polypropene or conventional (ie with predominantly intermediate double bonds) polybutene or polyisobutene with Mn = 300 to 5000. If one goes along with the production of the additives of polybutene or polyisobutene predominantly centered double bonds (usually in the beta and gamma position), the preparation route by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to the carbonyl or carboxyl compound and subsequent amination under reductive (hydrogenating) conditions. For amination here amines, such as. For example, ammonia, monoamines or polyamines, such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, are used. Corresponding additives based on polypropene are especially in the WO 94/24231 described.

Weitere bevorzugte Monoaminogruppen (a) 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.Further preferred monoamino groups (a) containing additives are the hydrogenation products of the reaction products of polyisobutenes having an average degree of polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular WO-A-97/03946 are described.

Weitere bevorzugte Monoaminogruppen (a) 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.Further preferred monoamino groups (a) 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 DE-A-196 20 262 are described.

Nitrogruppen (b), gegebenenfalls in Kombination mit Hydroxylgruppen, enthaltende Additive sind vorzugsweise Umsetzungsprodukte aus Polyisobutenen des mittleren Polymerisationsgrades P = 5 bis 100 oder 10 bis 100 mit Stickoxiden oder Gemischen aus Stickoxiden und Sauerstoff, wie sie insbesondere in WO-A-96/03367 und WO-A-96/03479 beschrieben sind. Diese Umsetzungsprodukte stellen in der Regel Mischungen aus reinen Nitropolyisobutenen (z. B. α,β-Dinitropolyisobuten) und gemischten Hydroxynitropolyisobutenen (z. B. α-Nitro-β-hydroxypolyisobuten) dar.Nitro groups (b), optionally in combination with hydroxyl groups, containing additives are preferably reaction products of polyisobutenes of average degree of polymerization P = 5 to 100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as in particular WO-A-96/03367 and WO-A-96/03479 are described. These reaction products are generally mixtures of pure nitropolyisobutenes (eg, α, β-dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (eg, α-nitro-β-hydroxy polyisobutene).

Hydroxylgruppen in Kombination mit Mono- oder Polyaminogruppen (c) enthaltende Additive sind insbesondere Umsetzungsprodukte von Polyisobutenepoxiden, erhältlich aus vorzugsweise überwiegend endständige Doppelbindungen aufweisendem Polyisobuten mit Mn = 300 bis 5000, mit Ammoniak, Mono- oder Polyaminen, wie sie insbesondere in EP-A-476 485 beschrieben sind.Hydroxyl groups in combination with mono- or polyamino groups (c) containing additives are in particular reaction products of polyisobutene epoxides obtainable from preferably predominantly terminal double bonds having polyisobutene with Mn = 300 to 5000, with ammonia, mono- or polyamines, as described in particular EP-A-476485 are described.

Carboxylgruppen oder deren Alkalimetall- oder Erdalkalimetallsalze (d) enthaltende Additive sind vorzugsweise Copolymere von C2-C40-Olefinen mit Maleinsäureanhydrid mit einer Gesamt-Molmasse von 500 bis 20000, deren Carboxylgruppen ganz oder teilweise zu den Alkalimetall- oder Erdalkalimetallsalzen und ein verbleibender Rest der Carboxylgruppen mit Alkoholen oder Aminen umgesetzt sind. Solche Additive sind insbesondere aus der EP-A-307 815 bekannt. Derartige Additive dienen hauptsächlich zur Verhinderung von Ventilsitzverschleiß und können, wie in der WO-A-87/01126 beschrieben, mit Vorteil in Kombination mit üblichen Kraftstoffdetergenzien wie Poly(iso)butenaminen oder Polyetheraminen eingesetzt werden.Carboxyl groups or their alkali metal or alkaline earth metal salts (d) containing additives 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 are reacted with alcohols or amines. Such additives are in particular from the EP-A-307,815 known. Such additives are primarily for preventing valve seat wear and can, as in the WO-A-87/01126 described, be used with advantage in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.

Sulfonsäuregruppen oder deren Alkalimetall- oder Erdalkalimetallsalze (e) enthaltende Additive sind vorzugsweise Alkalimetall- oder Erdalkalimetallsalze eines Sulfobernsteinsäurealkylesters, wie er insbesondere in der EP-A-639 632 beschrieben ist. Derartige Additive dienen hauptsächlich zur Verhinderung von Ventilsitzverschleiß und können mit Vorteil in Kombination mit üblichen Kraftstoffdetergenzien wie Poly(iso)butenaminen oder Polyetheraminen eingesetzt werden.Sulfonic acid groups or their alkali metal or alkaline earth metal salts (e) containing additives are preferably alkali metal or alkaline earth metal salts of a Sulfobernsteinsäurealkylesters, as described in particular in EP-A-639 632 is described. Such 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.

Polyoxy-C2-C4-alkylengruppierungen (f) enthaltende Additive sind vorzugsweise Polyether oder Polyetheramine, 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 EP-A-310 875 , EP-A-356 725 , EP-A-700 985 und US-A-4 877 416 beschrieben. Im Falle von Polyethern erfüllen solche Produkte auch Trägeröleigenschaften. Typische Beispiele hierfür sind Tridecanol- oder Isotridecanolbutoxylate, Isononylphenolbutoxylate sowie Polyisobutenolbutoxylate und -propoxylate sowie die entsprechenden Umsetzungsprodukte mit Ammoniak.Polyoxy-C 2 -C 4 alkylene groupings (f) containing additives are preferably polyethers or polyetheramines, which by reaction of 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 used in particular EP-A-310 875 . EP-A-356 725 . EP-A-700 985 and U.S. Patent 4,877,416 described. In the case of polyethers, such products also meet carrier oil properties. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.

Carbonsäureestergruppen (g) enthaltende Additive sind vorzugsweise Ester aus Mono-, Di- oder Tricarbonsäuren mit langkettigen Alkanolen oder Polyolen, insbesondere solche mit einer Mindestviskosität von 2 mm2/s bei 100 °C, wie sie insbesondere in 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 iso-Octanols, iso-Nonanols, iso-Decanols und des iso-Tridecanols. Derartige Produkte erfüllen auch Trägeröleigenschaften.Carboxylic ester groups (g) containing additives are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, in particular those having a minimum viscosity of 2 mm 2 / s at 100 ° C, as in particular DE-A-38 38 918 are described. As mono-, di- or tricarboxylic acids can aliphatic or aromatic acids are used, especially suitable as ester alcohols or polyols are long-chain representatives with, for example, 6 to 24 carbon atoms. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and of isotridecanol. Such products also meet carrier oil properties.

Aus Bernsteinsäureanhydrid abgeleitete Gruppierungen mit Hydroxy- und/oder Amino- und/oder Amido- und/oder Imidogruppen (h) enthaltende Additive sind vorzugsweise entsprechende Derivate von Alkyl- oder Alkenyl-substituiertem Bernsteinsäureanhydrid und insbesondere die entsprechenden Derivate von Polyisobutenylbernsteinsäureanhydrid, welche durch Umsetzung von konventionellem oder hochreaktivem Polyisobuten mit Mn = 300 bis 5000 mit Maleinsäureanhydrid auf thermischem Weg oder über das chlorierte Polyisobuten erhältlich sind. Von besonderem Interesse sind hierbei Derivate mit aliphatischen Polyaminen wie Ethylendiamin, Diethylentriamin, Triethylentetramin oder Tetraethylenpentamin. Bei den Gruppierungen mit Hydroxy- und/oder Amino- und/oder Amido- und/oder Imidogruppen handelt es sich beispielsweise um Carbonsäuregruppen, Säureamide von Monoaminen, Säureamide von Di- oder Polyaminen, die neben der Amidfunktion noch freie Amingruppen aufweisen, Bernsteinsäurederivate mit einer Säure- und einer Amidfunktion, Carbonsäureimide mit Monoaminen, Carbonsäureimide mit Di- oder Polyaminen, die neben der Imidfunktion noch freie Amingruppen aufweisen, oder Diimide, die durch die Umsetzung von Di- oder Polyaminen mit zwei Bernsteinsäurederivaten gebildet werden. Derartige Kraftstoffadditive sind insbesondere in US-A-4 849 572 beschrieben. Durch Mannich-Umsetzung von substituierten Phenolen mit Aldehyden und Mono- oder Polyaminen erzeugte Gruppierungen (i) enthaltende Additive sind vorzugsweise Umsetzungsprodukte von Polyisobuten-substituierten Phenolen mit Formaldehyd und Mono- oder Polyaminen wie Ethylendiamin, Diethylentriamin, Triethylentetramin, Tetraethylenpentamin oder 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.Succinic anhydride-derived groupings containing hydroxyl and / or amino and / or amido and / or imido groups (h) are preferably corresponding derivatives of alkyl- or alkenyl-substituted succinic anhydride and especially the corresponding derivatives of polyisobutenyl succinic anhydride prepared by reacting Conventional or highly reactive polyisobutene with Mn = 300 to 5000 with maleic anhydride by thermal means or via the chlorinated polyisobutene are available. Of particular interest here are derivatives with aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. The groups having hydroxyl and / or amino and / or amido and / or imido groups are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of diamines or polyamines which, in addition to the amide function, still have free amine groups, succinic acid derivatives with a Acid and an amide, Carbonsäureimide with monoamines, Carbonsäureimide with di- or polyamines, which still have free amine groups in addition to the imide function, or diimides, which are formed by the reaction of di- or polyamines with two succinic acid derivatives. Such fuel additives are particularly in U.S. Patent 4,849,572 described. By Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated groupings (i) containing additives are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine. The polyisobutenyl-substituted phenols can be derived from conventional or highly reactive polyisobutene having Mn = 300 to 5,000. Such "polyisobutene-Mannich bases" are particularly in the EP-A-831 141 described.

Zur genaueren Definition der einzelnen aufgeführten Kraftstoffadditive wird hier auf die Offenbarungen der oben genannten Schriften des Stands der Technik ausdrücklich Bezug genommen.For a more detailed definition of the individual listed fuel additives is hereby made to the disclosures of the above-mentioned documents of the prior art express reference.

Besonders bevorzugt sind Detergens-Additive aus der Gruppe (h). Hierbei handelt es sich vorzugsweise um die Umsetzungsprodukte von Alkyl- oder Alkenyl-substituierten Bernsteinsäureanhydriden, insbesondere von Polyisobutenylbernsteinsäureanhydriden, mit Aminen. Es versteht sich von selbst, dass diese Umsetzungsprodukte nicht nur bei Einsatz von substituiertem Bernsteinsäureanhydrid, sondern auch bei Verwendung von substituierter Bernsteinsäure oder geeigneten Säurederivaten, wie Bernsteinsäurehalogenide oder -ester, erhältlich sind.Particularly preferred are detergent additives from group (h). These are preferably the reaction products of alkyl- or alkenyl-substituted succinic anhydrides, in particular of polyisobutenylsuccinic anhydrides, with amines. It goes without saying that these reaction products are obtainable not only when substituted succinic anhydride is used, but also when substituted succinic acid or suitable acid derivatives such as succinic acid halides or esters are used.

Besonders bevorzugte Detergens-Additive sind Polyisobutenyl-substituierte Bernsteinsäureimide, speziell die Imide mit aliphatischen Polyaminen. Besonders bevorzugte Polyamine sind dabei Diethylentriamin, Tetraethylenpentamin und Pentaethylenhexamin, wobei Tetraethylenpentamin besonders bevorzugt ist. Der Polyisobutenylrest besitzt ein zahlenmittleres Molekulargewicht Mn von vorzugsweise 500 bis 5000, besonders bevorzugt von 500 bis 2000 und insbesondere von etwa 1000.Particularly preferred detergent additives are polyisobutenyl-substituted succinimides, especially the imides with aliphatic polyamines. Particularly preferred polyamines are diethylenetriamine, tetraethylenepentamine and pentaethylenehexamine, with tetraethylenepentamine being particularly preferred. The polyisobutenyl radical has a number average molecular weight M n of preferably 500 to 5000, particularly preferably 500 to 2000 and in particular about 1000.

Es versteht sich von selbst, dass die Detergens-Additive allein oder in Kombination mit wenigstens einem der vorstehend genannten Detergens-Additive eingesetzt werden können.It goes without saying that the detergent additives can be used alone or in combination with at least one of the aforementioned detergent additives.

In einer bevorzugten Ausführungsform wird das Detergens-Additiv in Kombination mit wenigstens einem Trägeröl verwendet.In a preferred embodiment, the detergent additive is used in combination with at least one carrier oil.

Trägerölecarrier oils

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 in petroleum processing, such as bright stock or base oils with viscosities such as from class SN 500-2000; but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. It is also useful as a "hydrocrack oil" known and obtained in the refining of mineral oil fraction (Vakuumdestillatschnitt with a boiling range of about 360 to 500 ° C, available from high pressure catalytically hydrogenated and isomerized and dewaxed natural mineral oil). Also suitable are mixtures of the abovementioned mineral carrier oils.

Beispiele für erfindungsgemäß verwendbare synthetische Trägeröle sind ausgewählt unter: Polyolefinen (Polyalphaolefine oder Polyinternalolefine), (Poly)estern, (Poly)alkoxylaten, Polyethern, aliphatischen Polyetheraminen, alkylphenolgestarteten Polyethern, alkylphenolgestarteten Polyetheraminen und Carbonsäureester langkettiger Alkanole.Examples of synthetic carrier oils which can be used according to the invention are selected from: polyolefins (polyalphaolefins or polyinternalolefins), (poly) esters, (poly) alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-initiated polyethers, alkylphenol-initiated polyetheramines and carboxylic esters of long-chain alkanols.

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 having Mn = 400 to 1800, especially based on polybutene or polyisobutene (hydrogenated or non-hydrogenated).

Beispiele für 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 EP-A-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. Typische Beispiele hierfür sind Tridecanol- oder Isotridecanolbutoxylate, Isononylphenolbutoxylate sowie Polyisobutenolbutoxylate und -propoxylate sowie die entsprechenden Umsetzungsprodukte mit Ammoniak.Examples of suitable polyethers or polyetheramines are preferably polyoxy-C 2 -C 4 -alkylene group-containing compounds 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 used in particular EP-A-310 875 . EP-A-356 725 . EP-A-700 985 and US-A-4,877,416 described. For example, as polyetheramines, poly-C 2 -C 6 alkylene oxide amines or functional derivatives thereof can be used. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobutenolbutoxylate 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, as are described in particular in US Pat DE-A-38 38 918 are described. As mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 C atoms. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and Isotridecanols, such as. As di (n- or iso-tridecyl) 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 , to which reference is expressly made.

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 und Nonylphenol.Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers with about 5 to 35, such as. B. about 5 to 30, C 3 -C 6 alkylene oxide, such as. B. selected from propylene oxide, n-butylene oxide and i-butylene oxide units, or mixtures thereof. Nonlimiting examples of 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. Preferred examples are tridecanol and nonylphenol.

Weitere geeignete synthetische Trägeröle sind alkoxylierte Alkylphenole, wie sie in der DE-A-10 102 913.6 beschrieben sind.Other suitable synthetic carrier oils are alkoxylated alkylphenols, as described in the DE-A-10 102 913.6 are described.

Bevorzugte Trägeröle sind synthetische Trägeröle, wobei Polyether besonders bevorzugt sind.Preferred carrier oils are synthetic carrier oils, with polyethers being particularly preferred.

Das Detergens-Additiv, gegebenenfalls in Kombination mit einem Trägeröl, wird dem Einspritzsystem vorzugsweise mit dem Dieselkraftstoff zugeführt.The detergent additive, optionally in combination with a carrier oil, is preferably supplied to the injection system with the diesel fuel.

Dabei wird dem Dieselkraftstoff das Detergens-Additiv bzw. das Gemisch verschiedener Detergens-Additive in einer Menge von vorzugsweise 10 bis 2000 Gew.-ppm, besonders bevorzugt von 20 bis 1000 Gew.-ppm, stärker bevorzugt von 50 bis 500 Gew.-ppm und insbesondere von 50 bis 200 Gew.-ppm, z.B. von 70 bis 150 Gew.-ppm, zugegeben.In this case, the diesel fuel, the detergent additive or the mixture of various detergent additives in an amount of preferably 10 to 2000 ppm by weight, more preferably from 20 to 1000 ppm by weight, more preferably from 50 to 500 ppm by weight and in particular from 50 to 200 ppm by weight, eg from 70 to 150 ppm by weight, added.

Wenn ein Trägeröl verwendet wird, so wird dieses dem Dieselkraftstoff in einer Menge von vorzugsweise 1 bis 1000 Gew.-ppm, besonders bevorzugt von 10 bis 500 Gew.-ppm und insbesondere von 20 bis 100 Gew.-ppm zugesetzt.When a carrier oil is used, it is added to the diesel fuel in an amount of preferably from 1 to 1000 ppm by weight, more preferably from 10 to 500 ppm by weight, and more preferably from 20 to 100 ppm by weight.

Außerdem kann der Dieselkraftstoff weitere übliche Coadditive enthalten, wie Kaltfließverbesserer, Korrosionsinhibitoren, Demulgatoren, Dehazer, Antischaummittel, Cetanzahlverbesserer, Verbrennungsverbesserer, Antioxidantien oder Stabilisatoren, Antistatika, Metallocene, Farbstoffe und dergleichen.In addition, the diesel fuel may contain other conventional co-additives, such as cold flow improvers, corrosion inhibitors, demulsifiers, dehazers, defoamers, cetane improvers, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, dyes, and the like.

Diese üblichen Coadditive werden, wenn gewünscht, in hierfür üblichen Mengen zugesetzt.These conventional co-additives are added, if desired, in customary amounts.

DieselkraftstoffeDiesel fuels

Bei den Dieselkraftstoffen handelt es sich beispielsweise um Erdölraffinate, die üblicherweise einen Siedebereich von 100 bis 400 °C haben. Dies sind meist Destillate mit einem 95%-Punkt bis zu 360 °C oder auch darüber hinaus. Dies können aber auch so genannte "Ultra Low Sulfur Diesel" oder "City Diesel" sein, gekennzeichnet durch einen 95%-Punkt von beispielsweise maximal 345 °C und einem Schwefelgehalt von maximal 0,005 Gew.-% oder durch einen 95%-Punkt von beispielsweise 285 °C und einem Schwefelgehalt von maximal 0,001 Gew.-%. Neben den durch Raffination erhältlichen Dieselkraftstoffen sind solche, die durch Kohlevergasung oder Gasverflüssigung ("gas to liquid" (GTL) Kraftstoffe) erhältlich sind, geeignet. Geeignet sind auch Mischungen der vorstehend genannten Dieselkraftstoffe mit regenerativen Kraftstoffen, wie Biodiesel oder Bioethanol.The diesel fuels are, for example, petroleum raffinates, which usually have a boiling range of 100 to 400 ° C. These are mostly distillates with a 95% point up to 360 ° C or even beyond. However, these may also be so-called "Ultra Low Sulfur Diesel" or "City Diesel", characterized by a 95% point of, for example, a maximum of 345 ° C and a maximum sulfur content of 0.005 wt .-% or by a 95% point of for example, 285 ° C and a maximum sulfur content of 0.001 wt .-%. In addition to the diesel fuels available through refining, those obtainable by coal gasification or gas liquefaction ("gas to liquid" (GTL) fuels) are suitable. Also suitable are mixtures of the abovementioned diesel fuels with regenerative fuels, such as biodiesel or bioethanol.

Besonders bevorzugt handelt es sich bei den Dieselkraftstoffen um solche mit niedrigem Schwefelgehalt, das heißt mit einem Schwefelgehalt von weniger als 0,05 Gew.-%, vorzugsweise von weniger als 0,02 Gew.-%, insbesondere von weniger als 0,005 Gew.-% und speziell von weniger als 0,001 Gew.-% Schwefel.The diesel fuels are particularly preferably those with a low sulfur content, ie with a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, in particular less than 0.005% by weight. % and especially less than 0.001% by weight of sulfur.

Durch die erfindungsgemäße Verwendung von Detergens-Additiven wird erreicht, dass in den Abgasemissionen von direkteinspritzenden Dieselmotoren, insbesondere von Dieselmotoren mit einem Common-Rail-Einspritzsystem, nach 100000 km Motorenbetrieb vorzugsweise höchstens die 2,5-fache Menge, besonders bevorzugt höchstens die 2,2-fache Menge und insbesondere höchstens die 2-fache Partikelmenge im Vergleich zu der Werkeinstellung enthalten ist. Insbesondere bleiben dabei die im Ausstoß enthaltenen Partikelmengen deutlich unter dem Grenzwert der Euro 4 Norm. Die angegebenen Werte beziehen sich auf die direkt hinter dem Motor ("engine out") entnommenen Abgasemissionen, d. h. vor einem eventuell eingebauten Partikelfilter, der ja die Partikelmenge im Ausstoß reduzieren würde. Mit Werkeinstellung ist derjenige Zustand des direkteinspritzenden Dieselmotors bzw. des Einspritzsystems gemeint, wie er am Werk, d. h. vor der Auslieferung an die Händler bzw. Endverbraucher, eingestellt ist (sozusagen Kilometer 0). Durch die erfindungsgemäße Verwendung von Detergens-Additiven wird nicht nur eine Einhaltung der Grenzwerte für Partikelemissionen gemäß Euro 4 Norm auch ohne zusätzlichen Partikelfilter über eine Motorlaufzeit von 100000 km gewährleistet, sondern auch für eine deutlich darüber hinaus gehende Betriebszeit.The inventive use of detergent additives ensures that in the exhaust emissions of direct-injection diesel engines, especially diesel engines with a common rail injection system, after 100000 km engine operation preferably at most 2.5 times the amount, more preferably at most 2, 2 times the amount and in particular at most 2 times the amount of particles compared to the factory setting is included. In particular, the quantities of particulates contained in the output remain well below the limit of the Euro 4 standard. The values given refer to the exhaust emissions taken directly after the engine ("engine out"), ie. H. in front of a possibly installed particle filter, which would reduce the amount of particles in the output. By factory setting is meant that state of the direct injection diesel engine or the injection system, as it is at the factory, d. H. before delivery to the dealer or end user (as it were kilometer 0). The use according to the invention of detergent additives not only ensures compliance with the limit values for particle emissions in accordance with the Euro 4 standard, but also without an additional particle filter over an engine running time of 100,000 km, but also for significantly longer operating times.

Beispielexample

Ein Motor mit einem Common-Rail-Einspritzsystem wurde mit einem Dieselkraftstoff gemäß EN 590, der mit 90 Gew.-ppm Kerocom PIBSI (ein Detergens-Additiv der BASF AG, der ein Polyisobutylenbernsteinsäureimid enthält) additiviert war, 70000 km betrieben. Zum Vergleich wurde ein baugleicher Motor mit einem Dieselkraftstoff gemäß EN 590, der kein Detergens-Additiv enthielt, unter gleichen Bedingungen ebenfalls 70000 km betrieben. Die im Ausstoß enthaltenen Partikelmengen wurden direkt hinter dem Motor ("engine out") gemessen. Die Ergebnisse sind in der nachfolgenden Tabelle aufgeführt. Tabelle Dieselkraftstoff Partikelmenge bei 0 km [g/km] Partikelmenge nach 70000 km [g/km] ohne Detergensadditiv 0,008 0,019 mit Detergensadditiv 0,008 0,011 An engine with a common rail injection system was operated with a diesel fuel according to EN 590, which was additized with 90 ppm by weight of Kerocom PIBSI (a detergent additive from BASF AG containing a polyisobutylenesuccinimide), 70,000 km. For comparison, an identical engine with a diesel fuel according to EN 590, which contained no detergent additive, was also operated under identical conditions for 70,000 km. The amounts of particulates in the exhaust were measured directly behind the engine ("engine out"). The results are listed in the table below. table Diesel fuel Particle quantity at 0 km [g / km] Particle quantity after 70,000 km [g / km] without detergent additive 0,008 0.019 with detergent additive 0,008 0.011

Wie die Ergebnisse zeigen, führt die Verwendung von Detergensadditiven zu einer verringerten Partikelmenge in den Abgasen.As the results show, the use of detergent additives leads to a reduced amount of particulates in the exhaust gases.

Claims (6)

Verwendung von Detergens-Additiven zur Verringerung ode Verhinderung der Bildung von Ablagerungen in den Einspritzsystemen von direkteinspritzenden Dieselmotoren.Use of detergent additives to reduce or prevent the formation of deposits in the injection systems of direct-injection diesel engines. Verwendung nach Anspruch 1, zur Verringerung oder Verhinderung der Bildung von Ablagerungen in Common-Rail-Einspritzsystemen.Use according to claim 1 for reducing or preventing the formation of deposits in common rail injection systems. Verwendung nach einem der vorhergehenden Ansprüche, wobei es sich bei den Detergens-Additiven um die Umsetzungsprodukte von Alkyl- oder Alkenyl-substituierten Bernsteinsäuren oder Derivaten davon mit Aminen handelt.Use according to any one of the preceding claims, wherein the detergent additives are the reaction products of alkyl- or alkenyl-substituted succinic acids or derivatives thereof with amines. Verwendung nach Anspruch 3, wobei es sich bei den Detergens-Additiven um Polyisobutenyl-substituierte Bernsteinsäureimide handelt.Use according to claim 3, wherein the detergent additives are polyisobutenyl-substituted succinimides. Verwendung nach einem der vorhergehenden Ansprüche, wobei die Detergens-Additive in Kombination mit wenigstens einem Trägeröl verwendet werden.Use according to any one of the preceding claims, wherein the detergent additives are used in combination with at least one carrier oil. Verwendung nach einem der vorhergehenden Ansprüche, wobei die in den Abgasemissionen der Dieselmotoren enthaltene und direkt hinter dem Motor gemessene Partikelmenge nach 100000 km Motorenbetrieb um einen Faktor von höchstens 2,5 höher ist als bei der Werkeinstellung und gleichzeitig der Grenzwert für die Partikelmenge der Euro 4 Norm nicht überschritten wird.Use according to one of the preceding claims, wherein the particle quantity contained in the exhaust emissions of the diesel engines and measured directly behind the engine is higher by a factor of at most 2.5 after 100000 km engine operation than at the factory setting and at the same time the limit value for the particle quantity of the Euro 4 Standard is not exceeded.
EP05006599A 2005-03-24 2005-03-24 Use of detergent additives to inhibit or reduce the formation of injection system deposits in direct injection diesel engines Withdrawn EP1705234A1 (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
EP05006599A EP1705234A1 (en) 2005-03-24 2005-03-24 Use of detergent additives to inhibit or reduce the formation of injection system deposits in direct injection diesel engines
AR20060101031A AR054240A1 (en) 2005-03-24 2006-03-16 USE OF DETERGENT ADDITIVES TO REDUCE THE AMOUNT OF PARTICLES IN THE EXHAUST GAS EMISSIONS OF DIRECT INJECTION DIESEL ENGINES
BRPI0609694-8A BRPI0609694A2 (en) 2005-03-24 2006-03-23 use of an additive composition
JP2008502332A JP2008534699A (en) 2005-03-24 2006-03-23 Use of cleaning additives to reduce particulate content in exhaust gas emissions of direct injection diesel engines.
US11/909,183 US20080196586A1 (en) 2005-03-24 2006-03-23 Use of Detergent Additives For Reducing a Particle Amount in the Exhaust Gas of Direct Injection Diesel Engines
AU2006226517A AU2006226517B2 (en) 2005-03-24 2006-03-23 Use of detergent additives for reducing a particle amount in the exhaust gas of direct injection diesel engines
CNA2006800094515A CN101146897A (en) 2005-03-24 2006-03-23 Use of detergent additives for reducing a particle amount in the exhaust gas of direct injection diesel engines
MX2007010950A MX2007010950A (en) 2005-03-24 2006-03-23 Use of detergent additives for reducing a particle amount in the exhaust gas of direct injection diesel engines.
EP06723673A EP1866396A1 (en) 2005-03-24 2006-03-23 Use of detergent additives for reducing a particle amount in the exhaust gas of direct injection diesel engines
KR1020077024495A KR20070116149A (en) 2005-03-24 2006-03-23 Use of detergent additives for reducing a particle amount in the exhaust gas of direct injection diesel engines
PCT/EP2006/002686 WO2006100083A1 (en) 2005-03-24 2006-03-23 Use of detergent additives for reducing a particle amount in the exhaust gas of direct injection diesel engines
CA002602275A CA2602275A1 (en) 2005-03-24 2006-03-23 Use of detergent additives for reducing a particle amount in the exhaust gas of direct injection diesel engines
NO20074587A NO20074587L (en) 2005-03-24 2007-09-11 Use of additives to reduce particulate matter in exhaust gas from direct injection diesel engines

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP05006599A EP1705234A1 (en) 2005-03-24 2005-03-24 Use of detergent additives to inhibit or reduce the formation of injection system deposits in direct injection diesel engines

Publications (1)

Publication Number Publication Date
EP1705234A1 true EP1705234A1 (en) 2006-09-27

Family

ID=34934523

Family Applications (2)

Application Number Title Priority Date Filing Date
EP05006599A Withdrawn EP1705234A1 (en) 2005-03-24 2005-03-24 Use of detergent additives to inhibit or reduce the formation of injection system deposits in direct injection diesel engines
EP06723673A Withdrawn EP1866396A1 (en) 2005-03-24 2006-03-23 Use of detergent additives for reducing a particle amount in the exhaust gas of direct injection diesel engines

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP06723673A Withdrawn EP1866396A1 (en) 2005-03-24 2006-03-23 Use of detergent additives for reducing a particle amount in the exhaust gas of direct injection diesel engines

Country Status (12)

Country Link
US (1) US20080196586A1 (en)
EP (2) EP1705234A1 (en)
JP (1) JP2008534699A (en)
KR (1) KR20070116149A (en)
CN (1) CN101146897A (en)
AR (1) AR054240A1 (en)
AU (1) AU2006226517B2 (en)
BR (1) BRPI0609694A2 (en)
CA (1) CA2602275A1 (en)
MX (1) MX2007010950A (en)
NO (1) NO20074587L (en)
WO (1) WO2006100083A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009040582A1 (en) 2007-09-27 2009-04-02 Innospec Limited Fuel compositions
WO2009040586A1 (en) * 2007-09-27 2009-04-02 Innospec Limited Additives for diesel engines
WO2009040584A1 (en) * 2007-09-27 2009-04-02 Innospec Limited Fuel compositions
WO2009040583A1 (en) * 2007-09-27 2009-04-02 Innospec Limited Fuel compositions
WO2009040585A1 (en) * 2007-09-27 2009-04-02 Innospec Limited Fuel compositions
WO2009130308A1 (en) * 2008-04-25 2009-10-29 Basf Se Use of detergent additives in combination with carrier oils for lowering the fuel consumption of direct injection diesel engines

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE482919T1 (en) * 2007-01-29 2010-10-15 Basf Se BRANCHED DECYL NITRATES AND THEIR USE AS COMBUSTION IMPROVERS AND/OR CETANE NUMBER IMPROVERS IN FUELS
US8292976B2 (en) * 2009-11-06 2012-10-23 Afton Chemical Corporation Diesel fuel additive for reducing emissions
JP2013529232A (en) 2010-04-27 2013-07-18 ビーエーエスエフ ソシエタス・ヨーロピア Quaternized terpolymer
US8790426B2 (en) 2010-04-27 2014-07-29 Basf Se Quaternized terpolymer
US8911516B2 (en) 2010-06-25 2014-12-16 Basf Se Quaternized copolymer
BR112012032534A2 (en) 2010-06-25 2019-09-24 Basf Se quaternized copolymer, process for preparing a combustible quaternized copolymer and use of a quaternized copolymer
EP2604674A1 (en) * 2011-12-12 2013-06-19 Basf Se Use of quaternised alkylamine as additive in fuels and lubricants
ES2964334T3 (en) * 2018-01-30 2024-04-05 Dorf Ketal Chemicals Fze Additive that improves performance for a fuel composition and procedure for using it
MX2021008204A (en) * 2019-01-10 2021-08-11 Evonik Operations Gmbh Organomodified polysiloxanes and their use for defoaming fuels.

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995010582A1 (en) * 1993-10-13 1995-04-20 Exxon Chemical Patents Inc. Fuel additives
WO2003091364A2 (en) * 2002-04-25 2003-11-06 Shell Internationale Research Maatschappij B.V. Diesel fuel compositions
DE10239841A1 (en) * 2002-08-29 2004-03-11 Basf Ag Fuel and lubricant additive mixture, especially for reducing fuel injector coke deposits in diesel engines and reducing corrosive action of fuels, comprises (partially) neutralized fatty acid and detergent

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3471458A (en) * 1966-12-16 1969-10-07 Chevron Res Polyimides of olefin-maleic anhydride copolymers as diesel fuel additives
JPH02147496A (en) * 1988-11-30 1990-06-06 Sanshin Ind Co Ltd Cowling of vessel propulsive machine
DE4020664A1 (en) * 1990-06-29 1992-01-02 Basf Ag FUELS CONTAINING ESTER FOR OTTO ENGINES AND DIESEL ENGINES
EP0482253A1 (en) * 1990-10-23 1992-04-29 Ethyl Petroleum Additives Limited Environmentally friendly fuel compositions and additives therefor
US6255258B1 (en) * 1998-11-04 2001-07-03 Infineum Usa L.P. Dispersant additive
US6284717B1 (en) * 1998-12-22 2001-09-04 Infineum Usa L.P. Dispersant additives
DE19908262A1 (en) * 1999-02-25 2000-08-31 Basf Ag Polyalkene alcohol polyalkoxylates and their use in fuels and lubricants
IT1308412B1 (en) * 1999-03-05 2001-12-17 Fiat Ricerche METHOD OF COMBUSTION CONTROL OF A DIRECT INJECTION DIESEL ENGINE THROUGH THE IMPLEMENTATION OF MULTIPLE INJECTIONS USING A SYSTEM
DE10021936A1 (en) * 2000-05-05 2001-11-08 Basf Ag Fuel additive composition comprises a detergent additive, a carrier oil mixture consisting of a synthetic carrier oil and a mineral carrier oil, and optionally further fuel additive components
US20040068922A1 (en) * 2002-02-13 2004-04-15 Barbour Robert H. Fuel additive composition and fuel composition and method thereof
GB0127953D0 (en) * 2001-11-21 2002-01-16 Shell Int Research Diesel fuel compositions
US6652667B2 (en) * 2002-01-23 2003-11-25 Chevron Oronite Company Llc Method for removing engine deposits in a gasoline internal combustion engine
US6616776B1 (en) * 2002-11-06 2003-09-09 Chevron Oronite Company Llc Method for removing engine deposits in a reciprocating internal combustion engine
DE10209830A1 (en) * 2002-03-06 2003-09-18 Basf Ag Fuel additive mixtures for petrol with synergistic IVD performance
EP1344812A1 (en) * 2002-03-13 2003-09-17 Infineum International Limited Overbased metallic salt diesel fuel additive compositions for improvement of particulate traps
US20040118036A1 (en) * 2002-12-20 2004-06-24 Graskow Brian R. Method of reducing particulate emissions in internal combustion engines
US20040261313A1 (en) * 2003-06-25 2004-12-30 The Lubrizol Corporation, A Corporation Of The State Of Ohio Gel additives for fuel that reduce soot and/or emissions from engines
US7744661B2 (en) * 2005-05-13 2010-06-29 Chevron Oronite Company Llc Fuel composition containing an alkylene oxide-adducted hydrocarbyl amide having reduced amine by-products

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995010582A1 (en) * 1993-10-13 1995-04-20 Exxon Chemical Patents Inc. Fuel additives
WO2003091364A2 (en) * 2002-04-25 2003-11-06 Shell Internationale Research Maatschappij B.V. Diesel fuel compositions
DE10239841A1 (en) * 2002-08-29 2004-03-11 Basf Ag Fuel and lubricant additive mixture, especially for reducing fuel injector coke deposits in diesel engines and reducing corrosive action of fuels, comprises (partially) neutralized fatty acid and detergent

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2008303345B2 (en) * 2007-09-27 2013-05-30 Innospec Limited Fuel compositions
WO2009040584A1 (en) * 2007-09-27 2009-04-02 Innospec Limited Fuel compositions
AU2008303344B2 (en) * 2007-09-27 2013-06-13 Innospec Limited Fuel compositions
RU2487924C2 (en) * 2007-09-27 2013-07-20 Инноспек Лимитед Fuel composition
WO2009040585A1 (en) * 2007-09-27 2009-04-02 Innospec Limited Fuel compositions
WO2009040582A1 (en) 2007-09-27 2009-04-02 Innospec Limited Fuel compositions
US20100258070A1 (en) * 2007-09-27 2010-10-14 Innospec Limited Fuel compositions
CN101874101A (en) * 2007-09-27 2010-10-27 因诺斯佩克有限公司 Fuel compositions
CN102007203A (en) * 2007-09-27 2011-04-06 因诺斯佩克有限公司 Diesel fuel compositions
CN102037104A (en) * 2007-09-27 2011-04-27 因诺斯佩克有限公司 Fuel compositions
GB2453248B (en) * 2007-09-27 2011-11-23 Innospec Ltd Fuel compositions
AU2008303343B2 (en) * 2007-09-27 2013-04-04 Innospec Limited Fuel compositions
EP3492562A1 (en) * 2007-09-27 2019-06-05 Innospec Limited Fuel compositions
WO2009040586A1 (en) * 2007-09-27 2009-04-02 Innospec Limited Additives for diesel engines
WO2009040583A1 (en) * 2007-09-27 2009-04-02 Innospec Limited Fuel compositions
RU2488628C2 (en) * 2007-09-27 2013-07-27 Инноспек Лимитед Fuel composition
RU2489477C2 (en) * 2007-09-27 2013-08-10 Инноспек Лимитед Fuel composition
US8715375B2 (en) 2007-09-27 2014-05-06 Innospec Limited Fuel compositions
CN102007203B (en) * 2007-09-27 2014-06-25 因诺斯佩克有限公司 Diesel fuel compositions
CN102037104B (en) * 2007-09-27 2014-12-31 因诺斯佩克有限公司 Fuel compositions
US9034060B2 (en) 2007-09-27 2015-05-19 Innospec Fuel Specialties Llc Additives for diesel engines
US9157041B2 (en) 2007-09-27 2015-10-13 Innospec Limited Fuel compositions
US9163190B2 (en) 2007-09-27 2015-10-20 Innospec Limited Fuel compositions
US9243199B2 (en) 2007-09-27 2016-01-26 Innospec Limited Fuel compositions
US9315752B2 (en) 2007-09-27 2016-04-19 Innospec Limited Fuel compositions
WO2009130308A1 (en) * 2008-04-25 2009-10-29 Basf Se Use of detergent additives in combination with carrier oils for lowering the fuel consumption of direct injection diesel engines

Also Published As

Publication number Publication date
CA2602275A1 (en) 2006-09-28
AU2006226517A1 (en) 2006-09-28
NO20074587L (en) 2007-10-23
WO2006100083A1 (en) 2006-09-28
BRPI0609694A2 (en) 2011-10-18
KR20070116149A (en) 2007-12-06
EP1866396A1 (en) 2007-12-19
JP2008534699A (en) 2008-08-28
CN101146897A (en) 2008-03-19
AU2006226517B2 (en) 2011-12-01
US20080196586A1 (en) 2008-08-21
MX2007010950A (en) 2007-09-21
AR054240A1 (en) 2007-06-13

Similar Documents

Publication Publication Date Title
EP1705234A1 (en) Use of detergent additives to inhibit or reduce the formation of injection system deposits in direct injection diesel engines
EP2270119B1 (en) Fuel composition
EP2114844B1 (en) Branched decyl nitrates and the use thereof as combustion improvers and/or cetane number improvers in fuels
EP2726580B1 (en) Quaternised nitrogen compounds and their use as additives in fuels and lubricants
EP1399490B1 (en) Method of producing polyisobutenylsuccinimide products, polyisobutenylsuccinimide products with improved properties, intermediate products and the use thereof
EP1155102A1 (en) Fuel composition
EP3099769A1 (en) Polymers as additives for fuels and lubricants
EP2585498B1 (en) Quaternized copolymer
EP2604674A1 (en) Use of quaternised alkylamine as additive in fuels and lubricants
EP1786888A1 (en) Heterocyclic compounds containing nitrogen as a fuel additive in order to reduce abrasion
EP1278814B1 (en) Fuel additive compositions for fuels for internal combustion engines with improved viscosity properties and good ivd performance
WO2011134923A1 (en) Quaternized terpolymer
EP2240519A1 (en) Special polyisobutene amines, and use thereof as detergents in fuels
EP2811007A1 (en) Alkylene oxide and hydrocarbyl-substituted polycarboxylic acid quaternised alkylamine as additives in fuels and lubricants and their use
WO2004024851A1 (en) Additive mixture for fuel and lubricants
EP2646530B1 (en) Use of the product of reaction of a hydrocarbyl substituted dicarboxylic acid and a nitrogen compound to reduce fuel consumption.
WO2009130308A1 (en) Use of detergent additives in combination with carrier oils for lowering the fuel consumption of direct injection diesel engines
WO2018188982A1 (en) Alkoxylated amines as fuel additives
DE102010039039A1 (en) Use of an organic compound as a fuel additive to reduce the fuel consumption of diesel engines, preferably direct-injection diesel engines, with common rail injection systems
DE10109260A1 (en) Fuel additive for spark-ignition engines, useful for increasing motor octane number, comprises high molecular weight polyalkene and detergent additive
EP3933014A1 (en) Addition of additives to fuel for reducing uncontrolled ignition in combustion engines
DE102010001408A1 (en) Use of ketone compounds as a fuel additive to reduce the fuel consumption of diesel engines, preferably direct injection diesel engines, and diesel engines with common rail injection systems

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR LV MK YU

AKX Designation fees paid
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20070328

REG Reference to a national code

Ref country code: DE

Ref legal event code: 8566