WO2006100083A1 - Use of detergent additives for reducing a particle amount in the exhaust gas of direct injection diesel engines - Google Patents

Use of detergent additives for reducing a particle amount in the exhaust gas of direct injection diesel engines Download PDF

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Publication number
WO2006100083A1
WO2006100083A1 PCT/EP2006/002686 EP2006002686W WO2006100083A1 WO 2006100083 A1 WO2006100083 A1 WO 2006100083A1 EP 2006002686 W EP2006002686 W EP 2006002686W WO 2006100083 A1 WO2006100083 A1 WO 2006100083A1
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Prior art keywords
diesel engines
additives
detergent additives
reducing
groups
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PCT/EP2006/002686
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German (de)
French (fr)
Inventor
Jörn KARL
Georg Schäper
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Basf Aktiengesellschaft
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Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to MX2007010950A priority Critical patent/MX2007010950A/en
Priority to JP2008502332A priority patent/JP2008534699A/en
Priority to EP06723673A priority patent/EP1866396A1/en
Priority to US11/909,183 priority patent/US20080196586A1/en
Priority to BRPI0609694-8A priority patent/BRPI0609694A2/en
Priority to AU2006226517A priority patent/AU2006226517B2/en
Priority to CA002602275A priority patent/CA2602275A1/en
Publication of WO2006100083A1 publication Critical patent/WO2006100083A1/en
Priority to NO20074587A priority patent/NO20074587L/en

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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
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    • C10L1/00—Liquid carbonaceous fuels
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    • 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
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    • 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
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    • 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
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    • C10L1/00—Liquid carbonaceous fuels
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    • 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
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    • 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
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    • 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
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • 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
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    • 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
    • C10L1/22—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
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    • 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
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    • 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 the amount of particulates in the exhaust emissions of direct injection diesel engines and more particularly diesel engines with 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 of up to 2000 bar into a high-pressure line, the common rail (literally "common line”). injecting the fuel directly into the combustion chamber, where full pressure is always available on the common rail, allowing for multiple injection or a special injection mode, while the other injection systems only allow one injection
  • the fuel is usually not burned, 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 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.
  • 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 an additive composition consisting of at least one detergent additive and optionally at least one Carrier oil for reducing the amount of particulates in exhaust emissions from direct-injection diesel engines.
  • direct-injection diesel engines are those with common-rail injection systems.
  • the reduction of particulate emissions is attributed, inter alia, to reducing or preventing the formation of deposits, particularly in the injectors.
  • the detergent additives are preferably amphiphilic substances which have 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 group selected from:
  • Polyamino groups wherein at least one nitrogen atom has basic properties, or terminated by carbamate groups;
  • the hydrophobic hydrocarbon radical in the above detergent additives which provides the sufficient solubility in the fuel, has a number average molecular weight (Mn) of 85 to 20,000, especially from 113 to 10,000, especially from 300 to 5000.
  • Mn number average molecular weight
  • As a typical hydrophobic hydrocarbon radical, in particular in connection with the polar groupings (a), (c), (h) and (i), longer-chain alkyl or alkenyl groups, in particular the polypropenyl, polybutenyl and polyisobutenyl radicals each having Mn 300 to 5000, in particular 500 to 2500, come , especially 700 to 2300, into consideration.
  • polypropene or conventional (ie, with predominantly central double bonds) polybutene or polyisobutene with Mn 300 to 5000.
  • the preparation route by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to carbonyl or carboxyl compound and subsequent amination under reductive (hydrogenating ) Conditions.
  • amines such as.
  • ammonia monoamines or polyamines, such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, are used.
  • Corresponding additives based on polypropene are described in particular in WO-A-94/24231.
  • monoamino groups (a) containing additives are the polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols obtainable compounds, as described in particular in DE-A-196 20 262.
  • these reaction products are mixtures of pure nitropolyisobutenes (for example ⁇ , ⁇ -dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (for example ⁇ -nitro- ⁇ -hydroxy-polyisobutene).
  • 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 known in particular from EP-A-307 815.
  • Such additives are primarily used to prevent valve seat wear and, as described in WO-A-87/01126, can be advantageously used in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.
  • Sulphonic 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 sulfosuccinic acid alkyl ester, as described in particular in EP-A-639 632.
  • 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 polyether or polyetheramines, which by reaction of C 2 -C 60 alkanols, C 6 -C 30 alkanediols, mono- or di-C 2 - C 3 o-alkylamines, CrCao-Alkylcyclohexanolen or CrC 3 o-alkylphenols with 1 to 30 moles 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 described in particular in EP-A-310 875, EP-A-356 725, EP-A-700 985 and US-A-4 877 416.
  • polyethers such products also meet carrier oil properties. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxyl- late 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, especially those having a minimum viscosity of 2 tnm 2 / s at 100 0 C, as described in particular in 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 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 more particularly described in US-A-4,849,572.
  • 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 described in particular in EP-A-831 141.
  • detergent additives from group (h) are preferably the reaction products of alkyl- or alkenyl-substituted succinic anhydrides, in particular 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, more preferably from 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. Also useful is a fraction known as "hydrocrack oil” and derived from the refining of mineral oil (vacuum distillate cut having 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 polyethylenemolefins), (poly) esters, (poly) alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-initiated polyethers, alkylphenol-initiated polyetheramines and carboxylic acid 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 6 -alkanols, C 6 -C 30 -alkanediols, mono- or di-C 2 -C 3 o-alkylamines, CrCao-alkylcyclohexanols or C r C 3 o-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 described in particular in EP-A-310 875, EP-A-356 725, EP-A-700 985 and US-A-4,877,416.
  • 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 Polyisobute- nolbutoxylate 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 described in particular in DE-A-38 38 918.
  • 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.
  • suitable representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and Isotridecanols, such as.
  • di (n- or iso-tridecyl) phthalate 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 e -C 8 -alkyl radical.
  • Preferred examples are tridecanol and nonylphenol.
  • suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A-10 102 913.6.
  • 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 additive, 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 wt. - ppm 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 1 to 1000 ppm by weight, more preferably 10 to 500 ppm by weight, and more preferably 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 number improvers, combustion improvers, antioxidants or stabilizers, antistatics, metallocenes, metal deactivators, dyes, solvents, and the like. It is believed that the use of these additives has essentially no effect on the reduction of particulate emissions.
  • Suitable cold flow improvers are e.g. Copolymers of ethylene with at least one other ethylenically unsaturated monomer, e.g. Ethylene / vinyl acetate copolymers.
  • Suitable corrosion inhibitors are e.g. Succinic esters, especially with polyols, fatty acid derivatives, e.g. Oleic acid esters, oligomerized fatty acids, substituted ethanolamines and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany) or HiTEC 536 (Ethyl Corporation).
  • Suitable demulsifiers are, for example, the alkali metal or alkaline earth metal salts of alkyl-substituted phenol and naphthalenesulfonates and the alkali metal or alkaline earth metal salts of fatty acids, furthermore neutral compounds, such as alcohol alkoxylates, for example alcohol ethoxylates, phenol alkoxylates, for example tert-butylphenol ethoxylate or tert-pentylphenol ethoxylate , Fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), for example in the form of EO / PO block copolymers, polyethyleneimines or else polysiloxanes.
  • EO ethylene oxide
  • PO propylene oxide
  • Suitable dehazers are, for example, alkoxylated phenol-formaldehyde condensates, such as, for example, the products NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite) available under the trade name.
  • Suitable antifoams are e.g. Polyether-modified polysiloxanes, such as the products available under the trade name TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc).
  • Suitable cetane number improvers are e.g. aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate, and peroxides such as di-tert-butyl peroxide.
  • Suitable antioxidants are e.g. substituted phenols such as 2,6-di-tert-butylphenol and, 6-di-tert-butyl-3-methylphenol, and phenylenediamines such as N, N'-di-sec-butyl-p-phenylenediamine.
  • Suitable metal deactivators are e.g. Salicylic acid derivatives, such as N, N'-disalicylidene-1, 2-propanediamine.
  • Suitable solvents are e.g. non-polar organic solvents, such as aromatic and aliphatic hydrocarbons, for example, toluene, the xylene, "white spirit" and products sold under the trade name SHELLSOL (Royal Dutch / Shell Group) and EXXSOL (ExxonMobil), and polar organic solvents, for example alcohols such as 2-ethylhexanol, decanol and isotridecanol.
  • non-polar organic solvents such as aromatic and aliphatic hydrocarbons, for example, toluene, the xylene, "white spirit" and products sold under the trade name SHELLSOL (Royal Dutch / Shell Group) and EXXSOL (ExxonMobil)
  • polar organic solvents for example alcohols such as 2-ethylhexanol, decanol and isotridecanol.
  • Preferred co-additives are demulsifiers, dehazers, defoamers, cetane improvers, antioxidants, metal deactivators, corrosion inhibitors and solvents.
  • the diesel fuels are, for example, crude oil raffinates instruments normally have a boiling range of 100 to 400 0 C. These are mostly distillates with a 95% point up to 360 0 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 0 C and a maximum sulfur content of 0.005 wt .-% or by a 95% point of for example, 285 0 C and a maximum sulfur content of 0.001 wt .-%.
  • Diesel fuels are those obtainable by coal gasification or gas liquefaction ("gas to liquid” (GTL) fuels). Also suitable are 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, the increase in the amount of particulates is significantly lower than in the exhaust emissions of direct-injection diesel engines, which without the Use of detergent additives are operated.
  • it is achieved that after 100,000 km of 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 is included in comparison to the factory setting.
  • 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 before any particulate filter that may have been installed, which would reduce the amount of particulate matter in the exhaust. as it is set at the factory, ie before delivery to the dealer or end user (kilometer 0, as it were)
  • the use according to the invention of detergent additives not only ensures compliance with the limit values for particulate emissions in accordance with Euro 4 standard, but also without additional fuel Particle filter over an engine running time of 100000 km guaranteed, but also for a much longer operating time.
  • 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 polyisobutylene succinimide), 70,000 km.
  • Kerocom PIBSI a detergent additive from BASF AG containing a polyisobutylene succinimide
  • 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 contained in the discharge were directly behind the Engine out, and the results are shown in the table below.

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Abstract

The invention relates to using detergent additives for reducing a particle amount in the exhaust gas of direct injection diesel engines, in particular, in diesel engines provided a common rail injection system.

Description

Verwendung von Detergens-Additiven zur Verringerung der Partikelmenge in Abgasemissionen von direkteinspritzenden DieselmotorenUse of detergent additives to reduce the amount of particulates in exhaust emissions from direct injection diesel engines
Beschreibungdescription
Die vorliegende Erfindung betrifft die Verwendung von Detergens-Additiven zur Verringerung der Partikelmenge in den Abgasemissionen von direkteinspritzenden Dieselmotoren und insbesondere von Dieselmotoren mit Common-Rail-Einspritzsystemen.The present invention relates to the use of detergent additives to reduce the amount of particulates in the exhaust emissions of direct injection diesel engines and more particularly diesel engines with common rail injection systems.
Bei 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 Pumpe- Düse-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 Lei- tung") 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 We- sentlichen 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 Nachein- spritzung 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. 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.In the common-rail system, the diesel fuel is pumped by a pump with pressures of up to 2000 bar into a high-pressure line, the common rail (literally "common line"). injecting the fuel directly into the combustion chamber, where full pressure is always available on the common rail, allowing for multiple injection or a special injection mode, while the other injection systems only allow one injection Substantially divided into three groups: (1) pilot injection, which substantially achieves softer combustion so that hard combustion noise ("nailing") is 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 usually not burned, 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 . Due to the variable, cylinder-specific injection of the common rail injection system, 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 zu einer Erhöhung des Partikelausstoßes kommt. Dies wird unter anderem auf die Bildung von Ablagerungen im Einspritzsystem zurückgeführt. 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, was dazu beiträgt, dass 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, increase particulate emissions. This is attributed, inter alia, to the formation of 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 to the fact that with increasing mileage, the combustion is always suboptimal, especially incomplete and thus under coking / soot formation, which contributes to the fact that the amount of particulates in the exhaust emissions of the engine increases and ultimately the limits of the Euro 4 norm should not be maintained for long periods of time or only with the help of elaborate particulate filter.
Aufgabe der vorliegenden Erfindung war es daher, Additive bereitzustellen, welche den im Laufe des Motorenbetriebs zunehmenden Partikelausstoß verringern, indem sie z.B. unter anderem die Bildung von Ablagerungen in den Einspritzsystemen von direkteinspritzenden Dieselmotoren, speziell in Common-Rail-Einspritzsystemen, verringern oder verhindern.It was therefore an object of the present invention to provide additives which reduce the particle output increase during engine operation by e.g. Among other things, 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 einer Additivzusammensetzung beste- hend aus wenigstens einem Detergens-Additiv und gegebenenfalls wenigstens einem Trägeröl zur Verringerung der Partikelmenge in Abgasemissionen von direkteinspritzenden Dieselmotoren.The object is achieved by the use of an additive composition consisting of at least one detergent additive and optionally at least one Carrier oil for reducing the amount of particulates in exhaust emissions from direct-injection diesel engines.
Insbesondere handelt es sich bei den direkteinspritzenden Dieselmotoren um solche mit Common-Rail-Einspritzsystemen. In diesen wird die Verringerung des Partikelausstoßes unter anderem darauf zurückgeführt, dass die Bildung von Ablagerungen insbesondere in den Injektoren verringert oder verhindert wird.In particular, direct-injection diesel engines are those with common-rail injection systems. In these, the reduction of particulate emissions is attributed, inter alia, to reducing or preventing the formation of deposits, particularly 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 zahlengemit- telten Molekulargewicht (Mn) von 85 bis 20000 und mindestens eine polare Gruppierung besitzen, die ausgewählt ist unter:The detergent additives are preferably amphiphilic substances which have 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 group selected from:
(a) Mono- oder Polyaminogruppen mit bis zu 6 Stickstoffatomen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat;(a) mono- or polyamino groups having up to 6 nitrogen atoms, at least one nitrogen atom having basic properties;
(b) Nitrogruppen, gegebenenfalls in Kombination mit Hydroxylgruppen;(b) nitro groups, optionally in combination with hydroxyl groups;
(c) Hydroxylgruppen in Kombination mit Mono- oder Polyaminogruppen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat;(c) hydroxyl groups in combination with mono- or polyamino groups, wherein at least one nitrogen atom has basic properties;
(d) Carboxylgruppen oder deren Alkalimetall- oder Erdalkalimetallsalzen;(d) carboxyl groups or their alkali metal or alkaline earth metal salts;
(e) Sulfonsäuregruppen oder deren Alkalimetall- oder Erdalkalimetallsalzen;(e) sulfonic acid groups or their alkali metal or alkaline earth metal salts;
(f) Polyoxy-C2-C4-alkylengruppierungen, die durch Hydroxylgruppen, Mono- oder(f) polyoxy-C 2 -C 4 -alkylene groups represented by hydroxyl groups, mono- or
Polyaminogruppen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat, oder durch Carbamatgruppen terminiert sind;Polyamino groups, wherein at least one nitrogen atom has basic properties, or terminated by carbamate groups;
(g) Carbonsäureestergruppen;(g) carboxylic acid ester groups;
(h) aus Bernsteinsäureanhydrid abgeleiteten Gruppierungen mit Hydroxy- und/oder Amino- und/oder Amido- und/oder Imidogruppen; und/oder(h) succinic anhydride-derived moieties having hydroxy and / or amino and / or amido and / or imido groups; and or
(i) durch Mannich-Umsetzung von substituierten Phenolen mit Aldehyden und Mo- no- oder Polyaminen erzeugten Gruppierungen; 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.(i) by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated groups; The hydrophobic hydrocarbon radical in the above detergent additives, which provides the sufficient solubility in the fuel, has a number average molecular weight (Mn) of 85 to 20,000, especially from 113 to 10,000, especially from 300 to 5000. As a typical hydrophobic hydrocarbon radical, in particular in connection with the polar groupings (a), (c), (h) and (i), longer-chain alkyl or alkenyl groups, in particular the polypropenyl, polybutenyl and polyisobutenyl radicals each having Mn = 300 to 5000, in particular 500 to 2500, come , 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 Polyalken- mono- 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 Carbo- nyl- 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, Diethy- lentriamin, Triethylentetramin oder Tetraethylenpentamin, eingesetzt werden. Entsprechende Additive auf Basis von Polypropen sind insbesondere in der WO-A-94/24231 beschrieben.Mono- or polyamino groups (a) containing additives are preferably polyalkylene mono- or Polyalkenpolyamine based on polypropene or conventional (ie, with predominantly central double bonds) polybutene or polyisobutene with Mn = 300 to 5000. Is one in the preparation of the additives of polybutene or Polyisobutene with predominantly intermediate 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 carbonyl or carboxyl compound and subsequent amination under reductive (hydrogenating ) Conditions. For amination here amines, such as. As ammonia, monoamines or polyamines, such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, are used. Corresponding additives based on polypropene are described in particular in WO-A-94/24231.
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 Sauer- stoff, wie sie insbesondere in WO-A-97/03946 beschrieben sind.Further preferred monoamino groups (a) containing additives are the hydrogenation 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 in WO-A-97/03946.
Weitere bevorzugte Monoaminogruppen (a) enthaltende Additive sind die aus Polyiso- butenepoxiden 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 polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols obtainable compounds, as described in particular in DE-A-196 20 262.
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,ß-Dinitropolyisobuten) und gemischten Hydroxynitropolyisobutenen (z. B. α-Nitro-ß-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 described in particular in WO-A-96/03367 and WO-A-96/03479 are described. As a rule, these reaction products are mixtures of pure nitropolyisobutenes (for example α, β-dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (for example 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 Polyiso- buten 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 containing polyisobutene having Mn = 300 to 5000, with ammonia, mono- or polyamines, as in particular in EP A-476 485 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 known in particular from EP-A-307 815. Such additives are primarily used to prevent valve seat wear and, as described in WO-A-87/01126, can be advantageously used in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.
Sulfonsäuregruppen oder deren Alkalimetall- oder Erdalkalimetallsalze (e) enthaltende Additive sind vorzugsweise Alkalimetall- oder Erdalkalimetallsalze eines Sulfo- bernsteinsäurealkylesters, 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.Sulphonic 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 sulfosuccinic acid alkyl ester, as described in particular in EP-A-639 632. 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 PoIy- ether oder Polyetheramine, welche durch Umsetzung von C2-C60-Alkanolen, C6-C30-Alkandiolen, Mono- oder Di-C2-C3o-alkylaminen, CrCao-Alkylcyclohexanolen oder CrC3o-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, Monoami- nen 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, Isononylphenolbutoxy- late sowie Polyisobutenolbutoxylate und -propoxylate sowie die entsprechenden Umsetzungsprodukte mit Ammoniak. Carbonsäureestergruppen (g) enthaltende Additive sind vorzugsweise Ester aus Mono-, Di- oder Tricarbonsäuren mit langkettigen Alkanolen oder Polyolen, insbesondere solche mit einer Mindestviskosität von 2 tnm2/s bei 100 0C, 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.Polyoxy-C 2 -C 4 alkylene groupings (f) containing additives are preferably polyether or polyetheramines, which by reaction of C 2 -C 60 alkanols, C 6 -C 30 alkanediols, mono- or di-C 2 - C 3 o-alkylamines, CrCao-Alkylcyclohexanolen or CrC 3 o-alkylphenols with 1 to 30 moles 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 described in particular in EP-A-310 875, EP-A-356 725, EP-A-700 985 and US-A-4 877 416. In the case of polyethers, such products also meet carrier oil properties. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxyl- late 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, especially those having a minimum viscosity of 2 tnm 2 / s at 100 0 C, as described in particular in 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 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 Polyisobutenylbernsteinsäurean- hydrid, welche durch Umsetzung von konventionellem oder hochreaktivem Polyisobu- ten 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, Triethylen- tetramin 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.Succinic anhydride-derived groupings containing hydroxyl and / or amino and / or amido and / or imido (h) -containing additives are preferably corresponding derivatives of alkyl- or alkenyl-substituted succinic anhydride, and especially the corresponding derivatives of polyisobutenyl succinic anhydride, which Reaction of 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 more particularly described in US-A-4,849,572.
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 Polyisobutenyl- substituierten 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.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 described in particular in EP-A-831 141.
Zur genaueren Definition der einzelnen aufgeführten Kraftstoffadditive wird hier auf die Offenbarungen der oben genannten Schriften des Stands der Technik ausdrücklich Bezug genommen. 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 Polyisobutenylbemsteinsäureanhydri- den, 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 Bemstein- säurehalogenide oder -ester, erhältlich sind.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. Particularly preferred are detergent additives from group (h). These are preferably the reaction products of alkyl- or alkenyl-substituted succinic anhydrides, in particular 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 Pentaethylenhexa- min, wobei Tetraethylenpentamin besonders bevorzugt ist. Der Polyisobutenylrest besitzt ein zahlenmittleres Molekulargewicht Mn von vorzugsweise 500 bis 5000, beson- ders 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, more preferably from 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" bekann- te und bei der Raffination von Mineralöl anfallende Fraktion (Vakuumdestillatschnitt mit einem Siedebereich von etwa 360 bis 500 °C, erhältlich aus unter Hochdruck kataly- tisch 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. Also useful is a fraction known as "hydrocrack oil" and derived from the refining of mineral oil (vacuum distillate cut having 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 Polyintemalolefine), (Poly)estern, (Poly)alkoxylaten, Polyethern, aliphatischen Polyetheraminen, alkylphenolgestarteten Polyethern, alkylphenolgestarteten Polyetheraminen und Carbonsäureester langketti- ger Alkanole. Beispiele für geeignete Polyolefine sind Olefinpolymerisate mit Mn = 400 bis 1800, vor allem auf Polybuten- oder Polyisobuten-Basis (hydriert oder nicht hydriert).Examples of synthetic carrier oils which can be used according to the invention are selected from: polyolefins (polyalphaolefins or polyethylenemolefins), (poly) esters, (poly) alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-initiated polyethers, alkylphenol-initiated polyetheramines and carboxylic acid esters of long-chain alkanols. 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-C6o-Alkanolen, C6-C30-Alkandiolen, Mono- oder Di-C2-C3o-alkylaminen, CrCao-Alkylcyclohexanolen oder CrC3o-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 Am- moniak, 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 Polyisobute- nolbutoxylate 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 6 -alkanols, C 6 -C 30 -alkanediols, mono- or di-C 2 -C 3 o-alkylamines, CrCao-alkylcyclohexanols or C r C 3 o-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 described in particular in EP-A-310 875, EP-A-356 725, EP-A-700 985 and US-A-4,877,416. 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 Polyisobute- nolbutoxylate 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 insbe- sondere 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 lso-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 described in particular in DE-A-38 38 918. 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. For example, 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-O 452 328 und EP-A-O 548617, worauf hiermit ausdrücklich Bezug genommen wird.Further 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 548617, to which reference is hereby 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 langket- tige Alkanole oder mit langkettigem Alkyl-substituierte Phenole, wobei der langkettige Alkylrest insbesondere für einen geradkettigen oder verzweigten Ce-Ci8-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 e -C 8 -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. Bevorzugte Trägeröle sind synthetische Trägeröle, wobei Polyether besonders bevorzugt sind.Further suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A-10 102 913.6. 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, be- sonders 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 additive, 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 wt. - ppm 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 1 to 1000 ppm by weight, more preferably 10 to 500 ppm by weight, and more preferably 20 to 100 ppm by weight.
Außerdem kann der Dieselkraftstoff weitere übliche Coadditive enthalten, wie Kaltfließ- verbesserer, Korrosionsinhibitoren, Demulgatoren, Dehazer, Antischaummittel, Cetan- zahlverbesserer, Verbrennungsverbesserer, Antioxidantien oder Stabilisatoren, Antista- tika, Metallocene, Metalldeaktivatoren, Farbstoffe, Lösungsmittel und dergleichen. Es wird davon ausgegangen, dass die Verwendung dieser Additive im Wesentlichen keinen Einfluss auf die Verringerung des Partikelausstoßes hat.In addition, the diesel fuel may contain other conventional co-additives, such as cold flow improvers, corrosion inhibitors, demulsifiers, dehazers, defoamers, cetane number improvers, combustion improvers, antioxidants or stabilizers, antistatics, metallocenes, metal deactivators, dyes, solvents, and the like. It is believed that the use of these additives has essentially no effect on the reduction of particulate emissions.
Geeignete Kaltfließverbesserer sind z.B. Copolymere von Ethylen mit wenigstens einem weiteren ethylenisch ungesättigten Monomer, z.B. Ethylen/Vinylacetat- Copolymere.Suitable cold flow improvers are e.g. Copolymers of ethylene with at least one other ethylenically unsaturated monomer, e.g. Ethylene / vinyl acetate copolymers.
Geeignete Korrosionsinhibitoren sind z.B. Bernsteinsäureester, vor allem mit Polyolen, Fettsäurederivate, z.B. Ölsäureester, oligomerisierte Fettsäuren, substituierte Ethano- lamine und Produkte, die unter dem Handelsnamen RC 4801 (Rhein Chemie Mannheim, Deutschland) oder HiTEC 536 (Ethyl Corporation) vertrieben werden.Suitable corrosion inhibitors are e.g. Succinic esters, especially with polyols, fatty acid derivatives, e.g. Oleic acid esters, oligomerized fatty acids, substituted ethanolamines and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany) or HiTEC 536 (Ethyl Corporation).
Geeignete Demulgatoren sind z.B. die Alkali- oder Erdalkalisalze von Alkyl- substituierten Phenol- und Naphthalinsulfonaten und die Alkali- oder Erdalkalisalze von Fettsäuren, außerdem neutrale Verbindungen, wie Alkoholalkoxylate, z.B. Alkoholetho- xylate, Phenolalkoxylate, z.B. tert-Butylphenolethoxylat oder tert-Pentylphenolethoxy- lat, Fettsäuren, Alkylphenole, Kondensationsprodunkte von Ethylenoxid (EO) und Pro- pylenoxid (PO), z.B. auch in Form von EO/PO-Blockcopolymeren, Polyethylenimine oder auch Polysiloxane. Geeignete Dehazer sind z.B. alkoxylierte Phenol-Formaldehyd-Kondensate, wie beispielsweise die unter dem Handelsnamen erhältlichen Produkte NALCO 7D07 (Nalco) und TOLAD 2683 (Petrolite).Suitable demulsifiers are, for example, the alkali metal or alkaline earth metal salts of alkyl-substituted phenol and naphthalenesulfonates and the alkali metal or alkaline earth metal salts of fatty acids, furthermore neutral compounds, such as alcohol alkoxylates, for example alcohol ethoxylates, phenol alkoxylates, for example tert-butylphenol ethoxylate or tert-pentylphenol ethoxylate , Fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), for example in the form of EO / PO block copolymers, polyethyleneimines or else polysiloxanes. Suitable dehazers are, for example, alkoxylated phenol-formaldehyde condensates, such as, for example, the products NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite) available under the trade name.
Geeignete Antischaummittel sind z.B. Polyether-modifizierte Polysiloxane, wie beispielsweise die unter dem Handelsnamen erhältlichen ProdukteTEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Coming) und RHODOSIL (Rhone Poulenc).Suitable antifoams are e.g. Polyether-modified polysiloxanes, such as the products available under the trade name TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc).
Geeignete Cetanzahlverbesserer sind z.B. aliphatische Nitrate, wie 2-Ethylhexylnitrat und Cyclohexylnitrat, und Peroxide, wie Di-tert-butylperoxid.Suitable cetane number improvers are e.g. aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate, and peroxides such as di-tert-butyl peroxide.
Geeignete Antioxidantien sind z.B. substituierte Phenole, wie 2,6-Di-tert-butylphenol und ,6-Di-tert-butyl~3-methylphenol, und Phenylendiamine, wie N,N'-Di-sec— butyl-p- phenylendiamin.Suitable antioxidants are e.g. substituted phenols such as 2,6-di-tert-butylphenol and, 6-di-tert-butyl-3-methylphenol, and phenylenediamines such as N, N'-di-sec-butyl-p-phenylenediamine.
Geeignete Metalldeaktivatoren sind z.B. Salicylsäurederivate, wie N,N'-Disalicyliden- 1 ,2-propandiamin.Suitable metal deactivators are e.g. Salicylic acid derivatives, such as N, N'-disalicylidene-1, 2-propanediamine.
Geeignete Lösungsmittel sind z.B. unpolare organische Lösungsmittel, wie aromatische und aliphatische Kohlenwasserstoffe, beispielsweise Toluol, die XyIoIe, „White spirit" und Produkte, die unter dem Handelsnamen SHELLSOL (Royal Dutch/Shell Group) und EXXSOL (ExxonMobil) vertrieben werden, und polare organische Lösungsmittel, beispielsweise Alkohole, wie 2-Ethylhexanol, Decanol und Isotridecanol.Suitable solvents are e.g. non-polar organic solvents, such as aromatic and aliphatic hydrocarbons, for example, toluene, the xylene, "white spirit" and products sold under the trade name SHELLSOL (Royal Dutch / Shell Group) and EXXSOL (ExxonMobil), and polar organic solvents, for example alcohols such as 2-ethylhexanol, decanol and isotridecanol.
Bevorzugte Coadditive sind Demulgatoren, Dehazer, Antischaummittel, Cetanzahlverbesserer, Antioxidantien, Metalldeaktivatoren, Korrosionsinhibitoren und Lösungsmittel.Preferred co-additives are demulsifiers, dehazers, defoamers, cetane improvers, antioxidants, metal deactivators, corrosion inhibitors and solvents.
Diese üblichen Coadditive werden, wenn gewünscht, in hierfür üblichen Mengen zuge- setzt.These customary co-additives are added, if desired, in customary quantities.
DieselkraftstoffeDiesel fuels
Bei den Dieselkraftstoffen handelt es sich beispielsweise um Erdölraffinate, die übli- cherweise einen Siedebereich von 100 bis 400 0C haben. Dies sind meist Destillate mit einem 95%-Punkt bis zu 360 0C 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 0C und einem Schwefelgehalt von maximal 0,005 Gew.-% oder durch einen 95%-Punkt von beispielsweise 285 0C 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, crude oil raffinates instruments normally have a boiling range of 100 to 400 0 C. These are mostly distillates with a 95% point up to 360 0 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 0 C and a maximum sulfur content of 0.005 wt .-% or by a 95% point of for example, 285 0 C and a maximum sulfur content of 0.001 wt .-%. In addition to those available through refining Diesel fuels are those obtainable by coal gasification or gas liquefaction ("gas to liquid" (GTL) fuels). 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, die Zunahme der Partikelmenge deutlich geringer ist als in den Abgasemissionen von direkteinspritzenden Die- selmotoren, die ohne den Einsatz von Detergens-Additiven betrieben werden. Insbesondere wird erreicht, dass 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 Auslie- ferung 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, the increase in the amount of particulates is significantly lower than in the exhaust emissions of direct-injection diesel engines, which without the Use of detergent additives are operated. In particular, it is achieved that after 100,000 km of 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 is included in comparison to the factory setting. 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 before any particulate filter that may have been installed, which would reduce the amount of particulate matter in the exhaust. as it is set at the factory, ie before delivery to the dealer or end user (kilometer 0, as it were) The use according to the invention of detergent additives not only ensures compliance with the limit values for particulate emissions in accordance with Euro 4 standard, but also without additional fuel Particle filter over an engine running time of 100000 km guaranteed, but also for a much longer operating time.
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 Polyisobutylenbemsteinsäureimid 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.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 polyisobutylene succinimide), 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 contained in the discharge were directly behind the Engine out, and the results are shown in the table below.
Tabelletable
Figure imgf000013_0001
Figure imgf000013_0001
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

Patentansprüche: claims:
1. Verwendung einer Additivzusammensetzung bestehend aus wenigstens einem Detergens-Additiv und gegebenenfalls wenigstens einem Trägeröl zur Verringe- rung der Partikelmenge in Abgasemissionen von direkteinspritzenden Dieselmotoren.1. Use of an additive composition consisting of at least one detergent additive and optionally at least one carrier oil for reducing the amount of particulates in exhaust emissions of direct-injection diesel engines.
2. Verwendung nach Anspruch 1 , zur Verringerung der Partikelmenge in Abgasemissionen von Dieselmotoren mit Common-Rail-Einspritzsystemen.2. Use according to claim 1, for reducing the amount of particulates in exhaust emissions of diesel engines with common-rail injection systems.
3. 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.3. Use according to 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.
4. Verwendung nach Anspruch 3, wobei es sich bei den Detergens-Additiven um Polyisobutenyl-substituierte Bernsteinsäureimide handelt.4. Use according to claim 3, wherein the detergent additives are polyisobutenyl-substituted succinimides.
5. Verwendung nach einem der vorhergehenden Ansprüche, wobei die Detergens- Additive in Kombination mit wenigstens einem Trägeröl verwendet werden.5. Use according to one of the preceding claims, wherein the detergent additives are used in combination with at least one carrier oil.
6. 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 Grenz- wert für die Partikelmenge der Euro 4 Norm nicht überschritten wird. 6. Use according to one of the preceding claims, wherein the particulate matter contained in the exhaust emissions of the diesel engines and measured directly behind the engine after 100000 km engine operation by a factor of at most 2.5 is higher than the factory setting and at the same time the limit value for the Particle quantity of Euro 4 norm is not exceeded.
PCT/EP2006/002686 2005-03-24 2006-03-23 Use of detergent additives for reducing a particle amount in the exhaust gas of direct injection diesel engines WO2006100083A1 (en)

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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.
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.
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
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
BRPI0609694-8A BRPI0609694A2 (en) 2005-03-24 2006-03-23 use of an additive composition
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
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

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