EP1866396A1 - Utilisation d'additifs detergents pour reduire la quantite de particules dans des emissions de gaz d'echappement de moteurs diesels a injection directe - Google Patents

Utilisation d'additifs detergents pour reduire la quantite de particules dans des emissions de gaz d'echappement de moteurs diesels a injection directe

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Publication number
EP1866396A1
EP1866396A1 EP06723673A EP06723673A EP1866396A1 EP 1866396 A1 EP1866396 A1 EP 1866396A1 EP 06723673 A EP06723673 A EP 06723673A EP 06723673 A EP06723673 A EP 06723673A EP 1866396 A1 EP1866396 A1 EP 1866396A1
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EP
European Patent Office
Prior art keywords
diesel engines
additives
detergent additives
reducing
groups
Prior art date
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Application number
EP06723673A
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German (de)
English (en)
Inventor
Jörn KARL
Georg Schäper
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BASF SE
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BASF SE
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Priority to EP06723673A priority Critical patent/EP1866396A1/fr
Publication of EP1866396A1 publication Critical patent/EP1866396A1/fr
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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
    • 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
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving 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
    • C10L1/18—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
    • C10L1/22—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
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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
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
    • C10L1/1983—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
    • C10L1/18—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 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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  • 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)
  • Emergency Medicine (AREA)
  • Health & Medical Sciences (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Treating Waste Gases (AREA)
  • Fuel-Injection Apparatus (AREA)

Abstract

La présente invention concerne l'utilisation d'additifs détergents pour réduire la quantité de particules dans les émissions de gaz d'échappement de moteurs diesels à injection directe et en particulier de moteurs diesels équipés d'un système d'injection à rampe commune.
EP06723673A 2005-03-24 2006-03-23 Utilisation d'additifs detergents pour reduire la quantite de particules dans des emissions de gaz d'echappement de moteurs diesels a injection directe Withdrawn EP1866396A1 (fr)

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EP06723673A EP1866396A1 (fr) 2005-03-24 2006-03-23 Utilisation d'additifs detergents pour reduire la quantite de particules dans des emissions de gaz d'echappement de moteurs diesels a injection directe

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EP05006599A EP1705234A1 (fr) 2005-03-24 2005-03-24 Utilisation d'additifs détergents afin d'empêcher ou de réduire la formation des dépôts dans les systèmes d'injection pour moteurs diesel à injection directe
PCT/EP2006/002686 WO2006100083A1 (fr) 2005-03-24 2006-03-23 Utilisation d'additifs detergents pour reduire la quantite de particules dans des emissions de gaz d'echappement de moteurs diesels a injection directe
EP06723673A EP1866396A1 (fr) 2005-03-24 2006-03-23 Utilisation d'additifs detergents pour reduire la quantite de particules dans des emissions de gaz d'echappement de moteurs diesels a injection directe

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EP1866396A1 true EP1866396A1 (fr) 2007-12-19

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EP06723673A Withdrawn EP1866396A1 (fr) 2005-03-24 2006-03-23 Utilisation d'additifs detergents pour reduire la quantite de particules dans des emissions de gaz d'echappement de moteurs diesels a injection directe

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US (1) US20080196586A1 (fr)
EP (2) EP1705234A1 (fr)
JP (1) JP2008534699A (fr)
KR (1) KR20070116149A (fr)
CN (1) CN101146897A (fr)
AR (1) AR054240A1 (fr)
AU (1) AU2006226517B2 (fr)
BR (1) BRPI0609694A2 (fr)
CA (1) CA2602275A1 (fr)
MX (1) MX2007010950A (fr)
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KR20070116149A (ko) 2007-12-06
MX2007010950A (es) 2007-09-21
CN101146897A (zh) 2008-03-19
EP1705234A1 (fr) 2006-09-27
AU2006226517B2 (en) 2011-12-01
BRPI0609694A2 (pt) 2011-10-18
AU2006226517A1 (en) 2006-09-28
NO20074587L (no) 2007-10-23
AR054240A1 (es) 2007-06-13
JP2008534699A (ja) 2008-08-28
CA2602275A1 (fr) 2006-09-28
WO2006100083A1 (fr) 2006-09-28
US20080196586A1 (en) 2008-08-21

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