WO2009074608A1 - Amines utilisées comme renforçateurs de nettoyage de soupape d'admission - Google Patents

Amines utilisées comme renforçateurs de nettoyage de soupape d'admission Download PDF

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Publication number
WO2009074608A1
WO2009074608A1 PCT/EP2008/067227 EP2008067227W WO2009074608A1 WO 2009074608 A1 WO2009074608 A1 WO 2009074608A1 EP 2008067227 W EP2008067227 W EP 2008067227W WO 2009074608 A1 WO2009074608 A1 WO 2009074608A1
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amine
fuel
component
additive composition
formula
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PCT/EP2008/067227
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English (en)
Inventor
Ludwig Völkel
Peter Schreyer
Christian Lockemann
Arno Lange
Gero Nordmann
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Basf Se
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Publication of WO2009074608A1 publication Critical patent/WO2009074608A1/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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/18—Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)

Definitions

  • the present invention relates to a novel fuel additive composition
  • a novel fuel additive composition comprising nitrogen- containing dispersants selected from polyisobutenyl monoamines and polyisobutenyl polyamines, carrier oils which are substantially free of nitrogen and which are selected from synthetic carrier oils and mineral carrier oils, and amines with at least one hydro- carbyl residue.
  • the present invention relates to a gasoline fuel composi- tion comprising a minor amount of the said fuel additive composition.
  • the present invention relates to the use of such amines as an intake valve clean-up booster in internal combustion engines operated with gasoline containing the above detergents and the above carrier oils.
  • Carburettors and inlet systems of automobile engines, and also injection systems for fuel proportioning, are subjected to increasing load due to contamination caused by dust particles from the air, unburned hydrocarbon residues from the combustion cham- ber and crankcase ventilation, and exhaust gas recycle passed to the intake system.
  • Fuel additives are i.a. used in order to avoid formation of deposits in the intake system and the intake valves of engines (keep-clean effect). On the other hand, fuel additives may be used in order to remove deposits already formed at the valves and in the intake system (clean-up effect).
  • Aliphatic primary, secondary and tertiary monoamines with Ci-C2o-alkyl residues, C3-C2o-cycloalkyl residues or cycloalkyl residues are known as dispersant additives in gasoline fuels, preferably in combination with Mannich-type dispersant additives, from WO 04/050806.
  • the said monoamines can bei used in gasoline fuels together with other dispersants additives, such as polyisobutenyl monoamines or polyisobutenyl polyamines based on polyisobutene with a number average molecular weight of from 600 to 5000, and with polyether carrier oils, such as tridecanol butoxylate or isotrideca- nol butoxylate.
  • the use of the said monoamines results in a reduction of injector nozzle fouling in direct injection spark ignition engines.
  • WO 03/076554 relates to the use of hydrocarbyl amines wherein the hydrocarbyl moi- ety has a number average molecular weight in the range of from 140 to 255 for reducing injector nozzle fouling in direct injection spark ignition engines, either for "keep clean” or for “clean-up” purposes of such engines.
  • Fuel D of the examples of WO 03/076554 a gasoline fuel was prepared by "dosing into the base fuel 645 ppmw of a commercial additive package ex BASF A.G., containing polyisobutylene monoam- ine (PIBA), in which the polyisobutylene (PIB) chain has a number average molecular weight (Mn) of approximately 1000, a polyether carrier fluid and an antioxidant, with further inclusion of 50 ppmw dodecylamine".
  • PIBA polyisobutylene monoam- ine
  • Mn number average molecular weight
  • Fuel D was subjected to a clean-up test determining the average injector diameter reduction after running a direct injection spark ignition engine with this Fuel.
  • WO 90/10051 relates to a gasoline fuel composition containing an intake valve deposit control additive formulation comprising (1 ) long-chain primary amines exhibiting typically C6-C40 aliphatic radicals as substituents, e.g. decyl amine, dodecyl amine (lauryl amine), or tallow amines containing tetradecyl amine, hexadecyl amine, octadecyl amine and octadecenyl amine (oleyl amine), in combination with (2) fuel dispersants selected from polyalkenylamines (such polyisobutyl amine) and Mannich bases, and with (3) fluidizer oils such as refined napthenic lubricating oil ar a polyolefin like polypropylene or polybutylene.
  • an intake valve deposit control additive formulation comprising (1 ) long-chain primary amines exhibiting typically C6-C40 aliphatic radicals as substituents, e.g
  • a fuel additive composition comprising: (A) at least one nitrogen-containing dispersant selected from polyisobutenyl monoamines and polyisobutenyl polyamines,
  • R 1 to R 3 is a Ci-C3o-hydrocarbyl residue which can contain a second nitrogen atom, or a polyoxyalkylene residue of formula Il
  • A is a C2-C6-alkylene group
  • n is a number of from 1 to 50
  • R 4 is a Ci-C3o-hydrocarbyl residue
  • the said fuel additive composition is a first subject matter of the instant invention.
  • a second subject matter of the instant invention is a fuel composition comprising a major amount of a liquid fuel in gasoline boiling range and a minor amount of the above fuel additive composition.
  • a third subject matter of the instant invention is the use of a amine (C) of formula I as set above as an intake valve clean-up booster in internal combustion engines operated with a liquid fuel in gasoline boiling range containing minor amounts of (A) at least one nitrogen-containing dispersant selected from polyisobutenyl monoamines and polyisobutenyl polyamines and (B) at least one carrier oil which is substantially free of nitro- gen, selected from synthetic carrier oils and mineral carrier oils.
  • polyisobutenes which are suitable for preparing the polyisobutenyl monoamines and polyisobutenyl polyamines used in the present invention include polyisobutenes which comprise at least about 20%, preferably at least 50% and more preferably at least 70% of the more reactive methylvinylidene isomer.
  • Suitable polyisobutenes include those prepared using BF3 catalysts. The preparation of such polyisobutenes in which the methylvinylidene isomer comprises a high percentage of the total composition is for example described in US-A 4,152,499 and US-A 4,605,808.
  • suitable polyisobutenes having a high alkylvinylidene content examples include Ul- travis® 30, a polyisobutene having a number average molecular weight of about 1300 and a methylvinylidene content of about 74%, and Ultravis® 10, a 950 molecular weight polyisobutene having a methylvinylidene content of about 76%, both available from British Petroleum.
  • Ul- travis® 30 a polyisobutene having a number average molecular weight of about 1300 and a methylvinylidene content of about 74%
  • Ultravis® 10 a 950 molecular weight polyisobutene having a methylvinylidene content of about 76%, both available from British Petroleum.
  • Another example of a suitable polyisobutene having a number average molecular weight of about 1000 and a high methylvinyliden content is GNs- sopal® 1000, available from BASF Aktiengesellschaft.
  • the polyisobutene precursors are not a pure single product, but rather a mixture of compounds having an average molecular weight in the above range.
  • the range of molecular weights will be relatively narrow having a maximum near the indicated molecular weight.
  • the amine component of the polyisobutenyl monoamines or polyisobutenyl poly- amines, respectively, may be derived from ammonia, a monoamine or a polyamine.
  • the monoamine or polyamine component comprises amines having from 1 to about 12 amine nitrogen atoms and from 1 to 40 carbon atoms.
  • the carbon to nitrogen ratio may be between about 1 :1 and about 10:1.
  • the monoamine will contain from 1 to about 40 carbon atoms and the polyamine will contain from 2 to about 12 amine nitrogen atoms and from 2 to about 40 carbon atoms.
  • the amine component may be a pure single product or a mixture of compounds having a major quantity of the designated amine.
  • the amine component when it is a polyamine, it will preferably be a polyalkylene polyamine, including alkylene diamine.
  • the alkylene group will contain from 2 to 6 carbon atoms, more preferably from 2, 3 or 4 carbon atoms.
  • examples of such polyamines include ethylene diamine, diethylene triamine, triethylene tetramine and tetra- ethylene pentamine.
  • Preferred polyamines are ethylene diamine and diethylene triamine.
  • Particularly preferred polyisobutenyl polyamines include polyisobutenyl ethylene diamine and polyisobutenyl amine. The polyisobutenyl group is substantially saturated.
  • polyisobutenyl monoamines or polyisobutenyl polyamines employed in the fuel additive composition of the instant invention are prepared by conventional procedures known in the art, especially by reductive amination. Such polyisobutenyl monoamines or polyisobutenyl polyamines and their preparations are described in detail e.g. in EP-A 0 244 616.
  • the amine portion of the molecule may carry one or more substituents.
  • the carbon and/or, in particular, the nitrogen atoms of the amine may carry substituents selected from hydrocarbyl groups of from 1 to about 10 carbon atoms, acyl groups of from 2 to about 10 carbon atoms, and monoketo, monohydroxy, mononitro, monocyano, lower alkyl and lower alkoxy derivatives thereof.
  • “Lower” as used herein means a group containing from 1 to about 6 carbon atoms. At least one of hydrogen atoms on one of the basic nitrogen atoms of the polyamine may not be substituted so that at least one of the basic nitrogen atoms of the polyamine is a primary or secondary amino nitrogen.
  • a polyamine finding use within the scope of the present invention as amine component for the polyisobutenyl polyamines may be a polyalkylene polyamine, including substituted polyamines, e.g., alkyl and hydroxyalkyl-substituted polyalkylene polyamine.
  • substituted polyamines e.g., alkyl and hydroxyalkyl-substituted polyalkylene polyamine.
  • the polyalkylene polyamines those containing 2-12 amino nitrogen atoms and 2-24 carbon atoms should be mentioned, in particular C2 -C3 alkylene polyamines.
  • the alkylene group contains from 2 to 6 carbon atoms, there being prefera- bly from 2 to 3 carbon atoms between the nitrogen atoms.
  • Such groups are exemplified by ethylene, 1 ,2-propylene, 2,2-dimethylpropylene, trimethylene, 1 ,3,2-hydroxy- propylene.
  • polyamines examples include ethylene diamine, diethylene triamine, di(trimethylene) triamine, 1 ,2-propylene diamine, 1 ,3-propylene diamine, dipropylene triamine, triethylene tetraamine, tripropylene tetraamine, tetraethylene pentamine, pen- taethylene hexamine. hexamethylene diamine, and dimethylaminopropylene diamine.
  • Such amines encompass isomers such as branched-chain polyamines and previously- mentioned substituted polyamines, including hydroxy- and hydrocarbyl-substituted po- lyamines.
  • the amine component for the polyisobutenyl monoamines or polyisobutenyl polyamines also may be derived from heterocyclic polyamines, heterocyclic substituted amines and substituted heterocyclic compounds, wherein the heterocycle comprises one or more 5-6 membered rings containing oxygen and/or nitrogen.
  • Such heterocyclic rings may be saturated or unsaturated and substituted with groups as defined above.
  • heterocyclic compounds there may be mentioned 2-methylpiperazine, N-(2-hydroxyethyl)-piperazine, 1 ,2-bis-(N-piperazinyl)ethane, N,N'-bis(N-piperazinyl)- piperazine, 2-methylimidazoline, 3-aminopiperidine, 3-aminopyridine, N-(3-amino-pro- pyl)-morpholine, N-(beta-aminoethyl)piperazine, N-(betaaminoethyl)piperidine, 3-ami- no-N-ethylpiperidine, N-(betaaminoethyl) morpholine, N,N'-di(beta-aminoethyl)-pipera- zine, N,N'-di(beta-aminoethyl)imidazolidone-2, 1 ,3-dimethyl-5(beta-a-a
  • the amine component for the polyisobutenyl monoamines may be derived from a monoamine having the formula HNR 5 R 6 wherein R 5 and R 6 are independently selected from the group consisting of hydrogen and hydrocarbyl of 1 to about 20 carbon atoms and, when taken together, R 5 and R 6 may form one or more 5- or 6-mem- bered rings containing up to about 20 carbon atoms.
  • R 5 is hydrogen and R 6 is a hydrocarbyl group having 1 to about 10 carbon atoms. More preferably, R 5 and R 6 are hydrogen.
  • the hydrocarbyl groups may be straight-chain or branched and may be aliphatic, alicyclic, aromatic or combinations thereof.
  • the hydrocarbyl groups may also contain one or more oxygen atoms.
  • Typical primary amines are exemplified by N-methylamine, N-ethylamine, N-n-propyl- amine, N-isopropylamine, N-n-butylamine, N-isobutylamine, N-sec.-butylamine, N-tert- butylamine, N-n-pentylamine, N-cyclopentylamine, N-n-hexylamine, N-cyclohexyl- amine, N-octylamine, N-decylamine, N-dodecylamine, N-octadecylamine, N-benzyl- amine, N-(2-phenylethyl)amine, 2-aminoethanol, 3-amino-1-proponal, 2-(2-amino- ethoxy)ethanol, N-(2-methoxyethyl)amine, N-(2-ethoxyethyl)amine, and the like.
  • Typical secondary amines include N,N-dimethylamine, N,N-diethylamine, N,N-di-n- propylamine, N,N-diisopropylamine, N,N-di-n-butylamine, N,N-di-sec-butylamine, N,N-di-n-pentylamine, N,N-di-n-hexylamine, N,N-dicyclohexylamine, N,N-dioctylamine, N-ethyl-N-methylamine, N-methyl-N-n-propylamine, N-n-butyl-N-methylamine, N-me- thyl-N-octylamine, N-ethyl-N-isopropylamine, N-ethyl-N-octylamine, N,N-di-(2-hydroxy- ethyl)amine, N,N-di(3-hydroxy
  • Cyclic secondary amines may also be employed to form the polyisobutenyl monoamines or polyisobutenyl polyamines used in the instant invention.
  • R 6 and R 7 of the formula hereinabove when taken together, form one or more 5- or 6-membered rings containing up to about 20 carbon atoms.
  • the ring containing the amine nitrogen atom is generally saturated, but may be fused to one or more saturated or unsaturated rings.
  • the rings may be substituted with hydrocarbyl groups of from 1 to about 10 carbon atoms and may contain one or more oxygen atoms.
  • Suitable cyclic secondary amines include piperidine, 4-methylpiperidine, pyrrolidine, morpholine, 2,6-dimethylmorpholine, and the like.
  • the number average molecular weight of the polyisobutenyl monoamines or polyisobu- tenyl polyamines used in the instant invention is usually in the range of from 500 to 2500, typically about 550, about 750, about 1000 or about 1300.
  • a preferred range for the number average molecular weight of the polyisobutenyl monoamines or polyisobutenyl polyamines is from 550 to 1000.
  • the polyisobutenyl monoamines or polyisobutenyl polyamines are mostly not pure single products, but rather mixtures of compounds having number average molecular weights as indicated above. Usually, the range of molecular weights will be relatively narrow having a maximum near the indicated molecular weight.
  • dispersant component (A) is a polyisobutenyl monoamine with a number average molecular weight of from 550 to 1000.
  • the said polyisobutenyl monoamine is preferably based on ammonia and preferably prepared via hydroformylation of polyisobutene and subsequent reductive amination with ammonia, as described in EP-A 0 244 616.
  • the fuel-soluble, nonvolatile carrier oil of component (B) is to be used as a necessary part of the fuel additive composition of the instant invention, in order to achieve the desired improvement in intake valve clean-up performance.
  • the carrier oil is a chemi- cally inert hydrocarbon-soluble liquid vehicle.
  • the carrier oil of component (B) may be a synthetic oil or a mineral oil; for the instant invention, a refined petroleum oil is also understood to be a mineral oil.
  • carrier oils also called carrier fluids
  • carrier oil (B) may also exhibit synergistic deposit control and deposit removing properties when used in combination with components (A) and (C) of the instant fuel additive composition.
  • the carrier oil of component (B) is typically employed in amounts ranging from about 50 to about 2,000 ppm by weight of the gasoline fuel, preferably from 100 to 800 ppm of the gasoline fuel.
  • the ratio of carrier oil (B) to nitrogen-containing dispersant (A) in the fuel additive composition as well as in the gasoline fuel will range from 0.5 : 1 to 10 : 1 , typically from 1 : 1 to 4 : 1.
  • carrier oils When employed in fuel additive compositions or fuel additive concentrates, such as in the instant fuel additive composition, carrier oils will generally be present in amounts ranging from about 10 to about 60 weight percent, preferably from 20 to 40 weight per- cent (referring to the amount of all components in the composition or concentrate, respectively, including possible solvents).
  • suitable mineral carrier oils are in particular those of viscosity class SoI- vent Neutral (SN) 500 to 2000, as well as aromatic and paraffinic hydrocarbons and alkoxyalkanols.
  • Another useful mineral carrier oil is a fraction known as "hydrocrack oil” which is obtained from refined mineral oil (boiling point of approximately 360 to 500 0 C; obtainable from natural mineral oil which is isomerized, freed of paraffin components and catalytically hydrogenated under high pressure).
  • Examples for synthetic carrier oils which can be used for the instant invention are olefin polymers with a number average molecular weight of from 400 to 1800, based on poly- alpha-olefins or poly-internal-olefins, especially those based on polybutene or on poly- isobutene (hydrogenated or nonhydrogenated).
  • suitable synthetic carrier oils are polyesters, polyalkoxylates, polyethers, alkylphenol-initiated polyethers, and carboxylic acids of long-chain alkanols.
  • suitable polyethers which can be used for the instant invention are compounds containing polyoxy-C2-C4-alkylene groups, especially polyoxy-C3-C4-alkylene groups, which can be obtained by reacting Ci-C3o-alkanols, C2-C6o-alkandiols, Ci-C3o-alkylcyclohexanols or Ci-C3o-alkylphenols with 1 to 30 mol ethylene oxide and/or propylene oxide and/or butylene oxides per hydroxyl group, especially with 1 to 30 mol propylene oxide and/or butylene oxides per hydroxyl group.
  • This type of compounds is described, for example, in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416.
  • Typical examples for suitable polyethers are tridecanol butoxylates, isotridecanol bu- toxylates, isononylphenol butoxylates, polyisobutenol butoxylates and polyisobutenol propoxylates.
  • Hydrocarbyl-terminated poly(oxyalkylene) polymers which may be employed in the present invention as component (B), are monohydroxy compounds, i.e., alcohols, and are often termed monohydroxy polyethers, or polyalkylene glycol monohydrocarbyleth- ers, or "capped" poly(oxyalkylene).
  • the hydrocarbyl-terminated poly(oxyalkylene) alcohols may be produced by the addition of lower alkylene oxides, such as ethylene oxide, propylene oxide, the butylene oxides, or the pentylene oxides to the hydroxy compound under polymerization conditions.
  • lower alkylene oxides such as ethylene oxide, propylene oxide, the butylene oxides, or the pentylene oxides.
  • alkylene oxide e.g., propylene oxide
  • the product is a homopolymer, e.g., a poly(oxyalkylene) propanol.
  • copoly- mers are equally satisfactory and random copolymers are readily prepared by contacting the hydroxyl-containing compound with a mixture of alkylene oxides, such as a mixture of propylene and butylene oxides.
  • Block copolymers of oxyalkylene units also provide satisfactory poly(oxyalkylene) polymers for the practice of the present invention. Random polymers are more easily prepared when the reactivities of the oxides are relatively equal.
  • Block copolymers are prepared by contacting the hydroxyl-containing compound with first one alkylene oxide, then the others in any order, or repetitively, under polymerization conditions.
  • a particular block copolymer is represented by a polymer prepared by polymerizing propylene oxide on a suitable monohydroxy compound to form a poly(oxypropylene) alcohol and then polymerizing butylene oxide on the poly(oxyalkylene) alcohol.
  • poly(oxyalkylene) polymers are mixtures of compounds that differ in polymer chain length. However, their properties closely approximate those of the polymer represented by the average composition and molecular weight.
  • carboxylic esters of long-chain alkanols are esters of mono-, di- and tri- carboxylic acids with long-chain alkanols or polyhydric alcohols such as described e.g. in DE-A 38 38 918.
  • Suitable mono-, di- and tricarboxylic acids are aliphatic or aromatic carboxylic acids.
  • Suitable alkanols and polyhydric alcohols contain 6 to 24 carbon atoms.
  • Typical examples of such esters are the adipates, phthalates, iso-phthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol, e.g. di-n-tridecyl phthalate or di-iso-tridecyl phthalate.
  • Examples for particularly useful synthetic carrier oils are alcohol-initiated polyethers containing about 5 to 35, e.g. 5 to 30 Cs-C ⁇ -alkylenoxide units, such as propylenoxide, n-butylenoxide and iso-butylenoxide units or mixtures thereof.
  • Non-limiting examples for alcoholic starters are long-chain alkanols or phenols substituted by long-chain alkyl groups, where the alkyl group preferably is linear or branched C ⁇ -Cis-alkyl.
  • Preferred examples for the alcoholic starters are tridecanol and nonylphenol.
  • suitable synthetic carrier oils are alkoxylated alkylphenols, such as described e.g. in DE-A 10 102 913.
  • synthetic carrier oils are used.
  • Preferred synthetic carrier oils are alkanol alkoxylates, in particular alkanol propoxylates and alkanol butoxylates.
  • carrier oil component (B) comprises at least one polyether obtained from Ci-C3o-alkanols, especially C ⁇ -ds-alkanols, or C2-C6o-al- kandiols, especially C8-C24-alkandiols, and from 1 to 30 mol, especially 5 to 30 mol, in sum, of propylene oxide and/or butylene oxides.
  • Other synthetic carrier oils and/or mineral carrier oils may be present in component (B) in minor amounts.
  • Hydrocarbyl residue for R 1 to R 3 in formula I and for R 4 in formula Il shall mean a residue which is essentially composed of carbon and hydrogen, however, it can contain in small amounts heteroatomes, especially oxygen and/or nitrogen, and/or functional groups, e.g. hydroxyl groups and/or carboxylic groups, to an extent which does not distort the predominantly hydrocarbon character of the residue.
  • Hydrocarbyl residues are preferably alkyl, alkenyl, alkinyl, cycloalkyl, aryl, alkylaryl or arylalkyl groups.
  • Especially preferred hydrocarbyl residues for R 1 to R 3 in formula I and for R 4 in formula Il are linear or branched alkyl or alkenyl groups.
  • the amines (C) of formula I may exhibit one ("primary” amines), two ("secondary” amines) or three Ci-C3o-hydrocarbyl residues ("tertiary” amines), one or two Ci-C3o-hydrocarbyl residues are of special interest, the remaining R 1 to R 3 substituents being hydrogen in case of open-chain amines. If the amine (C) exhibits more than one Ci-C3o-hydrocarbyl residue they can be the same or different.
  • the said hydrocarbyl residues contain especially 6 to 30 carbon atoms, preferably 8 to 22 carbon atoms, more preferably 10 to 20 carbon atoms, and most preferably 12 to 18 carbon atoms. Such oleophilic long-chain hydrocarbyl residues provide advantageous properties to the amines, i.e. high solubility for gasoline fuels and low volatility.
  • Ci-C3o-alkyl residues examples include: methyl, ethyl, n-pro- pyl, iso-propyl, n-butyl, iso-butyl, sec. -butyl, tert.
  • Examples for suitable linear or branched C2-C3o-alkenyl and -alkinyl residues are: vinyl, allyl, oleyl and propin-2-yl.
  • Amines of formula I with long-chain alkyl and alkenyl residues can also preferably be obtained form natural sources, i.e. from plant or animal oils and lards.
  • the fatty amines derived from such sources which are suitable as amines of formula I of component (C) normally form mixtures of differents similar species such as homologues, e.g. tallow amines containing as main components tetradecyl amine, hexadecyl amine, octadecyl amine and octadecenyl amine (oleyl amine).
  • suitable fatty amines are: coco amines and palm amines.
  • Unsaturated fatty amines which contain alkenyl residues can be hydrogenated und used as component (C) in this saturated form.
  • C3-C3o-cycloalkyl residues are: cyclopropyl, cyclobutyl, cyclopen- tyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-di- methylcyclohexyl, 2,4-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclo- hexyl, 3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2-ethylcyclohexyl, 3-ethylcyclo- hexyl, 4-ethylcyclohexyl, cyclooctyl and cyclodecyl.
  • C ⁇ -Cso-aryl, -alkylaryl or -arylalkyl residues examples are: phenyl, naphthyl, tolyl, xylyl, n-octylphenyl, n-nonylphenyl, n-decylphenyl, benzyl, 1-phenylethyl, 2-phe- nylethyl, 3-phenylpropyl and 4-butylphenyl.
  • the at least one Ci-C3o-hydrocarbyl residue in formula I of component (C) is a linear or branched Cs-C22-alkyl group, especially a Nn- ear or branched Cio-C2o-alkyl group, most preferably a linear or branched Cs-ds-alkyl group.
  • the at least one amine of formula I of component (C) exhibits preferably two linear or branched Cs-C22-alkyl groups, especially two linear or branched Cio-C2o-alkyl groups, most preferably two linear or branched Cs-ds-alkyl groups for R 1 and R 2 , wherein R 1 and R 2 are preferably the same, and the third sub- stituent R 3 is hydrogen.
  • Typical examples for suitable primary amines of formula I based on the above hydro- carbyl residues are: methylamine, ethylamine, n-propylamine, n-butylamine, n-pentyl- amine, n-hexylamine, n-heptylamine, n-octylamine, 2-ethylhexylamine, n-nonylamine, iso-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, iso- tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, eicosylamine, cyclopentylamine, cyclohexylamine, cycl
  • Typical examples for suitable secondary amines of formula I based on the above hy- drocarbyl residues are: dimethylamine, diethylamine, di-n-propylamine, di-iso-propyl- amine, di-n-butylamine, di-iso-butylamine, di-tert.-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-(2-ethylhexyl)amine, di-n-nonyl- amine, di-iso-nonylamine, di-n-decylamine, di-n-undecylamine, di-n-dodecylamine, di-n-tridecylamine, di-iso-tridecylamine, di-tetradecylamine, di-pentadecylamine, di-hexade
  • Typical examples for suitable tertiary amines of formula I based on the above hydro- carbyl residues are: trimethylamine, triethylamine, tri-n-propylamine, tri-iso-propyl- amine, tri-n-butylamine, tri-iso-butylamine, tri-tert.-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-(2-ethylhexyl)amine, tri-n-no- nylamine, tri-iso-nonylamine, tri-n-decylamine, tri-n-undecylamine, tri-n-dodecylamine, tri-n-tridecylamine, tri-iso-tridecylamine, tri-tetradecylamine, tri-pentadecylamine, tri-he-
  • the said Ci-C3o-hydrocarbyl residues can contain a second nitrogen atom, thus forming a polyamine.
  • open-chain polyamines are: 1 ,2-ethylene diamine, 1 ,3-proplyene diamine, N,N-dimethyl-1 ,3-propylene diamine, o-phenylene diamine, m-phenylene diamine, p-phenylene diamine and N,N'-di-sec.-butyl p-phenylene dia- mine.
  • Suitable amines of formula I for component (C) are monocyclic structures, wherein one hydrocarbyl residue forms with the first nitrogen atom and with another hydrocarbyl residue or with a polyoxyalkylene residue a five- or six-membered ring. If a polyoxyal- kylene residue takes part in forming such ring containing one or two oxygen atoms, n in formula Il is the number of 1 or 2. Examples for such monocyclic amines are: piperidine, piperazine and morpholine.
  • A is normally a linear or branched alkylene group derived from the corresponding alkylene oxide such as ethylene oxide, propylene oxide and/or butylene oxide.
  • the amine of formula I can also exhibit different alkylene oxide units in its polyoxyalkylene residue of formula II, caused by a manufacturing process for the amine of formula I using a mixture of different alkylene oxides resulting in a random structure or different alkylene oxides reacted one after another resulting in a block structure.
  • n is preferably a number of from 3 to 40, more preferably of from 5 to 35, most preferably of from 10 to 25.
  • the at least one polyoxyalkylene residue of formula Il in the amine of component (C) is a polyoxypropylene or polyoxybutylene group with 10 to 35 propylene oxide and/or butylenes oxide units, capped with a linear or branched Cs-C22-alkyl group, especially a linear or branched Cio-C2o-alkyl group, most preferably a linear or branched Cs-C-is-alkyl group.
  • formula I of component (C) exhibits preferably one such polyoxyalkylene residues of formula Il and R 2 and R 3 are hydrogen.
  • Suitable amines of formula I based on the above polyoxyalkylene residues are polyetheramines of formulas R 4 -(O-C3H6)n-NH2 or R 4 ⁇ O-C 4 He) n -N H2 wherein R 4 is a n-tridecyl, an iso-tridecyl or a nonylphenyl residue und n is a number of from 10 to 25.
  • the fuel additive composition is a mixture of the fuel additive composition
  • the instant fuel additive composition may be formulated as a concentrate, using an inert stable oleophilic (i.e., dissolves in fuel) organic solvent boiling in the range of about 65°C to 205 0 C.
  • an aliphatic or an aromatic hydrocarbon solvent is used, such as benzene, toluene, xylene or higher-boiling aromatics or aromatic thinners.
  • Aliphatic alcohols of about 3 to 8 carbon atoms, such as isopropanol, isobutylcar- binol, n-butanol, 2-ethylhexanol, and the like, in combination with hydrocarbon solvents, are also suitable for use in such concentrate.
  • the amount of the instant fuel additive composition will be ordinarily at least 10% by weight to about 90% by weight, as for example 40 to 85 weight percent or 50 to 80 weight percent.
  • additives of the present invention including, for example, oxygenates, such as tert. -butyl methyl ether, antiknock agents, such as methylcyclopentadienyl manganese tricarbonyl, and other dispersants/detergents, such as various hydrocarbyl amines, or succinimides.
  • oxygenates such as tert. -butyl methyl ether
  • antiknock agents such as methylcyclopentadienyl manganese tricarbonyl
  • other dispersants/detergents such as various hydrocarbyl amines, or succinimides.
  • polyetheramines i.e. hydrocarbyl poly(oxyalkylene) amines, which are known to function as detergents and/or carrier fluids, are excluded from the instant fuel additive composition if component (C) already comprises one or more species with polyoxyal- kylene residues of formula Il .
  • suitable other detergent additives is for example given in WO 00/47698 or in EP-
  • lead scavengers such as aryl halides, e.g., dichlorobenzene, or alkyl halides, e.g., ethylene dibromide.
  • aryl halides e.g., dichlorobenzene
  • alkyl halides e.g., ethylene dibromide.
  • antioxidants, metal deactivators, pour point depressants, corrosion inhibitors and demulsifiers may be present.
  • the weight ratio of dispersant component (A) to amine component (C) is in the range of from 0.3 : 1 to 3: 1 , especially of from 0.5 to 1.5 : 1 , thus provided the best improvement of intake valve clean-up performance of gasoline fuels.
  • the amine (C) may exhibit a synergistic effect in this respect when used in combination with components (A) and (B) of the instant fuel additive composition.
  • the fuel additive composition of the present invention will generally be employed in a liquid hydrocarbon distillate fuel boiling in the gasoline range. It is in principle suitable for use in all types of gasoline, including "light” and “severe” gasoline species.
  • the gasoline fuels may also contain amounts of other fuels such as, for example, ethanol.
  • the proper concentration of the instant fuel additive composition necessary in order to achieve the desired intake valve clean-up performance varies depending upon the type of fuel employed, and may also be influenced by the presence of other detergents, dis- persants and other additives, etc. Generally, however, from 200 to 10.000 weight ppm, especially from 400 to 2800 weight ppm, of the instant fuel additive composition per part of base fuel is needed to achieve the best results.
  • dispersant component (A) is present in the instant fuel composition at a level of from more than 50 to 3000 ppm, especially from 100 to 800 ppm, carrier oil component (B) at a level of from 50 to 2000 ppm, especially from 100 to 800 ppm, and amine component (C) at a level of from 100 to 3000 ppm, especially from 200 to 1200 ppm (all ppm values refer to the weight).
  • gasoline fuels which may be used according to the present invention exhibit, in addition, one or more of the following features:
  • the aromatics content of the gasoline is preferably not more than 50 volume % and more preferably not more than 45 volume %. Preferred ranges for the aromatics content are from 1 to 45 volume % and particularly from 5 to 40 volume %.
  • the sulfur content of the gasoline is preferably not more than 100 ppm by weight and more preferably not more than 50 ppm by weight.
  • Preferred ranges for the sulfur con- tent are from 0.5 to 150 ppm by weight and particularly from 1 to 100 ppm by weight.
  • the gasoline has an olefin content of not more than 21 volume %, preferably not more than 18 volume %, and more preferably not more than 10 volume %. Preferred ranges for the olefin content are from 0.1 to 21 volume % and particularly from 2 to 18 volume %.
  • the gasoline has a benzene content of not more than 1.0 volume % and preferably not more than 0.9 volume %. Preferred ranges for the benzene content are from 0 to 1.0 volume % and preferably from 0.05 to 0.9 volume %.
  • the gasoline has an oxygen content of not more than 45 weight %, preferably from 0 to 45 weight %, and most preferably from 0.1 to 2.7 weight % (first type) or most preferably from 2.7 to 45 weight % (second type).
  • the gasoline of the second type mentioned above is a mixture of lower alcohols such as methanol or especially ethanol, which derive preferably from natural source like plants, with mineral oil based gasoline, i.e. usual gasoline produced from crude oil.
  • An example for such gasoline is "E 85", a mixture of 85 volume % of ethanol with 15 volume % of mineral oil based gasoline.
  • the content of alcohols, especially lower alcohols, and ethers in a gasoline of the first type mentioned in the above paragraph is normally relatively low.
  • Typical maximum contents are for methanol 3 volume %, for ethanol 5 volume %, for isopropanol 10 volume %, for tert.-butanol 7 volume %, for isobutanol 10 volume %, and for ethers containing 5 or more carbon atoms in the molecule 15 volume %.
  • a gasoline which has an aromatics content of not more than 38 volume % and at the same time an olefin content of not more than 21 volume %, a sulfur content of not more than 50 ppm by weight, a benzene content of not more than 1.0 volume % and an oxygen content of from 0.1 to 2.7 weight % may be applied.
  • the summer vapor pressure of the gasoline is usually not more than 70 kPa and preferably not more than 60 kPa (at 37°C).
  • the research octane number ("RON") of the gasoline is usually from 90 to 100.
  • a usual range for the corresponding motor octane number (“MON”) is from 80 to 90.
  • the internal combustion engine is the internal combustion engine.
  • the above amine component (C) is preferably used as an intake valve clean-up booster in accordance with the instant invention in gasoline-operated port fuel injection internal combustion engines which are different in view of their construction and their mode of operation from direct injection spark ignition engines.

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

Abstract

La présente invention concerne une composition d'additif de carburant comprenant des monoamines ou des polyamines polyisobutènyle utilisées comme dispersants contenant de l'azote, des huiles support minérales ou synthétiques sensiblement exemptes d'azote et, des amines avec des résidus hydrocarbyle. Par ailleurs, l'invention concerne une composition de carburant essence comprenant une quantité mineure de cette composition d'additif de carburant. Enfin l'invention concerne l'utilisation de ces amines comme renforçateur de nettoyage de soupape d'admission dans des moteurs à combustion interne fonctionnant avec de l'essence contenant les détergents susmentionnés et les huiles support.
PCT/EP2008/067227 2007-12-11 2008-12-10 Amines utilisées comme renforçateurs de nettoyage de soupape d'admission WO2009074608A1 (fr)

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Cited By (8)

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US20110146144A1 (en) * 2009-12-21 2011-06-23 Bp Corporation North America Inc. Composition and Method for Reducing Friction in Internal Combustion Engines
US20110146143A1 (en) * 2009-12-21 2011-06-23 Bp Corporation North America Inc. Composition and Method for Reducing Friction in Internal Combustion Engines
WO2013075978A1 (fr) 2011-11-23 2013-05-30 Basf Se Mélange d'amines
WO2013174619A1 (fr) 2012-05-25 2013-11-28 Basf Se Amines tertiaires pour la réduction de l'encrassement d'injecteurs dans des moteurs à allumage par étincelles et à injection directe
WO2014023853A2 (fr) 2012-11-06 2014-02-13 Basf Se Amines tertiaires permettant de réduire l'encrassement des buses d'injecteur et de modifier le frottement dans les moteurs à allumage par étincelle avec injection directe
WO2014184066A1 (fr) 2013-05-14 2014-11-20 Basf Se Polyalcénylsuccinimides pour réduire l'encrassement d'injecteurs dans des moteurs à allumage commandé et injection directe
WO2014184013A1 (fr) 2013-05-14 2014-11-20 Basf Se Mélange d'amines
US9388354B2 (en) 2012-11-06 2016-07-12 Basf Se Tertiary amines for reducing injector nozzle fouling and modifying friction in direct injection spark ignition engines

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WO1990010051A1 (fr) * 1989-02-21 1990-09-07 Union Oil Company Of California Composition de carburant permettant la regulation de depots sur des soupapes d'admission
US5006130A (en) * 1989-06-28 1991-04-09 Shell Oil Company Gasoline composition for reducing intake valve deposits in port fuel injected engines
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WO2001023440A1 (fr) * 1999-09-28 2001-04-05 The Lubrizol Corporation Additifs pour carburant et compositions de carburant comprenant lesdits additifs
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US20050155280A1 (en) * 2002-03-06 2005-07-21 Harald Schwahn Fuel additive mixtures for gasolines with synergistic ivd performance
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110146144A1 (en) * 2009-12-21 2011-06-23 Bp Corporation North America Inc. Composition and Method for Reducing Friction in Internal Combustion Engines
US20110146143A1 (en) * 2009-12-21 2011-06-23 Bp Corporation North America Inc. Composition and Method for Reducing Friction in Internal Combustion Engines
WO2011084457A1 (fr) * 2009-12-21 2011-07-14 Bp Corporation North America Inc. Composition et méthode pour la réduction des frottements dans les moteurs à combustion interne
CN102666813A (zh) * 2009-12-21 2012-09-12 Bp北美公司 用于减少内燃机中的摩擦的组合物和方法
WO2013075978A1 (fr) 2011-11-23 2013-05-30 Basf Se Mélange d'amines
WO2013174619A1 (fr) 2012-05-25 2013-11-28 Basf Se Amines tertiaires pour la réduction de l'encrassement d'injecteurs dans des moteurs à allumage par étincelles et à injection directe
AU2013265575B2 (en) * 2012-05-25 2017-06-15 Basf Se Tertiary amines for reducing injector nozzle fouling in direct injection spark ignition engines
WO2014023853A2 (fr) 2012-11-06 2014-02-13 Basf Se Amines tertiaires permettant de réduire l'encrassement des buses d'injecteur et de modifier le frottement dans les moteurs à allumage par étincelle avec injection directe
WO2014023853A3 (fr) * 2012-11-06 2014-04-10 Basf Se Amines tertiaires permettant de réduire l'encrassement des buses d'injecteur et de modifier le frottement dans les moteurs à allumage par étincelle avec injection directe
US9388354B2 (en) 2012-11-06 2016-07-12 Basf Se Tertiary amines for reducing injector nozzle fouling and modifying friction in direct injection spark ignition engines
WO2014184066A1 (fr) 2013-05-14 2014-11-20 Basf Se Polyalcénylsuccinimides pour réduire l'encrassement d'injecteurs dans des moteurs à allumage commandé et injection directe
WO2014184013A1 (fr) 2013-05-14 2014-11-20 Basf Se Mélange d'amines

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