EP1098953B1 - Compositions de carburant contenant du propoxilate - Google Patents

Compositions de carburant contenant du propoxilate Download PDF

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Publication number
EP1098953B1
EP1098953B1 EP99932855A EP99932855A EP1098953B1 EP 1098953 B1 EP1098953 B1 EP 1098953B1 EP 99932855 A EP99932855 A EP 99932855A EP 99932855 A EP99932855 A EP 99932855A EP 1098953 B1 EP1098953 B1 EP 1098953B1
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Prior art keywords
additive
fuel
formula
additives
propoxylate
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EP1098953A1 (fr
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Wolfgang Günther
Knut Oppenländer
Harald Schwahn
Irene Trötsch-Schaller
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BASF SE
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BASF SE
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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
    • C10L1/18—Organic compounds containing oxygen
    • 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
    • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
    • 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
    • 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
    • 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 new propoxylate-containing Fuel compositions and new additive concentrates.
  • Carburetors and intake systems of gasoline engines, but also injection systems for fuel metering in petrol and diesel engines are increasingly contaminated.
  • the Impurities are caused by dust particles from the Air sucked in by the engine, unburned hydrocarbon residues from the combustion chamber and the ventilation gases led into the carburetor from the crankcase.
  • fuel additives for keeping valves and carburetor or injection systems clean can be used (see e.g. M. Rossenbeck in catalysts, Surfactants, mineral oil additives, ed. J. Falbe, U. Hasserodt, P. 223, G. Thieme Verlag, Stuttgart 1978).
  • the first generation of additives could only prevent the formation of deposits in the intake system, but do not remove any existing deposits.
  • the Second generation additives can prevent deposits and eliminate (keep-clean and clean-up effect). This is particularly due to their excellent thermal stability Zones of higher temperature, such as particularly at the inlet valves, allows.
  • Products are typical representatives of the second generation of additives based on polyisobutene in the non-polar part of the molecule, such as in particular Polyisobutylamine type additives.
  • Such detergents are based on polyisobutenes, according to two different Multi-stage synthesis process can be produced: The first process proceeds via chlorination of the polymeric base body, followed from a nucleophilic substitution of the polymeric base by amines or preferably ammonia.
  • a disadvantage of this Process is the use of chlorine, which has the consequence that Products containing chlorine or chloride occur, which is not the case today is more desirable.
  • the polyisobutylamines starting from polyisobutene via hydroformylation and then reductive amination according to EP-A-0 244 616.
  • Detergent additives from a variety of chemical substance classes can generally come in combination with a Carrier oil for use.
  • the carrier oils practice an additional one "Washing function", often support and promote the detergents in their effect and can reduce the needed Amount of detergent. Unfold certain detergents their effect only in combination with a carrier liquid. Viscous, high-boiling oils are usually used as carrier oils and in particular thermostable liquids are used. You overdraw the hot metal surface (e.g. the inlet valves) a thin film of liquid and thereby prevent or delay to a certain extent the formation or deposition of Decomposition products on the metal surfaces, but without the To be able to replace detergent additive component.
  • Suitable carrier oils for fuels for internal combustion engines are z. B. high-boiling, refined mineral oil fractions, but also synthetic liquids. Suitable mineral carrier oils are z. B. in the oil processing fractions.
  • suitable synthetic carrier oils are polyolefins, (Poly) esters, (poly) alkoxylates, and in particular aliphatic polyethers, aliphatic polyetheramines, alkylphenol-started polyethers and alkylphenol started polyetheramines.
  • Adducts of butylene oxide with alcohols are excellent Solubility in fuels, however, are comparatively expensive Products and butylene oxide must be proportionate are manufactured in a complex manner.
  • Inexpensive carrier oils can be in the form of adducts of propylene oxide of alcohols.
  • EP-A-0 704 519 describes propoxylates as a carrier oil component in combination with a high molecular amine and a hydrocarbon polymer.
  • EP-A-0 374 461 describes such propoxylates for use as a carrier oil in combination with esters from mono- or polycarboxylic acids and alcohols or polyols and amino or amido groups containing detergents.
  • EP-A-0 374 461 expressly teaches (see p. 4, lines 29ff.) that the sole use of the therein described propoxylates only an insufficient reduction in Inlet valve deposits, namely from 80 to 220 mg leads per valve.
  • the carrier oils contain on propylene oxide, but still show not the optimal cleaning effect in the engine.
  • the carrier oils contain on propylene oxide, but still show not the optimal cleaning effect in the engine.
  • Continue to prepare such adducts of propylene oxide with alcohols often cause problems their limited solubility in and due to fuels their lack of compatibility with other additives, so that segregation can occur. This effect occurs particularly come to light dramatically when additive concentrates - as such additive systems are usually marketed - formulated should.
  • the invention was therefore based on the object of novel fuel compositions for internal combustion engines with improved Provide properties.
  • the new Fuel compositions at significantly reduced intake valve deposits to lead.
  • the fuel compositions according to the invention have the surprising advantage that they have deposits in the area of Reduce intake valves significantly better than the corresponding ones shorter-chain or longer-chain propoxylates. This is particularly so surprising because so far assumed was that compounds of the type used only as carrier oils are useful for fuel compositions, carrier oils however, not a satisfactory intake system-cleaning per se Have an effect.
  • the fuel compositions of the invention which the have above-mentioned additive combination, also effect Surprisingly, significantly reduced intake valve deposits.
  • the hydrophobic hydrocarbon radical preferably has a number average molecular weight (M N ) of 113 to 10,000, in particular 300 to 5000.
  • M N number average molecular weight
  • additives containing monoamino groups (a) are that of polyisobutene epoxides by reaction with amines and subsequent ones Dehydration and reduction of the amino alcohols available Compounds as described in particular in DE-A 196 20 262 are.
  • These implementation products provide usually mixtures of pure nitropolyisobutanes (e.g. ⁇ , ⁇ -dinitropolyisobutane) and mixed hydroxynitropolyisobutanes (e.g. ⁇ -nitro- ⁇ -hydroxypolyisobutane).
  • Additives containing carboxyl groups or their alkali metal or alkaline earth metal salts (d) are preferably copolymers of C 2 -C 40 olefins with maleic anhydride with a total molar mass of 500 to 20,000, the carboxyl groups of which are wholly or partly to the alkali metal or alkaline earth metal salts and a remaining one The rest of the carboxyl groups are reacted with alcohols or amines.
  • Such additives are known in particular from EP-A-0 307 815.
  • Such additives mainly serve to prevent valve seat wear and, as described in WO-A 87/01126, can advantageously be used in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.
  • Additives containing (e) are preferably alkali metal or Alkaline earth metal salts of an alkyl sulfosuccinate, as described in particular in EP-A-0 639 632. Such Additives are mainly used to prevent valve seat wear and can be advantageous in combination with usual Fuel detergents such as poly (iso) butenamines or polyether amines be used.
  • Polyoxy-C 2 -C 4 -alkylene (f) additives are preferably polyethers or polyetheramines which are obtainable by reaction of C 2 - to C 60 alkanols, C 6 - to C 30 alkanediols, mono- or di-C 2 - C 30 alkyl amines, C 1 -C 30 alkylcyclohexanols or C 1 -C 30 alkyl phenols with 1 to 30 mol ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of the polyether amines, by subsequent reductive amination with Ammonia, monoamines or polyamines are available.
  • Such products are described in particular in EP-A-0 310 875, EP-A-0 356 725, EP-A-0 700 985 and US-A-4,877,416.
  • polyethers such products also have carrier oil properties. Typical examples of this are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates as well as the corresponding reaction products with ammonia.
  • Additives containing carboxylic acid ester groups (g) are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, in particular those with a minimum viscosity of 2 mm 2 / s at 100 ° C., as described in particular in DE-A-38 38 918 are described.
  • Aliphatic or aromatic acids can be used as mono-, di- or tricarboxylic acids, and long-chain representatives with, for example, 6 to 24 carbon atoms are particularly suitable as ester alcohols or polyols.
  • esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and iso-tridecanol.
  • Such products also have carrier oil properties.
  • Derivatives with aliphatic polyamines such as ethylene diamine, diethylene triamine, triethylene tetramine or tetraethylene pentamine are of particular interest.
  • Such gasoline fuel additives are described in particular in US-A-4,849,572.
  • Additives containing groups (i) produced by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine.
  • Such "polyisobutene Mannich bases” are described in particular in EP-A-0 831 141.
  • the second embodiment is the additives i) and the additives ii) such as B. of formula II, in a total proportion of together about 100 to 10,000 mg / kg, preferably about 300 to 5000 mg / kg, especially about 500 to 3000 mg / kg, contain fuel.
  • C 8 -C 18 alkyl radicals suitable according to the invention in additives of the formula I are straight-chain or branched, saturated carbon chains with 8 to 18 carbon atoms.
  • the following radicals can be mentioned: n-hexyl, 1-, 2- or 3-methylpentyl, unbranched heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl and the one - or multiply branched analogues thereof.
  • Preferred long-chain radicals are branched or unbranched C 10 -C 16 -, in particular C 12 -C 14 alkyl. Tridecyl residues are particularly preferred.
  • C 8 -C 18 alkenyl residues suitable according to the invention in additives of the formula I are straight-chain or branched carbon chains with at least one carbon-carbon double bond and with 8 to 18 carbon atoms.
  • monounsaturated C 8 -C 18 alkenyl radicals which can be mentioned are radicals such as unbranched octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, pentadecenyl, hexadecenyl, heptadecenyl and octadecenyl, and the branched analogues thereof, the double bond in any one Position can occur.
  • both the cis and the trans isomers of the above C 8 -C 18 alkenyl radicals are included.
  • Preferred monounsaturated long-chain radicals are the C 10 -C 16 alkenyl radicals.
  • Polyalkyl radicals suitable according to the invention in additives of the formula II are preferably obtainable by homo- or copolymerization of straight-chain or branched C 2 -C 30 -alkenes, C 2 -C 6 -alkenes and in particular C 2 -C 4 -alkenes being preferred.
  • Particularly preferred C 2 -C 4 alkenes are 1-alkenes, such as propylene, 1-butene and isobutene.
  • the number average molecular weight of such polyalkyl radicals is approximately in the range from 500 to 5000, preferably approximately 800 to 1500, in particular approximately 1000.
  • the polyalkyl radical can be derived from a copolymer of 1-butene and isobutene and z. B. have a number average molecular weight of about 800 to about 1500.
  • Propoxylates of the formula I which are particularly preferred according to the invention are compounds in which R 1 represents straight-chain or branched alkyl radicals having 10 to 16 carbon atoms, or mixtures thereof.
  • R 1 represents straight-chain or branched alkyl radicals having 10 to 16 carbon atoms, or mixtures thereof.
  • Propoxylates of the formula I in which the radical R 1 is an alkyl radical having 12 to 14 carbon atoms or a mixture of such alkyl radicals are particularly preferred.
  • a propoxylate of the formula I in which the radical R 1 has 13 carbon atoms is particularly preferred.
  • propoxylates preferred according to the invention consists of 14 to 18 repeating units of the formula, in particular 14 to 17 and especially 14 to 16 repeating units built up.
  • the most preferred class of propoxylates includes 15 repeating propoxylate units. It should be taken into account that the above numerical values for n can also represent mean values, since many of the known production methods for such adducts of alkylene oxides with alcohols usually lead to a product mixture with a different molecular weight distribution.
  • Most preferred alkoxylates of the formula I according to the invention are adducts of 14 to 16, in particular 15 propylene oxide units of the above formula, with a branched C 13 alcohol, in particular C 13 monoalcohol.
  • Branched C 13 alcohols which can be used according to the invention are, for. B. also obtainable by oligomerization of C 2 -C 6 olefins, in particular C 3 - or C 4 -olefins, and subsequent hydroformylation.
  • An optionally occurring reaction mixture, the z. B. could include various alcohol isomers, can be used directly for the preparation of the additive components used according to the invention. A previous separation of the reaction mixture can, however, also be carried out if necessary.
  • alkanol propoxylates preferably used according to the invention are made in a conventional manner by using an alcohol as a starter molecule with propylene oxide in the presence of alkali, such as B. sodium hydroxide solution, potassium hydroxide solution, sodium methylate, potassium methylate or other alkali alkoxides, at temperatures in the range of about 120 to 160 ° C, preferably about 130 to 160 ° C, to the desired ones Adducts implemented.
  • alkali such as B. sodium hydroxide solution, potassium hydroxide solution, sodium methylate, potassium methylate or other alkali alkoxides
  • Propoxylate for example by treatment with magnesium silicate, freed from the catalyst.
  • the production takes place in analogy to the phenol started described in DE-A-41 42 241 Alkoxylates.
  • the polyalkylamines of the general formula II are compounds known per se and can be prepared by hydroformylation of reactive polyalkenes and subsequent reductive amination of the oxo product.
  • the reactive polyalkenes with an average molecular weight of about 500 to 5000 are homo- or copolymers of straight-chain or branched C 2 -C 30 -alkenes, preferably C 2 -C 6 -alkenes, in particular C 2 -C 4 -alkenes.
  • Reactive polyalkenes comprise unsaturated polymers of high chemical homogeneity, with more than 10% of the double bonds being alpha-permanent.
  • One way of producing reactive polyalkenes is disclosed in DE-A-27 02 604. Those reactive polyalkenes which are produced from 1-alkenes, such as in particular propylene, 1-butene, isobutene or mixtures thereof, are particularly preferred.
  • EP-A-0 244 616 describes in particular those polyalklamines in which the radical R 2 is derived from isobutene and up to 20% by weight of n-butene.
  • EP-A-0 695 338 describes in particular those polyalkylamines in which the radical R 2 is derived from one or more 1-n-alkenes having 3 to 6 carbon atoms and up to 50% by weight of ethene.
  • Fuel compositions according to the invention include both diesel fuels as well as fuels for gasoline engines. As fuels leaded and especially unleaded come for gasoline engines Regular and super gasoline into consideration.
  • the gasoline can components other than hydrocarbons, e.g. B. alcohols, such as methanol, ethanol, tert-butanol, and ether, e.g. B. methyl tertiary butyl ether, contain.
  • B. alcohols such as methanol, ethanol, tert-butanol, and ether, e.g. B. methyl tertiary butyl ether
  • Fuel compositions contain other additive components.
  • liquid detergent additives are sold by BASF AG, Ludwigshafen, under the trade name Kerocom®PIBA. These contain polyisobutenamines dissolved in aliphatic C 10-14 hydrocarbons.
  • additives there may be other common fuel additives included, such as Corrosion inhibitors, demulsifiers, Stabilizers, antioxidants, antistatic agents, metallocenes, such as ferrocene or methylcyclopentadiene-manganese tricarbonyl, Lubricity improvers and dyes (markers).
  • Corrosion inhibitors demulsifiers, Stabilizers, antioxidants, antistatic agents, metallocenes, such as ferrocene or methylcyclopentadiene-manganese tricarbonyl, Lubricity improvers and dyes (markers).
  • Corrosion inhibitors are mostly ammonium salts of organic carboxylic acids, by the corresponding structure of the starting compounds tend to form films. Also amines for lowering the pH are often found in corrosion inhibitors or can be added to the fuel as such. As non-ferrous metal corrosion protection heterocyclic aromatics are mostly used.
  • Amines in particular are antioxidants or stabilizers such as para-phenylenediamine, dicyclohexylamine, morpholine or derivatives to call these amines.
  • Phenolic antioxidants such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxiphenylpropionic acid and their derivatives are added to fuels.
  • Salts of fatty and sulfonic acids are usually found as demulsifiers Use.
  • lubricity improvers are certain carboxylic acids or fatty acids, alkenyl succinic acid esters, Bis (hydroxyalkyl) fatty amines; Hydroxyacetamide or castor oil.
  • Suitable lubricity additives are e.g. B. described in EP-A-0 780 460, 0 829 527, 0 869 163, 0 605 857, WO 97/45507, 98/30658 and in US-A-5,756,435 and 5,505,867, which hereafter each explicit reference is made.
  • the carboxylic acids mentioned or fatty acids can be used as monomers and / or dimeric species available.
  • Carrier oils may also be added, where appropriate the carrier oils differ from the compounds of the formula I.
  • mineral carrier oils examples include synthetic carrier oils and Mixtures thereof with the above additive (s) and Are fuel compatible.
  • Suitable mineral carrier oils are fractions, such as kerosene, that occur during oil processing or naphtha, brightstock or mineral oils with viscosity in the range SN 500 - 900; but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols.
  • Suitable synthetic carrier oils are polyolefins, (poly) esters, (poly) alkoxylates, and in particular aliphatic polyethers, aliphatic polyetheramines, alkylphenol-started polyethers and alkylphenol-started polyetheramines.
  • Suitable carrier oil systems are described, for example, in DE-A-38 38 918, DE-A-38 26 608, DE-A-41 42 241, DE-A-43 09 074, US-A-4,877,416 and EP-A-0 452 328.
  • particularly suitable synthetic carrier oils are alcohol-initiated polyethers having about 20 to 25 C 3 -C 6 alkylene oxide units, such as, for example, selected from propylene oxide, n-butylene oxide and i-butylene oxide units or mixtures thereof.
  • At least one detergent additive such as. B. according to formula II above, according to at least one lubricity additive
  • lubricity additive The above definition and / or at least one corrosion inhibitor if necessary as defined above.
  • Fuel additive mixtures which are preferably in the form of additive concentrates and as an inlet valve cleaner component at least one propoxylate additive of the formula I as defined above, in particular an alkanol propoxylate of the formula I above, if appropriate in combination with at least one polyalkylamine of formula II as defined above and optionally at least contain another remaining fuel additive.
  • Fuel additive mixtures propoxylate and polyalkylamine in one indicated above for the fuel compositions according to the invention molar ratio.
  • Another object of the present invention relates to Use of at least one propoxylate of the above general Formula I optionally in combination with at least one detergent additive as defined above, in particular a polyalkylamine General Formula II above, as an intake valve cleaner additive for fuel compositions for internal combustion engines.
  • the additives used were according to the following general rule manufactured.
  • a dewatered mixture of the alcohol and KOH used as starter is placed in a pressure vessel, the amount of KOH used being about 0.01 to 1% by weight, preferably 0.05 to 0.5% by weight, of expected total weight of the reaction product is.
  • the apparatus is then flushed several times with nitrogen, heated to approximately 135 ° C. and the propylene oxide is then metered in with stirring at a constant temperature and a pressure between 3 and 30 bar via an immersion tube or onto the surface. After the metering has ended, the reaction mixture is stirred until the pressure is constant. After the reactor contents have cooled to about 50 ° C., the reaction vessel is let down and flushed with nitrogen. The product is freed from volatile constituents, advantageously in vacuo, and possibly clarified by filtration.
  • the carrier oil component by the tridecanol propoxylate according to the invention with 15 moles of propylene oxide or a corresponding one propoxilate not according to the invention replaced with 25 moles of propylene oxide.
  • the formulation with the component according to the invention was homogeneous, while in the comparison formulation when left standing phase separation occurred at 20 ° C.

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Claims (14)

  1. Composition de carburant pour moteur à combustion, comprenant une quantité principale d'un carburant hydrocarbure liquide, caractérisée par une quantité nettoyant le système d'admission d'au moins un additif propoxylate de la formule I :
    Figure 00220001
    où
    n représente un nombre entier allant de 14 à 18, et
    R1 représente un reste alkyle en C8-C18 ou alcényle en C8-C18 linéaire ou ramifié.
  2. Composition de carburant selon la revendication 1, caractérisée en ce qu'elle contient le propoxylate de la formule I en une quantité allant de 50 à 5000 mg/kg de carburant.
  3. Composition de carburant pour moteur à combustion, comprenant une quantité principale d'un carburant hydrocarbure liquide, caractérisée par une quantité nettoyant le système d'admission d'une combinaison d'additifs, comprenant
    i) au moins un additif propoxylate de la formule I selon la revendication 1, et
    ii) au moins un additif détergent, qui est choisi parmi les additifs polyalkylamine de la formule II : R2 - NH2    où
       R2 représente un reste polyalkyle linéaire ou ramifié, avec un poids moléculaire moyen en nombre allant de 500 à 5000 ;
       le cas échéant en combinaison avec au moins un agent améliorant le pouvoir lubrifiant.
  4. Composition de carburant selon la revendication 3, caractérisée en ce qu'elle contient les additifs i) et ii) en une quantité totale allant de 100 à 10 OOO mg/kg de carburant.
  5. Composition de carburant selon l'une des revendications 3 et 4, caractérisée en ce qu'elle contient les additifs i) et ii) en un rapport molaire de 1:10 à 10:1.
  6. Composition de carburant selon l'une des revendications 4 et 5, caractérisée par au moins un additif polyalkylamine de la formule II, où R2 est un reste dérivé d'alcènes en C2-C30 identiques ou différents.
  7. Composition de carburant selon l'une des revendications 4 à 6, caractérisée en ce qu'elle contient comme additif de la formule II, au moins une polyisobutèneamine avec un poids moléculaire moyen en nombre allant de 800 à 1500.
  8. Composition de carburant selon l'une des revendications précédentes, caractérisée en ce qu'elle comprend au moins un additif de la formule I, où n représente la valeur entière 15 et R1 représente un reste alkyle en C13 linéaire ou ramifié.
  9. Mélange d'additifs de carburant, caractérisé en ce qu'il contient comme composant nettoyant le système d'admission, au moins un propoxylate selon la définition de la revendication 1, le cas échéant en combinaison avec au moins un additif détergent et le cas échéant, avec d'autres additifs usuels de carburant.
  10. Mélange d'additifs de carburant selon la revendication 9, caractérisé en ce qu'il contient le propoxylate et la polyalkylamine en un rapport molaire de 1:10 à 10:1.
  11. Mélange d'additifs de carburant selon la revendication 9 ou 10, caractérisé en ce qu'il comprend comme autre composant additif, au moins un agent améliorant le pouvoir lubrifiant.
  12. Mélange d'additifs de carburant selon l'une des revendications 9 à 11, préparé sous la forme d'un concentré d'additifs.
  13. Utilisation d'au moins un propoxylate selon la formule I :
    Figure 00240001
       où
       n représente un nombre entier allant de 14 à 18, et
       R1 représente un reste alkyle en C8-C18 ou alcényle en C8-C18 linéaire ou ramifié
       comme additif nettoyant le système d'admission pour composition de carburant pour moteurs à explosion.
  14. Utilisation selon la revendication 13, en combinaison avec au moins un additif détergent.
EP99932855A 1998-07-09 1999-07-08 Compositions de carburant contenant du propoxilate Expired - Lifetime EP1098953B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19830818 1998-07-09
DE19830818A DE19830818A1 (de) 1998-07-09 1998-07-09 Propoxilat enthaltende Kraftstoffzusammensetzungen
PCT/EP1999/004818 WO2000002978A1 (fr) 1998-07-09 1999-07-08 Compositions de carburant contenant du propoxilate

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EP1098953B1 true EP1098953B1 (fr) 2004-11-24

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Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19908262A1 (de) * 1999-02-25 2000-08-31 Basf Ag Polyalkenalkohol-Polyalkoxylate und deren Verwendung in Kraft- und Schmierstoffen
GB0022473D0 (en) * 2000-09-13 2000-11-01 Ass Octel Composition
US7204863B2 (en) 2001-12-11 2007-04-17 Exxonmobil Research And Engineering Company Gasoline additives for reducing the amount of internal combustion engine intake valve deposits and combustion chamber deposits
US7226489B2 (en) 2001-12-12 2007-06-05 Exxonmobil Research And Engineering Company Gasoline additives for reducing the amount of internal combustion engine intake valve deposits and combustion chamber deposits
GB0204241D0 (en) * 2002-02-22 2002-04-10 Ass Octel Compound
DE10209830A1 (de) * 2002-03-06 2003-09-18 Basf Ag Kraftstoffadditivgemische für Ottokraftstoffe mit synergistischer IVD-Performance
DE10316871A1 (de) * 2003-04-11 2004-10-21 Basf Ag Kraftstoffzusammensetzung
EP1591466A1 (fr) * 2004-04-26 2005-11-02 Basf Aktiengesellschaft Préparation des compositions comprenant des polyethers
WO2009074606A1 (fr) * 2007-12-11 2009-06-18 Basf Se Hydrocarbylphénols utilisés comme renforçateurs de nettoyage de soupape d'admission
WO2009074608A1 (fr) * 2007-12-11 2009-06-18 Basf Se Amines utilisées comme renforçateurs de nettoyage de soupape d'admission
ES2383491T3 (es) * 2008-02-01 2012-06-21 Basf Se Poliisobutenaminas y su uso como detergentes en combustibles
WO2009108851A1 (fr) * 2008-02-29 2009-09-03 Novus International Inc. Compositions de stabilisation du biodiesel
AU2011260433A1 (en) * 2010-06-01 2012-12-13 Basf Se Low-molecular weight polyisobutyl-substituted amines as detergent boosters
US8641788B2 (en) 2011-12-07 2014-02-04 Igp Energy, Inc. Fuels and fuel additives comprising butanol and pentanol
CA2912513A1 (fr) * 2013-05-14 2014-11-20 Basf Se Composition d'additifs pour carburant
WO2017097685A1 (fr) 2015-12-09 2017-06-15 Basf Se Nouveaux alkoxylates et leur utilisation
WO2018095759A1 (fr) 2016-11-23 2018-05-31 Basf Se Liquide de refroidissement de systèmes de refroidissment de véhicules électriques équipés de piles à combustible et/ou de batteries contenant des dérivés d'azole et des agents anti-corrosifs supplémentaires
EP3555244B1 (fr) 2016-12-15 2023-05-31 Basf Se Polymère comme additif pour gazole pour moteurs diesel à injection directe
RO132925A3 (ro) * 2018-06-12 2019-12-30 Igor Statnîi Agent tensioactiv polimetilaminic multifuncţional, şi procedeu de preparare a acestuia
FR3103815B1 (fr) * 2019-11-29 2021-12-17 Total Marketing Services Utilisation de diols comme additifs de détergence
ES2964845T3 (es) 2020-07-14 2024-04-09 Basf Se Inhibidores de corrosión para combustibles y lubricantes
WO2022128569A2 (fr) 2020-12-16 2022-06-23 Basf Se Nouveaux mélanges pour améliorer la stabilité d'ensembles d'additifs
WO2022263244A1 (fr) 2021-06-16 2022-12-22 Basf Se Bétaïnes quaternisées servant d'additifs dans des carburants

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3901665A (en) 1972-10-06 1975-08-26 Du Pont Multi-functional fuel additive compositions
DE3611230A1 (de) 1986-04-04 1987-10-08 Basf Ag Polybutyl- und polyisobutylamine, verfahren zu deren herstellung und diese enthaltende kraft- und schmierstoffzusammensetzungen
JP2840350B2 (ja) * 1987-11-18 1998-12-24 シェブロン リサーチ アンド テクノロジー カンパニー 相乗効果を有する燃料組成物
DE3838918A1 (de) * 1988-11-17 1990-05-23 Basf Ag Kraftstoffe fuer verbrennungsmaschinen
US5006130A (en) * 1989-06-28 1991-04-09 Shell Oil Company Gasoline composition for reducing intake valve deposits in port fuel injected engines
GB9207383D0 (en) * 1992-04-03 1992-05-13 Ass Octel Multi-functional gasoline detergent compositions
US6302929B1 (en) 1994-04-04 2001-10-16 Rudolf W. Gunnerman Aqueous fuel for internal combustion engine and method of preparing
US5405419A (en) * 1994-05-02 1995-04-11 Chevron Chemical Company Fuel additive compositions containing an aliphatic amine, a polyolefin and a poly(oxyalkylene) monool
DE4434603A1 (de) * 1994-09-28 1996-04-04 Basf Ag Als Kraft- und Schmierstoffadditiv geeignete Mischung aus Aminen, Kohlenwasserstoffpolymeren und Trägerölen
FR2751982B1 (fr) 1996-07-31 2000-03-03 Elf Antar France Additif d'onctuosite pour carburant moteurs et composition de carburants
US6821308B2 (en) * 1997-04-02 2004-11-23 Bayer Antwerp N.V. Polyoxyalkylene monoethers with reduced water affinity
US5873917A (en) * 1997-05-16 1999-02-23 The Lubrizol Corporation Fuel additive compositions containing polyether alcohol and hydrocarbylphenol
US5993499A (en) * 1997-06-27 1999-11-30 Chevron Chemical Company Fuel composition containing an aliphatic amine and a poly (oxyalkylene) monool
US6348075B1 (en) 1998-04-14 2002-02-19 The Lubrizol Corporation Compositions containing polyalkene-substituted amine and polyether alcohol

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PT1098953E (pt) 2005-04-29
MY129096A (en) 2007-03-30
SK285356B6 (sk) 2006-11-03
EE200100018A (et) 2002-06-17
AU751122C (en) 2003-07-03
ES2234271T3 (es) 2005-06-16
ZA200101091B (en) 2002-05-22
PL345511A1 (en) 2001-12-17
HRP20010100A2 (en) 2002-02-28
JP2002520444A (ja) 2002-07-09
HUP0102857A2 (hu) 2001-11-28
BRPI9911936B1 (pt) 2016-03-15
IL140401A (en) 2004-03-28
KR20010089133A (ko) 2001-09-29
WO2000002978A1 (fr) 2000-01-20
DE59911148D1 (de) 2004-12-30
HRP20010100B1 (en) 2005-08-31
TR200100019T2 (tr) 2001-06-21
PL191308B1 (pl) 2006-04-28
US7250065B1 (en) 2007-07-31
AU4908999A (en) 2000-02-01
NO20010120L (no) 2001-01-08
JP4603161B2 (ja) 2010-12-22
KR100649460B1 (ko) 2006-11-24
NZ509226A (en) 2003-09-26
CZ2001113A3 (cs) 2001-08-15
AR019355A1 (es) 2002-02-13
DE19830818A1 (de) 2000-01-13
AU751122B2 (en) 2002-08-08
ATE283332T1 (de) 2004-12-15
CA2336878A1 (fr) 2000-01-20
IL140401A0 (en) 2002-02-10
SK20172000A3 (sk) 2001-07-10
CA2336878C (fr) 2008-09-30
HUP0102857A3 (en) 2003-04-28
EP1098953A1 (fr) 2001-05-16
NO20010120D0 (no) 2001-01-08
EE04554B1 (et) 2005-10-17

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