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WO1990010051A1 - Composition de carburant permettant la regulation de depots sur des soupapes d'admission - Google Patents

Composition de carburant permettant la regulation de depots sur des soupapes d'admission Download PDF

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Publication number
WO1990010051A1
WO1990010051A1 PCT/US1990/000973 US9000973W WO9010051A1 WO 1990010051 A1 WO1990010051 A1 WO 1990010051A1 US 9000973 W US9000973 W US 9000973W WO 9010051 A1 WO9010051 A1 WO 9010051A1
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Prior art keywords
amine
polyisobutyl
carbon atoms
group
polypropyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1990/000973
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English (en)
Inventor
Michael C. Croudace
Gerald A. Wessler
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Union Oil Company of California
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Union Oil Company of California
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Filing date
Publication date
Application filed by Union Oil Company of California filed Critical Union Oil Company of California
Publication of WO1990010051A1 publication Critical patent/WO1990010051A1/fr
Anticipated expiration legal-status Critical
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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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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 improved hydro ⁇ carbon fuel compositions which control the formation and buildup of intake valve deposits in spark-ignition engines and more particularly to a deposit controlling additive composition for gasoline fuels used in said engines.
  • BMW has proposed that the maximum limit of intake valve deposit buildup be 100 mg/10,000 miles of driving as established by a standard test procedure developed by them and run at the Southwest Research Institute. Gasolines passing this test are given a lifetime BMW approval.
  • the amounts of intake valve deposit control detergents which must be used to meet this standard are often so high, that it is not economical in all grades of fuel.
  • the gasoline detergent itself has been found to result in an increase in intake valve depos ⁇ its. Consequently, there is a need for motor fuels containing an additive composition to prevent or reduce the formation and buildup of intake valve deposits to levels below the BMW standard while keeping port fuel injectors clean at economic treatment levels.
  • an intake valve deposit control additive comprised of a detergent selected from the group con ⁇ sisting of one or more C 6 + aliphatic primary amines, one or more gasoline dispersants selected from the group consisting of polyalkylamines and Mannich bases, and a nonvolatile fluidizer oil is added to gasoline.
  • the amount of additive used in the fuel is typically in the range between about 50 and about 1000 PTB.
  • the invention provides a method for operating a spark-ignition internal combustion engine which comprises introducing with the fuel an intake valve deposit controlling amount of said intake valve deposit control additive.
  • the invention further provides a motor fuel compo ⁇ sition comprising (1) a gasoline suitable for combus ⁇ tion in an automotive multiport fuel injected internal combustion engine, usually boiling in the gasoline range of about 100° F to about 437° F and (2) an intake valve deposit controlling amount of said intake valve deposit control additive.
  • an intake valve deposit controlling additive concentrate comprising (a) from about 50 to about 4000 grams per gallon of said additive and (b) the balance being a fuel-compatible diluent suitable for combustion in an automotive spark-ignition internal combustion engine.
  • the compounded fuel When the additive is used in a typical premium grade unleaded gasoline, the compounded fuel produces a level of intake valve deposit formation and buildup which is well below both the level required for BMW lifetime certification and that exhibited by the fuel either by itself or with either additive component used alone.
  • detergent denotes that class of chemical compounds compositions which reduce or prevent deposits in automobile spark-ignition inter ⁇ nal combustion engines operated at high speeds and temperatures.
  • a dispersant is defined as a type of detergent primarily adapted to the dispersion of depos ⁇ it precursors formed during relatively low temperature operation of said engines. Detergents and dispersants are closely related in that both of them solubilize engine deposits.
  • BMW Test refers to a test procedure as described by Bitting et al. in "Intake Valve Deposits - Fuel Detergency Requirements Revisit ⁇ ed" (SAE Paper 872117) , the teaching of which is herein incorporated by reference, in its entirety.
  • the intake valve deposit control additive of the present invention comprises a mixture of a long chain primary amine carburetor detergent, a fuel dispersant, and a fluidizer oil.
  • the long chain primary amines suitable for use in the present invention are those having the formula RNH 2 , in which R is a C 6 +, typically C 6 to C 40 aliphatic radical, with R preferably being either (1) an alkyl or akenyl radical having from about 12 to about 22 carbon atoms or (2) a radical of the form R-O-R' wherein R and R 1 are independently C 2 to C 20 aliphatic radicals. It should also be noted that if R is chosen to be an alkenyl group, mono-olefins are preferred.
  • the amine to be employed may be a single amine or may comprise mixtures of such amines.
  • a particularly effective, and preferred, amine is an 18 carbon atom, mono-unsaturated amine, oleyl amine, which is obtainable from the Ar ak Chemicals Division of Akzo America under the trade names Armeen 0, Armeen OL or Armeen OD, ⁇ the distilled form thereof, and from Sherex Chemical Co. as Adogen 172 or Adogen 172D.
  • Suitable amines which are generally mixtures of aliphatic amines include Adogen 170, Adogen 170D, Armeen T and Armeen TD, the latter being the distilled form of Armeen T which contains a mixture of 0-2% of tetradecyl amine, 24% to 30% of hexadecyl amine, 25% to 28% of octadecyl amine, and 45% to 46% of octadecenyl amine.
  • Armeen T and TD and Adogen 170 and 170D are derived from tallow fatty acids and are usually termed "tallow amines.”
  • Lauryl amine is also suitable, as is Adogen 163 or Armeen 12, or the distilled form Armeen 12D, also obtainable from the above named suppliers.
  • the distilled product comprises 0-2% of decyl amine, 0- 3% of tetradecyl amine, 90% to 95% of dodecyl amine, 0- 1% of octadecenyl amine.
  • the mixture of amines derived from soya fatty acids also falls within the class of amines above described as suitable for use according to this invention.
  • those amines having about 16 to about 18 carbon atoms are most preferred, and oleyl amine is the most particularly preferred long chain amine for use in the present invention.
  • R and R 1 are aliphatic radicals, more preferred are hydrocarbyl radicals, with alkyl and alkenyl radicals being most preferred, said radicals independently ranging between about 2 and about 20 carbon atoms, with the combined total of carbon atoms in R and R' being between about 10 and about 30. More preferred are compounds where R ranges between 10 and 20, and R 1 ranges between 2 and 10 carbon atoms and, in the most preferred compounds, R is between 12 and 15 and the total number of carbon atoms in R and R 1 is between 15 and 20.
  • Adogen 185 which is a mixture of dodecyloxy to pentadecyloxy propyl amines.
  • Others are Sherex MG 98, which is a mixture of octyloxy to decyloxy propyl amines, and MG 70, which is 1-meth- ylnonyloxy propyl amine.
  • the correspond ⁇ ing ethyl and butyl amines are also useful.
  • the amount of detergent amine used in the fuel is typically between 0.01 and about 100 pounds per thou ⁇ sand barrels of fuel (0.0000004 to 0.004 weight per ⁇ cent) , preferably between 1 and about 50 pounds per thousand barrels and most preferably between 1 and about 30 pounds per thousand barrels. Smaller amounts of amine than those indicated do not appear to have much if any detergent effect as indicated by the build ⁇ up of intake valve deposits. On the other hand, larger amounts are not required to prevent the formation and buildup of intake valve deposits.
  • the second constituent in the intake valve deposit control additive of this invention is a fuel dispersant selected from the group consisting of polyalkylamines and Mannich bases.
  • Polyalkyl amines are defined herein as being limited to amines other than monoalkyl primary mono-amines containing at least-one substantially olefin-free, aliphatic, hydrocarbyl radical free of alkynyl unsaturation, said radical having been formed at least in part by the polymerization or copolymeriza- tion of one or more olefins.
  • the polyalkylamine dispersants are high molecular weight branched chain aliphatic hydrocarbon N-substituted amines or alkylene polyamines, said amines and polyamines having molecular weights from about 150 to about 5,000.
  • Particularly preferred compositions in the present invention will have the following formula:
  • A is hydrogen, a hydrocarbyl group having from 1 to about 10 carbon atoms or a hydroxyhy- drocarbyl group having from 1 to about 10 carbon atoms
  • X is hydrogen, a hydrocarbon group having from 1 to about 10 carbon atoms or a hydroxyhydrocarbyl group having from 1 to about 10 carbon atoms, with either of said groups being optionally taken with A to form a ring of from 5 to 6 annular atoms and up to about 12 carbon atoms
  • U is an alkylene group of from 2 to about 6 carbon atoms, there being at least 2 carbon atoms between the nitrogen atoms shown
  • R is an aliphatic radical of from about 40 to about 5000 average molecu ⁇ lar weight
  • a is an integer from 1 to about 10
  • b is an integer from 0 to 1 with the sum of a + 2b being an integer from 1 to 10
  • c is an integer of from 1 to 5 and equal to or less than the number
  • the hydrocarbon radical indicated by R is rela ⁇ tively free of aliphatic unsaturation; that is, it will usually have not more than two sites of olefinic unsat- uration, preferably not more than one site of olefinic unsaturation, and no acetylenic unsaturation.
  • Polyalkyl monoamine compositions for this use have the general formula:
  • R is a branched chain aliphatic radical, sub ⁇ stantially free of olefinic unsaturation, and A is a lower alkyl group.
  • R is preferably an alkyl group.
  • polyalkyl monoamine dispersants conforming to this formula are polypropyl amine, polyisobutyl amine, N-polyisobutyl dimethyl amine, N-polyisobutyl methylethylamine, N-polypropyl diethyl amine, N-polypropyl di(2-hydroxyethyl) amine, N-polyisobutyl N-methyl aniline, N-polyisobutyl morpho- line, N-polyisobutyl piperidine, N-poly(sec-butene) propylamine, N-polypropyl N-(2-hydroxyethyl) amine, etc.
  • Preferred for this use are those amines wherein R has a molecular weight from about 40 to about 1250 and A has between 1 and about 3 carbon atoms.
  • Polyalkyl polyamine dispersant compositions pre ⁇ ferred in this invention conform generally to formula (3) as shown below:
  • the dispersant may be com ⁇ prised of monosubstituted polyamines wherein R is a branched hydrocarbon chain derived from polymerizing olefins of from 2 to about 6 carbon atoms.
  • Illustra ⁇ tive compounds useful for this purpose include N-polyi ⁇ sobutyl ethylene diamine, N-polypropyldiamine, N-poly(l-butenyl) ethylene diamine, N-(alternating ⁇ opolymer of ethylene and isobutylene) ethylene dia ⁇ mine, N-polypropyl 2-aminoethylpiperazine, N- polyisobutyl 2-aminoethylpiperazine, N-polypropyl diethylene triamine, N-polyisobutyl diethylene tria- mine, N-poly(1-pentenyl) or diethylene triamine, N- polypropyl trimethylene diamine, N-polyisobutyl tri- methylene diamine, N-polypropyl di-(trimethylene) triamine, N-polyisobutyl di-(trimethylene) triamine, N- polyisobutyl 1,2-propylene diamine, N-polyisobut
  • Suitable dispersants may also be prepared from po lyhydrocarbon radical substituted alkylene polyamine compositions.
  • Illustrative compounds are N,N'- di(polypropyl) diethylene triamine, N,N'-di(polyisobu- tyl) diethylene triamine, N,N'-di(isobutyl) triethylene tetramine, N,N'- di(polypropyl) tetraethylene penta ⁇ mine, N,N'-di(polyisobutyl) tetraethylene pentamine, N,N*N"-tri(polyisobutyl) tetraethylene pentamine, N,N'- di(polyisobutyl) 2-aminoethylpiperazine, N,N*-di(poly 1-butyl) triethylene tetramine, N,N'-di(polyisobutyl) di(trimethylene) triamine, etc.
  • straight chain alkylene polyamines particularly ethylene diamine and polyethylene polya ⁇ mines, wherein a of formula (3) is from 1 to about 4, and R is a branched chain aliphatic radical having an average molecular weight ranging from about 40 to about 1500, preferably alkyl groups, most preferably polypro- pyl or polyisobutyl, and with the polyamine having fewer R groups than nitrogen atoms.
  • the dispersant constituent comprises one or more com ⁇ pounds known as Mannich bases. These are condensation products formed by reacting an alkyl substituted hy- droxy substituted aromatic compound, an aldehyde and an amine.
  • the alkyl substituent has an average molecular weight in the range between about 100 to about 100,000, and the compound is prefer ⁇ ably a polyalkyl phenol whose alkyl component is de ⁇ rived from 1-mono-olefinic polymers having an average molecular weight ranging between about 100 and about 3000, the aldehyde is a low molecular weight aldehyde, and the amine has at least one >NH group and is prefer ⁇ ably an alkylene polyamine of the formula: NH 2 -(A - N) ⁇ - H (4) H wherein A is a divalent alkylene radical having from about 2 to about 6 carbon atoms and x is an integer ranging from 1 to about 10.
  • condensation product is prepared according to conventional methods heretofore employed and well known in the art for preparing Mannich type products.
  • the molar ratios of the alkyl substituted hydroxyaromatic compound, amine and alde ⁇ hyde be between about 1:1:10 to about 10:0.1:10.
  • alkyl-substituted hydroxyar ⁇ omatic compounds are polypropylphenol, polybutylphenol and other polyalkylphenols.
  • the alkyl substituents thereon may be derived from polypropylenes, polybutenes and other polymers of mono-olefins , principally 1-mono- olefins.
  • copolymers of mono-olefins with monomers copolymerizable therewith wherein the copolymer molecule comprises at least 90%, by weight, of mono-olefinic units.
  • copoly ⁇ mers of butenes (butene-1, butene-2 and isobutylene) with monomers copolymerizable therewith wherein the copolymer molecule contains at least 90%, by weight, of propylene. and butene units, respectively.
  • the copoly ⁇ merizable monomers may be aliphatic and can also con ⁇ tain non-aliphatic groups, e.g., styrene, methyl sty- rene, p-dimethyl styrene, divinyl benzene, and the like.
  • alkyl substituted hydroxyaro- matic compounds include, exclusive of sulfurized derivatives, alkyl-substituted derivatives of resorcinol, hydroquinone, cresol, cate- col, xylenol, hydroxy diphenyl, benzylphenol, pheneth- ylphenol, naphthol, tolynaphthol, among others.
  • polyalkylphenol reactants e.g., polypropylphenol and polybutylphenol whose alkyl group has an average molecular weight between about 100 and 3000 with the preferred configuration being that of a para-substituted mono-alkylphenol.
  • Representative amine reactants are alkylene polya ⁇ mines, particularly polyethylene amines.
  • Other repre ⁇ sentative organic compounds containing at least one >NH group suitable for use herein include the mono- and di- amino alkanes and their substituted analogs, e.g., ethylamine, dimethylamine, dimethyl aminopropyl amine and dimethanol amine; aromatic diamines, e.g., phenyl- ene diamine, diamino naphthylenes; heterocyclic amines, e.g., morpholine, pyrrole, pyrrolidine, imidiazol, imidiazolidine and piperidine; melamine and their substituted analogs.
  • Suitable alkylene polyamine reactants include ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hexaethylene heptamine, heptaethylene octa- mine, octaethylene nonamine, nonaethylene decamine, decaethylene undecamine and mixtures of such amines having nitrogen contents corresponding to the alkylene polyamines in formula (4) above, with A therein being divalent ethylene.
  • Corresponding polypropylene polya ⁇ mines such as propylene diamine and di-, tri-, tetra-, penta-propylene tri-, tetra-, penta- and hex-amines are also sutable as reactants.
  • aldehydes for use herein include the aliphatic aldehydes such as formaldehyde (including paraformaldehyde and Formalin) , acetaldehyde, and aldol, (b-hydroxybutyraldehyde) with formaldehyde or a formaldehyde-yielding reactant.
  • formaldehyde including paraformaldehyde and Formalin
  • acetaldehyde acetaldehyde
  • aldol b-hydroxybutyraldehyde
  • Concentrations of either the polyalkylamine or Mannich base dispersant in the fuel are typically between 0.1 and about 200, preferably between about 10 and about 100, more preferably between about 10 and about 85, and most preferably between about 10 and about 75 pounds per thousand barrels of gasoline fuel.
  • the third constituent in the intake valve deposit control additive of the present invention is a fluidiz- er oil.
  • These oils are believed act as a carrier for the other detergent/dispersant additives and to assist in removing and preventing deposits.
  • One suitable oil for this purpose is a nonvolatile lubricating mineral oil, particularly a refined napthenic lubricating oil having a viscosity, at 100° F, of between about 500 and 2,000 SUS.
  • Another is a polyolefin carrier, particu- larly polypropylene or polybutene having a molecular weight in the range from about 600 to about 3000.
  • such oils are typically added to provide a concentration in the range from about 20 to 300 pounds, preferably between about 50 to about to 200 pounds per thousand barrels of gasoline fuel.
  • the concentration of intake valve deposit control additive formulated as hereinabove is preferably be ⁇ tween about 50 and 600 pounds per thousand barrels of fuel, with between about 75 and about 500 being more preferred and between about 100 to about 300 being most preferred.
  • the intake valve deposit control additive of the present invention can be added, with success, to either leaded gasolines or unleaded gasolines such as those used with catalytic convertors.
  • An unleaded gasoline is defined as one containing less than 0.05 grams of lead per gallon of gasoline.
  • Liquid hydrocarbons fuels suitable for combustion in automotive multport-injected internal combustion engines are usually mixtures of hydrocarbons boiling in the range from about 100° F. to about 437° F. , and often comprise mixtures of saturated hydrocarbons, olefinic hydrocarbons and aromatic hydrocarbons.
  • Preferred are gasoline blends comprising a mixture having a saturated hydrocarbon content ranging from about 40 to about 80 percent, by volume, an olefinic content from about 0 to about 30 percent, by volume, and an aromatic content ranging from about 10 to about 60 percent, by volume.
  • the base fuel can be derived from straight run gasoline, polymer gasoline, natural gasoline, dimer and trimer olefins, synthetically- produced hydrocarbon mixtures derived from coal or shale oil, from thermally or catalytically reformed hydrocarbons, from thermally or catalytically cracked petroleum stocks, and mixtures of these. While the hydrocarbon composition and octane level of the gaso ⁇ line base fuel are not critical, the composition and octane level typically considered to constitute a commercial grade of unleaded fuel are preferred.
  • the hydrocarbon mixtures to which the intake deposit reducing additive composition of the present invention is applied are substantially lead- free but .may contain minor amounts of blending agents such as methanol, ethanol, methyl tertbutyl ether (MTBE) , and the like.
  • the fuel may also contain an- tioxidants such as phenolics, e.g., 2,6 di-tert-butyl- phenol or phenolenediamines, metal deactivators, deha- zors such as polyester-type ethoxylated alkylphenol formaldehyde resins and the like.
  • the fuel may also contain anti-knock compounds such as tetraethyl lead, a methyl cyclopetadienyl manganese tricarbonyl, orthoazi- dophenol and the like.
  • anti-knock compounds such as tetraethyl lead, a methyl cyclopetadienyl manganese tricarbonyl, orthoazi- dophenol and the like.
  • Dyes, dispersants, corrosion inhibitors, anti-icing agents, demusifiers and deposit modifiers can also be contained in the fuels. Prefera ⁇ bly, however, such additives do not contain lead.
  • the intake valve deposit control additive of the present invention can be introduced into an operating engine in a variety of ways.
  • the additive can be injected directly into the intake manifold intermit ⁇ tently or substantially continuously, preferably in a hydrocarbon carrier suitable for combustion in a spark- ignited internal combustion engine, usually having a final boiling point (by ASTM D86) lower than about 437° F.
  • a preferred method is to incorporate the additive into the gasoline blend. In so doing the additive can be added separately to the gasoline or blended with other gasoline additives.
  • the invention further provides a concentrate, dis solvable or miscible in gasoline, comprising: (a) from about 50 to about 4000 grams per gallon of the hereina- bove described intake valve deposit control additive, and (b) optionally from about 0.01 to about 0.2 weight percent of a dehazer with the balance being a diluent suitable for combustion in a multiport fuel injected internal combustion engine, said diluent usually boil ⁇ ing in the range from about 100° F to about 437° F.
  • the ratio of the concentrations of the individual constituents in the total additive blend will be about the same as given hereinabove for those in the fuel, i.e., the amine will be comprised of between 0.1 to about 100, preferably 1 to about 50 and most preferably 1 to about 30 parts, by weight, the dispersant 1 to about 200, preferably about 10 to about 100 and most preferably about 10 to about 95 and very most prefera ⁇ bly about 10 to about 75 parts, by weight, and the fluidizer 20 to about 300, and preferably 50 to about 200 parts, by weight, for each liquid unit of additive.
  • Diluents may include hydrocarbons and oxygen-containing hydrocarbons.
  • Suitable oxygen-containing hydrocarbons include methanol, ethanol, propanol, methyl-tert-butyl ether, and ethylene glycol monobutyl ether.
  • the hydro ⁇ carbon diluent may be an alkane such as heptane but is preferably an aromatic hydrocarbon such as toluene or xylene, alone or in admixture with said oxygen-contain ⁇ ing hydrocarbon diluents.
  • the optional dehazer is usually a polyester-type ethoxylated alkyl phenolfor ⁇ maldehyde resin, but is not specifically limited there ⁇ to. A sufficient amount of concentrate should be used to assure that concentration in the fuel is as defined hereinabove.
  • the additive of the present invention When the additive of the present invention is used in a gasoline fuel, it is found that a relatively low concentration of dispersant in the fuel will reverse any intake valve deposit forming tendencies exhibited by the amine detergent constituent and, therefore, produce a total composition suitable for BMW certifica ⁇ tion. Likewise, the use of the additive of the inven ⁇ tion enables the use of far less dispersant to be effective for intake valve deposit control.
  • the combination of detergent and dispersant components in the present invention achieves two impor ⁇ tant results simultaneously: (1) the dispersant over ⁇ comes the deposit-promoting effect of the C 6 + primary amine detergent, and (2) the amine allows for a sub ⁇ stantial .reduction in the amount of dispersant needed to remove deposits than would otherwise be the case if the dispersant were used alone.
  • This reduction in dispersant level means that fuels containing the addi ⁇ tive of the present invention will substantially im ⁇ prove engine performance with a lower intake valve deposit controlling additive cost than heretofore possible. This is because the dispersant is relatively far more expensive than the detergent.
  • the following example demonstrates the sur ⁇ prising reduction in intake valve deposits and perform ⁇ ance improvement achieved when using a fuel containing the intake valve deposit control additive of the present invention.
  • This example is meant to be illus ⁇ trative of the present invention and are not intended to limit the scope of the appended claims.

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  • Engineering & Computer Science (AREA)
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Abstract

Une composition de carburant pour moteur comprend (1) une essence adaptée pour brûler dans un moteur d'automobile à combustion interne à allumage par étincelle, et (2) une quantité d'un additif de régulation de dépôt sur des soupapes d'admission, comprenant C6+ amines primaire aliphatiques, un ou plusieurs dispersants d'essence choisis dans le groupe composé de polyalkylamines et de bases Mannich, ainsi qu'une huile fluidifiante non volatile.
PCT/US1990/000973 1989-02-21 1990-02-20 Composition de carburant permettant la regulation de depots sur des soupapes d'admission Ceased WO1990010051A1 (fr)

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Cited By (23)

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WO1991012302A1 (fr) * 1990-02-09 1991-08-22 Exxon Chemical Patents Inc. Combustible a essence pour moteurs a combustion interne
WO2002006428A1 (fr) * 2000-07-19 2002-01-24 The Lubrizol Corporation Composition additive pour combustibles de distillat moyen et compositions de combustibles de distillat moyen les contenant
US6475251B1 (en) 2001-02-28 2002-11-05 Chevron Oronite Company Llc Method for controlling engine deposits in a direct injection spark ignition gasoline engine
US6616776B1 (en) 2002-11-06 2003-09-09 Chevron Oronite Company Llc Method for removing engine deposits in a reciprocating internal combustion engine
US6652667B2 (en) 2002-01-23 2003-11-25 Chevron Oronite Company Llc Method for removing engine deposits in a gasoline internal combustion engine
US6651604B2 (en) 2002-01-23 2003-11-25 Chevron Oronite Company Llc Delivery device for removing interior engine deposits in a reciprocating internal combustion engine
US6660050B1 (en) 2002-05-23 2003-12-09 Chevron U.S.A. Inc. Method for controlling deposits in the fuel reformer of a fuel cell system
EP1431374A1 (fr) 2002-12-20 2004-06-23 Chevron Oronite Company LLC Méthode pour réduire les émissions de particules dans les moteurs à combustion interne
WO2009074608A1 (fr) * 2007-12-11 2009-06-18 Basf Se Amines utilisées comme renforçateurs de nettoyage de soupape d'admission
BE1018138A5 (fr) * 2006-08-17 2010-06-01 Afton Chemical Corp Composes d'additifs de carburant et procede de fabrication de ces composes.
WO2010091069A1 (fr) 2009-02-05 2010-08-12 Butamax™ Advanced Biofuels LLC Compositions d'additif de régulation du dépôt d'essence
US7901470B2 (en) 2002-03-14 2011-03-08 Shell Oil Company Gasoline additives
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
WO2011151207A1 (fr) 2010-06-01 2011-12-08 Basf Se Amines à substitution polyisobutyle, de faible masse moléculaire, servant de renforçateurs de détergents
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
US8632638B2 (en) 2010-11-19 2014-01-21 Chevron Oronite Company Llc Method for cleaning deposits from an engine fuel delivery system
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
US8926763B2 (en) 2007-05-17 2015-01-06 Chevron Japan Ltd. Method for cleaning internal parts of gasoline engines
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
WO2022009105A1 (fr) 2020-07-07 2022-01-13 Chevron Oronite Company Llc Additifs de carburant pour atténuer l'encrassement d'une buse d'injecteur et réduire les émissions de particules
WO2022058894A1 (fr) 2020-09-17 2022-03-24 Chevron Oronite Company Llc Aryloxy alkylamines utilisées comme additifs de carburant pour réduire l'encrassement des injecteurs dans des moteurs à essence, allumage par étincelle et injection directe
WO2023057943A1 (fr) 2021-10-06 2023-04-13 Chevron Oronite Company Llc Additifs de carburant pour abaisser le dépôt et l'émission de particules

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FR1221034A (fr) * 1958-01-20 1960-05-30 Union Oil Co Carburant détergent pour automobiles
US3438757A (en) * 1965-08-23 1969-04-15 Chevron Res Hydrocarbyl amines for fuel detergents
US3752657A (en) * 1971-04-26 1973-08-14 Chevron Res Nonionic surfactant as a demulsifier for amine containing fuel detergents
US3849083A (en) * 1972-04-14 1974-11-19 Ethyl Corp Gasoline additive
US4231759A (en) * 1973-03-12 1980-11-04 Standard Oil Company (Indiana) Liquid hydrocarbon fuels containing high molecular weight Mannich bases
US4022589A (en) * 1974-10-17 1977-05-10 Phillips Petroleum Company Fuel additive package containing polybutene amine and lubricating oil
US4116644A (en) * 1975-03-24 1978-09-26 Jackisch Philip F Gasoline compositions
EP0294045A2 (fr) * 1987-05-11 1988-12-07 Exxon Chemical Patents Inc. Agent modifiant le mélange à base d'amine dans des compositions d'huile lubrifiante

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991012302A1 (fr) * 1990-02-09 1991-08-22 Exxon Chemical Patents Inc. Combustible a essence pour moteurs a combustion interne
WO2002006428A1 (fr) * 2000-07-19 2002-01-24 The Lubrizol Corporation Composition additive pour combustibles de distillat moyen et compositions de combustibles de distillat moyen les contenant
US6475251B1 (en) 2001-02-28 2002-11-05 Chevron Oronite Company Llc Method for controlling engine deposits in a direct injection spark ignition gasoline engine
US6652667B2 (en) 2002-01-23 2003-11-25 Chevron Oronite Company Llc Method for removing engine deposits in a gasoline internal combustion engine
US6651604B2 (en) 2002-01-23 2003-11-25 Chevron Oronite Company Llc Delivery device for removing interior engine deposits in a reciprocating internal combustion engine
US7901470B2 (en) 2002-03-14 2011-03-08 Shell Oil Company Gasoline additives
US6660050B1 (en) 2002-05-23 2003-12-09 Chevron U.S.A. Inc. Method for controlling deposits in the fuel reformer of a fuel cell system
US6616776B1 (en) 2002-11-06 2003-09-09 Chevron Oronite Company Llc Method for removing engine deposits in a reciprocating internal combustion engine
EP1431374A1 (fr) 2002-12-20 2004-06-23 Chevron Oronite Company LLC Méthode pour réduire les émissions de particules dans les moteurs à combustion interne
BE1018138A5 (fr) * 2006-08-17 2010-06-01 Afton Chemical Corp Composes d'additifs de carburant et procede de fabrication de ces composes.
US8926763B2 (en) 2007-05-17 2015-01-06 Chevron Japan Ltd. Method for cleaning internal parts of gasoline engines
WO2009074608A1 (fr) * 2007-12-11 2009-06-18 Basf Se Amines utilisées comme renforçateurs de nettoyage de soupape d'admission
WO2010091069A1 (fr) 2009-02-05 2010-08-12 Butamax™ Advanced Biofuels LLC Compositions d'additif de régulation du dépôt d'essence
US8465560B1 (en) 2009-02-05 2013-06-18 Butamax Advanced Biofuels Llc Gasoline deposit control additive composition
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
WO2011151207A1 (fr) 2010-06-01 2011-12-08 Basf Se Amines à substitution polyisobutyle, de faible masse moléculaire, servant de renforçateurs de détergents
US8632638B2 (en) 2010-11-19 2014-01-21 Chevron Oronite Company Llc Method for cleaning deposits from an engine fuel delivery system
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
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
WO2022009105A1 (fr) 2020-07-07 2022-01-13 Chevron Oronite Company Llc Additifs de carburant pour atténuer l'encrassement d'une buse d'injecteur et réduire les émissions de particules
WO2022058894A1 (fr) 2020-09-17 2022-03-24 Chevron Oronite Company Llc Aryloxy alkylamines utilisées comme additifs de carburant pour réduire l'encrassement des injecteurs dans des moteurs à essence, allumage par étincelle et injection directe
WO2023057943A1 (fr) 2021-10-06 2023-04-13 Chevron Oronite Company Llc Additifs de carburant pour abaisser le dépôt et l'émission de particules

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