EP0647700A1 - Kraftstoffzusammensetzungen, und Zusätze dafür - Google Patents

Kraftstoffzusammensetzungen, und Zusätze dafür Download PDF

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Publication number
EP0647700A1
EP0647700A1 EP94307322A EP94307322A EP0647700A1 EP 0647700 A1 EP0647700 A1 EP 0647700A1 EP 94307322 A EP94307322 A EP 94307322A EP 94307322 A EP94307322 A EP 94307322A EP 0647700 A1 EP0647700 A1 EP 0647700A1
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EP
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Prior art keywords
weight
additive composition
fuel additive
poly
oxyalkylene
Prior art date
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EP94307322A
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English (en)
French (fr)
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EP0647700B1 (de
Inventor
Dennis J. Malfer
Lawrence J. Cunningham
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Ethyl Corp
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Ethyl Corp
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    • C10LFUELS 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
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    • C10L10/04Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
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    • C10L1/1985Macromolecular 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
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02BINTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B1/00Engines characterised by fuel-air mixture compression
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    • F02B1/04Engines characterised by fuel-air mixture compression with positive ignition with fuel-air mixture admission into cylinder

Definitions

  • This invention relates to fuel additive compositions that can be used for control of intake valve deposits without significantly affecting octane requirement increase in the engine.
  • the additive systems described in U.S. 5,242,469 comprise an ester and at least one dispersant component chosen from certain monosuccinimides, bis(succinimides), polyolefin polyamines, and benzylamine derivatives.
  • the benzylamine derivatives appear to be Mannich-type detergents*.
  • These additive combinations may further contain a polyoxyalkylene glycol or derivative thereof having a molecular weight of 500-5000, preferably 1000-3000.
  • a specified type of lubricating oil fraction may be included in the additive mixture.
  • the polyoxyalkylene glycol derivatives referred to in the text of the patent include the ethers, esters and ether aminoacid esters of the polyoxyalkylene glycol.
  • hydroxybenzyl amine derivatives are made by alkylating a hydroxybenzyl amine which in turn presumably would be formed by a Mannich reaction among phenol, formaldehyde and polyamine.
  • the resultant product should be similar, if not identical, to a product made in the more usual sequence of alkylating the phenol and then conducting the Mannich reaction with the resultant alkylated phenol, formaldehyde and a polyamine.
  • the gasoline is to contain (a) from 75 to 450 ppmw of a specified group of Mannich base detergents in combination with (b) from 75 to 175 ppmw of an oil-soluble poly(oxyalkylene) alcohol, glycol or polyol or mono or di ether thereof, wherein the weight ratio of (a) to (b) in the mixture is at least 0.43.
  • oil-soluble poly(oxyalkylene) alcohols, glycols or polyols or mono or di ethers thereof do not yield equivalent results on intake valve cleanliness when used in conjunction with a Mannich base detergent, and that for reasons not presently understood, the viscosity properties of the poly(oxyalkylene) component appear to have a profound effect on the intake valve cleanliness performance of the overall composition.
  • this invention provides, a fuel-soluble additive composition which comprises
  • this invention provides a fuel composition which comprises gasoline containing a minor intake valve deposit controlling amount of
  • the proportions of a) to b) in the compositions of this invention are such that there are from about 0.2 to about 5 parts by weight of a) per part by weight of b), preferably from about 0.5 to about 3 parts by weight of a) per part by weight of b), and more preferably from about 0.8 to about 2 parts by weight of a) per part by weight of b), with the weight of a) being on an "active ingredient basis".
  • component a) will usually be supplied in admixture on a weight basis with a minor amount of a hydrocarbon diluent and a minor amount of unreacted polyolefin used in making the alkylated phenol from which the Mannich detergent is produced.
  • proportions of a) to b) are based on the content of Mannich base detergent in component a) excluding the weight of any diluent or solvent and any unreacted polyolefin which may be associated therewith in the form in which it is supplied.
  • Component b) will normally be supplied in undiluted form, and in such case its weight can be used directly in calculating the ratio of a) to b).
  • the weight of b) should be based on the weight of the poly(oxyalkylene) compound itself and should likewise exclude the weight of any such solvent or diluent associated therewith.
  • any such ancillary solvent or diluent must not adversely affect the intake valve deposit control performance of the above additive composition in any material way.
  • ethers, esters or other inert solvents or diluents may be present in the additive composition.
  • the only ancillary diluents or solvents in the additive composition are hydrocarbons which collectively have viscosities at 40°C and 100°C that are not substantially in excess of the viscosity of the poly(oxyalkylene) compound.
  • these collective hydrocarbon viscosities are preferably not more than approximately 25 percent higher than the corresponding 40°C and 100°C viscosities of the poly(oxyalkylene) compound being used. Not only does this ensure that the intake valve deposit control effectiveness of the composition will not be adversely affected in any material way, but it keeps the cost of the additive composition to a minimum.
  • this invention provides a method for reducing intake valve deposits in gasoline engines.
  • the method comprises fueling said engines with a fuel composition comprising (a) a major amount of hydrocarbonaceous fuel in the gasoline boiling range and (b) a minor intake valve deposit controlling amount of
  • the Mannich reaction product component of this invention typically contains a significant portion of hydrocarbonaceous ingredients which are inactive in the sense that they do not possess polarity or surface activity and therefore do not serve as detergents.
  • hydrocarbon solvent is typically added to dilute the product to facilitate handling and blending.
  • the Mannich product as received typically contains about 40 to about 55 wt.% of the active Mannich base ingredient, the balance being solvent or diluent, and unreacted materials from the synthesis steps, such as polyolefin polymer.
  • a generally used dilution solvent is a mixture of aromatic hydrocarbons such as o-, p-, and m-xylene, mesitylene, and higher boiling aromatics such as Aromatic 150 (commercially available from Chemtech).
  • the Mannich reaction products of this invention are obtained by condensing an alkyl-substituted hydroxyaromatic compound whose alkyl-substituent has a number average molecular weight of from about 600 to about 14,000, preferably - alkylphenol whose alkyl substituent is derived from 1-mono-olefin polymer having a number average molecular weight of from about 600 to about 3000, preferably about 750 to about 1200, more preferably about 800 to about 1200, and most preferably about 800 to about 950; an amine having at least one >NH group, preferably an alkylene polyamine of the formula H2N - (A - NH -) x H where A is a divalent alkylene radical having 1 to 10 carbon atoms and x is an integer from 1 to 10; and an aldehyde, preferably formaldehyde or a formaldehyde precursor, in the presence of a solvent.
  • Commercial grades of alkylene polyamines often contain mixture
  • High molecular weight Mannich reaction products useful as additives in the fuel additive compositions of this invention are preferably prepared according to conventional methods employed for the preparation of Mannich condensation products, using the above-named reactants in the respective molar ratios of (i) high molecular weight alkyl-substituted hydroxyaromatic compound, (ii) amine, and (iii) aldehyde of approximately 1.0 : 0.1-10 : 1-10. Usually the reactants are charged in proportions such that there are an excess of the aldehyde and an excess of a polyamine relative to the hydroxyaromatic compound such as an alkylphenol which thereby becomes the limiting reactant.
  • a suitable condensation procedure involves adding at a temperature of from room temperature to about 95°C, the formaldehyde reagent (e.g., Formalin) to a mixture of amine and alkyl-substituted hydroxyaromatic compounds alone or in an easily removed organic solvent, such as benzene, xylene, or toluene or in solvent-refined neutral oil and then heating the reaction mixture at an elevated temperature (120°-175°C) while preferably blowing with an inert stripping gas, such as nitrogen, carbon dioxide, etc., until dehydration is complete.
  • an inert stripping gas such as nitrogen, carbon dioxide, etc.
  • Preferred Mannich reaction product additives employed in this invention are derived from high molecular weight Mannich condensation products, formed by reacting an alkylphenol, an ethylene polyamine, and a formaldehyde affording reactants in the respective molar ratio of 1.0 : 0.5-2.0 : 1.0-3.0, wherein the alkyl group of the alkylphenol has a number average molecular weight (Mn) of from about 600 to about 3,000, and more preferably from about 750 to about 1,200.
  • Mn number average molecular weight
  • High molecular weight alkyl-substituted hydroxyaromatic compounds are polypropylphenol (formed by alkylating phenol with polypropylene), polybutylphenol (formed by alkylating phenol with polybutenes or polyisobutylene), and other similar long-chain alkylphenols.
  • Polypropylphenol is the most preferred reactant.
  • Polyalkylphenols may be obtained by the alkylation, in the presence of an alkylating catalyst such as BF3, of phenol with high molecular weight polypropylene, polybutylene and other polyalkylene compounds to give alkyl substituents on the benzene ring of phenol having a number average molecular weight (Mn) of from about 600 to about 14,000.
  • the alkyl substituents on the hydroxyaromatic compounds may be derived from high molecular weight polypropylenes, polybutenes, and other polymers of mono-olefins, principally 1-mono-olefins. Also useful are copolymers of mono-olefins with monomers copolymerizable therewith wherein the copolymer molecule contains at least 90% by weight, of mono-olefin units. Specific examples are copolymers 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 monomers copolymerizable with propylene or butenes include monomers containing a small proportion of unreactive polar groups such as chloro, bromo, keto, ether, aldehyde, which do appreciably lower the oil-solubility of the polymer.
  • the comonomers polymerized with propylene or such butenes may be aliphatic and can also contain non-aliphatic groups, e.g., styrene, methylstyrene, p-dimethylstyrene, divinyl benzene and the like.
  • the resulting polymers and copolymers are substantially aliphatic hydrocarbon polymers.
  • the resulting alkylated phenols contain substantially alkyl hydrocarbon substituents having a number average molecular weight (Mn) of from about 600 to about 14,000.
  • phenolic compounds which may be used include, high molecular weight alkyl-substituted derivatives of resorcinol, hydroquinone, cresol, catechol, xylenol, hydroxydi-phenyl, benzylphenol, phenethylphenol, naphthol, tolylnaphthol, among others.
  • Preferred for the preparation of such preferred Mannich condensation products are the polyalkylphenol reactants, e.g., polypropylphenol and polybutylphenol whose alkyl group has a number average molecular weight of 600-3000, the more preferred alkyl groups having a number average molecular weight of 740-1200, while the most preferred type of alkyl groups is a polypropyl group having a number average molecular weight of about 900-950.
  • polyalkylphenol reactants e.g., polypropylphenol and polybutylphenol whose alkyl group has a number average molecular weight of 600-3000, the more preferred alkyl groups having a number average molecular weight of 740-1200, while the most preferred type of alkyl groups is a polypropyl group having a number average molecular weight of about 900-950.
  • the preferred configuration of the alkyl-substituted hydroxyaromatic compound is that of a para-substituted monoalkylphenol.
  • any alkylphenol readily reactive in the Mannich condensation reaction may be employed.
  • Mannich products made from alkylphenols having only one ring alkyl substituent, or two ring alkyl substituents are suitable for use in this invention.
  • Representative amine reactants are alkylene polyamines, principally polyethylene polyamines.
  • Other representative organic compounds containing at least one HN ⁇ group suitable for use in the preparation of the Mannich reaction products are well known and include the mono and di-amino alkanes and their substituted analogs, e.g., ethylamine, dimethylamine, dimethylaminopropyl amine, and diethanol amine: aromatic diamines, e.g., phenylene diamine, diamino naphthalenes; heterocyclic amines, e.g., morpholine, pyrrole, pyrrolidine, imidazole, imidazolidine, and piperidine; melamine and their substituted analogs.
  • alkylene polyamine reactants which are useful with this invention include polyamines which are linear, branched or cyclic; or a mixture of linear, branched and/or cyclic polyamines wherein each alkylene group contains from about 1 to about 10 carbon atoms.
  • a preferred polyamine is a polyamine containing from 2 to 10 nitrogen atoms per molecule or a mixture of polyamines containing an average of from about 2 to about 10 nitrogen atoms per molecule such as ethylenediamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hexaethylene heptamine, heptaethylene octamine, octaethylene nonamine, nonaethylene decamine, and mixtures of such amines.
  • propylene polyamines such as propylene diamine, and dipropylene triamine, tripropylene tetramine, tetrapropylene pentamine, pentapropylene hexamine are also suitable reactants.
  • a particularly preferred polyamine is a polyamine or mixture of polyamines having from about 3 to 7 nitrogen atoms with diethylene triamine or a combination or mixture of ethylene polyamines whose physical and chemical properties approximate that of diethylene triamine being the most preferred. In selecting an appropriate polyamine, consideration should be given to the compatibility of the resulting detergent/dispersant with the gasoline fuel mixture with which it is mixed.
  • diethylene triamine will comprise a commercially available mixture having the general overall physical and/or chemical composition approximating that of pure diethylene triamine but which can contain minor amounts of branched-chain and cyclic species as well as some other linear polyethylene polyamines such as triethylene tetramine and tetraethylene pentamine.
  • such mixtures should contain at least 50% and preferably at least 70% by weight of the linear polyethylene polyamines of which at least 50 mole % is diethylene triamine.
  • the alkylene polyamines are usually obtained by the reaction of ammonia and dihaloalkanes, such as dichloroalkanes.
  • the alkylene polyamines are obtained from the reaction of 2 to 11 moles of ammonia with 1 to 10 moles of dichloroalkanes having 2 to 6 carbon atoms and chlorine atoms on different carbon atoms.
  • aldehydes for use in the preparation of high molecular weight Mannich products include the aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde, stearaldehyde.
  • Aromatic aldehydes which may be used include benzaldehyde and salicylaldehyde.
  • Illustrative heterocyclic aldehydes for use herein are furfural and thiophene aldehyde, etc.
  • formaldehyde-producing reagents such as paraformaldehyde, or aqueous formaldehyde solutions such as formalin. Most preferred is formaldehyde or formalin.
  • a key feature of this invention is that the Mannich reaction products are used in combination with one or more poly(oxyalkylene) compounds having the requisite viscosity parameters referred to hereinabove.
  • poly(oxyalkylene) compounds suitable for use in the practice of this invention comprise one or more gasoline-soluble poly(oxyalkylene) alcohols, glycols or polyols or mono or diethers thereof, with the proviso that such compounds have in their undiluted state a viscosity of at least about 70 centistokes (cSt) at 40°C and at least about 13 cSt at 100°C.
  • cSt centistokes
  • Such compounds can be represented by the following formula R1-(-R2O-) n -R3 (I) wherein R1 is a hydrogen atom, or hydroxy, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkoxy, cycloalkoxy, or amino group having in the range of 1-200 carbon atoms, R2 is an alkylene group having 2-10 carbon atoms (preferably 2-5 carbon atoms), R3 is a hydrogen atom or alkyl, cycloalkyl, aryl, alkaryl, aralkyl, or hydrocarbylamino group having 1-200 carbon atoms, and n is an integer in the range from 1 to 500 (and preferably in the range of from 3 to 120) representing the number of repeating alkyleneoxy groups, all with the proviso that the product in its undiluted state is a gasoline-soluble liquid having a viscosity of at least about 70 centistokes (cSt)- at 40°C and
  • the poly(oxyalkylene) compounds used in the practice of this invention will have viscosities of no more than about 400 cSt at 40°C and no more than about 50 cSt at 100°C.
  • the viscosities of the poly(oxyalkylene) compounds used will not exceed about 300 cSt at 40°C and about 40 cSt at 100°C.
  • the most preferred poly(oxyalkylene) compounds will have viscosities of no more than about 200 cSt at 40°C, and no more than about 30 cSt at 100°C.
  • Preferred poly(oxyalkylene) compounds are poly(oxyalkylene) glycol compounds and monoether derivatives thereof that satisfy the above viscosity requirements and that are comprised of repeating units formed by reacting an alcohol or polyalcohol with an alkylene oxide, such as propylene oxide and/or butylene oxide with or without use of ethylene oxide, and especially products in which at least 80 mole % of the oxyalkylene groups in the molecule are derived from 1,2-propylene oxide.
  • Preferred poly(oxyalkylene) compounds can be represented by the formula R4O-(R5O) p -R6 (II) wherein R4 is a hydrogen atom, or a hydrocarbyl group having up to 18 carbon atoms, and more preferably an alkyl group having up to 10-12 carbon atoms; R5 is an alkylene group of 2-5 carbon atoms which thus can be an ethylene group (i.e., dimethylene) group, but which preferably is a propylene (i.e., methyldimethylene) group, or a butylene (i.e., ethyldimethylene) group; R6 is a hydrogen atom, or a hydrocarbyl group having up to 18 carbon atoms, and more preferably an alkyl group having up to 10-12 carbon atoms; and p is a integer that yields a product having the viscosity parameters given above.
  • the alkylene groups R5 can all be the same or they can be different and if different, can be arranged either randomly or in prearranged blocks or sequences.
  • Particularly preferred are the poly(oxyalkylene) alcohols and glycols in which from 70 to 100% and especially 80 to 100% of the alkylene groups are propylene groups (methyldimethylene groups) derived from use 1,2-propylene oxide in the alkoxylation reaction usually employed in the production of such products.
  • glycols and diethers if less than 100% of the alkylene groups are propylene groups, the remainder are either ethylene or butylene groups, or both, proportioned to yield a liquid gasoline-soluble product having the requisite viscosity properties specified above.
  • Monools derived by propoxylation of alkanols R4 in Formula (II) is alkyl, R5 is methyldimethylene groups, R6 is a hydrogen atom, and p is as defined above
  • Such compounds can also be thought of as monoethers of poly(oxyalkylene) glycols.
  • R7O-(-R8O-) q -R9-(-OR10-) r -OR11 III
  • R7 and R11 can be the same or different and each is independently a hydrogen atom or a hydrocarbyl group, preferably an alkyl group of up to 18 carbon atoms, and more preferably of up to 10-12 carbon atoms
  • R8 and R10 can be the same or different and are alkylene groups of 2-5 carbon atoms each, which thus can be ethylene groups (i.e., dimethylene groups), but which preferably comprise or consist of propylene (i.e., methyldimethylene) groups, and/or butylene (i.e., ethyldimethylene) groups
  • R9 is an divalent hydrocarbylene group derived from the initiator, and thus can be a group such as a phenylene group or an alkylene group which is preferably an
  • the alkylene groups can all be the same or they can be different and if different, can be arranged either randomly or in blocks or sequences.
  • the poly(oxyalkylene) compounds used pursuant to this invention will contain a sufficient number of branched oxyalkylene units (e.g., methyldimethyleneoxy units and/or ethyldimethyleneoxy units) to render the poly(oxyalkylene) compound gasoline soluble.
  • branched oxyalkylene units e.g., methyldimethyleneoxy units and/or ethyldimethyleneoxy units
  • the most preferred poly(oxyalkylene) glycol derivative compound useful in the compositions and methods of this invention is known commercially as EMKAROX AF22 available from ICI Chemicals & Polymers Ltd.
  • This compound has a pour point of about -42°C, a density of about 0.980 g/ml at 20°C, an open cup flash point of about 230°C, a viscosity of about 90 cSt (typically in the range of about 87 to about 98 cSt) at 40°C and about 17 cSt (typically in the range of about 15 to about 19 cSt) at 100°C, an average molecular weight of about 1700, a viscosity index of about 200, and a volatility as determined by the Volatility Determination Method described hereinafter of less than about 50%.
  • the number average molecular weight of the poly(oxyalkylene) compounds of this invention is preferably in the range of from about 200 to about 5000, more preferably from about 500 to about 3
  • An optional hydrocarbon component of the fuel compositions of this invention is poly- ⁇ -olefin.
  • the poly- ⁇ -olefins (PAO) useful in compositions and methods of this invention can be fully hydrogenated (hydrotreated), partially hydrogenated, or unhydrogenated poly- ⁇ -olefins.
  • PAO poly- ⁇ -olefins
  • These materials are poly- ⁇ -olefin oligomers, primarily trimers, tetramers and pentamers of alpha-olefin monomers containing from 6 to 12, generally 8 to 12 and most preferably about 10 carbon atoms. Their synthesis is outlined in Hydrocarbon Processing , Feb. 1982, page 75 et seq.
  • PAO catalytic oligomerization of short chain linear alpha olefins (suitably obtained by catalytic treatment of ethylene).
  • the nature of an individual PAO depends in part on the carbon chain length of the original alpha-olefin, and also on the structure of the oligomer. The exact molecular structure may vary to some extent according to the precise conditions of the oligomerization, which is reflected in changes in the physical properties of the final PAO. Since the suitability of a particular PAO is determined primarily by its physical properties, and in particular its viscosity, the various products are generally differentiated and defined by their viscosity characteristics.
  • compositions of the present invention are poly- ⁇ -olefins having a viscosity (measured at 100°C) in the range of from 2 to 20 centistokes. More preferably, the poly- ⁇ -olefin has a viscosity of at least 8 centistokes, and most preferably about 10 centistokes at 100°C.
  • the volatility of the poly- ⁇ -olefin is also of significance and may be determined by the Volatility Determination Method described below.
  • the substance e.g., a poly- ⁇ -olefin (110-135 grams) is placed in a three-neck, 250 mL round-bottomed flask having a threaded port for a thermometer.
  • a flask is available from Ace Glass (Catalog No. 6954-72 with 20/40 fittings).
  • Ace Glass Catalog No. 6954-72 with 20/40 fittings.
  • a stirrer rod having a Teflon blade, 19 mm wide x 60 mm long (Ace Glass catalog No. 8085-07).
  • the substance e.g., poly- ⁇ -olefin
  • the substance is heated in an oil bath to 300°C for 1 hour while stirring the substance in the flask at a rate of 150 rpm.
  • the free space above the substance in the flask is swept with 7.5 L/hr of inert gas (e.g., nitrogen, argon, etc.).
  • inert gas e.g., nitrogen, argon, etc.
  • the fuel compositions of this invention include other conventional additives such as antioxidants, demulsifiers, corrosion inhibitors, aromatic solvents, etc. Accordingly, components for use in the formulations of this invention will now be described.
  • oxidation inhibitors Various compounds known for use as oxidation inhibitors can be utilized in the practice of this invention. These include phenolic antioxidants, amine anti-oxidants, sulfurized phenolic compounds, and organic phosphites, among others.
  • the antioxidant should be composed predominantly or entirely of either (1) a hindered phenol antioxidant such as 2-tert-butylphenol, 2,6-di-tert-butylphenol,2,4,6-tri-tert-butylphenol,4-methyl-2,6-di-tert-butylphenol, 4,4'-methylenebis(2,6-di-tert-butylphenol), and mixed methylene bridged polyalkyl phenols, or (2) an aromatic amine antioxidant such as the cycloalkyldi-lower alkyl amines, and phenylenediamines, or a combination of one or more such phenolic antioxidants with one or more such amine antioxidants.
  • a hindered phenol antioxidant such as 2-tert-but
  • tertiary butyl phenols such as 2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, o-tert-butylphenol, and mixtures thereof.
  • Demulsifier .
  • demulsifiers are available for use in the practice of this invention, including, for example, poly(oxyalkylene) glycols, oxyalkylated phenolic resins, and like materials. Particularly preferred are mixtures of poly(oxyalkylene) glycols and oxyalkylated alkylphenolic resins, such as are available commercially from Petrolite Corporation under the TOLAD trademark.
  • One such proprietary product, identified as TOLAD 9308, is understood to be a mixture of these components dissolved in a solvent composed of heavy aromatic naphtha and isopropanol. This product has been found efficacious for use in the compositions of this invention.
  • other known demulsifiers can be used such as TOLAD 286.
  • dimer and trimer acids such as are produced from tall oil fatty acids, oleic acid, linoleic acid, or the like. Products of this type are currently available from various commercial sources, such as, for example, the dimer and trimer acids sold under the HYSTRENE trademark by the Humko Chemical Division of Witco Chemical Corporation and under the EMPOL trademark by Emery Chemicals.
  • alkenyl succinic acid and alkenyl succinic anhydride corrosion inhibitors such as, for example, tetrapropenylsuccinic acid, tetrapropenylsuccinic anhydride, tetradecenylsuccinic acid, tetradecenylsuccinic anhydride, hexadecenylsuccinic acid, hexadecenylsuccinic anhydride, and the like.
  • half esters of alkenyl succinic acids having 8 to 24 carbon atoms in the alkenyl group with alcohols such as the polyglycols.
  • aminosuccinic acids or derivatives thereof represented by the formula: wherein each of R2, R3, R5 and R6 is, independently, a hydrogen atom or a hydrocarbyl group containing 1 to 30 carbon atoms, and wherein each of R1 and R4 is, independently, a hydrogen atom, a hydrocarbyl group containing 1 to 30 carbon atoms, or an acyl group containing from 1 to 30 carbon atoms.
  • R1, R2, R3, R4, R5, and R6 when in the form of hydrocarbyl groups can be, for example, alkyl, cycloalkyl or aromatic containing groups.
  • R1, R2, R3, R4 and R5 are hydrogen or the same or different straight-chain or branched-chain hydrocarbon radicals containing 1-20 carbon atoms.
  • R1, R2, R3, R4, and R5 are hydrogen atoms.
  • R6 when in the form of a hydrocarbyl group is preferably a straight-chain or branched-chain saturated hydrocarbon radical.
  • tetralkenyl succinic acid of the above formula wherein R1, R2, R3, R4 and R5 are hydrogen and R6 is a tetrapropenyl group.
  • aromatic hydrocarbon solvents can be used with this invention such as benzene, and alkyl substituted benzene or mixtures thereof. Particularly useful are mixtures of o-, p-, and m- xylenes and mesitylene and higher boiling aromatics such as Aromatic 150 which is available from Chemtech. However, other mixtures of aromatic hydrocarbon solvents may also be used.
  • the additive concentrate should contain, on an active ingredient basis, from about 20 to about 35 parts by weight (preferably from about 25 to about 30 parts by weight) of Mannich reaction product; up to about 50 parts by weight (preferably from about 20 to about 40 parts by weight) of poly(oxyalkylene) component; up to about 40 parts by weight (preferably from about 0 to about 30 parts by weight) of hydrotreated or unhydrotreated poly- ⁇ -olefin; 0 to 5 parts by weight (preferably, from 1 to 3 parts by weight) of antioxidant; from 0 to 10 parts by weight (preferably, from 0.1 to 3 parts by weight) of demulsifier; from 25 to 80 parts by weight (preferably 30 to 75 parts by weight) of aromatic hydrocarbon solvent (including any diluent or solvent present in the Mannich detergent as received); and from 0 to 5 parts by weight (preferably, from 0.025 to 1.0 parts by weight) of corrosion inhibitor per each one hundred
  • compositions of this invention are preferably employed in hydrocarbon mixtures in the gasoline boiling range or hydrocarbon/oxygenate mixtures, or oxygenates, but are also suitable for use in middle distillate fuels, notably, diesel fuels and fuels for gas turbine engines.
  • middle distillate fuels notably, diesel fuels and fuels for gas turbine engines.
  • oxygenates is meant alkanols and ethers such as methanol, ethanol, propanol, methyl-tert-butyl ether, ethyl-tert-butyl ether, tert-amyl-methyl ether and the like, or combinations thereof.
  • the base fuels may contain other commonly used ingredients such as cold starting aids, dyes, metal deactivators, lubricity additives, octane improvers, cetane improvers, emission control additives, antioxidants, metallic combustion improvers, and the like.
  • Cyclopentadienyl manganese tricarbonyl compounds such as methylcyclopentadienyl manganese tricarbonyl are preferred because of their outstanding ability to reduce tailpipe emissions such as NOX and smog forming precursors and to significantly improve the octane quality of gasolines, both of the conventional variety and of the newer "reformulated" types.
  • the additives are employed in amounts sufficient to reduce or inhibit deposit formation on intake valves. Deposits on fuel injectors may also be reduced or at least controlled.
  • the finished additized fuel will contain, by weight and on an active ingredient basis, no more than (and usually less than) about 5000 parts of the combination of components a) and b) per million parts of gasoline, and preferably, up to (and more preferably less than) about 3000 parts of the combination of components a) and b) per million parts of gasoline.
  • the total amount of components a) and b), proportioned as above, in the finished fuels of this invention is preferably no more than about 2000 ppm (by weight), and most preferably in the range of about 200 to about 1000 ppm (by weight).
  • An additive comprising a Mannich reaction product, a poly(oxyalkylene) compound, and at least one liquid hydrocarbon such as one or more low boiling aromatic hydrocarbons, a poly- ⁇ -olefin oligomer and/or a mineral oil of suitable viscosity will be employed in unleaded gasoline in minor amounts such that the gasoline portion of the fuel (including oxygenates such as ethers or alcohol blending agents) is the major component, usually amounting to over 95% by weight.
  • the other components which are preferably used in conjunction with the fuel additive composition can be blended into the fuel individually or in various sub-combinations.
  • the concentrations of additives are typically referred to in terms of pounds per thousand barrels (ptb).
  • ptb pounds per thousand barrels
  • One pound per thousand barrels of additive in a gasoline of typical specific gravity is generally equivalent to about 3.8 to about 4.0 parts per million (ppm) on a weight basis.
  • the amount of the Mannich dispersant is given on an "as received basis”. Since the Mannich dispersant contained approximately 40% by weight of active Mannich Reaction Product (the balance being hydrocarbon diluent and unreacted polyolefin), the actual quantity of active Mannich detergent is approximately 40% of the values reported in the examples.
  • the engine was rebuilt with new intake valves and the crankcase oil was changed.
  • the base fuel was a clear (i.e., unadditized) regular unleaded gasoline.
  • the crankcase oil used in the test runs was an SAE 5W-30 SG API-quality oil.
  • additive concentrates were formulated into additive concentrates in which the weight ratio of component a) (using the weight on an as received basis): component b) : aromatic hydrocarbon diluent was 70:35:100.
  • the additive concentrates were then blended into separate quantities of the same base fuel and the resultant fuel compositions were then evaluated in the above engine test.
  • a control run was also carried out in which the clear (i.e., unadditized) base fuel was used in the test.
  • the intake valve deposit performance of this series of tests is summarized in Table 1.
  • the fuels designated A through F contained the poly(oxyalkylene) compounds identified above as A through F, respectively. Thus fuels A and B were fuels of this invention whereas Fuels C, D, E and E were fuels not of this invention.
  • Fuels A through F each contained component a) at a concentration of 70 pounds per thousand barrels (equivalent to approximately 0.027 wt%), the respective poly(oxyalkylene) compound at a concentration of 35 pounds per thousand barrels (equivalent to approximately 0.013 wt%), and the aromatic hydrocarbon solvent (which in effect became part of the gasoline) at a concentration of 100 pounds per thousand barrels (equivalent to approximately 0.04 wt%).
  • some of the test fuels contained, in addition to the combination of the detergent and a poly(oxyalkylene) compound, a poly- ⁇ -olefin oligomer (a 10 cSt unhydrotreated poly- ⁇ -olefin of 1-decene, hereinafter referred to as PAO) or an antioxidant (HiTEC® 4733 additive (commercially available from Ethyl Petroleum Additives, Inc.).
  • a poly- ⁇ -olefin oligomer a 10 cSt unhydrotreated poly- ⁇ -olefin of 1-decene, hereinafter referred to as PAO
  • HiTEC® 4733 additive commercially available from Ethyl Petroleum Additives, Inc.
  • HiTEC® 4733 additive is a mixture of tert-butyl phenols containing about 10 wt.% 2-tert-butyl phenol, about 75 wt.% 2,6-di-tert-butyl phenol, about 2 wt.% 2,4-di-tert-butyl phenol, and about 13 wt.% 2,4,6-tri-tert-butyl phenol.
  • Table 2 gives the compositions of additives in the fuel for each run (where ptb is pounds per thousand barrels) as well as the average of the intake valve (IVD) and combustion chamber deposits (CCD) for each cylinder.
  • the combustion chamber deposits are a combination of the piston top deposits and the cylinder head deposits.
  • Runs 1 and 2 give base line results for the unadditized fuel, and fuel containing Mannich detergent and PA0 only.
  • Runs 3-8 are of the invention and illustrate the reduction in deposits that can be achieved by additive formulations containing Mannich detergent/dispersant and a poly(oxyalkylene) compound having the viscosity properties required pursuant to this invention.
  • Table 2 Run No. HiTEC® 4997, ptb HiTEC® 4733, ptb Prod.
  • the test is primarily an intake valve deposit test, but measurements of combustion chamber deposits and octane requirement increase can be made.
  • octane requirement increase is the difference in octane requirement of the engine as measured at 0 and 200 hours.
  • the crankcase oil used in the test runs was an SAE 5W-30 SG API-quality oil.
  • New intake valves and valve stem seals were installed after each test run, and new exhaust valves were installed every fourth test run. Prior to and subsequent to each test run, the intake valves, ports, manifolds, and throttle blade were weighed and/or rated. Runs 10, 11, and 12, are given for comparative purposes and represent the baseline case of fuel without additive.
  • Runs 10, 11, 12, and 13 were run with a different lot of the same fuel as runs 14, 15, 16, and 17. Results of the tests indicate a significant reduction in intake valve deposits (IVD) with surprisingly little change in ORI or combustion chamber deposits.
  • the poly(oxyalkylene) compound used pursuant to the invention was the same as product A of Example 1.
  • the fuel in Run 16 contained 4 ptb of sulfurized 2,6-di-tert-butylphenol as antioxidant and the fuel in run 17 had 4 ptb of nonyl phenol sulfide as antioxidant. No antioxidant was added to the other fuels of this series. Table 3 Run No.
  • HiTEC® 4997 (ptb) Product A (ptb) PAO (ptb) IVD (mg) CCD (mg) ORI 10 -- -- -- 721.0 1587 10 11 -- -- -- 519.8 1668 8 12 -- -- -- 577 1855 8-10 13 90 45 -- 28.3 2210 11 14 90 45 -- 43.1 1481 10 15 90 22.5 22.5 41.6 1655 11 16 90 45 -- 37.8 1745 11 17 90 45 -- 28.0 1740 9
  • This series of runs is similar to the runs of Example 2.
  • a 1985, 2.3L, 4 cylinder Ford engine containing a single spark plug was run for 112 hours, operating between a 3-minute "power" cycle (37 HP) at 2,800 rpm and a 1-minute "idle” cycle (0-4 HP) at 2,000 rpm.
  • the engine coolant temperature was maintained at about 74°C and the combustion air was not temperature and humidity controlled.
  • the octane requirement increase is the difference in octane requirement as measured at 0 and 112 hours.
  • the crankcase oil used in the test runs was an SAE 10W-40 SG API-quality oil. New intake valves and valve stem seals were installed after each test run, and new exhaust valves were installed every fourth test run.
  • Table 4 illustrates the advantages of fuel additives of this invention.
  • the poly(oxyalkylene) compound used pursuant to the invention was the same as product A of Example 1.
  • the fuel in Run 16 contained 4 ptb of sulfurized 2,6-di-tert-butylphenol as antioxidant and the fuel in run 17 had 4 ptb of nonyl phenol sulfide as antioxidant. No antioxidant was added to the other fuels of this series.
  • HiTEC® 4997 (ptb) Product A (ptb) PAO (ptb) IVD (mg) CCD (mg) ORI 18 90 45 -- 19.8 1348 7 19 90 45 -- 14.1 1469 8 20 90 22.5 22.5 22.5 1282 10 21 90 45 -- 29.6 1273 8 22 90 45 -- 24.9 1193 10
  • HiTEC® 4997 (ptb) Product A (ptb) PAO (ptb) IVD (mg) CCD (mg) ORI 23 -- -- -- 261.0 647 6 24 90 45 -- 41.6 961 5 25 90 22.5 22.5 29.5 1283 5 26 90 45 -- 31.2 1183 6 27 90 22.5 22.5 37.3 1258 6 28 -- -- -- 338.0 719 8 29 90 45 -- 29.5 1283 5
  • Runs 1 and 3 the same Mannich base detergent as in Example 1 was used whereas in Run 2 the Mannich base detergent was Amoco 596 additive, another Mannich base quite similar to that of Example 1.
  • the fuel also contained a phenolic antioxidant (HiTEC® 4733 additive) at a concentration of 5 pounds per thousand barrels.
  • the additive concentrates for Runs 1-4 were diluted with an aromatic hydrocarbon diluent having a flash point of about 40°C. In Runs 1-3 this diluent was proportioned such that the finished fuels contained 56 ptb of the aromatic hydrocarbon diluent, which in effect became part of the base gasoline.
  • the amount of hydrocarbon diluent added to Product X for the fuels of Run 4 was such that the finished fuels contained 125 ptb of added aromatic hydrocarbon diluent, which again became part of the base gasoline.
  • gasoline soluble means that the additive under discussion has sufficient solubility in the particular gasoline fuel composition in which it is being used to dissolve at 20°C to the extent of at least the minimum concentration required to achieve control of intake valve deposits in an internal combustion engine operated on the resulting fuel.
  • the additive should (and will) have a substantially greater gasoline solubility than this.
  • the term does not require that the additive be soluble in all proportions in the gasoline fuel composition.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
EP94307322A 1993-10-06 1994-10-05 Kraftstoffzusammensetzungen, und Zusätze dafür Expired - Lifetime EP0647700B1 (de)

Applications Claiming Priority (2)

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US13344293A 1993-10-06 1993-10-06
US133442 1993-10-06

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EP0647700A1 true EP0647700A1 (de) 1995-04-12
EP0647700B1 EP0647700B1 (de) 1999-11-24

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JP (1) JP2744205B2 (de)
AU (1) AU678514B2 (de)
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Cited By (20)

* Cited by examiner, † Cited by third party
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US5634951A (en) * 1996-06-07 1997-06-03 Ethyl Corporation Additives for minimizing intake valve deposits, and their use
EP0827999A1 (de) * 1996-09-05 1998-03-11 BP Chemicals (Additives) Limited Reinigungsmittel für Kohlenwasserkraftstoffe
EP0831141A1 (de) * 1996-09-05 1998-03-25 BP Chemicals (Additives) Limited Reinigungsmittel für Kohlenwasserkraftstoffe
EP0870819A2 (de) * 1997-04-10 1998-10-14 Ethyl Corporation Zusätze zur bedeutenden Herabminderung der Einlassventilablagerungen, und ihre Verwendung
EP0894844A1 (de) * 1997-07-30 1999-02-03 Tonen Corporation Brennstoffzusatz und den Zusatz enthaltende Brennstoffzusammensetzung
EP1008642A1 (de) * 1998-11-30 2000-06-14 Ethyl Corporation Polybutene mit einer enge Molekulargewichtsverteilung enthaltende Kraftstoffzusammensetzungen
EP1010747A1 (de) * 1998-12-18 2000-06-21 Ethyl Corporation Aminreiche mannich Dispergiermittel für Verdichtungszündungskraftstoffe
EP1132455A1 (de) * 2000-03-01 2001-09-12 Chevron Oronite Company LLC Mannichkondensationsprodukte und Amine mit hydrocarbylsubstituiertem Polyoxyalkylen enthaltende Brennstoffzusatzzusammenstzungen
WO2001066673A2 (en) * 2000-03-03 2001-09-13 The Lubrizol Corporation Fuel additive compositions and fuel compositions containing detergents and fluidizers
EP1193308A1 (de) * 2000-09-29 2002-04-03 Chevron Oronite Company LLC Ein Mannichkondensationsprodukt, ein Poly(oxyalkylen)monool, und eine Carbonsäure enthaltende Brennstoffzusatzszusammensetzungen
EP1193307A1 (de) * 2000-09-29 2002-04-03 Chevron Oronite Company LLC Ein Mannichkondensationsprodukt, ein Poly(oxyalkylen)monool, ein Polyolefin, und eine Carbonsäure enthaltende Brennstoffzusatzszusammensetzungen
WO2002035069A2 (en) * 2000-10-24 2002-05-02 Exxonmobil Research And Engineering Company A method for controlling deposit formation in gasoline direct injection engine by use of a fuel having particular compositional characteristics
US6514297B1 (en) 1999-11-24 2003-02-04 The Lubrizol Corporation Detergents for use in preventing formation of iron complexes in hydrocarbon fuels
EP1229100A3 (de) * 2001-02-02 2003-02-19 Ethyl Corporation Mannich-Detergens aus sekundärem Amin
WO2003078553A3 (en) * 2002-03-12 2004-02-19 Lubrizol Corp Method of operating a direct injection spark-ignited engine with a fuel composition
US6743266B2 (en) 2000-03-31 2004-06-01 Texaco, Inc. Fuel additive composition for improving delivery of friction modifier
US6835217B1 (en) 2000-09-20 2004-12-28 Texaco, Inc. Fuel composition containing friction modifier
WO2006044892A1 (en) 2004-10-19 2006-04-27 The Lubrizol Corporation Additive and fuel compositions containing detergent and fluidizer and method thereof
WO2007012580A1 (de) * 2005-07-26 2007-02-01 Basf Aktiengesellschaft Verwendung von tetrahydrobenzoxazinen als stabilisatoren
CN101983230B (zh) * 2008-03-31 2014-04-30 埃克森美孚研究工程公司 具有改进的抗清漆沉积性的润滑油组合物

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US6749651B2 (en) * 2001-12-21 2004-06-15 Chevron Oronite Company Llc Fuel additive compositions containing a mannich condensation product, a poly (oxyalkylene) monool, and a carboxylic acid
JP5197305B2 (ja) 2008-10-31 2013-05-15 油化産業株式会社 ディーゼル燃料添加剤組成物及びそれを用いた洗浄方法
US10584297B2 (en) 2016-12-13 2020-03-10 Afton Chemical Corporation Polyolefin-derived dispersants
US10221267B2 (en) 2016-12-13 2019-03-05 Afton Chemical Corporation Microstructure-controlled copolymers of ethylene and C3-C10 alpha-olefins

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FR1162768A (fr) * 1955-11-11 1958-09-17 Shell Res Ltd Carburants liquides pour moteurs à combustion interne
US3030939A (en) * 1958-07-10 1962-04-24 Standard Oil Co Method of operating spark-ignition combustion engine
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EP0398100A1 (de) * 1989-05-19 1990-11-22 BASF Aktiengesellschaft Kraftstoffzusammensetzungen mit einem Gehalt an Alkoxylierungsprodukten
EP0460957A2 (de) * 1990-06-07 1991-12-11 Tonen Corporation Zusätze für Benzinzusammensetzung
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EP0569228A1 (de) * 1992-05-06 1993-11-10 Ethyl Petroleum Additives, Inc. Inzufuhranlage für Niederschläge kontrollierende Zusammensetzungen
EP0588429A1 (de) * 1992-09-14 1994-03-23 Shell Internationale Researchmaatschappij B.V. Benzinzusammensetzung

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Publication number Priority date Publication date Assignee Title
EP0811672A2 (de) * 1996-06-07 1997-12-10 Ethyl Corporation Zusätze zur Verminderung der Einlassventilablagerungen, und ihre Verwendung
EP0811672A3 (de) * 1996-06-07 1998-02-04 Ethyl Corporation Zusätze zur Verminderung der Einlassventilablagerungen, und ihre Verwendung
US5634951A (en) * 1996-06-07 1997-06-03 Ethyl Corporation Additives for minimizing intake valve deposits, and their use
US6117198A (en) * 1996-09-05 2000-09-12 The Lubrizol Corporation Detergents for hydrocarbon fuels
EP0827999A1 (de) * 1996-09-05 1998-03-11 BP Chemicals (Additives) Limited Reinigungsmittel für Kohlenwasserkraftstoffe
EP0831141A1 (de) * 1996-09-05 1998-03-25 BP Chemicals (Additives) Limited Reinigungsmittel für Kohlenwasserkraftstoffe
US5876468A (en) * 1996-09-05 1999-03-02 Lubrizol Adibis Holdings (Uk) Limited Detergents for hydrocarbon fuels
EP0870819A2 (de) * 1997-04-10 1998-10-14 Ethyl Corporation Zusätze zur bedeutenden Herabminderung der Einlassventilablagerungen, und ihre Verwendung
EP0870819A3 (de) * 1997-04-10 1999-06-16 Ethyl Corporation Zusätze zur bedeutenden Herabminderung der Einlassventilablagerungen und ihre Verwendung
EP0894844A1 (de) * 1997-07-30 1999-02-03 Tonen Corporation Brennstoffzusatz und den Zusatz enthaltende Brennstoffzusammensetzung
EP1008642A1 (de) * 1998-11-30 2000-06-14 Ethyl Corporation Polybutene mit einer enge Molekulargewichtsverteilung enthaltende Kraftstoffzusammensetzungen
EP1010747A1 (de) * 1998-12-18 2000-06-21 Ethyl Corporation Aminreiche mannich Dispergiermittel für Verdichtungszündungskraftstoffe
SG87849A1 (en) * 1998-12-18 2002-04-16 Ethyl Corp High-amine mannich dispersants for compression-ignition fuels
US6514297B1 (en) 1999-11-24 2003-02-04 The Lubrizol Corporation Detergents for use in preventing formation of iron complexes in hydrocarbon fuels
EP1132455A1 (de) * 2000-03-01 2001-09-12 Chevron Oronite Company LLC Mannichkondensationsprodukte und Amine mit hydrocarbylsubstituiertem Polyoxyalkylen enthaltende Brennstoffzusatzzusammenstzungen
AU2001239902B2 (en) * 2000-03-03 2005-06-02 The Lubrizol Corporation Fuel additive compositions and fuel compositions containing detergents and fluidizers
WO2001066673A3 (en) * 2000-03-03 2002-03-28 Lubrizol Corp Fuel additive compositions and fuel compositions containing detergents and fluidizers
WO2001066673A2 (en) * 2000-03-03 2001-09-13 The Lubrizol Corporation Fuel additive compositions and fuel compositions containing detergents and fluidizers
US6743266B2 (en) 2000-03-31 2004-06-01 Texaco, Inc. Fuel additive composition for improving delivery of friction modifier
US6835217B1 (en) 2000-09-20 2004-12-28 Texaco, Inc. Fuel composition containing friction modifier
EP1193308A1 (de) * 2000-09-29 2002-04-03 Chevron Oronite Company LLC Ein Mannichkondensationsprodukt, ein Poly(oxyalkylen)monool, und eine Carbonsäure enthaltende Brennstoffzusatzszusammensetzungen
EP1193307A1 (de) * 2000-09-29 2002-04-03 Chevron Oronite Company LLC Ein Mannichkondensationsprodukt, ein Poly(oxyalkylen)monool, ein Polyolefin, und eine Carbonsäure enthaltende Brennstoffzusatzszusammensetzungen
SG112811A1 (en) * 2000-09-29 2005-07-28 Chevron Oronite Co Fuel additive compositions containing a mannich condensation product, a poly(oxyalkylene) monool, a polylefin, and a carboxylic acid
WO2002035069A2 (en) * 2000-10-24 2002-05-02 Exxonmobil Research And Engineering Company A method for controlling deposit formation in gasoline direct injection engine by use of a fuel having particular compositional characteristics
WO2002035069A3 (en) * 2000-10-24 2002-07-18 Exxonmobil Res & Eng Co A method for controlling deposit formation in gasoline direct injection engine by use of a fuel having particular compositional characteristics
US6746495B2 (en) 2000-10-24 2004-06-08 Exxonmobil Research And Engineering Company Method for controlling deposit formation in gasoline direct injection engine by use of a fuel having particular compositional characteristics
EP1229100A3 (de) * 2001-02-02 2003-02-19 Ethyl Corporation Mannich-Detergens aus sekundärem Amin
US6800103B2 (en) 2001-02-02 2004-10-05 Ethyl Corporation Secondary amine mannich detergents
WO2003078553A3 (en) * 2002-03-12 2004-02-19 Lubrizol Corp Method of operating a direct injection spark-ignited engine with a fuel composition
US7704289B2 (en) 2002-03-12 2010-04-27 The Lubrizol Corporation Method of operating a direct injection spark-ignited engine with a fuel composition
WO2006044892A1 (en) 2004-10-19 2006-04-27 The Lubrizol Corporation Additive and fuel compositions containing detergent and fluidizer and method thereof
EP3133141A1 (de) 2004-10-19 2017-02-22 The Lubrizol Corporation Additiv- und brennstoffzusammensetzung mit reinigungsmittel und fluidisierer sowie verfahren davon
WO2007012580A1 (de) * 2005-07-26 2007-02-01 Basf Aktiengesellschaft Verwendung von tetrahydrobenzoxazinen als stabilisatoren
US9062267B2 (en) 2005-07-26 2015-06-23 Basf Se Use of tetrahydrobenzoxazines as stabilisers
US9217115B2 (en) 2005-07-26 2015-12-22 Basf Se Use of tetrahydroberizoxazines as stabilisers
US9840608B2 (en) 2005-07-26 2017-12-12 Basf Se Use of tetrahydrobenzoxazines as stabilisers
US9951204B2 (en) 2005-07-26 2018-04-24 Basf Se Use of tetrahydrobenzoxazines as stabilizers
US10294350B2 (en) 2005-07-26 2019-05-21 Basf Se Use of tetrahydrobenzoxazines as stabilisers
CN101983230B (zh) * 2008-03-31 2014-04-30 埃克森美孚研究工程公司 具有改进的抗清漆沉积性的润滑油组合物

Also Published As

Publication number Publication date
JP2744205B2 (ja) 1998-04-28
EP0647700B1 (de) 1999-11-24
DE69421784T2 (de) 2000-05-18
DE69421784D1 (de) 1999-12-30
AU678514B2 (en) 1997-05-29
CA2133796A1 (en) 1995-04-07
AU7445294A (en) 1995-04-27
CA2133796C (en) 2005-08-23
JPH07197052A (ja) 1995-08-01

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