Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
  • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—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 invention relates to the use of synergistically acting gasoline fuel additive compositions with synergistic performance in the intake system purity for the addition of fuels for gasoline engines.
• Carburettors and intake systems of gasoline engines, but also injection systems for fuel metering are increasingly burdened by impurities caused by dust particles from the air, unburned hydrocarbon residues from the combustion chamber and the guided into the carburetor crankcase vent gases.
• the first additive generation could only prevent the formation of deposits in the intake system, but not remove already existing deposits, whereas the modern additives of the second generation can cause both (keep-clean and clean-up effect) and especially because of their excellent thermal stability at higher temperature zones, namely at the inlet valves.
• Such detergents which can come from a variety of chemical classes of substances, such as polyalkeneamines, polyetheramines, polybutene Mannich bases or Polybutensuccinimide, are generally used in combination with carrier oils and sometimes other additive components, such as corrosion inhibitors and demulsifiers, for use.
• the carrier oils perform a solvent or wash function in combination with the detergents.
• Carrier oils are typically high boiling, viscous, thermostable liquids which coat the hot metal surface thereby preventing the build-up of impurities on the metal surface.
• the EP-A-0 704 519 describes additive mixtures for fuels comprising at least one amine having a hydrocarbon radical with an average molecular weight of 500 to 10,000, at least one hydrocarbon polymer having an average molecular weight of 300 to 10,000 in hydrogenated or nonhydrogenated form and as a carrier oil component based on a mixture of polyethers of propylene oxide and / or butylene oxide and esters of mono- or polycarboxylic acids and alkanols or polyols.
• gasoline with polyisobuteneamine molecular weight about 1000
• an isotridecanol reacted with 22 mol of butylene oxide are additized in amounts of 300 ppm each.
• a possible synergistic interaction of carrier oil and detergent additive is not referred to in this document.
• the EP-A-0 548 617 describes gasoline fuels which are additized with an additive combination of 10 to 5000 ppm of a nitrogen-containing detergent additive and 10 to 5000 ppm of a phenol-initiated propoxylate.
• a single comparative example a mixture of polyisobutylamine and an unspecified alcohol butoxylate is described.
• a fuel is additized with 200 ppm each of these two components. There is no indication of a possibly synergistic interaction of these two components in the quantities indicated.
• the EP-A-0 374 461 describes gasoline fuels, additized with a mixture of 50 to 1000 ppm of nitrogen-containing detergent additive and 50 to 5000 ppm of a carrier oil mixture of a) a polyalkylene oxide based on propylene oxide and / or butylene oxide with a molecular weight of at least 500, with aliphatic or b) esters of monocarboxylic acids or polycarboxylic acids and alkanols or polyols, these esters having a minimum viscosity of 2 cm 2 / s at 100 ° C.
• a synergistic interaction of detergent additive and polyether component is also not referenced in this document.
• the EP-A-0 706 553 describes fuel additive compositions comprising a hydrocarbon-substituted amine having a molecular weight of about 700 to 2,000, a polyolefin polymer of a C 2 -C 6 monoolefin having a molecular weight of about 350 to 2,000, and a poly (oxyalkylene) monool having a terminal hydrocarbon group and an average molecular weight from about 500 to 5,000, wherein the terminal hydrocarbon group is a C 1 -C 30 hydrocarbyl group.
• polyether components are dodecylphenyl-initiated poly (oxy) butylenes having a molecular weight of about 1500, which are preferably used in combination with a polyisobutene amine having a molecular weight of 1300.
• Alkanol-initiated polyether compounds and their combined use with detergent additives are not described in this document.
• the EP-A-0 887 400 describes gasoline blends supplemented with 50 to 70 ppm N-containing detergent having a molecular weight in the range of 700 to 3000 and 35 to 75 ppm of hydrocarbyl-terminated poly (oxyalkylene) monool having a molecular weight of 500 to 5000.
• Preferred hydrocarbyl end groups are C 7 C 30 alkylphenyl groups, in particular dodecylphenyl.
• the WO-A-00/02978 describes fuel compositions for internal combustion engines, comprising a major amount of a liquid hydrocarbon fuel and a cleaning portion of at least one specific polypropoxylate additive, which may be additionally combined with at least one detergent additive.
• fuels comprising component (A) in a proportion of 50 to 150 ppm by weight, in particular in a proportion of 70 to 130 ppm by weight; and fuels containing component (B) in a proportion of 20 to 150 ppm by weight, in particular in a proportion of 60 to 130 ppm by weight.
• component (A) is a polyisobuteneamine.
• component (B) is a compound of formula I wherein R is a straight or branched C 8 -C 15 alkyl group; wherein A is butylene; and / or wherein x is an integer value of 16 to 25, in particular an integer value of 20 to 24.
• Particular preference is given to using as component (B) an isotridecanol butoxylate.
• Fuel additive compositions preferred according to the present invention comprise as detergent additive component (component A) a detergent additive selected from polyalkene moamines and mixtures thereof.
• a detergent additive selected from polyalkene moamines and mixtures thereof.
• useful polyalkenamines are poly-C 2 -C 6 -alkeneamines and functional derivatives thereof, each containing a hydrocarbyl radical having a preferred Mn of about 500 to 1500, preferably about 600 to 1200, in particular about 700 to 1100 g.
• Suitable amines include, in addition to ammonia, mono- and di-C 1 -C 6 -alkylamines, such as mono- and dimethylamine, mono- and diethylamine, mono- and di-n-propylamine, mono- and di-n-butylamine, mono- and Di-sec-butylamine, mono- and di-n-pentylamine, mono- and di-2-pentylamine, mono- and di-n-hexylamine, etc.
• mono- or dialkylamines in which the alkyl radicals are optionally substituted by an or several, non-adjacent oxygen atoms are interrupted and may optionally also have hydroxyl groups. These include, for example, ethanolamine, 3-aminopropanol and 2- (2-aminoethoxy) ethanol.
• polyalkene monoamines or functional derivatives thereof are in particular poly-C 2 -C 6 -alkeneamines, such as poly-C 3 -C 4 -alkeneamines, or functional derivatives thereof, for example compounds having a hydrocarbyl radical, prepared by polymerization of ethylene, Propene, 1- or 2-butene, i-butene, or mixtures thereof.
• Examples of functional derivatives of the above additives are compounds which, for example in the amine part, carry one or more polar substituents, in particular hydroxyl groups.
• Preferred additives which can be used according to the invention are polyalkene monoamines based on polypropene or of highly reactive (i.e., predominantly terminal double bonds) or conventional (i.e., predominantly intermediate double bonds) polybutene or polyisobutene.
• polyisobutenes are so-called "highly reactive" polyisobutenes, which are distinguished by a high content of terminal ethylenic double bonds.
• Suitable highly reactive polyisobutenes are, for example, polyisobutenes which have a proportion of vinylidene double bonds of greater than 70 mol%, in particular greater than 80 mol% and in particular greater than 85 mol%.
• Particular preference is given to polyisobutenes which have uniform polymer skeletons. Uniform polymer skeletons have, in particular, those polyisobutenes which are composed of at least 85% by weight, preferably at least 90% by weight and more preferably at least 95% by weight, of isobutene units.
• such highly reactive polyisobutenes have a number average molecular weight M N in the range mentioned above.
• the highly reactive polyisobutenes may have a polydispersity of less than 1.9, such as less than 1.5.
• polydispersity is meant the quotient of weight average molecular weight M W divided by the number average molecular weight M N.
• Such additives based on highly reactive polyisobutene which can be prepared from polyisobutene, which may contain up to 20% by weight of n-butene units, by hydroformylation and reductive amination with ammonia or monoamines, are known in particular from US Pat EP-A-0 244 616 or EP-A-0 578 323 known.
• the preparation path is suitable by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to the carbonyl or carboxyl compound and subsequent amination under reductive (hydrogenating) conditions.
• amination the same amines as described above can be used for the reductive amination of the hydroformylated highly reactive polyisobutene.
• Corresponding additives based on polypropene are especially in the WO 94/24231 described.
• monoamine-containing additives are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in US Pat DE-A 196 20 262 are described.
• polyalkenamine-type detergent additives are sold by BASF AG, Ludwigshafen under the tradename Kerocom PIBA. These contain polyisobuteneamines dissolved in aliphatic C 10 -C 14 hydrocarbons and can be used as such in the additive packages according to the invention.
• the hydrophobic hydrocarbon radical in the above detergent additives which provides sufficient solubility in the fuel, has a number average molecular weight (M N ) of from 85 to 20,000, especially from 113 to 10,000, especially from 300 to 5,000.
• M N number average molecular weight
• Additives based on highly reactive polyisobutene which are prepared from the polyisobutene, which may contain up to 20% by weight of n-butene units, by hydroformylation and reductive amination with ammonia, monoamines or polyamines, such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine in particular, are from the EP-A-244 616 known.
• monoamino groups (a) -containing additives are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as are described in particular in US Pat DE-A-196 20 262 are described.
• Carboxyl groups or their alkali metal or alkaline earth metal salts (d) containing additives are preferably copolymers of C 2 -C 40 olefins with maleic anhydride having a total molecular weight of 500 to 20 000, the carboxyl groups wholly or partially to the alkali metal or alkaline earth metal salts and a remaining Rest of the carboxyl groups are reacted with alcohols or amines.
• Such additives are in particular from the EP-A-307,815 known.
• Such additives are primarily for preventing valve seat wear and can, as in the WO-A-87/01126 described, be used with advantage in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.
• Sulfonic acid groups or their alkali metal or alkaline earth metal salts (e) containing additives are preferably alkali metal or alkaline earth metal salts of a Sulfobernsteinklaklalesters, as described in particular in EP-A-639 632 is described.
• Such additives are primarily used to prevent valve seat wear and can be used to advantage in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.
• Polyoxy-C 2 -C 4 alkylene groupings (f) containing additives are preferably polyethers or polyetheramines, which by reaction of C 2 -C 60 alkanols, C 6 -C 30 alkanediols, mono- or di-C 2 -C 30 alkylamines, C 1 -C 30 -alkylcyclohexanols or C 1 -C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia, Monoamines or polyamines are available.
• Such products are used in particular EP-A-310 875 .
• polyethers such products also meet carrier oil properties. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.
• Carboxylic ester groups (g) containing additives are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, in particular those having a minimum viscosity of 2 mm 2 / s at 100 ° C, as in particular DE-A-38 38 918 are described.
• mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable long-chain representatives having, for example, 6 to 24 carbon atoms as ester alcohols or polyols.
• esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and of isotridecanol. Such products also meet carrier oil properties.
• derivatives with aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine.
• Such gasoline additives are particularly useful in U.S. Patent 4,849,572 described.
• Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated groupings (i) containing additives are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine.
• Such "polyisobutene-Mannich bases" are particularly in the EP-A-831 141 described.
• radicals R are n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-tridecyl, n-tetradecyl, n-pentadecyl and n-hexadecyl and n-octadecyl and the mono- or polysubstituted analogs thereof, such as. Iso-tridecyl, and mixtures of such isomers.
• radicals A examples are propylene and 1- or 2-butylene and iso-butylene.
• suitable polyethers (B) are preferably polyoxy-C 2 -C 4 -alkylene group-containing compounds obtained by reacting C 6 -C 18 -alkanols with 5 to 35 mol of C 3 -C 4 -alkylene oxide are available per hydroxyl group.
• Such products are used in particular EP-A-0 310 875 .
• Further customary additives for the fuels according to the invention are corrosion inhibitors, for example based on film-forming ammonium salts of organic carboxylic acids or of heterocyclic aromatics in non-ferrous metal corrosion protection; Antioxidants or stabilizers, for example based on amines such as p-phenylenediamine, dicyclohexylamine or derivatives thereof or of phenols such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionklare; demulsifiers; Antistatic agents; Metallocenes such as ferrocene; methylcyclopentadienyl; Lubricity additives such as certain fatty acids, alkenyl succinic acid esters, bis (hydroxyalkyl) fatty amines, hydroxyacetamides or castor oil; as well as dyes (markers).
• amines are added to lower the pH of the fuel.
• the components or additives can be added to the gasoline fuel individually or as a previously prepared concentrate (additive package) together with the high molecular weight polyalkene according to the invention.
• the said (A) different detergent additives with the polar groups (a) to (i) are added to the gasoline usually in an amount of 10 to 5000 ppm by weight, in particular 50 to 1000 ppm by weight.
• the other components and additives mentioned are added, if desired, in customary amounts.
• additive compositions according to the invention can be used in all conventional gasoline fuels, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed. 1990, Vol. A16, p. 719 et seq.
• the aromatic content of the gasoline is, for example, from 30 to 42% by volume, in particular from 32 to 40% by volume.
• the sulfur content of the gasoline is for example 5 to 150 ppm by weight, in particular 10 to 100 ppm by weight.
• the gasoline for example, has an olefin content of 6 to 21% by volume, in particular 7 to 18% by volume.
• the gasoline may, for example, have a benzene content of from 0.5 to 1.0% by volume, in particular from 0.6 to 0.9% by volume.
• the gasoline for example, has an oxygen content of 1.0 to 2.7 wt .-%, in particular from 1.2 to 2.0 wt .-%, on.
• gasoline fuels may be mentioned by way of example, which at the same time has an aromatics content of not more than 38% by volume, an olefin content of not more than 21% by volume, a sulfur content of not more than 50 ppm by weight, a benzene content of not more than 1.0% by volume. and have an oxygen content of 1.0 to 2.7% by weight.
• the content of alcohols and ethers in gasoline is usually relatively low. Typical maximum contents for methanol are 3% by volume, for ethanol 5% by volume, for isopropanol 10% by volume, for tert-butanol 7% by volume, for isobutanol 10% by volume and for ethers 5 or more C atoms in the molecule 15 vol .-%.
• the summer vapor pressure of the gasoline is usually not more than 70 kPa, in particular 60 kPa (each at 37 ° C).
• the ROZ of the gasoline is usually 90 to 100.
• a common range for the corresponding MOZ is 80 to 90.
• the specified specifications are determined by conventional methods (DIN EN 228).
• iso-tridecanol etherified with 22 moles of butylene oxide, forth and thus additizes a commercially available base fuel according to DIN EN 228 in different Amounts.
• the same fuel is only additized with PIBA.

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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)
• Solid Fuels And Fuel-Associated Substances (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Lubricants (AREA)
• Chemical And Physical Treatments For Wood And The Like (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)

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• 2002
  • 2002-03-06 DE DE10209830A patent/DE10209830A1/de not_active Withdrawn
• 2003
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  • 2003-03-05 US US10/505,767 patent/US7601185B2/en not_active Expired - Fee Related
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