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
• • 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
  • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
  • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
  • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)

Definitions

• the present invention relates to a fuel composition containing, in a larger amount, a specific low alkanol-containing gasoline fuel and a smaller amount of selected gasoline additives.
• valve seat wear-inhibiting additives based on alkali metal or alkaline earth metal compounds have been developed.
• Modern gasoline engines require for a trouble-free use fuels with a complex property profile, which can be guaranteed only in combination with appropriate gasoline additives.
• Such gasoline fuels usually consist of a complex mixture of chemical compounds and are characterized by physical quantities.
• the interaction between gasoline fuels and corresponding additives is still in need of improvement in the case of the known fuel compositions with regard to the cleaning and / or retention effect and the valve seat wear-inhibiting effect. It was therefore an object of the present invention to find a more effective gasoline / gasoline fuel additive composition. In particular, more effective additive formulations should be found.
• a fuel composition which contains in a greater amount a gasoline having a sulfur content of at most 150 ppm by weight, and in a smaller amount at least one gasoline additive with detergent effect or valve seat wear-inhibiting effect, said gasoline fuel additive having at least one hydrophobic hydrocarbon radical having a number average molecular weight (MN) of 85 to 20,000 and at least one polar moiety, and wherein the fuel composition further has a content of at least one lower alkanol of about 5 to 75% by volume.
• MN number average molecular weight
• the polar grouping is selected under:
• the lower alkanol used according to the invention is preferably a straight-chain or branched, saturated C 1 -C 6 mono- or diol, in particular a C 1 -C 3 mono- alkanol, such as methanol, ethanol, n- or i-propanol, or a mixture of several of these alkanols.
• the alkanol content is, based on the total volume of the fuel composition a maximum of 75 vol .-%, such as. B. 5 to 75 vol .-%, preferably 10 to 65 vol .-%, in particular 20 to 55 vol .-%, such as. B. 30 - 40 vol .-% or 40 - 50 vol .-%.
• the content of other alcohols and ethers in gasoline is usually relatively low. Typical maximum contents are 7% by volume for tert-butanol, 10% by volume for isobutanol and 15% by volume for ethers having 5 or more C atoms in the molecule.
• the aromatic content of the gasoline is preferably not more than 40% by volume, in particular not more than 38% by volume. Preferred ranges for the aromatic content are from 20 to 42% by volume, in particular from 25 to 40% by volume.
• the sulfur content of the gasoline is preferably not more than 100 ppm by weight, in particular not more than 50 ppm by weight. Preferred ranges for the sulfur content are from 0.5 to 150 ppm by weight, in particular from 1 to 100 ppm by weight.
• the gasoline has an olefin content of not more than 21% by volume, preferably not more than 18% by volume, in particular not more than 10% by volume. Preferred ranges for the olefin content are from 6 to 21% by volume, in particular from 7 to 18% by volume.
• the gasoline has a benzene content of not more than 1, 0 vol .-%, in particular not more than 0.9 vol .-%, on.
• Preferred ranges for the benzene content are from 0.5 to 1, 0 vol .-%, in particular 0.6 to 0.9 vol .-%.
• the gasoline has an oxygen content of at most 2.7% by weight, preferably from 0.1 to 2.7% by weight, especially from 1, 0 to 2.7% by weight. , in particular from 1, 2 to 2.0 wt .-%, on.
• a gasoline fuel 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 a Has oxygen content of 1, 0 to 2.7 wt .-%.
• the above vol .-% - for olefin, benzene, aromatics and oxygen content are in each case based on the volume of the mineral gasoline component, ie without additives and without alkanol.
• the summer vapor pressure of the gasoline is usually not more than 70 kPa, in particular 60 kPa (each at 370C).
• the research octane number ("RON") of the gasoline is typically 90 to 100.
• a common range for the corresponding engine octane number (“MOZ”) is 80 to 90.
• the specified specifications are determined by conventional methods (DIN EN 228).
• the hydrophobic hydrocarbon radical in the gasoline fuel additives which provides sufficient solubility in the fuel, has a number average molecular weight (Mn) of 85 to 20,000, especially from 113 to 10,000, especially from 300 to 5000.
• Mn number average molecular weight
• 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 described in particular in DE-A 196 20 262.
• These reaction products typically are mixtures of pure nitropolyisobutanes (e.g., alpha.beta.-dinitropolyisobutane) and mixed hydroxynitropolyisobutanes (e.g., alpha-nitro-beta-hydroxypolyisobutane).
• 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 known in particular from EP-A 307 815. Such additives serve primarily to prevent valve seat wear and, as described in WO-A 87/01126, may advantageously be used in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.
• Sulphonic 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 sulfosuccinic acid alkyl ester, as described in particular in EP-A 639 632.
• Such additives are mainly 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 - to C 4 -alkylene (f) additives are preferably polyethers or polyetheramines which are obtainable by reaction of C 2 - to C 60 alkanols, C 6 - to C 30 alkanediols, mono- or di-C 2 C 30 -alkylamines, -CC 30 -alkylcyclohexanols or CC 30 -alkylphenols with 1 to 30 moles 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 described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416.
• such products also fulfill 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, especially those having a minimum viscosity of 2 mm2 / s at 100oC, as described in particular in DE-A 38 38 918.
• Aliphatic or aromatic acids can be used as the mono-, di- or tricarboxylic acids, and the ester alcohols or polyols which are suitable are above all long-chain representatives with, for example, 6 to 24 C atoms.
• 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 described in particular in US Pat. No. 4,849,572.
• 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 described in particular in EP-A 831 141.
• the fuel composition of the invention may further contain other conventional components and additives.
• Suitable solvents or diluents are aliphatic and aromatic hydrocarbons, e.g. Solvent naphtha, into consideration.
• corrosion inhibitors for example based on film-forming ammonium salts of organic carboxylic acids or of heterocyclic aromatics in the case of non-ferrous metal corrosion protection
• antioxidants or stabilizers for example based on amines such as p-phenylenediamine, dicyclohexylamine or derivatives thereof or on phenols such as 2,4 -Di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid, demulsifiers, antistatic agents, metallocenes such as ferrocene or methylcyclopentadienyl manganese tricarbonyl, lubricity improvers such as certain fatty acids, alkenyl succinic acid esters, bis (hydroxyalkyl ) fatty amines, hydroxyacetamides or castor oil as well as dyes (markers). Sometimes amines are also added to lower the pH of the fuel.
• Typical mixtures of this type include polyisobutene amines in combination with alkanol-initiated polyethers such as tridecanol or isotridecanol butoxylates or propoxylates, polyisobutene amines in combination with alkanol-initiated polyetheramines such as tridecanol or isotridecanol butoxylate ammonia reaction products and alkanol-initiated polyether amines such as tridecanol or isotridecaol butoxylate ammonia reaction products Combination with alkanol-initiated polyethers, such as tridecanol or isotridecanol butoxylates or propoxylates, in each case together with the abovementioned corrosion inhibitors or lubricity improvers.
• alkanol-initiated polyethers such as tridecanol or isotridecanol butoxylates or propoxylates
• the aforementioned gasoline additives with the polar groups (a) to (i) and the other components mentioned are added to the gasoline and unfold their effect there.
• the components or additives can be added to the gasoline fuel individually or as a previously prepared concentrate ("additive package").
• gasoline additives with the polar groups (a) to (i) are added to the gasoline usually in an amount of 1 to 5000 ppm by weight, in particular 5 to 3000 ppm by weight, especially 10 to 1000 ppm by weight ,
• the other components and additives mentioned are added, if desired, in customary amounts.
• the same cleaning or valve seat wear-inhibiting effect can be achieved as in comparable fuel compositions without low alkanol addition.
• the same amounts of detergent or valve seat wear-inhibiting agent in the inventive fuel composition compared to conventional fuel compositions surprisingly results in a significantly better cleansing or reinhaltende or valve seat wear-inhibiting effect kung.
• the fuel composition according to the invention additionally has advantages in that fewer deposits are formed in the combustion chamber of the gasoline engine and that less additive is introduced into the engine oil via the fuel dilution.
• Further objects of the invention relate to i) the use of a lower alkanol in low-sulfur gasoline fuels to improve the effect of a detergent-effect additive or valve seat wear-inhibiting effect as defined above; (ii) a method of improving the additive effect of a detergency-enhancing or valve-seat wear-inhibiting additive as defined above in low-sulfur gasoline fuels by adding an effective amount of a lower alcohol to the gasoline;
• valve seat wear inhibitor for gasoline fuels.
• Example 1 was repeated, but using OK 2 instead of OK 1.
• Example 1 was repeated but using OK 3 instead of OK 1.

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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)
• Detergent Compositions (AREA)

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