EP0301448B1 - Combustibles pour moteur à combustion interne - Google Patents

Combustibles pour moteur à combustion interne Download PDF

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Publication number
EP0301448B1
EP0301448B1 EP88111909A EP88111909A EP0301448B1 EP 0301448 B1 EP0301448 B1 EP 0301448B1 EP 88111909 A EP88111909 A EP 88111909A EP 88111909 A EP88111909 A EP 88111909A EP 0301448 B1 EP0301448 B1 EP 0301448B1
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EP
European Patent Office
Prior art keywords
fuel
acid
general formula
fuels
metal salts
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.)
Expired - Lifetime
Application number
EP88111909A
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German (de)
English (en)
Other versions
EP0301448A1 (fr
Inventor
Franz-Dieter Dr. Martischius
Knut Dr. Oppenlaender
Hans-Henning Dr. Vogel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
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BASF SE
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Publication date
Priority claimed from DE19873725272 external-priority patent/DE3725272A1/de
Priority claimed from DE19883801107 external-priority patent/DE3801107A1/de
Application filed by BASF SE filed Critical BASF SE
Priority to AT88111909T priority Critical patent/ATE76425T1/de
Publication of EP0301448A1 publication Critical patent/EP0301448A1/fr
Application granted granted Critical
Publication of EP0301448B1 publication Critical patent/EP0301448B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/224—Amides; Imides carboxylic acid amides, imides
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B1/00—Engines characterised by fuel-air mixture compression
    • F02B1/02—Engines characterised by fuel-air mixture compression with positive ignition
    • F02B1/04—Engines characterised by fuel-air mixture compression with positive ignition with fuel-air mixture admission into cylinder
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B75/00—Other engines
    • F02B75/02—Engines characterised by their cycles, e.g. six-stroke
    • F02B2075/022—Engines characterised by their cycles, e.g. six-stroke having less than six strokes per cycle
    • F02B2075/027—Engines characterised by their cycles, e.g. six-stroke having less than six strokes per cycle four

Definitions

  • the invention relates to fuels for gasoline engines containing alkali metal or alkaline earth metal salts of amides of di-, tri- or tetracarboxylic acids.
  • the task therefore was to find substances which, in addition to preventing or reducing wear and tear on the valves of gasoline engines, also reduce corrosion in the gasoline engines.
  • the new fuel additives have the advantage that they do not cause any contamination in the gasoline engines and at the same time prevent or at least greatly reduce the occurrence of wear on the valves and, surprisingly, further considerably reduce or even prevent the occurrence of corrosion in the gasoline engines.
  • the alkali metal or alkaline earth metal salts of the monoamides of dicarboxylic acids according to the invention are derived from the dicarboxylic acids maleic acid, succinic acid, glutaric acid or adipic acid. They are made according to methods known per se, e.g. by reacting maleic anhydride, succinic anhydride or glutaric anhydride, with the corresponding amines in a molar ratio of about 1: 1 at temperatures of generally 50 to 100 ° C., preferably 60 to 90 ° C., and subsequent reaction of the monoamides obtained with a basic alkali metal - Or alkaline earth metal compound, e.g. the hydroxides, carbonates or alcoholates.
  • a basic alkali metal - Or alkaline earth metal compound e.g. the hydroxides, carbonates or alcoholates.
  • the compounds derived from adipic acid are e.g. by reacting adipic acid with the corresponding amines in a molar ratio of about 1: 1 at temperatures of generally 120 to 180 ° C, preferably 130 to 170 ° C, in the presence of, for example, acidic catalysts such as p-toluenesulfonic acid with removal of the the reaction-forming water, e.g. by applying vacuum or by azeotropic distillation, and then reacting the obtained monoamide of adipic acid with a basic alkali metal or alkaline earth metal compound, e.g. the hydroxides, carbonates or alcoholates.
  • a basic alkali metal or alkaline earth metal compound e.g. the hydroxides, carbonates or alcoholates.
  • the maleic anhydride is reacted e.g. placed in a reaction vessel, for example in molten form, and the amine is introduced with stirring at temperatures from 60 to 80.degree.
  • a solution of the approximately stoichiometric amount of potassium methylate in methanol was added to the potassium salt and the methanol was then removed by distillation.
  • the alkali metal or alkaline earth metal salts of the amides of tri- or tetracarboxylic acids according to the invention are preferably derived from citric acid or nitrilotriacetic acid as tricarboxylic acids and ethylenediaminetetraacetic acid as tetracarboxylic acid.
  • amides in the tricarboxylic acids the mono- and / or diamides, preferably the diamides, are used, the remaining carboxylic acid groups which are not present as amides each being present as an alkali metal or alkaline earth metal salt.
  • the mono- and / or di- and / or triamides preferably the triamides, are used, the remaining carboxylic acid groups which are not present as amides again being present as alkali metal or alkaline earth metal salts.
  • the alkali metal or alkaline earth metal salts of the amides of the tri or tetracarboxylic acids are obtained by methods known per se, e.g. by reacting the tri- or tetracarboxylic acids with the corresponding amines in the corresponding molar ratio, for example in the molar ratio of approximately 1: 1 in the reaction to the monoamides, of approximately 1: 2 in the reaction to the diamides and of approximately 1: 3 the reaction to the triamides, at temperatures of generally 120 to 180 ° C, preferably 130 to 170 ° C, in the presence of, for example, acidic catalysts such as p-toluenesulfonic acid with removal of the water formed in the reaction, for example by applying vacuum or by azeotropic distillation, and then reacting the amides obtained with a basic alkali metal or alkaline earth metal compound, e.g. the hydroxides, carbonates or alcoholates.
  • one proceeds, for example, in the reaction of citric acid by placing the citric acid in a reaction vessel together with the required amount of amine and converting it to the corresponding amides at temperatures of 150 to 160 ° C. After the reaction has ended, e.g. a solution of the approximately stoichiometric amount of potassium methylate in methanol was added to the potassium salt and the methanol was then removed by distillation.
  • amines of the general formula are used for the preparation of the alkali metal or alkaline earth metal salts of the amides of di-, tri- or tetracarboxylic acids according to the invention used in which R1 and R2 are the same or different unsubstituted or substituted, optionally simply olefinically unsaturated hydrocarbon radicals which generally have 5 to 75, preferably 5 to 50, in particular 8 to 30 carbon atoms.
  • Suitable amines are, for example, di-2-ethylhexylamine, dioleylamine. Diisotridecylamine of the formula is particularly advantageous used for manufacturing.
  • R3 and R4 are identical or different unsubstituted or substituted hydrocarbon radicals having 1 to 18, preferably 4 to 13 carbon atoms.
  • the general formula therefore applies to these amines with the meanings given above for R3, R4, n and y.
  • the amines (I) are obtained by methods known per se, for example using an amine of the general formula with the meanings given above for R3 and R4 with propylene oxide or butylene oxide or with a mixture of propylene oxide and butylene oxide in the presence of alkali such as potassium hydroxide solution, sodium hydroxide solution, sodium methylate at elevated temperatures, for example at 120 to 150 ° C., to the compounds of the general formula with the meanings given above for R3, R4, n and y is implemented.
  • alkali such as potassium hydroxide solution, sodium hydroxide solution, sodium methylate at elevated temperatures, for example at 120 to 150 ° C.
  • the compounds (III) can also be obtained by first treating the amine (II) with propylene oxide or butylene oxide or a mixture thereof in a molar ratio of about 1: 1 at temperatures of generally 60 to 120 ° C., preferably 80 to 100 ° C in the absence of alkali to the compounds of the general formula which are then reacted in a second stage with further propylene oxide or butylene oxide or a mixture thereof in the presence of alkali, for example 0.1 to 3% by weight sodium or potassium hydroxide solution, to give the compounds (III).
  • the compounds (III) are finally in a further stage by aminating hydrogenation, i.e. by reaction with the approximately stoichiometric amount of NH3 and H2 over a conventional hydrogenation catalyst, e.g. Raney-Ni, converted to the amines (I).
  • a conventional hydrogenation catalyst e.g. Raney-Ni
  • pressures of 150 to 250 bar and temperatures of appropriately 200 to 250 ° C. are used.
  • the potassium salts are preferably used as a fuel additive.
  • the new fuel additives are generally added to the fuels for gasoline engines in amounts of 10 to 2000 ppm by weight, preferably 50 to 1000 ppm by weight.
  • the fuels according to the invention may additionally contain known phenol or amine-based antioxidants.
  • Residual oils from oxo alcohol synthesis have proven to be good solvents or solubilizers for the components to be added to the fuel.
  • Oxoalcohol residues from butanol, isobutanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol or dodecanol synthesis are preferably used.
  • the use of oxo alcohol residues from butanol synthesis is particularly advantageous.
  • other solvents or solvent mixtures can also be used which result in a homogeneous mixture of the components in the weight ratios mentioned above.
  • the effect of the gasoline additives according to the invention is not only limited to gasoline. It has been shown that they can also be used in aviation fuels, in particular in aviation fuels for piston engines.
  • the compounds according to the invention act not only in carburetor engines, but also in engines with fuel injection systems.
  • the fuels provided with the new additive can also contain other customary additives, e.g. additives to improve octane number or components containing oxygen, e.g. Contain methanol, ethanol or methyl tertiary butyl ether.
  • additives to improve octane number or components containing oxygen e.g. Contain methanol, ethanol or methyl tertiary butyl ether.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Lubricants (AREA)
  • Fuel-Injection Apparatus (AREA)

Claims (6)

  1. Carburants sans plomb pour moteurs à combustion interne, contenant de petites quantités de sels alcalins ou alcalino-terreux de monoamides d'acides dicarboxyliques de formule générale (1)
    Figure imgb0019
    ou d'amides d'acides tri- ou tétracarboxyliques, les groupements amide répondant à la formule générale (2)
    Figure imgb0020
    R¹ et R² étant identiques ou différents et représentant des restes hydrocarbonés à 5-75 atomes de carbone non substitués ou substitues, présentant éventuellement une seule insaturation oléfinique, ou R¹ étant mis pour H et R² pour
    Figure imgb0021
    avec n = 3 et/ou 4 et y = 5 à 100, R³ et R⁴ étant identiques ou différents et représentant des restes hydrocarbonés à 1-18, de préférence à 4-13 atomes de carbone, non substitués ou substitués, et
    -A- étant mis pour -CH=CH- ou -(CH₂)x avec x = 2 à 4.
  2. Carburants selon la revendication 1, caractérisés en ce que de l'acide citrique ou de l'acide nitrilotriacétique est utilisé en tant qu'acide tricarboxylique et de l'acide éthylènediaminetétraacétique est utilisé en tant qu'acide tétracarboxylique.
  3. Carburants selon la revendication 1 ou 2, caractérisés en ce que les sels utilisés sont des sels de lithium, de sodium, de potassium, de rubidium, de césium, de calcium et/ou de magnésium.
  4. Carburants selon l'une quelconque des revendications 1 à 3, caractérisé en ce que les sels utilisés sont des sels de potassium.
  5. Carburants selon l'une quelconque des revendications 1 à 4, caractérisés en ce que R¹ et R² représentent le reste hydrocarboné C₁₃H₂₇.
  6. Carburants selon l'une quelconque des revendications 1 à 5, caractérisés par une teneur en sels alcalins ou alcalino-terreux de 10 à 2000 ppm en poids.
EP88111909A 1987-07-30 1988-07-23 Combustibles pour moteur à combustion interne Expired - Lifetime EP0301448B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88111909T ATE76425T1 (de) 1987-07-30 1988-07-23 Kraftstoffe fuer ottomotoren.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19873725272 DE3725272A1 (de) 1987-07-30 1987-07-30 Kraftstoffe fuer ottomotoren
DE3725272 1987-07-30
DE19883801107 DE3801107A1 (de) 1988-01-16 1988-01-16 Kraftstoffe fuer ottomotoren
DE3801107 1988-01-16

Publications (2)

Publication Number Publication Date
EP0301448A1 EP0301448A1 (fr) 1989-02-01
EP0301448B1 true EP0301448B1 (fr) 1992-05-20

Family

ID=25858109

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88111909A Expired - Lifetime EP0301448B1 (fr) 1987-07-30 1988-07-23 Combustibles pour moteur à combustion interne

Country Status (7)

Country Link
US (1) US4871375A (fr)
EP (1) EP0301448B1 (fr)
JP (1) JPS6448893A (fr)
AT (1) ATE76425T1 (fr)
CA (1) CA1308253C (fr)
DE (1) DE3871274D1 (fr)
ES (1) ES2031185T3 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5282872A (en) * 1990-01-10 1994-02-01 Basf Aktiengesellschaft Fuel for Otto-cycle engines
DE4130352A1 (de) * 1991-09-12 1993-03-18 Basf Ag Des- und reaktivierte metallocenkatalysatorsysteme
CZ280251B6 (cs) * 1992-02-07 1995-12-13 Slovnaft A.S. Bratislava Deriváty dikarboxylových kyselín ako prísady do nizkoolovnatých alebo bezoolovnatých automobilových benzínov
DE4237662A1 (de) * 1992-11-07 1994-05-11 Basf Ag Erdölmitteldestillatzusammensetzungen
US5338470A (en) * 1992-12-10 1994-08-16 Mobil Oil Corporation Alkylated citric acid adducts as antiwear and friction modifying additives
DE4324394A1 (de) * 1993-07-21 1995-01-26 Basf Ag Umsetzungsprodukte von Aminoalkylencarbonsäuren sowie Erdölmitteldestillate, die diese enthalten
CN1368540A (zh) * 2001-02-01 2002-09-11 呼世滨 一种汽油抗爆添加剂及其配制的汽油
WO2009150145A1 (fr) * 2008-06-12 2009-12-17 Basf Se Utilisation d'agents solubilisants pour l'homogénéisation de concentrés d'additifs

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2654660A (en) * 1951-06-07 1953-10-06 Gulf Research Development Co Stable fuel oil compositions
US2699427A (en) * 1952-10-02 1955-01-11 Gulf Oil Corp Mineral oil compositions containing amidic acids or salts thereof
US2718503A (en) * 1953-02-20 1955-09-20 Gulf Research Development Co Anticorrosion agents consisting of the monamides of dimerized fatty acids
NL106289C (fr) * 1958-01-07
US3046102A (en) * 1958-10-06 1962-07-24 Socony Mobil Oil Co Inc Stabilized distillate fuel oil
US3192160A (en) * 1962-06-01 1965-06-29 Socony Mobil Oil Co Inc Mineral oil compositions containing metal salts of citramic acids
US3264075A (en) * 1962-07-06 1966-08-02 Mobil Oil Corp Metal salts of succinamic acids in distillate fuel oil
US3247110A (en) * 1963-05-16 1966-04-19 Socony Mobil Oil Co Inc Fuel oil and lubricating oil compositions containing metal salts of the mono-amidesof tetrapropenyl succinic acid
US3249541A (en) * 1963-12-23 1966-05-03 Socony Mobil Oil Co Inc Stabilized mineral oil compositions
US3804763A (en) * 1971-07-01 1974-04-16 Lubrizol Corp Dispersant compositions
DE2828038A1 (de) * 1978-06-26 1980-01-10 Basf Ag Kraftstoffe fuer ottomotoren
GB8515974D0 (en) * 1985-06-24 1985-07-24 Shell Int Research Gasoline composition

Also Published As

Publication number Publication date
US4871375A (en) 1989-10-03
EP0301448A1 (fr) 1989-02-01
ES2031185T3 (es) 1992-12-01
DE3871274D1 (de) 1992-06-25
ATE76425T1 (de) 1992-06-15
JPS6448893A (en) 1989-02-23
CA1308253C (fr) 1992-10-06

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