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
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters

Definitions

• the invention relates to fuels for internal combustion engines with improved properties containing esters of aromatic di-, tri- or tetracarboxylic acids and long-chain alcohols.
• the invention relates to fuel compositions for gasoline engines.
• additive packages are added to gasoline in amounts of up to 2500 mg / kg. These generally consist of detergents, corrosion inhibitors, oxidation inhibitors, anti-icing agents, carrier oils and solvents.
• Carrier oils primarily have the task of preventing the so-called valve plugging and ensuring a better distribution of the detergents.
• polyethers and esters as carrier oils are said to reduce the increase in the octane requirement of engines as the number of operating hours increases.
• esters as a gasoline additive has long been known. Their use as a gasoline additive is e.g. described in DE-OS 21 29 461. The esters mentioned there are, as expressly mentioned in the patent specification mentioned, thermally unstable.
• thermally stable esters with a high molecular weight and based on branched alcohols are excellent carrier oils, as a result of which up to 30% of the usual detergents can be saved without the gasoline quality, i.e. the purifying effect in the intake and mixture formation system deteriorates.
• the invention relates to fuel compositions which have a low content, e.g. 0.005 to 0.2 wt.%, Based on the composition of esters of aromatic di-, tri- and tetracarboxylic acids with long-chain aliphatic alcohols containing only carbon, hydrogen and oxygen, which have been prepared by hydroformylation of branched olefins, the Total carbon number of the esters is at least 36 carbon atoms and the molecular weight is 550 to 1500, preferably 600 to 1200.
• esters to be used are prepared in a manner known per se by esterification or transesterification processes, the carboxyl groups being essentially completely esterified.
• Aromatic di-, tri- or tetracarboxylic acids are o-phthalic acid, isophthalic acid, terephthalic acid, trimesic acid, trimellitic acid and pyromellitic acid. Of these, o-phthalic acid is preferred.
• Oxo alcohols from higher branched olefins with generally more than 13 carbon atoms for example oligomers of butene such as tetramer to octamer butene, ie C 2 , C 2 s, C 29 and / or C 33 oxo alcohols, serve as alcohol components and oxo oils, the residues of oxo alcohol distillation from the production of higher alcohols such as nonanol to pentadecanol.
• the oxo reaction or hydroformylation is the well-known reaction of olefins with CO / H 2 over a cobalt or rhodium catalyst to produce the homologous aldehydes and alcohols.
• the alcohols can be obtained from the aldehydes by hydrogenation. Details are described in Kirk-Othmer, Encyclopedia of Chemical Technology, third edition, vol. 16, pages 637ff, to which reference is hereby made.
• aliphatic ether alcohols each with an ether and hydroxyl group and with at least 17 carbon atoms, which can be isolated, for example, from the distillation residues of the oxo alcohols Cs, Cs, C10, C 13 and C 13 / C 15 and from which it is assumed that they can be characterized by the following general formula: where n is 7, 8, 9, 12 and 12 to 14.
• Fuels for internal combustion engines are organic, mostly hydrocarbon-containing liquids that are suitable for the operation of Otto, Wankel and diesel engines.
• hydrocarbons from coal hydrogenation hydrocarbons from coal hydrogenation, alcohols of various origins and compositions and ethers such as methyl tert-butyl ether are also included
• ethers such as methyl tert-butyl ether are also included
• the permissible mixtures are mostly nationally defined worldwide.
• esters to be used according to the invention are generally combined with detergents, such as amides of oleic acid, ethylenediaminetetraacetic acid according to EP-A-6527 or polyisobutenyl succinic acid, and in particular polybutenamines prepared from polybutene alcohol with NH 3 , aminoethylethanolamine, dimethylaminopropylamine, triethylene tetramine, or tetraethylene pentamine, or tetraethylene pentamine as described in US Pat. No. 3,756,793, DE-A-21 25 039, EP 244 616, to which reference is hereby made, corrosion inhibitors, mostly low molecular weight.
• detergents such as amides of oleic acid, ethylenediaminetetraacetic acid according to EP-A-6527 or polyisobutenyl succinic acid, and in particular polybutenamines prepared from polybutene alcohol with NH 3 , aminoethylethanolamine, dimethylamino
• 1150 g oxo oil from the cobalt-catalyzed production of iso-decanol with an OH number of 154, an acid number of 0.76, a saponification number of 36 and a CO number of 1.8 and with a predominant content of alcohols at 20 ° C -Atoms, are heated under reflux with 208 g phthalic anhydride, 0.2 g tetrabutyl orthotitanate and 150 g toluene on a water separator for 36 h. 28 g of water separate out and the acid number drops to 2.
• 1043 g of an ester mixture are obtained, which is characterized as follows:
• Example C 360 g of the ether alcohol with 21 carbon atoms (1.1 mol) mentioned in Example C are condensed in a stirred flask with 74 g of phthalic anhydride (0.5 mol) in the presence of 0.1 g of tetrabutyl orthotitanate at 200 ° C. in a stream of nitrogen. After 24 h the acid number is still 1.1.
• the procedure is as in Example C, but after the pressure distillation, a steam distillation is carried out to deplete the acid with 300 g of water.
• the following table shows the effect of known carrier oils and the esters to be used according to the invention in combination with known detergents in gasoline for internal combustion engines.
• the amounts of esters listed in the table were added unleaded premium petrol (RON 95; DIN 51607) and test bench tests were carried out with a 1.2 I Opel Kadett engine in accordance with CEC-F-02-T-79.
• the reference oil RL 51 was used as engine oil.
• the table shows an increasing effect on the inlet valves of the 1.2 I Opel Kadett with the molecular weight of the ester.
• Experiments 2 to 4 of the table show a gradual reduction in the intake valve deposits compared to operating with fuel without additives (experiment 1).
• a Solvent Neutral 500 with a viscosity of 17 mm 2 / s at 100 ° C was used.
• a polypropylene glycol with a viscosity of 100 mm 2 / s at 40 ° C was used.
• Experiments 4 to 8 are esters of high purity, ie OH number less than 1, acid number less than 0.1 and ash less than 1 mg / kg.
• the C 2 s phthalate was prepared with an alcohol which was obtained by hydroformylation of a hexa-isobutene from the preparation of reactive polyisobutene according to DE-AS 27 02 604.
• the viscosity of this ester is 31 mm 2 / s at 100 0 C.
• the recommended dosage of the commercial polybutenamine for formulations with mineral oil is 350 mg / kg.
• the esters according to the invention enable a saving of about 30% in polymeric detergent. Results with other higher viscosity detergents are comparable.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Detergent Compositions (AREA)

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Cited By (21)

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Citations (5)

• 1988
  • 1988-08-06 DE DE3826797A patent/DE3826797A1/de not_active Withdrawn
• 1989
  • 1989-07-29 EP EP89114039A patent/EP0356726B1/fr not_active Expired - Lifetime
  • 1989-07-29 ES ES198989114039T patent/ES2030945T3/es not_active Expired - Lifetime
  • 1989-07-29 DE DE8989114039T patent/DE58901397D1/de not_active Expired - Lifetime

Patent Citations (5)

Non-Patent Citations (1)

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