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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
  • C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition

Definitions

• the invention relates to the use of methyl formate as an additive to fuels and to a fuel for internal combustion engines with electrical ignition.
• the efficiency of heat engines increases the greater the temperature difference between the entering and leaving medium. In the case of internal combustion engines, this has the consequence that at the same time it is necessary to work with ever higher pressures in order to achieve a higher working temperature. In internal combustion engines with forced ignition of the mixture, the mixture must not ignite on its own.
• the octane number was introduced as a measure of this ability. Depending on the different determination methods, the research octane number (RON), the motor octane number (MOZ), the street octane number (SOZ) and the front octane number (FOZ) are spoken of.
• the front octane number is used in such a way that a fraction is drawn from the fuel that distills up to 100 ° C, and the research octane number is then determined from this.
• the FOZ is therefore a measure of the knock resistance of the fuel components that initially boil.
• iron or manganese compounds can also be used as anti-knock agents, for example.
• These compounds have a high toxicity, whereby oxides remain in the combustion chamber, which, if no further additives are provided in the fuel, can on the one hand lead to premature wear of the piston and cylinder and on the other hand can also cause premature ignition of the mixture due to glowing residues.
• This phenomenon is known in the literature under the designation "post-diesel". In the case of an engine that is subject to higher loads, however, this phenomenon can lead to the pistons melting.
• methyl tert-butyl ether As an anti-knock agent that has been used particularly recently, methyl tert-butyl ether should be mentioned. This compound has a boiling point of 55.3 ° C and a density at 15 ° C of 0.7458 g / cm3. With the addition of methyl tert-butyl ether (MTBE) an RON between 115 and 135 and an MOZ between 98 and 120 can be achieved depending on the composition of the base gasoline. MTBE is added in a range between 3.0% by volume and 15.0% by volume. A disadvantage of the addition of MTBE is that the increase in the number that is important for the normal operation of an engine, u. between the MOZ, not as much as desired with the ROZ.
• MTBE methyl tert-butyl ether
• Additives are known to avoid contamination of the carburetor. Additives to keep the gasoline from oxidizing so that no resinous sticky residues form. Additives to prevent gasoline from corroding metals. Additives that form a copper complex to prevent oxidation of the fuel and also additives to prevent carburetor icing. Under this group to prevent carburetor icing, either surface-active substances or compounds that lower the freezing point of the water are used.
• amines, diamines, amides, ammonium salts of diesters are the Phosphoric acid, glycerols, alcohols, glycols, ketones, dimethylformamide and dimethylacetamide are mentioned in the literature.
• DE-A1 2 447 345 discloses artificial fuel mixtures made from methanol, formaldehyde dimethyl acetal and methyl formate, which are intended to serve as artificial fuel mixtures.
• additions of iron carbonyl and organic manganese compounds are provided.
• GB-A-1,411,947 discloses a mixture of hydrocarbons with 1% by weight to 10% by weight of water and 12.5% by weight of methyl formate. According to this literature reference, methyl, ethyl or propyl formates are unsuitable as additives for fuels.
• Another object of the present invention is to lower the cloud point of gasolines and to reduce the risk of icing in both carburetor and injection engines.
• the invention consists in the use of methyl formate as an octane-increasing, in particular MOZ-increasing additive to a manganese, lead and iron-free fuel for internal combustion engines with electrical ignition with carburetor and / or fuel injection with a boiling fraction of 30 ° C to 200 ° C, in particular 30 ° C to 180 ° C, with paraffinic and / or olefinic and / or naphthenic and / or aromatic hydrocarbons, in particular in an amount of 1.0 vol.% to 50.0 vol.%, optionally 1.0 vol.% to 30.0 vol. -%. preferably 3.5% by volume to 10.0% by volume, based on the total solution of the fuel.
• methyl formate was already known as a fuel component, it was only used because of its good properties as a fuel because of its calorific value and as a solubilizer. In addition to the methyl formate, metallic compounds that increase the octane number have been provided. Although methyl formate has a lower RON than various other additives that increase the knock number, it has an identical RON and MOZ, which makes the suitability for practice particularly clear. Methyl formate already has an increase in small vol.% Limits, for example 1.0 vol.% Or 3.5 vol.% RON, although in addition to these properties, the properties for lowering the cloud point of the fuel as well as Separation of sediments from the fuel can be highlighted. The starting behavior of injection engines at low temperature is also improved.
• By volume to 10.0% by volume of methyl formate essentially consists in the fact that it contains an additional content of methyl tert-butyl ether, in particular in the same volume as that of methyl formate.
• the fuel can also contain alcohols, in particular methyl alcohol and / or ethyl alcohol, instead of methyl tert-butyl ether.
• Methyl formate is a large-scale chemical that meets all the requirements placed on an octane number improver.
• the starting product is synthesis gas, which is converted to methanol in a known manner and which also gives methyl formate by carbonylation using a known method.
• the toxicity has also been extensively investigated: there is no carcinogenic effect, the MAK value is the same as that of higher aromatics (ethylbenzene, xylenes), and it is even harmless in animal experiments; LCL0 values; Inhalation guinea pig: Xylene mixture 450 ppm toluene 1,600 ppm MF 10,000 ppm.
• Methyl formate has a boiling point of 31.5 ° C, so that it can also be used in larger quantities as an ingredient in gasoline. It was now quite surprising that additions of methyl formate, for example the addition of other knocking agents, such as lead compounds, can replace the properties of the carburetor and injection systems, and also prevent the aging by oxygen in the fuel to a lesser extent can. Despite the higher density of methyl formate compared to MTBE, it can already increase the FOZ. It is not necessary to add organometallic compounds to increase the number of knocks.
• the fuel contains 10.0% by volume to 60.0% by volume, in particular 30.0% by volume to 50.0% by volume, of a mixture of methyl formate and methyl tert-butyl ether, one becomes Get fuel that has a particularly high percentage of Products that distill up to 100 ° C, so that in addition to increasing the RON, a particularly favorable acceleration behavior of vehicles is achieved.
• a particularly significant increase in the practice-oriented properties of the fuel is obtained when about 30.0% by volume to 50.0% by volume of this mixture is present in the fuel.
• the fuel additionally has alcohols, in particular methyl alcohol and / or ethyl alcohol
• alcohols in particular methyl alcohol and / or ethyl alcohol
• an additional increase in both the RON and the MOZ can be achieved, the solubility of hydrophilic substances in the fuel being able to be increased at the same time, so that particularly trouble-free operation in the carburetor or in the injection system can be achieved.
• These properties are achieved in particular by the low alcohols, such as methyl alcohol or ethyl alcohol, and there is also a particularly good availability of these two chemicals.
• the fuel has 10.0% by volume to 60.0% by volume of a mixture of methyl formate, methyl tert-butyl ether and methyl alcohol, in particular in equal volumes, then trouble-free operation is possible even under difficult climatic conditions Conditions guaranteed.
• a boiling fraction of a petroleum base stock from 30 ° C to 180 ° C had a density of 0.740 g / cm3. After storing the mixture at - 22 ° C, turbidity occurred after 5 hours, since the water content of 250 ppm at this temperature could no longer be kept in solution. After 3 days of storage at room temperature, sedimentation in the gasoline was observed.
• the RON and MOZ were determined on the boiling fraction according to Example 1 without addition.
• the RON and MOZ were determined on pure methyl formate.
• Example 2 A boiling fraction according to Example 2 was mixed with 10.0% by volume of methyl tert-butyl ether and the RON and MOZ were determined.
• a boiling fraction according to Example 2 was mixed with 20.0% by volume of methyl tert-butyl ether and the RON and MOZ were determined.
• a boiling fraction according to Example 2 was mixed with 30.0% by volume of methyl tert-butyl ether and the RON and MOZ were determined.
• a mixture of one part by volume of methyl formate and one part by volume of methyl tert-butyl ether was prepared and a mixture with the boiling fraction according to Example 2 of 10.0% by volume of this mixture was prepared.
• the RON and MOZ were determined.
• a mixture was prepared analogously to Example 13, but with 20.0% by volume of the mixture of methyl formate and methyl tert-butyl ether. The RON and MOZ were determined.
• a fuel was prepared according to Example 14, 30.0% by volume of the mixture of methyl alcohol, methyl formate and methyl tert-butyl ether being present.
• a boiling fraction of a petroleum base stock from 30 ° C to 185 ° C had a density of 0.745 g / cm3. After storage The mixture at - 22 ° C. became cloudy after 5 hours, since the water content of 200 ppm was no longer kept in solution at this temperature. After the mixture had been stored for 3 days, sedimentation in the gasoline was observed.
• the RON and MOZ were determined on the boiling fraction according to Example 17 without addition.
• the RON and MOZ were determined on pure methyl formate.
• Example 18 A boiling fraction according to Example 18 was mixed with 10.0% by volume of methyl tert-butyl ether and the RON and MOZ were determined.
• a boiling fraction according to Example 18 was mixed with 20.0% by volume of methyl tert-butyl ether and the RON and MOZ were determined.
• a boiling fraction according to Example 18 was mixed with 30.0% by volume of methyl tert-butyl ether and the RON and MOZ were determined.
• a mixture of one part by volume of methyl formate and one part by volume of methyl tert-butyl ether was prepared and a mixture with the boiling fraction according to Example 18 of 10.0% by volume of this mixture was prepared and the RON and MOZ were determined.
• a mixture was prepared analogously to Example 18, but with 20.0% by volume of the mixture of methyl formate and methyl tert-butyl ether, and the RON and MOZ were determined.
• Example 18 A fuel was produced according to Example 18, 30.0% by volume of the mixture of methyl alcohol, methyl formate and methyl tert-butyl ether being present, and the RON and MOZ were determined.
• Table I REGULAR GASOLINE RON MOZ
• Example 2 90.3 81.6
• Example 3 91.1 82.3
• Example 4 91.8 83.0
• Example 5 93.1 84.2
• Example 6 94.2 85.1
• Example 7 95.2 86.1
• Example 8 96.1 87.0
• Example 10 91.9 82.4
• Example 11 93.1 84.0 Example 12 94.3 84.8
• Example 13 92.0 83.3
• Example 14 94.5 84.9
• Example 15 92.1 83.6
• Example 16 94.4 85.0 EUROSUPER RON MOZ
• Example 18 96.0 84.5
• Example 19 96.6 85.1
• Example 20 97.1 85.6
• Example 21 98.1 86.9
• Example 22 99.0 88.1
• Example 23 99.9 89.0
• Example 24 101.0 89

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• 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)
• Liquid Carbonaceous Fuels (AREA)

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• 1991
  • 1991-02-26 AT AT0040191A patent/AT404596B/de not_active IP Right Cessation
• 1992
  • 1992-01-01 EP EP91890292A patent/EP0501097B1/de not_active Expired - Lifetime
  • 1992-01-01 DE DE59203411T patent/DE59203411D1/de not_active Expired - Fee Related
  • 1992-02-19 YU YU16892A patent/YU16892A/sh unknown
  • 1992-02-21 US US07/838,927 patent/US5232464A/en not_active Expired - Fee Related
  • 1992-02-24 CS CS92537A patent/CS53792A3/cs unknown
  • 1992-02-25 HU HU9200619A patent/HU210759B/hu not_active IP Right Cessation

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