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
  • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
  • C10L1/328—Oil emulsions containing water or any other hydrophilic phase
• • 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

Definitions

• the invention relates to fuels for internal combustion engines such as gasoline and diesel engines, as well as rotary piston engines and turbines or heating oils for oil firing systems, which contain emulsifiers or emulsifying mixtures and water and, if appropriate, alcohols in the fuels or heating oils customary for the respective units; the invention further relates to a process for their preparation and their use.
• water, a nonionic emulsifier and optionally an alcohol-containing fuel or heating oil have been found, which are characterized in that the nonionic emulsifier used contains less than 1000 ppm of salt and less than 1% by weight of polyalkylene glycol ether.
• a process for the production of water, a nonionic emulsifier and, if appropriate, an alcohol-containing fuel or heating oil has also been found, which is characterized in that a nonionic emulsifier is used for the production, which is known per se, and which contains less than 1000 ppm of salt and contains less than 1% by weight polyalkylene glycol ether.
• nonionic - emulsifiers are emulsifiers of Alkyläther-, Alkancarbonklareester-, Alkancarbonamid- or alkylamine type.
• the nonionic emulsifiers are obtained, for example, by reacting 2-50 mol of ethylene oxide or ethylene oxide and propylene oxide with (a) an alcohol having 8-22 C atoms, which can be straight-chain or branched, saturated or unsaturated, with (b) an alkyl glycol 1,2 with 10 - 22 C atoms, with (c) a fatty acid with 10 - 22 C atoms, which can be saturated or unsaturated, straight-chain or branched, with (d) resin acids or naphthenic acids with (e) an alkylphenol, such as nonyl or dodecylphenol or aralkylphenols or with (f) fats, such as castor oil, coconut oil, palm oil, tallow oil or lard, sunflower oil, safflower oil, olive oil.
• an alcohol having 8-22 C atoms which can be straight-chain or branched, saturated or unsaturated
• an alkyl glycol 1,2 with 10 - 22 C atom
• nonionic emulsifiers to be used according to the invention can be found in _N.Schönfeldt, "Interface-active ethylene oxide adducts. Their preparation, properties, application and analysis", Stuttgart 1976, and MJSchick, "Nonionic Surfactants", M. Dekker, New York, 1976, to find.
• the property of the nonionic emulsifiers can be used to separate out from an aqueous solution when heated. If a mixture of water with emulsifier is heated in a ratio of 1: 1 to 90-100 ° C, a water-containing approx. 65% emulsifier layer separates out at the bottom and an aqueous layer deposited on top contains the polyglycol ether and the catalyst salts.
• the alkalinity from the oxyethylation catalyst (KOH, NaOH) is advantageously removed before the separation by neutralization with sulfuric acid or acetic acid. This procedure corresponds approximately to that in DE-PS 828 839.
• the emulsifiers contain less than 0.01% Salts (previously 0.3-0.5%) and preferably less than 0.5% polyethylene glycol ether (previously 3-8%).
• an organic water-immiscible solvent e.g. Toluene
• the emulsifier and solvent are mixed in a ratio of about 1: 1. 5-10% by weight of water and possibly acid (such as sulfuric acid or acetic acid) are stirred into the solution to neutralize basic fractions.
• acid such as sulfuric acid or acetic acid
• an aqueous layer separates at the bottom. This contains the polyglycol ether and the salts. Since this solution is approx. 50 - 60%, it can be easily removed by incineration.
• the toluene layer can be completely freed from water and toluene.
• the intended use according to the invention can dry the toluene emulsifier solution by azeotropic distillation of the water and to use it.
• the nonionic emulsifiers to be used according to the invention can be purified by the process of application P 28 54 541.7 (Le A 19 284).
• the fuels or heating oils according to the invention contain, for example
• Preferred is a fuel composition with 0.5-3% by weight of purified nonionic emulsifier and with 0.1-2.5% by weight of a fatty acid monoglyceride, an adduct of 1-3 mols of ethylene oxide with 1 mol of fatty acid amide or a mixture thereof, or a fatty acid partial ester of polyglycols.
• the hydrocarbons contained in the fuels according to the invention are generally the mixtures customary for this purpose, such as those with their physical data in DIN regulation 51 600 or in the United States Federal Specification VV-M-561 a-2, October 30, 1954 , Marked are. They are aliphatic hydrocarbons from gaseous, dissolved butane to C 20 hydrocarbons (as a residual fraction of diesel oil), e.g. cycloaliphatic, olefinic and / or aromatic hydrocarbons, natural naphthenic or refined technical hydrocarbons.
• the compositions according to the invention preferably contain no lead alkyls and similarly toxic additives.
• the heating oils according to the invention generally contain, as hydrocarbon content, the compositions which are commercially available under the name of light or medium-weight heating oil.
• the lower alcohols are used in the fuels and heating oils according to the invention in order to increase the spontaneity of the emulsion and the low-temperature stability and to control the temperature dependency in the emulsification of the water.
• the spontaneity can generally be brought about with the aid of mixed emulsifiers of different ionogenicity. Since water-oil emulsions are used in an engine fuel for corrosion reasons and because only nonionic emulsifiers can be used with some certainty, it must be described as extremely surprising that spontaneous water-in-oil emulsions are obtained with the emulsifiers according to the invention.
• the fuels and heating oils according to the invention have a considerably improved low-temperature stability, which is not only that the formation of ice crystals is prevented, but also is due to the failure of gel structures, which can cause an uncontrolled increase in viscosity.
• Straight-chain or branched aliphatic alcohols and cycloaliphatic alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, amyl alcohol, iso-amyl alcohol, hexyl alcohol, 1,3-dimethyl-butanol, cyclohexanol, methylcyclohexanol, may be mentioned as alcohols , Octanol, 2-ethyl-hexanol. Mixtures of these alcohols can also be used well. Alcohols which are readily available industrially are preferably used, e.g. Methanol, ethanol, isopropanol, isobutanol, 2-ethylhexanol.
• the fuel or heating oil emulsion according to the invention is prepared in a manner known per se by stirring the water into the solution of the purified emulsifier in the hydrocarbon which may contain alcohol, preferably using no further machines providing distribution energy.
• the emulsifier optionally also the alcohol, can be distributed over the hydrocarbon and / or water.
• fatty acid monoglycerides are used both to lower the viscosity of the system and to stabilize the emulsion. Due to the manufacturing process, significant amounts of glycerin (polyglycerin) are often still contained. These parts must also be removed by cleaning. Accordingly, glycerol and polyglycerol are also to be regarded as polyalkylene glycol ethers which can be removed from the emulsifier to be used according to the invention except for a residual content of less than 1% by weight.
• the fatty acid amide-ethylene oxide adducts can be obtained by direct amidation or by ester cleavage with ethanolamine.
• the monoethanolamides are used to lower the viscosity, stabilize the emulsion, but also to protect against corrosion and in connection with the emulsifiers as a cleaning agent for carburetors (detergents).
• the fine distribution of the water in the fuel or in the heating oil is substantially improved by the use of the emulsifiers in purified form.
• the surprising finding was gained that the quality of the fine distribution of the water for handling and the technical process of storing and supplying the fuel or heating oil to the combustion chamber is decisive for its fitness for purpose.
• the new fuels are suitable for reducing the energy consumption in our motor vehicles, reducing pollutant emissions, and increasing the risk posed by lead tetraalkyls and scavengers (dichloroethane, dibromoethane, cf. Chemiker-Zeitung 97 (1973), No. 9, p. 463) eliminate, to have a corrosion-inhibiting effect, without technically requiring a greater effort for changes to the vehicles. It may only be necessary to make minor corrections to the float or the nozzles of the carburetor to adapt to the somewhat higher density.
• Another advantage of the fuels according to the invention which contain emulsifiers and water and, if appropriate, alcohols is that their electrostatic charge is greatly reduced, so that a substantial danger when handling fuels is reduced (cf. Haase, static electricity as a danger, Verlag Chemie, Weinheim / Bergstrasse 1968, especially pages 69, 96 - 99, 114 and 115).
• the electrostatic charge of the fuels according to the invention is so low that dangerous discharges can no longer occur.
• the normal gasoline used shows values of around 1.10 12 ⁇ .cm at 20 ° C for the volume resistance, whereas the fuel according to the invention generally has a volume resistance of less than 1.10 10 ⁇ cm, for example 1.10 to 1.10 10 ⁇ .cm.
• the specific volume resistance of the fuels according to the invention is preferably 1.10 8 to 9.10 9 ⁇ cm. At values of t he un- 10 10 ⁇ . cm there is no longer any danger from electrostatic charging when filling, decanting and
• the heating oil emulsions according to the invention bring a better transfer of the heat of combustion to the heating medium system during combustion and less solid emissions through the chimneys.
• a fuel of the following composition was used to operate an Opel Kadett (1.1 liter, 45 hp): 10 - 20 seconds after (ie until every part of the contents of the vessel has been circulated).
• a milky, stable emulsion was obtained which had a viscosity of 2.7 m PA s.
• the specific electrical volume resistance was 5.10 9 ⁇ .cm.
• the car was tested on a roller dynamometer at 100 km / h for 15 minutes.
• the resistance on the rollers was set at 20 kg.
• the swimmer in the Verga The density of the fuel was adjusted from 0.797 at 20 ° C to 0.8 accordingly.
• the measurement of the consumption during these tests gave, after conversion to liters per 100 km, a consumption of 9 : 4 1 of this 72% petrol-containing fuel per 100 km. In the same vehicle under these test conditions with petrol, about 1 1/100 km more consumption was determined.
• the fuel was produced from unpurified emulsifiers, which contained 2.5% polyglycol ether and 0.23% ash in the fatty alcohol + 3 ⁇ O and 4% polyglycol ether and 0.23% ash in the fatty alcohol + 7 ⁇ O, briefly formed After the emulsification, two layers consisting of a W / O and an O / W emulsion. Although the layers could be re-emulsified by mechanical action, they did not form a stable emulsion for a long time.
• the emulsifiers used were purified by the following methods: 100 g of the synthetic C 9-11 alcohol reacted with 7 mol of ethylene oxide are mixed with 100 g of water and the alkali (approx. 0.2%) originating from the oxyethylation catalyst is neutralized with sulfuric acid . The neutral solution is heated to 98 - 100 0 C heated. After an hour, the two layers formed can be separated. At the top is the aqueous layer with the potassium sulfate (approx. 0.5 g) and the polyglycol ethers (approx. 4 g), at the bottom the viscous, approx. 60% emulsifier solution can be removed. The purified emulsifier can be obtained with approx. 95 g by distilling the water and drying in vacuo.
• the emulsifier contains only 0.006% ash and less than 0.2% polyglycol ether.
• Example 1 The fuel according to Example 1 was stirred well with 5% methanol (based on the total amount). The emulsion remained stable, was now protected against temperatures below 0 ° C and could be used as described above.
• Example 1 A standard commercial gasoline was included With stirring, 25% water, which contains no mineral components, is run in. After 5% there is still a clear, transparent emulsion which then changes with an increasing amount of water into a milky, stable emulsion which can be used as in Example 1.
• the emulsifier is purified by this process: 100 g of the synthetic C 9-11 alcohol reacted with 7 mol of ethylene oxide are mixed with 10 g Water is mixed and the alkali of the oxyethylation catalyst is neutralized with acetic acid. The solution is stirred with 100 cc of toluene. After 1 to 3 hours, 7.5 g of an aqueous layer which contains 4 g of polyglycol ether and about 0.5 g of potassium acetate separate from the cloudy mixture. After distilling the toluene, which at the same time drives out the water, about 95 g of the purified emulsifier are obtained.
• a fuel was produced from a lead-free regular gasoline with the following emulsifiers: A milky fuel is obtained which can be used as in Example 4 and does not tend to separate aqueous sediments.
• a regular unleaded gasoline is used to produce a fuel with the following composition: 10 - 13 ° C, 25% water is slowly stirred in.
• a fuel with a viscosity of 1.3 m PAs is obtained which changes only insignificantly even at temperatures down to -10 ° C.
• 3 parts of emulsifier in the composition mentioned in Example 6 can also be mixed with 3 parts of gasoline and 3 parts of water to give a clear solution. Then 70.5% of gasoline, 1.5% of isobutanol and 9% of the aforementioned mixture are metered in, and 22% of water can be mixed into a stream of this mixture via a suitable mixing chamber.
• the water is emulsified by the swirling process in the mixing chamber.
• the fuel obtained in this way fueled a 1.7 liter Opel record, which had had an air channel narrowed from 28 to 26 in the carburetor.
• the vehicle behaved normally in city traffic and showed no noticeable changes.
• the CO-Ab-; gas values were in operation for over 3 years located cars 1% lower than previously measured with premium gasoline.
• a commercially available regular gasoline was formed into a fuel with the following emulsifiers and solvents: Fuel stirred, which was used as in Example 7, but showed an even more favorable viscosity behavior at -10 ° C.
• the following fuel was set with a commercially available diesel oil for use in a motor vehicle with a diesel engine: With this, flawless driving results could be achieved.
• the fatty acid amide derivative leads to good rust protection in the tank and pipes.
• a petrol emulsion Petrol solved. 25% water is emulsified into the solution. If the emulsifier was used unwashed, a layer 0.001 cm thick showed a light absorption of 0.44 ( ⁇ 700 m ⁇ ) after 2 hours and a milky, water-rich layer below after 24 hours, which after stirring had roughly similar unfavorable values to the above Showed absorption.
• the gasoline emulsion with washed emulsifier had an absorption of 0.30 and after 24 hours formed only a few mm of a gasoline-rich surface. After stirring, an emulsion of the same absorption would be obtained.
• the following mixing can also be used to determine the effect of cleaning on stability.
• nonionic emulsifier made of cetyl stearyl alcohol with 12 moles of ethylene oxide was 10% dissolved in diesel oil and 0.5 cm of water was added for clarification.
• the unwashed emulsifier shows a permanent cloudiness, the washed emulsifier dissolves clearly.
• the unwashed emulsifier leads to a gelatinous, cloudy, unstable emulsion.
• the washed emulsifier forms a structurally viscous, stable, clear solution with a Tyndall effect, which can be mixed with the remaining components to form the fuel.
• the emulsification is carried out with the aid of an unwashed emulsifier, which contains approx. 10 - 12% polyglycol ether from the manufacture and by transesterification reactions, an emulsion is obtained which, after only 15 minutes, contains approx settles. If this layer first runs out of the vehicle tank and gets into the carburetor, there is no ignition.
• Example 12 The same raw materials as in Example 12 were used in the following amounts: 67% unleaded normal gasoline, 1.8% ethylene oxide adduct, 1.2% monoglyceride and 5% methanol mixed in with 25% water. In contrast to this stable emulsion, when using unwashed emulsifiers, a streaky, opalescent emulsion is obtained which separates into two emulsion phases in a few hours, in which the lower contains the predominant amount of the water used.
• a commercially available, light heating oil marked EL was mixed with an emulsifier from 1 mol of nonylphenol and 5.6 mol of ethylene oxide in amounts of 2.6 parts of this emulsifier in the purified form, 77 parts of heating oil EL and 20 parts of water were emulsified. Immediately afterwards there were still 0.4 parts of a reaction product of 1 mole of tallow with 2 moles of ethanolamine (160 ° C, 5 hours). A reduction in the emulsion viscosity is also observed, and an anti-rust effect is also achieved.
• the soot number 1 was measured with the heating oil and a soot number 0 with the emulsion.
• the transfer of the heat of combustion was particularly favorable.

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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)
• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
• Lubricants (AREA)
• Fats And Perfumes (AREA)
• Physical Or Chemical Processes And Apparatus (AREA)

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• 1978
  • 1978-12-16 DE DE19782854437 patent/DE2854437A1/de not_active Withdrawn
• 1979
  • 1979-11-30 US US06/099,124 patent/US4295859A/en not_active Expired - Lifetime
  • 1979-12-01 AT AT79104804T patent/ATE589T1/de active
  • 1979-12-01 DE DE7979104804T patent/DE2961910D1/de not_active Expired
  • 1979-12-01 EP EP79104804A patent/EP0012292B1/fr not_active Expired
  • 1979-12-12 DD DD79217600A patent/DD147683A5/de unknown
  • 1979-12-13 JP JP16092679A patent/JPS5582190A/ja active Pending
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  • 1979-12-14 CA CA000341969A patent/CA1137314A/fr not_active Expired
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