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EP0012345B1 - Fuel oils and their application - Google Patents

Fuel oils and their application Download PDF

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Publication number
EP0012345B1
EP0012345B1 EP79104931A EP79104931A EP0012345B1 EP 0012345 B1 EP0012345 B1 EP 0012345B1 EP 79104931 A EP79104931 A EP 79104931A EP 79104931 A EP79104931 A EP 79104931A EP 0012345 B1 EP0012345 B1 EP 0012345B1
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EP
European Patent Office
Prior art keywords
acid amide
fuel
ethylene oxide
mol
adduct
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
Application number
EP79104931A
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German (de)
French (fr)
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EP0012345A1 (en
Inventor
Günther Dr. Boehmke
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Bayer AG
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Bayer AG
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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
    • C10L1/32—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
    • F02B3/00—Engines characterised by air compression and subsequent fuel addition
    • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents

Definitions

  • the invention relates to fuels for internal combustion engines such as gasoline and diesel engines as well as rotary piston machines and turbines which contain emulsifiers or emulsifier mixtures and water and, if appropriate, alcohols in the fuels customary for the respective units.
  • Japanese Patent Application 124102 (Application No. 73 / 36,662) published in "Japanese Patents Gazette, Part I, Chemical, Week X 25, July 28, 1976" (U.S. Patent No. 73 / 36,662) describes a smoke-inhibiting gelatinous fuel composition made from a hydrocarbon ( Boiling point higher than 30 ° C), water and a non-ionic surfactant of the carboxamide type.
  • This gel-like hydrocarbon composition is said to reduce air pollution, which has been determined by burning the gel and examining the smoke with the help of the Bacharach-Rauch knife in a spray combustion test, that is to say in a stationary unit. It is therefore a fuel gel that is not suitable for passing lines, filters, feed pumps and the finest injection nozzles in an automobile.
  • micro-emulsions described in US Pat. No. 3,876,391 contain a total of 5 components, namely, in addition to gasoline and water, 3 to 8 parts by volume of gasoline-soluble surface-active substance, namely esters and ethers (Claim 1 c), 3 to 8 parts of a water-soluble surface-active substance, where salts such as amine acetates, hydrochlorides, sulfates and phosphates and nonylphenol and in addition to polyoxyethylated alcohols and esters also 3 amides (polyoxyalkylated stearylamides, laurylamides and oleylamides) are mentioned (claim 1d); finally, these compositions must also contain 0.5 to 10 parts by volume of an additive, as specifically mentioned in claim 1e.
  • gasoline-soluble surface-active substance namely esters and ethers (Claim 1 c)
  • salts such as amine acetates, hydrochlorides, sulfates and phosphates and nonyl
  • the surface-active additives and additives mentioned are e.g. T. um very undesirable substances in an internal combustion engine, because the salts mentioned in claim 1d can be used for emulsions in general, but when burned in an engine provide acids such as acetic acid (from the acetates), sulfuric acid (from the sulfates), Phosphoric acid (from phosphates) or hydrochloric acid (from hydrochlorides).
  • acids such as acetic acid (from the acetates), sulfuric acid (from the sulfates), Phosphoric acid (from phosphates) or hydrochloric acid (from hydrochlorides).
  • the addition of amines is also corrosive to the engine due to the high temperatures.
  • the in the fuels of the invention are generally the mixtures customary for this purpose, as are identified with their physical data in DIN specification 51 600 or in the United States Federal Specification VV-M-561 a-2, October 30, 1954.
  • the compositions according to the invention preferably contain no lead alkyls and similarly toxic additives.
  • the nonionic emulsifier is preferably a fatty acid amide, which is to be thought of by adding 1 to 50 mol of ethylene oxide or propylene oxide to a fatty acid amide, with the formula in which R, R 2 and n have the meaning given above.
  • the radical R generally means the radical of a saturated or unsaturated carboxylic acid, which can be varied within the broadest limits with regard to its molecular structure.
  • fatty acids such as. B. octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, arachidic acid or oleic acid, erucic acid, ricinoleic acid or mixtures thereof, as described, for. B. in coconut oil, palm oil, sunflower oil, safflower oil, soybean oil, castor oil, whale oil, fish oil, tallow fat, pork fat.
  • the proposed emulsifiers of the formula (I) are already known (cf. M. J. Schick, Nonionic Surfactans, Volume 1, pages 209-211; M. Dekker, New York 1976); they are physiologically very compatible (use in hand washing detergents) and biodegradable.
  • the raw materials from the fat side are available in large quantities and can also be multiplied for a long time, since they are independent of fossil deposits.
  • synthetic acids can also be used, such as those formed in the paraffin oxidation or in the oxidation of ⁇ -olefins or tri- and tetrapropylene. If the amides are produced from the natural triglycerides, the monoglycerides of these fats can still be present if only two of the fatty acid residues of the triglyceride are used for the amide formation.
  • the type and number of groupings Y of the formula (I) vary within wide limits.
  • compounds of the formula (I) are used as emulsifiers which are adducts of 1-3 mol of ethylene oxide with 1 mol of carboxylic acid amide and / or of 5-25 mol of ethylene oxide and / or propylene oxide with 1 mol of carboxylic acid amide.
  • the 1-3: 1 adduct content can be 15-70% by weight and the 5-25: 1 adduct content can be 30-85% by weight of the fuel according to the invention.
  • the emulsifier is particularly preferably the adduct of 1-2 moles of ethylene oxide with 1 mole of fatty acid amide (optionally mixed with production-related proportions of a fatty acid monoglyceride) and / or the adduct of 5-10 moles of ethylene oxide and / or propylene oxide with 1 mole of fatty acid amide and optionally the adduct of 20-30 moles of ethylene oxide with 1 mole of fatty acid amide.
  • the emulsifiers are most advantageously produced via the fatty acids and ethanolamine (see M. Schick, Nonionic Surfactants, op. Cit., Pp. 213-214). From these components, by splitting off water at 160-180 ° C. in about 60-90 minutes, a fatty acid amide according to the invention containing 1 mol of ethylene oxide and having a very high degree of purity can be produced. If one starts from the fatty acid amide (see M. Schick, Nonionic Surfactans, op. Cit., P. 213), 1 mol of ethylene oxide is added, advantageously at elevated temperature, e.g. B. at 100-140 ° C, possibly with weakly acidic or weakly basic catalysis.
  • customary oxyalkylation catalysts such as sodium hydroxide, sodium methylate, potassium hydroxide, only from the 1: 1 adduct and to add the desired amount of ethylene oxide under pressure.
  • the non-ionic emulsifiers can contain impurities from the technical production, which from impurities in the preliminary product, for. B. come from the ethylene oxide, are due to moisture or come from the oxyethylation catalyst. These are preferably polyethylene glycols, which can be responsible for the deterioration in the emulsion quality and for the formation of an aqueous sediment. If they are present in the emulsifiers in amounts of more than 1%, it is advisable to remove them by one of the known cleaning operations for nonionic emulsifiers, e.g. B. according to DE-PS 828 839. For this purpose, a new cleaning method, as proposed in patent application P 2 854 541.7, is preferably suitable on an industrial scale.
  • the lower alcohols are used in the fuels according to the invention in order to control the spontaneity of the emulsion, the low-temperature stability and the temperature dependence in the emulsification of the water.
  • the spontaneity can generally be brought about with the aid of mixed emulsifiers of different ionicity. Since only nonionic and residue-free combustible emulsifiers can be used in a motor fuel for reasons of corrosion without difficulty, it must be described as extremely surprising that spontaneous water-in-oil emulsions are obtained with the emulsifiers according to the invention.
  • the fuels 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, may be mentioned as alcohols.
  • Alcohols which are readily available industrially are preferably used, for. B. methanol, ethanol, isopropanol, iso-butanol, 2-ethylhexanol.
  • the fuel emulsion according to the invention is produced by stirring the water into the solution of the emulsifier in the hydrocarbon which may contain alcohol, preferably no further machines providing distribution energy being used.
  • the emulsifier optionally also the alcohol, can be distributed over petrol and / or water.
  • the viscosity of the emulsion rise to significantly higher values than 10 mPa s (cf. DIN regulation 9040), because a viscosity of over 100 PA s can already lead to the normal filters , Pumps and nozzles of the motor vehicles can no longer be passed without problems. It is therefore preferable to have a viscosity of 5 mPas, e.g. B. for gasoline emulsions below 2 mPA s to be observed. The viscosity should not increase significantly even when it cools down to approx. -15 ° C, and the emulsion should remain stable.
  • the monoamides to be used as emulsifiers for the fuels according to the invention have a pronounced rust protection effect.
  • methylpolyether amides used to date are largely ineffective.
  • the other emulsifiers described so far for use in fuels show a rather increased rust formation in the presence of water - probably due to their degreasing effect.
  • the type of emulsifier according to the invention does not lead to increased swelling or detachment neither in the plastic parts coming into contact with the fuel system nor in the paint surfaces, as can be observed with the esters of the polyethers.
  • Another advantage of the fuels according to the invention is that the use of lead tetraalkylene with the required extremely low value for the maximum workplace concentration (MAK value) of 0.01 ppm can be avoided.
  • the "fluids” or so-called scavenger, cf. Chemiker-Zeitung 97 (1973) No. 9, p. 463 necessary to remove the lead oxide in the engine, which are classified in Class III B in the latest accident prevention regulations, can also be omitted (accident prevention regulations of the professional association of the chemical industry, appendix 4, list of MAK values from October 1st, 1978).
  • the lowering of the temperature of the combustion process reduces the amount of pollutants in the exhaust gas (e.g. the NO content) and because of this "built-in cooling", the "lean" mixture can be used economically. It is no longer necessary to lower the combustion chamber temperature by means of a "rich” mixture, which corresponds to an unnecessarily increased fuel consumption. Since the additives are emulsifiers, aggregate contamination due to their detergent effect is also avoided.
  • the ratio of fuel used and only necessary in terms of machine technology is, of course, particularly unfavorable in the case of high-speed drive units, such as. B. the Wankel engine and turbines, which develop their driving force only at high speeds.
  • the necessary heat of combustion quickly leads to heat accumulation problems and thus to unfavorable exhaust gas values.
  • the use of the fuel-water emulsion according to the invention is particularly suitable for achieving a more favorable specific consumption and for solving the heat and exhaust gas problems.
  • 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 for the specific volume resistance at 20 ° C, whereas the fuel according to the invention generally shows a volume resistivity of less than 1.10 10 ⁇ ⁇ cm, for example 1.10 7 to 1.10 10 n - cm.
  • the volume resistivity of the fuels according to the invention is preferably 1.10 8 to 9.10 9 ⁇ ⁇ cm. At values below 10 10 ⁇ ⁇ cm there is no longer any danger from electrostatic charging when filling, decanting and drain
  • the ignitability of the fuel emulsions according to the invention is in no way impaired, so that vehicles start without delay even after a break of several weeks spent outdoors.
  • This operational safety is also achieved by the excellent storage stability of the emulsions to be used according to the invention, which do not settle water in the carburetor, in the gasoline pump or in the tank - not even in small quantities.
  • Previously known emulsifier systems tend - particularly because of the by-products they contain - to form these so-called water sumps.
  • the viscosity at 20 ° C was 0.96 mPA s and the throughput times through a Bosch gasoline filter did not differ from that of an equal amount of gasoline.
  • An Opel Kadett with an output of 45 hp and a displacement of 1.1 liters was tested on an HPA tester (roller test bench) for 15 minutes at 100 km / h speed and with a resistance of 20 kg on the rollers.
  • the fuel was fed to the carburetor separately from a measuring vessel. In accordance with the higher surface viscosity and higher density, the idle and full load nozzles have been slightly enlarged. The outside temperature was 14 ° C. The following consumption was determined from the measured fuel quantity and the number of kilometers traveled at approx. 100 km / h:
  • the car could be driven with one tank of the fuel emulsion and restarted immediately after it had been left standing.
  • the CO exhaust gas values were 2.5% by volume.
  • This emulsion can be used for carburetor engines at temperatures above 15 ° C.
  • a stable, opal-milky emulsion was obtained which had a viscosity of less than 1 mPA and did not form any gel-like streaks even at -10 ° C.
  • This fuel became a motor vehicle of the type Fiat 128, with 55 HP and 1180 cc capacity, which had been run with super fuel until then. With a slight increase in the suction pressure in the carburetor by partially activating the choke, the vehicle could be used for lively city traffic without any noticeable loss of driving characteristics. An accelerating knock (ringing), as is found in gasoline of insufficient quality, was not observed when the engine was cold or warm. The low contamination of the candles after the short distance traffic was striking.
  • the fuel formed an opal-milky water-in-oil emulsion and had a viscosity of 1.1 mPAs, which showed no gel-like streaks even at -15 ° C.
  • the 3% emulsifier is formed with 3% gasoline and 3% water to form a clear, low-viscosity solution. This can then be easily dissolved in 64% petrol, possibly using mechanical dosing devices, and immediately emulsified with 22% water.
  • the fuel of Example 5 is obtained in the same composition and quality.
  • This emulsion can be used directly or can be mixed with 5% methanol if low outside temperatures are expected.
  • a car with a 2-liter diesel engine could be operated without impairment.
  • the fuel could be obtained with the castor fatty acid amide with 1 mol of ethylene oxide, which can be produced in technical quality from 1 mol of castor oil and 2 mol of ethanolamine at 160-180 ° C in about 5 hours, in the same quality if this instead of the coconut fatty acid amide with 1 Mol ⁇ O was used.
  • This fuel can be used in a diesel powered vehicle without the difficulties of an unstable and stratified fuel.
  • a regular gasoline that is free of lead alkylene and its "fluids" is used with a share of 79%; 1.2% addition product of 1 mol oleic acid amide and 7 mol ethylene oxide (containing less than 0.8% PEG (polyethylene glycol) and less than 0.07% salts by purification) and 1.8% coconut fatty acid diethanolamide are dissolved therein.
  • An opal emulsion is prepared by stirring in a mixture of 15% water and 4% methanol. The density is 0.778. This fuel was run in a 1.71 Opel record; the services corresponded to those prescribed for this vehicle. The consumption is the same as for the usual (water and emulsifier free) fuels.
  • Example 10 The fuel of Example 10 according to the invention was measured in a 3-year-old vehicle for the CO content in the exhaust gas with the engine warm when the engine was idling. The value was 0.3% CO. Regular gasoline gave 3.0% CO. Mixtures of this gasoline with 15% methanol or 15% ethanol led to CO values which deviate less than 0.3% from the value of normal gasoline (details in DE-OS 2806673, Figure 2, confirm our measurements for ethanol).
  • Lead-free regular gasoline was processed into a fuel according to the invention as follows: 80% normal gasoline, 1.2% adduct from 1 mol oleic acid amide + 7 mol AIO, 1.8% coconut fatty acid diethanolamide (made from coconut oil and diethanolamine) were mixed; then 15% water, 2% methanol and 1% ethanol were emulsified in with stirring.
  • This opal fuel brings the top speed in a Mercedes 250 with 95 kW (130 HP) engine power.
  • the main nozzle was adapted to the slightly changed behavior of the fuel by expanding from 97.5 to 105.
  • the consumption value, determined on a roll stand under high load (180 kp) was to be equated with premium gasoline. No engine knock was observed despite the normal use of petrol.
  • the following diesel fuel was formulated for the operation of a small truck: in 82.5% diesel oil with 0.9% addition product from 1 mol oleic acid amide + 7 mol ⁇ O, 2.1% coconut fatty acid diethanolamide (made from coconut fat and diethanolamine) and 0.5% 2- Ethylhexanol was emulsified with 14% water.
  • This fuel satisfactory driving and consumption values could be achieved in short-haul traffic.
  • Compared to conventional diesel fuel however, only a barely noticeable contamination was observed within 3 minutes when a partial flow was removed from the exhaust gases over a white filter paper, while the diesel fuel without emulsifiers and water caused the filter to become very black.
  • Aromatic and additive-free gasoline was mixed with 20% toluene. In 85% of this mixture 1.8% coconut fatty acid diethanolamide and 1.2% oleic acid amide were dissolved with 7 ⁇ O; 10% water and 2% ethanol were emulsified therein.
  • This opal fuel emulsion was used in a VW vehicle (1.6 liter engine, 62 kw (85 hp)) under DIN consumption conditions, 8.4 liters / 100 km. In short-haul traffic, this value was 9.11 / 100 km. The same consumption values were measured with normal gasoline under the same conditions.
  • Example 14 In 75% of the gasoline mixture of Example 14, 2% of a coconut fatty acid ethanoiamide, which had been reacted with one mole of ethylene oxide under the usual oxyethylation conditions, and 1% oleic acid amide with 7 ⁇ O were dissolved. A mixture of 10% water and 2% ethanol was emulsified therein. The same values as in Example 14 were achieved with the fuel.

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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)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
  • Control Of The Air-Fuel Ratio Of Carburetors (AREA)
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  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
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Abstract

A fuel especially a fuel for an automobile, internal combustion engine or a diesel engine comprising a hydrocarbon water and emulsifier wherein the emulsifier is a non-ionic emulsifier and comprises the addition product of ethylene oxide or propylene oxide and a carboxylic acid amide with 9 to 21 carbon atoms.

Description

Die Erfindung betrifft Kraftstoffe für Verbrennungskraftmaschinen wie Otto- und Dieselmotoren sowie Rotationskolbenmaschinen und Turbinen, die in den für die jeweiligen Aggregate üblichen Treibstoffen Emulgatoren bzw. Emulgatormischungen und Wasser sowie gegebenenfalls Alkohole enthalten.The invention relates to fuels for internal combustion engines such as gasoline and diesel engines as well as rotary piston machines and turbines which contain emulsifiers or emulsifier mixtures and water and, if appropriate, alcohols in the fuels customary for the respective units.

Die Verwendung von Wasser und Emulgatoren in Kraftstoffen zur Förderung der Verbrennung ist bereits bekanntgeworden (DE-OS 1 545 509 und DE-OS 2633462). So wird z. B. das Klopfverhalten von Benzin in höherverdichteten Motoren durch Wasser stärker positiv beeinflußt als durch den vielfach vorgeschlagenen Methanolzusatz (Motorzeitschrift, Jahrg. 37, Nr.5, S. 187 (1976);. SAE-Veröffentlichung 750123). Bei den dabei bisher eingesetzten Emulgatoren mußte jedoch eine Reihe von zum Teil erheblichen Nachteilen in Kauf genommen werden, insbesondere die mangelhafte Kältestabilität.The use of water and emulsifiers in fuels to promote combustion has already become known (DE-OS 1 545 509 and DE-OS 2633462). So z. B. the knocking behavior of gasoline in higher compression engines is influenced more positively by water than by the frequently proposed addition of methanol (Motorzeitschrift, Jahrg. 37, No. 5, p. 187 (1976); SAE publication 750123). In the case of the emulsifiers used hitherto, however, a number of disadvantages, some of which were considerable, had to be accepted, in particular the poor stability to cold.

In der in »Japanese Patents Gazette, Teil I, Chemical, Woche X 25, 28. 7. 1976« veröffentlichten japanischen Patentanmeldung 124102 (Anmelde-Nr. 73/36.662) wird eine rauchhemmende gelatinöse Brennstoff-Zusammensetzung beschrieben, die aus einem Kohlenwasserstoff (Siedepunkt höher als 30°C), Wasser und einer nicht-ionischen oberflächenaktiven Substanz vom Carbonsäureamid-Typ besteht. Diese gelartige Kohlenwasserstoff-Zusammensetzung soll die Luftverschmutzung herabsetzen, was durch Verbrennung des Gels und Untersuchung des Rauchs mit Hilfe des Bacharach-Rauch-Messers in einem Spray-Combustion-Test, also in einem stationären Aggregat, festgestellt worden ist. Es handelt sich somit um ein Brennstoff-Gel, das nicht geeignet ist, in einem Automobil Leitungen, Filter, Förderpumpen und feinste Einspritzdüsen zu passieren.Japanese Patent Application 124102 (Application No. 73 / 36,662) published in "Japanese Patents Gazette, Part I, Chemical, Week X 25, July 28, 1976" (U.S. Patent No. 73 / 36,662) describes a smoke-inhibiting gelatinous fuel composition made from a hydrocarbon ( Boiling point higher than 30 ° C), water and a non-ionic surfactant of the carboxamide type. This gel-like hydrocarbon composition is said to reduce air pollution, which has been determined by burning the gel and examining the smoke with the help of the Bacharach-Rauch knife in a spray combustion test, that is to say in a stationary unit. It is therefore a fuel gel that is not suitable for passing lines, filters, feed pumps and the finest injection nozzles in an automobile.

Die in der US-PS 3876391 beschriebenen Mikro-Emulsionen enthalten insgesamt 5 Komponenten, nämlich neben Benzin und Wasser noch 3 bis 8 Volumenteile benzinlösliche oberflächenaktive Substanz, und zwar Ester und Ether (Anspruch 1 c), 3 bis 8 Teile einer wasserlöslichen oberflächenaktiven Substanz, wobei Salze wie Aminacetate, Hydrochloride, Sulfate und Phosphate sowie Nonylphenol und neben polyoxyethylierten Alkoholen und Estern auch 3 Amide (polyoxyalkylierte Stearylamide, Laurylamide und Oleylamide) genannt werden (Anspruch 1d); schließlich müssen diese Zusammensetzungen noch 0,5 bis 10 Volumenteile eines Additivs enthalten, wie sie im einzelnen in Anspruch 1e genannt sind.The micro-emulsions described in US Pat. No. 3,876,391 contain a total of 5 components, namely, in addition to gasoline and water, 3 to 8 parts by volume of gasoline-soluble surface-active substance, namely esters and ethers (Claim 1 c), 3 to 8 parts of a water-soluble surface-active substance, where salts such as amine acetates, hydrochlorides, sulfates and phosphates and nonylphenol and in addition to polyoxyethylated alcohols and esters also 3 amides (polyoxyalkylated stearylamides, laurylamides and oleylamides) are mentioned (claim 1d); finally, these compositions must also contain 0.5 to 10 parts by volume of an additive, as specifically mentioned in claim 1e.

Wie ersichtlich handelt es sich bei den genannten oberflächenaktiven Zusätzen und Additiven z. T. um in einer Verbrennungskraftmaschine sehr unerwünschte Stoffe, denn die in Anspruch 1d erwähnten Salze können zwar für Emulsionen im allgemeinen verwendet werden, liefern aber bei der Verbrennung in einem Motor Säuren wie Essigsäure (von den Acetaten), Schwefelsäure (von den Sulfaten), Phosphorsäure (von den Phosphaten) oder Salzsäure (von den Hydrochloriden). Auch die Zugabe von Aminen wirkt im Motor im Hinblick auf die hohen Temperaturen korrosiv.As can be seen, the surface-active additives and additives mentioned are e.g. T. um very undesirable substances in an internal combustion engine, because the salts mentioned in claim 1d can be used for emulsions in general, but when burned in an engine provide acids such as acetic acid (from the acetates), sulfuric acid (from the sulfates), Phosphoric acid (from phosphates) or hydrochloric acid (from hydrochlorides). The addition of amines is also corrosive to the engine due to the high temperatures.

Es wurden nun Kraftstoffe für Verbrennungskraftmaschinen, die einen nichtionischen Emulgator, Wasser und gegebenenfalls einen Alkohol enthalten, gefunden, die dadurch gekennzeichnet sind, daß sie als Emulgator ein Anlagerungsprodukt von Äthylenoxid oder Propylenoxid an ein Carbonsäureamid mit 8-22 Kohlenstoffatomen enthalten.There have now been found fuels for internal combustion engines which contain a nonionic emulsifier, water and optionally an alcohol, which are characterized in that they contain, as emulsifier, an adduct of ethylene oxide or propylene oxide with a carboxamide having 8-22 carbon atoms.

Bevorzugt enthalten die erfindungsgemäßen Kraftstoffe

  • 40-95 Gew.-% Kohlenwasserstoffe,
  • 0,5- 6 Gew.-% eines nichtionischen Emulgators der Formel
    Figure imgb0001
    in der
    • R für einen gegebenenfalls substituierten, geradkettigen oder verzweigten oder cyclischen, gesättigten oder ungesättigten Kohlenwasserstoffrest steht,
    • Y die Gruppierung
      Figure imgb0002
      bedeutet, wobei
    • R2 Wasserstoff oder Methyl bedeutet, und in der
    • n für eine ganze Zahl von 1 bis 50 .eht, und
    • R1 Wasserstoff darstellt oder die Bedeutung der Gruppierung (̵Y)̵nH hat,
  • 0-20 Gew.-% eines 1 - 8 Kohlenstoffatome enthaltenden Alkohols, der geradkettig oder verzweigt, gesättigt oder ungesättigt sein kann, und
  • 0,5-35 Gew.-% Wasser.
The fuels according to the invention preferably contain
  • 40-95% by weight of hydrocarbons,
  • 0.5-6% by weight of a nonionic emulsifier of the formula
    Figure imgb0001
     in the
    • R represents an optionally substituted, straight-chain or branched or cyclic, saturated or unsaturated hydrocarbon radical,
    • Y the grouping
      Figure imgb0002
       means where
    • R 2 is hydrogen or methyl, and in the
    • n is an integer from 1 to 50, and
    • R 1 represents hydrogen or has the meaning of the grouping (̵Y) ̵ n H,
  • 0-20% by weight of an alcohol containing 1-8 carbon atoms, which may be straight-chain or branched, saturated or unsaturated, and
  • 0.5-35 wt% water.

Besonders bevorzugt ist eine Kraftstoffzusammensetzung mit 60­95 Gew.-% eines Kohlenwasserstoffs oder Kohlenwasserstoffgemisches, 1,0-3,5 Gew.-% eines oder mehrerer Emulgatoren der Formel (I), gegebenenfalls 0,5-10 Gew.-% eines C1-C8-Alkohols und Wasser als Rest.A fuel composition with 6095% by weight of a hydrocarbon or hydrocarbon mixture, 1.0-3.5% by weight of one or more emulsifiers of the formula (I), optionally 0.5-10% by weight of a C 1 , is particularly preferred -C 8 alcohol and water as the rest.

Die in den erfindungsgemäßen Kraftstoffen enthaltenen Kohlenwasserstoffe sind im allgemeinen die für diesen Zweck üblichen Gemische, wie sie mit ihren physikalischen Daten in der DIN-Vorschrift 51 600 oder in der United States Federal Specification VV-M-561 a-2, 30. Oktober 1954, gekennzeichnet sind. Es sind aliphatische Kohlenwasserstoffe vom gasförmigen, gelösten Butan bis zu C2o-Kohlenwasserstoffen (als Restfraktion des Dieselöls), z. B. cycloaliphatische, olefinische und/oder aromatische Kohlenwasserstoffe, natürliche naphthenbasische oder raffinierte technische Kohlenwasserstoffe. Bevorzugt enthalten die erfindungsgemäßen Zusammensetzungen keine Bleialkyle und ähnlich giftige Additive.The in the fuels of the invention The hydrocarbons contained are generally the mixtures customary for this purpose, as are identified with their physical data in DIN specification 51 600 or in the United States Federal Specification VV-M-561 a-2, October 30, 1954. There are aliphatic hydrocarbons from gaseous, dissolved butane to C 2o hydrocarbons (as a residual fraction of the diesel oil), e.g. B. 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.

Der nichtionische Emulgator stellt vorzugsweise ein Fettsäureamid dar, das durch Anlagerung von 1 bis 50 Mol Äthylenoxid oder Propylenoxid an ein Fettsäureamid zustandegekommen zu denken ist, mit der Formel

Figure imgb0003
in welcher R, R2 und n die oben angegebene Bedeutung haben.The nonionic emulsifier is preferably a fatty acid amide, which is to be thought of by adding 1 to 50 mol of ethylene oxide or propylene oxide to a fatty acid amide, with the formula
Figure imgb0003
 in which R, R 2 and n have the meaning given above.

Der Rest R bedeutet im allgemeinen den Rest einer gesättigten oder ungesättigten Carbonsäure, die hinsichtlich ihres Molekülaufbaus in weitesten Grenzen variiert werden kann. Beispielsweise seien Fettsäuren genannt, wie z. B. Octan-, Decan-, Laurin-, Myristin-, Palmitin-, Stearin-, Behen-, Arachinsäure oder Ölsäure, Erucasäure, Rizinolsäure oder deren Gemische, wie sie z. B. im Kokosfett, Palmöl, Sonnenblumenöl, Safloröl, Sojaöl, Rizinusöl, Walöl, Fischöl, Talgfett, Schweinefett vorkommen.The radical R generally means the radical of a saturated or unsaturated carboxylic acid, which can be varied within the broadest limits with regard to its molecular structure. Examples include fatty acids, such as. B. octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, arachidic acid or oleic acid, erucic acid, ricinoleic acid or mixtures thereof, as described, for. B. in coconut oil, palm oil, sunflower oil, safflower oil, soybean oil, castor oil, whale oil, fish oil, tallow fat, pork fat.

Die vorgeschlagenen Emulgatoren der Formel (I) sind bereits bekannt (vgl. M. J. Schick, Nonionic Surfactans, Volume 1, Seite 209-211; M. Dekker, New York 1976); sie sind physiologisch sehr verträglich (Verwendung in Handwaschmitteln) und biologisch abbaubar. Die Rohstoffe von der Fettseite her sind in großer Menge vorhanden und auf lange Zeit auch vermehrbar, da sie von fossilen Lagerstätten unabhängig sind. Selbstverständlich sind auch synthetische Säuren einsetzbar, wie sie bei der Paraffinoxidation oder bei der Oxidation von α-Olefinen oder Tri- und Tetrapropylen entstehen. Werden die Amide aus den natürlichen Triglyceriden hergestellt, so können die Monoglyceride dieser Fette noch enthalten sein, wenn nur zwei der Fettsäurereste des Triglycerids für die Amidbildung genutzt werden.The proposed emulsifiers of the formula (I) are already known (cf. M. J. Schick, Nonionic Surfactans, Volume 1, pages 209-211; M. Dekker, New York 1976); they are physiologically very compatible (use in hand washing detergents) and biodegradable. The raw materials from the fat side are available in large quantities and can also be multiplied for a long time, since they are independent of fossil deposits. Of course, synthetic acids can also be used, such as those formed in the paraffin oxidation or in the oxidation of α-olefins or tri- and tetrapropylene. If the amides are produced from the natural triglycerides, the monoglycerides of these fats can still be present if only two of the fatty acid residues of the triglyceride are used for the amide formation.

Der Oxiäthylierungsgrad, d. h. Art und Zahl der Gruppierungen Y der Formel (I), ist in weiten Grenzen varrieren. Vorteilhafterweise werden als Emulgatoren Verbindungen der Formel (I) eingesetzt, die Addukte von 1 -3 Mol Äthylenoxid an 1 Mol Carbonsäureamid und/oder von 5-25 Mol Äthylenoxid und/oder Propylenoxid an 1 Mol Carbonsäureamid darstellen. Beispielswei- 'se kann dabei der Gehalt an 1-3: 1-Addukt 15-70 Gew.-% und der Gehalt an 5-25: 1-Addukt 30-85 Gew.-% des erfindungsgemäßen Kraftstoffs betragen. Besonders bevorzugt ist der Emulgator das Addukt von 1 -2 Mol Äthylenoxid an 1 Mol Fettsäureamid (gegebenenfalls vermischt mit herstellungsbedingten Anteilen eines Fettsäuremonoglycerids) und/ oder das Addukt von 5-10 Mol Äthylenoxid und/oder Propylenoxid an 1 Mol Fettsäureamid und gegebenenfalls das Addukt von 20-30 Mol Äthylenoxid an 1 Mol Fettsäureamid.The degree of oxyethylation, i.e. H. The type and number of groupings Y of the formula (I) vary within wide limits. Advantageously, compounds of the formula (I) are used as emulsifiers which are adducts of 1-3 mol of ethylene oxide with 1 mol of carboxylic acid amide and / or of 5-25 mol of ethylene oxide and / or propylene oxide with 1 mol of carboxylic acid amide. For example, the 1-3: 1 adduct content can be 15-70% by weight and the 5-25: 1 adduct content can be 30-85% by weight of the fuel according to the invention. The emulsifier is particularly preferably the adduct of 1-2 moles of ethylene oxide with 1 mole of fatty acid amide (optionally mixed with production-related proportions of a fatty acid monoglyceride) and / or the adduct of 5-10 moles of ethylene oxide and / or propylene oxide with 1 mole of fatty acid amide and optionally the adduct of 20-30 moles of ethylene oxide with 1 mole of fatty acid amide.

Die Herstellung der Emulgatoren geschieht am vorteilhaftesten über die Fettsäuren und Äthanolamin (vgl. M. Schick, Nonionic Surfactants, a.a.O., S. 213-214). Aus diesen Komponenten läßt sich durch Wasserabspaltung bei 160-180°C in etwa 60-90 Minuten ein erfindungsgemäßes, 1 Mol Äthylenoxid enthaltendes Fettsäureamid mit sehr hohem Reinheitsgrad herstellen. Wenn man vom Fettsäureamid ausgeht (vgl. M. Schick, Nonionic Surfactans, a.a.O., S. 213), addiert man 1 Mol Äthylenoxid, vorteilhaft bei erhöhter Temperatur, z. B. bei 100-140° C, eventuell unter schwach saurer oder schwach basischer Katalyse. Zur Erzielung einer größeren Gleichmäßigkeit der Produkte kann es zweckmäßig sein, erst vom 1 : 1-Addukt an mit den üblichen Oxialkylierungskatalysatoren, wie Natriumhydroxid, Natriummethylat, Kaliumhydroxid, zu arbeiten und die gewünschte Menge Äthylenoxid unter Druck zu addieren.The emulsifiers are most advantageously produced via the fatty acids and ethanolamine (see M. Schick, Nonionic Surfactants, op. Cit., Pp. 213-214). From these components, by splitting off water at 160-180 ° C. in about 60-90 minutes, a fatty acid amide according to the invention containing 1 mol of ethylene oxide and having a very high degree of purity can be produced. If one starts from the fatty acid amide (see M. Schick, Nonionic Surfactans, op. Cit., P. 213), 1 mol of ethylene oxide is added, advantageously at elevated temperature, e.g. B. at 100-140 ° C, possibly with weakly acidic or weakly basic catalysis. To achieve greater uniformity of the products, it may be advisable to work with the customary oxyalkylation catalysts, such as sodium hydroxide, sodium methylate, potassium hydroxide, only from the 1: 1 adduct and to add the desired amount of ethylene oxide under pressure.

Wenn vom natürlichen Fett ausgegangen wird, setzt man dieses mit 2 Mol Äthanolamin um. Nach etwa 2-5 Stunden und ca. 140-180°C Reaktionstemperatur können im allgemeinen kein Äthanolamin und kein Triglycerid mehr nachgewiesen werden. Diese 1:2-Mol-Mischung von Fettsäure-monoglycerid und Fettsäureamid-1 : 1-Äthylenoxid-Addukt kann vorteilhafterweise in einer Menge von 15-70 Gew.-% des nichtionischen Emulgators eingesetzt werden.If natural fat is used as a starting point, this is reacted with 2 mol ethanolamine. After about 2-5 hours and about 140-180 ° C reaction temperature generally no ethanolamine and no triglyceride can be detected. This 1: 2 mole mixture of fatty acid monoglyceride and fatty acid amide 1: 1 ethylene oxide adduct can advantageously be used in an amount of 15-70% by weight of the nonionic emulsifier.

Die nichtionischen Emulgatoren können von der technischen Herstellung her Verunreinigungen enthalten, die aus Verunreinigungen im Vorprodukt, z. B. aus dem Äthylenoxid stammen, durch Feuchtigkeit bedingt sind oder aus dem Oxiäthylierungskatalysator herrühren. Es handelt sich dabei bevorzugt um Polyäthylenglykole, die für die Verschlechterung der Emulsionsqualität und für die Bildung eines wäßrigen Bodensatzes verantwortlich sein können. Falls sie in Mengen von über 1% in den Emulgatoren vorliegen, empfiehlt es sich, sie durch eine der bekannten Reinigungsoperationen für nichtionische Emulgatoren zu entfernen z. B. gemäß DE-PS 828 839. Hierfür eignet sich im technischen Maßstab vorzugsweise eine neuartige Reinigungsmethode, wie sie in Patentanmeldung P 2 854 541.7 vorgeschlagen wird.The non-ionic emulsifiers can contain impurities from the technical production, which from impurities in the preliminary product, for. B. come from the ethylene oxide, are due to moisture or come from the oxyethylation catalyst. These are preferably polyethylene glycols, which can be responsible for the deterioration in the emulsion quality and for the formation of an aqueous sediment. If they are present in the emulsifiers in amounts of more than 1%, it is advisable to remove them by one of the known cleaning operations for nonionic emulsifiers, e.g. B. according to DE-PS 828 839. For this purpose, a new cleaning method, as proposed in patent application P 2 854 541.7, is preferably suitable on an industrial scale.

Von den niederen Alkoholen wird in den erfindungsgemäßen Kraftstoffen Gebrauch gemacht, um die Spontanität der Emulsion, die Kältestabilität und die Temperaturabhängigkeit bei der Emulgierung des Wassers zu steuern. Die Spontanität läßt sich im allgemeinen mit Hilfe von Mischemulgatoren verschiedener lonogenität hervorrufen. Da in einem Motorentreibstoff aus Korrosionsgründen nur nichtionische und rückstandsfrei verbrennbare Emulgatoren ohne Schwierigkeiten verwendet werden können, muß es als ausgesprochen überraschend bezeichnet werden, daß mit den erfindungsgemäßen Emulgatoren spontane Wasser-in-Öl-Emulsionen erhalten werden. Die erfindungsgemäßen Kraftstoffe weisen infolgedessen eine erheblich verbesserte Kältestabilität auf, die nicht nur darin besteht, daß die Bildung von Eiskristallen verhindert wird, sondern auch auf das Nichtzustandekommen von Gelstrukturen, die einen unkontrollierten Viskositätsanstieg verursachen können, zurückzuführen ist.The lower alcohols are used in the fuels according to the invention in order to control the spontaneity of the emulsion, the low-temperature stability and the temperature dependence in the emulsification of the water. The spontaneity can generally be brought about with the aid of mixed emulsifiers of different ionicity. Since only nonionic and residue-free combustible emulsifiers can be used in a motor fuel for reasons of corrosion without difficulty, it must be described as extremely surprising that spontaneous water-in-oil emulsions are obtained with the emulsifiers according to the invention. As a result, the fuels 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.

Als Alkohole seien geradkettige oder verzweigte aliphatische Alkohole sowie cycloaliphatische Alkohole genannt wie Methanol, Äthanol, Propanol, Isopropanol, Butanol, iso-Butanol, tert.-Butanol, Amylalkohol, iso-Amylalkohol, Hexylalkohol, 1,3-Dimethyl-butanol, Cyclohexanol, Methylcyclohexanol, Octanol, 2-Äthylhexanol. Auch Gemische dieser Alkohole sind gut verwendbar. Bevorzugt werden technisch gut zugängliche Alkohole eingesetzt, z. B. Methanol, Äthanol, Isopropanol, iso-Butanol, 2-Äthylhexanol.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, may be mentioned as alcohols. Methylcyclohexanol, octanol, 2-ethylhexanol. Mixtures of these alcohols can also be used well. Alcohols which are readily available industrially are preferably used, for. B. methanol, ethanol, isopropanol, iso-butanol, 2-ethylhexanol.

Die erfindungsgemäße Kraftstoff-Emulsion wird durch Verrühren des Wassers in die Lösung des Emulgators in dem gegebenenfalls Alkohol enthaltenden Kohlenwasserstoff hergestellt, wobei vorzugsweise keine weitere Verteilungsenergie liefernden Maschinen eingesetzt werden. In einer Abwandlung hiervon kann der Emulgator, wahlweise auch der Alkohol, auf Benzin und/oder Wasser verteilt werden.The fuel emulsion according to the invention is produced by stirring the water into the solution of the emulsifier in the hydrocarbon which may contain alcohol, preferably no further machines providing distribution energy being used. As a modification of this, the emulsifier, optionally also the alcohol, can be distributed over petrol and / or water.

Nach Bildung der Emulsion ist es zweckmäßig, die Viskosität der Emulsion nicht auf wesentlich höhere Werte als 10 mPa s (vgl. DIN-Vorschrift 9040) ansteigen zu lassen, denn eine Viskosität von über 100 PA s kann bereits dazu führen, daß die normalen Filter, Pumpen und Düsen der Kraftfahrzeuge nicht mehr störungsfrei passiert werden können. Vorzugsweise empfiehlt es sich daher, für die erfindungsgemäßen Kraftstoffe eine Viskosität von 5 mPA s, z. B. für Benzinemulsionen unter 2 mPA s, einzuhalten. Die Viskosität sollte auch bei Abkühlung auf ca. -15°C nicht wesentlich ansteigen, und die Emulsion soll stabil bleiben.After the emulsion has been formed, it is advisable not to let the viscosity of the emulsion rise to significantly higher values than 10 mPa s (cf. DIN regulation 9040), because a viscosity of over 100 PA s can already lead to the normal filters , Pumps and nozzles of the motor vehicles can no longer be passed without problems. It is therefore preferable to have a viscosity of 5 mPas, e.g. B. for gasoline emulsions below 2 mPA s to be observed. The viscosity should not increase significantly even when it cools down to approx. -15 ° C, and the emulsion should remain stable.

Die für die erfindungsgemäßen Kraftstoffe als Emulgatoren einzusetzenden Monoamide, insbesondere solche der Formel (11), zeigen eine ausgeprägte Rostschutzwirkung. Bislang beispielsweise eingesetzte Methylpolyätheramide sind demgegenüber weitgehend wirkungslos. Die übrigen bisher für den Einsatz in Kraftstoffen beschriebenen Emulgatoren zeigen - wahrscheinlich aufgrund ihrer entfettenden Wirkung - in Gegenwart von Wasser eine eher vermehrte Rostbildung.The monoamides to be used as emulsifiers for the fuels according to the invention, in particular those of the formula (11), have a pronounced rust protection effect. In contrast, methylpolyether amides used to date are largely ineffective. The other emulsifiers described so far for use in fuels show a rather increased rust formation in the presence of water - probably due to their degreasing effect.

Weiterhin führt der erfindungsgemäße Emulgatortyp weder bei den mit dem Kraftstoffsystem in Berührung kommenden Kunststoffteilen noch den Lackflächen zu vermehrten Quellungen oder Ablösungen, wie dies bei den Estern der Polyäther beobachtet werden kann.Furthermore, the type of emulsifier according to the invention does not lead to increased swelling or detachment neither in the plastic parts coming into contact with the fuel system nor in the paint surfaces, as can be observed with the esters of the polyethers.

Ein weiterer Vorteil der erfindungsgemäßen Kraftstoffe besteht darin, daß der Einsatz von Bleitetraalkylen mit dem dafür geforderten extrem niedrigen Wert für die Maximale Arbeitsplatz-Konzentration (MAK-Wert) von 0,01 ppm vermieden werden kann. Es können weiterhin die zur Entfernung des Bleioxids im Motor notwendigen »Fluide« (oder sog. Scavenger, vgl. Chemiker-Zeitung 97 (1973) Nr. 9, S. 463) entfallen, die in den letzten Unfallverhütungsvorschriften in die Klasse III B eingestuft worden sind (Unfallverhütungsvorschriften der Berufsgenossenschaft der chemischen Industrie, Anlage 4, MAK-Werte-Liste vom 01. 10. 1978).Another advantage of the fuels according to the invention is that the use of lead tetraalkylene with the required extremely low value for the maximum workplace concentration (MAK value) of 0.01 ppm can be avoided. The "fluids" (or so-called scavenger, cf. Chemiker-Zeitung 97 (1973) No. 9, p. 463) necessary to remove the lead oxide in the engine, which are classified in Class III B in the latest accident prevention regulations, can also be omitted (accident prevention regulations of the professional association of the chemical industry, appendix 4, list of MAK values from October 1st, 1978).

Weiterhin vermindert die Erniedrigung der Temperatur des Verbrennungsvorganges die Schadstoffmengen im Abgas (z. B. den NO-Gehalt) und wegen dieser »eingebauten Kühlung« kann mit dem »abgemagerten« Gemisch sparsam gefahren werden. Es ist nicht mehr notwendig, die Brennraumtemperatur durch ein »fettes« Gemisch, das einem unnötig erhöhten Treibstoffverbrauch entspricht, herabzusetzen. Da die Zusätze Emulgatoren sind, wird auch die Aggregatverschmutzung durch ihre Detergent-Wirkung vermieden.Furthermore, the lowering of the temperature of the combustion process reduces the amount of pollutants in the exhaust gas (e.g. the NO content) and because of this "built-in cooling", the "lean" mixture can be used economically. It is no longer necessary to lower the combustion chamber temperature by means of a "rich" mixture, which corresponds to an unnecessarily increased fuel consumption. Since the additives are emulsifiers, aggregate contamination due to their detergent effect is also avoided.

Das Verhältnis von genutztem und nur maschinen-technisch notwendigem Treibstoff ist natürlich bei schnellaufenden Antriebsaggregaten besonders ungünstig, wie z. B. beim Wankelmotor und bei Turbinen, die ihre Antriebskraft nur bei hohen Umdrehungszahlen entfalten. Außerdem führen die notwendigen Verbrennungswärmen hier schnell zu Wärmestauproblemen und damit auch zu ungünstigen Abgaswerten. Hier ist der Einsatz der erfindungsgemäßen Treibstoff-Wasser-Emulsion besonders dazu geeignet, einen günstigeren spezifischen Verbrauch zu erzielen und die Wärme- und Abgasprobleme zu lösen.The ratio of fuel used and only necessary in terms of machine technology is, of course, particularly unfavorable in the case of high-speed drive units, such as. B. the Wankel engine and turbines, which develop their driving force only at high speeds. In addition, the necessary heat of combustion quickly leads to heat accumulation problems and thus to unfavorable exhaust gas values. Here, the use of the fuel-water emulsion according to the invention is particularly suitable for achieving a more favorable specific consumption and for solving the heat and exhaust gas problems.

Ein weiterer Vorteil der Emulgatoren und Wasser sowie gegebenenfalls Alkohole enthaltenden erfindungsgemäßen Kraftstoffe besteht darin, daß ihre elektrostatische Aufladung stark herabgesetzt ist, so daß eine wesentliche Gefahr beim Umgang mit Treibstoffen herabgesetzt wird (vgl. Haase, Statische Elektrizität als Gefahr, Verlag Chemie, Weinheim/Bergstraße 1968, insbesondere Seite 69, 96-99, 114 und 115). Die elektrostatische Aufladung der erfindungsgemäßen Treibstoffe ist so gering, daß keine gefährlichen Entladungen mehr auftreten können. Das verwendete Normalbenzin zeigt bei 20° C für den spezifischen Durchgangswiderstand Werte um 1.1012 Ω · cm, der erfindungsgemäße Treibstoff dagegen weist im allgemeinen einen spezifischen Durchgangswiderstand von kleiner als 1.1010 Ω · cm, beispielsweise 1.107 bis 1.1010 n - cm, auf. Bevorzugt beträgt der spezifische Durchgangswiderstand der erfindungsgemäßen Kraftstoffe 1.108 bis 9.109 Ω · cm. Bei Werten von unter 1010 Ω · cm findet keine Gefährdung durch elektrostatische Aufladung beim Abfüllen, Umfüllen und Auslaufen mehr statt.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 Ω · cm for the specific volume resistance at 20 ° C, whereas the fuel according to the invention generally shows a volume resistivity of less than 1.10 10 Ω · cm, for example 1.10 7 to 1.10 10 n - cm. The volume resistivity of the fuels according to the invention is preferably 1.10 8 to 9.10 9 Ω · cm. At values below 10 10 Ω · cm there is no longer any danger from electrostatic charging when filling, decanting and draining.

Überraschenderweise bleibt trotz des zum Teil erheblichen Wassergehalts die Brennbarkeit des Treibstoffes - sogar unter Herabsetzung der Rußentwicklung - erhalten. Für erfindungsgemäß zusammengesetzte Dieselkraftstoffe wird die Toleranzgrenze im Treibstoff-Luft-Verhältnis bis zum stark belästigenden, rußigen Qualmen der Dieselfahrzeuge weit nach oben verschoben.Surprisingly, despite the sometimes considerable water content, the combustibility of the fuel - even while reducing the soot development - is preserved. For diesel fuels composed according to the invention, the tolerance limit in the fuel-air ratio is shifted far upwards to the very annoying, sooty smoke of the diesel vehicles.

Die Zündwilligkeit der erfindungsgemäßen Treibstoffemulsionen ist in keiner Weise beeinträchtigt, so daß Fahrzeuge auch nach vielwöchiger, im Freien verbrachter Pause ohne Verzögerung beim Starten anspringen. Diese Betriebssicherheit wird auch durch die hervorragende Lagerstabilität der erfindungsgemäß einzusetzenden Emulsionen erreicht, die weder im Vergaser noch in der Benzinpumpe oder im Tank Wasser - auch nicht in geringen Mengen - absetzen. Die bekannten Schwierigkeiten beim Starten und die Zündaussetzer beim Fahrbetrieb entfallen infolgedessen. Bisher bekannte Emulgatorsysteme neigen - insbesondere wegen der in ihnen enthaltenen Nebenprodukte - zur Bildung dieser sog. Wassersümpfe.The ignitability of the fuel emulsions according to the invention is in no way impaired, so that vehicles start without delay even after a break of several weeks spent outdoors. This operational safety is also achieved by the excellent storage stability of the emulsions to be used according to the invention, which do not settle water in the carburetor, in the gasoline pump or in the tank - not even in small quantities. As a result, the known difficulties when starting and the misfires when driving are eliminated. Previously known emulsifier systems tend - particularly because of the by-products they contain - to form these so-called water sumps.

Schließlich wird durch den Einsatz der erfindungsgemäßen Kraftstoffe auch noch eine Verbesserung der Oktanzahl erreicht.Finally, an improvement in the octane number is also achieved by using the fuels according to the invention.

Die in den folgenden Beispielen enthaltenen Prozentangaben sind, soweit nichts anderes gesagt ist, Gewichtsprozente.Unless stated otherwise, the percentages contained in the following examples are percentages by weight.

Beispiel 1example 1

In einem Normaltreibstoff käuflicher Qualität (spezifischer Durchgangswiderstand 1.1012 Ω · cm) werden 2,4% eines nichtionischen, von Polyäthylenglykol gereinigten Ölsäureamids mit 7 Mol Äthylenoxid (Addukt aus 7 Mol Äthylenoxid an 1 Mol Ölsäureamid), 0,6% eines Kokosfettsäureamids mit 1 Mol Äthylenoxid (frei von Esteranteilen) und 1,5% Isobutanol gelöst.In a standard fuel of commercial quality (volume resistivity 1.10 12 Ω · cm), 2.4% of a non-ionic oleic acid amide cleaned from polyethylene glycol with 7 moles of ethylene oxide (adduct of 7 moles of ethylene oxide with 1 mole of oleic acid amide), 0.6% of a coconut fatty acid amide with 1 Dissolved in moles of ethylene oxide (free of ester components) and 1.5% isobutanol.

Unter Rühren mit einem Rührwerk (ca. 200-300 U/Min.) läßt man in die Benzin-Emulgator-Lösung (70,5% Normalbenzin) 25% Wasser einlaufen. Wenn die Emulsion durch und durch umgewälzt worden ist, ist ein opalmilchiger Treibstoff zur Verwendung fertig. Unter dem Mikroskop sind bei 900facher Vergrößerung nur gleichmäßige, feinste Tröpfchen und keine, vom Objektträger breitgedrückten Wasserinseln sichtbar. Der so hergestellte Kraftstoff besitzt einen spezifischen Durchgangswiderstand von 3.109 92 - cm.While stirring with a stirrer (approx. 200-300 rpm), 25% water is run into the gasoline emulsifier solution (70.5% normal gasoline). When the emulsion has been thoroughly circulated, an opal milky fuel is ready for use. At a 900x magnification only microscopic, fine droplets and no water islands that are pushed wide by the slide are visible under the microscope. The fuel produced in this way has a volume resistance of 3,109 92 cm.

Die Viskosität bei 20° C betrug 0,96 mPA s und die Durchlaufzeiten durch ein Boschbenzinfilter unterschieden sich nicht von der einer gleichen Menge Benzin. Ein Opel Kadett von der Leistung 45 PS mit 1,1 Liter Hubraum wurde auf einem HPA-Testgerät (Rollenprüfstand) 15 Minuten bei 100 km/h Geschwindigkeit und mit einem Widerstand von 20 kg auf den Rollen geprüft.The viscosity at 20 ° C was 0.96 mPA s and the throughput times through a Bosch gasoline filter did not differ from that of an equal amount of gasoline. An Opel Kadett with an output of 45 hp and a displacement of 1.1 liters was tested on an HPA tester (roller test bench) for 15 minutes at 100 km / h speed and with a resistance of 20 kg on the rollers.

Der Treibstoff wurde dem Vergaser separat aus einem Meßgefäß zugeführt. Der höheren Oberflächenviskosität und höheren Dichte entsprechend wurden die Leerlauf- und die Vollastdüse etwas vergrößert. Die Außentemperatur betrug 14°C. Aus der gemessenen Treibstoffmenge und der bei ca. 100 km/h zurückgelegten Kilometerzahl wurde folgender Verbrauch ermittelt:

Figure imgb0004
The fuel was fed to the carburetor separately from a measuring vessel. In accordance with the higher surface viscosity and higher density, the idle and full load nozzles have been slightly enlarged. The outside temperature was 14 ° C. The following consumption was determined from the measured fuel quantity and the number of kilometers traveled at approx. 100 km / h:
Figure imgb0004

Mit einer Tankfüllung der Treibstoffemulsion konnte der Wagen gefahren und nach beliebigem Stehenlassen direkt wieder gestartet werden. Die CO-Abgaswerte lagen bei 2,5 Vol.-%.The car could be driven with one tank of the fuel emulsion and restarted immediately after it had been left standing. The CO exhaust gas values were 2.5% by volume.

Beispiel 2Example 2

3% des in Beispiel 1 verwendeten Emulgators Ölsäureamid mit 7 Mol ÄO (= Äthylenoxid) wird in 72% Normalbenzin gelöst und durch langsames Einrühren von 25% Wasser zu einer Emulsion der gleichen Qualität wie in Beispiel 1 verarbeitet. Diese Emulsion ist bei Temperaturen über 15° C für Vergasermotoren einsatzfähig.3% of the emulsifier oleic acid amide used in Example 1 with 7 mol of ÄO (= ethylene oxide) is dissolved in 72% normal gasoline and processed into an emulsion of the same quality as in Example 1 by slowly stirring in 25% water. This emulsion can be used for carburetor engines at temperatures above 15 ° C.

Beispiel 3Example 3

Werden der Treibstoffemulsion aus Beispiel 2 noch 0,3% des 1 : 1-Addukts aus Rizinusölsäureamid und Äthylenoxid (ÄO) zugegeben, so bleibt die Gebrauchsfähigkeit bei 0° C erhalten.If 0.3% of the 1: 1 adduct of castor oleic acid amide and ethylene oxide (ÄO) is added to the fuel emulsion from Example 2, the serviceability remains at 0 ° C.

Beispiel 4Example 4

Zur Herstellung eines Treibstoffes wurden in eine Mischung aus 70% bleifreiem Normal-Benzin, 2,4% Ölsäureamid mit 7 Mol Äthylenoxid, 0,6% technischem Kokosfettsäureamids mit 1 Mol ÄO (hergestellt durch Erhitzen von 1 Mol Kokosfett mit 2 Mol Äthanolamin auf 160°C bis kein freies Amin mehr titriert werden konnte) und 5% eines Gemisches aus Methanol und iso-Butanol (4:1) unter gutem Rühren bei Außentemperaturen von ca. 15° C 22% Wasser einemulgiert.To produce a fuel, a mixture of 70% unleaded normal gasoline, 2.4% oleic acid amide with 7 moles of ethylene oxide, 0.6% technical coconut fatty acid amide with 1 mole of AO (prepared by heating 1 mole of coconut oil with 2 moles of ethanolamine to 160 ° C until no free amine could be titrated) and 5% of a mixture of methanol and iso-butanol (4: 1) emulsified with good stirring at outside temperatures of approx. 15 ° C 22% water.

Es wurde eine stabile, opal-milchige Emulsion erhalten, die eine Viskosität von unter 1 mPA s aufwies und auch bei -10°C noch keine gelartigen Schlieren bildete.A stable, opal-milky emulsion was obtained which had a viscosity of less than 1 mPA and did not form any gel-like streaks even at -10 ° C.

Mit diesem Treibstoff wurde ein Kraftfahrzeug vom Typ Fiat 128, mit 55 PS Leistung und 1180 ccm Hubraum, betankt, das bis dahin mit Superkraftstoff gefahren worden war. Bei leichter Erhöhung des Saugdruckes im Vergaser durch eine teilweise Betätigung des Chokes konnte mit dem Fahrzeug ein lebhafter Stadtverkehr ohne nennbare Einbußen der Fahreigenschaften absolviert werden. Ein Beschleunigungsklopfen (Klingeln), wie es bei Benzin ungenügender Qualität festgestellt wird, ließ sich weder bei kaltem noch betriebswarmem Motor beobachten. Auffallend war die geringe Verschmutzung der Kerzen nach dem Kurzstrekkenverkehr.This fuel became a motor vehicle of the type Fiat 128, with 55 HP and 1180 cc capacity, which had been run with super fuel until then. With a slight increase in the suction pressure in the carburetor by partially activating the choke, the vehicle could be used for lively city traffic without any noticeable loss of driving characteristics. An accelerating knock (ringing), as is found in gasoline of insufficient quality, was not observed when the engine was cold or warm. The low contamination of the candles after the short distance traffic was striking.

Beispiel 5Example 5

Mit dem. wie folgt hergestellten Treibstoff wurde ein 1,7-Liter-Opel Rekord gefahren: Eine Mischung aus 67% eines bleifreien Normalkraftstoffes, 2,25% Ölsäureamid mit 7 Mol Äthylenoxid (gereinigt), 0,75% eines technischen Kokosfettsäureamids mit 1 Mol Äthylenoxid (hergestellt durch Amidierung von 1 Mol Kokosfett mit 2 Mol Äthanolamin bei 160-170°C) und 5% eines Alkoholgemisches aus Methanol, Isobutanol, 2-Äthylhexanol (17 : 2 : 1) wurde bei 11 -14°C (Erdtanktemperatur) mit 25% Wasser unter Rühren emulgiert. Der Treibstoff bildete eine opal-milchige Wasser-in-ÖI-Emulsion und hatte eine Viskosität von 1,1 mPAs, die auch bei -15°C keine gelartigen Schlieren zeigte.With the. The fuel produced as follows drove a 1.7 liter Opel record: A mixture of 67% of a lead-free normal fuel, 2.25% oleic acid amide with 7 moles of ethylene oxide (purified), 0.75% of a technical coconut fatty acid amide with 1 mole of ethylene oxide ( prepared by amidation of 1 mole of coconut fat with 2 moles of ethanolamine at 160-170 ° C) and 5% of an alcohol mixture of methanol, isobutanol, 2-ethylhexanol (17: 2: 1) at 25-14 ° C (earth tank temperature) with 25 % Water emulsified with stirring. The fuel formed an opal-milky water-in-oil emulsion and had a viscosity of 1.1 mPAs, which showed no gel-like streaks even at -15 ° C.

Im Vergaser des Fahrzeugs wurden die Leerlauf- und die Hauptdüse durch Düsen mit ca. 10% und 15% erweitertem Durchmesser ersetzt. Bei normalem Mischbetrieb von Stadtverkehr und Autobahn wurde ein Verbrauch von 10,7-11,71 ermittelt. Dieser Verbrauch wurde vorher auch mit Benzin gemessen. Das Fahrverhalten und die Höchstgeschwindigkeit entsprach der vorher mit verbleitem Benzin gemessenen. Die Beobachtung des Zustandes der Kerzen wies auf eine saubere, rückstandsfreie Verbrennung bei diesem gemischten Verkehr hin. Abgasmessungen zeigten einen CO-Wert von 0,5-1,0% an, während das gleiche Fahrzeug mit Superbenzin bei CO-Werten von 3,5-4,5% lag. Beim Dauerbetrieb konnte eine weniger starke Aufheizung des Motors beobachtet werden, als beim Fahren mit vorgeschriebenem Benzin gemessen wird.In the vehicle's carburetor, the idle and main nozzles were replaced by nozzles with an enlarged diameter of approx. 10% and 15%. A consumption of 10.7-11.71 was determined for normal mixed operation of city traffic and motorway. This consumption was previously measured with petrol. The driving behavior and the maximum speed corresponded to those previously measured with leaded petrol. The observation of the condition of the candles indicated a clean, residue-free combustion in this mixed traffic. Exhaust gas measurements showed a CO value of 0.5-1.0%, while the same vehicle with premium petrol had CO values of 3.5-4.5%. During continuous operation, the engine heated up less than measured when driving with prescribed petrol.

Beispiel 6Example 6

Zur besseren Handhabung der hochviskosen Emulgatormischung aus Beispiel 5' werden die 3% Emulgator mit 3% Benzin und 3% Wasser zu einer klaren, niedrigviskosen Lösung formiert. Diese kann dann leicht, eventuell unter Verwendung mechanischer Dosiervorrichtungen, in 64% Benzin klar gelöst werden und direkt anschließend mit 22% Wasser emulgiert werden. Man erhält den Treibstoff nach Beispiel 5 in der gleichen Zusammensetzung und Qualität.For better handling of the highly viscous emulsifier mixture from Example 5 ', the 3% emulsifier is formed with 3% gasoline and 3% water to form a clear, low-viscosity solution. This can then be easily dissolved in 64% petrol, possibly using mechanical dosing devices, and immediately emulsified with 22% water. The fuel of Example 5 is obtained in the same composition and quality.

Beispiel 7Example 7

Für den Betrieb eines Dieselmotors wurde der folgende Treibstoff hergestellt:

  • 70,5% handelsübliches Dieselöl, 2,3% Stearinsäureamid und 5 Mol Äthylenoxid (gereinigte Ware), 0,7% Kokosfettsäureamid und 1 Mol Äthylenoxid und 1,5% Isobutanol werden miteinander gelöst, und sodann werden 25% Wasser einemulgiert. Es genügt die Anwendung eines einfachen Rührwerkes.
The following fuel was produced for the operation of a diesel engine:
  • 70.5% of commercially available diesel oil, 2.3% of stearic acid amide and 5 moles of ethylene oxide (purified goods), 0.7% of coconut fatty acid amide and 1 mole of ethylene oxide and 1.5% of isobutanol are dissolved together, and then 25% of water are emulsified. The use of a simple agitator is sufficient.

Diese Emulsion kann direkt verwendet werden oder bei Erwartung von tiefen Außentemperaturen noch mit 5% Methanol vermischt werden. Ein Wagen mit einem 2-Liter-Dieselmotor konnte ohne Beeinträchtigung betrieben werden.This emulsion can be used directly or can be mixed with 5% methanol if low outside temperatures are expected. A car with a 2-liter diesel engine could be operated without impairment.

Der Treibstoff ließ sich mit dem Rizinusfettsäureamid mit 1 Mol Äthylenoxid, das in technischer Qualität aus 1 Mol Rizinusöl und 2 Mol Äthanolamin bei 160-180°C in etwa 5 Stunden herstellbar ist, in der gleichen Qualität erhalten, wenn dies anstelle des Kokosfettsäureamids mit 1 Mol ÄO eingesetzt wurde.The fuel could be obtained with the castor fatty acid amide with 1 mol of ethylene oxide, which can be produced in technical quality from 1 mol of castor oil and 2 mol of ethanolamine at 160-180 ° C in about 5 hours, in the same quality if this instead of the coconut fatty acid amide with 1 Mol ÄO was used.

Beispiel 8Example 8

Es wird wie in Beispiel 7 verfahren, wobei jedoch ein Dieselöl der folgenden Zusammensetzung eingesetzt wird:

Figure imgb0005
The procedure is as in Example 7, but using a diesel oil of the following composition:
Figure imgb0005

Ohne die Schwierigkeiten, wie sie durch einen instabilen und sich in Schichten trennenden Treibstoff entstehen können, ist dieser Treibstoff in einem dieselbetriebenen Fahrzeug verwendbar.This fuel can be used in a diesel powered vehicle without the difficulties of an unstable and stratified fuel.

Beispiel 9Example 9

67% Normalbenzin wurden mit 1,8% Kokosfettsäureamid + 2 Mol ÄO (hergestellt aus Kokosfettsäuren und Diäthanolamin im Verhältnis 1 :1), 1,2% Ölsäureamid und 7 Mol ÄO (gereinigt) und 5% Alkoholgemisch (84% Methanol, 10% Isobutanol, 6% 2-Äthylhexanol) vermischt und anschließend mit 25% Wasser versetzt, das eingerührt wurde. Mit diesem niedrigviskosen und stabilen Treibstoff lassen sich die in Beispiel 4, 5 und 6 beschriebenen Fahrzeuge in gleicher Weise wie dort beschrieben, betreiben.67% regular gasoline was treated with 1.8% coconut fatty acid amide + 2 moles of AO (made from coconut fatty acids and diethanolamine in a ratio of 1: 1), 1.2% oleic acid amide and 7 moles of AO (purified) and 5% alcohol mixture (84% methanol, 10% Isobutanol, 6% 2-ethylhexanol) mixed and then mixed with 25% water, which was stirred in. With this low-viscosity and stable fuel, the vehicles described in Examples 4, 5 and 6 can be operated in the same way as described there.

Die gleichen guten Ergebnisse werden erzielt, wenn anstelle des Alkoholgemisches 1,5% Isopropanol verwendet werden (unter Erhöhung des Benzinanteils auf 70,5%).The same good results are achieved if 1.5% instead of the alcohol mixture Isopropanol can be used (increasing the gasoline percentage to 70.5%).

Beispiel 10Example 10

Ein Normalbenzin, das frei von Bleialkylen und dessen »Fluiden« ist, wird mit einem Anteil von 79% eingesetzt; darin werden 1,2% Additionsprodukt aus 1 Mol Ölsäureamid und 7 Mol Äthylenoxid (durch Reinigung weniger als 0,8% PEG (Polyethylenglykol) und weniger als 0,07% Salze enthaltend) und 1,8% Kokosfettsäuredi- äthanolamid gelöst. Durch Einrühren von einer Mischung aus 15% Wasser und 4% Methanol stellt man eine opale Emulsion her. Die Dichte liegt bei 0,778. Dieser Treibstoff wurde in einem 1,71 Opel Rekord gefahren; die Leistungen entsprachen dabei den für dieses Fahrzeug vorgeschriebenen. Der Verbrauch ist der gleiche wie für die üblichen (Wasser- und Emulgatorfreien) Kraftstoffe. Nach einer Nacht im Freien, bei der die Morgentemperatur -19°C betrug, ließ sich der Motor nach wenigen Sekunden problemlos starten. Eine Vergleichsmessung des Abgaswertes lag für Wasser- und Emulgatorfreies Benzin bei 1,5% CO, für den erfindungsgemäßen Kraftstoff bei 0,1% CO (gemessen bei betriebswarmem Motor im Leerlauf). Dabei wurde keine Erhöhung des N02-Wertes gemessen.A regular gasoline that is free of lead alkylene and its "fluids" is used with a share of 79%; 1.2% addition product of 1 mol oleic acid amide and 7 mol ethylene oxide (containing less than 0.8% PEG (polyethylene glycol) and less than 0.07% salts by purification) and 1.8% coconut fatty acid diethanolamide are dissolved therein. An opal emulsion is prepared by stirring in a mixture of 15% water and 4% methanol. The density is 0.778. This fuel was run in a 1.71 Opel record; the services corresponded to those prescribed for this vehicle. The consumption is the same as for the usual (water and emulsifier free) fuels. After a night outdoors, where the morning temperature was -19 ° C, the engine could be started easily after a few seconds. A comparative measurement of the exhaust gas value for water- and emulsifier-free gasoline was 1.5% CO, for the fuel according to the invention 0.1% CO (measured when the engine was warm and idling). No increase in the N0 2 value was measured.

Beispiel 11Example 11

Der erfindungsgemäße Kraftstoff des Beispiels 10 wurde in einem 3 Jahre alten Fahrzeug auf den CO-Gehalt im Abgas bei betriebswarmem Motor im Leerlauf gemessen. Der Wert betrug 0,3% CO. Normalbenzin ergab 3,0% CO. Mischungen dieses Benzins mit 15% Methanol bzw. 15% Äthanol führten zu CO-Werten, die weniger als 0,3% vom Wert des Normalbenzins abweichen (Angaben in der DE-OS 2806673, Figur 2, bestätigen unsere Messungen für Äthanol).The fuel of Example 10 according to the invention was measured in a 3-year-old vehicle for the CO content in the exhaust gas with the engine warm when the engine was idling. The value was 0.3% CO. Regular gasoline gave 3.0% CO. Mixtures of this gasoline with 15% methanol or 15% ethanol led to CO values which deviate less than 0.3% from the value of normal gasoline (details in DE-OS 2806673, Figure 2, confirm our measurements for ethanol).

Beispiel 12Example 12

Bleifreies Normalbenzin wurde zu einem erfindungsgemäßen Kraftstoff wie folgt verarbeitet: 80% Normalbenzin, 1,2% Addukt aus 1 Mol Ölsäureamid + 7 Mol ÄO, 1,8% Kokosfettsäurediäthanolamid (aus Kokosfett und Diäthanolamin hergestellt) wurden vermischt; sodann wurden unter Rühren 15% Wasser, 2% Methanol und 1% Äthanol einemulgiert. Dieser opale Treibstoff bringt in einem Mercedes 250 mit 95 kw (130 PS) Motorleistung die Höchstgeschwindigkeit. Dafür wurde die,Hauptdüse dem etwas veränderten Verhalten des Treibstoffes durch Erweiterung von 97,5 auf 105 angepaßt. Der Verbrauchswert war, auf einem Rollenstand bei hoher Belastung (180 kp) ermittelt, dem Superbenzin gleichzusetzen. Ein Motorklopfen war trotz des Normalbenzineinsatzes nicht zu beobachten.Lead-free regular gasoline was processed into a fuel according to the invention as follows: 80% normal gasoline, 1.2% adduct from 1 mol oleic acid amide + 7 mol AIO, 1.8% coconut fatty acid diethanolamide (made from coconut oil and diethanolamine) were mixed; then 15% water, 2% methanol and 1% ethanol were emulsified in with stirring. This opal fuel brings the top speed in a Mercedes 250 with 95 kW (130 HP) engine power. The main nozzle was adapted to the slightly changed behavior of the fuel by expanding from 97.5 to 105. The consumption value, determined on a roll stand under high load (180 kp), was to be equated with premium gasoline. No engine knock was observed despite the normal use of petrol.

Es wurden die gleichen Ergebnisse erzielt, wenn ein oxyalkyliertes Ölsäureamid (aus Ölsäure, Aminopropanolamin durch Wasserabspaltung und anschließende Oxyäthylierung mit 6,5 Mol Äthylenoxid hergestellt) verwendet wurde anstelle der 1,2% des Ölsäureamids mit 7 Äthylenoxideinheiten.The same results were obtained when an oxyalkylated oleic acid amide (made from oleic acid, aminopropanolamine by dehydration and subsequent oxyethylation with 6.5 mol of ethylene oxide) was used instead of the 1.2% of the oleic acid amide with 7 ethylene oxide units.

Beispiel 13Example 13

Für den Betrieb eines Kleinlastwagens wurde folgender Dieselkraftstoff formuliert: in 82,5% Dieselöl mit 0,9% Additionsprodukt aus 1 Mol Ölsäureamid + 7 Mol ÄO, 2,1% Kokosfettsäurediäthanolamid (aus Kokosfett und Diäthanolamin hergestellt) und 0,5% 2-Äthylhexanol wurden 14% Wasser einemulgiert. Mit diesem Kraftstoff konnten im Kurzstreckenverkehr befriedigende Fahr- und Verbrauchswerte erzielt werden. Gegenüber dem üblichen Dieselkraftstoff wurde jedoch beim Entnehmen eines Teilstroms aus den Abgasen über ein weißes Filterpapier innerhalb von 3 Minuten nur eine kaum merkliche Anschmutzung beobachtet, während der Dieselkraftstoff ohne Emulgatoren und Wasser eine starke Schwärzung des Filters verursachte.The following diesel fuel was formulated for the operation of a small truck: in 82.5% diesel oil with 0.9% addition product from 1 mol oleic acid amide + 7 mol ÄO, 2.1% coconut fatty acid diethanolamide (made from coconut fat and diethanolamine) and 0.5% 2- Ethylhexanol was emulsified with 14% water. With this fuel, satisfactory driving and consumption values could be achieved in short-haul traffic. Compared to conventional diesel fuel, however, only a barely noticeable contamination was observed within 3 minutes when a partial flow was removed from the exhaust gases over a white filter paper, while the diesel fuel without emulsifiers and water caused the filter to become very black.

Beispiel 14Example 14

Einem Aromaten- und Additiv-freiem Benzin wurden 20% Toluol zugemischt. In 85% dieser Mischungwurden 1,8% Kokosfettsäurediäthanolamid und 1,2% Ölsäureamid mit 7 ÄO gelöst; darin wurden 10% Wasser und 2% Äthanol emulgiert.Aromatic and additive-free gasoline was mixed with 20% toluene. In 85% of this mixture 1.8% coconut fatty acid diethanolamide and 1.2% oleic acid amide were dissolved with 7 ÅO; 10% water and 2% ethanol were emulsified therein.

Mit dieser opalen Kraftstoffemulsion wurde in einem VW-Fahrzeug (1,6 Liter Motor, 62 kw (85 PS)) unter DIN-Verbrauchsbedingungen 8,4 Liter/100 km verbraucht. Im Kurzstreckenverkehr lag dieser Wert bei 9,11/100 km. Mit Normalbenzin wurden unter den gleichen Bedingungen dieselben Verbrauchswerte gemessen.This opal fuel emulsion was used in a VW vehicle (1.6 liter engine, 62 kw (85 hp)) under DIN consumption conditions, 8.4 liters / 100 km. In short-haul traffic, this value was 9.11 / 100 km. The same consumption values were measured with normal gasoline under the same conditions.

Wenn der in diesem Beispiel beschriebene Kraftstoff direkt nach der Herstellung mit dem genannten Benzingemisch im Verhältnis 1 : 1 verdünnt wurde, ließen sich dieselben Werte bei einem störungsfreien Fahrverhalten erzielen.If the fuel described in this example was diluted with the mentioned gasoline mixture in a ratio of 1: 1 immediately after production, the same values could be achieved with a trouble-free driving behavior.

Beispiel 15Example 15

In 75% der Benzinmischung des Beispiels 14 wurden 2% eines Kokosfettsäureäthanoiamids, das unter den üblichen Oxyäthylierungsbedingungen mit einem Mol Äthylenoxid zur Reaktion gebracht worden war, und 1% Ölsäureamid mit 7 ÄO gelöst. Darin wurde eine Mischung aus 10% Wasser und 2% Äthanol emulgiert. Mit dem Kraftstoff wurden dieselben Werte wie in Beispiel 14 erreicht.In 75% of the gasoline mixture of Example 14, 2% of a coconut fatty acid ethanoiamide, which had been reacted with one mole of ethylene oxide under the usual oxyethylation conditions, and 1% oleic acid amide with 7 ÅO were dissolved. A mixture of 10% water and 2% ethanol was emulsified therein. The same values as in Example 14 were achieved with the fuel.

Claims (6)

1. A liquid fuel emulsion for combustion engines, having a viscosity of no more than 100 PAs, which contains a non-ionic emulsifier, water and, if appropriate, an alcohol, characterised in that it contains 40-95% by weight of hydrocarbons, 0.5-6% by weight of a non-ionic emulsifier of the carboxylic acid amide type of the formula
Figure imgb0008
in which
R represents an optionally substituted, straight-chain or branched or cyclic, saturated or unsaturated hydrocarbon radical,
Y denotes the grouping
Figure imgb0009
wherein
R2 denotes hydrogen or methyl, and

in which
n represents an integer from 1 to 50 and
R1 represents hydrogen or denotes the grouping (̵Y)̵nH,
0-20% by weight of a straight-chain or branched, saturated or unsaturated alcohol containing 1-8 carbon atoms, and 0.5-35% by weight of water.
2. Fuel emulsion according to Claim 1, characterised in that it contains, as the non-ionic emulsifier, an adduct of 1-3 mols of ethylene oxide and 1 mol of carboxylic acid amide and an adduct of 5-25 mols of ethylene oxide and/or propylene oxide and 1 mol of carboxylic acid amide.
3. Fuel emulsion according to Claim 1 and 2, characterised in that it contains, as the non-ionic emulsifier, an adduct of 1-2 mols of ethylene oxide and 1 mol of fatty acid amide and an adduct of 5-10 mols of ethylene oxide and/or propylene oxide and 1 mol of fatty acid amide and, if appropriate, an adduct of 20-30 mols of ethylene oxide and 1 mol of fatty acid amide.
4. Fuel emulsion according to Claim 1-3, containing hydrocarbons which are free from lead tetraalkyls and solubilising agents thereof.
5. Fuel emulsions according to Claim 1 -4, characterised in that they have a specific volume resistivity of <1.1010 Ω · cm.
6. Use of the fuel emulsion according to Claim 1 for petrol engines, diesel engines, rotary piston engines, orturbines.
EP79104931A 1978-12-16 1979-12-05 Fuel oils and their application Expired EP0012345B1 (en)

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EP0012345A1 (en) 1980-06-25
US4297107A (en) 1981-10-27
ZA796799B (en) 1980-12-31
DD147854A5 (en) 1981-04-22
BR7908185A (en) 1980-07-22
ATE1247T1 (en) 1982-07-15
AU5392579A (en) 1980-06-19
JPS5582191A (en) 1980-06-20
CA1137751A (en) 1982-12-21
DE2963192D1 (en) 1982-08-12
DE2854540A1 (en) 1980-06-26

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