Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/32—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 Vorhrcnnungskraftmaschinen such as gasoline and diesel engines as well as rotary piston machines and turbines, which contain emulsifiers or emulsifier mixtures and water and optionally alcohols in the fuels customary for the respective units.
• Fuels for internal combustion engines have now been found 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.
• 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 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 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 e.g. 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 degree of oxyethylation, i.e. The type and number of groupings Y of the formula (I) can be varied within wide limits.
• the emulsifiers used are compounds of the formula (I) which are adducts of 1-3 moles of ethylene oxide with 1 mole of carboxylic acid amide and / or of 5-25 moles of ethylene oxide and / or propylene oxide with 1 mole 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 (cf. M. Schick, Nonionic Surfactants, loc. Cit., Pp. 213-214). These components can be used to produce a fatty acid amide according to the invention containing 1 mole of ethylene oxide and having a very high degree of purity by elimination of water at 160-180 ° C. in about 60-90 minutes. If one starts from the fatty acid amide (see M.Schick, Nonionic Surfactants, loc. Cit., P.213), 1 mol of ethylene oxide is added, advantageously at elevated temperature, for example at 100 - 140 o C, possibly with weakly acidic or weakly basic catalysis.
• the customary oxyalkylation catalysts such as sodium hydroxide, sodium methylate, potassium hydroxide, from 1: 1 adduct and add the desired amount of ethylene oxide under pressure. If natural fat is assumed, this is reacted with 2 moles of 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 molar mixture of fatty acid mono- g lycerid.und fatty acid amide 1: 1 ethylene oxide adduct can be advantageously used in an amount of 15-70 wt .-% of the nonionic emulsifier can be used.
• the non-ionic emulsifiers can contain impurities from the industrial production, which result from impurities in the preliminary product, e.g. come from the ethylene oxide, are caused by moisture or come from the oxyethylation catalyst.
• impurities in the preliminary product e.g. come from the ethylene oxide
• 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. according to DE-PS 828 839.
• a new cleaning method as proposed in patent application P 28 54 541.7, 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 ionogenicity. Since only nonionic and residue-free combustible emulsifiers can be used in motor fuel for corrosion reasons without difficulty, it must be used as are said to be 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 stability to cold, which consists not only in preventing the formation of ice crystals, but also in the failure to form gel structures which can cause an uncontrolled increase in viscosity.
• Alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, amyl alcohol, iso-amyl alcohol, hexyl alcohol, 1,3-dimethyl-butanol, cyclohexanol, methylcyclohexanol, Octanol, 2-ethylhexanol. 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 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 After formation of the emulsion, it is expedient not to allow the viscosity of the emulsion to rise to much higher values than 1 0 mPa s (vgl.DIN regulation 9040), as a viscosity of about 100 PA s can already lead to the normal Filters, pumps and nozzles of motor vehicles can no longer be passed without problems. It is therefore advisable to maintain a viscosity of 5 m PA s for the fuels according to the invention, for example for gasoline emulsions below 2 m PA s. 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 previously used, for example 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. Furthermore, the "fluids" (or so-called scavenger, cf. Chemiker-Zeitung 97 (1973) No. 9, p. 463) necessary for removing the lead oxide in the engine can be omitted, which are classified in Class III B in the last accident prevention regulations (accident prevention regulations of the professional association of the chemical industry, appendix 4, list of MAK values from 01.10.1978).
• 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.
• 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 around 1.10 12 ⁇ .am for the specific volume resistance at 20 ° C, whereas the fuel according to the invention generally has a volume resistance of less than 1.10 10 ⁇ .cm, for example 1 . 10 7 to 1.10 10 ⁇ cm, on.
• the specific volume resistance of the fuels according to the invention is 1.10 to 9.10 9 ⁇ ⁇ cm. At values below 10 10 ⁇ ⁇ cm there is no longer any danger from electrostatic charging when filling, decanting and draining.
• the ignition of the fuel emulsions of the invention is in no way impaired, so that vehicles even after he sauwöchi g, jump when starting outdoor verbrachter break without delay.
• 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 m PA 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 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 being left standing.
• the CO exhaust gas values were 2.5 vol%.
• This emulsion can be used for carburetor engines at temperatures above 15 ° C.
• This fuel was used to fuel a Fiat 128 motor vehicle with 55 hp and a displacement of 1180 cc that had previously been run on super fuel. 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 opal formed a milky water-in-oil emulsion, and had a viscosity of 1.1 mPa s, which showed no gel-like Schlieren also at -15 0 C.
• Example 5 For better handling of the highly viscous emulsifier mixture from Example 5, the 3% emulsifier with 3% gasoline and 3% water are formed into 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 in the same quality 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, 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 which is free from 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 1.7 1 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 at operating temperature while 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 that deviate less than 0.3% from the value of normal gasoline (details in DE-OS 2 806 673, 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 was worth, on a reel stand under high load (180 kp), 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.
• This opal fuel emulsion was used in a VW vehicle ( ⁇ 1.6 liter engine, 62 kw (85 PS)) under DIN consumption conditions 8.4 liters / 100 km. In short-haul traffic, this value was 9.1 1/100 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 ethanol amide 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)
• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
• Catalysts (AREA)
• Magnetic Heads (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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• 1978
  • 1978-12-16 DE DE19782854540 patent/DE2854540A1/de not_active Withdrawn
• 1979
  • 1979-11-30 US US06/099,122 patent/US4297107A/en not_active Expired - Lifetime
  • 1979-12-05 EP EP79104931A patent/EP0012345B1/fr not_active Expired
  • 1979-12-05 AT AT79104931T patent/ATE1247T1/de not_active IP Right Cessation
  • 1979-12-05 DE DE7979104931T patent/DE2963192D1/de not_active Expired
  • 1979-12-13 JP JP16092579A patent/JPS5582191A/ja active Pending
  • 1979-12-14 CA CA000341973A patent/CA1137751A/fr not_active Expired
  • 1979-12-14 BR BR7908185A patent/BR7908185A/pt unknown
  • 1979-12-14 ZA ZA00796799A patent/ZA796799B/xx unknown
  • 1979-12-17 AU AU53925/79A patent/AU5392579A/en not_active Abandoned
• 1980
  • 1980-12-13 DD DD80217654A patent/DD147854A5/de unknown

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