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)
• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
• Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
• Control Of The Air-Fuel Ratio Of Carburetors (AREA)
• Magnetic Heads (AREA)
• Catalysts (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 DE DE7979104931T patent/DE2963192D1/de not_active Expired
  • 1979-12-05 AT AT79104931T patent/ATE1247T1/de not_active IP Right Cessation
  • 1979-12-05 EP EP79104931A patent/EP0012345B1/de not_active Expired
  • 1979-12-13 JP JP16092579A patent/JPS5582191A/ja active Pending
  • 1979-12-14 CA CA000341973A patent/CA1137751A/en not_active Expired
  • 1979-12-14 ZA ZA00796799A patent/ZA796799B/xx unknown
  • 1979-12-14 BR BR7908185A patent/BR7908185A/pt 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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