EP0058605B1 - Mikroemulsion von Wasser in einem flüssigen Brennstoff - Google Patents

Mikroemulsion von Wasser in einem flüssigen Brennstoff Download PDF

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Publication number
EP0058605B1
EP0058605B1 EP82400233A EP82400233A EP0058605B1 EP 0058605 B1 EP0058605 B1 EP 0058605B1 EP 82400233 A EP82400233 A EP 82400233A EP 82400233 A EP82400233 A EP 82400233A EP 0058605 B1 EP0058605 B1 EP 0058605B1
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EP
European Patent Office
Prior art keywords
water
microemulsion
amine
alkyl
alcohol
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Expired
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EP82400233A
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English (en)
French (fr)
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EP0058605A3 (en
EP0058605A2 (de
Inventor
Maurice Bourrel
Alain Sanchez
Jean-Claude Soula
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Societe National Elf Aquitaine
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Societe National Elf Aquitaine
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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
    • 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
    • Y10S516/06—Protein or carboxylic compound containing

Definitions

  • the present invention relates to microemulsions of water in liquid fuels, in particular hydrocarbons or mixtures of hydrocarbons with oxygenated organic compounds. It also includes the process for their preparation as well as the application of such microemulsions as fuels which can be used in particular in engines or burners.
  • Microemulsions consisting of hydrocarbons with a lower proportion of water and possibly alcohols, are well known at the present time: many works have been devoted to the preparation of this type of systems, whose industrial interest is undeniable. . It is known, in fact, that a fuel containing water and alcohol, in the form of microemulsion, brings marked advantages over the fuel alone; used in an engine, it can in fact give rise to a much reduced formation of carbon monoxide, nitrogen oxides and hydrocarbons in the gases formed. It can also improve the anti-detonating properties. Thus, the incorporation of water, and preferably also alcohol, into a liquid fuel, makes it possible to increase the rate of combustion and to attenuate the effects of pollution.
  • HLB hydrophilic-lipophilic balance
  • the present invention brings, in this way, an important improvement by the choice of an unforeseen surfactant compound, very different from all those found in the prior art, and which has the advantage of providing emulsions perfectly homogeneous, clear, isotropic, Newtonian and stable.
  • the microemulsions according to the invention have the property of being independent of the order in which their constituents are introduced.
  • the process according to the invention for the preparation of a microemulsion of water, optionally accompanied by another adjuvant, in particular alcohol, in a liquid fuel, in the presence of a surfactant is characterized in that that the surfactant is an alkylphenoxyalkanoate of a metal, of ammonium or of organic base of formula: in which at least one of the radicals R 1 and R 2 denotes an alkyl, linear or branched, which can contain 1 to 24 preferably 6 to 18 carbon atoms; the second radical is hydrogen when a single radical is an alkyl; n is generally an integer from 1 to 6 and, most often, 1 or 2.
  • the cation M is preferably monovalent, in particular Na, K, Li, NH 4 or RNH 3 where R is a hydrocarbon group, which can carry substituents, in particular hydroxyls.
  • Typical surfactants which are very suitable for carrying out the invention, are alkylphenoxyacetates, the phenyl nucleus of which carries a relatively long alkyl, in particular in C 18 -C 18. These are, by way of nonlimiting examples : sodium p-octyl-phenoxyacetate, potassium p-decyl-phenoxyacetate, ammonium m-nonylphenoxyacetate, sodium dioctyl-3,5-phenoxyacetate, ammonium p-laurylphenoxyacetate, p-nonylphenoxyacetate of hexylamine, m- diethanolamine stearyl phenoxyacetate, etc. However, other corresponding alkanoates, for example alkyl phenoxy propionates or alkyl phenoxy butyrates, are also suitable.
  • the surfactants according to the invention can be used alone or in admixture with other surfactants whose activity they enhance.
  • microemulsions which are generally designated by the term co-surfactants, in particular such as alcohols and amines, are very compatible with the alkylphenoxyalkanoates used according to the invention.
  • co-surfactants in particular such as alcohols and amines
  • the excellent stability of microemulsions obtained, with alcohols as co-surfactants makes it possible, according to the invention, to have very stable fuels, containing water and alcohols, in a wide range of concentration.
  • alcohols as co-surfactants constitutes a preferred form of the invention: in fact it has a double advantage; first of all alcohol being a fuel in itself, the co-surfactant is part of the combustible mixture; moreover, since the fuel is a microemulsion of water in a hydrocarbon, it is possible to use alcohols which are not completely dehydrated, which constitutes an advantage from an economic point of view, especially when it is known that in the case of Ethanol-water mixture in particular, there is an azeotrope which makes it difficult and expensive to extract the alcohol in its pure state.
  • the composition of the microemulsion it is possible to adapt the composition of the microemulsion to the temperature range, where the microemulsion must remain stable (between - 20 ° and 100 ° C and particularly between -10 ° and + 20 ° C ), by adjusting the proportion and / or the nature of the phenoxyalkanoate.
  • the process for the preparation of microemulsions, according to the invention, characterized in that the surfactant is an alkylphenoxyalkanoate, can be carried out in the manner known per se, that is to say by mixing adjuvants affected with liquid fuel. A slight agitation is enough to obtain a stable microemulsion.
  • An advantage of this process is that the adjuvants can be mixed with the fuel in any order: thus one can first dissolve the surfactant in water, in the co-surfactant, or in a mixture of the two, and introduce the solution or dispersion obtained in the liquid fuel, with gentle and brief agitation. However, it is also possible to put these various additives directly into the fuel and to stir them just for the time necessary for homogenization.
  • the stirring of the medium can be carried out by means of a paddle stirrer, rotating at about 20 to 100 rpm (peripheral speed of the order of 0.5 to 5 m / s ), for 1 to 10 minutes.
  • Microemulsions of water with different co-surfactants were prepared by the above-mentioned method, in which water, previously mixed with the co-surfactant and the surfactant, according to the invention, was added to ordinary auto gasoline (fraction of oil boiling between 20 ° and 200 ° C). The operations related to 1 liter of gasoline which was agitated for 3 minutes, after the addition of the adjuvants.
  • the table below indicates the proportions of the components in% of the total weight of microemulsion, the surfactant being sodium p-lauryl-phenoxyacetate. It can be seen that it is possible to vary the proportions of water and of co-surfactants within fairly wide limits, which are advantageous for practice.
  • microemulsions 1 to 10 are homogeneous, clear, isotropic, Newtonian and stable at room temperature. Their viscosities are close to those of the gasoline used.
  • Microemulsions of water or water and an adjuvant can contain from 1 to 10% of water, 1 to 27% of an alcohol or an amine, 1 to 10% of surfactant, and preferably 1 to 6%, microemulsified in a liquid fuel.
  • the surfactant used was monoethanolamine p-lauryl-phenoxyacetate, that is to say that its cation was [NH 3 CH 2 CH 2 OH] + .
  • the emulsions of these examples are very stable and leave only very small proportions of carbon monoxide on combustion.
  • sodium p-nonyl-phenoxyacetate was used as surfactant in an amount of 3.5% of the total.
  • isobutanol and 9.5% water a perfectly stable emulsion was obtained, containing 85.7% gasoline.
  • Example 1 we replace ordinary auto gasoline with light fuel oil, known under the name of “domestic fuel oil”.
  • the stable microemulsion obtained is used in a central heating boiler burner.
  • Example 6 The microemulsion of Example 6 is used to power an automobile engine with a capacity of 1,200 ml, at an average speed of 3,500 rpm.
  • the fuel consumption is then 9.25 per 100 km (which corresponds to a consumption of 7.9 1 of petrol), the CO release being 6 g / km and that of NO, 0.4 g / km, while - under the same operating conditions - petrol alone leads to a consumption of 9.6 liters per 100 km, with a CO emission of 26 g / km and NO x of 1.6 g / km .
  • microemulsified fuel comprises by weight 1 to 10% water, 1 to 27% alcohol and 1 to 6% surfactant, the rest being liquid fuel.
  • the invention also comprises, as new surfactants, the alkyl-phenoxy-alkanoates of a metal, of ammonium or of organic base of general formula in which R 1 , R 2 , n, M have meanings given during the description.

Claims (11)

1. Verfahren zur Herstellung einer Mikroemulsion aus Wasser oder aus Wasser und einem anderen Hilfsmittel, insbesondere einem Alkohol oder Amin in einer brennbaren Flüssigkeit in Gegenwart eines oberflächenaktiven Mittels, dadurch gekennzeichnet, dass dieses Mittel ein Alkylphenoxyalcanoat eines Metalls, von Ammonium oder einer organischen Base ist.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das oberflächenaktive Mittel der Formel
Figure imgb0011
entspricht, worin mindestens einer der Reste R1 und R2 eine lineare oder verzweigte Alkylgruppe mit 1 bis 24 Kohlenstoffatomen ist, der zweite Rest Wasserstoff ist, wenn ein Rest allein Alkyl ist; n eine ganze Zahl von 1 bis 6, insbesondere 1 oder 2 ist und M ein vorzugsweise einwertiges Kation ist.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass mindestens einer der Reste R1 und R2 ein Alkylrest mit 6 bis 18 C-Atomen ist.
4. Verfahren nach Anspruch 1 oder 3, dadurch gekennzeichnet, dass das Kation Na, K, Li, NH, oder RNH3 ist oder R eine Kohlenwasserstoffgruppe ist, die Substituenten, insbesondere Hydroxylgruppen tragen kann.
5. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das oberflächenaktive Mittel ein Alkylphenoxyacetat von Na, K, Li, NH, oder von einem Amin ist, wobei die Alkylgruppe 6 bis 18 C-Atome besitzt.
6. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das ebenfalls oberflächenaktive Hilfsmittel bzw. Co-oberflächenaktive Mittel ein Alkohol mit insbesondere 1 bis 8 C-Atomen ist.
7. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das Hilfsmittel oder Co-oberflächenaktive Mittel ein Amin, insbesondere Benzylamin, ist.
8. Mikroemulsion aus Wasser oder aus Wasser und einem Hilfsmittel, insbesondere Alkohol oder Amin, in einer brennbaren Flüssigkeit, enthaltend ein geeignetes oberflächenaktives Mittel, dadurch gekennzeichnet, dass das oberflächenaktive Mittel ein Alkylphenoxyalcanoat eines Metalls oder eines Amins ist.
9. Mikroemulsion nach Anspruch 8, dadurch gekennzeichnet, dass sie 1 bis 10 Gew.-% Wasser, 1 bis 27 Gew.-% Alkohol oder Amin und 1 bis 10 Gew.-% oberflächenaktives Mittel enthält.
10. Anwendung einer Mikroemulsion aus Wasser oder aus Wasser zusammen mit einem Alkohol oder einem Amin in einer brennbaren Flüssigkeit zur Verbrennung in einem Motor oder einem Brenner, dadurch gekennzeichnet, dass die Mikroemulsion ein oberflächenaktives Mittel aus einem Alkylphenoxyalcanoat eines Metalls oder einer organischen Base, insbesondere eines Alkalimetalls, von Ammoniak oder eines aliphatischen Amins umfasst.
11. Oberflächenaktives Mittel, das eine Alkylaryl-Gruppe enthält, dadurch gekennzeichnet, dass es aus einem Phenoxyalcanoat eines Metalls, von Ammonium oder einer organischen Base besteht, entsprechend der Formel
Figure imgb0012
worin wenigstens einer der Reste R1 und R2 eine lineare oder verzweigte Alkylgruppe mit 1 bis 24 C-Atome bedeutet, der zweite Rest Wasserstoff ist, wenn ein Rest allein eine Alkylgruppe ist, n eine ganze Zahl von 1 bis 6, insbesondere 1 oder 2 ist und M ein Kation, vorzugsweise ein einwertiges Kation ist.
EP82400233A 1981-02-17 1982-02-10 Mikroemulsion von Wasser in einem flüssigen Brennstoff Expired EP0058605B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8103084 1981-02-17
FR8103084A FR2500006A1 (fr) 1981-02-17 1981-02-17 Microemulsion de l'eau dans un combustible liquide

Publications (3)

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EP0058605A2 EP0058605A2 (de) 1982-08-25
EP0058605A3 EP0058605A3 (en) 1984-09-05
EP0058605B1 true EP0058605B1 (de) 1986-08-27

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US (1) US4465494A (de)
EP (1) EP0058605B1 (de)
JP (1) JPS57153089A (de)
BR (1) BR8200826A (de)
CA (1) CA1197523A (de)
DE (1) DE3272796D1 (de)
DK (1) DK150545C (de)
ES (1) ES8307284A1 (de)
FR (1) FR2500006A1 (de)

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Publication number Priority date Publication date Assignee Title
USRE36983E (en) * 1983-11-02 2000-12-12 Petroferm Inc. Pre-atomized fuels and process for producing same
JPS60166389A (ja) * 1984-02-09 1985-08-29 Nippon Oil & Fats Co Ltd 燃料油用流動性向上剤
US4666457A (en) * 1984-09-24 1987-05-19 Petroleum Fermentations N.V. Method for reducing emissions utilizing pre-atomized fuels
DE3525124A1 (de) * 1985-07-13 1987-01-15 Huels Chemische Werke Ag Kraftstoffe und heizoele und verwendung eines emulgatorsystems zur herstellung dieser kraftstoffe und heizoele
US4744796A (en) * 1986-02-04 1988-05-17 Arco Chemical Company Microemulsion fuel system
US4907368A (en) * 1987-11-23 1990-03-13 Atlas Powder Company Stable fluid systems for preparing high density explosive compositions
IT1229787B (it) * 1989-05-26 1991-09-11 Eniricerche Spa Composizione ibrida di carburante diesel.
US5480583A (en) * 1991-12-02 1996-01-02 Intevep, S.A. Emulsion of viscous hydrocarbon in aqueous buffer solution and method for preparing same
JPH06322382A (ja) * 1993-03-17 1994-11-22 Kao Corp 重質油エマルジョン燃料組成物
US5992354A (en) * 1993-07-02 1999-11-30 Massachusetts Institute Of Technology Combustion of nanopartitioned fuel
DE10334897A1 (de) * 2003-07-29 2005-03-10 Univ Koeln Mikroemulsionen und deren Verwendung als Kraftstoff
ATE491861T1 (de) 2006-02-07 2011-01-15 Diamond Qc Technologies Inc Mit kohlendioxid angereicherte rauchgaseinspritzung zur kohlenwasserstoffgewinnung
EP2145940A1 (de) 2008-07-15 2010-01-20 Bp Oil International Limited Verwendung und Fahrzeug
EP2253692A1 (de) 2009-05-19 2010-11-24 Universität zu Köln Biohydrofuel-Zusammensetzungen
DE102009048223A1 (de) 2009-10-05 2011-06-16 Fachhochschule Trier Verfahren zur In-Situ-Herstellung von Treibstoff-Wasser-Gemischen in Verbrennungsmotoren
DE202011107729U1 (de) 2011-11-11 2012-01-12 Elmar Vitt Herstellung und Stabilisierung von Wasser-Öl-Emulsionen durch Elektroosmose
DE102014225815A1 (de) 2014-12-15 2016-06-16 Fachhochschule Trier In-situ-Herstellung von Treibstoff-Wasser-Gemischen in Verbrennungsmotoren
DE202015003014U1 (de) 2015-04-26 2015-05-28 Elmar Vitt Vorrichtung zur indirekten Nutzung von Wasser-Öl-Emulsionen in Fahrzeugen und anderen externen Nutzern

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US2110847A (en) * 1937-06-21 1938-03-08 Tret O Lite Company Process for breaking petroleum emulsions
US2370256A (en) * 1940-01-09 1945-02-27 Joseph B Niederl Alkylated phenolic glycolic acids
US3630953A (en) * 1968-01-02 1971-12-28 Chevron Res Tailored surfactants for use in forming oil-in-water emulsions of waxy crude oil
US3876391A (en) * 1969-02-28 1975-04-08 Texaco Inc Process of preparing novel micro emulsions
US4002435A (en) * 1971-11-17 1977-01-11 Wenzel Edward C Clear and stable liquid fuel compositions for internal combustion engines
US4046519A (en) * 1975-10-31 1977-09-06 Mobil Oil Corporation Novel microemulsions
FR2468402B2 (fr) * 1978-11-13 1983-11-04 Elf Aquitaine Microemulsions aqueuses de substances organiques
DE2854540A1 (de) * 1978-12-16 1980-06-26 Bayer Ag Kraftstoffe

Also Published As

Publication number Publication date
BR8200826A (pt) 1982-12-28
JPS57153089A (en) 1982-09-21
FR2500006A1 (fr) 1982-08-20
ES509675A0 (es) 1983-07-01
DE3272796D1 (en) 1986-10-02
DK150545C (da) 1987-10-19
EP0058605A3 (en) 1984-09-05
EP0058605A2 (de) 1982-08-25
US4465494A (en) 1984-08-14
FR2500006B1 (de) 1983-03-25
DK150545B (da) 1987-03-23
DK66682A (da) 1982-08-18
CA1197523A (fr) 1985-12-03
ES8307284A1 (es) 1983-07-01

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