WO1998018884A2 - Carburants aqueux de structure nanometrique - Google Patents

Carburants aqueux de structure nanometrique Download PDF

Info

Publication number
WO1998018884A2
WO1998018884A2 PCT/US1997/019368 US9719368W WO9818884A2 WO 1998018884 A2 WO1998018884 A2 WO 1998018884A2 US 9719368 W US9719368 W US 9719368W WO 9818884 A2 WO9818884 A2 WO 9818884A2
Authority
WO
WIPO (PCT)
Prior art keywords
composition
aqueous
emulsion
surfactant
phase
Prior art date
Application number
PCT/US1997/019368
Other languages
English (en)
Other versions
WO1998018884A3 (fr
Inventor
Jackie Y. Ying
Andrey Zarur
Tao Sun
Anne T. Heibel
Original Assignee
Massachusetts Institute Of Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Massachusetts Institute Of Technology filed Critical Massachusetts Institute Of Technology
Priority to AU54259/98A priority Critical patent/AU5425998A/en
Priority to EP97948127A priority patent/EP0934374A2/fr
Publication of WO1998018884A2 publication Critical patent/WO1998018884A2/fr
Publication of WO1998018884A3 publication Critical patent/WO1998018884A3/fr

Links

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

Definitions

  • the present invention relates to multi-phase aqueous/nonaqueous compositions, and more particularly to a water-in-oil emulsion useful as a fuel.
  • surfactant molecules arrange themselves as a layer with polar portions facing in one direction and non-polar portions facing in the opposite direction, the polar portions arranged adjacent a water phase and the non-polar portions arranged adjacent a fuel phase.
  • water-in-oil emulsions isolated regions of water are surrounded by surfactant molecules which separate the water from a continuous, oil phase.
  • oil-in-water emulsions the reverse exists, namely, isolated portions of oil are formed, surrounded by surfactant molecules which separate the oil from a continuous, aqueous phase.
  • water-in-water or water-in-oil depends upon several factors that are known, and the formation of water-in-oil emulsions is somewhat challenging in that a surfactant or mixture of surfactants must be used whose ratio of hydrophilic to lipophilic portions matches the HLB of the desired water-oil ratio, while the solubility of the surfactants in water in this case must be low to induce the formation of a continuous oil phase. Selection of suitable surfactants for water-in-oil emulsions therefore is non-trivial. In addition, in order to provide for an economically-viable fuel mixture, the amount of surfactant employed must be relatively small.
  • U.S. Patent No. 4,877,414 (Mekonen) describes use of certain types of mono olefin (alpha olefin) compounds in relatively minor amounts in water-fuel-surfactant mixtures. Water is preferably present at a level of from about 5% to about 25% by weight. Mekonen hypothesizes that the mono (alpha) olefinic additives (and/or alkyl benzene additives) provide good results in that they in some way initiate or promote reactions analogous to cracking during the combustion of the fuel composition, producing smaller, lower molecular weight hydrocarbons known to be more readily combustible.
  • U.S. Patent No. 5,156,114 (Gunnerman) describes an aqueous fuel including about 20- 80%o by volume water that purportedly produces approximately as much power as a similar volume of gasoline.
  • a hydrogen-producing catalyst is included, and is believed to act as a catalyst for the dissociation of water molecules during ignition, releasing hydrogen and oxygen which increases the amount of energy delivered by the fuel.
  • U.S. Patent No. 4,804,495 reports a heavy hydrocarbon/water multiple emulsion having an internal phase that is a water-in-hydrocarbon emulsion and an external phase including water containing a surfactant which defines a continuous phase within which the internal phase is emulsified.
  • the mixture is reported to include about 20-30% water with water droplets of the internal emulsion being on the order of 1-5 microns in dimension.
  • U.S. Patent No. 4,395,266 (Han) describes a stabilized, water-in-mineral oil emulsion including 1-50% by volume water, in which the average particle size of the water droplets is 0.1- 25 microns.
  • U.S. Patent No. 4,083,698 (Wenzel) describes a water-in-oil emulsion of a hydrocarbon fuel, water, a water-soluble alcohol, and a combination of various surfactants. Wenzel teaches that the percentage of water by weight in the composition should range from about 0.1-10%. and reports that clear compositions that are stable against phase separation over a wide range of temperatures result.
  • U.S. Patent No. 4,048,963 (Cottell) describes production of a water-in-oil emulsion including 10-50% water via sonic agitation in a continuous process just upstream of a combustion chamber. Very fine water droplets are reportedly produced, and it is reported that the flame temperature of combustion in internal combustion engines using the mixture is decreased while the total amount of power produced by the engine is as great as that produced by burning a comparable amount of unemulsified fuel.
  • the present invention involves, according to one aspect, the recognition that water-in-oil emulsions, as opposed to oil-in-water emulsions, and in particular water-in-oil emulsions having extremely small aggregates exhibit improved characteristics as fuels combustible in internal combustion engines and the like. It has been found that such fuels can be produced using components which minimize emission of certain toxic pollutants by careful selection and tailoring of components other than water and oil, and can be produced at commercially- viable expense.
  • the discoveries of the invention allow production of a variety of aqueous/nonaqueous mixtures not limited to mixtures of water and fuel.
  • the invention is a composition that is an emulsion of an aggregate component partitioned into a plurality of discontinuous aqueous aggregates in a continuous nonaqueous component phase.
  • the aqueous aggregates together have an average cross-sectional dimension of not more than about 100 run.
  • the emulsion has an aqueous content of at least about 8 wt %.
  • a composition of the invention includes a mixture of an aqueous phase and a nonaqueous phase including at least about 8 wt % aqueous component.
  • the mixture has a phase boundary area between aqueous and nonaqueous phases of at least about 5 m /g aqueous phase.
  • the aqueous component is water and the nonaqueous component is fuel, and a surfactant that is free of certain toxic pollutant precursors, for example a surfactant free of nitrogen, is used.
  • a surfactant that is free of certain toxic pollutant precursors for example a surfactant free of nitrogen.
  • the water phase of fuel mixtures of the invention can form micelles having average cross-sectional dimensions, or average dynamic diameters, that are very small. High water contents, and high phase boundary areas are achievable.
  • the invention provides a kit.
  • the kit includes surfactant molecules that each have a polar section and a non-polar section.
  • the surfactant molecules are constructed such that when they are mixed with a composition including a set ratio of an aqueous component and a nonaqueous component they will form an aqueous-in-nonaqueous emulsion that includes aqueous aggregates of a first cross-sectional dimension in the nonaqueous component, and the surfactant molecules arranged at interfaces between the aqueous aggregates and a nonaqueous phase defined by the nonaqueous component, with the non-polar sections of the surfactant are oriented away from the aqueous micelles into the nonaqueous phase.
  • the kit also includes co- surfactant molecules that each include a polar section less hydrophilic than the polar section of the surfactant molecules, and a non-polar section.
  • the co-surfactant molecules are constructed such that, when mixed with the surfactant and the composition, the co-surfactant molecules are able to insert between the non-polar sections of the surfactant molecules to form micelles of a second cross-sectional dimension less than the first cross-sectional dimension.
  • the kit can include the surfactant molecules and co-surfactant molecules mixed together, mixed together as a part of an overall composition including other species, packaged together but separately, packaged together and separately with other components, and the like.
  • the surfactant/co- surfactant kit can be used as a surfactant system in an aqueous/nonaqueous emulsion of the invention.
  • the invention provides a method of combustion. The method involves igniting fuel in the presence of water under conditions in which the water participates in a fuel reforming reaction. Products of the fuel reforming reaction then are combusted.
  • the fuel is ignited in the presence of water and a catalyst that catalyzes the fuel reforming reaction.
  • the catalyst can be a surface of an internal combustion engine.
  • the invention provides a method involving combusting fuel under set conditions in the presence of water at a temperature lower than that at which the fuel would combust under the set conditions in the absence of water.
  • the method is carried out by creating radical species at the surface of a catalyst that participate in the combusting step.
  • the invention provides a method of making an aqueous-in-nonaqueous emulsion.
  • the method involves providing a nonaqueous component and adding a surfactant system to the nonaqueous component to form a mixture.
  • a surfactant system to the nonaqueous component to form a mixture.
  • an aqueous component and a stabilizer are alternately added to the mixture. That is, following formation of the mixture, first an aqueous component is added, then stabilizer, then aqueous component again, or after formation of the mixture first stabilizer is added, then aqueous component, then stabilizer.
  • Fig. 1 is a schematic illustration of a portion of a micelle of a water-in-oil emulsion having a relatively large diameter
  • Fig. 2 is a schematic illustration of a portion of a micelle of a water-in-oil emulsion having a small diameter relative to the micelle of Fig. 1;
  • Fig. 3 is a schematic illustration of a portion of a reduced-size aqueous-in-nonaqueous micelle including surfactant molecules having non-polar sections between which are inserted co- surfactant molecules;
  • Fig. 4 is a schematic illustration of a stabilizing surfactant of the invention including polar portions that interact in a stabilizing manner with water.
  • the present invention provides two-phase, aqueous/nonaqueous systems having improved properties.
  • the systems can find use in any of a wide variety of applications as described above and, in a particularly preferred embodiment, the invention provides water-in-oil emulsions useful as combustible fuels. While fuel emulsions are described hereinafter, it is to be understood that the disclosure herein of exemplary components and combinations of components for use in the invention, and selection criteria and screening techniques for formulating emulsions of the invention, are applicable to any useful aqueous-in-nonaqueous emulsion.
  • the aqueous/nonaqueous mixture of the invention is preferably an isotropic micellar phase of the "reversed” type, that is, micelles surrounded by surfactant molecules arranged with polar sections pointing toward the micelle and non-polar sections facing outward.
  • micelle means an isolated aqueous aggregate having any shape, for example cylindrical, spherical, ellipsoidal, irregular shapes, etc. Generally, in emulsions of the invention, the aqueous aggregates will form spherical micelles.
  • the aqueous and nonaqueous components are preferably liquids at room temperature, but need not be.
  • One component of the two components, or both components, can be solid enough at room temperature to be self-supporting.
  • a cosmetic micellar formulation including a nonaqueous component that is soft but solid at room temperature, in which aqueous aggregates are contained, the overall composition being in the form of a cream at room temperature, is one example of aqueous-in-nonaqueous emulsions encompassed by the invention.
  • the arrangement has high combustibility, which can be achieved by selection of surfactant systems that themselves are combustible, as described below.
  • compositions of the invention are, according to preferred embodiments, stable for at least about 20 microseconds within a temperature range of from about 0.5 °C to about 45 °C, more preferably for about 1 minute, more preferably for about 1 hour, more preferably still for about one day, more preferably still for about one month, and more preferably still for about one year within this temperature range of from about -5 °C to about 45 °C.
  • the composition is preferably stable for at least about one minute within a temperature from about -10°C to about 50°C, more preferably within a range from about -20°C to about 60°C.
  • the emulsion is stable for at least about 10 microseconds and a temperature of at least about 2000 °C.
  • the emulsions of the invention include discontinuous aqueous aggregates in a continuous nonaqueous phase. This means that separate, isolated regions of aggregates of an aqueous component are contained within a continuous nonaqueous phase defined by a nonaqueous component.
  • the discontinuous aqueous aggregates in the nonaqueous phase typically take the form of micelles having an average cross-sectional dimension of not more than about 100 nm.
  • the micelles preferably have an average dynamic diameter of not more than about 100 nm.
  • Average dynamic diameter is meant to define micelle diameters in which the micelles are relatively set in shape, or the average diameters of micelles which are fluid and are constantly changing in shape.
  • the average dynamic diameter is the average diameter of the micelle in a state in which it is essentially spherical.
  • Average cross-sectional dimensions or average dynamic diameters of micelles of the invention preferably are not more than about 50 nm, more preferably not more than about 25 nm, more preferably not more than about 15 nm, more preferably not more than about 10 nm, and most preferably not more than about 5 nm, although micelles smaller than 5 nm and even 3 nm are effective.
  • the composition is a mixture of an aqueous phase and a nonaqueous phase, the mixture including a phase boundary area between the aqueous and nonaqueous phases of at least about 5 rtr/g aqueous phase.
  • This mixture can take the form of an emulsion including a discontinuous aqueous phase component, for example micelles, in a continuous nonaqueous phase, and the aqueous phase is present in an amount of at least about 8 wt %>.
  • the phase boundary area is at least about 10 m 2 /g aqueous phase, more preferably at least about 15 m 2 /g, more preferably at least about 20 m 2 /g, more preferably at least about 25 m 2 /g, more preferably at least about 50 m 2 /g, more preferably still at least about 70 m 2 /g, and most preferably at least about 90 m 2 /g of the mixture.
  • the aqueous phase is present in an amount preferably of at least about 12 wt %, more preferably at least about 15 wt %>, more preferably at least about 20 wt %>, more preferably at least about 25 wt %, more preferably at least about 30 wt %, which has been found to be optimum in some embodiments.
  • the aqueous phase is present in an amount of at least about 40 wt % may be advantageous, and in others at least about 50 wt %> based on the weight of the emulsion or mixture.
  • the aqueous/nonaqueous mixture or emulsion of the invention preferably has an electrical conductivity essentially equal to that of the nonaqueous phase. This is because the aqueous phase, which could be conductive, is in the form of isolated regions, and the only continuous phase is nonaqueous and non-electrically conductive.
  • the composition according to preferred embodiments, has an electrical conductivity no more than about 450 microsiemens, the approximate electrical conductivity of tap water. According to a more preferred embodiment, the composition has an electrical conductivity of no more than about 20 microsiemens. Where the mixture or emulsion involves a continuous diesel fuel component, the composition will have a conductivity of about 2-4 microsiemens, which is the approximate conductivity of diesel fuel.
  • compositions of the invention When used as a fuel, compositions of the invention preferably are not acidic since acidity generally causes corrosion in engines. Accordingly, the aqueous phase of compositions of the invention preferably has a pH of greater than about 3, more preferably greater than about 5, and more preferably greater than about 6. The composition as a whole preferably has a pH of greater than about 3, more preferably greater than about 5, and more preferably greater than about 6, as well. The aqueous phase of compositions of the invention preferably has a purity level of at least about 95%.
  • compositions that are aqueous/nonaqueous mixtures having good viscosity values according to preferred embodiments.
  • Viscosity of aqueous-in-nonaqueous emulsions typically increases as the size of isolated phase regions, or micelle, increases.
  • Compositions of the invention include isolated phases of average dynamic diameter, or average cross-sectional dimension low enough that viscosity is low.
  • compositions of the invention have a viscosity of less than about 50 centipoise at 25 ° C according to preferred embodiments.
  • compositions of the invention have a viscosity of less than about 40, more preferably less than about 30, more preferably less than about 20, more preferably still less than about 15 centipoise at 25° C, and most preferably less than 10 centipoise at 25 °C.
  • nonaqueous is meant to define material such as a fluid that is immiscible with water. That is, a liquid that when mixed with water will form a two-phase mixture.
  • the non-aqueous phase need not be liquid, but can be a solid or semi-solid lipid or other nonpolar substance that is not soluble in water.
  • oils such as coconut oil and other hydrocarbons used in cosmetics, moisturizers, and the like are included.
  • non-aqueous phase corn oil, cottonseed oil, soya, fish oil, lanolin, and the like can define the non-aqueous phase.
  • the non-aqueous phase is a combustible, carbonaceous fuel such as gasoline, kerosene, diesel fuel, aviation fuel such as jet fuel, and in some cases petroleum, especially petroleum that is of relatively low molecular weight in its crude form, and the like.
  • “Fuels” is meant to define substances which are combustible in the presence of oxygen and heat to produce energy.
  • Fuels of the invention can include, in general, any products of petroleum distillation that are immiscible with water.
  • the nonaqueous phase can include a mixture of any of a plurality of nonaqueous components, such as are typically found in commercial fuels.
  • the aqueous phase can be any liquid miscible with water, that is, any liquid that, when admixed with water, can form a room-temperature, single-phase solution.
  • the aqueous phase if solid at the temperature being tested, will interact with water to form a water contact angle of less than about 80°.
  • the aqueous phase is water at a purity level of at least about 95%, or preferably at least about 98%, and more preferably still water at a purity level of at least about 99.5%.
  • surfactant defines a molecule that, when combined with an aqueous component and a nonaqueous component, will facilitate assembly of separate aqueous and nonaqueous phases.
  • Surfactants of the invention can be selected from any of a wide variety of known surface-active species in accordance with selection criteria below. Surfactants which can be selected includes those in U.S. Patent Nos. 4,083,698 and 4,821,757, both incorporated herein by reference, as well as commonly-owned, co-pending U.S. application serial no. 08/500,710, filed July 11, 1995 by Ahern, et al., entitled “Combustion of Nanopartitioned Fuel", incorporated herein by reference.
  • alkyl sulfates and quaternaries including heterogeneous polyoxyethylenes, glucamides, digitonin, bile acids, sulfo betaines, betaines, alkyldimethylamine oxides, alkyl glucosides, alkyl maltosides, lecithins and lysolecithins, homogeneous polyoxyethylenes, and alkyl thioglucosides.
  • Particularly preffered classes include polyglyceral-derived esters and ethers, polyethoxylated-derived esters and ethers, polysubstituted amines, aryl and alkyl ethylene oxide adducts,and phenolic ethylene adducts.
  • surfactants that are most preferred do not include nitrogen, sulfur, phosphorous, or acids as these species can raise pollutant levels and/or cause corrosion of engines. Additionally, most preferred surfactants for fuels are low in C-O, C-OH, and C-O-C bonds, which are less-readily combustible than some other species. Accordingly, for fuels it is preferred that these species be minimized.
  • Criteria in accordance with the invention that can be used to select suitable aqueous phases, nonaqueous phases, and surfactants suitable for use in the invention include, first, a simple screening test to determine whether an aqueous-in-nonaqueous emulsion has been created.
  • aqueous phase can be made slightly electrically conductive and, if the emulsion is slightly electrically conductive, then the continuous phase is aqueous, i.e.
  • a nonaqueous-in-aqueous phase results. If the mixture is not electrically conductive, then an aqueous-in-nonaqueous emulsion results.
  • a third screening step if the mixture is optically clear, then very small aqueous aggregates in a nonaqueous, continuous phase has been formed. For example, preferred cross-sectional dimensions and preferred dynamic diameters of emulsions of the invention will exhibit optical clarity. Predictive criteria for surfactant system selection now will be discussed. As used herein,
  • surfactant system defines one or more types of molecules that, when combined with an aqueous component and a nonaqueous component, will facilitate assembly of separate aqueous and nonaqueous phases.
  • a relationship between the balance of hydrophilic and lipophilic portions of a surfactant is matched with the probability, in an overall aqueous component/nonaqueous component mixture, of having a polar group as a nearest neighbor. The relationship is expressed as Equation 1
  • HLB is the approximate minimum hydrophilic/lipophilic balance required in the surfactant.
  • the minimum approximate HLB of the surfactant is matched with the polar neighbor probability of the mixture.
  • the probability of having a polar group as nearest neighbor in the overall aqueous component/nonaqueous component mixture can be determined by one of ordinary skill in the art via a Monte Carlo simulation.
  • the approximate HLB required also can be approximated as follows, especially in the case of a mixture having approximately 30%) or less water.
  • the HLB required according to this method is approximately equal to the molecule volume fraction of water times the energy involved in a bond between a water molecule and a surfactant molecule, considering interactions including hydrogen bonding and Van der Waals interactions, and assuming that the volume of a CH 2 group of a hydrocarbon chain is equal to the volume of a water molecule.
  • the system works as follows. For isooctane, for example, with 20 wt %> water, the probability of having a polar group as the nearest neighbor is 41, therefore the approximate HLB required should be at least 8.26. With 30 wt % water in isooctane the probability is 61, therefore the approximate HLB required is 12.25. For 50 wt % water, the probability is 81, therefore the approximate HLB required is 16.21. If, for example, an ethylene oxide surfactant is being tailored for use with an isooctane/water system, one would select a main hydrocarbon chain that is good for interaction with isooctane, for example a chain length of C5 (pentyl).
  • chain length means degree of CH 2 group present, for example in a branched chain; it is not to be implied that a linear chain need be used, or that a dimension of the molecule is defined by chain length.
  • FIG. 1 illustrates a portion of an aqueous-in- nonaqueous micelle 10 including an aqueous phase 12 separated from a nonaqueous, continuous phase 14 by a partition 16 defined by an aggregation of individual surfactant molecules 18.
  • Surfactant molecules 18 include polar portions 20 that face and/or integrate with aqueous phase 12 and non-polar portions 22 that face and/or integrate with nonaqueous phase 14.
  • Fig. 2 is a schematic illustration of an arrangement similar to that of Fig. 1 but in which a smaller micelle 24 is formed.
  • surfactant molecules must promote smaller micelle formation.
  • surfactant molecules 26 should include smaller polar sections 20, or larger non- polar sections 25, or both, or non-polar sections 25 that are sterically bulkier than non-polar sections 22 of surfactant molecules 18, to encourage spreading of the non-polar sections.
  • This arrangement has its limits, however, and therefore according to one embodiment of the invention a co-surfactant is added that aids in creating smaller micelles by creating spacing between hydrophobic portions of surfactants increasing the radius of curvature achievable with a micelle.
  • an aqueous-in-nonaqueous emulsion 28 is illustrated including an aqueous phase 30, a nonaqueous phase 32, and surfactant molecules 34 separating the phases.
  • the system includes a co-surfactant molecule 36 having a polar portion 38 and a non-polar portion 40.
  • the polar portion 38 of co-surfactant molecule 36 is smaller than the polar portion 33 of surfactant molecule 34 and the non-polar portion 40 of the co-surfactant molecule 36 is smaller than the non-polar portion 35 of surfactant molecule 34.
  • Polar portion 38 of co- surfactant molecule 36 also may be selected to be slightly less polar than polar portion 33 of surfactant molecule 34.
  • co-surfactant molecules 36 will insert to a greater degree between non-polar portions 35 of surfactant molecules 34 and aid in spreading, rather than inserting between polar portions 33 of surfactant molecules 34.
  • Those of ordinary skill in the art can select surfactant molecules suitable for use as co-surfactant molecules 36 based upon these teachings.
  • An additional, relatively non-polar co-surfactant molecule 42 is provided which inserts between non-polar portions 35 of surfactant molecules 34.
  • the relatively non-polar co- surfactant molecules 42 are slightly more polar than the non-polar components that make up nonaqueous phase 32.
  • co-surfactant molecules 42 are not dissolved within nonaqueous phase 32 but are attracted by the polar nature of aqueous aggregate 30 and polar portions 33 and 38 of surfactant molecules 34 and 36, respectively.
  • Co-surfactant molecules 42 are also non-polar to the extent that they are attracted to non-polar portions 35 of surfactant molecules 34.
  • suitable co-surfactant molecules 42 include hydrocarbons of from about C2 to about C20 in size containing sufficient polar heteroatoms or side groups, for example ketone functionalities, to result in chemical attraction sufficient to cause molecules 42 to be retained in the vicinity of aqueous aggregates 30, between non-polar portions 35 of surfactant molecules 34.
  • chemical attraction means bonding such as hydrogen bonding, Van der Waals interaction and the like that causes molecules to remain together rather than integrating into or dissolving within the aqueous component 30 or nonaqueous component 32. This attraction leads to binding.
  • bind is meant to define interaction between two molecules in a manner defined by chemical attraction, about.
  • co-surfactant molecules 36 are stabilizers of the micelle arrangement.
  • "Stabilizer” is meant to define a co-surfactant molecule that, when mixed with a surfactant molecule, will interact with its hydrophilic head group with the arrangement of hydrophilic head groups 33 of surfactant molecules 34 in a manner interfering with any ordered assembly of head groups 33 in a manner that would improve flexibility of the surface of the micelle.
  • the head groups 38 of co-surfactant molecules 36 that are stabilizers interfere with ordered arrangement of head groups 33 of surfactant 34 thereby imparting flexibility to the surface of the aqueous aggregate 30 and stabilizing the system.
  • a preferred class of stabilizers are alcohols ROH, where R is an alkyl chain of from about C2 to about CIO in length. The stabilizer is less polar than the surfactant 35.
  • the non-polar section of surfactant molecules of the invention typically comprises a hydrocarbon chain at least C2 in length.
  • the hydrocarbon chain of the non-polar section is at least C4 in length, more preferably at least C6 in length, and more preferably still at least C8 in length.
  • Another embodiment of the invention is a method of making an aqueous-in-nonaqueous emulsion.
  • the method involves providing a nonaqueous component, and adding a surfactant system to the nonaqueous component to form a mixture. Then, an aqueous component and stabilizer are alternately added to the mixture. That is, the aqueous component is added, then stabilizer, then aqueous component, or stabilizer is added, then aqueous component, and then stabilizer. The aqueous component and stabilizer are alternately added until the emulsion is of proper component ratio.
  • Adding aqueous component and stabilizer alternately prevents the composition from falling into metastable wells by preventing over-concentration of either the aqueous component or stabilizer that could lead to phase separation or gelation.
  • the aqueous component and stabilizer are added, alternately, preferably in amounts less than about 30%o of their total final concentration, more preferably less than about 15% of their total final concentration. Equation 1 , above, and its related discussion can be used to select a combination of surfactant molecules 34 and co-surfactant molecules 36 and/or 42 useful in forming very small micelles.
  • the selectability and predictability of surfactant systems for use in the invention allows use of less wt% surfactant per weight composition or, in another aspect, less surfactant per aqueous content.
  • the surfactant is present in the emulsion in an amount not more than about 40 wt % based on the weight of the composition, more preferably not more than about 30 wt %>, more preferably not more then about 20 wt %>, more preferably not more than about 10 wt % and most preferably not more than about 5 wt %> based on the weight of the composition.
  • the emulsion has an aqueous content of at least 20 wt %> and includes surfactant in an amount of not more than 10 wt %.
  • the emulsion has an aqueous content of at least 30 wt %> and includes surfactant in an amount not more than about 15 wt %>.
  • the emulsion has an aqueous content of at least 40 wt %> and includes surfactant in an amount not more than about 20 wt %>.
  • One class of preferred surfactant molecules have polar sections that can "wrap" about water molecules, that is, polar portions which have the length and flexibility to interweave with water molecules.
  • This arrangement is illustrated in Fig. 4 in which an aqueous-in-nonaqueous micelle 44 is made up of water molecules 46, nonaqueous phase 48, and surfactant molecules 50.
  • the surfactant molecules each include a non-polar portion 52 that interacts with nonaqueous phase 48 and a polar portion 54 having the length, polarity, and flexibility to interweave with water molecules 46.
  • Polar portions 54 of surfactant molecules 50 preferably are created from species that can hydrogen bond with water, and can rotate about single bonds (preferably free of multiple bonds) for flexibility, for example ethylene oxide units.
  • polyethoxylated alcohols such as those of the formula (CH 2 ) x (EO) y where X and Y are each about 2 to about 12 are preferred which can be synthesized by those of ordinary skill in the art using alcohol, an epoxide, and a catalyst that can be of alkaline or acid character.
  • alkaline catalysts are sodium hydroxide, potassium hydroxide, and magnesium oxide.
  • One set of preferred surfactant, co-surfactant, emulsion arrangements include those listed in Table 1 below.
  • Ethylene oxide surfactants offer the advantage of flexible polarity through the manipulation of the number of ethylene oxide units, flexible hydrophobicity through the manipulation of carbon tail chain length, and flexible hydrophilicity through terminal group selection, and the ability to interweave with water molecules.
  • Polyglycerides offer the advantage that particle sizes are particularly small when using the surfactants.
  • Polyethoxylated carboxylic acid surfactants increase overall polarity, and reduce chain length. The use of linear alcohols also is avoided, and high water solubilization is achieved. Viscosity is reduced. Additionally, with these surfactants ethylene oxide wrapping, or interweaving with water is achieved. Polyethoxylated amines do not require the need for co-surfactants and decreased head group volume is achieved. Particles of less than 10 nm are created with these species.
  • a surfactant that has a polar section and a non-polar section in which the polar section includes at least two hydrophilic chains of at least C2 in length that are joined to a non-polar hydrocarbon chain via linkage that is free of N S, and P, are provided.
  • double-chain ethoxylated alcohols can be used which reduce need for co-surfactants by decreasing head group volume with increased polarity and decrease the need for hydrophobic character.
  • Functionality is similar to polyethoxylated amines, although no nitrogen is present, reducing emissions in combustion of fuels.
  • aqueous component of the fuel mixture of the invention is that, by introducing water in the combustion chamber, the temperatures during the cycle are effectively reduced, typically on the order of 200° C. Under lower temperature conditions, the expansion coefficient ⁇ , calculated as the ratio of the heat capacity at constant pressure, Cp, divided by the heat capacity at constant volume, Cv, effectively increases.
  • ⁇ calculated as the ratio of the heat capacity at constant pressure, Cp, divided by the heat capacity at constant volume, Cv
  • the value of ⁇ is increased from 1.25, typical value for diesel engines, to 1.4.
  • the thermal efficiency is increased from 50 to 65%> accounting for an effective 30% increase in overall fuel efficiency.
  • aqueous-in-nonaqueous emulsions of the invention form particularly efficient combustible fuel mixtures due to their participation in a water reforming reaction.
  • the reaction requires a catalyst which can be a metallic surface such as a surface of an internal combustion engine, or an added catalyst.
  • a catalyst such a Si, Al, a transition metal, a rare earth compound, a noble metal, or any oxide, nitride, or carbide of these can be used.
  • the catalyst can be a surface of the combustion chamber of the internal combustion engine.
  • the reaction scheme proceeds as in Equations 3-5, below which equations are intended to represent chemistry taking place in the presence of the catalysts.
  • characterization of emulsions was made using dynamic laser light-scattering techniques.
  • Example 1 Formulation of Stable. Aqueous-in-Nonaqueous Emulsion
  • a clear, stable, fuel-water nanoemulsion was prepared by mixing 80 wt %> of a polyethoxylated alcohol with 20 wt %> of polyglyceryl-4-monooleate at 15° C and 60 RPM for 20 minutes.
  • the alcohol had the formula R(OCH 2 CH 2 ) 6 OH, where R is a C8 paraffinic chain. 18 grams of this mixture were added slowly while stirring to 50 grams of low- sulfur diesel fuel (average carbon chain length of 16) at the same temperature.
  • the mixture showed a viscosity of 12.13 cP, a density of 0.87 g/cc, and micellar average diameter of 7.5 nm at 15° C.
  • Fuel mixtures were prepared in the fashion described in Example 1 , using the following hydrocarbon mixtures instead of diesel: gasoline (C6-C10), kerosene (C10-C14), light diesel (C14-C18), heavy diesel (C12-C24), gasoil, and heating oil (> C24). All formed stable water-in- fuel nanoemulsions.
  • Examples 8-13 Preparation of Water-in-Fuel Emulsions Using Tap Water Fuel mixtures were prepared as in Examples 2-7, using tap water rather than deionized water. Stable nanoemulsions resulted.
  • Emulsions were prepared as in Example 1 , using the systems as in Table 1.
  • Fuel mixtures were prepared as described above with fuel: water ratios (wt %>) of from 1 :1 to 6.5:1. Diesel fuel was used.

Landscapes

  • 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)

Abstract

L'invention porte sur un émulsion eau dans carburant, stable thermiquement et dans le temps, dont la taille des micelles est inférieure à 100 nm et dont la teneur en eau est d'au moins 8 % en poids. Cette émulsion, brûlée comme carburant dans un moteur à combustion interne possède de remarquables qualités de combustibilité et ce, avec une production de suie réduite de manière significative.
PCT/US1997/019368 1996-10-28 1997-10-28 Carburants aqueux de structure nanometrique WO1998018884A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU54259/98A AU5425998A (en) 1996-10-28 1997-10-28 Nanostructured aqueous fuels
EP97948127A EP0934374A2 (fr) 1996-10-28 1997-10-28 Carburants aqueux de structure nanometrique

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US73950996A 1996-10-28 1996-10-28
US08/739,509 1996-10-28

Publications (2)

Publication Number Publication Date
WO1998018884A2 true WO1998018884A2 (fr) 1998-05-07
WO1998018884A3 WO1998018884A3 (fr) 1998-09-03

Family

ID=24972629

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1997/019368 WO1998018884A2 (fr) 1996-10-28 1997-10-28 Carburants aqueux de structure nanometrique

Country Status (3)

Country Link
EP (1) EP0934374A2 (fr)
AU (1) AU5425998A (fr)
WO (1) WO1998018884A2 (fr)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2352246A (en) * 1999-07-17 2001-01-24 Abu Jawdeh Pauline An emulsifier composition for a water in fuel emulsion
US6413489B1 (en) * 1997-04-15 2002-07-02 Massachusetts Institute Of Technology Synthesis of nanometer-sized particles by reverse micelle mediated techniques
WO2004062013A2 (fr) * 2002-12-20 2004-07-22 Exxonmobil Research And Engineering Company Compositions d'emulsion d'un complexe huile dans eau dans huile (o/w/o) destinees a la mise en route de reformeur de cellules electrochimiques
US7094730B2 (en) 2002-10-31 2006-08-22 Delphi Technologies, Inc. Gas treatment device, methods for making and using the same, and a vehicle exhaust system
WO2007054339A1 (fr) * 2005-11-10 2007-05-18 Vortex-Nanofluid Gmbh Dispersion a stabilite a long terme et procede pour produire ladite dispersion
WO2007112967A1 (fr) * 2006-03-31 2007-10-11 Eni S.P.A. Procédé pour la préparation de nanoémulsions eau dans l'huile et huile dans l'eau
WO2007083106A3 (fr) * 2006-01-20 2008-03-13 Palox Offshore S A L Emulsions de type eau dans l’huile, procedes et utilisations d’agents emulsifiants
WO2009068540A1 (fr) * 2007-11-30 2009-06-04 Shell Internationale Research Maatschappij B.V. Formulations de carburant
WO2011015844A1 (fr) 2009-08-05 2011-02-10 Palox Offshore S.A.L. Composition pour la préparation d’une émulsion
WO2011045334A1 (fr) 2009-10-14 2011-04-21 Palox Offshore S.A.L. Protection de combustibles liquides
WO2011095825A1 (fr) 2010-02-05 2011-08-11 Palox Limited Protection de combustibles liquides
WO2013158883A1 (fr) * 2012-04-20 2013-10-24 Broadleaf Energy, Llc. Biocarburant renouvelable
US8883865B2 (en) 2006-09-05 2014-11-11 Cerion Technology, Inc. Cerium-containing nanoparticles
US9221032B2 (en) 2006-09-05 2015-12-29 Cerion, Llc Process for making cerium dioxide nanoparticles
WO2016074904A1 (fr) * 2014-11-10 2016-05-19 Eme International Limited Micro-emulsions de l'eau dans fioul lourd
US9493709B2 (en) 2011-03-29 2016-11-15 Fuelina Technologies, Llc Hybrid fuel and method of making the same
US10143661B2 (en) 2013-10-17 2018-12-04 Cerion, Llc Malic acid stabilized nanoceria particles
WO2019036695A1 (fr) * 2017-08-18 2019-02-21 Fuel Technology Llc Nano-emulsion de l'eau dans le carburant et son procédé de fabrication
US10308885B2 (en) 2014-12-03 2019-06-04 Drexel University Direct incorporation of natural gas into hydrocarbon liquid fuels
US10435639B2 (en) 2006-09-05 2019-10-08 Cerion, Llc Fuel additive containing lattice engineered cerium dioxide nanoparticles
US11015126B2 (en) 2016-12-30 2021-05-25 Eme International Limited Apparatus and method for producing biomass derived liquid, bio-fuel and bio-material
US11084004B2 (en) 2014-11-10 2021-08-10 Eme International Lux S.A. Device for mixing water and diesel oil, apparatus and process for producing a water/diesel oil micro-emulsion

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1983001210A1 (fr) * 1981-09-29 1983-04-14 Patterson, William, P. Emulseur de grande puissance
GB2109405A (en) * 1981-11-12 1983-06-02 Tsai Mao Wu John Fuel oil compositions and use
US4394131A (en) * 1977-10-14 1983-07-19 Entoleter, Inc. Combustion fuel emulsion
US4599088A (en) * 1984-08-30 1986-07-08 Texaco Inc. Clear stable gasoline-alcohol-water motor fuel composition
CH678283A5 (en) * 1989-07-11 1991-08-30 Zugol Ag Low-viscosity water-in-oil emulsions with submicron droplet size - esp. useful as fuels, contain water insol. substance

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4394131A (en) * 1977-10-14 1983-07-19 Entoleter, Inc. Combustion fuel emulsion
WO1983001210A1 (fr) * 1981-09-29 1983-04-14 Patterson, William, P. Emulseur de grande puissance
GB2109405A (en) * 1981-11-12 1983-06-02 Tsai Mao Wu John Fuel oil compositions and use
US4599088A (en) * 1984-08-30 1986-07-08 Texaco Inc. Clear stable gasoline-alcohol-water motor fuel composition
CH678283A5 (en) * 1989-07-11 1991-08-30 Zugol Ag Low-viscosity water-in-oil emulsions with submicron droplet size - esp. useful as fuels, contain water insol. substance

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6413489B1 (en) * 1997-04-15 2002-07-02 Massachusetts Institute Of Technology Synthesis of nanometer-sized particles by reverse micelle mediated techniques
GB2352246A (en) * 1999-07-17 2001-01-24 Abu Jawdeh Pauline An emulsifier composition for a water in fuel emulsion
US7094730B2 (en) 2002-10-31 2006-08-22 Delphi Technologies, Inc. Gas treatment device, methods for making and using the same, and a vehicle exhaust system
WO2004062013A2 (fr) * 2002-12-20 2004-07-22 Exxonmobil Research And Engineering Company Compositions d'emulsion d'un complexe huile dans eau dans huile (o/w/o) destinees a la mise en route de reformeur de cellules electrochimiques
WO2004062013A3 (fr) * 2002-12-20 2004-08-26 Exxonmobil Res & Eng Co Compositions d'emulsion d'un complexe huile dans eau dans huile (o/w/o) destinees a la mise en route de reformeur de cellules electrochimiques
WO2007054339A1 (fr) * 2005-11-10 2007-05-18 Vortex-Nanofluid Gmbh Dispersion a stabilite a long terme et procede pour produire ladite dispersion
EP2343353A3 (fr) * 2006-01-20 2011-11-30 Palox Limited Utilisations d'agents émulsifiants dans des combustibles et huiles non-aqueux
WO2007083106A3 (fr) * 2006-01-20 2008-03-13 Palox Offshore S A L Emulsions de type eau dans l’huile, procedes et utilisations d’agents emulsifiants
US8247359B2 (en) 2006-01-20 2012-08-21 Palox Limited Water-in-oil emulsions, methods and uses of emulsifying agents
EP2343353A2 (fr) 2006-01-20 2011-07-13 Palox Limited Utilisations d'agents émulsifiants dans des combustibles et huiles non-aqueux
WO2007112967A1 (fr) * 2006-03-31 2007-10-11 Eni S.P.A. Procédé pour la préparation de nanoémulsions eau dans l'huile et huile dans l'eau
US8431620B2 (en) 2006-03-31 2013-04-30 Eni S.P.A. Process for the preparation of water-in-oil and oil-in-water nanoemulsions
JP2009538221A (ja) * 2006-03-31 2009-11-05 エニ、ソシエタ、ペル、アチオニ 油中水滴及び水中油滴のナノエマルジョンの調製方法
NO345201B1 (no) * 2006-03-31 2020-11-02 Eni Spa Lavenergi-fremgangsmåte for fremstilling av vann-i-olje og olje-i-vann nanoemulsjoner
US9993803B2 (en) 2006-09-05 2018-06-12 Cerion, Llc Method of preparing cerium dioxide nanoparticles
US8883865B2 (en) 2006-09-05 2014-11-11 Cerion Technology, Inc. Cerium-containing nanoparticles
US10435639B2 (en) 2006-09-05 2019-10-08 Cerion, Llc Fuel additive containing lattice engineered cerium dioxide nanoparticles
US9221032B2 (en) 2006-09-05 2015-12-29 Cerion, Llc Process for making cerium dioxide nanoparticles
WO2009068540A1 (fr) * 2007-11-30 2009-06-04 Shell Internationale Research Maatschappij B.V. Formulations de carburant
US20120165434A1 (en) * 2009-08-05 2012-06-28 Palox Offshore S.A.L. Composition for preparing an emulsion
WO2011015844A1 (fr) 2009-08-05 2011-02-10 Palox Offshore S.A.L. Composition pour la préparation d’une émulsion
WO2011045334A1 (fr) 2009-10-14 2011-04-21 Palox Offshore S.A.L. Protection de combustibles liquides
WO2011095825A1 (fr) 2010-02-05 2011-08-11 Palox Limited Protection de combustibles liquides
US9493709B2 (en) 2011-03-29 2016-11-15 Fuelina Technologies, Llc Hybrid fuel and method of making the same
US9109179B2 (en) 2012-04-20 2015-08-18 Broadleaf Energy, LLC Renewable biofuel
WO2013158883A1 (fr) * 2012-04-20 2013-10-24 Broadleaf Energy, Llc. Biocarburant renouvelable
US10143661B2 (en) 2013-10-17 2018-12-04 Cerion, Llc Malic acid stabilized nanoceria particles
WO2016074904A1 (fr) * 2014-11-10 2016-05-19 Eme International Limited Micro-emulsions de l'eau dans fioul lourd
US10316264B2 (en) 2014-11-10 2019-06-11 Eme International Limited Water in diesel oil fuel micro-emulsions
US11084004B2 (en) 2014-11-10 2021-08-10 Eme International Lux S.A. Device for mixing water and diesel oil, apparatus and process for producing a water/diesel oil micro-emulsion
US10308885B2 (en) 2014-12-03 2019-06-04 Drexel University Direct incorporation of natural gas into hydrocarbon liquid fuels
US11015126B2 (en) 2016-12-30 2021-05-25 Eme International Limited Apparatus and method for producing biomass derived liquid, bio-fuel and bio-material
WO2019036695A1 (fr) * 2017-08-18 2019-02-21 Fuel Technology Llc Nano-emulsion de l'eau dans le carburant et son procédé de fabrication

Also Published As

Publication number Publication date
AU5425998A (en) 1998-05-22
WO1998018884A3 (fr) 1998-09-03
EP0934374A2 (fr) 1999-08-11

Similar Documents

Publication Publication Date Title
EP0934374A2 (fr) Carburants aqueux de structure nanometrique
RU2167920C2 (ru) Эмульгированное топливо, присадочный состав для топлива, способ получения эмульгированного топлива, устройство для его осуществления
EP0754214B1 (fr) Carburant aqueux pour moteurs a combustion interne et son procede d'obtention
CA2708437C (fr) Agents dispersants d'emulsification, methode d'emulsification et de dispersion utilisant lesdits agents dispersants d'emulsification, emulsions connexes et combustibles emulsionnes
US7977389B2 (en) Microemulsions and use thereof as a fuel
EP3218452B1 (fr) Micro-emulsions de l'eau dans fioul lourd
US5997590A (en) Stabilized water nanocluster-fuel emulsions designed through quantum chemistry
Abrar et al. Microemulsion fuels for compression ignition engines: A review on engine performance and emission characteristics
WO1998021294A1 (fr) Emulsions stabilisees de combustibles a nanogroupes aqueux conçues par chimie quantique
JP3819008B2 (ja) 組合せ界面活性剤及び組合せ界面活性剤を使用する炭化水素中水型エマルション
US11634653B2 (en) Droplet for fuels
CN102358854B (zh) 环保型柴油乳化剂
CN104232184A (zh) 一种电气石节能减排添加剂
RU2367683C2 (ru) Топливно-водная эмульсия
Md Ishak et al. Ternary phase behavior of water microemulsified diesel-palm biodiesel
WO2012012644A1 (fr) Carburant émulsionné à trois phases et procédés de préparation et d'utilisation
Bora Formulation of micro-emulsion based hybrid biofuels from non-edible vegetable oil using non-ionic surface active agents
KR19990085956A (ko) 벙커-씨유를 원료로 하는 정제연료유의 제조방법과 그 장치
Onuoha et al. Impact of water‐in‐diesel emulsion on compression ignition engine's emissions and its challenges—A detailed review
CN1023608C (zh) 柴油乳化剂
CN115572630A (zh) 一种微乳化柴油的高效复配表面活性剂及制备工艺
GB2352246A (en) An emulsifier composition for a water in fuel emulsion
CN110177860A (zh) 燃料微滴
RU2253667C1 (ru) Топливная эмульсия сжиженного газа в воде
WO2003016439A1 (fr) Carburant sous forme d'emulsion eau dans l'huile

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AU CA JP

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
AK Designated states

Kind code of ref document: A3

Designated state(s): AU CA JP

AL Designated countries for regional patents

Kind code of ref document: A3

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1997948127

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1997948127

Country of ref document: EP

NENP Non-entry into the national phase in:

Ref country code: CA

WWW Wipo information: withdrawn in national office

Ref document number: 1997948127

Country of ref document: EP