KR20090003360A - Biofuel composition and method of producing a biofuel - Google Patents

Abstract

(A) a continuous phase comprising about 50-95 wt% of at least one liquid oil of vegetable or animal origin or mixtures thereof; (B) a water-containing dispersed phase comprising about 1-50 wt% water; (C) about 1-25 wt% of hydroxyl-containing organic compound selected from the group consisting of mono-, di-, tri-and polyhydric alcohols, provided that when a monohydric alcohol is used there is also present at least one of tert-butyl alcohol, at least one C2-C4 alkylene glycol or a mixture of both; (D) about 0.05-10 wt% of at least one emulsifier; wherein the dispersed water-containing droplets have an average particle size of less than about 20 microns. The biofuel is prepared from these components by mixing under high shear conditions, preferably with ultrasonic energy. The emulsifier(s) preferably exhibit a hydrophilic-lipophilic balance of about 8.5 to about 18 and the biofuel includes a cetane enhancer and mixture of an alcohol and mono-or poly-alkylene glycol.

Description

Biofuel composition and manufacturing method of biofuel {BIOFUEL COMPOSITION AND METHOD OF PRODUCING A BIOFUEL}

Cross reference

This application claims the priority of U.S. Application Serial No. 60 / 795,365, filed April 27, 2006 entitled 'Methods for Manufacturing Biofuel Additives and Biofuels,' the entirety of which is incorporated by reference. Included herein.

Field of technology

The present invention relates to fuel additives, methods of making such additives, and fuel compositions using such additives, wherein the fuel is substantially based on a source of plant or animal.

Efforts to find alternative fuels for petroleum-based fuels such as gasoline and diesel fuel have led to the development of biodiesel fuels. Conventional biodiesel is prepared by transesterification of vegetable oils or fats. In such a process, the vegetable fat or oil is reacted with an esterifying agent, typically an alcohol such as methanol or ethanol, with or without additional catalyst, usually supplying additional energy under atmospheric pressure. The time of the reaction may range from 0.5 hour to 8 hours depending on the temperature.

The terms "oil" and "fat" are often considered synonymous and may be considered chemically interchangeable in the present invention, and the differences between such products are distinguished solely on the basis of their physical state. For example, "oil" is typically used to describe a product that is liquid at ambient or room temperature, and the term "fat" is typically used to describe a product that is substantially solid at room temperature. However, such distinction is somewhat artificial in that it depends on the definition of room temperature. For example, the same product may be considered "fat" at some time of the year at some latitude, and "oil" at other times of the year or at other times of the year. In order not to be confused with other types of oils, these products will be identified as possible to "vegetable or animal oils" or vegetable or animal fats, but, unless the context clearly indicates otherwise, to refer to fats and oils, It is to be understood, for example, to mean a vegetable or animal oil component useful in the present invention as opposed to petroleum, in other words, if any oil derived from petroleum such as diesel oil, gas oil, etc. is present in the composition of the present invention, As an additive or as an auxiliary component, ie, present in an amount of less than 50% by weight, such as in an amount of less than about 40, 30, 20, 10, 5% or even less than 3% by weight; % To about 5%, or 10%, or 15%, or 20%, or 25% by weight.

Fuel derived from conventional vegetable oils, typically used as fuel for diesel engines, is referred to as "biodiesel." Biodiesel is prepared using a chemical reaction known as transesterification. The process forms two main products: fatty acid methyl ester (FAME, chemical name for biodiesel) and glycerin. In this reaction, the vegetable oil or fat is reacted with an esterifying agent, usually alcohol (e.g. methanol or ethanol), generally with additional energy, with or without a catalyst at atmospheric pressure. The reaction time may vary from about 0.5 hours to about 8 hours depending on the temperature and the use of the catalyst. Biodiesel fuel generated in this way and used in 100% pure form (ie, not "diluted" with other fuels, petroleum fuel or ethanol) is referred to as "B 100". When the fuel is diluted with other fuels such as diesel fuel or gas oil, it is typically identified by the percentage of biodiesel present such as B5, B20, B30 and the like. The main physical and chemical properties of conventional biodiesel are as follows: methyl ester content,> 96.5%; Density at 15 ° C., from about 0.86 g / cc to about 0.90 g / cc; Viscosity at 40 ° C., from about 3.5 mm 2 / s to about 5.0 mm 2 / s; Flash point,> 110 ° C; Cetane number,> 51; Net heating value, about 33175 kJ / L (compared to a typical No. 2 diesel fuel, the biodiesel heating value is about 8.65% less than 129,500 compared to 129,500 when compared to BTU / gal).

In addition, conventional biodiesel fuels exhibit different distillation curves than conventional gas oils. This results in a longer and denser flame profile due to the higher viscosity and density of biodiesel compared to petroleum diesel fuels. Such flames can cause operational problems if the pressure of the volumetric fuel pump is not slightly increased, for example from 1 to 1.5 atm. For the same reason, modified fuel nozzles having a form more suitable for the characteristics of the biodiesel should be used; For example, the performance of a 60 ° nozzle that opens in the center is best.

In addition, when using biodiesel, the relationship between primary air and secondary air needs to be further adjusted (adjustment of the combustion head). However, the increase in secondary air improves the low temperature performance of the engine but slightly worsens the equilibrium combustion and vice versa, thus bringing more complexity. Another disadvantage of conventional biodiesel results from the high solvent power of the methyl esters. This can cause damage to incompatible plastics, which are generally present as liners and seals, and can also cause problems due to the deposition of gas oils unknowingly left in the storage tank. Thus, replacement of these polymeric components or at least periodic maintenance of the components is also necessary (including suction and conveying tubes, compression seals of pumps, bending members and liners and seals). Furthermore, cleaning of tanks and heaters to remove all residues of fossil fuels is highly recommended.

Conventional biodiesel mixed with lubricating oils can also cause various problems due to the increased iodine value in the mixture; Iodine is an indicator of organic unsaturation. If the iodine value of the oil is greater than about 115, the mixture is liable to polymerize and a gum deposit may form in the lubrication line, which may inhibit the flow of lubricant. This can make the lubricant of the motor unnecessarily replaced. In addition, because the composition of biodiesel is very different from gas oil, the behavior of biodiesel on exhaust emissions may be significantly different from gas oil, especially with regard to NOx emissions.

When conventional biodiesel is used in an engine with a fuel injector, at least two to three times more deposits are formed in the injector than when gas oil is used. Such deposits are usually carbon deposits and are subject to wear over time, especially for motors in the form of "common rail". However, increasing the injection pressure, for example up to about 100 bar, avoids the deposition problems associated with conventional biodiesel fuel.

Methanol used in the transesterification process results in the addition of minimal amounts of fossil CO _{2 to} the balance of conventional biodiesel. If the source of oil used to make biodiesel is from a renewable source (typically referred to as biomass), it is possible to regenerate all the CO ₂ produced by the combustion of biodiesel. However, the problem of nitrogen oxides, which is considered the most undesirable byproduct of combustion today, is a weakness of conventional biodiesel fuels. On average, NOx emissions are 10-13% higher than gas oils due to the high oxygen content of biofuels. Mixtures containing less than 100% biodiesel also result in an increase in NOx emissions. For example, in B20, the increase rate is about 2-3% compared to gas oil. On the other hand, for B100 CO emissions are on average about 40% less than gas oils, and the B20 biodiesel mixture emits about 15% less CO. Carbon monoxide around the motor does not cause serious problems and can be regarded as a relatively minor pollutant. Carbon monoxide is a kind of poor combustion indicator because oxygen deficiency is the result.

Particulate emissions from the combustion of biodiesel can be related to the chemical composition of the source used for the synthesis of biodiesel and can also be an indicator of combustion related problems. The risks associated with such particulate matter vary depending on the chemical composition and the average dimensions of the particles. In addition, the particulate material may absorb and / or adsorb a certain amount of aromatic material which is considered to be carcinogenic and / or mutagenic to some extent. If the biodiesel is not completely sulfur-free, SO ₂ emissions can be a problem. It is obvious that a mixture of gas oil and biodiesel will increase the amount of SO ₂ released in proportion to the fogging of fossil fuels. The use of conventional biofuels in boilers has not been studied yet. For example, comparing the measurements of particulate emissions from the chimneys of a 1750 kWatt boiler fed with biodiesel, the amount of NOx, SO2 and CO and emissions from the chimneys of the gas oil containing 0.25% by weight of sulfur, Except for NOx, pollutants released from biodiesel appear to be less than those released from gas oil.

Finally, based on raw material prices, biodiesel is significantly more expensive than conventional diesel fuels, for example, based on current European prices. As there are currently government incentives to promote the use of non-petroleum fuels, the final price "at the pump" may be equivalent.

Thus, further improvements in non-petroleum fuels, particularly fuels based on renewable plant sources, are urgently needed, especially where such fuels exhibit acceptable performance characteristics.

In one embodiment, an emulsified biofuel composition suitable for use in diesel engines comprises (A) a continuous phase comprising from about 50 to 95% by weight of one or more liquid oils or mixtures thereof from a plant or animal. phase); (B) a water containing dispersed phase comprising about 1-50% by weight of water; (C) a hydroxyl group-containing organic compound selected from the group consisting of monovalent, divalent, trivalent and polyhydric alcohols, provided that at least one tert-butyl alcohol, at least one C2-C4, if monohydric alcohol is used Alkylene glycol or a mixture of both materials is also present) about 1-25 wt%; (D) about 0.05 to 10 weight percent of one or more emulsifiers; The dispersed water-containing droplets have an average particle diameter of less than about 20 μm. The biofuel is prepared from these components by mixing under high shear conditions, preferably using ultrasonic energy. The at least one emulsifier preferably exhibits a hydrophilic-lipophilic balance of about 8.5 to about 18, wherein the biofuel is a cetane enhancer and a mixture of alcohols and mono- or poly-alkylene glycols. It includes.

In one embodiment, the aqueous phase dispersed in the emulsified fuel comprising the vegetable oil continuous phase exhibits an average droplet particle size of about 0.01 to about 15 μm and the emulsifier (s) has a hydrophilic-lipophilic balance of about 8.5 to about 18 Indicates.

In another embodiment, the emulsified fuel mixture is prepared from the following components: (A) vegetable or animal oils or fats, or mixtures thereof; (B) water; (C) at least one alcohol selected from the group consisting of C1 to C4 alcohols; And (D) at least one surfactant or emulsifier and optionally a supplemental low viscosity, low density combustible liquid selected from the group consisting of hydrocarbon solvents, paint diluents, terpentine, mineral spirits and mixtures thereof. In one embodiment, the latter emulsified fuel mixture can be prepared according to the following method: (I) components (C) and (D) are mixed with each other to prepare an additive, and the additive is combined with water (B). Combine to form mixture (II). To prepare a substantially emulsified mixture, mixture (II) is added to component (A) which is a vegetable oil while simultaneously mixing at a suitable rate.

details

The following terms or phrases used herein have the meanings indicated.

The term "emulsion" means a mixture or dispersion of a liquid which is two non-mixable substances in the present invention, one of which is a dispersed phase dispersed in a continuous phase which is another substance. The emulsion is stabilized, that is to say that the dispersed phase remains dispersed under the aid of one or more substances known as emulsifiers, for example for a suitable time, such as for a storage period and / or immediately before and during use. Emulsions may be water-in-oil emulsions or oils depending on the amount of oil (as well as oil) and water present, the conditions used in the preparation of the emulsion, the type and amount of the emulsifier, the temperature, and combinations of these variables. It may be an oil-in-water emulsion. The particle size or droplet size of the dispersed phase can vary over a significant range, and the emulsion can remain stable, but its properties and suitability for a particular application can vary depending on the particle size of the dispersed phase. Particle size is typically expressed as an average size, since the uniformity of the dispersed phase can also vary with the aforementioned variables. Particle size does not require particles to be spherical, and particle size may be based on the major or average dimensions of each particle, but fluid dynamics in systems involving dispersed liquid phases in a continuous liquid phase ) Suggests that dispersed particles tend to be substantially spherical.

The term "emulsifier" means a compound or mixture of compounds that has the ability to promote the formation of an emulsion and / or to substantially stabilize the emulsion for at least a short time, ie for a time of substantial or commercial interest. Emulsifiers provide stability against significant or substantial aggregation or coalescence of the dispersed phase of the emulsion. Emulsifiers are typically regarded as surface active materials in that they can interact with the two phases at the interface between the dispersed and continuous phases of the emulsion. For the purposes of this specification, "surfactant" and "emulsifier" are considered equivalent or interchangeable terms. In addition, within the scope of the general term, surfactants may be used in various forms of surfactants, such as nonionic, ionic or partially ionic, anionic, amphoteric, cationic and zwitterionic surfactants. Include.

The term "cetane number" means a measure of diesel fuel ignition characteristics, similar to the octane number for gasoline, and likewise higher values indicate better performance. Specific tests have been developed and accepted by the fuel industry, which are defined by various standards setting bodies including, for example, ASTM D613, IP 41 and EN ISO 5165. The test method uses a standard single cylinder, four stroke cycle, variable compression ratio, and indirect injection diesel engine to determine the grade of diesel fuel oil in terms of the arbitrary scale. Although the cetane number scale ranges from 0 to 100, typical test results for diesel fuels and fuels intended for use in diesel applications show cetane numbers in the range of 30 to 65.

The term "flash point" generally refers to how easily a material or composition, typically a fluid, can be ignited or burned. Flash point measurement is defined in test methods maintained by standardization bodies such as the Energy Institute in the UK, the ASTM in the US, the CEN in Europe and the international ISO. For example, for diesel fuel, the test procedure is defined in ASTM D975. The flash point of the fuel is essentially the lowest temperature at which steam from the test portion combines with air to form a combustible mixture and "flashes" when an ignition source is applied. Materials with relatively high flash points are less likely to ignite than materials with relatively low flash points. For example, flash points of 66 ° C. to 93 ° C. (150 ° F. to 200 ° F.) are considered to have a moderately low ignition risk, and flash points of 38 ° C. to 66 ° C. (100 ° F. to 150 ° F.) are considered to exhibit a moderately high ignition risk. . For reference, diesel fuel has a flash point of about 38 ° C. to 54 ° C. (100 ° F. to 130 ° F.), and gasoline has a flash point of about −40 ° C. to −46 ° C. (-40 ° to −50 ° F.). The flash point of a fuel is one property that needs to be considered in determining the suitability of a fuel composition for practical use.

The term "mixing" when used generically or without a modifier includes each of the processes described herein for dispersing one component in another.

The term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary meaning well known to those skilled in the art. Specifically, the term refers to a group having carbon atoms directly bonded to the remainder of the molecule and having mainly hydrocarbon properties. Examples of hydrocarbyl groups include: (1) hydrocarbon substituents, ie aliphatic (eg, alkyl or alkenyl), alicyclic (eg, cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and As well as cycloaliphatic-substituted aromatic substituents, cyclic substituents in which the ring is complete through another part of the molecule (eg, two substituents together form an alicyclic radical); (2) substituted hydrocarbon substituents, i.e. substituents containing non-hydrocarbon groups, in the context of the present invention, substituents which do not change substituents which are predominantly hydrocarbons (e.g. halo (specifically chloro and fluoro), hydroxy , Alkoxy, mercapto, alkyl mercapto, nitro, nitroso, and sulfoxy); (3) hetero substituents, that is, substituents containing atoms other than carbon in a ring or chain composed of carbon atoms while having mainly hydrocarbon properties, are included in the context of the present invention. Heteroatoms include sulfur, oxygen and nitrogen, and also include substituents such as pyridyl, furyl, thienyl and imidazolyl. Generally, there are up to two, preferably up to one non-hydrocarbon substituents for every ten carbon atoms in the hydrocarbyl group; Typically, there are no non-hydrocarbon substituents in the hydrocarbyl group.

The term "lower" is used to describe groups containing up to seven carbon atoms in total when used in combination with terms such as alkyl, alkenyl and alkoxy.

In the description set forth below, "oil" generally refers to vegetable oils, oils derived from animals, mixtures of oils derived from plants and animals, and also includes recycled products thereof. Unless otherwise indicated by the context of the description, the term "vegetable oil" is to be understood to include references to oils of animal origin and mixtures of plant and animal oils.

The term "stable" or "stable" refers to a dispersed or hydrophilic phase that, when used to refer to an emulsion, remains substantially dispersed in a lipophilic phase (vegetable and / or animal oils and / or fats). That is, substantially no phase separation as indicated by visual observation after a period of at least about 24 hours, preferably at least about 48 hours, more preferably at least about 72 hours after preparation of the emulsion; Substantially no phase separation is observed even after at least about 4 days have elapsed at ambient temperature suitable for use in emulsified fuel compositions, for example for use in burners, automobiles and the like. Alternatively, the stability can be characterized by measuring sediment formation according to the ASTM D96 test method.

The composition of the invention, characterized as a fuel composition for the purposes of the present invention and referred to as "biofuel", is not only suitable for use in internal combustion engines, preferably various types of diesel engines, but also includes gas or combustion turbines. It is suitable for use in a device for burning fuel to generate heat such as a heating furnace, a boiler, a power generation facility, and the like. Diesel engines that can be operated by the compositions of the present invention include all compression-ignition engines used in both mobile power plants (including locomotives and ships) and stationary power plants. This includes diesel engines in the form of two strokes per cycle and four strokes per cycle. Such diesel engines include, but are not limited to, light duty and heavy duty diesel engines, on- and off-highway engines, new engines as well as engines in use. The diesel engine includes those used in passenger cars, trucks, buses including city buses, locomotives, stationary generators, and the like. For example, with regard to use in burners, the compositions of the present invention include sleeve burners, natural draft port burners, forced draft port burners, rotating wall flame burners, air-spray and pressure-spray gun burners, and Useful in various types of oil burners for other heating purposes; Especially in the United States, the latter type of burner is the most commonly used burner for home heating. In particular, the compositions are fuels useful for diesel motors (both new and used generators) and / or boilers and one-stage or multistage burners, also referred to in the art as staged burners.

Various mixing devices that are well known in the art can be used to facilitate the formation of the emulsifying composition of this embodiment, and the present invention generally utilizes, for example, a high speed rotor that typically operates in close proximity to the stator. Mixer-emulsifiers (e.g., Charles Ross & Sons Co., NY), paddles with various design shapes, such as reverse pitch, anchor, leaf, gate paddle mixers using paddles such as gate, finger, double-motion, helical and the like, and placement and in-line equipment and the like. The present embodiment and other mixing methods generally useful in the present invention are further described below. The processes of the various embodiments of the present invention can be performed, for example, at an ambient temperature of about 20 ° C. to about 22 ° C., even 25 ° C. or at room temperature. The mixing time and temperature can be varied until the desired emulsifying composition is obtained and used properly on the basis of subsequent observations and / or tests, and during use. Under conditions where sediments may form after mixing the components of the fuel composition, it may be desirable to settle and then wait for some time for such sediments to be removed or separated from the emulsified fuel composition. Typically, such time is at least about 4 minutes, preferably about 5 minutes; More preferably about 6 minutes or more. Preferred times can be readily determined by defined simple experiments, and such times can be adjusted based on other components of the mixture including the emulsifier (s), including, for example, the form, quality and composition of the vegetable oil used.

Mixing methods in addition to those described above are suitable for use in the present invention and in some cases are particularly preferred. The mixture may be prepared using conventional mixing or blending apparatus such as a batt or tank equipped with a motor driven stirrer with various shapes, such as paddles, helix and the like. Mixing performed in such an apparatus is time consuming and often requires a mixing time of more than 10 minutes to obtain a uniform and stable emulsion, for example about 10 minutes to about 30 minutes, or about 15 minutes to about 20 minutes. Takes However, such emulsions may have an average particle size such as a diameter or average dimension greater than about 20 μm; For example about 20 to about 50 μm; Or about 20 to about 35 microns of dispersed particles. Emulsions having an average particle size of at least about 20 μm are referred to herein as " macroemulsions. &Quot; Fuel compositions with macroemulsion properties typically exhibit different properties from those of the same fuel composition with significantly smaller average particle sizes, ie, microemulsions or particle sizes of less than about 20 μm, such as 19 μm or less. For example, a given composition in the form of a macroemulsion is not only prolonged in the recycling of the fuel composition to produce a satisfactory and stable emulsion compared to the same composition in the form of a microemulsion, but more in processes requiring a greater amount of emulsifier. High viscosity, lower flash point and poor stability.

In a preferred method, the fuel mixture of the present invention is ultrasonic, for example an apparatus which is a particularly advantageous device for the preparation of stable emulsions, ie microemulsions, having a small particle size of on average less than about 10 μm, or from about 0.01 to about 5 μm. It is made using a mixing device. A preferred device of this type is Sonic Corp., Connecticut. A commercially available product "Sonolator" ultrasonic homogenization system. Such microemulsions can be prepared at ambient temperatures, such as about 22 ° C., and pressures from about 500 psi to about 1500 psi, but stable microemulsions can be produced using high pressures up to 5000 psi. Sonolator systems are particularly useful in that they can be operated in other useful ways, including semi-continuous, continuous, single-feed or multiple-feed modes. The system, in particular operating in a multi-feed mode, can utilize feed tanks containing, for example, vegetable oils, water, emulsifiers and other components such as alcohols, cetane enhancers, alkyl glycols or alkyl glycol derivatives. With such a system, one or more components may be fed simultaneously, sequentially or intermittently to obtain particularly desirable results including, but not limited to, particular emulsion particle sizes, particle size distributions, mixing times, and the like. As mentioned above, fuel compositions prepared using ultrasonic emulsification can be obtained using lower concentrations of emulsifiers for the same concentrations of other components, especially vegetable oil (s) and water. For example, if a composition prepared without an ultrasonic mixing process requires about 1.0% by weight of an emulsifier to obtain a satisfactory emulsion, it is enhanced in that a satisfactory emulsion, preferably a smaller particle size, results in a microemulsion. Only less than about 0.5% by weight emulsifier may be needed in the same composition to obtain a prepared emulsion. Typically, the amount of emulsifier is about 10% less than the amount required in the absence of ultrasonic emulsification, preferably about 20%, more preferably about 30%, even more preferably about 40% less; For example, about 50%, 60%, 70%, 80% or even 90% less than the amount of emulsifier required for a satisfactory emulsion without supplying ultrasonic energy. For example, an emulsified fuel composition that requires 1% by weight of an emulsifier to obtain an average emulsion particle size of about 20 μm may be 0.2% by weight of the same emulsifier in the same composition to obtain an emulsion having a particle size of about 5 μm. Can be replaced. For the purposes of the present invention, the use of an apparatus for introducing ultrasonic energy for mixing and emulsification is referred to as a "high shear" method, which differs from a physical process that can occur on an ultrafine or molecular scale. Irrelevant

For example, emulsification with high shear imparted by an ultrasonic device may have an average particle size or droplet size in the range of about 0.01 μm to about 20 μm; Such as about 0.01 to about 15 μm; Or about 0.1 to about 10 μm; About 0.1 to about 8 microns; About 0.2 to about 6 microns; About 0.5 to about 5 microns; About 0.5 to about 4 μm; About 0.5 to about 3 μm; About 0.5 to about 2 μm; About 0.1 to about 2 μm; About 0.1 to about 1 μm; Or an emulsion that is about 0.1 to less than about 1 μm, for example about 0.8 μm. According to a preferred embodiment of the invention, the dispersed phase or water containing phase of the fuel composition comprises droplets having an average diameter or major dimension of 5 μm or less. As such, emulsification is performed under conditions sufficient to provide such average droplet particle size.

High shear devices that can be used include, but are not limited to, Sonolator homogenization systems from Sonic Corporation, where the pressure can vary, for example, in a wide range from about 500 to about 5,000 psi; IKA Work Dispax, and shear mixers comprising multiple stages, such as a three stage rotor / stator combination. The tip speed of the rotor / stator generator can be varied by a variable frequency drive controlling the motor. Similarly, the Silverson mixer, a two-stage mixer with a rotor / stator design, uses high-capacity pumping characteristics similar to centrifugal pumps. In-line shear mixers include rotor-stator emulsification methods (Silverson Corporation); Jet mixers, venturi-type / cavitation shear mixers; Microfluidizer shear mixers; High pressure homogenization shear mixer (Microfluidics Inc.); And any other available high shear generation mixer capable of producing the desired microemulsion, which also includes an Aquahear mixer (Flow Process Technologies Inc.), a pipeline static mixer. ), A hydraulic shear device, a rotary shear mixer, an ultrasonic mixer, and a combination thereof, a high shear mixer selected from the group consisting of.

Mixing of the components is preferably carried out at ambient temperature conditions, or substantially at ambient temperature conditions. In some cases it has been observed that mixing to obtain an emulsified fuel composition is accomplished by some exothermic response. The mixing may be at a temperature in the range of about 5 ° C. to about 75 ° C., for example about 10 ° C. to about 65 ° C .; Or about 15 ° C. to about 55 ° C .; Or about 20 ° C. to about 45 ° C .; It may be satisfactorily carried out at temperatures in the range of 22 ° C. to about 35 ° C.

The water used in the compositions of the present invention may be provided from any source. The water used in the preparation of the fuel composition of the present invention may be deionized, for example purified using reverse osmosis or distillation, and / or desalted to dissolve dissolved minerals such as salts of calcium, sodium and magnesium Is contained in a low content, likewise contains very little chlorine and / or fluorine and is substantially free of undissolved particulate matter. Preferably, the water is substantially desalted by methods well known to those skilled in the water treatment field to remove dissolved inorganic salts, and is also treated to remove other additives or chemicals, including chlorine and fluorine. It is. It is anticipated to improve the conditions of metal surfaces in engines and burners, in particular of inner surfaces of cylinders and nozzles, by substantially free of such materials. The water may be present in the water-vegetable oil fuel emulsion at a concentration of about 1% to about 50% by weight; Or about 2 wt% to about 50 wt%; About 3 wt% to about 40 wt%; About 4 wt% to about 35 wt%; And from about 5% to about 30% by weight.

Fuels useful in the present invention are based on animal oils and fats as well as vegetable oils and fats, and mixtures thereof. Vegetable oils and fats are substances present in various percentages in seeds or berries of various plants. In addition to those typically available in nature, the present invention can utilize vegetable oils and fats obtained from genetically treated plants, which are particularly high so as to be particularly preferred sources of algae and materials used as fuel. Included are those that can be developed to yield levels of oils and fats. Since the fats and oils will be used in the compositions of the present invention and burned as fuel, such fats and oils do not necessarily have to be edible. Currently, the oils which are particularly useful in the present invention as the most common and commercially available vegetable oils are peanuts, sunflowers, soybeans, sesame seeds, rapeseeds (although similar in nature to rapeseed oils, but the oilseed rape plants (Brassica campestris, var. Oleifera). ), Seeds of rapeseed or canola, corn and cotton, and fruits of palm, olive and coconut. Fatty substances may be obtained by treating the whole fruit (eg olive oil), pulp (palm oil), or only nuclei (palm seed oil). All such plant based or plant derived oils are examples of suitable oils for use in the present invention. Other vegetable oils that may be useful in the present invention include, in Rome, 1992, such as crambe oil, jatropha oil, linseed oil, tung oil, and oils generally including: FAO Agricultural Services Bulletin No. of the United Nations Food and Agriculture Organization Other so-called small oil harvests described in 94 (incorporated herein by reference) include: argan in small amounts of edible oil harvest; avocado; Babassu palm; Balanite; Borneo tallow nut; Brazil nuts; Caryocar spp .; Cashew nut; Chinese vegetable tallow; Cohune palm; Cucurbitaceae and plants, including gourd, buffalo goad, fluted pumpkin and marrow; Smooth loofah; Grape seed; Elipe; Kusum; Macadamia nut; Mango seed; Noog abyssinia; Nutmeg; Perilla; Pili nut; Rice bran; Cuphea spp .; Seje; Shea nut; And teased. Among the small amounts of non-edible oil harvests are: alanblackia; almond; Chaulmoogra; Cupia species; Jatropa curgas; Karanja seed; Neem; papaya; Tonka beans; Tung; And yucuuba. Vegetable oils are obtained from their plants, seeds, etc., by methods well known in the art, including mechanical or solvent extraction, including mechanical extraction or compaction, and typically remove unnecessary materials to deliver substantially clean products. It is filtered to However, it is within the scope of the present invention that used vegetable oils or fats from commercial sources can also be used, including for example food frying operations.

In addition, oils and fats useful in the present invention can be obtained from a source derived from an animal. Such animal derived or extracted oils include, but are not limited to, animal tissue extracts, fish oils (piscine oils), cod liver and shark liver oils, general fish oils, and fish oils currently promoted by the Alaskan fisheries. A wide variety of oil-containing fish, tallows and mixtures thereof can be cultured for the purpose. For the purposes of the present invention, tallow refers to cattle, sheep, bulls, horses, chickens, other birds raised for food purposes, and the like, and similar fats such as those obtained from plants are also called tallows. Large amounts of animal derived fats and oils can be obtained as a by-product from meat livestock processing facilities. Mixtures of oils and fats obtained from plant and animal sources are also useful in the present invention.

In addition to, or as part of, the categories of oils and fats derived from plants and animals, oils and fats derived from renewable oils and greases, usually from restaurants and food processing plants, are also included. Such fats and oils may originally be derived from plant or animal sources. Oils and fats from these sources may require some pretreatment using methods well known to those skilled in the art to remove food and other particulate matter, and to lower acidity from free fatty acids or sulfur containing compounds that may be present. It should be understood, however, that it can also be useful.

Surfactants are known to increase the stability of emulsions. Surfactants can be used according to the invention, in particular, to increase the stability of fuel-water emulsions over time. The following table shows examples of surfactants envisioned by the present invention, but useful surfactants are not limited to those listed in the table. For example, as disclosed in the comprehensive list of surfactants found in the spectral database of Bio-Rad Laboratories (www.informatics.bio-rad.com), including the infrared spectrum, and in many cases, by reference Chemical compositions, chemical and physical properties and sources included herein are also useful. The compounds generally include alcohols, nitrogen containing compounds, esters of long chain carboxylic acids, hydrocarbons, various esters and salts of long chain carboxylic acids, alkylaryl sulfonate isothionates, lignosulfonates, sulfated and sulfonated alcohols. Sulfated and sulfonated compounds, amines, amides, carboxylic acids, carboxylic acid esters, sulfated and sulfonated polyalkoxylated materials such as esters, ethers, nitrogen compounds, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepenta Aminopolycarboxylic acids such as acetic acid (DTPA) and nitrilotriacetic acid (NTA), namely EDTA, DTPA, NTA acid and salts, phosphates, silicates and silicones. In the sense that particular surfactants include atoms, groups or compounds that can cause unwanted contamination such as sulfur, their use may be limited to the amount necessary to produce and / or maintain a stable emulsion or fuel composition. Particularly preferred surfactants include cetyl alcohol, hydrogenated perm oil and a mixture of cetyl alcohol and hydrogenated castor oil. The following materials, referred to herein as surfactants, can be used according to the water-fuel composition of the present invention.

List of Useful Surfactants

(A) Nonionic Surfactants:

Esters of polyhydric alcohols; Alkoxylated amides; Esters of polyoxyalkylenes, polyoxypropylenes and polyoxyethylene-polyoxypropylene glycols; Esters of polyoxyalkylene glycols; Tertiary acetylene glycol; And polyoxyethylated alkyl phosphates.

(B) anionic surfactants:

Carboxylic acids and soaps; Sulfated esters, amides, alcohols, ethers and carboxylic acids (all salts); Sulfonated petroleum, aromatic hydrocarbons, aliphatic hydrocarbons, esters, amides, amines, ethers, carboxylic acids, phenols and lignin (all salts); Acylated polypeptides (salts); And phosphates.

The following specific compounds are also included. In the list below, the abbreviation "P.O.E." means polyoxyethylene (polyethylene glycol) and the abbreviation "P.O.P." means polyoxypropylene.

(C) fatty acids:

Caprylic acid, abiesic acid, pelagonate, coconut oil fatty acid, capric acid, corn oil fatty acid, lauric acid, cottonseed oil fatty acid, myristic acid, soybean oil fatty acid, palmitic acid, tallow fatty acid, stearic acid, Hydrogenated fish oil Fatty acid, behenic acid, toll acid fatty acid, undecylenic acid, dimer acid, oleic acid, trimeric acid, erucic acid, palma oil, linoleic acid, hydrogenated castor oil, lishi Nooleic acid, lanolin, naphthenic acid, and lanolin fatty acids.

(D) fatty acid salts:

Lithium Stearate, Ammonium Olate, Tadmium Stearate, Sodium Caprate, Ammonium Linoleate, Calcium Stearate, Sodium Laurate, Ammonium Ricinolate, Calcium Olate, Sodium Myristate, Ammonium Naphthenate, Calcium Linoleate , Sodium palmitate, ammonium abietate, calcium ricinolate, sodium stearate, morpholine laurate, calcium naphthenate, sodium undecylenate, morpholine myristate, cobalt stearate, sodium oleate, morpholine palmi Tate, cobalt naphthenate, sodium linoleate, morpholine stearate, cupper oleate, sodium naphthenate, morpholine oleate, cupper naphthenate, sodium abietate, morpholine linoleate, iron stearate, polymerization Sodium carboxylate, morpholine ricinolate, iron naphthenate, Morpholine naphthenate, red stearate, sodium salt of tall oil, morpholine abietate, red oleate, potassium caprate, triethanolamine caprate, red naphthenate, potassium laurate, triethanolamine Laurate, magnesium stearate, potassium myristate, triethanolamine myritate, magnesium oleate, potassium palmitate, manganese stearate, potassium stearate, triethanolamine palmitate, manganese naphthenate, potassium undecylenate, Triethanolamine stearate, nickel oleate, potassium oleate, strontium stearate, potassium linoleate, triethanolamine undecylenate, tin oleate, potassium ricinolate, zinc laurate, potassium naphthenate, triethanolamine oleate, Zinc Palmitate, For Calcium abietate, triethanolamine linoleate, zinc stearate, ammonium caprate, triethanolamine ricinolate, zinc oleate, ammonium laurate, zinc linoleate, ammonium myristate, triethanolamine naphthenate, zinc naphthenate , Ammonium palmitate, zinc lysinate, ammonium stearate, triethanolamine abietate, ammonium undecylenate, aluminum palmitate, aluminum stearate, aluminum oleate, barium stearate, and barium naphthenate.

(E) olefins:

Straight chain C ₁₄ alpha-olefins, and straight chain C ₁₆ alpha-olefins.

(F) phosphorus compounds and mercaptans:

POE octyl phosphate, sodium phosphated castor oil, ammonium phosphated castor oil, 2-ethylhexyl polyphosphate sodium salt, capryl polyphosphate sodium salt, sodium di (2-ethylhexyl) phosphate, lecithin (soy phosphide), And POE tert-dodecylmercaptoethanol.

(G) polyethylene and propylene glycol esters:

Hydroxyethyl laurate, PEG monooleate, propylene glycol monolaurate, hydroxyethoxyethyl laurate, PEG dioleate, ethylene glycol monoricinoleate, propylene glycol monostearate, hydroxy ethoxyethoxy ethyl laurate Latex, diethylene glycol monoricinoleate, propylene glycol dilaurate, PEG monolaurate, PEG monoricinolate, propylene glycol distearate, PEG dilaurate, diethylene glycol cotonate, ethylene glycol monostearate, Dipropylene glycol monostearate, POE caco fatty acid ester, diethylene glycol monostearate, propylene glycol monooleate, POE castor oil, triethylene glycol monostearate, ethylene glycol hydroxystearate, propylene glycol monorisinate, PEG mono Stearate, PEG trihydroxy stearate, propylene glycol monoisostearate, ethylene glycol distearate, POE hydrogenated castor oil, propylene glycol monohydroxystearate, PEG distearate, POE tall oil, PEG monoisostea Latex, POE abiate, propylene glycol dipellagonate, PEG diisostearate, POE lanolin, hydroxyethyl oleate, acetylated lanolin, isopropyl ester of lanolin fatty acid, hydroxyethoxyethyl oleate, acetylated POE Lanolin, methoxy PEG monooleate, POE propylene glycol monostearate, and hydroxy ethoxyethoxy ethyl oleate.

(H) alcohols, phenols and polyoxyethylene derivatives:

Stearyl alcohol, oleyl alcohol, octyl phenol, nonyl phenol, tert-octylphenoxy ethanol, p-dodecyl phenol, dinonyl phenol, tridecyl alcohol, tetradecyl alcohol, lanolin alcohol, cholesterol, dimethyl hexinol, dimethyl octin Diol, tetramethyl descindiol, POE tridecyl phenyl ether, POE lanolin alcohol ether, POE cholesterol, POE n-octylphenol, POE tert-octylphenol, POE nonylphenol, POE dinonyl phenol, POE dodecyl phenol, POE ranol Usyl alcohol ether, POE cetyl alcohol ether, POE stearyl alcohol ether, POE tetramethyldecyndiol, POE oleyl alcohol ether, POP EtO, POE isohexadecyl alcohol ether, 2,6,8-trimethyl-4-nonyloxypolyethylene Oxyethanol, polyoxypropylene-polyoxyethylene block copolymers, alkyl ethers of POE / POP, and POE tridecyl alcohol ethers.

(J) Glycerol Esters:

Glycerol Monocaprylate, Glycerol Monolaurate, Glycerol Mono / Dicocoate, Glycerol Dilaurate, Glycerol Monostearate, Glycerol Monostearate Distilled, Glycerol Distearate, Glycerol Monooleate, Glycerol Diol Glycerol trioleate, glycerol monoisostearate, glycerol monorisinate, glycerol monohydroxystearate, POE glycerol monostearate, acetylated glycerol monostearate, succinylated glycerol monostearate, diacetylated glycerol Monostearate tartrate, modified glycerol phthalate resin, trisleycerol monostearate, triglycerol monooleate, triglycerol monoisostearate, decaglycerol tetraoleate, decaglycerol decastarate, Pentaerythritol monolaurate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tetrastearate, pentaerythritol monooleate, pentaerythritol dioleate, pentaerythritol trioleate, pentaerythrate Lithol tetraricinolate, sorbitan monolaurate, POE sorbitan monolaurate, sorbitan monopalmitate, POE sorbitan monopalmitate, sorbitan monostearate, POE sorbitan monostearate, sorbitan tristearate , POE sorbitan tristearate, sorbitan monooleate, POE sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, POE sorbitan trioleate, POE sorbitan hexaoleate, POE sorbitol allol Laurate, POE sorbitol polyoleate, POE sorbitol, wheat Beeswax-ester, sucrose monolaurate, sucrose cocoate, sucrose monomyristate, sucrose monopalmitate, sucrose depalmitate, sucrose monostearate, sucrose distearate, su Cross monooleate, sucrose dioleate, lauryl lactate, cetyl lactate, sodium lauryl lactate, sodium stearoyl lactate, sodium isostearole-2-lactylate, sodium stearoyl-2- Lactylate, calcium stearoyl-2-lactylate, sodium capryl lactate, lauryl alcohol, and cetyl alcohol.

(K) Amides and Amide Derivatives:

Stearamide, oleamide, erucamide, behenamide, lauric monoethanolamide, tallow monoethanolamide, POE lauric amide, myritic acid diethanolamide, stearic acid diethanolamide, oleic acid diethanolamide, POE Oleic amide, cocoic acid diethanol amide, POE cocoamide, POE hydrogenated tallow amide, lauric acid monoisopropanolamide, and oleic acid monoisopropanolamide.

(L) sulfate:

Sodium n-octyl sulfate, sodium 2-ethylhexyl sulfate, sodium decyl sulfate, sodium lauryl sulfate, sodium tridecyl sulfate, sodium sec-tetradecyl sulfate, sodium cetyl sulfate, sodium sec-heptadecyl sulfate, sodium oleyl sulfate, Sodium oleyl stearate sulfate, sodium tridecyl ether sulfate, potassium lauryl sulfate, magnesium lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, diethanolamine lauryl sulfate, triethanol ammonium lauryl sulfate, POE octylphenol Sodium salt, alkylaryl polyether sulfate sodium salt, sulfated POE nonylphenol sodium salt, sulfated nonylphenyl ether of tetraethylene glycol ammonium salt, sulfated lauryl ether of tetraethylene glycol sodium salt, POE sodium lauryl monoether sulfate, POE Sodium lauryl ether sulfide Pate, POE ammonium lauryl sulfate, sulfated sodium oleate, sulfated castor oil-fatty acid sodium salt, sulfated propyloleate sodium salt, sulfated isopropyloleate sodium salt, sulfated butyloleate sodium salt, sulfated Glycerol monolaurate sodium salt, sulfated glycerol trioleate sodium salt, sulfated castor oil sodium salt, sulfated marine oil, sulfated neatsfoot oil sodium salt, sulfated rice bean oil (rice bean oil) sodium salts, sulfated soybean oil sodium salts, sulfated synthetic stem oils, and sulfated tallow sodium salts.

(M) other surfactant compounds:

Perfluoro anionic surfactant (surfactant-anionic), perfluoro cationic surfactant (surfactant-cationic), ethylenediamine tetraacetic acid disodium salt, ethylenediamine tetraacetic acid tetrasodium salt, sodium dihydroxyethyl glycinate , Trisodium nitrilotriacetate, sodium citrate, silicone defoamer-oil, silicone defoamer-water dispersible, sodium tetraborate, sodium carbonate, tribasic sodium phosphate, sodium silicate, and alkyl Benzene sulfonic acid-propylene tetramer.

(N) sulfonates:

Sodium toluene sulfonate, sodium xylene sulfonate, sodium cumene sulfonate, sodium dodecylbenzene sulfonate, sodium tridecylbenzene sulfonate, sodium kerylbenzene sulfonate, calcium dodecylbenzene sulfonate, ammonium xylene sulfonate, triethanol ammonium dode Silbenzene sulfonate, alkylammonium dodecyl-benzene sulfonate, aliphatic hydrocarbon-sulfonic acid, sodium petroleum sulfonate, calcium petroleum sulfonate, Briton barium sulfonate, magnesium petroleum sulfonate, ammonium petroleum sulfo , Isopropylamine petroleum sulfonate, ethylenediamine petroleum sulfonate, triethanolamine petroleum sulfonate, sulfated naphthalene sodium diisopropyl naphthalene sulfonate, sodium dibutyl naphthalene sulfonate, sodium benzyl naphthalene sulfonate, sodium naphthalene Formaldehyde Condensate sulfonate, sodium polymerized alkylnaphthalene sulfonate, potassium polymerized alkylnaphthalene sulfonate, ammonium dibutylnaphthalene sulfonate, ethanolamine dibutylnaphthalene sulfonate, sodium sulfolate, sodium monobutylphenylphenol monosulfo Acetate, disodium dibutylphenylphenol disulfonate, potassium monoethylphenylphenol monosulfonate, ammonium monoethylphenylphenol monosulfonate, guanidinium monoethylphenylphenol monosulfonate, sodium decyldiphenylether disulfonate, Sodium dodecyldiphenylether disulfonate, calcium polymerized alkyl-benzene sulfonate, sulfonated polystyrene, sulfonated aliphatic polyester, sodium-2-sulfoethyl oleate, sodium amyl sulfolate, sodium lauryl sulfoacetate, sodium Diisobutyl sulfosuccinate, sodium diamyl sulfosuccinate, sodium dihexyl Sulfosuccinate, sodium dioctyl sulfosuccinate, sodium ditridecyl sulfosuccinate, sodium alkylarylpolyether sulfonate, and sodium lignosulfonate.

(O) amines and amine derivatives:

tert-C ₁₁ -C ₁₄ amine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine, C ₁₈ -C ₂₄ amine, oleylamine, cocoamine, hydrogenated talal Low amine, tallow amine, POE tert-amine, POE stearyl amine, POE oleyl amine, C ₁₂ -C ₁₄ tert-alkylamine, ethoxylated POE cocoamine, POE tallow amine, POE soya amine, POE octadecyl Amine, Nb-hydroxyethyl stearyl imidazoline, POE (3) N-tallow trimethylene diamine, Nb-hydroxyethyl cocoimidazoline, Nb-hydroxyethyl oleyl imidazoline, n-dodecyl Amine acetate, hexadecylamine acetate, octadecylamine acetate oleylamine acetate, cocoamine acetate, hydrogenated tallow amine acetate, tallow amine acetate, soya amine acetate, N-stearyl-N ', N'-diethyl Ethylene-diamine acetate, N-oleylethylenediamine formate, Coamidopropyl dimethyl amine oxide, lauryl dimethylamine oxide, myristyl dimethylamine oxide, soya amine, diocoamine, dihydrogenated tallow amine, dimethyl hexadecylamine, dimethyl octadecylamine, dimethyl cocoamine, Dimethyl soyaamine, N-coco-1,3-diaminopropane, N-soya-1,3-diaminopropane, N-tallow-1,3-diaminopropane, N-coco-b-aminobutyric acid, Stearamidoethyl diethylamine, sodium-N-coco-b-amino propionate, N-tallow trimethylene diamine diacetate, disodium-N-tallow-b-imino dipropionate, disodium -N-lauryl-b-imino dipropionate, cetyl betaine, coco betaine, myristamidopropyl betaine, oleyl betaine, coconut amido betaine, oleyl amido betaine, sodium Coconut oil acid ester of isothionate, cocoamido alkyldi Methylamine, behenic amido alkyl dimethylamine, isostearic amido alkyl dimethylamine, oleic amido alkyl dimethylamine, sodium-N-methyl-N-palmitoyl taurate, sodium-N-methyl-N-ole Yl taurate, sodium-N-coconut acid N-methyl taurate, sodium-N-methyl-N-tol oil taurate, N-lauryl sarcosine, cocoyl sarcosine, N-oleyl sarcosine, sodium- N-lauryl sarcosinate, sodium carboxymethylnonylhydroxy-ethyl imidazolinium hydroxide, sodium carboxymethyl undecylhydroxy-ethyl imidazolinium hydroxide, sodium carboxymethyl cocohydroxy-ethyl imi Dazolinium hydroxide, sodium carboxyethyloleylhydroxy-ethyl imidazolinium hydroxide, sodium carboxymethylstearylhydroxy-ethyl imidazolinium hydroxide, and sodium carboxymethylsodiumcarbox Dipty-ethyl cocoether imidazolinium.

(P) quaternary amine salts:

Dodecyltrimethyl ammonium chloride, hexadecyltrimethyl ammonium chloride, octadecyltrimethyl ammonium chloride, cetyltrimethyl ammonium bromide, cetyldimethylethyl ammonium bromide, coco trimethyl ammonium chloride, tallow trimethyl ammonium chloride, soya trimethyl ammonium chloride, dico dimethyl ammonium chloride , Dimethyl 80% behenyl benzyl ammonium chloride, methyl bis (2-hydroxyethyl) coco ammonium chloride, dihydrogen tallow dimethyl ammonium chloride, methyldodecylbenzyl trimethyl ammonium chloride, n-alkyl dimethyl benzyl ammonium chloride, alkyldimethyl -3,4-dichlorobenzyl ammonium chloride, octylphenoxyethoxyethyl dimethylbenzyl ammonium chloride, octylcresoxyethoxyethyl dimethylbenzyl ammonium chloride, cocoamidopropyl PG-dimonium Chloride phosphate, 2-hydroxyethylbenzyl stearyl imidazolinium chloride, 2-hydroxyethylbenzyl coco imidazolinium chloride, ethyl bis (polyethoxyethanol) alkyl ammonium chloride, diethyl heptadecyl imidazolinium Ethylsulfate, lauryldimethylbenzyl ammonium chloride, stearyldimethylbenzyl ammonium chloride, laurylpyridinium chloride, 1-hexadecylpyridinium chloride, cetylpyridinium bromide, lauryl isoquinolinium bromide, and substituted oxazolines .

In one embodiment, the emulsifier or surfactant comprises one or more sorbitan esters. Sorbitan esters include sorbitan fatty acid esters, wherein the fatty acid component of the ester comprises carboxylic acids having about 10 to about 100 carbon atoms, in one embodiment about 12 to about 24 carbon atoms. Sorbitan is a mixture of anhydrous sorbitols, mainly 1,4-sorbitan (formula I) and isosorbide (formula II):

Sorbitan (also known as monoanhydrosorbitol or anhydrous sorbitol) is a generic name for anhydrides that can be derived from sorbitol by removing one water molecule. The sorbitan fatty acid esters of the present invention are partial esters of sorbitol and mixtures of anhydrides and fatty acids thereof. Such sorbitan esters can be represented by the following structures and can be any of monoesters, diesters, triesters, tetraesters, or mixtures thereof (Formula III):

In formula (III), each Z independently represents a hydrogen atom or C (O) R--, each R independently of each other has from about 9 to about 99 carbon atoms, more preferably from about 11 to About 23 hydrocarbyl groups are shown. Examples of sorbitan esters include sorbitan stearate (ie monostearate), sorbitan distearate, sorbitan tristearate, sorbitan monooleate and sorbitan sesquioleate and sorbitan Contains teen oleate. Sorbitan esters are commercially available from ICI under the trade names "Span" and "Arlacel". Sorbitan esters also include polyoxyalkylene sorbitan esters with alkylene groups having about 2 to about 30 carbon atoms. These polyoxyalkylene sorbitan esters can be represented by formula IV:

In formula IV, each R is independently an alkylene group having from about 2 to about 30 carbon atoms; R 'is a hydrocarbyl group having from about 9 to about 99, more preferably from about 11 to about 23 carbon atoms; w, x, y and z represent the number of oxyalkylene repeat units. For example, the ethoxylation of sorbitan fatty acid esters forms a series of more hydrophilic surfactants, which is the result of the reaction of hydroxy oxide with ethylene oxide of sorbitan. The main commercial class of such ethoxylated sorbitan esters contains from about 2 to about 80 ethylene oxide units, in one embodiment from about 2 to about 30 ethylene oxide units, in one embodiment about 4, one embodiment In about 5 and in one embodiment in about 20 ethylene oxide units. These are available under the trade name "POLYSORBATE" from Calgene Chemical and under the trade name "TWEEN" from ICI. Typical examples include polyoxyethylene (hereinafter referred to as "POE") (20) sorbitan tristearate (Tween 65), POE (4) sorbitan monostearate (Tween 61), POE ( 20) sorbitan trioleate (Tween 85), POE (5) sorbitan monooleate (Polysorbate 81; Tween 81), and POE (80) sorbitan monooleate (Tween 80) . The number in parentheses used herein refers to the number of ethylene oxide units present in the composition.

The following is a list of emulsifiers that may be particularly useful:

product name* synonym HLB  2,4,7,9-tetramethyl-5-decine-4,7-diol 4.0  PEG-Block-PPG-Block-PEG, Mn = 1100 4.0  PEG-Block-PPG-Block-PEG, Mn = 2000 4.0  PEG-Block-PPG-Block-PEG, Mn = 2800 4.0  PEG-Block-PPG-Block-PEG, Mn = 4400 4.0  Ethylenediamine tetrakis (PO-b-EO) tetratrole, Mn = 3600 4.0  Ethylenediamine Tetrakis (PO-b-EO) Tetrol, Mn = 7200 4.0  Ethylenediamine Tetrakis (PO-b-EO) Tetrolo, Mn = 8000 4.0  Igepal CA-210  Olyoxyethylene (2) isooctylphenyl ether 4.3  Span 80  Sorbitan monooleate 4.3  PPG-Block-PEG-Block-PPG, Mn = 3300 4.5  Igepal CI-210  Polyoxyethylene (2) nonylphenyl ether 4.6  Span 60  Sorbitan monostearate 4.7  Brij 92  Polyoxyethylene (2) Oleyl Ether 4.9  Brij 72  Polyoxyethylene (2) Stearyl Ether 4.9  Brij 52  Polyoxyethylene (2) Cetyl Ether 5.3  Span 40  Sorbitan Monopalmitate 6.7  Merpol A Surfactant  Nonionic, Ethylene Oxide Condensate 6.7  2,4,7,9-tetramethyl-5-decine-4,7-diol ethoxylate 8.0  Triton SP-135 8.0  Span 20  Sorbitan monolaurate 8.6  PEG-Block-PPG-Block-PEG, Mn = 5800 9.5  PPG-Block-PEG-Block-PPG, Mn = 2700 9.5  Brij 30  Polyoxyethylene (4) Lauryl Ether 9.7  Igepal CA-520  Polyoxyethylene (5) isooctylphenyl ether 10.0  Igepal CO-520  Polyoxyethylene (5) Nonylphenyl Ether 10.0  Polyoxyethylene sorbitol hexaoleate 10.2  Merpol SE Surfactant 10.5  Tween 85  Polyoxyethylene (20) sorbitan trioleate 11.0  8-Methyl-1-nonanol propoxylate-block-ethoxylate 11.0  Polyoxyethylene sorbitan tetraoleate 11.4  Triton X-114  Polyoxyethylene (8) isooctylphenyl ether 12.4  Brij 76  Polyoxyethylene (10) Stearyl Ether 12.4  Brij 97  Polyoxyethylene (10) Oleyl Ether 12.4  Merpol OJ Surfactant 12.5  Brij 56  Polyoxyethylene (10) Cetyl Ether 12.9  Merpol SH Surfactant 12.9

product name* synonym HLB  2,4,7,9-tetramethyl-5-decine-4,7-diol ethoxylate (5 EO / OH) 13.0  Triton SP-190 13.0  Igepal CO-630  Polyoxyethylene (9) nonylphenyl ether 13.0  Triton N-101  Polyethylene Branched Nonylphenyl Ether 13.4  Triton X-100  Polyoxyethylene (10) isooctylphenyl ether 13.5  Igepal CO-720  Polyoxyethylene (12) Nonylphenyl Ether 14.2  Polyoxyethylene (12) Tridecyl Ether 14.5  Polyoxyethylene (18) Tridecyl Ether 14.5  Igepal CA-720  Polyoxyethylene (12) isooctylphenyl ether 14.6  Tween 80  Polyoxyethylene (20) sorbitan monooleate 14.9  Tween 60  Polyoxyethylene (20) sorbitan monostearate 15.0  PEG-Block-PPG-Block-PEG, Mn = 2900 15.0  PPG-Block-PEG-Block-PPG, Mn = 2000 15.0  Brij 78  Polyoxyethylene (20) Stearyl Ether 15.3  Brij 98  Polyoxyethylene (20) Oleyl Ether 15.3  Merpol HCS Surfactant 15.5  Tween 40  Polyoxyethylene (20) sorbitan monopalmitate 15.6  Brij 58  Polyoxyethylene (20) Cetyl Ether 15.7  Polyoxyethylene (20) hexadecyl ether 15.7  Polyethylene-block-poly (ethyleneglycol), Mn = 2250 16.0  Tween 20  Polyoxyethylene (20) sorbitan monolaurate 16.7  Brij 35  Polyoxyethylene (23) Lauryl Ether 16.9  2,4,7,9-tetramethyl-5-decine-4,7-diol ethoxylate (15 EO / OH) 17.0  Igepal CO-890  Polyoxyethylene (20) Nonylphenyl Ether 17.8  Triton X-405  Polyoxyethylene (40) isooctylphenyl ether 17.9  Brij 700  Polyoxyethylene (100) Stearyl Ether 18.8  Igepal CO-990  Polyoxyethylene (100) Nonylphenyl Ether 19.0  Igepal DM-970  Polyoxyethylene (150) dinonylphenyl ether 19.0  PEG-Block-PPG-Block-PEG, Mn = 1900 20.5  PEG-Block-PPG-Block-PEG, Mn = 8400 24.0  Ethylenediamine Tetrakis (PO-b-EO) Tetrol, Mn = 15000 24.0  PEG-block-PPG-block-PEG, mean Mn = about 14,600 27.0

* Abbreviation: Mn = number average molecular weight; PEG = polyethylene glycol; PPG = polypropylene glycol; EO = ethylene oxide; PO = propylene oxide; HLB = hydrophilic-lipophilic balance

Useful emulsifiers in the forms listed in the above table may generally be represented by the following classes of compounds, which are commercially available and suitable for producing stable emulsifying compositions if used according to the teachings herein:

(a) Sorbitol ester of the general formula

Wherein radical X is the same or different and each is OH or R ¹ COO ^each other, wherein R ¹ is optionally substituted by hydroxyl group and having 7-22 carbon atoms, straight-chain or branched, saturated or unsaturated , An aliphatic hydrocarbon radical, wherein at least one of the radicals X is R ¹ COO ⁻ ,

(b) fatty acid esters of the general formula

Wherein R ² is a straight or branched, saturated or unsaturated, aliphatic hydrocarbon radical, optionally substituted by hydroxyl group, having 7 to 22 carbon atoms, and R ³ is straight or branched C ₁ -C ₁₀ Alkylene,

n is an integer of 6 or more,

R ⁴ is H, straight or branched C ₁ -C ₁₀ alkyl or

(여기서 R⁵는 R²에 대해 앞에서 정의한 것과 같음)이고;

Where R ⁵ is as defined above for R ² ;

(c) polyalkoxylated alkylphenols of the general formula

Wherein R ⁶ is straight or branched C ₁ -C ₂₀ alkyl,

m is an integer of 8 or more,

R ⁷ and R ⁸ are the same as defined above for R ³ and R ⁴ in formula (II), respectively.

Particularly useful emulsifiers are typically of a hydrophilic-lipophilic balance (HLB, emulsifier or surfactant molecule comprising a polar (hydrophilic) and nonpolar (lipophilic) group of about 1 to about 40, in another embodiment. Implying size and strength). HLB is a well known parameter utilized by those skilled in the art to characterize emulsifiers. It is specifically described, for example, in "The chemistry of emulsifying agents" (pg. 232 et seq.) In Emulsions: Theory and Practice, P. Becher, Reinhold Publishing Corp., ACS Monograph, ed. 1965; And Handbook of Applied Surface and Colloid Chemistry, K. Holmberg (Ed.), "Chapter 11, Surface Chemistry in the Petroleum Industry," J.R. Kanicky et al., 251-267, which also describes a method for calculating HLB values based on chemical structure; These references are incorporated herein by reference to the extent permitted. Established experimental procedures for determining HLB values for a given emulsifier are described in W.C. Griffin, J. Soc. Cosmetic Chem., 1, 311 (1949) can be determined experimentally, the contents of which are incorporated herein by reference to the extent allowed. Examples of suitable compounds are included in the table above and are also disclosed in McCutcheon's Emulsifiers and Detergents, 1998, North American Edition (pages 1-235) & International Edition (pages 1-199), the contents of which are incorporated by reference. Included in the specification, the disclosed compounds have an HLB in the range from about 1 to about 40; In one embodiment, from about 1 to about 30; In other embodiments, from about 1 to about 20; In another embodiment, from about 4 to about 18; Otherwise it has an HLB of at least about 8, for example about 8.5 or about 9 to about 18. Various useful compounds include those listed in the table above, for example sorbitan monolaurate, polyoxyethylene (20) sorbitan monooleate, and polyoxyethylene (20) sorbitan monolaurate.

Combinations of emulsifiers may be used to obtain stable emulsified fuel compositions. For illustrative purposes, but not limiting, an emulsified fuel composition, for example, is a 50/50 mixture of two emulsifiers instead of a single emulsifier with an HLB value of about 12, one having an HLB value of about 16 and the other about 8 It can be prepared using a mixture of emulsifiers with an HLB value of. Similarly, a combination of three or more emulsifiers may be used provided that the HLB value of the mixture represents the desired total value and that the effect of the mixture provides a stable emulsion. For the purposes of mixed emulsifier compositions, the HLB value of the emulsifier mixture is calculated as a linear sum weighted average based on the weight ratio each emulsifier represents relative to the total amount of emulsifier present:

HLB _m = Σ [(HLB _n ) (wt _n / wt _tot )]

Where:

Σ = sum of values in braces;

HLB _m = HLB value of one emulsifier or mixture of emulsifiers;

n = as the number of emulsifiers present in the mixture, any number of emulsifiers can be used; Typically n = 1 to about 5; More typically from 1 to about 4; Or 1 to about 3; Or 1 to about 2. For example, it is suitable to use a mixture of two, three or four emulsifiers to obtain a stable emulsion;

When HLB _n = n, the HLB value of a single emulsifier, or the HLB value of each emulsifier in a mixture of emulsifiers;

wt _n = weight of each emulsifier in the mixture of emulsifiers, unit being eg g;

wt _tot = total weight of all emulsifiers present in the mixture of emulsifiers.

In a preferred embodiment, a mixture of two or more emulsifiers is used, one of which is an HLB value of about 6 or less, such as about 1 to about 6.0, or about 2 to about 5.9, or about 3 to about 5.5, Or has an HLB value such as about 4 to about 5.9; Second emulsifiers have HLB values greater than about 6, such as from about 6 to about 20; Or about 6.1 to about 18, or about 6.5 to about 16, or about 7 to about 15, etc., but the two emulsifiers do not have the same HLB value 6. Alternatively, one emulsifier can be used that includes a biomodal distribution of chemical species exhibiting their respective HLB properties.

The use of multiple emulsifiers in the same emulsified fuel composition may be advantageous in compositions with low total concentrations of hydrophilic components. Such compositions have, for example, a water concentration of less than about 5% by weight, such as about 1% to about 5%, or about 1% to about 4%, or 1% to about 3%, or 1 Composition by weight to about 2% by weight. Alternatively, the concentrations of the various hydrophilic or substantially hydrophilic components can be combined taking into account the concentrations mentioned above as well as the concentration of hydroxy containing component (s) such as water, one or more alcohols or glycols and the like. In particular, the ratio of the total amount of said hydrophilic components to the total amount of lipophilic components, including but not limited to animal and vegetable fats and oils, is not greater than about 0.25, for example about 0.05 to about 0.25, or a specific value within the range, for example For about 0.06, 0.08, 0.10, 0.12, 0.14, 0.16, 0.18, 0.20, 0.22 or 0.24, a mixture of emulsifiers as described above; In other words, it is preferred to use a mixture of emulsifiers wherein at least one emulsifier has an HLB value of about 6 or less and at least one emulsifier has an HLB value greater than about 6 (under the conditions described above). For example, a composition comprising 80 wt% vegetable oil, 4 wt% water and 14 wt% ethanol (eg, 95 wt% ethanol containing 5 wt% water and / or denaturant) may comprise 18 Gives a value of the calculated ratio of /80=0.225. In order to prepare a stable emulsion using such components, it is preferred to use a mixture of emulsifiers, for example a 50/50 mixture of an emulsifier with an HLB value of about 4 and an emulsifier with an HLB value of about 15, for example. In contrast, a single emulsifier can be prepared using a single emulsifier, wherein the lipophilic and hydrophilic components comprise 75% by weight vegetable oil, 1% water, and 23% alcohol by weight. Alternatively, a mixture of emulsifiers can be used even if the value of the calculated ratio is greater than 0.25, especially if the value is only slightly larger by about 5% to about 10%. Optionally, a mixture of emulsifiers can be used if necessary; This is especially the case when the user of such a fuel composition is expected to introduce additives into the composition which may have the effect of changing the value of the subsequently calculated ratio.

Alcohols useful in the present invention include hydroxy containing organic compounds selected from the group consisting of: (A) (1) linear and branched chains, within which are paraffinic (eg ethanol) and olefins; Aliphatic sub-characterized as system (eg allyl alcohol), (2) cycloaliphatic (eg cyclohexanol); (3) aromatics (eg phenol, benzyl alcohol); (4) heterocycle type (eg furfuryl alcohol); (5) polycycles (eg, sterols); (B) divalents (two OH groups) (eg, diols) comprising glycerol and derivatives; (C) trivalent (three OH groups) containing glycerol and derivatives; And (D) a polyhydric (polyol) having three, four or more OH groups. Particularly useful alcohols include C2 to C4 mono- and polyalkylenes, including C1 to C4 straight and branched monoalcohols, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol. Glycols, polyalkylene glycols include alcohols selected from the group consisting of derivatives of C2 to C4 mono- and polyalkylene glycols and mixtures thereof when suitable for the fuel compositions of the present invention. The fuel composition comprising monoalcohols also preferably comprises at least one tert-butyl alcohol, at least one C2-C4 alkylene glycol, or a mixture of both. Ethyl alcohol ie ethanol and propylene glycol are particularly preferred in the compositions of the present invention. Ethanol is commercially available in anhydrous form (also known as absolute alcohol or 100% alcohol) and is available as various proofs or as various percentages of ethanol, where the additional component in ethanol is water, and 190 proofs or 95% by volume Most common. When ethanol is used for purposes other than beverages, ethanol is modified by the addition of substances such as methanol, 2-propanol, ethyl acetate, methyl isobutyl ketone, heptane or kerosene, making the product undesirable for human consumption. It is made, but it can be used for the industrial use included as a fuel component or fuel. As described, ethanol that is not an absolute alcohol is typically identified by using the term "proof" and 2 proof is 1 vol% when the conversion between the proof and the concentration of ethyl alcohol is measured at 20 ° C, for example Measurements at other temperatures including 15.6 ° C. are also acceptable. There may be a number of denaturing agents that may make ethanol unsuitable for human consumption (with or without moisture or water), but certain of such denaturing agents are not suitable for use in connection with fuels, which are fuel stability, This is because there is an adverse effect on vehicle engines, fuel systems and emissions. A list of denaturants used in connection with various purposes of ethyl alcohol is listed in the Merck Index, 13th Edition 2001, entries 3796, 670, the contents of which are incorporated by reference. The ethanol's physical properties can vary depending on whether the ethanol is dry, mixed with water at various concentrations, modified, and the type of denaturing agent used. Denaturants that may be unsuitable for use in connection with fuels are known to those skilled in the art and are usually prescribed by various government agencies. For example, the government of India prohibits the use of methanol, pyrrole, terpentine, ketones and tars (high molecular weight materials that are pyrolysis products of fossil or non-fossil vegetable materials). The standards described in ASTM D4806 and ASTM D5798, incorporated herein by reference, typically describe the amount and form of denaturant that can be used in fuels, and also other materials that should not be used in view of potential adverse effects as mentioned above. Is identified. ASTM D5798 also describes standards for fuels that can be used in engines that are designed to use ethanol as a substitute for petroleum, that is, materials that contain substantially high proportions of ethanol. Absolute ethyl alcohol is generally understood to mean ethyl alcohol containing up to 0.5% by volume of water, but for the purposes of the present invention such a moisture limit is of little significance. When used in the vegetable oil emulsion fuel compositions of the present invention, alcohols or mixtures of alcohols found to be useful herein have a concentration of about 1% to about 25% by weight based on the total weight of the fuel composition; Or about 2% to about 22% by weight; Or about 3% to about 20% by weight; Or about 4% to about 18% by weight; Or about 5% to about 20% by weight; Or about 1 wt% to about 15 wt%; Or about 1% to about 10% by weight; Or about 1% to about 5% by weight; Or about 2% to about 6% by weight; Otherwise it is included in a concentration of about 3% to about 8% by weight.

Alternatively, C4 butyl alcohol can also be used in the present invention. If butyl alcohol is used, it is preferable to use tert-butyl alcohol because it is more readily soluble in water than other butyl alcohols. However, since n-butyl alcohol and sec-butyl alcohol are not completely dissolved in water, it may be necessary to further control the form and amount of the emulsifier in the fuel composition in order to obtain a stable emulsion. tert-butyl alcohol is used instead of ethanol or, for example, the relative amount of ethanol relative to tert-butyl alcohol is about 95/5 to 5/95 by weight; Examples of useful amounts among them are about 85/15, 80/20, 75/25, 70/30, 65/35, 60/40, 55/45, 50/50, 45/55, 40/60, 35/65 , 30/70, 25/75, 20/80, 15/85, and about 10/90, including mixtures that can be used in combination with ethanol.

Water-vegetable oil fuel emulsions include the phases of a continuous vegetable oil fuel; Discontinuous water or aqueous phase, preferably consisting of water drops having an average diameter of about 10 μm or less, for example 5 μm; And emulsifying amounts of one or more emulsifiers. The emulsion may be prepared by various steps or series of additions as described herein, for example by using (1) standard mixing techniques to blend vegetable oils, emulsifiers and other preferred additives to produce vegetable oils- Forming an emulsifier mixture; And (2) the desired water by mixing the vegetable oil-emulsifier mixture with water (optionally including additional additives such as ethanol, propylene glycol, cetane modifier, or mixtures thereof) under emulsified mixing conditions. Forming a vegetable oil fuel emulsion.

Optionally, additives may be added to the emulsifiers, vegetable oils, water or combinations thereof. Such additives include, but are not limited to, cetane modifiers, organic solvents, other fuels such as diesel fuels, glycols, surfactants or emulsifiers, other additives known to be used in fuels, and the like. The additive is added to the emulsifier, vegetable oil or water in the emulsifying device (s) in advance and alternately depending on the solubility of the additive or other fluid properties. The additives generally range from about 5% to about 40% by weight of the fuel mixture, in another embodiment from about 5% to about 30% by weight, and in still other embodiments from about 7% to about 25% by weight.

The vegetable oil fuel emulsifier mixture contains from about 50 wt% to about 95 wt% vegetable oil fuel, in another embodiment from about 55 wt% to about 90 wt%, in another embodiment from about 60 wt% to about 85 wt% And, further, from about 0.05% to about 10% by weight, in another embodiment from about 0.1% to about 10% by weight, and in another embodiment, from about 1% to about 5% by weight.

Water may optionally include, but is not limited to, one or more alkylene glycols, alcohols, cetane modifiers or mixtures thereof. In one embodiment, water, alcohol and / or alkylene glycol and / or cetane modifiers are mixed with each other and continuously fed to the fuel additive stream. In another embodiment, water, alcohols and / or alkylene glycols and / or cetane modifiers, or mixtures thereof, flow out of the separation tank and / or the combination of tanks and enter into or mix with the emulsifier. In one embodiment, the water, alcohol and / or alkylene glycol and / or cetane modifier mixture meets the vegetable oil fuel additive immediately before or in the emulsification apparatus.

Another method for making one example of the emulsified fuel of the present invention can be used. For example, most or all of the desired amount of a C1-C4 alcohol, such as a vegetable oil or vegetable oil mixture and ethanol, is mixed with each other to form a two phase composition in which the top layer is an alcohol. The remaining component (s), including water and emulsifier (s), are added under stirring to yield a stable, emulsified composition. Alternatively, the C1-C4 alcohol or part thereof may be mixed with components other than water, including a major portion, such as more than 50% by weight, to which a vegetable oil is added so that the upper layer is an oil Is obtained. When the alcohol is added separately, any convenient ratio can be used since a biphasic mixture is obtained until water is added. Adding water to this mixture with stirring produces a stable emulsifying composition. If necessary, a stable emulsifying composition is formed by preparing any of the two-phase mixtures described above and preserving to the point where it is desirable to add the water component together with additional component (s), if necessary. In addition, the biphasic mixture may be shipped to a desired point to reduce the loading of shipping water in the mixture before adding water.

An optional component of the fuel mixture, referred to as a supplementary combustible liquid, may be a "paint diluent", terpentine or mineral spirit. Materials of this type are generally described in US Pat. No. 5,609,678, the entire contents of which are incorporated herein by reference. In contrast, the use of this component in the present invention may be characterized as a low viscosity, low density supplementary flammable liquid additive. Such optional components may be useful for the purpose of modifying one or more of the properties of the fuel composition, such as properties including cetane number, density and viscosity. Thus, the amount and form of such components may be selected based on the combustibility measured by the effect on the phase distribution of the microemulsion, taking into account the cetane number of the resulting fuel composition, the density and viscosity of the composition obtained as well as the amount and form of the surfactants used. Can be. In each case, the amount of liquid added is such as to produce a fuel composition with an overall balance of properties suitable for the end use of the fuel product, for example as a fuel for use in diesel engines, furnaces and the like, or for example in winter or It may be suitably adjusted to control the properties of the fuel composition for the ambient temperature environment intended for use, such as automotive diesel fuel for summer use.

Useful as supplementary flammable liquid additives in the form of paint diluents are those identified as naphtha, petroleum, hydrogenated hard steam cracked naphtha residue (petroleum), also referred to as hydrotreated heavy, and CAS 64742-48- Product identified as 9 is included. This product has also been described as a complex combination of hydrocarbons obtained by treating the petroleum fraction with hydrogen in the presence of a catalyst. It typically includes hydrocarbons with predominantly carbon numbers ranging from C6 to C13 and boiling points in the range of about 65 ° C to 230 ° C (149 ° F to 446 ° F). Some of its characteristic physical properties include: boiling point, 155-217 ° C .; Melting point, 0 ° C .; Density, 0.76-0.79 g / cm 3; Vapor pressure, 0.1-0.3 kpa @ 20 ° C; Flash point, 40-62 ° C .; Auto ignition temperature, 255-270 ℃; Explosion limit, 0.7-6.0% by volume in air. Suitable materials are commercially available from Italchimica Lazio S.r.l. (Scalo, Monterotondo, Italy). Particularly useful products are further processed to be described as "odorless" since this is a term understood in the art. This product has a viscosity of 1.23 mm 2 / s (ASTM D445) and a density of 0.772 kg / DM 3 (ASTM D4052). It corresponds to the product used in the examples below.

For the purposes of the present invention, it should be understood that supplementary flammable liquid components useful in the present invention generally include complementary flammable liquids from other sources, such as tree or plant sources, as well as a wide range of petroleum distillate materials. . Useful products generally boil in the range of about 145 ° C to about 200 ° C. Terpentine is a supplementary flammable fluid that can be used. Specifications for "Terpentine's gum spirit" (natural, organic or plant-based terpentines) include several, including the American Society for Testing and Materials (ASTM D 13-92) and the Indian Bureau of Standards (IS 533: 1973). It was announced by two national authorities. These standards are intended primarily for the quality assessment of terpentains intended to be used as a solvent, i.e. in its entirety, not as a chemical feedstock of which the composition is of paramount importance. The standard generally defines such parameters as relative density or specific gravity, refractive index, distillation and evaporation residues. The International Organization for Standardization (ISO), a worldwide federation of national standards bodies, has issued standards whose main requirements are those shown in the table below. The ISO standard for “terpentine oil, Portuguese type, pinus pinaster (1994)” is very similar to that shown in the table below, but the range for optical rotation (20 ° C.) -28 ° C to -35 ° C) includes the added physical data. In addition, composition ranges are given for several constituents of terpentine, including alpha-pinene (72-85%) and beta-pinene (12-20%).

[table]

Physical Properties Requirements for Glove Spirits of Terpentine (ISO Standard 412-1976)

  Property value   Relative Density (20/20 ℃) 0.862-0.872   Refractive Index (20 ℃, D Line) 1.465-1.478   Distillation (% v / v) Up to 1 below 150 ° C; Up to 87 below 170 ° C   Evaporation Residue (% m / m) 2.5 max   Residue after Polymerization (% v / v) Up to 12   Acid Up to 1   Flash point (℃) 32 minimum

"Turpentine substitutes" are substitutes based on "mineral oils" for the plant-based organic solvent terpentine, which are suitable for use in the present invention. It is a hydrogenated light distillate of petroleum, which forms a clear liquid at ambient or room temperature. It is a complex mixture of highly purified hydrocarbon distillates, mainly in the C9-C16 range. The liquid is very volatile and its vapor is combustible. It is widely available as an inexpensive alternative to terpentine. It is commonly used as an organic solvent for diluting oil-based paints and for cleaning brushes in painting and decorating. It is also known as turpentine substitute, mineral terpentine, or simply turpentine, which can be confused with plant-based penpentines.

White spirit, also known as Stoddard solvent, is also suitable for use in the present invention. It is a clear, transparent liquid of paraffin induction and is a common organic solvent used in the painting and decoration fields. It is a mixture of saturated aliphatic and cycloaliphatic C7 to C12 hydrocarbons with a maximum content of 25% of C7 to C12 alkyl aromatic hydrocarbons. White spirits are typically used as extraction solvents, cleaning solvents, degreasing solvents and aerosols, paints, wood preservatives, lacquers, vices and asphalt products. In Western Europe, about 60% of the total white spirit consumption is used for paints, lacquers and varnishes. White spirit is the most widely used solvent in the paint industry.

Three different shapes and three different grades of white spirit are available. The above form means whether the solvent has been subjected to hydrodesulfurization (sulfur removal) alone (form 1), solvent extraction treatment (form 2) or hydrogenation treatment (form 3). Each form includes three different grades: low flash grade, regular grade, and high flash grade. The grade is determined by the crude oil and distillation conditions used as starting materials. Additionally, there is Form 0, which means that the untreated further distillation fraction contains saturated C9 to C12 hydrocarbons having a boiling point of mainly 140 to 200 ° C.

The physical properties of the three types of white spirits are shown in the table below:

 Property  T1: low flash  T2: normal  T3: high flash  Initial boiling point (IBP) (° C) 130-144 145-174 175-200  Final boiling point (℃) IBP + 21, up to 220  Average relative molecular mass 140 150 160  Relative Density (15 ℃) 0.765 0.780 0.795  Flash point (℃) 21-30 31-54 ＞ 55  Vapor Pressure (kPa, 20 ℃) 1.4 0.6 0.1  Volatile (n-Butyl Acetate = 1) 0.47 0.15 0.04  Auto Ignition Temperature (℃) 240 240 230  Explosion limit (% of air) 0.6-6.5 0.6-6.5 0.6-8  Vapor density (air = 1) 4.5-5 4.5-5 4.5-5  Refractive index (at 20 ℃) 1.41-1.44 1.41-1.44 1.41-1.44  Viscosity (cps, 25 ℃) 0.74-1.65 0.74-1.65 0.74-1.65  Solubility (wt% in water) <0.1 <0.1 <0.1  Kauri-butanol values 29-33 29-33 29-33  Aniline Point (℃) 60-75 60-75 60-75  Responsive Reaction with strong oxidants  Odor Threshold (mg / ㎥) - 0.5-5 4

Various fluids identified as "mineral spirits" are suitable for use as supplementary flammable fluids in the present invention. Mineral spirits are commonly used as paint diluents and mild solvents and are suitable for use in the present invention. In Europe, mineral spirits are referred to as petroleum spirits. They are particularly effective at removing oil, grease, carbon and other substances from metals. Mineral spirits are derived from light distillate fractions in crude oil refining and contain C6 to C11 compounds, most of which are C9 to C11. There are many different materials commonly referred to as mineral spirits, each of which generally has a different CAS number. One common form is mineral oil spirit, identified as CAS 64475-85-0. The aforementioned sotodard solvent is a subcategory or subset of a special form of mineral spirit, identified as CAS 8052-41-3 and containing 30-62% by weight of alkanes, 27-40% by weight of cyclone. Alkanes, 0.3-20 wt% alkylbenzenes, 0.007-0.1 wt% other benzenes, 0.2 wt% naphthalene, and 0.3 wt% acenaphthalene. Commercial stodard solvent products are available under the trade names Varsol 1 and Texsolve S. Likewise, benzene is another subset of mineral spirin, comprising C5 to C9 hydrocarbons, and boiling at about 154 ° C to about 204 ° C. Mineral spirits, on the other hand, comprise 20-65% by weight of alkanes, 15-40% by weight of cycloalkanes and 10-30% by weight of aromatics; Each particular amount is varied according to the particular "mineral spirit" contemplated. General properties in mineral spirits include vapor pressure of 2.53 mmHg; An API gravity of about 48 to about 51; A density of about 0.793 at 15 ° C. and about 0.779 at 20 ° C .; Kinematic viscosity at 1,43 cSt (or mm 2 / sec) at 15 ° C. and 1,78 cSt at 20 ° C.

Another supplementary flammable liquid that can be used is kerosene. Kerosene is typically a petroleum solvent (usually a C ₉ -C ₁₆ hydrocarbon), 25% normal paraffin, 11% branched paraffin, 30% monocycloparaffin, 12% dicycloparaffin, 1% tricycloparaffin , A mixture of 16% mononuclear aromatic, and 5% dinuclear aromatic. (NIOSH Pocket Guide, www.cdc.gov) Alternatively, a product known as hydrogenated kerosene (CAS No. 64742-47-8) can be used. As its name implies, it is derived from kerosene or straight run kerosene by hydrogenation to saturate the double bonds present in the various molecules of kerosene. Its physical properties are no different from kerosene. Typical physical properties and other properties are shown in the table below.

Physical and descriptive information

 Property   value  CAS No .:   8008-20-6  Melting Point: 170 (approximate, C ₉ -C ₁₆ hydrocarbons)  Molecular Weight:   -51 ℃  boiling point:   175 ~ 325 ℃  Exterior:   Colorless to pale yellow  density:   0.8 g / ml  importance:   0.95 (30 ℃)  Kinetic Viscosity:   2.7 cSt (20 ℃)  smell:   Odorless  flash point:   65 ~ 85 ℃  Molecular Formula: C ₉ -C ₁₆ hydrocarbons and others  synonym:   Kerosine; oil; Fuel oil no. 1; Range oil  Solubility:   Insoluble in water, miscible in all petroleum solvents  Structural Composition: Compositions vary widely and include C ₉ -C ₁₆ hydrocarbons (aliphatic and aromatic) with boiling points ranging from about 175 to 325 ° C.

Source: Budavari, S. Ed, The Merck Index, 12th edition Merck & Co. Inc., Rahway, N. J., 1997, p 903; MSDS: Brown oil, www.brownoil.com/msdskerosene.htm; www.engineeringtoolbox.com/kinematic-viscosity-d_397.html

In one embodiment, the additive composition of the present invention comprises one or more alcohols and one or more surfactants or emulsifiers, and optionally, low viscosity and low density supplemental flammable liquids such as paint diluents and other components described herein. do. Various embodiments of the fuel composition of the present invention are generally prepared according to the methods described herein. In one embodiment, to prepare a mixture, an additive composition comprising the components described herein is slowly added to the water, or conversely, water is added to the composition, preferably mixed upon addition, but the mixing adds the components to each other. May be carried out afterwards. Alternatively, each component of the additive mixture and water may be mixed in any convenient order as long as a uniform mixture is obtained. Mixing continues until a satisfactory distribution, dispersion or emulsion of the components is obtained. Typically the additive composition is used in an amount of about 20% by weight based on the amount of vegetable oil present in the final mixture. The amount of additive used can be varied as appropriate. Typically, the additives are, based on the weight of oil present, from about 2% to about 30% by weight for engines; Preferably from about 20% to about 28% by weight; More preferably about 10% to about 30% by weight is used, and about 10% to about 20% by weight is used for burners and heaters. Further, with the costs in mind, up to about 35% by weight or about 40% by weight, or up to about 45% by weight, keeping costs in mind so that a suitable amount is used at a cost consistent with economic requirements while obtaining the desired effect. Additives may be used. In contrast, useful amounts are about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, Specific concentrations of at least 24, 25, 26, 27, 28, 29, and 30% by weight, and ranges of values based on any two of the aforementioned individual values, for example 2-30%, 5-25% It may include the concentration of. In this embodiment, the additive is used in an amount sufficient to obtain a substantially complete emulsion of water and oil present in the composition. Mixtures comprising water and additives are added to oils or fats of vegetable origin, for example colza or canola oil. The weight ratio of water to oil can typically vary over a range and is still useful in the present invention, for example from about 4: 1 to about 1: 4; Preferred ratios of water to oil are about 3: 1 to about 1: 3, more preferably about 2: 1 to about 1: 2, more preferably about 1: 1. The mixing of the water-additive combination with the vegetable oil is continued until a substantially complete or suitable emulsion of the components is obtained.

The cetane number, or CN, for diesel fuel corresponding to the octane number for gasoline is generally recognized as a measure of the combustion quality of the fuel. Cetane is an alkane molecule, specifically C16H34, and is very easily ignited in the compressed state, so the cetane is assigned 100. All other hydrocarbons in diesel fuel, and other fuels intended to be used in diesel engines including biodiesel and the biofuel compositions of the present invention, are indexed on the basis of cetane as an indicator of how well ignited in compression. Thus, cetane number measures how quickly fuel begins to burn (auto ignite) under a standardized series of diesel engine conditions. Typical hydrocarbon-based diesel fuels contain many hydrocarbon compounds, and there may be one or more compounds that can be ignited in other fuels, including the fuels of the present invention. Since each component exhibits a different cetane number or can adjust the cetane number of a fuel containing the component, the overall cetane number of the fuel is an indicator of the average cetane quality of all components present. Fuels with a high cetane number start to burn shortly after being injected into the cylinder, resulting in short ignition delays. Conversely, fuels with a low cetane number suppress auto ignition and therefore have longer ignition delay times. Typical diesel engines have acceptable performance by fuel with CN in the range of about 45 to about 50. Typically, a CN greater than 50 has no advantage in terms of performance or emissions, after which the performance of the fuel reaches a parallel state. Commercially available hydrocarbon diesel fuels are available in two CN ranges: 40 to 46 for regular diesel and 45 to 50 for premium. In addition to the relatively high CN, premium diesel also contains additives to improve the effective CN and lubricity of the fuel, cleaners to clean the fuel injectors and minimize carbon deposits, as well as water dispersants (because water in hydrocarbon diesel fuel is considered unnecessary), And other additives according to geographic and seasonal needs. Cetane number can be determined using standard tests including ASTM D613 and EN ISO 5165. The cetane number rating in this test compares the performance of diesel fuel in a standard engine with that of a mixture of cetane and α-methyl-naphthalene. Cetane number is the volume percentage of cetane in the mixture with the same performance as the fuel under test. Suitable fuels typically have a CN value of at least 35 and up to about 55; Preferably about 40 to about 50; More preferably about 45 to about 50; For example, it has a CN value of at least 45, 46, 47, 48, 49, 50, 51, 52, 53, 54 or 55. Alternatively, cetane number can be estimated using the density of the fuel and its intermediate distillation temperature according to the procedure specified in ASTM D976, or using an equation with four parameters according to ASTM D4737. When the estimated cetane number is determined in this way, it is also referred to as the cetane index to distinguish it from the value determined by engine testing, as in ASTM 613. Those skilled in the art will understand that when the cetane index is calculated, its value depends on the final properties and is not affected by additives that may be included to improve the cetane number. Such additives, of course, affect the cetane number determined by the engine test, since the entire fuel composition affects the value measured in the test. Cetane index values are also useful for characterizing fuel compositions of the present invention. In use, the cetane number enhancing additive or mixture of additives may be present in an amount effective to enhance the CN of the fuel composition of the present invention to the desired range, ie to a level suitable for the particular application or application in which the emulsified vegetable fuel will be used. In one embodiment, the concentration of cetane improver is at a level of about 10 weight percent or less, and in another embodiment, from about 0.05 to about 10 weight percent; From about 0.05 to about 5 weight percent in yet another embodiment; From about 0.05 to about 1 weight percent in yet another embodiment; Otherwise about 0.1 to about 1 weight percent.

Various compounds have been identified that can improve the cetane number of diesel fuel. One embodiment of the vegetable oil-based water-fuel emulsion composition of the present invention may optionally include one or more compounds capable of selectively increasing cetane number, if necessary or desired to meet defined performance requirements in a particular application. . Useful cetane improvers include, but are not limited to, one or more of peroxides, nitrates, nitrites, nitrocarbamates, mixtures thereof. Useful cetane improvers include, but are not limited to, nitropropane, dinitropropane, tetranitromethane, 2-nitro-2-methyl-1-butanol, 2-methyl-2-nitro-1-propanol, and the like. It also includes nitrate esters of substituted or unsubstituted aliphatic or cycloaliphatic alcohols, which may be monovalent or polyvalent. Such compounds include substituted and unsubstituted alkyl or cycloalkyl nitrates having up to about 10 carbon atoms, in one embodiment about 2 to about 10 carbon atoms. The alkyl group may be a straight or branched alkyl group, or a mixture of straight or branched alkyl groups. Examples of such compounds are methyl nitrate, ethyl nitrate, n-propyl nitrate, isopropyl nitrate, allyl nitrate, n-butyl nitrate, isobutyl nitrate, sec-butyl nitrate, tert-butyl nitrate Late, n-amyl nitrate, isoamyl nitrate, 2-amyl nitrate, 3-amyl nitrate, tert-amyl nitrate, n-hexyl nitrate, n-heptyl nitrate, n-octyl nitrate, 2 Ethylhexyl nitrate, sec-octyl nitrate, n-nonyl nitrate, n-decyl nitrate, cyclopentyl nitrate, cyclohexyl nitrate, methylcyclohexyl nitrate, and isopropylcyclohexyl nitrate . Also, alkoxy-substituted aliphatic alcohols such as 2-ethoxyethyl nitrate, 2- (2-ethoxyethoxy) ethyl nitrate, 1-methoxypropyl-2-nitrate, 4-ethoxybutyl nitrate and the like In addition to nitrate esters, diol nitrates such as 1,6-hexamethylene dinitrate are also useful. A useful cetane improver is 2-ethylhexyl nitrate.

Organic peroxides may also be useful as cetane improvers in the fuel compositions of the present invention. Generally useful compounds are dialkyl peroxides of the formula R 10 OR 2, wherein R 1 and R 2 are the same or different and are alkyl groups having from 1 to about 10 carbon atoms. Suitable peroxide cetane improver compounds must be soluble in the fuel composition and thermally stable at typical fuel temperatures of the engine being operated. Particularly useful are peroxides wherein R 1 and R 2 are tertiary alkyl groups having from about 4 to about 5 carbon atoms. Examples of suitable peroxides include di-tert-butyl peroxide, di-tert-amyl peroxide, methyl ethyl peroxide, methyl-t-butyl peroxide, ethyl-t-butyl peroxide, propyl-t-amyl peroxide, Mixtures thereof and the like. Preferred peroxides generally exhibit one or more, preferably almost all of the following properties: good solubility in the fuel, suitable water partition coefficient properties, good thermal stability and handling properties, fuel quality or fuel system No impact on ingredients, and low toxicity. Useful peroxides are di-tert-butyl peroxides, often referred to as tertiary butyl peroxides.

Biofuels of the present invention typically have a density suitable as fuel in diesel engines and fuels in other applications where diesel fuel is useful, including furnaces, gases or combustion turbines and other combustion devices. Density can be measured at 15 ° C., in accordance with standard test method EN ISO 3675, and suitable fuels range from about 850 kg / m 3 to about 950 kg / m 3; Preferably from about 860 kg / m 3 to about 910 kg / m 3; For example, from about 870 kg / m 3 to about 890 kg / m 3. In contrast, in the United States, diesel fuel density is characterized by a standard developed by the American Petroleum Institute called API gravity. Typical API degree values for fuels of the invention useful as fuels for diesel engines range from about 25 API degrees to about 40 APIs corresponding to specific gravity values of about 0.904 to about 0.825 (60 ° F. 15.6 ° C.); Preferably from about 26 API degrees to about 38 API degrees; More preferably about 27 API degrees to about 37 API degrees; For example, about 35 API degrees, corresponding to a specific gravity of about 0.850.

The acceptable formulas for the API plot for specific gravity are: API = (141.5 / Sp.Gr.)-131.5, where the abbreviation Sp.Gr. means specific gravity, which is determined at 60 ° F. or 15.6 ° C. as described above. .

Biofuel compositions of the invention typically have a viscosity suitable as fuel in diesel engines and fuels in other applications where diesel fuel is useful, including furnaces and other combustion devices. Viscosity can be measured according to standard test methods EN ISO 3104 or ASTM D445 (kinetic viscosity at 40 ° C.), with potentially useful values ranging from about 3 mm 2 / s to about 60 mm 2 / s; Or about 3.5 mm 2 / s to about 50 mm 2 / s; Or for example from about 3.6 mm 2 / s to about 40 mm 2 / s; From about 3 mm 2 / s to about 40 mm 2 / s; From about 3 mm 2 / s to about 30 mm 2 / s; From about 1 mm 2 / s to about 25 mm 2 / s; From about 2 mm 2 / s to about 12 mm 2 / s; From about 3 mm 2 / s to about 10 mm 2 / s; From about 4 mm 2 / s to about 8 mm 2 / s, from about 2 mm 2 / s to about 6 mm 2 / s; Tests include viscosity values suitable for the application of suitable biofuel compositions or for use in the environment.

Other suitable optional ingredients can also be included in the compositions of the present invention as long as they do not substantially adversely affect the performance and intended use of the composition. Examples of such other optional ingredients that may be included include heat and aging stabilizers; Colorants, dyes and markers, in particular those permitted in the European Union as set forth in EN 14214: 2003-5.1; Additives that control the odor of the mixture to prevent involuntary inhalation, such as alkyds and the like, are included. Alternatively, if desired, the additive may be added in a suitable amount, typically at a low concentration, to control or block the unpleasant odor of the gas emitted after combustion. Other conventional additives and admixtures may be present for the fuel compositions of the present invention. For example, the fuels of the present invention include corrosion inhibitors such as alkylated succinic acid and anhydrides, gum formation inhibitors, metal deactivators, upper cylinder lubricants, friction modifiers, cleaning agents, antioxidants, heat stabilizers, bacterial growth inhibitors ( conventional additives such as bacteriostatic agents, microbiocide, fungicides and the like. Such conventional additives may be present in the fuel composition at a concentration of about 1% by weight or less, such as about 0.01% to about 1% by weight, based on the total weight of the water-vegetable oil fuel emulsion.

In particular emulsions based on animal or vegetable fats or oils and water, which are stable over extended temperature ranges, for example from about −10 ° C. to about + 50 ° C. for extended periods of time by practicing the present invention comprising the additive composition described above. A fuel composition in a state can be prepared. In addition, in tests run at −25 ° C., the compositions of the present invention, such as the compositions shown in Examples 1 and 2, including paint diluent and 30 g of cetyl alcohol, showed no evidence of freezing, clouding, or phase separation. . Fuels prepared according to the compositions and methods of the present invention can be used without modification to tanks and / or piping systems of commonly used motors and burners. Thus, another advantage of the present invention is that it can be returned to the use of conventional fuel at any time without modifying the system in which the fuel is used.

Still other advantages can be realized by certain preferred methods and compositions of the present invention, including:

(a) the presence of water in the composition, in particular, lowers product costs and manufacturing costs and is competitive with other fuels;

(b) The present invention relates to the high solvent power of methyl esters present in conventional biodiesel, which may cause problems with polymeric materials present in storage systems, burners and engines, including linings, packing rings and seals. Does not represent;

(c) the fuel of the present invention does not leave deposits in storage tanks and fuel lines, thus reducing the need for frequent maintenance;

(d) The fuel of the present invention is renewable because it is based on vegetable and animal products that can be replaced regularly. Furthermore, not only are the energy sources renewable, but the amount of carbon dioxide released during combustion is very close to the amount of carbon dioxide used in the plant to produce the vegetable material that is the source of the oil or fat. This of course cannot occur with petroleum based fuels.

(e) The emissions of nitrogen oxides, which are particularly undesirable contaminants, are reduced compared to conventional biodiesel based fuels, especially when considering water and additive mixtures. In a test using a diesel engine operated at 1500 rpm, conventional biodiesel produced 196 mg / Nm3, while the composition of the present invention produced 160 mg / Nm3 under the same conditions, which resulted in a reduction rate of at least 18%. (Where Nm 3 means “normal” cubic meter, defined by volume at temperature T = 20.0 ° C. (68 ° F.), pressure P = 1.01 bar (14.72 psia));

(f) The non-combustible hydrocarbons produced upon combustion of the fuel composition of the present invention are considered to be less than those produced by conventional biodiesel based fuels and CO emissions, and are typically considered to be about 15% to 20% less. In a test of a fuel composition similar to that shown in Example 1 (containing 30 g cetyl alcohol but no paint solvent) in a diesel engine running at 1500 rpm, CO emissions were observed to be reduced by 37% by weight (838 mg). 1248 mg / Nm3 relative to / Nm3).

(g) The average size of chemical compositions and particulate matter obtained from the combustion of conventional biodiesel based fuels and fuels of the present invention is variable. Limited testing of smoke was performed using the Bacharach Scale (values from 0 to 9, where 0 represents the lowest level) and a 3 meter long exhaust pipe connected to the Zambelli Emicont 50 test machine and diesel engine (Bacharach The scale may also be referred to in test method ASTM D 2156, which measures the density of smoke in flue gas from petroleum distillate heating fuel). A comparative value of 6 was observed using the fuel composition of the present invention as described in paragraph (f) above. Although particulate matter generated during the combustion of conventional biodiesel based fuels is believed to have a useful function by absorbing some of the undesirable contaminating aromatic compounds produced upon combustion of the fuel, the fuels of the present invention are firstly such aromatic compounds. It is thought to produce very little. In addition, the particulate matter produced during the combustion of the fuel of the present invention is at most about 70% less than that produced by petroleum based fuels and on average larger than that produced by such petroleum based fuels. In addition, larger particles are less dangerous because they are less likely to remain permanently in the lung than smaller particles. The particulate matter measured in accordance with UNICHIM 494 (Association for Unity in the Chemical Industry, Standard Setting Agency in Italy) was found to be 0.16 mg / Nm3, which means gas oil (0.30 mg / Nm3) and biodiesel ( 0.24 mg / Nm3), much lower than the level observed.

(h) Since vegetable oils or fats are free of sulfur and the amount and form of other components present can be controlled to limit, reduce or eliminate the presence of sulfur (as well as nitrogen), the release of SO ₂ is an effect of the invention. This is not a problem for fuel.

(j) The biofuel compositions of the present invention, particularly those comprising hydrogenated castor oil and / or cetyl alcohol and ethanol, have been observed to exhibit microbial, bacterial and fungal properties. To confirm this activity of the biofuel of the new formulation of Example 1, containing 30 g of hydrogenated castor oil and 500 g of paint solvent, and of Example 2, containing 25 g of cetyl alcohol, three different tests, namely Tests were run against bacteria, spores and fungi / fungi, respectively. Biofuel compositions have shown successful results in the following tests:

Test of activity against spores: Successful sterilization according to the British standard (BS EN 1276) occurs when there is a 5 log reduction in cell number within 5 minutes, which means that the reduction in spore count should be at least 95% for a specified time. do. Based on this, the biofuel composition was tested for bacteria (spores) of the following strains: Mycobacterium smegmatis and Bacillus Stearothermophilus.

Test of Activity Against Fungi: Tests against fungi and fungi followed the guidelines of European Standard 1275 which required a minimum of 4 log reduction in cell count within 5 minutes. The strain used was Candida albicans, strain ATCC No. 10231.

Biofuel compositions prepared according to the methods and components described above include, for example, those useful in conventional diesel engines as well as multi-jet new generation diesel engines. Such compositions may include, for example, about 25 to about 30 weight percent water, about 40 to about 60 weight percent vegetable oil, and about 15 to about 30 weight percent additives.

The following aspects of the invention represent another possible embodiment:

1. Fuel mixture prepared from the following components: (A) 1500 parts of vegetable oil or fat; (B) 900 parts of water; (C) 400 parts of denatured ethanol 90% by weight (180 proofs); And (D) (1) hydrogenated castor oil: (2) cetyl alcohol; And (3) 30 parts of at least one component selected from the group consisting of a mixture of (1) and (2).

2. The fuel mixture of sun 1 further comprises 500 parts of odorless paint solvent.

3. The following components: (A) 1500 parts vegetable oil or fat; (B) 900 parts of water; (C) 400 parts of denatured ethanol 90% by weight (180 proofs); And (D) (1) hydrogenated castor oil: (2) cetyl alcohol; And (3) from 30 parts of at least one component selected from the group consisting of a mixture of (1) and (2), a fuel mixture prepared according to the following method: (I) by mixing components (C) and (D) An additive is formed, (II) the additive is mixed with component (B) to form mixture (II), and (III) mixture (II) is added to (A) at a suitable rate with stirring to substantially emulsify Produces a mixture.

4. A fuel additive comprising the following mixture: (A) 400 parts by weight 90% (180 proofs) of modified ethanol; And (B) (1) hydrogenated castor oil: (2) cetyl alcohol; And (3) 30 parts of at least one component selected from the group consisting of a mixture of (1) and (2).

The following examples are provided as specific illustrations of embodiments of the claimed subject matter. However, the invention is not limited to the specific details set forth in the examples. All parts and percentages in the examples and specification are by weight unless otherwise specified. In addition, all ranges of numbers stated in the specification or claims, such as indicating a particular set of properties, units of measurement, conditions, physical state or percentages, are used herein to refer to all numbers included in such ranges, either intact or otherwise. It is intended to be included explicitly in, including all subsets of the numbers included in all such ranges. For example, whenever a numerical range with a lower limit R _L and an upper limit R _U is disclosed, all numbers R falling within the range are specifically disclosed. In particular, the following numbers within this range are specifically disclosed: R = R _L + k (R _U -R _L ), where k is a variable ranging from 1% to 100% with an increment of 1%, for example k is 1%, 2%, 3%, 4%,… , 50%, 51%, 52%,… 95%, 96%, 97%, 98%, 99%, or 100%. Also specifically disclosed are all numerical ranges represented by the two R values calculated above.

For the purposes of the present invention, the term "substantially" applied to any criteria such as any property, property or variable, unless otherwise defined with respect to a particular property, property or variable, is an advantage to those skilled in the art Or to meet the stated criteria such that the condition or property value desired is understood.

Throughout the specification, including the claims, the word "comprises" and variations thereof, such as "comprising" and "having", "having", "including" and "comprising," and variations thereof, are While the term refers to the designated steps, members or materials being essential, it means that other steps, members or materials can be added and yet still form a structure within the scope of the claims or the disclosure. When referred to in the description and claims of the present invention, it is believed that the present invention and claimed subject matter entail, and potentially be, further. This term is inclusive or open-ended, especially when applied to the claims, and does not exclude additional non-mentioned absence or method steps.

As used throughout the specification, including the described embodiments, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a surfactant” includes not only a single surfactant but also two or more different surfactants in a combined state, and the term “vegetable oils or fats” refers to vegetable oils or fats of two xiangs. As well as containing a single vegetable oil or fat.

The term “about” is in excess of that specifically stated if the value of the relevant property or condition can reasonably meet the technical object (s) of the invention as described in detail in the specification and claims. Contains values that are less than or equal to More specifically, the term "about" when used as a modifier for, or in conjunction with, a variable is intended to be flexible to the numbers and ranges disclosed herein and to one of ordinary skill in the art, for example, By carrying out the present invention using properties such as concentration, amount, content, carbon number, temperature, density, purity, etc. that are outside or different from a single value, the biofuel additive composition or fuel composition or mixture comprising such additive To convey that you will get.

Example 1 New Generation High Pressure Injection Diesel

A fuel mixture is prepared from the following ingredients:

1500 g of vegetable oil or fat;

900 g of water (eg tap water);

400 g of denatured ethanol 90 ° (180 proof);

(a) 30 g of hydrogenated oil of lysine (castor oil); or

(b) a mixture prepared using 30 g of cetalol (cetyl alcohol); And

(c) another mixture prepared by combining (a) + (b) (30 g in total);

And optionally

500 g of odorless paint solvent is included in one or more of the mixtures.

The mixture is suitable for use in new generation high pressure injection diesel engines. Estimated based on current raw material costs, the composition costs about 204 € / 1000L (about $ 0.94 / gal at current exchange rates). The cost for preparing the composition on a commercial scale is expected to be lower. In comparison, the raw material cost of commercial biodiesel fuel is about 492 € / 1000L (about $ 2.26 / gal at current exchange rates).

Example 2 Conventional Tractor Type Low Pressure Injection Diesel

A fuel mixture is prepared from the following ingredients:

1100 g of vegetable oil;

500 g of water;

250 g of ethyl alcohol (180 proof); And

Hydrogenated castor oil; Or cetalol (cetyl alcohol); Or castor oil and

25 g of a mixture of cetalol; And

25 g of paint thinner.

The mixture is suitable for use in conventional tractor type low pressure injection diesel engines. Estimated based on current raw material costs, the composition costs about 243 € / 1000L (about $ 1.12 / gal at current exchange rates). The cost for preparing the composition on a commercial scale is expected to be lower.

Example 3 Modified Conventional Tractor Type Low Pressure Injection Diesel

A fuel mixture is prepared from the following ingredients:

1100 g of vegetable oil;

900 g of water;

250 g of ethyl alcohol (180 proof);

(a) hydrogenated castor oil; Or (b) cetalol; or

25 g of a mixture of (a) and (b); And

300 g of odorless paint thinner.

The mixture is suitable for use in modified conventional tractor type low pressure injection diesel engines.

Example 4 Fuel for Oil Burners

A fuel mixture is prepared from the following ingredients:

900 g of oil;

500 g of water;

(a) castor oil; Or (b) cetalol; or

(c) 25 g of a mixture of (a) and (b); And

250 g of ethyl alcohol.

The mixture is suitable for use in oil burners.

Example 5 Fuel for Modified Oil Burners

A fuel mixture is prepared from the following ingredients:

1100 g of oil;

900 g of water;

375 g of ethyl alcohol;

(a) hydrogenated castor oil; Or (b) 30 g of cetalol.

The mixture is suitable for use in modified oil burners.

Example 6

The fuel mixture of the present invention was prepared as follows: First, water and ethanol were mixed with each other. Then, vegetable oil was slowly added to the alcohol-water mixture with stirring, and finally an emulsifier or surfactant was added to the mixture containing the oil. For the compositions in which the cetane improver was used, the above ingredients were finally added to the mixture. The mixtures were all prepared at ambient temperature or room temperature, 22 ° C. Corresponding mixtures were prepared using an ultrasonic mixing device (“Sonolator”, Ultrasonic Homogenization System, manufactured by Sonic Corp., Connecticut, USA), which is a particularly advantageous device for producing stable emulsions of small particle size, eg, on average less than about 5 μm. Manufactured. The compositions described herein are suitable for preparing emulsions, also referred to herein as microemulsions. Microemulsions can also be prepared at temperatures of 22 ° C. and pressures from about 500 psi to about 1500 psi, and stable microemulsions are produced even at high pressures up to 5000 psi. Fuel components and amounts are shown in the table below:

Fuel mixture vegetable oil**  water  ethanol  Emulsifier ‡ Cetane additive * Biofuel 1 1200g 72.95% by weight 335g 20.36% by weight 105 g 6.38 wt% HCO: 5g 0.31% by weight Biofuel 2 1200g 80.53% by weight 225g 15.11% by weight 53g 3.56% by weight HCO: 5g 0.33% by weight 7g 0.47% by weight Biofuel 3 900 g 59.40 wt% 350g 23.10% by weight 250g 16.50% by weight Tween: 15g 1.00% by weight

** Refined Soybean Oil

• HCO = hydrogenated castor oil, purity 98%; Tween 80

* 2-ethylhexyl nitrate

The mixtures were tested for various properties and performance characteristics using various standard fuels for comparison under various test conditions.

Specifically, Biofuel 3 was tested in a stationary burner and its performance compared to gas oil, biodiesel and BTZ fuel oil and water-based emulsion mixtures. The description and properties of the reference fuel are published by Stazione Sperimentale per i Combustibili (SSC) and Consorzio Ingengneria per l'Ambiente e lo Sviluppo Sosteniblile (IPASS) on December 5, 2005, and can be found at http://www.ssc.it A reported paper (title: "Sperimentazione Combustibili Analisi comparativa di combustibili per uso civile" (fuel experiments, comparative analysis of urban fuels)), the contents of which are incorporated herein by reference. Biofuel 3 was tested using an experimental thermal plant melted with an inverted flame Ravasio Model TRM 150 boiler with an Elco klockner Model EK 3.50 S-Z burner with a nominal heat capacity of 175 kW. The heat generated was discharged to a heat exchanger for performance measurements, and the exhaust gases were also analyzed for emissions. The following conditions were used: fuel tank temperature, about 16 ° C .; Burner preheat temperature, about 60 ° C .; Spray pressure, 28 bar; Fuel feed rate, 23 kg / h; Thermal power, 160 kW; Excess oxygen in the exhaust gas, 6%. BTZ fuel oil was mixed with 13% by weight of water and it was mixed with 20% by weight of biodiesel (standard mixture of fatty acid methyl esters). The test results are reported in the table below.

Test results

fuel BTZ BTZ + water BTZ + Biodiesel Biofuel 3 Test* PM, mg / N㎥ 21.1 10.0 11.1 13.4 PM10, mg / N㎥ 20.9 10.0 11.1 10.8 NOx, mg / A / ㎥ 560.4 469.3 543.7 122 CO, mg / N㎥ 10.7 37.7 10.5 138 UHC, mg / N㎥ <0.4 0.9 <0.4 17.5 Organic matter 2 Formaldehyde, μg / N㎥ 20 10 30 6.44 Acetaldehyde, pg / N㎥ 20 60 - 1.93 Propionaldehyde, pg / N㎥ - - - 0.41 Combustion yield,% 93.4 94.4 92.8 92

* Abbreviations and tests: PM = total particulate matter, UNI 13284-1; PM10 = fine particles, <10 μm, EPA 201A; NOx, nitrogen oxides, UNI 10878; CO, carbon monoxide, UNI 9969; UHC = unburned hydrocarbon, UNI EN 12619; Organic material, SSC test method; Combustion yield or energy efficiency, UNI 10389.

In another laboratory test, Biofuel 3 showed a good flow point of -42 ° C (measured according to ISO 3016-94) and a low heat capacity value typical of viscosity and fuel oil classes (ASTM D 240-02). . As indicated above, Biofuel 3 also produced low NOx and other emissions. Biofuel 3 was also observed to exhibit a balanced and stable dark yellow flame in the burner. It has been observed that the density of the recycled fuel is increased, such a response may be mitigated by further improvement of the emulsion particle size and adjustment to the composition according to the method described above.

The heat capacity and low temperature properties of Biofuel 2 and Biofuel 3 were measured using standard thermogravimetric analysis (TGA) and new modulation differential scanning calorimetry (MTDSC) techniques. For TGA, a heating rate of 10 ° C./min was used until it reached 100 ° C., then the sample was heated in an isothermal manner for 1 hour and then using the same heating rate until reaching 1000 ° C. Completely disassembled. MTDSC was characterized by a linear slope (5 ° C./min) in an inert nitrogen atmosphere; The sinusoidal heating wave (± 0.5 ° C., 60 second period) is superimposed at a temperature interval of −20 ° C. to + 250 ° C. The heating test reflected the stability of the emulsifier (s) as the solvent and water were evaporated at 100 ° C. Laboratory tests indicated that Biofuel 1 was stable up to 200 ° C., while Biofuel 2 was stable up to about 165 ° C. The heat capacity was about 1.6 for biofuel 1 and about 1.8 for biofuel 2, similar to the heat capacity of gas oil. In addition, both Biofuel 1 and Biofuel 2 showed no thermal effect or freezing at -20 ° C.

Further testing was carried out at "Centro Universitario di Ricerca per lo Sviluppo sostenibile" (CIRPS, University Center for Research and Sustainable Development) near Rome, Italy. Biofuel 1 and biofuel 2 for power performance and emissions using two different automotive engines, Fiat Multipla 1.9 jtd (common rail engine) and Fiat Punco 1.7 td (suction engine, also referred to as Fiat Punto TD 70 ELX). Tested it. Power tests were performed using a dynamometer, Cartec LPS 2510, with the following results:

Test Fuel form vehicle Power (kW) Torque (Nm) One diesel Multipla 84.3 215 2 Biofuel 1 " 71.7 160 3 Biofuel 2 " 81.5 209 4 diesel Punto 47.7 123 5 Biofuel 1 " 42.5 117 6 Biofuel 2 " 45.8 127

Compared to conventional diesel, Fiat Multipla power was reduced by about 3% for Biofuel 1 and about 15% for Biofuel 2. In Fiat Punto, the power was reduced by about 4% for Biofuel 2 and about 11% for Biofuel 1 compared to conventional diesel. However, it has been reported that power is reduced by about 11% when comparing conventional biodiesel with conventional diesel. (Energy Intelligence Agency, www.eia.doe.gov/oiaf/analysispaper/biodiesel).

UNICHIM 422, 467 and 494 methods for measuring sulfur and nitrogen oxides; UNI 10169 regulations; And emissions tests were conducted on Biofuel 2 using the same vehicle according to various standards and criteria of DM 25/08/00. The results are summarized in the table below:

Vehicle / fuel Temperature ℃ O ₂ % CO ppm SOx ppm NOx ppm Total amount of carbon dispersed Mg / N㎥ Smoke Index Bacharach Scale * Fiat multipla diesel 62 20.6 147 51.1 35 160.3 6 Biofuel 2 62.5 20.6 123 <1 One 105.7 4 Fiat punto diesel 57 18.4 330 57 36 157 6 Biofuel 2 54.3 18.4 313 <1 33 117 4

Lower values indicate better performance.

The results of these tests indicate that the performance of Biofuel 2 is very good compared to conventional diesel fuel.

Example 7

Compositions of the present invention, referred to as biofuel compositions, include stationary burners or furnaces; For example, they have components that provide compositions that are particularly useful in burners used to generate heat and power. The components are shown in the table below.

 Biofuel 7A Ingredients Sheep, g Volume, wt% Useful range, weight percent  vegetable oil 900 63.649 55-70  water 300 21.216 15-30  Ethyl alcohol, 95% 200 14.144 5-20  Emulsifier * 14 0.990 0.1-5  Sum 1414 100.000 100.000

* Polyoxyethylene (20) sorbitan monooleate (Tween 80)

The composition represented as biofuel 7A was evaluated in several standard fuel tests. Such tests and results are summarized in the table below:

 Test  Way  result  API degree @ 60 ℉  ASTM D4052  21.04 Deg. API  sulfur  ASTM D4294  0.0206 wt%  flash point  ASTM D93A  72 ℉  Sedimentation and water  ASTM D1796  0.05 volume%  Viscosity Kin @ 100 ℉  ASTM D445  22.93 cSt  10% bottom of carbon residue  ASTM D4530  <0.05 wt%  Sulfated ash  ASTM D874  <0.001 wt%  Hydrogen  ASTM D5291  12.27 wt%  Copper corrosion  ASTM D130  1a rating  Total acidity  ASTM D664  0.040 mg KOH / g  Solubility (BS & W)  ASTM D96  <0.1%  Specific Gravity @ 60 ℉ / 60 ℉  AOCS Cc 10a-25  0.9341  Bomb calorimetry  ASTM D240  11,900 BTU / lb  sign  ASTM D1091  3.4 ppm  sulfur  ASTM D129  18 ppm  Blur point (gel point)  EN ISO 6245  -28 ℉  potassium  EPA 258.1  <0.1 ppm  salt  EPA 273.1  <0.1 ppm  calcium  EPA 215.1  3.6 ppm  BTU / gal *  92,600

* Calculated from density and bomb calorimetry data

Another biofuel composition, particularly useful for vehicles such as passenger cars, trucks, farm equipment, etc., preferably having a diesel engine or an engine suitable for burning diesel fuel or equivalents thereof, is prepared according to the following formula:

 Biofuel 7B Ingredients  Sheep, g  Volume, wt%  Useful range  vegetable oil 1200 80.53 75-85%  water 225 15.11 5-20%  Ethyl alcohol, 95% 53 3.56 1-5%  Emulsifier * 5 0.33 0.1-5  Cetane improver ** 7 0.47 0.1-1%               Sum 1490 100.00 100.00

* Mixture: 50% by weight of polyoxyethylene (20) sorbitan monooleate (Tween 80) + 50% by weight of sorbitan monolaurate (Span 20)

** 2-ethylhexyl nitrate

Example 8

Another biofuel composition of the invention was prepared as follows: Water and propylene glycol were first mixed together. A small amount of vegetable oil was then slowly added to the alcohol-water mixture, stirred after each addition, and finally an emulsifier or surfactant was added to the mixture containing the oil. The mixture was prepared at 22 ° C. near room temperature. As an alternative, the mixture was prepared using an ultrasonic mixing device as described above. However, using all of these components at the same time, it was possible to obtain a stable emulsion, ie a microemulsion with a small particle diameter of, for example, about 5 μm on average. As noted above, microemulsions could also be prepared at temperatures of 22 ° C. and pressures from about 500 psi to about 1500 psi, as well as high pressures up to 5000 psi. The fuel composition of this embodiment has resulted in a composition particularly useful for applications requiring elevated flash points compared to the compositions identified above, including but not limited to applications such as diesel engines for vehicles and burners, utilizing the above components. . The fuel components are shown in the table below:

 Biofuel 8 Ingredients Volume, wt% Useful range, weight percent  vegetable oil 66 55-75  water 23.5 15-30  Propylene glycol 9.5 5-20  Emulsifier * One 0.1-5               Sum 100.000 100.000

* Polyoxyethylene (20) sorbitan monooleate (Tween 80)

The composition represented as Biofuel 8 was evaluated in several standard fuel tests. Such tests and results are summarized in the table below:

 Test  Way  result  unit  API degree @ 60 ℉  ASTM D4052  15.7  Deg. API  sulfur  ASTM D4294  0.0202  weight%  flash point  ASTM D93A  167-205  ℉  Sedimentation and water  ASTM D1796  1-4  volume%  Viscosity Kin @ 100 ℉  ASTM D445  11-52.4  cSt  10% bottom of carbon residue  ASTM D4530  <0.05  weight%  Sulfated ash  ASTM D874  <0.001  weight%  Hydrogen  ASTM D5291  12.23  weight%  Copper corrosion  ASTM D130  1a  Rating  Total acidity  ASTM D664  0.039  mg KOH / g

Clearly, the flash point of biofuel 8 is significantly higher than the flash point of biofuel 7A. In addition, a mixture of up to 25% by weight of biofuel 8 and conventional diesel fuel, biodiesel fuel and ethanol can be prepared, and the two fuel mixtures can be easily dispersed with each other and are stable. That is, the mixture does not separate into different phases.

Example 9

In another example, 0.5% by weight of cetane improver 2-ethyl hexyl nitrate was added to the composition of Biofuel 8 to produce a stable biofuel composition that is included in the scope of the present invention and exhibits increased cetane number.

Example 10

Another formulation was prepared and tested to evaluate the stability of the vegetable oil based emulsion composition. The formulation is shown in the table below:

 Example 10 Ingredients, Weight%  One  2  3  vegetable oil 75.9 80 80  water 18.5 4 4  Ethyl alcohol (95%) 4.5 14 14  Emulsifier (s) * 0.6 One 0.5 + 0.5  Cetane improver ** 0.5 One One                   Sum 100.0 100.0 100.0  Emulsion stability weight%, (ASTM D96) <0.1 5 none

10-1 and 10-2: polyoxyethylene (20) sorbitan monooleate (Tween 80);

  10-3: Mixture of Tween 80 and Sorbitan Monooleate (Span 80)

** 2-ethylhexyl nitrate

Based on the amount of sediment that can be separated, Example 10-1 in the table is characterized as a stable emulsion fuel, while Example 10-2 is considered unstable. However, by using a blend of emulsifiers with an effective HLB of 9.6 ((0.5 × 14.9) + (0.5 × 4.3)), the properties of the composition could be altered to obtain a sufficiently stable emulsified fuel.

While the invention has been described above with reference to specific embodiments, it should be understood that these embodiments are merely illustrative of the principles and applications of the invention. Accordingly, it should be understood that various modifications may be made to the exemplary embodiments, and that other methods may be devised without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (37)

(A) a continuous phase comprising about 50-95% by weight of one or more liquid oils or mixtures thereof from a plant or animal; (B) a water containing dispersed phase comprising about 1 wt% to about 50 wt% water; (C) a hydroxyl group-containing organic compound selected from the group consisting of monohydric, dihydric, trihydric and polyhydric alcohols, provided that at least one tert is present -Butyl alcohol, one or more C2-C4 alkylene glycols or a mixture of both materials are also present) about 1% to about 25% by weight; And (D) about 0.05% to about 10% by weight of one or more emulsifiers As a biofuel (biofuel) composition comprising an aqueous emulsion comprising a, Wherein said dispersed phase comprises water containing droplets having an average particle diameter of less than about 20 μm, wherein all amounts are expressed based on the total weight of the composition. The method of claim 1, Wherein said at least one emulsifier exhibits a hydrophilic-lipophilic balance (HLB) of about 8.5 to about 18. The method of claim 2, The at least one emulsifier is polyethylene glycol-polypropylene glycol block copolymer, sorbitan monooleate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monolaurate, polyoxyethylene (20) sorbitan triol Biofuel selected from the group consisting of latex, polyethylene (20) sorbitan monooleate, polyethylene (20) sorbitan monolaurate, and mixtures thereof. The method of claim 1, A biofuel further comprising an amount of an additive effective to increase the cetane number of the biofuel composition. The method of claim 4, wherein The cetane additive is selected from the group consisting of peroxides, nitrates, nitrites, nitrocarbamate, and mixtures thereof. The method of claim 5, The cetane additive is selected from the group consisting of substituted or unsubstituted alkyl or cycloalkyl nitrates having about 10 carbon atoms, and mixtures thereof. The method of claim 5, The cetane additive is selected from the group consisting of dialkyl peroxides of the formula R1OOR2, where R1 and R2 are the same or different alkyl groups having from 1 to about 10 carbon atoms. The method of claim 5, The cetane additive is selected from the group consisting of 2-ethylhexyl nitrate, di-tert-butyl peroxide, and mixtures thereof. The method of claim 1, The hydroxyl group-containing organic compound consists of C1 to C4 straight and branched monoalcohols, C2 to C4 mono- and poly-alkylene glycols, derivatives of C2 to C4 mono- and poly-alkylene glycols, and mixtures thereof. And at least one selected from the group wherein the molecular weight of the polyalkylene glycol is suitable for the fuel composition. The method of claim 9, The alcohol is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and mixtures thereof. The method of claim 1, A biofuel further comprising a complementary low viscosity and low density flammable liquid, selected from the group consisting of hydrocarbon solvents, paint thinners, terpenes, mineral spirits, and mixtures thereof. As a method of preparing an emulsified fuel composition, (A) preparing the following ingredients based on the total weight of the composition: (1) about 50% to about 95% by weight of one or more liquid oils or mixtures thereof from a plant or animal; (2) an amount of water sufficient to produce a water-containing dispersed phase comprising from about 1% to about 50% by weight of water; (3) hydroxyl group-containing organic compounds selected from the group consisting of monovalent, divalent, trivalent and polyhydric alcohols, provided that at least one tert-butyl alcohol and at least one C2-C4 alkylene glycol are present Or a mixture of these two materials is also present) about 1% to about 25%; And (4) about 0.05% to about 10% by weight of one or more emulsifiers; And (B) mixing the components (A) (1) to (A) (4) under conditions of high shear to produce a dispersed phase comprising water-containing droplets having an average particle diameter of less than about 20 μm. step Method of producing an emulsified fuel composition comprising a. The method of claim 12, Wherein said dispersed phase comprises water-containing droplets having an average particle diameter of about 0.1 μm to about 10 μm. The method of claim 13, Wherein said at least one emulsifier exhibits a hydrophilic-lipophilic balance, HLB of about 8.5 to about 18. The method of claim 14, The at least one emulsifier is polyethylene glycol-polypropylene glycol block copolymer, sorbitan monooleate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monolaurate, polyoxyethylene (20) sorbitan triol A method for producing an emulsified fuel composition selected from the group consisting of latex, polyethylene (20) sorbitan monooleate, polyethylene (20) sorbitan monolaurate, and mixtures thereof. The method of claim 13, And further providing an additive in an amount effective to increase the cetane number of the biofuel composition. The method of claim 14, And the cetane additive is selected from the group consisting of peroxides, nitrates, nitrites, nitrocarbamates, and mixtures thereof. The method of claim 12, The hydroxyl group-containing organic compound consists of C1 to C4 straight and branched monoalcohols, C2 to C4 mono- and poly-alkylene glycols, derivatives of C2 to C4 mono- and poly-alkylene glycols, and mixtures thereof. And at least one selected from the group, wherein the molecular weight of said polyalkylene glycol is suitable for said fuel composition. The method of claim 12, Wherein said components are prepared and mixed at substantially the same time. The method of claim 16, Premixing the water with components other than the vegetable oil to produce an aqueous mixture, and then mixing the aqueous mixture with the vegetable oil. The method of claim 13, A method for producing an emulsified fuel composition using a high shear generation mixing device. The method of claim 21, A method for producing an emulsified fuel composition, wherein high shear is generated using a mixing device capable of generating ultrasonic energy to introduce ultrasonic energy into the mixture. The method of claim 22, Wherein the amount of emulsifier is from about 20% to about 90% of the amount of emulsifier required to obtain the dispersed particle diameter without using ultrasonic energy. As an emulsified fuel according to claim 1, The average droplet diameter is about 0.01 μm to about 15 μm; 0.1 μm to about 10 μm; An emulsified fuel selected from the group consisting of 0.5 μm to about 5 μm, and combinations thereof. The method of claim 24, An emulsified fuel further comprising an amount of an additive effective to increase the cetane number of the biofuel composition. The method of claim 25, The cetane additive is an emulsified fuel selected from the group consisting of peroxides, nitrates, nitrites, nitrocarbamates, and mixtures thereof. As an emulsified fuel according to claim 1, Heat stabilizers, aging stabilizers, antioxidants, colorants, dyes, markers, odor modifying agents, rust inhibitors, gum forming inhibitors, metal activity removers, upper cylinder lubricants, An emulsified fuel further comprising at least one selected from the group consisting of friction modifiers, cleaners, bacteriostatic agents, fungicides, microbiocides, and mixtures thereof. The method of claim 25, The emulsifier is polyethylene glycol-polypropylene glycol block copolymer, sorbitan monooleate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monolaurate, polyoxyethylene (20) sorbitan trioleate, Selected from the group consisting of polyethylene (20) sorbitan monooleate, polyethylene (20) sorbitan monolaurate, and mixtures thereof, wherein the alcohol is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, di An emulsified fuel selected from the group consisting of propylene glycol, tripropylene glycol, and mixtures thereof. The method of claim 28, An emulsified fuel further comprising a complementary low viscosity and low density combustible liquid, selected from the group consisting of hydrocarbon solvents, paint diluents, terpentine, mineral spirits, and mixtures thereof. The method of claim 1, A biofuel composition comprising an oil obtained from a plant seed or fruit, or a mixture thereof. The method of claim 12, A method of making an emulsified fuel composition comprising an oil obtained from a seed or fruit of a plant, or a mixture thereof. The method of claim 2, At least one of the emulsifiers comprises a mixture of two or more emulsifiers, at least one of the two emulsifiers exhibits a low HLB value of about 1 to about 6, and at least one of the two emulsifiers has a high HLB of about 6 to about 20 Biofuel, wherein both the low and high HLB values are not six. 33. The method of claim 32, A biofuel having the sum of (I) the weight of (a) water and (b) the weight of hydroxyl-containing organic compounds divided by (II) the weight of vegetable and animal fats and oils. The method of claim 14, At least one of the emulsifiers comprises a mixture of two or more emulsifiers, at least one of the two emulsifiers exhibits a low HLB value of about 1 to about 6, and at least one of the two emulsifiers has a high HLB of about 6 to about 20 A value, wherein both the low and high HLB values are not six. The method of claim 34, wherein A method of producing an emulsified fuel composition, wherein the sum of (I) the weight of water and (b) the weight of the hydroxyl group-containing organic compound divided by the weight of (II) vegetable and animal fats and oils is about 0.25 or less. The following ingredients: (A) 1500 parts of vegetable or animal oils or fats; (B) 900 parts of water; (C) 400 parts of 90% by weight (180 proof) of denatured ethanol; And (D) (1) hydrogenated castor oil; (2) cetyl alcohol; And (3) 30 parts of at least one component selected from the group consisting of a mixture of (1) and (2) above; An emulsified fuel mixture prepared from and optionally further comprising 500 parts of supplementary flammable liquid. (I) (A) 400 parts of 90% by weight (180 proofs) of modified water-containing ethanol; (B) (1) hydrogenated castor oil; (2) cetyl alcohol; And (3) mixing 30 parts of at least one component selected from the group consisting of a mixture of (1) and (2) to form an additive; And (II) mixing the additive with component (B), which is 900 parts of water, to form a mixture (II); (III) adding said mixture (II) to 1500 parts of (D) vegetable or animal oil or fat and mixing at the same time to produce a substantially emulsified mixture.