WO2007127059A2 - Composition de biocombustible et procédé de production d'un biocombustible - Google Patents

Composition de biocombustible et procédé de production d'un biocombustible Download PDF

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Publication number
WO2007127059A2
WO2007127059A2 PCT/US2007/008955 US2007008955W WO2007127059A2 WO 2007127059 A2 WO2007127059 A2 WO 2007127059A2 US 2007008955 W US2007008955 W US 2007008955W WO 2007127059 A2 WO2007127059 A2 WO 2007127059A2
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WIPO (PCT)
Prior art keywords
biofuel
mixtures
mixture
oil
water
Prior art date
Application number
PCT/US2007/008955
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English (en)
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WO2007127059A3 (fr
Inventor
Ferdinando Petrucci
Andrea Festuccia
Original Assignee
New Generation Biofuels, Inc.
Ptj Bioenergy Holding Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to AU2007243536A priority Critical patent/AU2007243536A1/en
Priority to MX2008013727A priority patent/MX2008013727A/es
Priority to US12/226,637 priority patent/US20100037513A1/en
Priority to CA002650333A priority patent/CA2650333A1/fr
Priority to JP2009507709A priority patent/JP2009535449A/ja
Priority to BRPI0710806-0A priority patent/BRPI0710806A2/pt
Application filed by New Generation Biofuels, Inc., Ptj Bioenergy Holding Ltd. filed Critical New Generation Biofuels, Inc.
Priority to EP07755282A priority patent/EP2010631A4/fr
Priority to AP2008004651A priority patent/AP2008004651A0/xx
Publication of WO2007127059A2 publication Critical patent/WO2007127059A2/fr
Publication of WO2007127059A3 publication Critical patent/WO2007127059A3/fr
Priority to IL194795A priority patent/IL194795A0/en
Priority to TNP2008000421A priority patent/TNSN08421A1/en

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C10L1/328—Oil emulsions containing water or any other hydrophilic phase
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/12—Use of additives to fuels or fires for particular purposes for improving the cetane number
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/1802—Organic compounds containing oxygen natural products, e.g. waxes, extracts, fatty oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/1811—Organic compounds containing oxygen peroxides; ozonides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
    • C10L1/231—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites nitro compounds; nitrates; nitrites
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to fuel additives, methods of making such additives and fuel compositions employing such additives, wherein the fuel is substantially based on vegetable or animal sources .
  • biodiesel fuel Efforts to find alternative fuels to those derived from petroleum, such as gasoline and diesel fuel, have led to the development of biodiesel fuel.
  • Traditional biodiesel is produced by transesterification of vegetable oils or fats.
  • a vegetable fat or oil reacts with an esterifying agent, typically an alcohol, for example methanol or ethanol, with or without a catalyst and with the input of additional energy usually at atmospheric pressure .
  • the time of the reaction can range from 0.5 to 8 hours depending on the temperature .
  • oils and fats are often considered synonyms, and for the purposes of the present application can be considered chemically interchangeable, the distinction between such products being that they are merely distinguished on the basis of their physical state.
  • an "oil” is typically used to describe products that are liquid at ambient or room temperature whereas the term “fat” is used to describe products that are typically substantially solid at room temperature.
  • fat is typically used to describe products that are typically substantially solid at room temperature.
  • room temperature may be considered a "fat” in one latitude at a given time of the year
  • fats and oils should be understood to refer to vegetable or animal oil components useful in the present invention, as opposed to, e.g., petroleum oils.
  • an oil obtained from petroleum such as diesel oil, gas oil and the like
  • it is present as an additive or minor component, in other words, in an amount less than 50 wt%; for example, less than about 40, 30, 20, 10, 5 or even 3 wt%,- such as from greater than about 0 wt% to less than about 5 wt%, or 10 wt%, or 15 wt% or 20 wt%, or 25 wt%.
  • Biodiesel A common vegetable-oil-derived fuel, typically used as a fuel for diesel engines is referred to as “biodiesel .
  • Biodiesel is made utilizing the chemical reaction known as transesterification. The process forms two principal products, fatty acid methyl esters (FAME, the chemical name for biodiesel) and glycerin. In this reaction a vegetable oil or fat reacts with an esterifying agent, usually an alcohol
  • a biodiesel fuel generated in this way and used in its pure form (in other words without being "diluted” with another fuel, whether a petroleum based fuel or ethanol) at 100% is referred to as "B 100". If it is diluted with another fuel, e.g., diesel fuel or gas oil, it is typically identified by the percentage of biodiesel present, e.g., B5, B20, B30, etc.
  • biodiesel fuel exhibits a distillation curve that is different from traditional gas oil.
  • biodiesel requires further adjustments of the relationship of primary air to secondary air (regulation of the combustion head) .
  • this introduces further complications since increasing secondary air improves cold performance of the engine, but slightly worsens equilibrium combustion and vice versa.
  • Another disadvantage of traditional biodiesel arises from the high solvent power of methyl ester. This can cause damage to incompatible plastics, generally present as liners and seals, and may also create problems with deposits of gas oil inadvertently left in the storage tanks. Therefore, substitution for, or at least the periodic maintenance of the polymeric components, is also required (including, for example, the intake and return tubes, the compression seals of the pump, the bending elements, and the liners and seals) .
  • Methanol used in the transesterification process results in a minimal addition of fossil-based CO 2 in the balance of traditional biodiesel.
  • the source of oil used to produce the biodiesel is derived from renewable sources (typically referred to as biomass)
  • biomass typically referred to as biomass
  • all of the CO 2 produced by the combustion of the biodiesel is renewable .
  • the problem of nitrogen oxides, currently considered among the most undesirable by-products of combustion is the weak point of traditional biodiesel fuel .
  • NOx emissions increase 10-13% with respect to gas oil on account of the high oxygen content of the biofuel .
  • Even mixes containing less than 100% biodiesel cause an increase in NOx emissions. For example, for B20, the increase is around a 2-3 % over gas oil.
  • Particulate emissions from the burning of biodiesel may be related to the chemical composition of the source used to synthesize the biodiesel and also may be indicative of combustion-related problems.
  • the danger associated with such particulates varies with their chemical composition and to the average dimension of the particles.
  • the particles can also absorb and/or adsorb a certain amount of aromatic substances that are considered more or less carcinogenic and/or mutagenic.
  • SO 2 emission can be a problem if the biodiesel is not entirely devoid of sulfur. Obviously the mixture of gas oil and biodiesel leads to an increase in emissions of SO 2 that is proportionate to the content of fossil fuel .
  • the use of traditional biofuel in boilers has not yet been the subject of in-depth study.
  • the measured quantity of particulate emissions, NOx, SO 2 and CO, from the stack of a 1750 kWatt boiler fed with biodiesel compared with those emitted from one that burns gas oil containing 0.25 wt% sulfur show that the pollutants emitted by biodiesel are less than those of gas oil-with the exception of NOx, which is higher.
  • an emulsified biofuel composition suitable for use in diesel engines comprises: (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 at least one emulsifier preferably exhibits 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 .
  • the dispersed aqueous phase in an emulsified fuel comprising a vegetable oil continuous phase exhibits an average droplet particle size of about 0.01 to about 15 microns and the emulsifier (s) exhibit a hydrophilic- lipophilic balance, HLB, of about 8.5 to about 18.
  • an emulsified fuel mixture is prepared from the following components : (A) vegetable or animal oil or fat, including mixtures thereof; and B) water; and (C) at least one alcohol selected from the group consisting of Cl to C4 alcohols; and, (D) at least one surfactant or emulsifier and optionally a supplementary low viscosity, low density combustible liquid selected from the group consisting of hydrocarbon solvents, paint thinner, turpentine, mineral spirits and mixtures thereof.
  • the latter emulsified fuel mixture can be prepared according to the following method: (I) components (C) and (D) are mixed with one another to produce an additive and the additive is combined with water (B) to form mixture (II) . Mixture (II) is added with concurrent mixing, at a suitable rate to the vegetable oil, component (A) , in order to produce a substantially emulsified mixture.
  • emulsion refers to a mixture or dispersion of two immiscible substances, liquids in the present invention, in which one substance, the dispersed phase, is dispersed in the other substance, the continuous phase.
  • An emulsion is stabilized, in other words the dispersed phase remains dispersed during the relevant time period, such as during storage and/or immediately prior to and during use, with the assistance of one or more substances known as emulsifiers.
  • An emulsion can be a water-in-oil emulsion or an oil-in-water emulsion depending on such variables as the amount of oil (as well as type of oil) and water present, the conditions used to prepare the emulsion, the emulsifier type and amount, the temperature and combinations of such variables.
  • 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 specific use may vary depending on the particle size of the dispersed phase. Particle size is typically expressed in terms of mean or average size since the uniformity of the dispersed phase can also vary depending on the variables noted above.
  • Particle size does not require that the particles are necessarily spheres and the size of the particles can be based on a major or average dimension of each particle, although in a system comprising a dispersed liquid phase in a continuous liquid phase, fluid dynamics suggest that the dispersed particles will tend to be substantially spherical .
  • emulsifier refers to a compound or mixture of compounds that has the capacity to promote formation of an emulsion and/or substantially stabilize an emulsion, at least for the short-term, i.e., during the time of practical or commercial interest.
  • An emulsifier provides stability against significant or substantial aggregation or coalescence of the dispersed phase of an emulsion.
  • An emulsifier is typically considered to be a surface active substance in that it is capable of interacting with the dispersed and continuous phases of an emulsion at the interface between the two.
  • a "surfactant” and an “emulsifier” are considered equivalent or interchangeable terms .
  • surfactant are included the various types of surfactants such as nonionic, ionic or partially ionic, anionic, amphoteric, cationic and zwitterionic surfactants .
  • cetane number refers to a measure of diesel fuel ignition characteristics which is analogous to octane number for gasoline and, similarly, higher values indicate better performance.
  • a specific test has been developed and accepted by the fuel industry and it is defined, for example, by various standards setting organizations including ASTM D613, IP 41, and EN ISO 5165.
  • the test method determines the rating of diesel fuel oil in terms of an arbitrary scale of cetane numbers using a standard single cylinder, four-stroke cycle, variable compression ratio, indirect injected diesel engine.
  • the cetane number scale covers the range from zero to 100 but typical test results for diesel fuel and fuels intended for use in diesel applications are typically in the range of 30 to 65 cetane number.
  • flash point generally refers to how easily a substance or composition, typically a fluid, may ignite or burn.
  • the measurement of flash point is defined in test methods that are maintained by standardization bodies such as the Energy Institute in the UK, ASTM in the USA, CEN in Europe and ISO internationally.
  • ASTM D975. The flash point of a fuel is essentially the lowest temperature at which vapors from a test portion combine with air to give a flammable mixture and "flash" when an ignition source is applied. Materials with higher flash points are less likely to ignite than those with lower flash points.
  • a flash point of 66 0 C to 93 0 C (150 0 F to 200 "F) is considered to present a moderately low ignition hazard and a flash point of 38 0 C to 66 ⁇ C (100 0 F to 150 0 F) is considered to present a moderate to high ignition hazard.
  • diesel fuel has a flash point of about 38 ⁇ C to 54 0 C (100 0 F- 130 °F) and gasoline a flash point of about -40 0 C to -46 °C
  • 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 .
  • mixing when used generically or without a modifier includes each of the processes described herein for dispersing one ingredient in another.
  • hydrocarbyl substituent or "hydrocarbyl group” is used in its ordinary sense, which is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
  • hydrocarbyl groups include: (1) hydrocarbon substituents , that is, aliphatic (e.g., alkyl or alkenyl) , alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form an alicyclic radical) ; (2) substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon substituent (e.g.
  • hetero substituents that is, substituents which, while having a predominantly hydrocarbon character, in the context of this invention, contain other than carbon in a ring or chain otherwise composed of carbon atoms.
  • Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituents as pyridyl, furyl, thienyl and imidazolyl.
  • no more than two, preferably no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; typically, there will be no non-hydrocarbon substituents in the hydrocarbyl group.
  • stable when used in reference to an emulsion refer to the dispersed or hydrophilic phase remaining substantially dispersed in the lipophilic phase (vegetable and/or animal oil and/or fat) .
  • substantially no phase separation occurs as indicated by visual observation after a period following preparation of the emulsion of at least about 24 hours; preferably at least about 48 hours, more preferably at least about 72 hours; for example, substantially no phase separation is observable after about 4 days or more, at ambient temperatures suitable for use of the emulsified fuel composition in its directed application, for example, use in burners, motor vehicles and the like.
  • stability can be characterized by measuring sediment formation according to the test method ASTM D96.
  • compositions of the present invention characterized for purposes of the present invention as fuel compositions, and referred to as "biofuel, " are suitable for use in internal combustion engines, preferably diesel engines of various configurations as well as in equipment that combusts fuels to generate heat, such as furnaces, boilers, power generating equipment and the like, including gas or combustion turbines.
  • Diesel engines that may be operated with compositions of the present invention include all compression-ignition engines for both mobile (including locomotive and marine) and stationary power plants. These include diesel engines of the two-stroke- per-cycle and four-stroke-per-cycle types.
  • the diesel engines include but are not limited to light and heavy duty diesel engines and on and off-highway engines, including new engines as well as in-use engines .
  • the diesel engines include those used in automobiles, trucks, buses including urban buses, locomotives, stationary generators, and the like.
  • the compositions are useful in different types of oil burners for domestic and other heating purposes including sleeve burners, natural-draft pot burners, force-draft pot burners, rotary wall flame burners, and air-atomizing and pressure-atomizing gun burners; with the latter type of burner being the most commonly used burner for home heating, particularly in the United States.
  • such compositions are useful fuels for diesel motors (both new and old generation) and/or boilers and single- or multi-step burners, also referred to in the art as staged burners.
  • Various mixing devices well known in the art can be employed to facilitate formation of an emulsified composition of the instant embodiment as well as the present invention generally including, for example, mixer-emulsifiers, which typically utilize a high speed rotor operating in close proximity to a stator (such as a type made by Charles Ross & Sons Co. , NY) , paddle mixers utilizing paddles having various design configurations including, for example, reverse pitch, anchor, leaf, gate, finger, double-motion, helix, etc., including batch and in-line equipment, and the like.
  • mixer-emulsifiers typically utilize a high speed rotor operating in close proximity to a stator (such as a type made by Charles Ross & Sons Co. , NY)
  • paddle mixers utilizing paddles having various design configurations including, for example, reverse pitch, anchor, leaf, gate, finger, double-motion, helix, etc., including batch and in-line equipment, and the like.
  • the processes of various embodiments of the present invention can be carried out at a convenient temperature, including, for example, at ambient or room temperature, such as about 20 0 C to about 22 0 C or even as high as 25 0 C.
  • the time and temperature of mixing can be varied provided that the desired emulsified composition is achieved and, based on subsequent observation and/or testing, it is suitably stable until it is used, as well as during use.
  • it can be desirable to wait for a period of time in order to allow for sedimentation, if any, to occur, such material to subsequently be removed or separated from the emulsified fuel composition.
  • time period is at least about 4 minutes; preferably about 5 minutes; more preferably about 6 minutes or more.
  • time can readily be determined with limited and simple experiments and such, time can be adjusted, based on, for example, the type, quality and composition of the vegetable oil employed, as well as the other components of the mixture, including emulsifier (s) .
  • Mixing methods in additions to those described above are suitable for use in the present invention and in some instances are particularly preferred.
  • Mixtures can be prepared with traditional mixing or blending equipment such as vats or tank equipped with motor driven stirrers having various configurations, e.g., paddle, helix, etc.
  • mixing carried out in such equipment is time consuming, often requiring greater than 10 minutes of mixing, for example, about 10 to about 30 minutes, alternately about 15 to about 20 minutes in order to achieve a uniform and stable emulsion.
  • Such emulsions contain dispersed particles having an average particle size, e.g., diameter or average dimension on the order of greater than about 20 microns,- for example, about 20 to about 50 microns; alternatively about 20 to about 35 microns.
  • Emulsions having an average particle size of about 20 microns or greater are referred to herein as "macroemulsions . "
  • a fuel composition having macroemulsion characteristics will typically exhibit properties that differ from the same fuel composition having an average particle size that is significantly smaller, in other words, a microemulsion or one in which the particle size is less than about 20 microns, such as 19 microns or less.
  • a given composition in macroemulsion form may exhibit a higher viscosity, lower flash point and poorer stability in a process requiring extended recirculation of the fuel composition as well as requiring a greater amount of emulsifier in order to produce a satisfactory and stable emulsion compared to the same composition in microemulsion form.
  • fuel mixtures of the present invention are prepared using ultrasonic mixing equipment, which equipment is particularly advantageous for preparing stable emulsions having a small particle size, for example less than about 10 microns , or about 0.01 to about 5 microns on average, in other words embodiments of a microemulsion.
  • Nonolator ultrasonic homogenizing system
  • Sonic Corp. Conn.
  • Such microemulsions can be prepared at ambient temperature, for example about 22 0 C, and at pressures of about 500 psi to about 1500 psi, although pressures as high as 5000 psi can also be used to produce stable microemulsions.
  • the Sonolator system is particularly useful in that it can be operated in alternative, useful modes, including semi-continuous, continuous, single-feed or multiple-feed.
  • such a system operated in multiple-feed mode can utilize feed tanks containing, for example, vegetable oil, water, emulsifier and other components, such as alcohol, cetane enhancer, alkyl glycol or alkyl glycol derivative, etc.
  • feed tanks containing, for example, vegetable oil, water, emulsifier and other components, such as alcohol, cetane enhancer, alkyl glycol or alkyl glycol derivative, etc.
  • Such a system allows feeding of one or more of the components simultaneously, sequentially or intermittently in order to achieve a particularly desirable result, including but not limited to a specific emulsion particle size, particle size distribution, mixing time, etc.
  • fuel compositions prepared using ultrasonic emulsification can be accomplished using a lower concentration of emulsifier for the same concentration of other components, particularly the vegetable oil(s) and water.
  • a composition prepared without ultrasonic mixing requires about 1.0 wt% emulsifier to obtain a satisfactory emulsion, it may only require less than about 0.5 wt% emulsifier with the same composition in order to obtain a satisfactory emulsion, preferably an enhanced emulsion in that the particle size is smaller, resulting in a microemulsion.
  • the amount of emulsifier is about 10% less than would be required in the absence of ultrasonic emulsification; preferably about 20% less; more preferably about 30% less; still 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 the use of ultrasonic energy input.
  • an emulsified fuel composition requiring 1 wt% emulsifier to obtain an average emulsion particle size of about 20 microns can be replaced with 0.2 wt% of the same emulsifier in the same composition to obtain an emulsion having a particle size of about 5 microns.
  • a device that introduces ultrasonic energy for mixing and emulsification is referred to as a "high shear" method, regardless of the physical processes that may occur on a microscopic or molecular scale.
  • Emulsification using high shear such as imparted by an ultrasonic device results in an emulsion having a mean particle or droplet size in the range of about 0.01 microns to less than about 20 microns; such as about 0.01 microns to about 15 microns; or about 0.1 microns to about 10 microns; about 0.1 microns to about 8 microns ; about 0.2 microns to about 6 microns; about 0.5 microns to about 5 microns; about 0.5 microns to about 4 microns; about 0.5 microns to about 3 microns; about 0.5 microns to about 3 microns; about 0.1 microns to about 2 microns ; about 0.1 microns to about 1 micron; or about 0.1 microns to about 1 micron or less, for example about 0.8 microns .
  • the dispersed phase or the water- containing phase of the fuel composition comprises droplets having a mean diameter, or major dimension, of 5 microns or less.
  • emulsification is conducted under conditions sufficient to provide such a mean droplet particle size.
  • High-shear devices include but are not limited to the Sonic Corporation Sonolator Homogenizing System, in which pressure can be varied over a wide range, for example about 500 to about 5,000 psi; IKA Work Dispax, and shear mixers including multistage, for example, three stage rotor/stator combinations.
  • the tip speed of the rotor/stator generators may be varied by a variable frequency drive that controls the motor.
  • Silverson mixer two-stage mixer which also incorporates a rotor/stator design and the mixer employs high-volume pumping characteristics similar to a centrifugal pump.
  • Inline shear mixers employing a rotor-stator emulsification approach (Silverson Corporation) ; Jet Mixers, venturi-style/cavitation shear mixers; Microfluidizer shear mixers, high-pressure homogenization shear mixers (Microfluidics Inc.); and any other available high-shear generating mixer capable of producing the desired microemulsion, including high shear mixers selected from the group consisting of Aquashear mixers (Flow Process Technologies Inc.), pipeline static mixers, hydraulic shear devices, rotational shear mixers, ultrasonic mixing, and combinations thereof .
  • Mixing of the components is preferably conducted at ambient, or substantially ambient, temperature conditions. It has been observed that in some instances mixing to obtain the emulsified fuel composition is accompanied by a slight exothermic response. Mixing can be satisfactorily conducted at temperatures in the range of about 5 0 C to about 75 0 C; for example about 10 ⁇ C to about 65 0 C; or about 15 0 C to about 55 0 C; or about 20 0 C to about 45 0 C; such as 22 0 C to about 35 0 C.
  • the water used in the compositions of the present invention can be from any source.
  • the water employed in preparing the fuel compositions of the present invention can be deionized, purified for example using reverse osmosis or distillation, and/or demineralized and have a low content of dissolved minerals, for example, salts of calcium, sodium and magnesium, and will similarly include little, if any, chlorine and/or fluorine as well as being substantially free of undissolved particulate matter.
  • the water has been substantially demineralized by methods well known to those skilled in the art of water treatment in order to remove dissolved mineral salts and has also been treated to remove other additives or chemicals, including chlorine and fluorine.
  • the substantial absence of such materials is expected to lead to improvements in the condition of metal surfaces in engines and burners, particularly the inner surfaces of cylinders and nozzles.
  • the water may be present in the water-vegetable oil fuel emulsions at a concentration of about 1% to about 50% by weight; alternatively about 2% to about 50% by weight; about 3% to about 40% by weight; about 4% to about 35% by weight; and about 5% to about 30% water.
  • the fuels useful in the present invention are based on animal derived oils and fats as well as on vegetable oils and fats, including mixtures thereof.
  • Vegetable oils and fats are substances that are present, in variable percentages, in the seeds or in the fruits of various plants .
  • the present invention can also utilize vegetable oils and fats that are obtained from genetically engineered plants, including algae, and including those that may be developed to yield particularly high levels of oils and fats so that they are particularly preferred sources of such materials for use as fuels. Since the fats and oils are to be used in the compositions of the present invention and burned as fuel, it is not necessary that such fats and oils be edible.
  • the most common, commercially available vegetable oils are obtained from the seeds of peanuts, sunflowers, soy, sesame, colza (similar in its properties to rapeseed oil, but obtained from the seeds of Brassica campestris, var. oleifera) , rape or canola, corn and cotton and from the fruits of palm, olive, and coconut.
  • the fatty substance can be obtained from treatment of the entire fruit (for example, olive oil) , the pulp (palm oil) , or just the kernel (palm seed oil) . All of these vegetable based or derived oils are examples of oils suitable for use in the present invention.
  • Other vegetable oils that may be useful in the present invention include crambe oil, jatropha oil, linseed oil, tung oil, as well as other so-called minor oil crops as described in "Minor Oil Crops," FAO Agricultural Services Bulletin No.
  • oils generally including: among the minor edible oil crops, argan; avocado; babassu palm; balanites; borneo tallow nut; brazil nut; caryocar spp; cashew nut; Chinese vegetable tallow; cohune palm; the cucurbitaceae family including gourd, buffalo gourd, fluted pumpkin, and marrow; smooth loofah; grapeseed; illipe; kusum; macadamia nuts; mango seed; noog abyssinia; nutmeg; perilla; pili nut; rice bran; sacha inche; seje; shea nut; and teased.
  • Vegetable oils are obtained from their vegetable plants, seeds, etc. by methods well known in the art, including mechanical extraction or pressing as well as chemical or solvent extraction, and are typically filtered to remove extraneous matter in order to deliver a substantially clean product.
  • used vegetable oil or fat from commercial sources can also be used, including, for example, food frying operations .
  • oils and fats useful in the present invention can be obtained from animal derived sources.
  • animal derived or extracted oils include animal tissue extract, piscine oil, cod-liver and shark-liver oil, fish, oil in general, including oil from. a wide variety of oil bearing fish some of which may be farmed for that purpose including fish oil currently being promoted by the Alaskan fish industry, tallow and mixtures thereof .
  • tallow refers to fat obtained from parts of the bodies of cattle, sheep, oxen, horses, chickens and other birds raised for food purposes, and the like as well as similar fats, such as those obtained from plants and also referred to as tallow.
  • Large quantities of animal derived fats and oils can be obtained as byproducts from meat rendering facilities .
  • oils and fats obtained from vegetable and animal sources are also useful in the present invention.
  • oils and fats obtained from recycled oil and grease usually from restaurants and food processing plants are those oils and fats obtained from recycled oil and grease usually from restaurants and food processing plants.
  • Such fats and oils may originally be from vegetable or animal sources . It is to be understood that oils and fats from these sources can still be useful even though they may require some pretreatment in order to remove food and other particulate matter as well as to reduce acidity from free fatty acids or sulfur-containing compounds that may be present, using methods well known to those skilled in the art.
  • Surfactants are known to enhance the stability of an emulsion.
  • a surfactant may be employed in accordance with the present invention to enhance the stability of fuel-water emulsion, particularly over time.
  • the following tabulation provides examples of surfactants contemplated by the invention, although useful surfactants are not limited to those in the table.
  • Also useful are surfactants disclosed in a comprehensive listing of surfactants that can be found in the spectral database of Bio-Rad Laboratories (www.informatics.bio-rad.com), including infrared spectra and. in a number of cases, chemical composition and chemical and physical properties and sources, incorporated herein by- reference.
  • the compounds are generally characterized as alcohols, nitrogen-containing compounds, esters of long chain carboxylic acids, hydrocarbons, various esters and salts of long chain carboxylic acids, sulfated and sulfonated compounds including alkylaryl sulfonates isothionates, lignosulfonates, sulfated and sulfonated alcohols, amines, amides, carboxylic acids, carboxylic acid esters, sulfated and sulfonated polyalkoxylated materials such as esters, ethers, nitrogen compounds, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA) , diethylenetriaminepentaacetic acid (DTPA) , and nitrilotriacetic acid (NTA) , in other words EDTA, DTPA, NTA acids and salts, phosphates, silicates and silicones.
  • EDTA ethylenediaminetetraacetic acid
  • surfactant includes atoms, groups or compounds that may unnecessarily contribute to pollution, e.g., sulfur, its use can be limited to the amount necessary for producing and/or maintaining a stable emulsion or fuel composition.
  • Particularly preferred surfactants include cetyl alcohol, hydrogenated castor oil and mixtures of cetyl alcohol and hydrogenated castor oil.
  • the following materials, referred to as surfactants herein, can be employed in accordance with the water-fuel composition of the present invention.
  • Anionic surfactants :
  • (F) Phosphorous 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 phosphatides), and POE tert-dodecylmercaptoethanol .
  • Glycerol monocaprylate glycerol monolaurate, glycerol mono/dicocoate, glycerol dilaurate, glycerol monostearate, glycerol monostearate distilled, glycerol distearate, glycerol monooleate, glycerol dioleate, glycerol trioleate, glycerol monoisostearate, glycerol monoricinoleate, glycerol monohydroxystearate, POE glycerol monostearate, acetylated glycerol monostearate, succinylated glycerol monostearate, diacetylated glycerol monostearate tartrate, modified glycerol phthalate resin, triglycerol monostearate, triglycerol monooleate, triglycerol monoisostearate, decaglycerol tetraoleate
  • the emulsifier or surfactant comprises at least one sorbitan ester.
  • the sorbitan esters include sorbitan fatty acid esters wherein the fatty acid component of the ester comprises a carboxylic acid of about 10 to about 100 carbon atoms, and in one embodiment about 12 to about 24 carbon atoms .
  • Sorbitan is a mixture of anhydrosorbitols, principally 1,4-sorbitan and isosorbide (Formulas I and II) :
  • Sorbitan (also known as monoanhydrosorbitol , or sorbitol anhydride) is a generic name for anhydrides derivable from sorbitol by removal of one molecule of water.
  • the sorbitan fatty acid esters of this invention are a mixture of partial esters of sorbitol and its anhydrides with fatty acids .
  • These sorbitan esters can be represented by the structure below which may be any one of a monoester, diester, triester, tetraester, or mixtures thereof (Formula III) :
  • each Z independently denotes a hydrogen atom or C(O)R--, and each R mutually independently denotes a hydrocarbyl group of about 9 to about 99 carbon atoms, more preferably about 11 to about 23 carbon atoms.
  • sorbitan esters include sorbitan stearates and sorbitan oleates , such as sorbitan stearate (i.e., monostearate) , sorbitan distearate, sorbitan tristearate, sorbitan monooleate and sorbitan sesquioleate . Sorbitan esters are available commercially under the trademarks "Span” and "Arlacel” from ICI.
  • the sorbitan esters also include polyoxyalkylene sorbitan esters wherein the alkylene group has about 2 to about 30 carbon atoms. These polyoxyalkylene sorbitan esters can be represented by Formula IV:
  • each R independently is an alkylene group of about 2 to about 30 carbon atoms;
  • R 1 is a hydrocarbyl group of about 9 to about 99 carbon atoms, more preferably about 11 to about 23 carbon atoms,- and w, x, y and z represent the number of repeat oxyalkylene units.
  • ethoxylation of sorbitan fatty acid esters leads to a series of more hydrophilic: surfactants, which is the result of hydroxy groups of sorbitan reacting with ethylene oxide .
  • ethoxylated sorbitan- esters are those containing about 2 to about 80 ethylene oxide units, and in one embodiment from about 2 to about 30 ethylene oxide units, and in one embodiment about 4, in one embodiment about 5, and in one embodiment about 20 ethylene oxide units. They are available from Calgene Chemical under the trademark "POLYSORBATE” and from ICI under the trademark "TWEEN”.
  • Typical examples are polyoxyethylene (hereinafter "POE") (20) sorbitan tristearate (Polysorbate 65; Tween 65), POE (4) sorbitan monostearate (Polysorbate 61; Tween 61) , POE (20) sorbitan trioleate (Polysorbate 85; Tween 85), POE (5) sorbitan monooleate (Polysorbate 81; Tween 81), and POE (80) sorbitan monooleate (Polysorbate 80; Tween 80) .
  • POE polyoxyethylene
  • Mn number average molecular weight
  • PEG polyethylene glycol
  • PPG polypropylene glycol
  • EO ethylene oxide
  • P ⁇ pr ⁇ pylene oxide
  • HLB hydrophilie-lipophilic balance.
  • Useful emulsifiers of the types listed in the above table can be generically represented by the following classes of chemical compounds, members of which are commercially available and are suitable provided that they are used in accordance with the teachings herein such that stable emulsified compositions are produced: £0059] (a) sorbitol esters of the general formula
  • radicals X are identical to or different from one another and are each OH or R 1 COO " , where R 1 is a linear or branched, saturated or unsaturated, aliphatic hydrocarbon radical optionally substituted by hydroxyls and having from 7 to 22 carbon atoms, provided that at least one of said radicals X is R 1 COO " , [0060] (b) fatty acid esters of the general formula
  • R 2 is a linear or branched, saturated or unsaturated, aliphatic hydrocarbon radical optionally substituted by hydroxyl groups and having from 7 to 22 carbon atoms
  • R 3 is a linear or branched C 1 -C 10 alkylene
  • n is an integer greater than or equal to 6
  • R 4 is H, linear or branched Ci-Ci 0 alkyl or
  • R 5 is as defined above for R 2 ;
  • R s is a linear or branched Ci-C 2 O alkyl
  • m is an integer greater than or equal to 8
  • R 7 and R 8 are respectively as defined above for R 3 and R 4 of formula (II) .
  • Particularly useful emulsifiers include compounds exhibiting a hydrophilic-lipophilic balance (HLB, which refers to the size and strength of the polar (hydrophilic) and non- polar (lipophilic) groups that comprise the emulsifier or surfactant molecule) typically in the range of about 1 to about 40; in another embodiment about 5 to about 20.
  • HLB is a well-known parameter utilized by those skilled in the art for characterizing emulsifiers. It is defined in detail, for example, in the references “Emulsions: Theory and Practice, P. Becher, Reinhold Publishing Corp. , ACS Monograph, ed. 1965", in the chapter “The chemistry of emulsifying agents” (pg. 232 et seg.
  • Suitable compounds are included in the above table and are also disclosed in McCutcheon's Emulsifiers and Detergents, 1998, North American Edition (pages 1-235) & International Edition (pages 1-199) , incorporated herein by reference for their disclosure of compounds having an HLB in the range of about 1 to about 40; in one embodiment about 1 to about 30; in one embodiment about 1 to 20; and in another embodiment about 4 to about 18; alternatively, greater than about 8 , for example about 8.5 or about 9 to about 18.
  • Various useful compounds include those identified in the above table, including for example, sorbitan monolaurate, polyoxyethylene (20) sorbitan monooleate, and polyoxyethylene (20) sorbitan monolaurate.
  • an emulsified fuel composition can be prepared using a mixture of emulsifiers, such as a 50/50 mixture two emulsifiers, one having an HLB value of about 16 and the other an HLB value of about 8.
  • a mixture of emulsifiers such as a 50/50 mixture two emulsifiers, one having an HLB value of about 16 and the other an HLB value of about 8.
  • combinations of three or more emulsifiers can also be used, provided that the HLB value of the mixture exhibits the desired overall value and the effect of the mixture is to provide a stable emulsion.
  • the HLB value of the emulsifier mixture is calculated as a linear sum weighted average based on the weight fraction that each of the emulsifiers represents compared to the total amount of emulsifier present:
  • HLB m ⁇ [ (HLB n ) (wtn/wttot) ] where :
  • a mixture of two emulsifiers wherein one emulsifier has an HLB value of equal to or less than about 6 , for example about 1 to about 6.0, or about 2 to about 5.9, or about 3 to about 5.5, or about 4 to about 5.9, and the like; and the second emulsifier has an HLB value of greater than about 6 , for example 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, and the like,- provided that both emulsifiers do not have an HLB value of 6.
  • one emulsifier comprising a bimodal distribution of chemical species exhibiting each of the HLB properties can be used.
  • compositions in which the total concentration of hydrophilic components is low can be advantageous in compositions in which the total concentration of hydrophilic components is low.
  • the water concentration is less than about 5 wt%, such as about 1 wt% to about 5 wt%, or about 1 wt% to about 4 wt%, or 1 wt% to about 3 wt%, or 1 wt% to about 2 wt% .
  • the concentrations of various hydrophilic or substantially hydrophilic components can be added together for consideration of the above recited concentrations, including water, hydroxyl-containing component (s) such as one or more alcohols or glycols and the like.
  • the ratio of the total amount of such hydrophilic components to the total amount of lipophilic components is equal to or less than about 0.25, for example, about 0.05 to about 0.25 or any specific value therebetween, including, for example, 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 for example, a 50/50 mixture of an emulsifier having an HLB value of, for example, about 4 and one having an HLB value of about 15.
  • a stable emulsified composition can be prepared using a single emulsifier where the lipophilic and hydrophilic components comprise 75 wt% vegetable oil, 1 wt% water, and 23 wt% alcohol.
  • a mixture of emulsifiers can be used even where the calculated ratio is greater than 0.25, particularly if the value is only slightly greater, for example about 5% to about 10% greater.
  • a mixture of emulsifiers can be used if desired; particularly if it is anticipated that the user of such a fuel composition may subsequently introduce an additive into the composition that might have the effect of changing the calculated ratio.
  • Alcohols useful in the present invention include hydroxyl-containing organic compounds selected from the group consisting of (A) monohydric (one OH group) alcohols characterized as (1) aliphatic, including straight and branched chain, and sub-characterized within this group as paraffinic (for example, ethanol) and olefinic (for example, allyl alcohol); (2) alicyclic (for example, cyclohexanol) ;
  • aromatic for example, phenol, benzyl alcohol
  • heterocyclic for example, furfuryl alcohol
  • polycyclic for example, sterols
  • dihydric two OH groups
  • glycols and derivatives for example, diols
  • trihydric three OH groups
  • glycerol and derivatives including glycerol and derivatives
  • polyhydric polyols
  • useful alcohols include alcohols selected from the group consisting of Cl to C4 straight and branched chain m ⁇ noalcohols, C2 to C4 mon ⁇ - and polyalkylene glycols including ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, derivatives of C2 to C4 mono- and polyalkylene glycols provided that the molecular weights of such polyalkylene glycols are suitable for use in the fuel compositions of the present invention, and mixtures thereof.
  • Fuel compositions in which a monoalcohol is included also preferably include at least one of tert-butyl alcohol, at least one C2-C4 alkylene glycol or a mixture of both.
  • Ethyl alcohol or ethanol and propylene glycol are particularly preferred in the compositions of the present invention.
  • Ethanol is available commercially in the anhydrous form (also referred to as absolute alcohol or 100% ethanol) and as various proofs or percentages of ethanol where the additional component in the ethanol is water, the most common being 190 proof or 95 vol%. If ethanol is used for purposes other than as a beverage, it is denatured by addition of substances, such as methanol, 2-propanol, ethyl acetate, methyl isobutyl ketone, heptane or kerosene, to make the product undesirable for human consumption, but allows for its use for industrial purposes , including as a component in fuel or as a fuel .
  • ethanol other than absolute ethanol is typically- identified by use of the term "proof," where the conversion between proof and the concentration of ethyl alcohol is that 2 proof equals 1% by volume, typically measured at 20 0 C, although measurements at other temperatures are also accepted, including e.g., 15.6 0 C.
  • proof the conversion between proof and the concentration of ethyl alcohol is that 2 proof equals 1% by volume, typically measured at 20 0 C, although measurements at other temperatures are also accepted, including e.g., 15.6 0 C.
  • denaturants are available that can render ethanol (with or without the presence of moisture or water) unsuitable for human consumption, certain of such denaturants may not be suitable for use in connection with fuels because of their adverse effects on fuel stability, vehicle engines and fuel systems and emissions.
  • a list of denaturants used in connection with ethyl alcohol for various purposes can be found in The Merck Index, Thirteenth Edition, 2001, entry 3796, page 670, incorporated herein by reference.
  • ethanol Physical properties of ethanol can vary depending on whether ethanol is anhydrous, mixed with water to various concentrations, and whether it is denatured and the type of denaturant used. Denaturants that may be unsuitable for use in connection with fuels are known to those skilled in the art and are often specified by various governmental agencies. For example, the Indian government prohibits the use of methanol, pyrroles, turpentine, ketones and tars (high molecular weight pyrolysis products of fossil or non-fossil vegetable matter) .
  • ASTM D4806 and ASTM D5798 describe the amount and types of denaturants typically permitted for use in fuels and also identifies others that should not be used in view of their potentially adverse effects, as noted above.
  • ASTM D5798 also describes the standards for fuels for use in engines that are designed to utilize ethanol as a substitute for petroleum, i.e., that include substantially high percentages of ethanol.
  • Absolute ethyl alcohol is ordinarily understood to mean ethyl alcohol containing no more than 0.5 vol.% water, although for purposes of the present invention, such a moisture limitation has little significance.
  • alcohol or a mixture of the alcohols identified herein as useful are included at a concentration of about 1 wt% to about 25 wt% based on the total weight of the fuel composition; or about 2 wt% to about 22 wt%; or about 3 wt% to about 20 wt%; or about 4 wt% to about 18 wt%; or about 5 wt% to about 20 wt%; or about 1 wt% to about 15 wt%; or about 1 wt% to about 10 wt%; or about 1 wt% to about 5 wt%; or about 2 wt% to about 6 wt%; alternatively, about 3 wt% to about 8 wt%.
  • the C4 alcohol butyl alcohol is also useful in the present invention. Where butyl alcohol is used it is preferred to use tert-butyl alcohol because it is more readily soluble in water. However, since n-butyl alcohol and sec-butyl alcohol are not completely soluble in water, their use can require a further adjustment in the type and amount of emulsifier in the fuel composition in order to obtain a stable emulsion.
  • Tert-butyl alcohol can be used in place of or in combination with ethanol, for example including mixtures in which the relative amount, by weight, of ethanol to tert-butyl alcohol is about 95/5 to 5/95; including useful amounts therebetween such as 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.
  • the water-vegetable oil fuel emulsions comprise: a continuous vegetable oil fuel phase; a discontinuous water or aqueous phase being comprised of aqueous droplets preferably having a mean diameter of about 10 microns or less, for example, 5 microns; and an emulsifying amount of at least one emulsifier.
  • the emulsions may be prepared by various steps or sequences of addition as described herein, including for example, (1) mixing the vegetable oil, emulsifier and other desired additives using standard mixing techniques to form a vegetable oil-emulsifier mixture; and (2) mixing the vegetable oil-emulsifier mixture with water (and optionally additional additives, including for example ethanol, propylene glycol, cetane improver, or mixtures thereof) under emulsifying mixing conditions to form the desired water-vegetable oil fuel emulsion.
  • additional additives including for example ethanol, propylene glycol, cetane improver, or mixtures thereof
  • additives may be added to the emulsifier, the vegetable oil, the water or combinations thereof.
  • the additives include but are not limited to cetane improvers, organic solvents, other fuels such as diesel fuel, glycols, surfactants or emulsifiers, other additives known for their use in fuel and the like.
  • the additives are added to the emulsifier, vegetable oil or the water prior to and in the alternative at the emulsification device (s) depending upon the solubility or other fluid properties of the additive.
  • the additives are generally in the range of about 1% to about 40% by weight, in another embodiment about 5% to about 30% by weight, and in another embodiment about 7% to about 25% by weight of the fuel mixture.
  • the vegetable oil fuel emulsifier mixtures contain about 50% to about 95% by weight, in another embodiment about 55% to about 90% by weight; and in another embodiment about 60% to about 85% by weight vegetable oil fuel, and it further contains about 0.05% to about 10%, in another embodiment about 0.1% to about 10%, and in another embodiment about 1% to about 5% by weight of at least one emulsifier.
  • the water which can optionally include but is not limited to one or more alkylene glycol, alcohol, cetane improver or mixtures thereof.
  • the water, alcohol and/or alkylene glycol and/or the cetane improver are mixed with one another and fed continuously to the fuel additives stream.
  • the water, alcohol and/or alkylene glycol and/or the cetane improver or mixtures thereof flow out of separate tanks and/or combinations thereof into or mixed prior to the emulsification device.
  • the water, alcohol and/or alkylene glycol and/or the cetane improver mixture meets . the vegetable oil fuel additives mixture immediately prior to or in the emulsification device.
  • emulsified fuel of the present invention alternatives are available for preparing one embodiment the emulsified fuel of the present invention.
  • vegetable oil or a vegetable oil mixture and a major proportion, or all, of the desired amount of C1-C4 alcohol, such as ethanol are mixed with one another to form a two phase composition with the alcohol as the upper phase.
  • C1-C4 alcohol such as ethanol
  • water and remaining component (s), including emulsifier (s) are added with agitation, a stable, emulsified composition is produced.
  • the C1-C4 alcohol, or a proportion thereof, including a major proportion, e.g., greater than 50 wt%, can be mixed with the components other than the water, to which the vegetable oil is added, which results in a two phase mixture with the oil as the upper phase .
  • a split addition of alcohol any convenient fraction can be used as a two-phase mixture results until the water is added. Addition of water to this mixture with agitation produces a stable, emulsified composition.
  • either of the described two phase mixtures can be produced and stored until such time as it is desired to add the water component, with the additional component (s) if required, to form the stable, emulsified composition.
  • the two-phase mixtures can be shipped to a desired location before addition of the water in order to reduce the burden of shipping water in the mixture .
  • An optional component of the fuel mixture referred to as supplementary combustible liquid can be "paint thinner, " turpentine or mineral spirits. Materials of this type are generally described in U.S. 5,609,678, incorporated herein by reference in its entirety.
  • the use of this component in the present invention can be characterized as a low viscosity, low density supplementary combustible liquid additive.
  • Such an optional component can be useful for the purpose of modifying one or more properties of the fuel composition, including, for example, the cetane number, density and viscosity.
  • the amount and type of such component can be selected based on its combustion properties as measured by the cetane number of the resulting fuel composition, by the density of the resulting composition and by its viscosity as well as its effect on the phase distribution of the microemulsion in view of the amount and type of surfactant used.
  • the amount of the liquid added can be suitably adjusted to produce a fuel composition having the overall balance of properties suitable for the end use of the fuel product, for example, as a fuel for a diesel engine, a furnace, etc., or for adjusting the properties of the fuel composition for the ambient temperature environment in which it is intended to be used, for example, as an automotive diesel fuel for winter or summer use.
  • Useful supplementary combustible liquid additives of the paint thinner type include products identified as hydrotreated, light steam cracked naphtha residuum (petroleum) , also referred to as naphtha, petroleum, hydrotreated heavy, and identified as CAS 64742-48-9.
  • This product has also been described as a complex combination of hydrocarbons obtained by treating a petroleum fraction with hydrogen in the presence of a catalyst. It typically comprises hydrocarbons having carbon numbers predominantly in the range of C6 through C13 and boiling in the range of approximately 65 0 C to 230 0 C (149 0 F to 446 0 F) .
  • a supplementary combustible liquid component useful in the present invention can be generally understood by those skilled in the art to include a broad range of petroleum distillate materials as well as supplementary combustible liquids from other sources, for example, plant or vegetable sources. Useful products generally boil in the range of about 145 0 C to about 200 0 C.
  • Turpentine is a supplementary combustible fluid that could be used. Specifications for "gum spirit of turpentine" (natural, organic or vegetable-based turpentine) have been published by several national bodies including the American Society for Testing and Materials (ASTM D 13-92) and the Bureau of Indian Standards (IS 533:1973) .
  • Tropentine substitute is a "mineral oil” based replacement for the vegetable-based organic solvent turpentine and it is suitable for use herein. It is a hydrotreated light distillate of petroleum, which forms a clear transparent liquid at ambient or room temperature. It is a complex mixture of highly refined hydrocarbon distillates mainly in the C9-C16 range. The liquid is highly volatile and the vapours are flammable. It is a widely available as a less costly substitute for turpentine . It is commonly used as an organic solvent in painting and decorating, for thinning oil based paint and cleaning brushes . Also known as turps substitute, mineral turpentine, or simply turps, which can cause confusion with vegetable-based turpentine .
  • White spirit also known as Stoddard solvent is also suitable for use herein. It is a paraffin-derived clear, transparent liquid which is a common organic solvent used in painting and decorating. It is a mixture of saturated aliphatic and alicyclic C7 to C12 hydrocarbons with a maximum content of 25% of C7 to C12 alkyl aromatic hydrocarbons.
  • White spirit typically is used as an extraction solvent, as a cleaning solvent, as a degreasing solvent and as a solvent in aerosols, paints, wood preservatives, lacquers, varnishes, and asphalt products. In western Europe about 60% of the total white spirit consumption is used in paints, lacquers and varnishes . White spirit is the most widely used solvent in the paint industry.
  • Type 3 Three different types and three different grades of white spirit are available.
  • the type refers to whether the solvent has been subjected to hydrodesulfurization (removal of sulfur) alone (Type 1) , solvent extraction (Type 2) or hydrogenation (Type 3) .
  • Each type comprises three different grades: low flash grade, regular grade, and high flash grade. The grade is determined by the crude oil used as the starting material and the conditions of distillation.
  • Type 0 which is referred to as distillation fraction with no further treatment, comprising predominantly saturated C9 to C12 hydrocarbons with a boiling range of 140-200 0 C.
  • the physical properties of the three types of white spirit are shown in the following table:
  • mineral spirits are suitable for use as a supplementary combustible fluid in the present invention.
  • Mineral spirits is commonly used as a paint thinner and mild solvent and it is suitable for use herein. In Europe, it is referred to as petroleum spirit. They are especially effective in removing oils, greases, carbon and other material from metal .
  • Mineral spirits is derived from the light distillate fractions during crude oil refining and comprise C6 to CIl compounds, with the majority being C9 to CIl. There are many different substances generally referred to as mineral spirits and each generally has a different CAS number.
  • One common type is mineral oil spirits identified as CAS 64475-85-0.
  • Stoddard solvent is a particular type, subcategory or subset of mineral spirits, identified as CAS 8052-41-3 and contains 30-62 wt% alkanes, 27-40 wt% cycloalkanes , 0.3-20 wt% alkylbenzenes , 0.007-0.1 wt% other benzenes, 0.2 wt% naphthalenes and 0.3 wt% acenaphthalenes .
  • Commercial Stoddard Solvent products are available under the tradenames Varsol 1 and Texsolve S.
  • benzine is another, subset of mineral spirits comprising C5 to C9 hydrocarbons and boiling at about 154 0 C to about 204 0 C.
  • Mineral spirits on the other hand comprise 20-65 wt% alkanes, 15-40 wt% cycloalkanes and 10-30 wt% aromatics; the specific amount of each varying depending on the particular "mineral spirit" being considered.
  • General properties for mineral spirits include vapor pressure of 2.53 mttiHg; API gravity of about 48 to about 51; density of about 0.793 at 15 0 C and about 0.779 at 20 0 C; kinematic viscosity of 1.43 cSt (or mm2/sec) at 15 0 C and 1.78 cSt at 0 0 C.
  • Kerosene is typically defined as a refined petroleum solvent (predominantly C 9 -CiS hydrocarbon, which is typically a mixture of 25% normal paraffins, 11% branched paraffins, 30% monocycloparraffins, 12% dicycloparaffins, 1% tricycloparrafins, 16% mononuclear aromatics and 5% dinuclear aromatics . (NIOSH Pocket Guide, www.cdc.gov)
  • a product known as hydrotreated kerosene (CAS No. 64742-47-8) can be used.
  • an additive composition of the present invention comprises at least one alcohol and at least one surfactant or emulsifier and, optionally, a low viscosity, low density supplementary combustible liquid, such as paint thinner as well as other components described herein.
  • the various embodiments of the fuel compositions of the present invention are generally prepared according to the methods described herein.
  • an additive composition the components of which are described herein, is added gradually to water, or vice versa, in order to prepare a mixture, preferably with mixing during the addition, although mixing can be carried out after the components are added to one another.
  • the individual components of the additive mixture and the water can be combined in any convenient order provided that a uniform mixture is obtained. Mixing is continued until a satisfactory distribution, dispersion or emulsion of components is achieved.
  • the additive composition is used in an amount of about 20% by weight based on the amount of the vegetable oil that will be present in the final mixture . The amount of additive used can be suitably varied.
  • the additive is used at about 2 wt% to about 30 wt% based on the weight of the oil present; preferably about 20 wt% to about 28 wt%; more preferably about 10 wt% to about 30 wt% for engines and about 10 wt% to about 20 wt% for burners and heaters.
  • higher amounts of the additive can be used, for example, about 35 wt% or about 40 wt% or up to about 45 wt%, keeping cost in mind so that a suitable amount is used to achieve the desired effect and at a cost consistent with economic requirements.
  • useful amounts may include specific concentrations of about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 and 30 wt% or more, as well as ranges of values based on any two of the individual values recited; for example, 2- 30%, 5-25%, etc.
  • the additive is used in an amount sufficient to obtain a substantially complete emulsion of water and oil present in the composition.
  • the mixture comprising water and additive is added to an oil or a fat of vegetable origin, for example, colza or canola oil.
  • the weight ratio of water to oil typically can be varied over a range and still be useful in the present invention, for example, from about 4:1 to about 1:4; a preferred ratio of water to oil is about 3:1 to about 1:3; more preferably about 2:1 to about 1:2; still more preferably about 1:1.
  • Mixing of the water-additive combination with the vegetable oil is continued until a substantially complete, or suitable, emulsion of the components is obtained.
  • Cetane number or CN is to diesel fuel what octane rating is to gasoline, it is generally recognized as a measure of the fuel's combustion quality. Cetane is an alkane molecule, specifically Ci 6 H 34 , that ignites very easily under compression, so it is assigned a cetane number of 100. All other hydrocarbons in diesel fuel, as well as other fuels intended for use in diesel engines, including biodiesel and the biofuel compositions of the present invention, are indexed to cetane as an indicator of how well they ignite under compression. The cetane number therefore measures how quickly the fuel starts to burn (auto-ignites) under a standardized set of diesel engine conditions.
  • Typical hydrocarbon-based diesel fuel contains many hydrocarbon compounds and there can be more than one compound susceptible to ignition in other fuels, including the fuels of the present invention. Since each component can exhibit a different cetane number or modify the centane number of the fuel of which it is a component, the overall cetane number of the fuel is an indicator of the average cetane quality of all of the components present.
  • a fuel with a high cetane number starts to burn shortly after it is injected into the cylinder; it has a short ignition delay period. Conversely, a fuel with a low cetane number resists auto- -ignition and has a longer ignition delay period.
  • a typical diesel engine has acceptable performance with a fuel having a CN between about 45 to about 50.
  • Hydrocarbon diesel fuel sold commercially is said to be available in two CN ranges: 40-46 for regular diesel, and 45-50 for premium.
  • premium diesel includes additives to improve the effective CN and lubricity of the fuel as well as detergents to clean the fuel injectors and minimize carbon deposits, water dispersants (since water in hydrocarbon diesel fuel is considered objectionable) , and other additives depending on geographical and seasonal needs . Cetane number can be determined using standardized tests, including ASTM D613 and EN ISO 5165.
  • the cetane number rating in this test compares the diesel fuel ' s performance in a standard engine with that of a mixture of cetane and alpha-methyl-naphthalene.
  • the cetane number is the percentage by volume of cetane in the mixture that has the same performance as the fuel being tested.
  • Suitable fuels typically will have CN values of at least about 35 to about 55; preferably about 40 to about 50; more preferably about 45 to about 50; for example at least about 45, 46, 47, 48, 49, 50, 51, 52, 53, 54 or 55.
  • cetane number can be estimated by calculating the value according to the procedures specified in ASTM D976, using the density of the fuel and its mid-distillation temperature, or in ASTM D4737 using a four variable equation.
  • cetane index When an estimated cetane number is determined in this manner, it is sometimes referred to as cetane index to distinguish it from the value determined according to the engine test, as in ASTM 613.
  • cetane index it is understood by those skilled in the art that where a cetane index is calculated, the value is dependent on the fuel properties and is not affected by additives that may be included to improve cetane number. Such additives will, of course, affect the cetane number determined by use of an engine test since the overall fuel composition affects the value measured in that test.
  • Cetane index values can also be useful for characterizing a fuel composition of the present invention.
  • a cetane number improving additive or mixture of additives can be present in an amount effective to improve the CN of the fuel compositions of the present invention to the extent desired; in other words, to a level suitable for the particular application or use to which the emulsified vegetable fuel will be put.
  • the concentration of the cetane improver is at a level of up to about 10% by weight; in another embodiment about 0.05 to about 10% by weight; in a further embodiment about 0.05 to about 5% by weight; in a still further embodiment about 0.05 to about 1% by weight; alternatively, about 0.1 to about 1% by weight.
  • one embodiment of the vegetable oil-based water-fuel emulsion compositions of the present invention can optionally include one or more compounds having the ability to increase cetane number.
  • Useful cetane improvers include but are not limited to one or more of peroxides, nitrates, nitrites, nitrocarbamates, mixtures thereof and the like .
  • Useful cetane improvers include but are not limited to nitropropane, dinitropropane, tetranitromethane, 2-nitro-2-methyl-l-butanol, 2-methyl-2 ⁇ nitro-1-propanol, and the like.
  • nitrate esters of substituted or unsubstituted aliphatic or cycloaliphatic alcohols which may be monohydric or polyhydric .
  • These compounds include substituted and unsubstituted alkyl or cycloalkyl nitrates having up to about 10 carbon atoms, and in one embodiment about 2 to about 10 carbon atoms.
  • the alkyl group may be either linear or branched, or a mixture of linear or branched alkyl groups .
  • Examples of such compounds include methyl nitrate, ethyl nitrate, n-propyl nitrate, isopropyl nitrate, allyl nitrate, n-butyl nitrate, isobutyl nitrate, sec-butyl nitrate, tert-butyl nitrate, n-amyl nitrate, isoamyl nitrate, 2-amyl nitrate, 3-a ⁇ nyl 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 n
  • nitrate esters of alkoxy-substituted aliphatic alcohols such as 2-ethoxyethyl nitrate, 2- (2-ethoxy- ethoxy) ethyl nitrate, 1-methoxypropyl-2-nitrate, 4-ethoxybutyl nitrate, etc., as well as diol nitrates such as 1, 6-hexamethylene dinitrate.
  • a useful cetane improver is 2-ethylhexyl nitrate .
  • Organic peroxides can also be useful as cetane improvers in the fuel compositions herein.
  • Generally useful compounds are dialkyl peroxides of the formula R1OOR2 wherein Rl and R2 are the same or different alkyl groups having 1 to about 10 carbon atoms.
  • Suitable peroxide cetane improver compounds should be soluble in the fuel composition and thermally stable at typical fuel temperatures of operating engines .
  • Peroxides wherein Rl and R2 are tertiary alkyl groups having about 4 or about 5 carbon atoms are especially useful.
  • suitable peroxides include di-tertiary butyl peroxide, di-tertiary amyl peroxide, diethyl peroxide, di-n-propyl peroxide, di-n-butyl 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 and preferably most of the following characteristics : good solubility in the fuel, suitable water partition coefficient characteristics, good thermal stability and handling characteristics, have no impact on fuel quality or fuel system components, and have low toxicity.
  • a useful peroxide is di-tertiary butyl peroxide, also sometimes referred to as tertiary butyl peroxide .
  • the biofuel of the present invention typically has a density suitable for its use as a fuel in diesel engines and in other applications where diesel fuel would otherwise be useful, including in furnaces, gas or combustion turbines and other combustion equipment. Density can be measured according to the standard test method, EN ISO 3675, at 15 0 C and suitable fuels have a density of about 850 kg/m 3 to about 950 kg/m 3 ; preferably about 860 kg/m 3 to about 910 kg/m 3 ; for example about 870 kg/m 3 to about 890 kg/m 3 .
  • diesel fuel density is characterized by the standard developed by the American Petroleum Institute, referred to as API gravity.
  • Typical API gravity values for fuels of the present invention useful as fuels for diesel engines range from about 25 API to about 40 API, corresponding to specific gravity values of about 0.904 to about 0.825 (at 60 0 F or 15.6 0 C); preferably about 26 API gravity to about 38 API gravity; more preferably about 27 API gravity to about 37 API gravity; for example, about 35 API gravity, corresponding to a specific gravity of about 0.850.
  • Biofuel compositions of the present invention typically have a viscosity so that they are suitable for use as a fuel in diesel engines and in other applications where diesel fuel would otherwise be useful, including furnaces and other combustion equipment. Viscosity can be measured according to the standard test methods, EN ISO 3104 or ASTM D445 (kinematic viscosity at 40 0 C) , wherein potentially useful values can be about 3 mm 2 /s to about 60 mm 2 /s; alternatively about 3.5 mm.
  • compositions of the present invention can be included in the compositions of the present invention provided that they do not substantially adversely affect performance of the composition and its intended use. Included in the category of such other optional ingredients would be, for example, thermal and aging stabilizers; coloring agents, dyes and markers, particularly those permitted in the European Union as set forth in EN 14214:2003-5.1; agents to modify the odor of the mixture in order to prevent inadvertent ingestion, including, for example, alkyds; etc. Alternatively, and if necessary, agents can be added in a suitable amount, typically at a low concentration, that are capable of modifying or masking an unpleasant odor or smell, if any, of the exhausted gas after combustion.
  • the fuels of this invention may contain conventional quantities of such conventional additives as rust inhibitors such as alkylated succinic acids and anhydrides, inhibitors of gum formation, metal deactivators, upper cylinder lubricants, friction modifiers, detergents, antioxidants, heat stabilizers, bacteriostatic agents, microbiocides, fungicides and the like.
  • rust inhibitors such as alkylated succinic acids and anhydrides
  • metal deactivators such as alkylated succinic acids and anhydrides
  • upper cylinder lubricants such as rust inhibitors such as alkylated succinic acids and anhydrides, inhibitors of gum formation, metal deactivators, upper cylinder lubricants, friction modifiers, detergents, antioxidants, heat stabilizers, bacteriostatic agents, microbiocides, fungicides and the like.
  • Such conventional additives can be present in the fuel composition at concentrations of up to about 1 wt% based on the total weight of the water-vegetable oil fuel emul
  • the practice of the present invention results in the preparation of a fuel composition based on animal or vegetable fats or oils and water in an emulsion that is stable for an extended time and over a wide range of temperatures, for example about -10 0 C to about +50 0 C. Furthermore, in a test conducted at -25 0 C, a composition of the present invention, for example compositions as shown in Examples 1 and 2, including paint thinner and 30 grams of cetyl alcohol, did not exhibit any evidence of freezing, cloudiness or phase separation.
  • the fuel produced according to the compositions and methods of the present invention can be used without modification to the tanks and/or piping systems of the motors and burners in common use .
  • another advantage of the present invention is that it permits the return at any moment to the use of traditional fuels without modification of the systems in which the fuel is used.
  • the fuel of the invention is renewable since it is based on vegetable and animal products that can be regularly replaced. Furthermore, not only is the energy source renewable, but the amount of carbon dioxide emitted during combustion corresponds very closely to the amount of carbon dioxide used by the plants in generating the vegetable matter which is the source of the oils or fats. This, of course, cannot occur in the case of petroleum based fuels ;
  • Incombustible hydrocarbons produced during the combustion of a fuel composition of the present invention are less than those produced by traditional biodiesel-based fuels and CO emissions and are believed typically to be about 15%- 20% less.
  • CO emissions were observed to be reduced by 37 wt%
  • particulate matter generated during combustion of traditional biodiesel based fuels is thought to serve a useful function by absorbing some of the undesirable and polluting aromatic compounds produced during combustion of that fuel, the fuel of the present invention is believed to produce very little of such aromatic compounds in the first place.
  • particulate matter produced during combustion of the fuel of the present invention is up to about 70% less than that produced by petroleum-based fuels and are, on average, larger than those produced by such petroleum-based fuels. Additionally, it is generally believed that larger particles are less dangerous since they are less likely to be permanently retained in the lungs than smaller particles.
  • Test for activity against spores Successful disinfection according to the British Standard (BS EN 1276) occurs when there is a five log reduction in cell number within 5 minutes, meaning that the reduction of spore number must be at least of 95% in an assigned period of time. Based on this, the biofuel composition was tested against germs
  • Test for activity against fungi The tests against mold and fungi followed the guidelines of the European standard 1275 that requires a minimum of a four log reduction in cell number within five minutes .
  • the strain used was Candida albicans, strain ATCC number 10231.
  • Biofuel compositions made according the methods and components previously described include those useful, for example, in multi-jet new generation diesel engines as well as traditional diesel engines .
  • Such compositions can comprise for example, about 25 to about 30 vrt% water, about 40 to about 60 wt% vegetable oil and about 15 to about 30 wt% additive.
  • A 1500 parts vegetable oil or fat; and (B) 900 parts water; and (C) 400 parts denatured ethanol 90 wt% (180 proof) ; axid, (D) 30 parts of at least one component selected from the group consisting of (1) hydrogenated castor oil; (2) cetyl alcohol; and (3) a mixture of (1) and (2) .
  • the fuel mixture of aspect 1 further comprising 500 parts of odorless paint solvent.
  • a fuel additive comprising a mixture of: (A) 400 parts denatured ethanol 90 wt% (180 proof) ,- and, (B) 30 parts of at least one component selected from the group consisting of (1) hydrogenated castor oil; (2) cetyl alcohol; and (3) a mixture of (1) and (2) .
  • R R L + k(Ru -R L ), where k is a variable ranging from 1% to 100% with a 1% increment, e.g., k is 1%, 2%, 3%, 4%, 5%. ... 50%, 51%, 52%. ... 95%, 96%, 97%, 98%, 99%, or 100%.
  • any numerical range represented by any two values of R, as calculated above is also specifically disclosed.
  • Example 1 New Generation Hi-Pressure Injection Diesel
  • a fuel mixture is prepared from the following components : 1500 grams vegetable oil or fat; and 900 grams water (e.g., tap water); and 400 grams denatured ethanol 90° (180 proof) ; and, (a) 30 grams hydrogenated oil of ricin (castor oil) ,- alternatively, a mixture using (b) 30 grams cetalol (cetyl alcohol) is prepared; and (c) a further alternative mixture using (a) + (b) together (30 grams total) is also prepared; and optionally,
  • 500 grams odorless paint solvent is also included in one or more of the above described mixtures.
  • the mixture is suitable for use with a new generation high pressure injection diesel engine. Based on current raw material costs it is estimated that the above composition costs about 204 €/lOOOL (about $0.94/gal at current exchange rates) . It is expected that the cost for producing the composition on a commercial scale will be lower.
  • the raw material cost of commercial biodiesel fuel is about 492 €/lOOOL (about $2.26/gal at current exchange rates) .
  • a fuel mixture is prepared from the following components :
  • a fuel mixture is prepared from the following components :
  • a fuel mixture is prepared from the following components :
  • a fuel mixture is suitable for use in oil burners.
  • Example 5 Fuel for Use in Modified Oil Burners
  • a fuel mixture is prepared from the following components :
  • the mixture is suitable for use in modified oil burners .
  • Fuel mixtures of the present invention were prepared as follows: the water and ethanol were first mixed with one another. The vegetable oil was then added slowly to the alcohol-water mixture with stirring and finally the emulsifier or surfactant was added to the mixture containing the oil . For the composition in which a cetane improver was used, that component was added to the mixture at the end. The mixtures were all prepared at about ambient or room temperature, 22 0 C. Corresponding mixtures have been prepared using ultrasonic mixing equipment, which equipment particularly advantageous for preparing stable emulsions having a small particle size, for example less than about 5 microns on average (“Sonolator” ultrasonic homogenizing system, Sonic Corp., Conn.).
  • compositions described herein are amenable to preparing such emulsions, also referred to herein as microemulsions .
  • the microemulsions could also be prepared at 22 0 C and at pressures of about 500 psi to about 1500 psi, although pressures as high as 5000 psi also produced stable microemulsions.
  • the fuel components and amounts are shown in the following table:
  • HCO hydrogenated castor oil, 98% pure
  • Biofuel 3 was tested in a stationary burner and its performance compared to gas oil, biodiesel and BTZ fuel oil and water emulsion mixture. Descriptions and properties of the reference fuels can be found in a published report titled, "Sperimentazione Combustibili Analisi comparativa di combustibili per uso civile” (Fuel Experimentation. Comparative analyses of fuels for civic use) December 5, 2005, by Stazione Sperimentale per i Combustibili
  • Biofuel 3 was tested using an experimental thermal plant consisting of a reversed flame Ravasio Model TRM 150 boiler with a nominal thermal capacity of 175 kW and a Elco Klockner Model EK 3.50 S-Z burner for fuel oil. Heat generated is discharged to a heat exchanger for measurement of performance and exhaust gasses are also analyzed for emissions.
  • Biofuel 3 exhibited an excellent flow point of -42 0 C (measured according toISO 3016-94) as well as viscosity and lower heating capacity values (ASTM D 240-02) typical of the class of fuel oils. As shown above, Biofuel 3 also resulted in low NOx and other emissions. It was also observed that Biofuel 3 exhibited a regular, stable, deep yellow flame at the burner. An increase in density of the recirculated fuel was observed, which response can probably be mitigated by further improvements in emulsion particle size as well as adjustments to the composition, according to the methods described above.
  • the heating tests reflected the stability of the emulsifier (s) since the solvents and water are evaporated at 100 0 C.
  • the laboratory test showed that Biofuel 1 was stable until 200 0 C whereas Biofuel 2 was stable until about 165 0 C.
  • Heat capacity (J/g*°C) was about 1.6 for Biofuel 1 and about 1.8 for Biofuel 2, similar to that of gas oil. Furthermore, both Biofuel 1 and Biofuel 2 did not exhibit thermal effects or freezing at -20 0 C.
  • Biofuel 2 compared to traditional diesel fuel.
  • a composition of the present invention referred to as a biofuel composition, having components that provided a composition particularly useful in stationary burners or furnaces; for example, burners used for generating heat and power.
  • the components are shown in the following table:
  • biofuel composition particularly useful in vehicles for example, cars, trucks, farm equipment, etc., preferably having diesel engines or engines suitable for burning diesel fuels or their equivalent, was also prepared according to the following formula:
  • a further Biofuel composition of the present invention was prepared as follows: the water and propylene glycol were first mixed with one another. Small amounts of the vegetable oil were then added slowly to the alcohol-water mixture with stirring after each addition and finally the emulsifier or surfactant was added to the mixture containing the oil .
  • the mixture was prepared at about room temperature, 22 0 C.
  • the mixture was prepared using ultrasonic mixing equipment also as described above. However, using such equipment it was possible to add all ingredients simultaneously and still obtain a stable emulsion, a. microemulsion, having a small particle size, for example less than about 5 microns on average.
  • the microemulsion could also be prepared at 22 0 C and at pressures of about 500 psi to about 1500 psi, as well as pressures as high as 5000 psi.
  • the fuel composition of this example utilized components resulting in a composition particularly useful in applications requiring an elevated flashpoint compared to the compositions identified above, including but not limited to uses such as diesel engines for vehicles and burners .
  • the fuel components are shown in the following table:
  • Biofuel 8 is significantly higher than that of Biofuel 7A.
  • mixtures of up to 25 wt% Biofuel 8 with traditional diesel fuel, biodiesel fuel and ethanol can be prepared and the two fuel mixtures can be readily dispersed in one another and are stable, in other words they do not separate into different phases .
  • Example 10-1 in the table above is characterized as a stable emulsion fuel whereas Example 10-2 is considered unstable.
  • HLB effective HLB

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Abstract

Composition de biocombustible émulsionnée comprenant : (A) une phase continue comprenant environ 50-95 % en poids d'au moins une huile liquide d'origine végétale ou animale ou de mélanges de celles-ci ; (B) une phase dispersée contenant de l'eau comprenant environ 1-50 % en poids d'eau ; (C) environ 1-25 % en poids d'un composé organique contenant un ou plusieurs hydroxyles sélectionné dans le groupe constitué de monoalcools, de diols, de triols et de polyols, à condition que, lorsqu'on utilise un monoalcool, soit également présent l'alcool tert-butylique, d'au moins un (alkylène en C2-C4)glycol ou un mélange des deux ; (D) environ 0,05-10 % en poids d'au moins un émulsifiant ; les gouttelettes contenant de l'eau dispersées ayant une taille moyenne de particule inférieure à environ 20 microns. Le biocombustible est préparé à partir de ces composants en les mélangeant sous un cisaillement élevé, de préférence avec une énergie ultrasonique. Le ou les émulsifiants présentent de préférence une balance hydrophile-lipophile d'environ 8,5 à environ 18 et le biocombustible comprend un agent augmentant l'indice de cétane et un mélange d'un alcool et d'un monoalkylèneglycol ou d'un polyalkylèneglycol.
PCT/US2007/008955 2006-04-27 2007-04-10 Composition de biocombustible et procédé de production d'un biocombustible WO2007127059A2 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
MX2008013727A MX2008013727A (es) 2006-04-27 2007-04-10 Composicion de biocombustible y metodo para producir un biocombustible.
US12/226,637 US20100037513A1 (en) 2006-04-27 2007-04-10 Biofuel Composition and Method of Producing a Biofuel
CA002650333A CA2650333A1 (fr) 2006-04-27 2007-04-10 Composition de biocombustible et procede de production d'un biocombustible
JP2009507709A JP2009535449A (ja) 2006-04-27 2007-04-10 バイオ燃料組成物およびバイオ燃料の製造方法
BRPI0710806-0A BRPI0710806A2 (pt) 2006-04-27 2007-04-10 composição de biocombustìvel, método para preparar uma composição de combustìvel emulsificado, combustìvel emulsificado, mistura de combustìvel emulsificado, e, método para preparação de uma mistura de combustìvel emulsificado
AU2007243536A AU2007243536A1 (en) 2006-04-27 2007-04-10 Biofuel composition and method of producing a biofuel
EP07755282A EP2010631A4 (fr) 2006-04-27 2007-04-10 Composition de biocombustible et procédé de production d'un biocombustible
AP2008004651A AP2008004651A0 (en) 2006-04-27 2007-04-10 Biofuel composition and method of producing a biofuel
IL194795A IL194795A0 (en) 2006-04-27 2008-10-22 Biofuel composition and method of producing a biofuel
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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009144039A (ja) * 2007-12-13 2009-07-02 Adeka Corp バイオディーゼル燃料用の安定化剤及びバイオディーゼル燃料組成物
EP2115103A2 (fr) * 2007-01-31 2009-11-11 Biothermie Procede de preparation d'un biocombustible, biocombustible ainsi prepare et systeme de production de chaleur mettant en oeuvre un tel biocombustible
DE102008032254A1 (de) * 2008-07-09 2010-01-21 Man Nutzfahrzeuge Ag Rußarme Dieselkraftstoffe, enthaltend einen Kraftstoffzusatz, deren Verwendung sowie die Verwendung des Kraftstoffzusatzes zur Herstellung von rußarmen Dieselkraftstoffen
WO2010032013A1 (fr) * 2008-09-17 2010-03-25 Petroleo Brasileiro S.A.-Petrobras Compositions de carburant diesel contenant des dianhydro-hexitols et produits associés
WO2010099058A2 (fr) * 2009-02-24 2010-09-02 University Of Georgia Research Foundation, Inc. Production de bio-huiles de qualité supérieure par estérification en ligne de vapeur de pyrolyse
WO2011026742A1 (fr) * 2009-09-03 2011-03-10 Bundesanstalt für Materialforschung und -Prüfung (BAM) Combustible propre et efficace pour l'industrie de processus
US20120096763A1 (en) * 2007-09-24 2012-04-26 William H. Klausmeier Family Trust Method of formulating a fuel composition for use in internal-combustion engines
US20130276359A1 (en) * 2012-04-20 2013-10-24 Broadleaf Energy, LLC Renewable biofuel
EP2873714A1 (fr) * 2013-11-18 2015-05-20 Nanotechlab S.A. Emulsion d'eau/huile végétale
US20160257896A1 (en) * 2007-09-24 2016-09-08 Sylvatex, Inc. Compositions for use in internal-combustion engines and methods of forming and using such compositions
RU2643728C1 (ru) * 2017-02-27 2018-02-05 Федеральное государственное бюджетное образовательное учреждение высшего образования "Уфимский государственный нефтяной технический университет" Антисептик нефтяной на основе Универсина для пропитки древесины
US9944871B2 (en) 2011-07-20 2018-04-17 Genuine Bio-Fuel, Inc. Method and system for production of biodiesel utilizing ultrasonic shear mixing to reduce the amount of energy needed by 45 to 50% and eliminate the use of water
CN112175688A (zh) * 2020-10-22 2021-01-05 安徽海螺新材料科技有限公司 水泥熟料煅烧燃煤助剂及其制备方法

Families Citing this family (69)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BRPI0806614A2 (pt) * 2007-01-16 2011-09-20 Earthfly Holding Gmbh combustìvel
MY150409A (en) * 2007-05-15 2014-01-15 Malaysian Palm Oil Board Mpob A fuel composition
JP4551944B2 (ja) * 2007-05-15 2010-09-29 利春 深井 油分乳化物
US20090260278A1 (en) * 2008-04-17 2009-10-22 Klausmeier William H Fuel compositions
US20090260279A1 (en) * 2008-04-17 2009-10-22 Klausmeier William H Biodiesel and diesel compositions
US8142524B2 (en) * 2008-09-30 2012-03-27 Chevron U.S.A. Inc. Biodiesel-derived combustion improver
US9307758B2 (en) 2009-06-19 2016-04-12 Exacto, Inc. Polyacrylamide based agricultural compositions
US9309378B2 (en) 2009-06-19 2016-04-12 Exacto, Inc. Emulsion compositions comprising polyacrylamide copolymer and ethylene oxide—propylene oxide copolymer
US9428630B2 (en) 2009-06-19 2016-08-30 Exacto, Inc. Water-in-oil polyacrylamide-based microemulsions and related methods
CN102021051A (zh) * 2009-09-18 2011-04-20 泷住武司 油水燃料的乳化添加剂
JP5670459B2 (ja) * 2009-10-14 2015-02-18 パロックス リミテッド 液体燃料の保護
CN102093917B (zh) * 2009-12-09 2013-11-13 济南开发区星火科学技术研究院 一种可替代柴油的调和燃料油及其制备方法
WO2011126771A2 (fr) * 2010-03-27 2011-10-13 Perfectly Green Corporation Système, procédé et produit programme d'ordinateur pour l'attribution d'énergie
WO2012006316A1 (fr) * 2010-07-06 2012-01-12 New Generation Biofuels Holdings, Inc. Carburant à base d'huile de pyrolyse et procédé de fabrication
CN102071079A (zh) * 2011-01-13 2011-05-25 中国科学院青岛生物能源与过程研究所 一种微乳化生物柴油及其制备方法
CA2831839A1 (fr) 2011-03-29 2012-10-04 Fuelina Technologies, Llc Combustible hydride et son procede de fabrication
CA2738194C (fr) * 2011-04-27 2015-06-16 Imperial Oil Resources Limited Methode de traitement d'un circuit d'alimentation en bitume au moyen d'une emulsion
US8679202B2 (en) * 2011-05-27 2014-03-25 Seachange Group Llc Glycerol containing fuel mixture for direct injection engines
CN102417840A (zh) * 2011-10-09 2012-04-18 中国科学院青岛生物能源与过程研究所 一种微乳化生物柴油及其生产方法
CN103131481B (zh) * 2011-11-22 2016-03-30 柏富军 一种生物合成燃料
CN102660335B (zh) * 2012-06-06 2014-06-11 刘一江 一种由地沟油生成物制备的生物醇油
US8894726B2 (en) 2012-06-13 2014-11-25 Afton Chemical Corporation Fuel additive for improved performance in fuel injected engines
CN103911190B (zh) * 2013-01-09 2015-12-02 刘粤荣 一种多元配方组合的生物燃油及其制备方法
WO2014158262A1 (fr) 2013-03-14 2014-10-02 Rolls-Royce Corporation Émulsion carburant/eau issue d'algues
CN103421553A (zh) * 2013-04-11 2013-12-04 襄阳客瑞客化工科技有限公司 节能减排柴油添加剂
CN103409183A (zh) * 2013-05-20 2013-11-27 冯智勇 一种供汽车使用的微乳化生物柴油
CN103409177B (zh) * 2013-08-29 2015-03-04 胡荣汉 一种船用甲醇燃料油及其制备方法
CN104726151A (zh) * 2013-12-20 2015-06-24 永港伟方（北京）科技股份有限公司 一种生物柴油添加剂及其制备方法
CA2948363C (fr) 2014-05-15 2024-01-02 Seachange Group Llc Melanges de carburants a base de biodiesel et d'emulsion de glycerol
US10316264B2 (en) * 2014-11-10 2019-06-11 Eme International Limited Water in diesel oil fuel micro-emulsions
ES2719875T3 (es) 2014-11-10 2019-07-16 Eme Finance Ltd Dispositivo para mezclar agua y gasoil, aparato y proceso para producir una microemulsión de agua/gasoil
JP6371687B2 (ja) * 2014-11-21 2018-08-08 日本油化工業株式会社 燃料油の防カビ性および潤滑性を向上させる組成物
MX2017007234A (es) 2014-12-03 2018-04-10 Univ Drexel Incorporacion directa de gas natural en combustibles liquidos de hidrocarburo.
CN107429179A (zh) * 2014-12-23 2017-12-01 罗地亚经营管理公司 液体生物燃料组合物
US9340742B1 (en) 2015-05-05 2016-05-17 Afton Chemical Corporation Fuel additive for improved injector performance
CN105038901B (zh) * 2015-05-06 2017-01-25 湖南省生物柴油工程技术研究中心 一种低温稳定剂的制备方法
WO2016196402A1 (fr) 2015-05-29 2016-12-08 Perfectly Green Corporation Système, procédé et produit de programme informatique pour attribution d'énergie
CN104845683A (zh) * 2015-06-03 2015-08-19 泰安华秦化工有限责任公司 一种高效环保型乳化剂
CN104962325B (zh) * 2015-07-13 2016-11-30 上海婉静纺织科技有限公司 环保生物燃油及其制备方法
US20170241308A1 (en) * 2016-02-24 2017-08-24 Ford Global Technologies, Llc Oil maintenance strategy for electrified vehicles
CN106244254B (zh) * 2016-08-25 2018-06-05 山东恒利热载体工程技术有限公司 生物质锅炉燃料油生产工艺及装置
IT201600132801A1 (it) 2016-12-30 2018-06-30 Eme International Ltd Apparato e processo per produrre liquido derivante da biomassa, biocarburante e biomateriale
KR101889822B1 (ko) * 2017-03-21 2018-09-28 애경유화 주식회사 캐슈넛 껍질 오일 및 기타 조동식물성 유지의 정제방법
CN110730815B (zh) * 2017-04-10 2022-01-18 金德燮 燃料添加剂的制备方法及使用其的燃料
CR20170215A (es) * 2017-05-24 2017-08-11 3-102-733702 Soc De Responsabilidad Ltda Proceso de mezcla orgánica para la potencialización de gasolina fósil y bioethanol con reducción de emisiones.
CR20170211A (es) * 2017-05-24 2017-08-11 3-102-735850 Soc De Responsabilidad Ltda Procedimiento orgánico para la potencialización del avgas convencional y el bioavgas con reducción de emisiones
CR20170213A (es) * 2017-05-24 2017-08-11 3-102-735873 Soc De Responsabilidad Ltda Proceso organico para la prevención de corrosión y temperaturas extremas en motores de combustión interna y procesos industriales enfriados por liquidos.
WO2019186794A1 (fr) * 2018-03-28 2019-10-03 理研計器株式会社 Procédé de détection de gaz et dispositif de détection de gaz
WO2019187710A1 (fr) * 2018-03-28 2019-10-03 理研計器株式会社 Procédé et dispositif de détection de gaz
WO2019215023A1 (fr) * 2018-05-08 2019-11-14 Nouryon Chemicals International B.V. Dérivés alkylimino destinés à être utilisés dans des émulsions de carburant diesel
CN108641757A (zh) * 2018-05-30 2018-10-12 北京三聚绿能科技有限公司 一种生物质油的处理方法
CN108753382A (zh) * 2018-05-30 2018-11-06 北京三聚绿能科技有限公司 一种提高生物质油燃烧性能的添加剂及其制备方法
TWI653330B (zh) * 2018-08-31 2019-03-11 澤田重美 以新式燃料組成作為一改良式柴油引擎之燃料的方法
US11390821B2 (en) 2019-01-31 2022-07-19 Afton Chemical Corporation Fuel additive mixture providing rapid injector clean-up in high pressure gasoline engines
GB2598470A (en) * 2019-02-01 2022-03-02 Antonio Trevino Quintanilla Sergio Process for the production of an improved diesel fuel
MX2021009224A (es) * 2019-02-07 2021-09-08 Shell Int Research Composicion de combustible con aditivos de lubricidad.
US10947469B2 (en) * 2019-05-13 2021-03-16 James Chun Koh Apparatus and method for manufacturing bio emulsion fuel using vegetable oil
US11492498B2 (en) * 2019-07-30 2022-11-08 Estron Chemical Isosorbide-based degassing agent
CN110412248A (zh) * 2019-07-31 2019-11-05 肖建华 一种压缩比调整方式对柴油十六烷值快速测定及使用方法
EP4017945A1 (fr) * 2019-08-22 2022-06-29 ExxonMobil Research and Engineering Company Additifs pour carburants à faibles émissions de nox
CN110791363B (zh) * 2019-09-27 2022-05-27 佳化化学(上海)有限公司 一种全合成切削液及其制备方法
CN113430020A (zh) * 2020-03-08 2021-09-24 上海吉油环保科技有限公司 一种提升燃油效率的添加剂及其制备方法
KR102332935B1 (ko) * 2020-04-06 2021-11-30 한국조선해양 주식회사 바이오 연료 시스템 및 이를 포함하는 해양구조물
KR102503505B1 (ko) * 2020-12-02 2023-02-23 이경은 내연기관용 연료첨가제 조성물
KR102503500B1 (ko) * 2020-12-02 2023-02-28 이경은 내연기관용 연료첨가제 조성물
CN114672351A (zh) * 2022-03-28 2022-06-28 成都瑞厅科技有限公司 一种燃烧用的新型安全助燃剂及其制备方法
US11873461B1 (en) 2022-09-22 2024-01-16 Afton Chemical Corporation Extreme pressure additives with improved copper corrosion
CN115449417B (zh) * 2022-09-23 2023-07-14 神华准能资源综合开发有限公司 萘系复配分散剂、包含其的活化纳米原浆及其制备方法
US11795412B1 (en) 2023-03-03 2023-10-24 Afton Chemical Corporation Lubricating composition for industrial gear fluids

Family Cites Families (64)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2229215A (en) * 1938-02-23 1941-01-21 Carter Carburetor Corp Antifreeze substance for fuel tanks
US2243198A (en) * 1939-01-28 1941-05-27 Du Pont Fuel oil
US3876391A (en) * 1969-02-28 1975-04-08 Texaco Inc Process of preparing novel micro emulsions
DE2653026A1 (de) * 1975-06-30 1978-05-24 Edward C Wenzel Als kraftstoff fuer verbrennungsmotoren verwendbares fluessigkeitsgemisch
FR2313078A1 (fr) * 1975-02-07 1976-12-31 Anvar Composition a base d'huile vegetale metabolisable et d'eau, utilisable notamment pour la constitution de preparations adjuvantes, ces preparations adjuvantes et leur procede d'obtention
DE2542671C3 (de) * 1975-09-25 1979-12-06 Kawasaki Jukogyo K.K., Kobe Verfahren zum Verbrennen eines Emulsionsöles
JPS5560960A (en) * 1978-10-31 1980-05-08 Agfa Gevaert Nv Composition for developing electrostatic image and method of development
DE2854540A1 (de) * 1978-12-16 1980-06-26 Bayer Ag Kraftstoffe
DE2854437A1 (de) * 1978-12-16 1980-06-26 Bayer Ag Kraftstoffe, verfahren zu ihrer herstellung und ihre verwendung
IT1141984B (it) * 1981-02-26 1986-10-08 Ernesto Marelli Apparecchiatura ad ultrasuoni per il trattamento particolarmente di liquidi
US4526586A (en) * 1982-09-24 1985-07-02 The United States Of America As Represented By The Secretary Of Agriculture Microemulsions from vegetable oil and aqueous alcohol with 1-butanol surfactant as alternative fuel for diesel engines
US4451267A (en) * 1982-09-29 1984-05-29 The United States Of America As Represented By The Secretary Of Agriculture Microemulsions from vegetable oil and aqueous alcohol with trialkylamine surfactant as alternative fuel for diesel engines
US4557734A (en) * 1984-08-08 1985-12-10 The United States Of America As Represented By The Secretary Of Agriculture Microemulsions from vegetable oil and lower alcohol with octanol surfactant as alternative fuel for diesel engines
US4744796A (en) * 1986-02-04 1988-05-17 Arco Chemical Company Microemulsion fuel system
US4696638A (en) * 1986-07-07 1987-09-29 Denherder Marvin J Oil fuel combustion
IT1227882B (it) * 1988-12-05 1991-05-14 Ernesto Marelli Carburante per riduzione della nocivita' dei gas di scarico particolarmente per motori a combustione interna
CA2000964A1 (fr) * 1989-03-02 1990-09-02 Richard W. Jahnke Emulsions huile-eau
US5380343A (en) * 1993-02-01 1995-01-10 Hunter; Herbert F. Method for preparing an alcohol modified vegetable oil diesel fuel
JPH06322382A (ja) * 1993-03-17 1994-11-22 Kao Corp 重質油エマルジョン燃料組成物
US5372613A (en) * 1993-04-19 1994-12-13 Mekonen; Kenneth Fuel compositions
WO1994024215A1 (fr) * 1993-04-20 1994-10-27 The American Color Company, Inc. Formulations de solvants pour peinture et procedes d'utilisation
US5992354A (en) * 1993-07-02 1999-11-30 Massachusetts Institute Of Technology Combustion of nanopartitioned fuel
US6302929B1 (en) * 1994-04-04 2001-10-16 Rudolf W. Gunnerman Aqueous fuel for internal combustion engine and method of preparing
US6380264B1 (en) * 1994-06-23 2002-04-30 Kimberly-Clark Corporation Apparatus and method for emulsifying a pressurized multi-component liquid
FR2746106B1 (fr) * 1996-03-15 1998-08-28 Combustible emulsionne et l'un de ses procedes d'obtention
US6695890B1 (en) * 1996-10-18 2004-02-24 Aae Technologies International Plc Fuel composition
AU761457B2 (en) * 1998-01-12 2003-06-05 Deborah Wenzel An additive composition also used as a fuel composition comprising water soluble alcohols
US6211253B1 (en) * 1998-05-20 2001-04-03 Ernesto Marelli Process for producing emulsions, particularly emulsions of liquid fuels and water, and apparatus used in the process
US6383237B1 (en) * 1999-07-07 2002-05-07 Deborah A. Langer Process and apparatus for making aqueous hydrocarbon fuel compositions, and aqueous hydrocarbon fuel compositions
US20020088167A1 (en) * 1998-09-14 2002-07-11 The Lubrizol Corporation Emulsified water-blended fuel compositions
US6368366B1 (en) * 1999-07-07 2002-04-09 The Lubrizol Corporation Process and apparatus for making aqueous hydrocarbon fuel compositions, and aqueous hydrocarbon fuel composition
US20060048443A1 (en) * 1998-09-14 2006-03-09 Filippini Brian B Emulsified water-blended fuel compositions
US6368367B1 (en) * 1999-07-07 2002-04-09 The Lubrizol Corporation Process and apparatus for making aqueous hydrocarbon fuel compositions, and aqueous hydrocarbon fuel composition
US6648929B1 (en) * 1998-09-14 2003-11-18 The Lubrizol Corporation Emulsified water-blended fuel compositions
US6017369A (en) * 1998-11-23 2000-01-25 Pure Energy Corporation Diesel fuel composition
FR2786780B1 (fr) * 1998-12-08 2001-03-02 Elf Antar France Procede de preparation d'un combustible emulsionne et son dispositif de mise en oeuvre
US6652607B2 (en) * 1999-07-07 2003-11-25 The Lubrizol Corporation Concentrated emulsion for making an aqueous hydrocarbon fuel
US6913630B2 (en) * 1999-07-07 2005-07-05 The Lubrizol Corporation Amino alkylphenol emulsifiers for an aqueous hydrocarbon fuel
US20040111956A1 (en) * 1999-07-07 2004-06-17 Westfall David L. Continuous process for making an aqueous hydrocarbon fuel emulsion
US6827749B2 (en) * 1999-07-07 2004-12-07 The Lubrizol Corporation Continuous process for making an aqueous hydrocarbon fuel emulsions
US6530964B2 (en) * 1999-07-07 2003-03-11 The Lubrizol Corporation Continuous process for making an aqueous hydrocarbon fuel
IT1313901B1 (it) * 1999-10-25 2002-09-26 Ernesto Marelli Apparecchio e metodo per la formazione di microemulsioni atomizzatestabilizzate
IT1314228B1 (it) * 1999-11-16 2002-12-06 Ernesto Marelli Carburante per motori diesel in forma di microemulsione e procedimentoper preparare lo stesso.
FR2802941B1 (fr) * 1999-12-23 2002-04-05 Elf Antar France Combustible emulsionne stable en temperature
CA2398006C (fr) * 2000-01-12 2010-01-05 Cam Tecnologie S.P.A. Combustible contenant une emulsion eau-hydrocarbure liquide
US20030084658A1 (en) * 2000-06-20 2003-05-08 Brown Kevin F Process for reducing pollutants from the exhaust of a diesel engine using a water diesel fuel in combination with exhaust after-treatments
WO2002059236A2 (fr) * 2000-12-29 2002-08-01 Ge Betz, Inc. Melanges stabilisants de l'alcool dans un combustible hydrocarbone
US20030163946A1 (en) * 2002-03-01 2003-09-04 Berlowitz Paul Joseph Low emissions fuel emulsion
JP2005520033A (ja) * 2002-03-14 2005-07-07 ザ　ルブリゾル　コーポレイション エタノール−ディーゼル燃料組成物およびそれらの方法
CN1622988A (zh) * 2002-03-28 2005-06-01 Cam技术股份公司 降低内燃机污染物排放的方法,以及包含水和液态烃的燃料乳液
US20040020105A1 (en) * 2002-07-23 2004-02-05 The Lubrizol Corporation A Corporation Of The State Of Ohio Emulsified water fuel blend containing an aqueous organic ammonium salt
FR2842820B1 (fr) * 2002-07-26 2005-06-17 Totalfinaelf France Combustible emulsionne eau/hydrocarbures, sa preparation et ses utilisations
JP2004091625A (ja) * 2002-08-30 2004-03-25 Eng Kk ボイラ用乳化植物油燃料
JP2004098748A (ja) * 2002-09-05 2004-04-02 Honda Motor Co Ltd 車両用サンバイザ
US20040111957A1 (en) * 2002-12-13 2004-06-17 Filippini Brian B. Water blended fuel composition
FR2855525B1 (fr) * 2003-06-02 2005-07-08 Total France Combustible emulsionne eau/hydrocarbures, sa preparation et ses utilisations
DE10334897A1 (de) * 2003-07-29 2005-03-10 Univ Koeln Mikroemulsionen und deren Verwendung als Kraftstoff
US7413583B2 (en) * 2003-08-22 2008-08-19 The Lubrizol Corporation Emulsified fuels and engine oil synergy
ES2670344T3 (es) * 2003-09-05 2018-05-30 Infineum International Limited Composiciones de aditivo para combustible diésel estabilizado
EP1718394A4 (fr) * 2004-02-09 2008-05-28 O2Diesel Corp Procedes de reduction d'emissions de matieres particulaires provenant de l'echappement de moteur diesel utilisant des melanges de carburant ethanol/diesel en combinaison avec des catalyseurs d'oxydation pour diesel
ITMI20040296A1 (it) * 2004-02-20 2004-05-20 Ernesto Marelli Carburante per motori diesel in forma di microemulsione e procedimento per preparare lo stesso
WO2005087903A1 (fr) * 2004-03-09 2005-09-22 Conocophillips Company Melanges de distillat synthetique et de biodiesel pour de faibles emissions d'oxydes d'azote provenant de moteurs diesel
US7072778B2 (en) * 2004-06-17 2006-07-04 Stmicroelectronics, Inc. Method and system for determining a rotor position in a wound field DC motor
FR2875810B1 (fr) * 2004-09-29 2008-03-14 Ecole Des Mines De Nantes Combustible liquide et procede de production d'un tel combustible

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None
See also references of EP2010631A4

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2115103A2 (fr) * 2007-01-31 2009-11-11 Biothermie Procede de preparation d'un biocombustible, biocombustible ainsi prepare et systeme de production de chaleur mettant en oeuvre un tel biocombustible
US20120096763A1 (en) * 2007-09-24 2012-04-26 William H. Klausmeier Family Trust Method of formulating a fuel composition for use in internal-combustion engines
US20180291294A1 (en) * 2007-09-24 2018-10-11 William H. Klausmeier Family Trust Method of formulating a fuel composition for use in internal-combustion engines
US20160257896A1 (en) * 2007-09-24 2016-09-08 Sylvatex, Inc. Compositions for use in internal-combustion engines and methods of forming and using such compositions
JP2009144039A (ja) * 2007-12-13 2009-07-02 Adeka Corp バイオディーゼル燃料用の安定化剤及びバイオディーゼル燃料組成物
DE102008032254A1 (de) * 2008-07-09 2010-01-21 Man Nutzfahrzeuge Ag Rußarme Dieselkraftstoffe, enthaltend einen Kraftstoffzusatz, deren Verwendung sowie die Verwendung des Kraftstoffzusatzes zur Herstellung von rußarmen Dieselkraftstoffen
DE102008032254B4 (de) * 2008-07-09 2010-10-21 Man Nutzfahrzeuge Ag Rußarme Dieselkraftstoffe, enthaltend einen Kraftstoffzusatz, deren Verwendung sowie die Verwendung des Kraftstoffzusatzes zur Herstellung von rußarmen Dieselkraftstoffen
WO2010032013A1 (fr) * 2008-09-17 2010-03-25 Petroleo Brasileiro S.A.-Petrobras Compositions de carburant diesel contenant des dianhydro-hexitols et produits associés
WO2010099058A2 (fr) * 2009-02-24 2010-09-02 University Of Georgia Research Foundation, Inc. Production de bio-huiles de qualité supérieure par estérification en ligne de vapeur de pyrolyse
US8900416B2 (en) 2009-02-24 2014-12-02 University Of Georgia Research Foundation, Inc. Production of higher quality bio-oils by in-line esterification of pyrolysis vapor
WO2010099058A3 (fr) * 2009-02-24 2011-01-27 University Of Georgia Research Foundation, Inc. Production de bio-huiles de qualité supérieure par estérification en ligne de vapeur de pyrolyse
WO2011026742A1 (fr) * 2009-09-03 2011-03-10 Bundesanstalt für Materialforschung und -Prüfung (BAM) Combustible propre et efficace pour l'industrie de processus
US9944871B2 (en) 2011-07-20 2018-04-17 Genuine Bio-Fuel, Inc. Method and system for production of biodiesel utilizing ultrasonic shear mixing to reduce the amount of energy needed by 45 to 50% and eliminate the use of water
US20130276359A1 (en) * 2012-04-20 2013-10-24 Broadleaf Energy, LLC Renewable biofuel
US9109179B2 (en) * 2012-04-20 2015-08-18 Broadleaf Energy, LLC Renewable biofuel
EP2873714A1 (fr) * 2013-11-18 2015-05-20 Nanotechlab S.A. Emulsion d'eau/huile végétale
RU2643728C1 (ru) * 2017-02-27 2018-02-05 Федеральное государственное бюджетное образовательное учреждение высшего образования "Уфимский государственный нефтяной технический университет" Антисептик нефтяной на основе Универсина для пропитки древесины
CN112175688A (zh) * 2020-10-22 2021-01-05 安徽海螺新材料科技有限公司 水泥熟料煅烧燃煤助剂及其制备方法

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WO2007127059A3 (fr) 2008-02-07
JP2009535449A (ja) 2009-10-01
PE20080047A1 (es) 2008-02-14
BRPI0710806A2 (pt) 2011-08-16
AU2007243536A1 (en) 2007-11-08
HN2008001586A (es) 2011-07-22
ZA200808955B (en) 2010-10-27
MA30947B1 (fr) 2009-12-01
RU2008146727A (ru) 2010-06-10
ECSP088848A (es) 2008-12-30
CA2650333A1 (fr) 2007-11-08
MX2008013727A (es) 2009-02-05
GT200800232A (es) 2009-04-07
CO6140066A2 (es) 2010-03-19
EP2010631A4 (fr) 2010-03-17
IL194795A0 (en) 2009-08-03
KR20090003360A (ko) 2009-01-09
CR10378A (es) 2009-01-07
EP2010631A2 (fr) 2009-01-07
US20100037513A1 (en) 2010-02-18
CN101506336A (zh) 2009-08-12
AR060499A1 (es) 2008-06-25

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