Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
• • 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
  • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
  • C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark 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
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
  • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only 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
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives

Definitions

• the present invention relates to enhanced structured fuel compositions for use in jet, turbine, diesel, gasoline, and other combustion systems. More particularly, the present invention relates to fuel compositions using viscous hydrocarbons, which are substantially neutral pH, and which employ a silicon based combustion catalyst.
• such free radical generating oxygenates include C2 - C12 aldehydes, aldehydic acids, C2 -C12 ethers, C1 - C15 alcohols, C2 - C12 oxides, C3 - C15 ketones, ketonic acids, C3 - C15 esters, othroesters, C3 - C12 diesters, C5 -C12 phenols, C5 - C20 glycol ethers, C2 - C12 glycols, C3 - C20 alkyl carbonates, C3 - C20 dialkyl carbonates, C3 - C20 di-carbonates, C1 to C20 organic and inorganic peroxides, hydroperoxides, carboxylic acids, amines, nitrates, di-nitrates, oxalates, phenols, acetic acids, boric acids, orthoborates, hydroxyacids, orthoacids, anhydrides, acetates, acety
• Said enhanced combustion structure oxygenates, when in combination with a combustible non-lead metal or non-metal (as set forth below), exhibit high heats of enthalpy capable, improved combustion, thermal efficiency, fuel economy, and power.
• a combustible non-lead metal or non-metal as set forth below
• the enhanced combustion struture oxygenates of symmetrical dialkyl carbonates especially dimethyl and diethyl carbonates.
• a primary object of the present invention is the development and utilization of fuels having enhanced combustion structure which have increased stability.
• a further object of the present invention is the development of enhanced combustion structured in which the base fuel may be more viscous, or not as highly refined, as now required to meet minimum fuel standards.
• a further object is the employment of a co-metallic catalyst, which further enhances the combustion structure of the DMC and metal/non-metals component, further improving thermal efficiency, fuel economy, power and emissions.
• the substantially non-alkaline fuel compositions of the present invention exhibits improved stability, with no apparent hydrolysis after storage for six months or more.
• the presence of lower dialkyl carbonates and metals in the fuel compositions of the present invention allows for the use of highly viscous base fuels.
• the improved fuels described herein contain a base hydrocarbon fuel or propellant (including hydrogen) co-fuel, as provided in the PCT applications referenced above.
• Such co-fuels may be viscous, moderately viscous, or highly viscous (e.g. having viscosities outside industry standards).
• Said viscous fuels are combined with high energy non-lead metallic or non-metallics (presented below), together with symmetrical dialkyl carbonates, e.g. , dimethyl or diethyl carbonate, and preferably a silicon co-metallic combustion catalyst.
• the fuel compositions of the present invention When the fuel compositions of the present invention are then constructed to a weakly alkaline (7.5 to 1 1.0 pH), substantially neutral (6.5 to 7.5 pH), or acidic (4.5 to 6.5 pH), whether or not water is present, they exhibit improved stability with no substantial hydrolytic propensity.
• a weakly alkaline 7.5 to 1 1.0 pH
• substantially neutral 6.5 to 7.5 pH
• acidic 4.5 to 6.5 pH
• the improved fuel composition of the present invention includes an alkyl carbonate (dimethyl and/or diethyl carbonate) a metal or non- metallic compound, more fully described below, and optionally a silicon catalyst, co-fuel(propellant), and/or oxidizer. So long as the composition is not strongly alkaline, i.e. , has a pH of from 3.0 to about 10.5, hydrolysis of the fuel composition is avoided.
• a desirable pH range of the fuel composition of the present invention is from approximately 4.5 to approximately 10.5, with a more desirable pH range of from approximately 4.5 to approximately 9.5. An even more desireable pH range is from approximately 4.5 to 9.0.
• Another highly preferred pH range is from approximately 5.5. to 8.0.
• a preferred pH range is from approximately 4.5 to approximately 6.5.
• the most preferred pH range for the fuel composition of the present invention is from approximately 6.3 to approximately 6.8.
• the fuel when the pH of the fuel composition of the present invention is less than 1 1.0, preferably 10.5 or below, 9.5 or below, and more preferably 8.5 or below, the fuel, whether anhydrous or hydrous, may be stored at ambient temperature for up to 6 six months without substantial apparent hydrolysis.
• fuel composition was titrated with acetic acid to a pH of 6.4, still containing 5% by volume of water (Fuel B) and was then stored for six months, the fuel exhibited no apparent hydrolysis.
• acetic acid was used to acidify the pH of the fuel in the present case
• many other fuel soluble acids including but not limited to benzoic acid derivatives e.g. 2,4- dimethyl benzoic acid, methyl red, p-tert- butylbenzoic acid, 2-(1 - methylethyl) benzoic acid, benzoic acid anhydride, 4-benzoyl benzoic acid, 2,4-dihdroxy benzoic acid, 2,4- dimethyl-benzoic acid, 3-ethoxy benzoic acid, 2-hydroxy-4-methyl benzoic acid, 2-hydroxy benzontrile, 4-methoxy benzotrile, acetic acid derivatives, e.g.
• anhydride acetic acid chloroacetic acid, decyl ester acetic acid, dibromoacetic acid, and the like, may be employed. See for example CRC Handbook of Chemistry and Physics, 75th Ed, Lide, CRC Press (1994-1995) "Dissociation Constants for Inorganic Acids and Bases," and “Dissociation Constants for Organic Acids and Bases,” incorporated herein by reference.
• acidic fuel components which are indigenous to the either the base fuel composition, e.g. individual fuel components, metallic, DMC, or an additional ECS component (e.g. aldehydic acids, ketonic acids, carboxylic acids, hydroxyacids, orthoacids, formic acids, and the like) are desireable, and should be employed/modified first to achieve minimum pH's, prior to addition of an additive acid.
• ECS component e.g. aldehydic acids, ketonic acids, carboxylic acids, hydroxyacids, orthoacids, formic acids, and the like
• the pH of the composition may be tailored using normal hydrocarbon fuel components, dialkyl carbonates, and metallic(s) to achieve requisite pH.
• individual circumstances will dictate proper approach and additive acids are contemplated.
• acidic metals of this invention may be used individually and/or in conjunction with one or more other metallics to reduce pH.
• Such acidic metallics include binary, ternary and higher metallic acid salts, hydroxy acids, etc.
• Other non-limiting compounds are set forth below and include for example, oxamic acid, lithium acetate acid, lithium salt acetic acid, propanoic acid lithium salt, cyclohexanebutyric acid lithium salt, aminobenzole acid lithium salt, borate ester, dimethyl borate, di- n-butyl borate, dicyciohexyl borate, didodecylborate, di-p-cresyl borates, boric acids, orthoborates, henylboronic acid, diphenylboronic acid, o-tolylboronic acid, p- tolylboronic acid, m- tolylboronic acid, cylohexylboronic acid, cylohexenylbor
• an additive acid it is preferred it be compatible with the base fuel and have low toxicity, low corrosivity, and be as envirnomentally friendly as possible.
• PCT/US95/02691 and PCT/US95/06758 disclose compositions and methods achieving vapor phase combustion employing symmetrical dialkyl carbonates and certain non-leaded high energy metals and non-metals (herein "metals"). It has been discovered in the construction of a fuel composition, which employs one metal or a mixture of metals, together with at least one C3 to C13 dialkyl symmetrical carbonate, as taught therein, improved fuel stability can be obtained when the pH is kept as close to neutral as possible, such that if alkaline, it is only weakly alkaline (i.e., preferably equal or less than 1 1.0, 10.5, 10.0, 9.5, 9.0, 8.5, 8.0 pH), but that it preferably be either substantially neutral (i.e., 6.5 to 7.5) or slightly acidic (6.3 to 6.9 pH).
• Anhydrous fuels or substantially anhydrous fuels are contemplated and particularly preferred when employing water reactive group la, lla, lib, MIA metals and derivative compounds. Other circumstances will require anhydrous fuels as well, e.g. jet aviation applications, etc.
• anhydrous fuels are preferable, when the fuel compositions of the present invention have a pH in the preferred range of from approximately 10.5 to 4.5, there is no apparent hydrolysis, even when such fuels include an aqueous layer.
• the pH of the fuel composition is in the preferred range, the composition may contain water up to 10.0% by volume of the fuel with no apparent hydrolysis of the organic phase after six months of storage.
• a hydrocarbon fuel containing a lower dialkyl carbonate have a pH of less than 10.5.
• the addition of metals or non-metals herein, co-metallics, viscous hydrocarbons are further embodiments, and not necessary elements to this aspect of the invention.
• the claims below may reflect only a hydrocarbon fuel containing a lower dialkyl carbonate having a pH of less than 10.5, absent any additional limitation.
• a composition of this invention includes a hydrocarbon base together with dimethyl carbonate or diethyl carbonate, said composition adjusted such that its maximum pH is 10.5 of less, a more preferred pH is 6.8 or less.
• Acidity level of fuels is sometimes measured in terms of equivalents, e.g., equivalents of KOH required to neutralize the fuel composition.
• the fuels of the present invention show improved operation at acidity levels which are 100%, 150%, 200%, 300%, or more, above such standards. Acidity levels below such standards, including those at least 50% less, are expressly contemplated.
• ASTM D 1655 specifications incorporated herein by reference
• other international specifications including maximum acidity levels ASTM D 3242 and IP 354 standards.
• ASTM D 1655 specifications incorporated herein by reference
• IP 354 maximum acidity levels ASTM D 3242 and IP 354
• the fuel compositions of the present invention have a pH in the desired range of from approximately 4.5 to 1 1 .0, stability is maintained and hydrolysis is substantially avoided so long as fuel storage temperature is at or below 90°F.
• the fuel compositions of the present invention have pH's less than 10.5 and are stored at or below 65°F.
• Fuels A and B, described above were stored at 65°F during the period from 6 months after mixing to 9 months after mixing, fuel stability was maintained without apparent hydrolysis.
• Applicant's pH adjusted hydrocarbon based fuels will additionally contain known additive, including but not limited to antioxidants, co-solvents, metal deactivators, detergents, dispersants, corrosion inhibitors, mutual solvents, oxygenated antiknock compound (e.g. hydrocarbyl ethers, alcohols, etc.), other additive, and additive set forth in incorporated PCT Applications. Said known additive is incorporated herein by reference.
• a preferred fuel of the present invention comprises 1 ) dimethyl carbonate or dimethyl carbonate, representing 0.1 % to 99.5% wt of composition; 2) at least one metal as set forth below, representing 0.01 % to 99.5% wt of composition; optionally a metal deactivator representing 0.00001 % to 10.0% wt of composition, or an antioxidant representing 0.00001 % to 10.0% wt, or a detergent/dispersant representing 0.00001 % to 10.0% wt, or an ignition promoter representing 0.000001 % to 20.0% wt, or a demulsifier representing 0.00001 % to 10.0% wt, or a co-solvent or salt representing 0.000001 % to 40.0% wt, or a hydrocarbon representing 0.1 % to 99.0% volume of the composition, or a silicon based combustion catalyst (described below) representing 0.000001 % to 80.0% wt, or mixture.
• a metal deactivator representing 0.00001 % to 10.0% wt of composition
• Said fuel is constructed with a pH no greater than 1 1 .0 or 10.5, and preferrably less than 9.5. More preferably, the pH is from 6.3 to 6.8. When such fuel is a jet aviation turbine hydrocarbon based-fuel, preferred acidity does not exceed equivalent of 0.1 mg KOH/g.
• co-solvents that enhance mutual solubility of fuel components, fuel stability, water tolerance are preferred (e.g. C1 to C12 alcohols, alkanolamines, etc.). These are known in the art and incorporated herein by reference. Additionally, co-solvents that increase flash point or reduce vapor pressure are contemplated.
• Non-limiting examples include, ethanetriols, propanetriols, butanetriols, 1 ,2,3 butanetriol, pentanetriols, 1 ,2,3 pentanetriol, 2,3,4 pentanetriol, hexanetriols, septanetriols, octanetriols, or tertraethylene glycol, triethylene glycol, 1 -octene, high flash point ketone, naphthalenes, triethylene glycol, trimethylene glycol, isopropyl acetone, diisopropyl acetone, diisopropyl diacetone, diethylene acetate, diethylene diacetate, ethylene acetate compound, phenol, or other flash point temperature reducing co-solvent set forth in aforementioned PCT Applications. Co-solvents should not be corrosive or hazardous to fuel systems.
• the resultant fuel be constructed to have an average latent heat of vaporization (LHV) no less than typical industry standards.
• LHV's are generally greater.
• the latent heat of vaporization or enthalpy of vaporization ( vapH(Tb)/kJ mol-1 ) for commercial grade diesel, gas turbine, or fuel oils range from about 90 to 105 btu/lb (at 60°F) or 18 to 21 jK/mole or (at boiling temperatures).
• commercial motor gasolines have a LHV ranging from 135 to 145 btu/lb or 27 to 29 jK/mole, aviation gasolines about 130 to 150 btu/lb or 26 to 30 jk/mole, and aviation jet fuels about 105 to 1 15 btu/lb or 21 to 23 jK/mole.
• the LHV for commercial grade diesel, gas turbine, or fuel oils at 60°F exceed 105 btu/lb or 21 jK/mole (at boiling temperatures), for commercial motor gasolines LHV's should exceed 145 btu/lb or 29 jK/mole, for aviation gasolines LHV's should exceed 150 btu/lb or 30 jk/mole, and for aviation jet fuels LHV's should exceed 1 15 btu/lb or 23 jK/mole. LHV's at least 2%, 5%, 10%, 20%, 30% or greater than these amounts are however preferred.
• the burning velocities (as measured by laminar Bunsen burner flame) for commercial grade diesel, gas turbine, and fuel oils range from about 35-37 cm/sec, kerosine about 36 cm/sec, automotive gasoline about 47-50 cm/sec, aviation gasoline about 45-47 cm/sec, aviation jet fuels about 36-38 cm/sec. Methanol is reported at 57.2 cm/sec.
• burning velocities for commercial grade diesel, gas turbine, and fuel oils exceed 37 cm/sec
• kerosine exceed 36 cm/sec
• automotive gasoline exceed 50 cm/sec
• aviation gasoline exceed 47 cm/sec
• aviation jet fuels exceed 38 cm/sec.
• BV's at least 2%, 5%, 10%, 20%, 30%, or greater than above speeds are preferred.
• the hydrocarbon based fuels have high possible allowable densities.
• High densities of base fuels permit higher concentrations of metallics and dialkyl carbonates.
• aviation turbine densities equal or exceeding 841 kg/m3 @ 15°C are contemplated.
• the fuel compositions of the present invention allow for base fuel densities of from 840 to 1200 kg/m3 @ 15°C, and even 900 to over 1200 kg/ m3 @ 15°C.
• Moderate, low, to very low densities are also contemplated so long as the increased burning velocity object of above PCT Applications is accomplished and a pH is not greater than 10.5, preferably below 9.0, and most preferably from 6.3 to 6.8 is maintained.
• highly viscous hydrocarbon fuel bases with viscosities above fuel specification are unexpectedly brought to within fuel viscosity limits by the addition of dialkyl carbonates and metal.
• a diesel fuel oil having a viscosity of 2.6 mm2/S at 40o C was acceptably combined with dimethyl carbonate representing 5% volume of the composition, and 2.0 grs Mn/gal of methylcyclopentadienyl manganese tricarbonyl (MMT).
• MMT methylcyclopentadienyl manganese tricarbonyl
• the resultant fuel composition had a lower viscosity of 2.4 mm2/S at 40o C.
• highly viscous fuels can be adapted by the addition of applicant's ingredients, whereby non-conforming highly viscous fuels can be made less viscous and brought into compliance with ASTM or other specification (herein incorporated by refererence).
• Jet A hydrocarbon bases having a viscosity of 8.1 to 15.0 or more can be adapted to meet the current 8.0 mm2/sL at -20°C standard by addition of the components described above.
• base fuel viscosity of from 13.5 to 23.0 Cs at -30°F, or more may be met by the addition of the components described above.
• a gas oil turbine hydrocarbon base may have maximum kinetic viscosities at 40°C equal or exceeding 2.45 to 7.0, or greater, mm2/s for ASTM D 445 No. 1 -GT fuels, and be adapted to meet the 2.4 standard, by addition of the components described herein.
• base fuel kinetic viscosities of 4.15 to 6.0, or more, mm2/s for ASTM D 445 No. 2-GT fuels may be adapted to meet the 4.1 standard by addition of applicantps additives, as described herein.
• a diesel fuel oil base may have maximum kinetic viscosities at 40°C equal or exceeding 2.45 to 7.0, or greater, mm2/s for ASTM D 445 low sulfur or regular No. 1 -D fuels, and be adapted to meet the 2.4 standard by addition of applicantps additives.
• a diesel fuel oil base having maximum kinetic viscosities of 4.15 to 9.0 or more, mm2/s for ASTM D 445 low sulfur or regular No. 2-D fuels and be adapted to meet the 4.1 standard, by addition of applicantps additives.
• a fuel oil base may have kinetic viscosities equal or exceeding 2.15 10.0, or more, rnm2/s at 40°C ASTM D 445 for No. 1 fuels, and can be adapted to the 2.1 standard by addition of applicantps additives.
• a fuel base having kinetic viscosities of from 3.45 to 10,0, or more, mm2/s at 40°C ASTM D 445 for No. 2 fuels can be similarly adapted to meet 3.4.
• a fuel base having kinetic viscosities of 5.55 to 25.0 or more, mm2/s at 40°C ASTM for D 445 No. 4 fuels (Light), may be similarly adapted to meet 5.5.
• a fuel base having kinetic viscosities of from 24.5 to 40.0, or more, mm2/s at 40°C ASTM D 445 for No. 4 fuels (regular), may be adapted to meet 24.
• a fuel base having kinetic viscosities of from 8.95 to 25.0, or more, mm3/s at 100°C ASTM D 445 for No. 5 fuels (Light), may be adapted to meet 8.9.
• a fuel base having kinetic viscosities of from 15.0 to 30.0, or more, mm3/s at 100°C ASTM D 445 for No. 5 fuels (Heavy), may be adapted to meet 14.9.
• a heavy diesel, locomotive or marine engine base fuel exceeding ISO DIS 8217, BS MA 100, government and/or other industry viscosity specifications, but adapted to meet such standards (incorporated by reference), typically uncorrected viscosity exceeds such standards by 1.0, 2.0, 10.0, 50.0, or more centistokes at 50°C.
• Applicant has discovered by incorporating his lower dialkyl carbonates and metals, fuels having excessive viscosities can meet government, or other viscosity standards.
• an enhanced combustion aviation turbine fuel composition of the present invention includes a symmetrical alkyl dicarbonate, preferably dimethyl carbonate, a metal, an aviation turbine hydrocarbon base having a viscosity of from 8.1 to 9.0 MM2/S (ASTM 445); optionally one or more of the following: a salt, a co- solvent, antioxidant, freeze point additive, anti- icing additive, metal deactivator, corrosion inhibitor, hydroscopic control additive, lubricity agent, lubricant or friction modifier, anti-wear additive, combustion chamber or deposit control additive, any other recognized additive, additive disclosed in aforementioned PCT Applications, or mixture thereof.
• a salt a co- solvent, antioxidant, freeze point additive, anti- icing additive, metal deactivator, corrosion inhibitor, hydroscopic control additive, lubricity agent, lubricant or friction modifier, anti-wear additive, combustion chamber or deposit control additive, any other recognized additive, additive disclosed in aforementioned PCT Applications, or mixture thereof.
• the resultant fuel is characterized as being slightly alkaline, substantially neutral or acidic, and having a maximum viscosity equal or less than 8.2 MM2/SI (ASTM 445).
• the fuel preferably has a density of from 840.5 to 850, or greater, kg/m3 @ 15°C, a flash point of at least 38°C, a maximum vapor pressure of 21 kPa @ 38°C, minimum thermal stability meeting ASTM D 1655 standards, a heat of combustion or equivalent equal to or exceeding 42.8 MJ/kg (lower heats of combustion are contemplated, including those less than or equal to 42.5, 42, 41 , 40, 39, 38, 37, 36 MJ/kg, based upon additive heats of individual components), and a maximum freezing temperature of from - 40 to - 50°C, optionally a LHV not less than 1 15 btu/lb or 23 jK/mole, optionally a burning velocity exceeding 37 cm/sec.
• a diesel fuel composition of the present invention includes dimethyl carbonate representing 0.01 % to 40.0% oxygen by weight of the fuel; a compound or element containing a combustion improving amount of transition metal, alkaline metal, alkaline earth, group Il ia, IVa, Va, Via, Vila element or derivative compound, or mixture, optionally in an concentration of 0.001 to about 100.0 gr element/gal, preferably 2.0 to 20.0 gr element/gal; and a No.
• ASTM ASTM
• diesel fuel base having a viscosity of from 2.45 to 3.0, MM2/S at 40°C,; said fuel base optionally characterized as having one or more of the following: a density ranging from 880 to 800 kg/m3 , a cetane index of 40 to 70, an aromatic content by vol.
• a T10 fraction temperature of about 190 to 230°C, a T 50 fraction temperature of about 220 to 280°C, a T90 fraction of about 260 to 340°C, a cloud point temperature of °C -10, - 28, -32 or 6°C above tenth percentile minimum ambient temperature, a sulfur content preferably not greater than 250 ppm, more preferably not greater than 50 ppm, most preferably not exceeding 5 ppm, a bunsen laminar burning velocity of at preferably greater than 37, more preferably greater than 44, most preferably 50 ore more, cm/sec, a latent heat of vaporization of preferably at least 105, more preferably at least 120, most preferably 130 or more, BTU/lb.
• the resultant fuel is characterized as having a pH less than 10.5 and a viscosity equal to or less than 2.4 MM2/S at 40°C, optionally a LHV at 60°F equal or in excess of 105 btu/lb or 21 , 22, 23, 25, 27 jK/mole (at boiling temperatures), optionally a minimum laminar bunsen burner flame of 37, 39, 40, 41 cm/sec.
• An aviation gasoline fuel composition of the present invention includes a dialkyl carbonate, a metal and an aviation gasoline base.
• the resultant fuel is characterized as having a pH less than 7.0 and a minimum octane or performance number of from 87 to 130 (ASTM 909).
• a gasoline composition of the present invention includes an dialkyl carbonate, a metal and an unleaded base fuel composition.
• the resultant composition is characterized as having a pH less than 10.5, and optionally being phosphorus free hydrocarbons, a maximum Reid Vapor Pressure of from 6.0 to 12.0 psi, 6.0 to 10 psi, 6.0 to 9.0 psi; a maximum of 12% to 5.0% by volume, or less of olefins, a maximum of 30% to 20% or less by volume of aromatics (more preferably 15% to 10%, or less), a maximum of 2.0% to 0.8% or less benzene, a maximum of 40 ppm sulfur, most preferably sulfur free, a total O2 concentration ranging of 0.5% to 10.0% wt of dimethyl carbonate, a manganese tricarbonyl compound at 1/64 to 3/16 gr.
• Mn/gal preferably 1/32 gr. Mn or other metallic in a combustion improving amount, a maximum T-90 temperature of 330°F to 280°F, a T-50 temperature of approx. 170°F to 230°F. , 175°F preferred, a minimum (R+M)/2 octane of 85, to 92, a bromine number of 20 or less, an average latent heat of vaporization of 880 to 920, or more, BTU/gal at 60°F; a heating value greater than 106,000 btu/gal at 60°F (more preferably greater than 108,000, 1 14,000 btu/gal), as measured by the sum of individual fuel substituents.
• Another gasoline composition of the present invention includes an dialkyl carbonate, a metal and an unleaded base fuel composition, characterized as having a pH less than 10.5, and optionally characterized as having one or more of the following: being phosphorus free hydrocarbons, with a maximum Reid Vapor Pressure of 12.0 psi, a maximum of 12% olefins, a maximum of 30% aromatics, a maximum of 2.0% benzene, a maximum of 50 ppm sulfur or sulfur free, a total O2 concentration ranging from 0.5% to 10.0% wt of dialkyl carbonate, a combustible metal or non-metal selected from groups set forth below including (but not limited to ) those consisting of the preferred manganese, silicon, potassium, and iron compounds, or mixture, a maximum T-90 temperature of 330°F to 280°F, a T-50 temperature of approx.
• At least one combustible reactive non-lead transition metal, alkaline metal, alkaline earth, group Ilia, IVa (except carbon), Va, Via (except oxygen), Vila element, or derivative thereof, as set forth herein, or mixture (herein referred to as "metal” or "metallic") be together with at least one C3 to C13 symmetrical dialkyl ester of carbonic acid, and mixture, in a fuel stable composition; said composition optionally containing a combustion catalyst as set forth below, a hydrocarbon, and/or an oxidizer; resultant composition as having a pH slightly alkaline, neutral or acidic.
• Non-limiting examples of suitable dialkyl carbonates include, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, diisobutyl carbonate, ditertiary butyl carbonate, diisoamyl carbonate, methyl ethyl carbonate, diphenyl carbonate, or mixture.
• C3 to C8 symmetrical dialkyl carbonates are more desirable, with C3 to C5 being preferred. It is contemplated that such carbonates will be introduced into the composition in concentrations of 0.01 to 100.0 volume percent in an amount sufficient to improve combustion.
• the carbonates may be additionally combined with one or more oxygenated compounds, including but not limited to alkyl butyl ethers (e.g.
• methylal, ethylal, C1 to C6 aliphatic alcohols may be substituted for dialkyl carbonates, absent compromise of vapor phase combustion.
• Non-limiting examples of optional fuel which may be additionally contained with the dialkyl carbonate and metal, include hydrogen or any hydrocarbon, including but not limited to carbonaceous liquid or solid fuels, alternative fuels, gaseous fuels (including natural gas, methane, ethane, propane, butane, etc.), automotive gasolines, diesel fuel oils, heavy diesel fuel oils, aviation gasoline, gas oils, fuel oils, aviation jet turbine oils, coal, coal oils, coal liquids, and the like.
• metallics include all non-lead metals, metalloids, and non-metals (herein “metals” or “metallics”), and their derivative compounds, whose combustion product accomplishes primary object of vapor phase combustion, which is evidenced by a brilliant luminous reaction zone extending some distance from the metal's surface.
• metals metalloids
• metalics metalics
• Such combustion does not take place on the surface of the metal, or on and/or within the molten layer of oxide covering the metal, typical of heretofore metallic combustion.
• Distinguishing vapor phase combustion is that its combustion is expansive with elevated exhaust velocities, and resultant metallic oxide particles are formed in the submicron range.
• fuel economy, power output, exhaust emissions, combustion temperatures are materally improved.
• Group IA alkali metals
• MA alkaline earths
• the elements of group lb, lib, Ilia, IVa (absent carbon), and group Va, Via, Vila elements are contemplated.
• Non- limiting examples include aluminum, boron, bromine, bismuth, beryllium, calcium, cesium, chromium, cobalt, copper, francium, gallium, germanium, iodine, iron, indium, lithium, magnesium, manganese, molybdenum, nickel, niobium, phosphorus, potassium, palladium, rubidium, sodium, tin, zinc, praseodymium, rhenium, silicon, vanadium, strontium, barium, radium, scandium, yttrium, lanthanum, actinium, cerium, thorium, titanium, zirconium, hafium, praseodymium, protactinium, tantalum, neodyium, uranium, tungsten, promethium, neptunium, samarium, plutonium, ruthenium, osmium, europium, americium, rhodium, i
• Applicant's metals, including derivative compound may be organo-metallic or inorganic. Accordingly, the inorganic and organic compounds of CRC Handbook of Chemistry and Physics, Lide, 75th (1994-1995) and earlier editions, Ann Arbor, CRC Press; Sigma-Aldrich Chemical Directory, Aldrich Chemical Company (1997), Chemical Abstract Service (CAS), on line Registry File [1 ], American Chemical Society, Chemical Abstract Service, Ohio State University, A Manual of Inorganic Chemistry, Thorpe, N.Y. , Putnam & Son's (1896), Inorganic Materials, 2 ed., Ducan, N.Y.
• Cyclomatic compounds are particularly desireable.
• Non-limiting examples of cyclomatic compounds include compounds with one or more rings systems, including alicylic or aromatic ring systems. Ring systems which may be wholely organic, wholely inorganic, or heterocyclic.
• Such ring systems may include cyclic borons (borazoles), cyclic silanes (silacyclobutane, 2,4,6,8, 10- pentamethylcyclopentasilazane, cyclohexasilanes, cyclopropenyl silanes, etc.), cyclic nitrogens (pyrazoles, pyridines, pyrroles, piperazines, imidazals, etc.), cyclic oxygens (benzoyls, furans, pyrans, e.g.
• Cyclomatic organic ring systems include saturated rings (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, etc.), unsaturated rings, rings with one or more multiple or double bonds (cyclohexadiene, cyclopentadiene, cyclotetraene, etc.), aromatic rings/cycloalkyl radicals (phenyl, benzyl, styryl, etc.), fused rings, fused aromatic rings (naphthls, naphthenates, etc.), fused ring with cyclopentadienyl moiety, rings containing oxygen or a hydroxyl (phenol, etc.).
• Desireable metal containing cyclomatic compounds are those with cyclic rings having high burning velocities. The higher the burning the velocity, generally the higher the preference. Generally larger rings have higher burning velocities compared to smaller rings. Thus, a cyclooctane ring is preferred over cyclohexane, which is perferred over a cyclobutane ring. Saturated rings are normally more perferred over unsaturated rings. The more saturated the ring the more preferred. Thus, cyclohexane is preferred over benzene. Ring systems where the metal is in turn attached to one or more a hydroxyl, carbonyl, an alkyloxy radicals is preferred.
• Non-limiting examples of desireable ring systems/complexes include: cyclohexane, cyclohexene, cyclopentane, cyclobutane, cyclopentadiene, phenyl, benzene, and naphthalene. More desireable are cyclohexane, cyclohexene, and cyclopentadienyl. It is contemplated each elemental metal of this invention can be employed in a cyclomatic compound.
• Transition metal ring systems are well known in the art and highly desireable. See U.S. Patents Nos. 2,818,416, 3, 127,351 , 2,818,417, 2,839,552, 2,680, ; 2,804,468; 3,341 ,31 1 , 3,272,606, 3,718,444), Canadian Patent #1073207, European Patent Application # 93303488.6, pages 6-8 (1993), incorporated herein by reference.
• attachment may be direct or indirect. Attachment may be via molecular bond, ionic bond, coordination bond or other bond known in the art. Indirect attachment may be via one or more radical or element, or be via other bond as described below or known in the art. See The Chemistry of Organometallic Compounds, Rochow, Hurd, Lewis, New York, John Wiley & Sons, Inc. (latest edition), incorporated by reference.
• One or more radicals including cyclic radicals
• side chains saturated or unsaturated
• the metal may contain between one to as many radicals as available valence electrons (oxidation states) permit. See Handbook of Data on Organic Compounds 2ed, Weast, Grasselli, CRC (185).
• Non-limiting examples of radicals include organic or inorganic, saturated or unsaturated, or combinations thereof, including: hydrogen (hydride), hydroxyl, hydrocarbyl group radicals, including alkyl radicals (e.g. methyl, ethyl, propyl, issopropyl, butyl, isobutyl, sec-butyl, tert- butyl, amyl, pentyl, hexyl, etc.), alkyloxy radicals, various positional isomers thereof (e.g.
• aryl radicals e.g. phenyl, a-napthyl, b-naphthyl, a- anthryl, b- anthryl, etc.
• aryloxy radicals including monovalent radicals of such aromatics (e.g. indene, isoindene, acenaphthene, flourene, phenanthrene, naphthacene, chrysene, pyrene, triphenylene, etc.), aralkyl radicals (e.g.
• benzyl a-phenyl-ethyl, b-phenyl-ethyl, a-phenyl- propyl, etc.
• aralkyloxy radicals various positional isomers thereof (e.g. derivatives of 1 -methyl- butyl, 2-methyl-butyl, 3-methyl-butyl, 1 , 1 dimethyl-propyl, etc.), corresponding alkyl derivatives of phenanthrene, flourene, acenapthene, etc. , alkaryl radicals, (e.g.
• o-tolyl m-tolyl, p- tolyl, o-ethylphenyl, etc.
• arylalkenyl cycloalkyl radicals (benzyl, etc.)
• cycloalkyloxy radicals aliphatic radicals, mesityl.
• Hydroxyl, alkanol, alkanolamine, oxy and/or oxygen containing radicals, including derivatives of thereof and derivative of above radical are also contemplated.
• Non-limiting examples include hydroxy, methoxide, ethoxide, propoxide, isopropoxide, butoxide, isobutoxide, sec-butoxide, tert-butoxide, pentoxide, amyloxide, phenyloxidesperhydroxy, methoxy, methylol, methylenedioxy, ethoxy, ethylol, ethylenedioxy, enanthyl, propoxy, proprylol, propylene- dioxy, isopropoxy, isopropylol, isopropylenedioxy, butoxy, butylenedioxy, butylol, iso-butoxy, iso-butylol, isobutylenedioxy, isobutyryl, sec-butoxy, sec-butylol,
• Additional non-limiting oxygen containing radicals include acetyl, acetamido, acetoacetyl, acetonyl, acetonylidene, acrylyl, alanyl, B- alanyl, allophanoyl, anisyl, benzamido, butryl, carbonyl, carboxy, carbazoyl, caproyl, capryl, caprylrl, carbamido, car- bamoyl, carbamyl, carbazoyl, chromyl, cinnamoyl, crotoxyl, cyanato, decanoly, disiloxanoxy, epoxy, formamido, formyl, furyl, furfuryl, furfurylidene, glutaryl, glycinamido, glycolyl, glycyl, glyocylyl, heptadecanoyl, heptanolyl, hydroperoxy, hydroxamino, hydroxylamido
• radicals include: acetimido, amidino, amido, amino, aniline, anilino, arsino, azido, azino, azo, azoxy, benzylidine, benzldyne, biphenylyl, butylene, iso-butylene, sec-butylene, tert-butylene, cyano, cyanamido, diazo, diazoamino, ethylene, disilanyl, glycidyl, guanidino, guanyl, heptanamido, hydrazino, hydrazo, hypophosphite (hypophosphito), imido, isobutylidene, isopropylidene, silyl, silylene, methylene, mercapto, methylene, ethylene, naphthal, napthobenzyl, naphthyi, naphthylidene, propylene, propylene, propylene,
• One or more of the above radicals may be attached directly or indirectly to another. Indirect attachment may be via one or more intermediate atom, including but not limited to carbon, nitrogen, oxygen, phosophorus, silicon, boron, sulfur, or another metal.
• Metallic compounds may have one or more non-ring radicals attached.
• Desireable metals may for example have one or more alkyl, alkylene or similar radical attached to the metal, or one or more hydroxyl, carbonyl, alkyloxy, alkanol radicals, or combination thereof.
• Other metallic compounds may have one or more ring systems attached directly or indirectly to a metal, with or without an attached non- ring radical to the metal.
• One or more cyclic rings maybe attached, fused or indirectly attached together or linked together via one or more radicals, one or more atoms, including but not limited to carbon, nitrogen, oxygen, phosophorus, silicon, boron, sulfur, or a metal.
• One or more metals may be attached to each other, for example hexamethyldisilane, which is a preferred metallic.
• Indirect attachment herein includes attachment via one or more radicals, and/or one or more atoms, including but not limited to carbon, nitrogen, oxygen, phosophorus, silicon, boron, sulfur, or another metal.
• said carbon, nitrogen, oxygen, phosophorus, silicon, boron, sulfur, or other metal atom may be attached to itself or to another herein, one or more times, with each atom optionally having one or more hydrogen and/or radical(s). Said attachment may be independent of attachment to any other radical or metal, or may include an attachment to another radical or metal.
• one or more cyclic rings may be attached directly to the metal, or indirectly via one or more non-ring radicals, and/or via one or more intermediate atoms, including but not limited to carbon, nitrogen, oxygen, phosophorus, silicon, boron, sulfur, or another metal.
• one or more metals may be attached at one, or up to every location possible on the ring system, directly and/or indirectly.
• one or more ring systems may be attached at one, or up to every metal location possible, directly and/or indirectly.
• a non-ring radical may be independently attached directly or indirectly to the metal, absent its attachment of a ring system.
• the attachment of one or more non-ring radical(s) to a metal, absent a ring system is expressly contemplated.
• Contemplated oxygenated metallic compounds include metallic alkanols, ethers, ketones, hydroxides, alkyloxy, including methoxy, dimethoxy, trimethoxy, ethoxy, diethoxy, triethoxy, oxalate, carbonate, dicarbonate, tricarbonate, and similar structured compounds, including mixture thereof.
• trimethoxymethyisilane as set forth below
• Metallic carbonates including dimetallic carbonates, dimetallic dicarbonates, and the like, are also contemplated. It is contemplated these oxygenated metallic or organometallic compounds may be employed absent a dialkyl carbonate or other oxygenated ECS structure.
• non-ring radicals may be independently attached directly or indirectly to the ring system, absent attachment of a metal.
• An independent attachment of a metal may be via intermediate radical, one or more intermediate atoms, including but not limited to carbon, nitrogen, oxygen, phosophorus, silicon, boron, sulfur, or another metal.
• a cyclic ring/radical/side chain may be indirectly attached to the metal through one of more atom, including but not limited to carbon, nitrogen, oxygen, phosophorus, silicon, boron, sulfur, or a metal. Indirect attachment via oxygen is contemplated but less desireable.
• Cyclic rings may be attached to one or more non-ring radicals, atoms and/or ring systems prior to a direct or indirect attachment of the metal.
• [2-(cyclohexenyl)ethyl]triethoxysilane contains a ethyl radical attached to the cyclohexenyl ring, which is then attached to silicon. This is a preferred metallic structure.
• cyclomatic compounds may contain one or more ring systems, optionally with one or more non-ring radicals attached thereto.
• Said ring(s) then may be attached directly or indirectly to a metal, with said metal in turn optionally attached directly or indirectly to a radical, with said radical being optionally a non- ring radical selected from one or more hydrogen, hydroxyl, alkyl, aryl, carbonyl, alkanol, alkanolamine, alkyloxy, oxy or oxygen containing radical.
• Non-limiting examples include methylcyclopentadienyl manganese tricarbonyl, [2- (cyclohexenyl)ethyl]triethoxysilane, and cyclohexenyl dimethoxymethylsilane.
• a class of metallics which are capable of vapor phase combustion include spiral compounds based for example upon ferricyanhydric acid derivatives, namely ferricyanides. See Dictionary of Chemical Solubilties, supra, pages 334-342, which lists various ferrocyanides, incorporated herein by reference. Alkali metals and alkali earth metals are desireable ferricyanides. Potassium hexacyanoferrate (II) and potassium hexacyanoferrate (III) are desireable.
• Non-limiting examples of substitutes include potassium hexacyanocobalt II- ferrate, potassium Hexacyanocobalt III , potassium hexachloroosmate (IV), potassium hexachloroplatinate (IV), potassium hexafluorosilicate, potassium hexafluoromanganate (IV), potassium Hexaflourozirconate.
• potassium hexathiocyanatoplatinate (IV) potassium sodium ferricyanide, potassium hexacyanoplatinate, potassium hexacyanoruthinate (ll)hydrate, potassium hexacyanoplatinate (IV), potassium hexafluoroaluminate, potassium hexafluoroarsenate, potassium hexafluorophosphite, potassium hexafluorophosphite, potassium hexafluorosilicate, potassium hexahydroxyantimonate, potassium hexafluoro titante, Potassium copper ferracyanide, potassium cyanide, iron (II I) ferrocyanide, sodium ferrocyanide decahydrate.
• cyano-spiral including hexacyano compounds
• substitutions for potassium and/or iron are also contemplated. Examples of such substitution include potassium hexacyanocobaltate (III), sodium hexacyanocobaltate (I II), etc.
• Structurally similar compounds, analogues, and homologues, ect. are incorporated herein by reference.
• solvents include alkyl ketones (acetone, etc.), alkyl alcohols, alkyl ethers, glycerols, alkanol amines (ethanolamine, etc.), and the like.
• alkyl ketones acetone, etc.
• alkyl alcohols alkyl alcohols
• alkyl ethers glycerols
• alkanol amines ethanolamine, etc.
• Other contemplated solvents are known in the art and those which are both soluable with said hexacyanides and DMC are incorporated herein by reference.
• this fuel composition would include those already provided herein, except the metal component would be a hexacyanide, preferrably potassium hexacyanoferrate (II) or (II I).
• a fuel composition including DMC and potassium hexacyanoferrate (II) with a mutual solvent, optionally containing trimethoxymethylsilane, a hydrocarbon/hydrogen, and/or an oxidizer, formulated to acheive vapor phase combustion.
• Said composition may also be constructed to have maximum pH of 10.5.
• metallic hydrides include metal hydrides or metallic hydryls.
• metallic hydryls include sodium hydride, lithium hydride, aluminum hydride, aluminum borohydride, boron hydride, boron anhydride, beryllium borohydride, lithium borohydride, lithium aluminum hydride, lithium borohydride, sodium borohydride, transition-metal hydrides, transition-metal carbonyl hydrides, transition-metal cyclopentadienyl hydrides, and mixture.
• Organometallic nitrosyls are also desireable. See for example Metal Nitrosyls, Richter-Addo, Oxford University Press, U.K. (1992).
• Alkyl metal carbonates, multi-metal alkyl carbonates, or carbonates including those with a hydrogen e.g. LiHCO3, Na2C03, NaHCO3, MnCO3, MgC03, CaCO3, CaMg(CO3)2, etc.
• alkali metal carbonates e.g. AgCO3, TI2CO3, etc.
• Contemplated salts also include acid salts containing replaceable hydrogen. Double oxides and hydroxides are also contemplated.
• Transition metals and their known cyclomatic compounds, including carbonyl compounds are expressly contemplated. See Fundamental Transition Metal Organometallic Chemistry, Lukehart, Monteray, Calif, Brooks/Cole (1985), Transition Metal Compounds, King, New York, Academic Press (1965), Transition-Metal Organometallic Chemistry, King, New York, Academic Press (1969), Fundamental Transition Metal Organometallic Chemistry, lukehart, Monterey, Ca. , Brooks/Cole (1985), incorporated herein by reference.
• a preferred cyclomatic transition metallic is MMT.
• Non-transition-metal compounds known in the art. See Nontransition-Metal Compounds, Eisch, New York, Academic Press (1981 ). Non-transition metal compounds that accomplish primary object of vapor phase combustion are contemplated in the claims below and incorporated herein by reference.
• Non-limiting examples include alkylmetallocenes, arylmetallocenes, including dicyclopentadienyl-metal with the general formula (C5H5)2M, dicyclopentadienyl-metal halides with the general formula (C5H5)2MX1 -3, monocyclopentadienyl-metal compounds with the general formula C5H5MR1 -3, where R is CO, NO, halide group, alkyl group, etc.
• Non-limiting examples include napthacenes, ferrocene, methylferrocene, cobaltocene, nickelocene, titanocene dichloride, zirconocene dichloride, uranocene, decamethylferrocene, decamethylsilicocene, decamethylgermaniumocene, decamethylstannocene, decamethylphosocene, decamethylosmocene, decamethylruthenocene, decamethylzirconocene, silicocene, decamethylsilicocene, etc.). are also contemplated. Metallocenes that accomplish primary object of vapor phase combustion are contemplated in the claims below and incorporated herein by reference. See also Hawley's Condensed Chemical Dictionary 12th ed, Lewis, Van Nostrand Reinhold Company, New York (1993), also incorporated by reference.
• Carbonyl compounds are expressly contemplated.
• a limited number of examples include decacarbonyl dimanganese, (acetylacetonato)di- carbonylrhodium. See for example Carbonylation: Direct Synthesis of Carbonyl Compounds, H.M. Colquhoun, Plenum Press (1991 ), incorporated herein by reference.
• Alkyl metal and alkyl earth metal salts and derivative compound are expressly contemplated.
• potassium salts are contemplated including those commercially marketed by Shell Chemical, known as “SparkAid or SparkAde.”
• Other acceptable potassium salts include potassium alkanols, e.g. potassium methoxide, potassium ethoxide, potassium propoxide, potassium isopropoxide, potassium butoxide, potassium sec-butoxide, potassium tert-butoxide, potassium pentoxide, potassium tert-pentoxide, etc.
• potassium salts include potassium hydrogenphthalate, potassium hydrogensulfate, monopotassium acetylenedicarboxylic acid, potassium phenoxide, potassium pyrophosphate, potassium dihydrogenphosphate, potassium benzoate, potassium chloride, potassium hexoate (potassium salt hexoic acid), potassium acetate, potassium diphenylphosphide, potassium trimethylsilonalate, potassium phthalic acid, P-aminobenzoic acid potassium salt, monopotassium L- aspartic acid.
• potassium salts include potassium hydrogenphthalate, potassium hydrogensulfate, monopotassium acetylenedicarboxylic acid, potassium phenoxide, potassium pyrophosphate, potassium dihydrogenphosphate, potassium benzoate, potassium chloride, potassium hexoate (potassium salt hexoic acid), potassium acetate, potassium diphenylphosphide, potassium trimethylsilonalate, potassium phthalic acid, P-aminobenzoic acid potassium salt, mono
• non-limiting non-leaded simple binary/ternary metallic compounds including binary/ternary and higher metallic salts, acid salts, including those with replaceable hydrogen, etc.
• Hydroxy acids, perchlorates, sulfates, nitrates, carbonates, hydroxides, methylates, ethylates, propylates, and others are also contemplated.
• Non-limiting examples include potassium nitrite, sodium nitrite, lithium nitrite, and hexamethylphosphoric triamide.
• Silicon containing metallics are particularly preferred.
• preferred silicons include [2- (cyclohexenyl)ethyl]triethoxysilane, cyclohexenyl dimethoxymethylsilane, benzyltrimethylsilane, N-(3- (trimethoxysilyl)propyl)ethylenediamine, N-1 -(3- (trimethoxysilyl)propyl)diethylenetriamine, N-(3- (trimethoxysilyl)propyl)ethylenediamine, 1 - (trimethyl(silyl)pyrrolidine, triphenylsilanol, octamethyltrisiloxane, 2,2,4,4,6,6- hexamethylcyclotrisilazane, hexamethylcyctrisiloxane, hexamethyldisilane, 1 , 1 , 1 ,3,3,3- hexamethyl disilazane, hexamethyldilane
• An an example of a desirable fuel composition of this invention would then include a lower molecular weight dialkyl carbonate (preferrably DMC or EMC), a silane selected from preferred silicons immediately above (or as set forth elsewhere in this specification), and optionally trimethoxymethylsilane as a co- metallic, a hydrogen or a hydrocarbon co-fuel, and/or an oxidizer.
• a lower molecular weight dialkyl carbonate preferrably DMC or EMC
• silane selected from preferred silicons immediately above or as set forth elsewhere in this specification
• trimethoxymethylsilane as a co- metallic, a hydrogen or a hydrocarbon co-fuel, and/or an oxidizer.
• Preferrable tin compounds include benzltriphenyltin and allyltributyltin.
• a preferrable phosphorus compound includes benzyldiethylphosphite.
• oxygenated containing metallic compounds including oxygenated organo metallic compounds, which are metallic alcohols, alkanolamines, ketones, esters, ethers, carbonates, and the like, which are themselves ECS compounds, in hydrocarbon fuels with or absent additional dialkyl carbonate or other ECS structure.
• oxygenated organo metallic compounds which are metallic alcohols, alkanolamines, ketones, esters, ethers, carbonates, and the like, which are themselves ECS compounds, in hydrocarbon fuels with or absent additional dialkyl carbonate or other ECS structure.
• these metallics are incorporated herein by reference.
• this invention contemplates one or more similar organo oxygen containing metallics, including mixture, with or without an ECS compound, to act as neat "stand alone” fuel.
• metallic compounds alone, as singular means of enhancing fuel combustion.
• the metallic be added to DMC, optionally a co- fuel, an oxidizer, catalyst, and/or a hydrocarbon.
• compositions of this invention contemplate usage of an oxidizer and other ingredients. See incorporated references, including aforementioned PCT applications, for the definitions incorporated in the claims below.
• a metallic compound including homologue, analogue, isomer, or derivative thereof, having a structure or structure similar to M-Rn, Rn-M-M-Rn, Rn-M-Q-M-Rn, Rn-M-Q'-M-Rn, Rn-M-R'-M-Rn, wherein M is one or more non-leaded metal(s), metalloid(s), or non-metal element(s), and R is one or more hydrogen, cyclic ring system/radical/side chain(s), and/or non-ring radical/side chain(s) as provided herein above, including but not limited to alkyl, aryl, alkyloxy, alkylanol (alkanol), hydroxyl, aryloxy, polyalkyl, polyaryl, polyalkyloxy, polyalkylanol, polyaryloxy, polyhydroxyl radicals.
• R' is one or more cyclic ring system/radical/side chain(s), and/or non-ring radical/side chain(s) as provided herein. If R is greater than 1 , then subsequent R's may be same or different radical, etc. R also be a single radical or one radical attached to one or more radicals, "n" is an interger ranging from 1 to the number of valence electrons (or common oxidation states) available of M.
• Q is an atom having a minimum oxidation available of 2, including but not limited to carbon, nitrogen, oxygen, phosophorus, silicon, boron, sulfur, or a differing metal than M.
• Q' is an atom with a minimum available oxidation state of 2, including but not limited to carbon, nitrogen, oxygen, phosophorus, silicon, boron, sulfur, or a differing metal than M, also containing one or more radicals.
• Additional oxygenated-organo or oxygenated metallic structure includes M1 -O(CO)O-M2, wherein M 1 or M2 are the same or different metal or element.
• M1 may be a double valence cation, wherein M2 is absent from above structure, unless additional carbonate is included.
• Preferred M valences are 1 or 2.
• M valences or multiple M1 M2 combinations having combined valence greater than two are acceptable. In which case, additional carbonate structure would be added, e.g. CaMg(CO3)2.
• M1/M2 valence's may be greater than one, wherein excess valence is occupied by same or additional metal (element), and/or wherein M1 or M2 are substituted for a single or double bond oxygen, and/or by one or more radicals.
• M1 or M2 also may be substituted for single bond oxygen, or nitrogen, and/or by one or more radicals, including methyl, hydrogen, hydroxy, ethoxy, carbethoxy, carbomethoxy, carbonyl, carbonyldioxy, carboxy, methyoxy, isonitro, isonitroso, or methylenedioxyl radical.
• Non-limiting examples include carbonates of lithium [Li2O2(CO)j, ammonium manganese, potassium [K2O2(CO)], sodium, calcium, cesium, copper, rubidium, lithium hydrogen, sodium hydrogen, potassium hydrogen, potassium sodium, magnesium, and the like.
• C2 to C8 metallic ethers C2 to C4/C5 metallic ethers being more desireable, will be used as metallic structure in this invention.
• M'1 -CH2-CH2-O-CH2-CH2- M'2 structure is contemplated wherein M'1 and M'2 may be same or different metallic or wherein one M'1 or M'2 may be hydrogen, or other atom, or radical with one available valence.
• M'1 -C- OH3- R wherein M'1 is one or more metallic comprising valence of 3 or greater, and R is radical, whereby resulting structure is ketone, ester, acid, alcohol, or ether.
• Other structure include M'1 -C2O4, wherein M'1 has a valence of 2.
• M 1 -C-C-O-C-C-M2 structure is also contemplated wherein M1 and M2 may be same or different metallic or wherein M2 may be hydrogen or atom of one valence.
• Other structure includes RO- M, where RO is an alkanol and M is a metal. Similar structure is contemplated for M have available valence greater than 1.
• an oxygenated organo-metallic compound it is preferred, it have ECS properties when ever possible, e.g. higher heats of vaporization, high burning velocities, favorable decomposition characteristic (e.g. decomposition at post ignition pre-combustion temperatures into enhanced combustion or free radicals structure), be thermally stable at normal handling temperatures, etc.; and have high heat and energy releasing characteristics of metals, etc..
• ECS properties when ever possible, e.g. higher heats of vaporization, high burning velocities, favorable decomposition characteristic (e.g. decomposition at post ignition pre-combustion temperatures into enhanced combustion or free radicals structure), be thermally stable at normal handling temperatures, etc.; and have high heat and energy releasing characteristics of metals, etc.
• Non limiting examples of lithium derivative compounds of this invention include: lithium bis(dimethylsilyl)amide, lithium bis(trimethylsilyl)amide, oxamic acid, P-aminosalicylic acid lithium salt, lithium salt 5-nitroorotic acid, lithium D-gluconate, lithium hexacyanoferrate(lll) (Li3Fe(CN)6), lithium diphenylphosphide, lithium acetate, lithium acetate acid, lithium salt acetic acid, lithium acetamide, lithium anilide, lithium azide, lithium benzamide, lithium antimonide, lithium orthoarsenate, lithium orthoarsenite, lithium meta-arsenite, lithium diborane, lithium pentaborate, lithium dihydroxy diborane, lithium borohydride, lithium cadium iodide, lithium chloride, lithium calcium chloride, lithium carbide, lithium carbonate, lithium hydrogen carbonate, lithium carbonate, lithium carbonyl, lithium cobalt (II) cyanide, lithium cobalt (III)
• lithium- p-nitrobenzene lithium nitrophenoxide, lithium etherate, lithium chromate, lithium oleate, lithium oxalate, lithium oxalatoferrate (II), lithium oxalatoferrate (III), lithium monoxide, lithium oxide, lithium peroxide, lithium , lithium mono- orthophosphate, lithium hypophosphite, lithium orthophosphite, lithium hydroxoplumbate, lithium rhodium cyanide, lithium selenide, lithium selenite, lithium selenocynate, lithium selenocyanoplatinate, lithium disilicate, lithium metasilicate, lithium sodium carbonate, lithium sodium ferricyanide, lithium hydroxostannate, lithium disufide, lithium hydrosulfide, lithium pentasulfide, lithium tetrasulfide, lithium trisulfide, lithium telluride, lithium thioarsenate, lithium thioarsenite, lithium trithiocarbonate, lithium
• Non limiting examples of the boron derivative compounds of this invention include: alkyl boron compounds, aryl boron compounds, 1 ,3,2-benzodioxaborole, diisopropoxymethylborane, ethylborane, diethylborane, diemthylborane, dicyclohexylborane, boric acid esters (e.g.
• borate ester dimethyl borate, di-n-butyl borate, dicyclohexyl borate, didodecylborate, di-p-cresyl borates), phenylboronic acid, 2- phenyl-1 ,3,2-dioxborinane, pyrrolyboranes (e.g.
• o-tolylboronic acid p-tolylboronic acid, m- tolylboronic acid
• tributoxyborane tributylborane, tri-sec-butylborane, tri- tert-butylborane, tributylborate, tri-tert-butylborate, tri- methoxyboroxine, trimethylamineboran, trimethylborate, trimethyl- boroxine, trimethylborazine, trimethylene borate, triphenylborate, triphenylborane, tribenzyl borate, borate, trisiamylborane, tris(2- methoxyethyl)borate, boron hydride, lithium borohydride, sodium borohydride, boron hydrate, boron hydride, boron anhydride, triethylboron (C2H5)3, decaborane, borazoles, aluminimum borohydride, be
• Corresponding compounds of aluminum, gallium, indium, and thallium are contemplated. See Organo Boron Chemistry, Volumes I & II (and subsequent volumes, editions, or supplements), Howard Steinberg, InterScience Publishers (1966), Boron-Nitrogen Compounds, Niedenzu, Dawson, New york, Academic Press (1965), The Organic Compounds of Boron , Aluminum, Gallium, Indium, and Thallium, Nesmeianov, Nikolaevich, Amterdam, North- Holland Pub. Co. (1967), Peroxides, Superperoxides, and azomides of Alkali and Alkali Earth Metals, Perekisi, N.Y., Plenum Press (19966), incorporated herein by reference.
• Non-limiting examples of sodium derivative compounds of this invention include: sodium bis(dimethylsilyl)amide, sodium bis(trimethylsilyl)amide, oxamic acid, P-aminosalicylic acid sodium salt, sodium salt 5-nitroorotic acid, sodium D-gluconate, sodium hexacyanoferrate(lll) (Li3Fe(CN)6), sodium diphenylphosphide, sodium acetate, sodium acetate acid, sodium salt acetic acid, sodium acetamide, sodium anilide, sodium azide, ammonium diisodium amminepentacyanoferrate, sodium benzamide, sodium antimonide, sodium orthoarsenate, sodium orthoarsenite, sodium meta-arsenite, sodium diborane, sodium pentaborate, sodium dihydroxy diborane, sodium borohydride, sodium cadium iodide, sodium chloride, sodium calcium chloride, sodium carbide, sodium carbonate, sodium hydrogen carbonate, sodium carbonate, sodium carbonyl, sodium cobal
• sodium-p- nitrobenzene sodium nitrophenoxide, sodium etherate, sodium chromate, sodium oleate, sodium oxalate, sodium oxalatoferrate (II), sodium oxalatoferrate (III), sodium monoxide, sodium oxide, sodium peroxide, sodium, sodium mono-orthophosphate, sodium hypophosphite, sodium orthophosphite, sodium hydroxoplumbate, sodium rhodium cyanide, sodium selenide, sodium selenite, sodium selenocynate, sodium selenocyanoplatinate, sodium disilicate, sodium metasilicate, lithium sodium carbonate, lithium sodium ferricyanide, sodium hydroxostannate, sodium disufide, sodium hydrosulfide, sodium pentasulfide, sodium tetrasulfide, sodium trisulfide, sodium telluride, sodium thioarsenate, sodium thioar- senite, sodium trithiocarbonate,
• aluminum derivative compounds of this invention include: diisobutylaluminum hydride, dimethylaluminum hydride, dimethylaluminum hydride, dipropylaluminumhydride, diisopropylaluminumhydride, dibutylaluminumhydride, di-tert- butylaluminum hydride, di-sec-butylaluminum hydride, diisobutylaluminum chloride, ethylaluminum sesquichloride, lithium aluminum hydride, lithium tri-tert-butoxyaluminum hydride, lithium- aluminum alloy, aluminum triethoxide, aluminum trimethoxide, aluminum tripropoxide, aluminum triisopropoxide, aluminum tri-tert- butoxide, aluminum tri-sec-butoxide (aluminum sec-butoxide), aluminum tri-isobutoxide, aluminum tributoxide, aluminum pentoxide, diethylaluminum ethoxide, aluminum
• silicon derivative compounds of this invention include: dimethoxymethylsilane, dimethoxyethylsilane, diethoxymethylsilane, dipropoxymethylsilane, diisoprop- oxymethylsilane, dibutoxymethylsilane, diisobutoxymethylsilane, di- sec-butoxymethylsilane, di-sec-butoxymethylsilane, diethoxyethyl- silane, dipropoxyethylsilane, diisopropoxyethylsilane, dibut- oxyethylsilane, diisobutoxyethylsilane, di-sec-butoxyethylsilane, di-sec- butoxyethylsilane, diethoxydimethylsilane, dimethoxydi- methylsilane, dipropoxydimethylsilane, diisopropoxydimethylsilane, dibutoxydimethyisilane, diisobutoxydi
• silicon derivatives can be found in Silicon Compounds, Register and Review, Petrarch Systems, Inc. (1984), Frontiers of Organosilicon Chemistry, Bassindale, Gaspar, The Royal Society of Chemistry, (1991 ), incorporated herein by reference.
• Corresponding compounds of germanium, tin, titanium, zirconium, selenium, tellurium, are contemplated in the practice of this invention.
• germanium derivative compounds include: decamethylgermaniumocene (bis(pentamethylcyclopentadienyl)ger- manium), tertbutylgermanium, tetramethylgermanium, tetraethylger- manium, tetrapropylgermanium, tetraisopropylgermanium, tetrabutyl- germanium, tetraisobutylgermanium, tetra-tert-butylgermanium, tetra- sec-butylgermanium, tetra-phenylgermanium, phenylgermanium, methylphenylgermanium, methylphenolgermanium, including analogues, homologues, isomers and derivatives thereof.
• non-limiting derivative tin compounds include: deca- methylstannocene (bis(pentamethylcyclopentadienyl)tin), dibutyltin bis(2-ethylhexanoate), dibutyltin diacetate, dibutyloxo- tin (dibutyltin oxide), dimethyltin, diethyltin, dipropyltin, diisopropyltin, dibutyltin, diisobutyltin, di-tert-butyltin, di- sec-butyltin, di-phenyltin, tetramethyltin, tetraethyltin, tetrapropyltin, tetraisopropyltin, tetrabutyltin, tetraisobutyltin, tetra-tert-butyltin, tetra-sec-butyltin, tetraphen
• phosphorus derivative compounds of this invention include: tetrabutylphosphonium hydroxide, allyldiphenylphospine, diphenylphosphine, phenylphosphine, diphenyl phosphate, diphenylphosphine, diphenylphosphinic acid, diphenylethoxyphospine, diphenylmethoxyphospine, diphenylpropoxy- phospine, diphenylisopropoxyphospine, diphenylbutoxyphospine, diphenyl-sec- butoxyphospine, diphenyl-tert-butoxyphospine, diphenyl-iso- butoxyphospine, dicyclohexylethoxyphospine, dicyclo- hexylmethoxyphospine, dicyclohexylpropoxyphospine, dicyclohexyliso- propoxyphospine, dicycl
• tri(o-toly)phosphine tri(m- toly)phosphine, tri(p-toly)phosphine), tri(toly)phosphite (e.g. tri(o-toly)phosphite, tri(m- toly)phosphite, tri(p-toly)phosphite), tri(toly)phosphate, tri(toly)hydrophosphate, tri(toly)phosphonic acid [(CH3C6H4)3P(OH)2], bis(2-ethylhexel) phosphite, diallyphenyl- phosphine, dibenzylphosphite, dibenzylphosphate, dibutyl phosphite, dimethyl methylphosphonate, dimethyl methylphosphine, dimethyl methylphosphonite, dimethylphenylphosphine, dimethylphenyl- phosphonite, dimethylphenylphosphite, dimethylphosphinic acid, dimethyl(
• antimony derivative compounds include: alkyl antimony compounds, trialkyl compounds, cyclomatic/ring system compounds, including, trimethylantimony, triethylantimony, tripropylantimony, triisopropylantimony, tributylantimony, triisobutylantimony, tri-tert-butylantimony, tri-sec-butylantimony, tri- phenylantimony, phenylantimony, tri(methylphenyl)antimony, triphenylantimony oxide, tri(methylphenol)antimony, antimony ethoxide, pentamethylantimony, phenyldimethylantimony, phenyl- stibinic acid, tetramethyldistibyl, tributylstibene, triethylan- timony, triethylantimony chloride, trimethylantimony, triphenylan- timony, triphenylantimony dichloride, triphenylantimony sulfide,
• Non-limiting arsenic derivative compounds include: alkyl arsenic compounds, dialkyl compounds, cyclomatic/ring system compounds including, trimethylarsine, triethylarsine, tripropylar- sine, triisopropyiarsine, tributylarsine, triisobutylarsine, tri- tert-butylarsine, tri-sec-butylarsine, tri-phenylarsine, phenylar- sine, tri(methylphenyl)arsine, triphenylarsine oxide, tri(methyl- phenol)arsine, phenylarsenic acid, phenylcyclotetramethylenearsine, arsenobenzene, cacodyl oxide, cacodyl amide, dimethylarsine, dimethylchlorarsine, dimethylcyanoarsine, diphenylarsinic acid, diphenylchloroarsine, ethylar
• Non-limiting bismuth derivative compounds include: alkyl bismuth compounds, dialkyl compounds, cyclomatic/ring system compounds including, triphenylbismuth, triphenylbismuth carbonate, diphenylbismuthine, methylbismuthine, triethylbismthine, trimethyl- bismthine, triphenylbismuthine, tri-n-propylbismuth, including analogue, homologue, isomers and derivative thereof.
• Non-limiting potassium derivative compounds of this invention include: potassium bis(dimethylsilyl)amide, potassium acetamide, potassium bis(trimethylsilyl)amide, oxamic acid, P-aminosalicylic acid potassium salt, potassium salt 5-nitroorotic acid, potassium D- gluconate, potassium hexacyanoferrate(l ll) (K3Fe(CN)6), potassium diphenylphosphide, potassiumetherate, potassium acetate, potassium acetate acid, potassium salt acetic acid, potassiumbenzamide, potassium azide, potassium antimonide, potassium orthoarsenate, potassium orthoarsenite, potassium meta-arsenite, potassium diborane, potassium pentaborate, potassium dihydroxy diborane, potassium borohydride, potassium anilide, potassium cadium iodide, potassium chloride, potassium calcium chloride, potassium carbide, potassium carbonate, potassium hydrogen carbonate, potassium carbonate, potassium carbonyl, potassium cobalt (II) cyanide, potassium cobalt (III
• potassium-p- nitrobenzene)potassium oleate potassium oxalate, potassium oxalatoferrate (II), potassium oxalatoferrate (III), potassium monoxide, potassium oxide, potassium peroxide, potassium mono- orthophosphate, potassium hypophosphite, potassium orthophosphite, potassium hydroxoplumbate, potassium rhodium cyanide, potassium selenide, potassium selenite, potassium selenocynate, potassium selenocyanoplatinate, potassium disilicate, potassium metasilicate, potassium sodium carbonate, potassium sodium ferricyanide, potassium hydroxostannate, potassium disufide, potassium hydrosulfide, potassium pentasulfide, potassium tetrasulfide, potassium trisulfide, potassium telluride, potassium thioarsenate, potassium thioarsenite, potassium trithiocarbonate, potassium thiocyanate, potassium amide, potassium salt (E,E)-2
• Non-limiting derivative magnesium compounds contemplated by this invention include: alkyl manganese compounds, dialkyl magnesium compounds, magnesium ethylate (ethoxide), magnesium methoxide, dimethylmagnesium, diethylmagnesium, dipropylmagnesium, diisopropylmagnesium, dibutylmagnesium, ditertbutylmagnesium, di- iso-butylmagnesium, di-sec-butylmagnesium, diphenylmagnesium, methylmagnesium chloride, methylmagnesium iodide, magnesium methylcarbonate, magnesium hydroxide, magnesium anthracene dianion, bromomagnesium isopropylcyclohexylamide, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium chloride, magnesium floride, magnesium chloride, butylmagnesium chloride, isopropylmag- nesium chloride, cyclopentylmagnesium
• beryllium, calcium, strontium, barium, radium and zinc compounds are contemplated in the practice of this invention. See The Organic Compounds of Magnesium, Beryllium, Calcium, Strontium, and Barium, loffe, Nesmeyanov, Amsterdam (1967), Organomagnesium Methods in Organic Synthesis, Wakefield, Academic Press, FL (1995), incorporated by reference. The mixture of dialkyl magnesium compounds with pyrophoric metallics is specifically contemplated.
• Non-limiting selenium derivative compounds include: alkyl and dialkyl selenium compounds, dimethylselenium, dimethyl selenide, diethylselenium, dipropylselenium, diaisopropylselenium, diabutyl- selenium, diaisobutylselenium, dia-tert-butylselenium, dia-sec- butylselenium, di-phenylselenium, tetramethylselenium, tetraethyl- selenium, tetrapropylselenium, tetraisopropylselenium, tetrabutyl- selenium, tetraisobutylselenium, tetra-tert-butylselenium, tetra-sec- butyiselenium, tetra-phenylselenium, methyl-
• Non-limiting telluride derivative compounds include: di-n- butylphosphane selenide, selenanthrene, selenourea, selenophene, allylphenylselenide, dimethyltelluride, diethyltelluride, dipropyl- telluride, diisopropyltelluride, dibutyltelluride, diaisobutyltel- luride, dia- tert-butyltelluride, dia-sec-butyltelluride, di- phenyltelluride, tetramethyltelluride, tetraethyltelluride, tetrapropyltelluride, tetraisopropyltelluride, tetrabutyltelluride, tetraisobutyltelluride, tetra- tert-butyltelluride, tetra-sec-butyltelluride, tetra-phenyl
• Non-limiting iron derivative compounds include: [cyclopentadienyl] methylcyclopentadienyl iron, ferrocene, methylferrocene, and butadiene iron tricarbonyl, [butadiene iron tricarbonyl,] dicyclopentadienyl iron and dicyclopentadienyl iron compounds;ferrocene, methylferrocenes, decamethylferrocene (bis(pentamethylcyclopentadienyl)iron), 1 , 1 '-diacetylferrocene, ferrocenecarboxylic acid, 1 , 1 '-ferrocenecarboxylic acid, ferroceneacetic acid, ferroceneacetronitrile, 1 , 1 '-ferrocene- bis(diphenylphosphine), ferrocenecarbonxaldehyde, ferrocenecarboxylic acid, 1 , 1 'ferrocenedicarboxylic acid
• Non-limiting nickel derivative compounds include: alkyl, aryl, alkyloxy, alkylanol, aryloxy, di/trialkyl, di/triaryl, di/trialkyloxy, di/trialkylanol, di/triaryloxy, and/or cyclomatic complexes, including, biscyclopentadienyl nickel, cyclopentadienyl methylcyclopentadienyl nickel, bis(methylcyclopentadienyl) nickel, bis(triphenylphosphine)dicarbonyl nickel, bis(isopropylcyclopenta- dienyl) nickel, bisindenyl nickel, cyclopentadienyl nickel nitrosyl, methylcyclopentadienyl nickel nitrosyl, including analogue, homologue, isomer, and derivative thereof.
• cyclomatic complexes including, biscyclopentadienyl nickel, cyclopentadienyl methyl
• Non-limiting cobalt derivative compounds include: biscyclopentadienyl cobalt, bis(methylcyclopentadienyl) cobalt, bis(dimethyl- cyclopentadienyl) cobalt, cyclopentadienyl cobalt, dicarbonyl, cobalt(ous) hexamethylenetetramine, cobalt(ous) hydroxyquinone, cyclopentadienylcobalt dicarbonyl, including analogue, homologue, isomer, and derivative thereof.
• Non-limiting zinc derivative compounds include: alkyl zinc, aryl zinc, alkyloxy zinc, aryloxy zinc, dialkyl zinc, diaryl zinc, dialkyloxy zinc, diaryloxy zinc, cyclomatic zinc complexes, including, dimethylzinc, diethylzinc, dipropylzinc, diisopropyl- zinc, dibutylzinc, diisobutylzinc, di-tert-butylzinc, di-sec- butylzinc, di-phenylzinc, zinc acetate, zinc ethoxide, zinc arsenide, zinc hydroxide, zinc selenide, zinc selenite, zinc flouride, zinc chloride, zinc cyanide, zinc floride, zinc chloride, zinc undecylenate, zinc nitrate, zinc acrylate, zinc methacrylate, methyl zinc chloride, isobutylzinc chloride, zinc stearate, zinc dimethyldiethiocarbamate, di-n-propylzin
• Non-limiting examples of transition metal derivative compounds include transition metal alkyl, aryl, alkyloxy, aryloxy, and/or ring system type compounds. Multiple alkyl, alkyloxy radicals per metal are contemplate. Cyclomatic transition metal compounds are expressly contemplated. See Organometallic Chemistry of Transition Metals, 2 Ed, Crabtree, John Wiley & Sons, N.Y. (1994), incorporated herein by reference.
• Non-limiting examples of manganese compounds include benzyleyelopentadienyl manganese tricarbonyl; 1.2-dipropyl 3- cyclohexylcyclopentadienyl manganese tricarbonyl; 1.2- diphenyicyclopentadienyl manganese tricarbonyl; 3-propenylienyl manganese tricarbonyl; 2-tolyindenyl manganese tricarbonyl; fluorenyl manganese tricarbonyl; 2.3.4.7 - propyflourentyl manganese tricarbonyl; 3-naphthylfluorenyl manganese tricarbonyl; 4.5.6.7- tetrahydroindenyl manganese tricarbonyl; 3-3ethenyl-4, 7- dihydroindenyl manganese tricarbonyl; 2-ethyl 3 (a-phenylethenyl) 4,5,6,7 tetrahydroindenyl manganese
• a preferred cyclomatic manganese tricarbonyl is cyclopentadienyl manganese tricarbonyl.
• a more preferred cyclomatic manganese tricarbonyl is methyl cyclopentadienyl manganese (MMT).
• MMT methyl cyclopentadienyl manganese
• acceptable substitutes include the alkyl, aralkyl, aralkenyl, cycloalkyl, cycloalkenyl, aryl and alkenyl groups.
• the above compounds can be generally prepared by methods that are known in the art. Corresponding compounds of technetium and rhenium (see Canadian Patent #1073207) are contemplated.
• Non-limiting nitrogen derivative compounds include: 2- methoxybenzylamine, 2-methoxybenzylamine, 2-(4-methoxyben- zylamino)pyridine, nitroanline, 1 -nitroanline, 2-nitroanline, 3- nitroanline, 4-nitroanline, nitroanisole, 1 -nitroanisole, 2- nitroanisole, 3- nitroanisole, 4-nitroanisole, aniline, 2-anilino- ethanol, anisamide, anisonitrile, acetonitrile, nitromethane, nitroethane, picoline, 1 -picoline, 2-picoline, 3-picoline, 4- picoline, tetramethyiammoniumhydroxide, tetraethylammoniumhydroxide, N,N,N',N'-tetramethylethylenediamine, toluic hydazide, toluidine, m-toluidine, o-toluidine, p-tolui
• Non-limiting titanium derivative compounds include: titanium diisopropoxide bis(2,4-pentanedionate), titanium methoxide, titanium ethoxide, titanium (IV) 2-ethylexoxide, titanium isopro- poxide, tetraethylorthotitanate, including analogues, homologues, isomers and derivatives thereof.
• Non-limiting zirconium derivative compounds include: zirconium carbide, zirconium propoxide, zirconium ethoxide, decamethylzir- conocene, decamethylzirconocene dichloride, bis-cyclopentadienyl zirconium, including analogues, homologues, isomers and derivatives thereof.
• Non-limiting molybdenum derivative compounds include: molyb- denumcarbonyl, molybdenum hexacarbonyl, tripyridine tricarbonyl- molybdenum, molybdenumoxytetrachloride, cyclopentadienyl molybdenum carbonyls, including but not limited to benzenemolybdenumtricar- bonyl, bicycloheptadienemolybdenum tetracarbonyl, cycloheptatrien- molybdenum tricarbonyl, bis- cyclopentadienylbimolybdenum pentacar- bonyl, mesitylenemolybdenum tricarbonyl, tropeniummolybdenum tricarbonyl fluoroborate, cyclopentadienylmolybdenum tricarbonyl dimer, methylcyclopentadienylmolybdenum tricarbonyl dimer, anisole molybdenum tricarbonyl
• Non-limiting copper derivative compounds include: alkyl copper compounds, bis(ethyienediamine)copper(ll) hydroxide, copper carbonate, cyclopentadienyltriethylphosphine copper, diazoaminobenzene (ous), copper acetate, copper acetylacetonate, copper aminoacetate, copper ethylacetate, copper ferrocyanide, copper potassium ferrocyanide, copper nathenate, copper nitrate, copper phosphide, copper phthalate, including analogue, homologue, isomers and derivative thereof. See Copper, The Science and Technology of the Metal, Its Alloys & Compounds, Butts, N.Y., Reinhold (1954), incorporated by reference.
• organometallic compounds are metallocenes, non-limiting example compounds include, ferrocene, cobaltocene, nickelocene, titanocene dichloride, zirconocene dichloride, uranocene, decamethylferrocene, decamethylsilicocene, decamethyl-germaniumocene, decamethylstannocene, decamethylphosocene, decamethylosmocene, decamethylruthenocene, decamethylzirconocene, including analogue, homologue, isomers and derivative thereof.
• metals and their derivative compounds of this invention include every metal, metalloid, and/or non-metal (herein “metal” or “metallic”) capable of acheiving vapor phase combustion, individually or incombination with DMC.
• Applicant's invention contemplates wide variation in metal substitution and mixing practice.
• the non-lead organo-metallics, non-lead inorganic metallics, and/or their related high heat releasing compounds including those set forth above may be mixed in varying proportions, and/or substituted and/or replaced by any non-lead metallic or non-metallic (organic or inorganic [atom, molecule or compound, including those containing nitrogen, sulfur, chlorine, fluorine, helium, neon, argon, krpton, xenon, or radon atoms]) accomplishing the object of this invention.
• Derivative compounds and combinations may be entirely or may contain in part or whole non-metal atoms, e.g. nitrogen, sulfur, chlorine, fluorine, helium, neon, argon, krpton, xenon, or radon, etc., so long as primary object of vapor phase combustion is accomplished. It is contemplated said non-metals will employed in varying proportions within the compound or combination compounds to achieve synergistic improvements in heat releases, burning velocity, thermal efficiency, emissions, power generation, and the like.
• non-metal atoms e.g. nitrogen, sulfur, chlorine, fluorine, helium, neon, argon, krpton, xenon, or radon, etc.
• hexamethylphosphoric triamide, N,N,N',N'- hexamethylsiianediamine, bis(diethylamono)-dimethylsilane may be added as a co-metallic in minor amounts to the composition to further improve vapor phase combustion (e.g further enhancing fuel ecomony or power, etc.).
• Ranges vary depending upon the specific metallic, fuels, fuel weight, regulations, advance applications, thermodynamics, and the extent combustion systems are modified to enhance the accelerated low temperature high energy nature of Applicant's invention.
• metallic concentrations that maximize combustion velocity and/or the vapor phase combustion object of this invention are expressly contemplated.
• Applicant's metals are substitutents in the fuel, itself, which may also contain certain non-metals and their derivative compounds, including but not limited to nitrogen, sulfur, fluorine, chlorine, helium, neon, argon, krpton, xenon, or radon, in combination with dialkyl carbonates. These non-metals, and their derivative compound, may be employed with or without any other contemplated metals.
• Applicant's invention by accelerating burning velocity and/or increasing latent heat of vaporization, adn/or reducing combustion temperatures by fuel substituent tailoring, chemical and/or mechanical means, as set forth herein or in my co-pending Applications, said fuel can be employed absent either DMC or a metallic or non-metallic.
• Applicant's fuels will contain that amount of at least non-lead metallic, which constitutes a combustion improving amount consistent with the fuel composition, stoichiometry, combustion system, efficiencies, fuel economy and power desired, as well as legal and/or environmental considerations.
• Applicant's metallics be incorporated into liquid fuel systems by means of mutual solvents, mutual dispersents/solvents, colloidal media, suspension media, or other known means, or being separately injected.
• Metallic's, which are solid at ambiant temperatures may be introduced into the combustor/combustion chamber by liquidification or gasification means.
• the metallics of this invention be relatively inexpensive to manufacture on a mass production basis.
• the metal and concentration amounts are to be optimized, such that vapor phase combustion results.
• the metal and its optimum concentration amount is an amount that results in vapor phase combustion, which is evidenced by improved fuel economy, emissions, power, etc.
• the ratio of dialkyl carbonates (DMC) by weight to elemental metal weight concentration is equal to or less than 10,000: 1 (by parts) to 1 : 1 , including from 1,000,000:1, 100,000:1, 50,000:1, 25,000:1, 15,000:1, 10,000:1, 5,000:1, 1,000:1, 500:1, 300:1, 200:1, 150:1, 100:1, 90:1, 80:1, 75:1, 70:1, 60:1, 50:1, 40:1, 30:1, 20:1, 10:1, 5:1 to 3:1, or interval ratio contained therein (e.g.50:1 to 30:1) and also 1:1 to 1:20, or other ratio that maximizes vapor phase combustion.
• DMC dialkyl carbonates
• Metallic salts may be employed in fuels at 0.01 to 4000.0 parts metallic per million fuel, 1.0 to 150 ppm metallic being contemplated, with concentrations equal or less than 50.0, 40.0, 30.0, 20.0, 16.0, 10.0, 5.0 ppm metallic also contemplated. Other salt concentrations will vary from 0.10 to 75.0 ppm metal per million, from 30.0 to 2000.0 per million, from 25 to 750 parts metallic or salt per million fuel. In the application of Applicant's invention elemental metal concentrations from 3.0 to 500.0 ppm metal are expressly contemplated and desirable. Concentrations outside these ranges are contemplated.
• elemental metallic concentrations will vary substantially.
• Non-limiting examples include elemental metallic concentrations equal to or greater than 1/64 grams/gal, preferably 1.0 or more grams/gal, more preferably 10 or more grams/gal, even up to 90 grams/gal.
• elemental metal concentrations can be on the order of 100 to 1000 or more grams/gal, especially in hypergolic conditions. Concentrations above these ranges are also contemplated. All combustion improving or stoichiometric amounts of elemental metal are contemplated, which maximize combustion so long as the resultant fuel's burning velocity increases compared to fuel absent metallic.
• metallic concentrations that maximize combustion velocity and/or other objects of this invention are expressly contemplated. Ranges will vary depending upon the specific metallic, its concentration, concentration and type of dialkyl carbonate, concentration and nature of hydrocarbon fuel composition, including its density, the intended application, relevant thermodynamics, extent combustion systems are modified to enhance the accelerated low temperature high energy nature of Applicant's invention, environmental regulation, and the like.
• Metallics used in the fuel compositions of the present invention should be fuel soluble generally having melting and boiling ranges compatible with liquid hydrocarbons, or be incorporated into liquid fuel systems by means of mutual solvents, dispersants, or other means, as required. Alternatively, the metallics may be introduced into the combustor/combustion chamber of liquide or gaseous fuels (e.g.
• the metallic In solid fuel applications, the metallic may be introduced as a solid. In hybrid applications, it may be introduced as either as solid, liquid or gas, together with the balance of the invention's ingredients. Most preferably, the metallic is employed as a propellant or co- propellant, or jointly together with a propellant. Hydrogen content of the metallic and/or metallic containing fuel should be maximized, to the extent possible.
• metals herein have oxides whose heats of formation are negative, and should be equal or exceed (e.g. be more negative) about -10,000 to -75,000 calories/mole. More preferred are those equal or exceeding -100,000 to -400,000 gr calories/mole, and greater (more negative). Acceptable simple oxides containing one or two oxygens may have heats of formation equal or exceeding -50,000 to -200,000, or greater, calories/mole.
• the element metal employed in this invention be of a low relative molecular weight.
• Acceptable metals have molecular weights of 100 or less, preferably 79 or less, more preferably 40 or less, and most preferably 30 or less.
• Applicant's fuel may include gaseous and solid metals and/or their related compounds. It is preferred the combustion products of the metals be environmentally friendly, e.g. low or no toxicity. Potassium, sodium, magnesium, lithium, born, silicon, sodium, iron, copper, calcium, aluminum, and phosphorus are acceptable. Potassium, sodium, magnesium, lithium, born, silicon, sodium, iron, and phosphorus are also acceptable. The related high energy combustible compounds of these metals are beleive to be environmentally friendly.
• Applicant's metals also include a full range of combustion catalysts including ferrous picrate, potassium salts, Li and LH promoters. As presented below trimethoxymethylsilane has immediate application in instant invention and is preferred.
• Applicant's invention by accelerating burning velocity and/or reducing combustion temperatures by fuel substituent tailoring, chemical and/or mechanical means as set forth in above PCT Applications, can be employed absent a metallic.
• any example or disclosure of Mn may be substituted for any metal or derivative compound set forth in herein, under proviso said metallic causes vapor phase combustion.
• any metal, metalloid, or non- metal may be substituted with any other in a particular metallic compound. That is not to say substitution is blind, but rather if the element is likely to be advantageously impacted, it may be substituted.
• non-leaded elements and their compounds may be freely substituted for one another, herein.
• metals in the fuel composition of the present invention including oxygenated metallic compounds, contribute to the fuel's heat of vaporization, its burning velocity, post ignition and pre- combustion temperatures which enhance generation and combustion of free radicals, thermal stability at ambient temperature, and have high heat and energy releasing characteristics, etc.
• TMMS TMMS to be a catalyst, when in combination with a large population of metallics disclosed herein, and acts to remedially improve the overall results of this invention.
• TMMS is a desireable co-metallic of this invention. Its use is contemplated with a majority of the metallics, which may be utilized in the practice of this invention, including cyclomatic metallics, alkali metal alkanols, inorganic metallics such as the metallic hexacyanides, etc. Thus, it is an embodiment herein that disclose to any metallic also includes TMMS as a co-metallic.
• TMMS substitutes include those compounds, including metallic and non-metallic organics, whose structure is similar to TMMS's, thus including derivative, analogue, homologue and isomers of TMMS. Other subsitutes are also contemplated.
• ethoxytrimethylsilane isobutyltriethoxysilane, tetramethylsilane, dimethoxy-methyl-vinyl- silane, methyltriethoxysilane, 3-aminopropyl- triethoxysilane, 3- aminopropyl-trimethoxysilane, vinyltrimethoxysilane, diethoxydimethylsilane, dimethoxydimethylsilane, vinyltris(2- butyldenaminooxy)silane, tetraalkyloxysilanes (e.g.
• dialkylphosphites e.g. dimethylphosphite, dipropylphosphite, diethylphosphite, dibutylphosphite, di-tert- butylphosphite, etc.
• trialkylphosphites e.g.
• trimethylphosphite triethylphosphite, triisopropylphosphite, tributylphosphite), dimethylmethylphosphonate, diethylmethylphosphonate, potassium pryophosphite, trimethylorthoacetate, triethylorthoacetate, trimethylorthobutyrate, triethylorthobutyrate, trimethylorthovalerate, trimethylorthoformate, including homolgues, analogues, isomers, and derivatives thereof.
• PCT Applications are incorporated herein and are optionally modified for pH limitation, non- manganese metallics, and addition of a co-metallic catalyst. They are also optionally modifed for the viscosity, burning velocity, and enthalpy of vaporization limitations contained either therein or herein.
• a vapor phase method of the present invention for combusting a metallic includes the steps of introducing kinetic free radicals into a combustor from a dialkyl carbonate (dimethyl carbonate); igniting and combusting a flammable metallic or metal compound in presence of said free radicals at temperature below said metal's oxide boiling point and preferably above said metal or metallic compound's boiling point; combusting said metal; whereby accelerated burning occurs, evidenced by a brilliant luminous reaction zone extending some distance from the metal's surface; and wherein metallic oxide particles resulting from combustion range in low to submicron range and/or remain in a gaseous state.
• Contemplated metallics include all non-lead metals and their related compounds whose combustion product has negative high heat of formation. As provided herein metals also refer to non-metals. Contemplated compounds of said elemental metals are those with have high heats of combustion. Metallics may be organo-metallics or inorganic compounds.
• a fuel composition of the present invention may include a combustion improving amount of a lower dialkyl carbonate; a combustion improving amount of at least one high heating (exceeding 2,000 to 8,000 to 12,000, or more, Kcal/kg) combustible compound containing at least one element selected from the group consisting of aluminum, boron, bromine, bismuth, beryllium, calcium, cesium, chromium, cobalt, copper, francium, gallium, germanium, iodine, iron, indium, lithium, magnesium, manganese, molybdenum, nickel, niobium, phosphorus, potassium, palladium, rubidium, sodium, tin, zinc, praseodymium, rhenium, silicon, vanadium, strontium, barium, radium, scandium, yttrium, lanthanum, actinium, cerium, thorium, titanium, zirconium, hafium, praseodymium
• Said fuel optionally containing hydrogen or a viscous hydrocarbon base fuel, an oxidizer, or a co-metallic catalyst (as set forth above).
• Said fuel further characterized as having a pH of 10.5 or less.
• this fuel composition contains a hydrocarbon base, said base may have a viscosity outside normal industry standards (as set forth above). However, resultant fuel's viscosity is to be within industry standards.
• Said result fuel is characterized as being a vapor phase composition wherein a luminous reaction zone extends from surface of said element, typically evidenced by increased fuel economy, range, thrust, emissions, or power, as compared to the hydrocarbon base alone.
• a method for minimizing hydrolysis of a fuel compositions comprising the steps of: providing or introducing a symmetrical lower dialkyl carbonate to a combustion improving amount of at one least metal or non-metal as set forth above (combustible compound) containing at least one element selected from the group consisting of aluminum, boron, bromine, bismuth, beryllium, calcium, cesium, chromium, cobalt, copper, francium, gallium, germanium, iodine, iron, indium, lithium, magnesium, manganese, molybdenum, nickel, niobium, phosphorus, potassium, palladium, rubidium, sodium, tin, zinc, praseodymium, rhenium, silicon, vanadium, strontium, barium, radium, scandium, yttrium, lanthanum, actinium, cerium, thorium, titanium, zirconium, hafium, praseodymium

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Combustion & Propulsion (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Solid Fuels And Fuel-Associated Substances (AREA)
• Cosmetics (AREA)

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• 1997
  • 1997-12-08 EP EP97954909A patent/EP0954558B1/de not_active Revoked
  • 1997-12-08 AU AU64323/98A patent/AU6432398A/en not_active Abandoned
  • 1997-12-08 CA CA002274607A patent/CA2274607A1/en not_active Abandoned
  • 1997-12-08 WO PCT/US1997/022046 patent/WO1998026028A1/en active IP Right Grant
  • 1997-12-08 DE DE69736123T patent/DE69736123T2/de not_active Expired - Lifetime

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