US20110308143A1 - Composition for use as a fuel or fuel additive in a spark ignition engine, its manufacture and use - Google Patents

Composition for use as a fuel or fuel additive in a spark ignition engine, its manufacture and use Download PDF

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US20110308143A1
US20110308143A1 US13/162,327 US201113162327A US2011308143A1 US 20110308143 A1 US20110308143 A1 US 20110308143A1 US 201113162327 A US201113162327 A US 201113162327A US 2011308143 A1 US2011308143 A1 US 2011308143A1
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composition
fuel
oxygenate
alcohol
optionally
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Noel Boux
Anne Moya Flanagan
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Novaera Fuels
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Novaera Fuels
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/02Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • C10L10/02Use of additives to fuels or fires for particular purposes for reducing smoke development
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/16Hydrocarbons
    • C10L1/1608Well defined compounds, e.g. hexane, benzene
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/16Hydrocarbons
    • C10L1/1616Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/182Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/182Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/185Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852Ethers; Acetals; Ketals; Orthoesters
    • C10L1/1855Cyclic ethers, e.g. epoxides, lactides, lactones
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L2300/00Mixture of two or more additives covered by the same group of C10L1/00 - C10L1/308
    • C10L2300/20Mixture of two components

Definitions

  • Disclosed embodiments concern a fuel that can be used as a replacement for conventional fossil-based fuels. It can also be used as an additive to conventional fossil-based fuels, or alternative fuels.
  • U.S. Pat. No. 7,399,323 a fuel composition that comprises farnesane and/or farnesane derivatives and a conventional fuel component selected from diesel fuel, jet fuel, kerosene or gasoline is disclosed.
  • the farnesane or farnesane derivative can be used as a fuel component or as a fuel additive in the fuel composition.
  • U.S. Pat. No. 5,575,822 discloses a number of fuel and fuel additives.
  • the fuels range from two component formulations, such as 10 to about 42% terpene, preferably limonene, and from about 1 to about 90% naphtha compound to more complex formulations such as 10 to about 16 w/w % limonene, from about 19 w/w % to about 45 w/w % aliphatic hydrocarbons having a flash point between 7° C., to about 24° C., most preferably Varnish Makers and Painters (VM&P) naptha, from about 20 w/w % to about 40% w/w % alcohol, most preferably methanol, from about 9 w/w % to about 36 w/w % surfactant, most preferably glycol ether EB and a preferred fuel comprising about 11.4 w/w % limonene, about 40.7 w/w % VM&P naptha, about 15.5 w/w % glycol ether EB, about 22 w/w % methanol, and
  • Terpenoid based fuels have been disclosed in U.S. Pat. No. 5,186,722. Disclosed are a very wide range of terpenes, terpenoids and derivatives thereof, including limonenes, menthols, linalools, terpinenes, camphenes and carenes.
  • the fuels are produced by a cracking/reduction process or by irradiation. Limonene was shown to produce 84% 1-methyl-4-(1-methylethyl) benzene by this process. While the fuel is superior to that of Whitworth, production costs are relatively high.
  • a spark ignition motor fuel composition consisting essentially of: a hydrocarbon component containing one or more hydrocarbons selected from five to eight carbon atoms straight-chained or branched alkanes, wherein the hydrocarbon component has a minimum anti-knock index of 65 as measured by ASTM D-2699 and D-2700 and a maximum dry vapor pressure equivalent (DVPE) of 15 psi (one atmosphere (atm.)) as measured by ASTM D-5191; a fuel grade alcohol; and a co-solvent for the hydrocarbon component and the fuel grade alcohol; wherein the hydrocarbon component, the fuel grade alcohol and the co-solvent are present in amounts selected to provide a motor fuel with a minimum anti-knock index of 87 as measured by ASTM D-2699 and D-2700, and a maximum DVPE of 15 psi (1 atm.) as measured by ASTM D-5191, and wherein the fuel composition is essentially free of olefin
  • US patent publication number 20080104884 discloses a fuel comprising mid to low flash point naptha, at least one alcohol having a ratio of between about 1 to about 4 carbon atoms to 1 hydroxyl functional group, at least one lubricating oil, and at least one oxygenated natural aromatic compound, wherein the oxygenated natural aromatic compound has a flash point between about 6° C. and about 16° C., has at least one oxygenated functional group, and is soluble in the composition.
  • compositions for use as a fuel or fuel additive concern compositions that provide an alternative fuel and a fuel additive that compares favourably to existing fuels with regard to horsepower and torque, for use in spark ignition engines in the absence of hardware modifications.
  • the resulting composition when combusted, reduces harmful emissions, whether used alone or as a gas additive.
  • an alternative fuel or fuel additive is provided that contains up to about 56% biologically derived components, all of which are readily renewable. Finally, the remaining about 44% can be produced with a minimum of refining.
  • Alcohols in the present working examples typically are lower alkyl alcohols, such as C1 to C3 alcohols, more specifically methanol, ethanol (95% ethanol), propanol and isopropanol.
  • the ratio of carbon atoms to hydroxyl functional group should preferably be 4-to-1, more preferably be 3-to-1 and most preferably 2- to 1 or 1-to-1, to promote solubility in an aqueous environment and to promote miscibility between the polar and non-polar components of the composition.
  • Petroleum distillate Petroleum distillate in the present context, for use in gas-powered engines, has a flashpoint of no greater than about 3° C., and more preferably between about 1° C. and about ⁇ 15° C., still more preferably between about ⁇ 5° C. and about ⁇ 10° C.
  • Oxygenate An oxygenate in the present context is selected from low carbon ethers, for example, but not limited to dimethyl ether, tetrahydrofuran, methyl tetrahydrofuran, furan, 2,5 dimethyl furan—in general, a straight chain or cyclic ether. It should be noted that it is recommended that the tetrahydrofuran be stabilized.
  • the oxygenates have a flash point between about ⁇ 10° C. and about ⁇ 50° C. D.
  • a water tolerance adjustor in the present context preferably has a Kauri butanol value of at least about 80, preferably at least about 90 and more preferably over 100 and is preferably not chlorinated nor aromatic.
  • the preferred adjustors are selected from propanol and butanol, preferably t-butanol.
  • a terpene in the present context is a non-oxygenated compound comprising isoprenoid units, for example, but not limited to pinene, limonene, turpentine.
  • a fuel composition that uses a high percentage of components derived from renewable resources has been developed, as exemplified in both working embodiments and prophetic examples. Unless otherwise noted, the percentage of each component is on the basis of v/v, regardless of whether the component is liquid or solid. Table 1 shows the general formula.
  • a generator was hooked up to two heaters, to provide a load.
  • a four gas analyzer was used to collect emissions data, a tachometer was used to measure RPM, and a heat probe was used to measure exhaust temperature.
  • the emissions probe was uniformly placed in the exhaust pipe for the duration of each run and multiple readings were taken.
  • the heat probe was placed in an aperture in the exhaust pipe to measure the temperature and multiple readings were taken.
  • the drift in CH was 0 to 8 ppm.
  • the CO 2 drift was 0.05% and the oxygen always read 0.13%. It was noted that the equipment was not able to zero and consequently, the data obtained were not absolute values, but were considered to be relatively values, but accurate nonetheless.
  • the engine was heated using 87 octane gas, and then a 200 mL sample of 87 octane gas was run as the first sample. Three samples of 200 mL were then run, followed by a gas sample of 200 mL, then three more samples of 200 mL per run, again followed by a gas sample of 200 mL. A final gas sample of 200 mL was run. As the results were consistent, they were averaged before correcting for run time, which was very consistent.
  • Steps 1 to 8 can be skipped if not measuring emissions
  • Steps 9 to 12 can be skipped if the car has been set to run on the auxiliary fuel delivery system. Additional testing involved road testing and 1 ⁇ 4 mile drag testing to determine the torque and horsepower.
  • Formulations were predicted to pass or fail as a fuel based on a modeling spreadsheet.
  • a fail based on octane can be rectified by adding any octane enhancer as would be known to one skilled in the art.
  • a fail based on vapour pressure can be rectified by adding components to raise or lower the vapour pressure. Once adjusted, these formulations will function well as fuels.
  • Formulation A passes.
  • Formulation B fails due to being over 72.
  • Formulation A passes.
  • Formulation B fails due to the vapor pressure being over 72.
  • Formulation A passes.
  • Formulation B fails due to the vapor pressure being over 72.
  • Formulation A passes.
  • Formulation B fails due to the vapor pressure being over 72.
  • Formulation A passes.
  • Formulation B fails due to the vapor pressure being over 72.
  • the foregoing is a description of an embodiment of the invention. As would be known to one skilled in the art, variations are contemplated that do not alter the scope of the invention. These include but are not limited to, different combinations of alcohols, different alcohol isomers, and derivatives and analogues of, different water tolerance adjustors, oxygenates and terpenes.
  • the formulation may comprise from about 44% to about 70% v/v petroleum distillate, from about 10% to about 25% v/v ethanol, from about 5% to about 15% v/v butanol as the water tolerance adjustor and from about 5% to 25% v/v oxygenate.

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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)

Abstract

Embodiments of a composition useful as a fuel or fuel additive are provided. Certain disclosed embodiments of the composition comprise petroleum distillate, at least one alcohol having a ratio of between about 1 to about 4 carbon atoms to 1 hydroxyl functional group, at least one oxygenate, optionally, at least one lubricating oil, optionally, at least one water tolerance adjustor and optionally at least one terpene, wherein the oxygenate has a flash point between about −10° C. and about −50° C., has at least one oxygenated functional group, and is soluble in the composition.

Description

    RELATED APPLICATIONS
  • The present applications claims priority to U.S. provisional application No. 61/355,897 filed 17 Jun. 2010, and entitled COMPOSITION FOR USE AS A FUEL OR FUEL ADDITIVE IN A SPARK IGNITION ENGINE, ITS MANUFACTURE AND USE, incorporated in its entirety herein.
  • FIELD
  • Disclosed embodiments concern a fuel that can be used as a replacement for conventional fossil-based fuels. It can also be used as an additive to conventional fossil-based fuels, or alternative fuels.
  • BACKGROUND
  • Numerous formulations have been developed as alternative fuels to replace the conventional fossil-based fuels. An example of such a fuel is disclosed in Canadian patent 1340871, in which alcohol is mixed with ether and a lubricant such as mineral oil or a vegetable oil, such as castor oil. Formulations have also been developed for use as alternative fuels that combine renewable carbon sources such as alcohols with fossil fuels. An example of such a fuel is disclosed in Canadian patent 2513001, in which alcohol is mixed with naptha and an aliphatic ester.
  • In U.S. Pat. No. 7,399,323 a fuel composition that comprises farnesane and/or farnesane derivatives and a conventional fuel component selected from diesel fuel, jet fuel, kerosene or gasoline is disclosed. The farnesane or farnesane derivative can be used as a fuel component or as a fuel additive in the fuel composition. U.S. Pat. No. 5,575,822 discloses a number of fuel and fuel additives. The fuels range from two component formulations, such as 10 to about 42% terpene, preferably limonene, and from about 1 to about 90% naphtha compound to more complex formulations such as 10 to about 16 w/w % limonene, from about 19 w/w % to about 45 w/w % aliphatic hydrocarbons having a flash point between 7° C., to about 24° C., most preferably Varnish Makers and Painters (VM&P) naptha, from about 20 w/w % to about 40% w/w % alcohol, most preferably methanol, from about 9 w/w % to about 36 w/w % surfactant, most preferably glycol ether EB and a preferred fuel comprising about 11.4 w/w % limonene, about 40.7 w/w % VM&P naptha, about 15.5 w/w % glycol ether EB, about 22 w/w % methanol, and about 10.6 w/w % castor oil.
  • Terpenoid based fuels have been disclosed in U.S. Pat. No. 5,186,722. Disclosed are a very wide range of terpenes, terpenoids and derivatives thereof, including limonenes, menthols, linalools, terpinenes, camphenes and carenes. The fuels are produced by a cracking/reduction process or by irradiation. Limonene was shown to produce 84% 1-methyl-4-(1-methylethyl) benzene by this process. While the fuel is superior to that of Whitworth, production costs are relatively high.
  • In U.S. Pat. No. 6,309,430 a spark ignition motor fuel composition is disclosed consisting essentially of: a hydrocarbon component containing one or more hydrocarbons selected from five to eight carbon atoms straight-chained or branched alkanes, wherein the hydrocarbon component has a minimum anti-knock index of 65 as measured by ASTM D-2699 and D-2700 and a maximum dry vapor pressure equivalent (DVPE) of 15 psi (one atmosphere (atm.)) as measured by ASTM D-5191; a fuel grade alcohol; and a co-solvent for the hydrocarbon component and the fuel grade alcohol; wherein the hydrocarbon component, the fuel grade alcohol and the co-solvent are present in amounts selected to provide a motor fuel with a minimum anti-knock index of 87 as measured by ASTM D-2699 and D-2700, and a maximum DVPE of 15 psi (1 atm.) as measured by ASTM D-5191, and wherein the fuel composition is essentially free of olefins, aromatics, and sulfur.
  • More recently, US patent publication number 20080104884 discloses a fuel comprising mid to low flash point naptha, at least one alcohol having a ratio of between about 1 to about 4 carbon atoms to 1 hydroxyl functional group, at least one lubricating oil, and at least one oxygenated natural aromatic compound, wherein the oxygenated natural aromatic compound has a flash point between about 6° C. and about 16° C., has at least one oxygenated functional group, and is soluble in the composition.
  • SUMMARY
  • Certain disclosed embodiments concern a composition for use as a fuel or fuel additive. For example, particular disclosed embodiments concern compositions that provide an alternative fuel and a fuel additive that compares favourably to existing fuels with regard to horsepower and torque, for use in spark ignition engines in the absence of hardware modifications. By selecting the specific components and mixing them in defined ratios, the resulting composition, when combusted, reduces harmful emissions, whether used alone or as a gas additive. Further, by selecting the specific components, an alternative fuel or fuel additive is provided that contains up to about 56% biologically derived components, all of which are readily renewable. Finally, the remaining about 44% can be produced with a minimum of refining.
  • DETAILED DESCRIPTION I. Definitions
  • The following definitions are provided solely to aid the reader. These definitions should not be construed to provide a definition that is narrower in scope than would be apparent to a person of ordinary skill in the art.
  • A. Alcohol: Alcohols in the present working examples typically are lower alkyl alcohols, such as C1 to C3 alcohols, more specifically methanol, ethanol (95% ethanol), propanol and isopropanol. The ratio of carbon atoms to hydroxyl functional group should preferably be 4-to-1, more preferably be 3-to-1 and most preferably 2- to 1 or 1-to-1, to promote solubility in an aqueous environment and to promote miscibility between the polar and non-polar components of the composition. It would be further known to a person of ordinary skill in the art, that any alcohol or mixture of alcohols providing a ratio of between about 1 carbon to about 1 hydroxyl functional group and about 4 carbon to about 1 hydroxyl functional group would be suitable, hence mixtures of longer chain alcohols with shorter chain alcohols, for example, a C4 alcohol and a C1 alcohol.
    B. Petroleum distillate: Petroleum distillate in the present context, for use in gas-powered engines, has a flashpoint of no greater than about 3° C., and more preferably between about 1° C. and about −15° C., still more preferably between about −5° C. and about −10° C. and is composed of from about 35% v/v to about 75% v/v paraffins and isoparaffins, and about 20% v/v to about 60% v/v naphthenes, with no greater than about 5% v/v aromatic hydrocarbons, preferably from about 40% v/v to about 67% v/v paraffins and isoparaffins and about 30% v/v to about 57% v/v napthenes, with no greater than about 3% v/v aromatic hydrocarbons, and most preferably from about 45% v/v to about 53% v/v paraffins and isoparaffins and about 45% v/v to about 53% v/v napthenes with no greater than about 2% v/v aromatic hydrocarbons. Petroleum distillate can be replaced with commercial gasoline formulations having octane ratings from about 87, to about 89 to about 91 to about 94.
    C. Oxygenate: An oxygenate in the present context is selected from low carbon ethers, for example, but not limited to dimethyl ether, tetrahydrofuran, methyl tetrahydrofuran, furan, 2,5 dimethyl furan—in general, a straight chain or cyclic ether. It should be noted that it is recommended that the tetrahydrofuran be stabilized. The oxygenates have a flash point between about −10° C. and about −50° C.
    D. Water tolerance adjustor: A water tolerance adjustor in the present context preferably has a Kauri butanol value of at least about 80, preferably at least about 90 and more preferably over 100 and is preferably not chlorinated nor aromatic. The preferred adjustors are selected from propanol and butanol, preferably t-butanol.
    E. Terpene: A terpene in the present context is a non-oxygenated compound comprising isoprenoid units, for example, but not limited to pinene, limonene, turpentine.
  • II. Description
  • A fuel composition that uses a high percentage of components derived from renewable resources has been developed, as exemplified in both working embodiments and prophetic examples. Unless otherwise noted, the percentage of each component is on the basis of v/v, regardless of whether the component is liquid or solid. Table 1 shows the general formula.
  • TABLE 1*
    Water
    Petroleum tolerance
    distillate Alcohol Oxygenate adjustor Terpene
    % 44-70, 10-25, 10-25 0-15, 0-17,
    preferably preferably preferably preferably preferably
    45-60, 12-20, 12-20, 5-12, more 5-15,
    more more more preferably more
    preferably preferably preferably 10 preferably
    50 15 15 10
    *all values are “about”, for example, about 44 to about 70, preferably about 50 to about 60, more preferably about 55.

    Of the components, up to 56% can be obtained from renewable resources.
  • Example 1
  • TABLE 2
    Formulation M
    Petroleum 63%
    distillate
    Ethanol 16%
    Tetrahydrofuran 16%
    Limonene 5%
  • TABLE 3
    Formulation D
    Petroleum 45%
    distillate
    Ethanol 25%
    Tetrahydrofuran 25%
    Limonene 5%
  • A generator was hooked up to two heaters, to provide a load. A four gas analyzer was used to collect emissions data, a tachometer was used to measure RPM, and a heat probe was used to measure exhaust temperature. The emissions probe was uniformly placed in the exhaust pipe for the duration of each run and multiple readings were taken. The heat probe was placed in an aperture in the exhaust pipe to measure the temperature and multiple readings were taken. Prior to running the testing, it was determined that the drift in CH was 0 to 8 ppm. The CO2 drift was 0.05% and the oxygen always read 0.13%. It was noted that the equipment was not able to zero and consequently, the data obtained were not absolute values, but were considered to be relatively values, but accurate nonetheless.
  • The engine was heated using 87 octane gas, and then a 200 mL sample of 87 octane gas was run as the first sample. Three samples of 200 mL were then run, followed by a gas sample of 200 mL, then three more samples of 200 mL per run, again followed by a gas sample of 200 mL. A final gas sample of 200 mL was run. As the results were consistent, they were averaged before correcting for run time, which was very consistent.
  • Results
  • TABLE 4
    87 OCTANE GAS
    GAS Average Corrected (.898)
    CH ppm 181 201 ppm
    CO2 % 0.11 12.30%
    Lambda 0.84 0.84
    CO % 0.062 6.9%
    O2 % 0.13
    AFR 11.9 11.9
    Run time 4.48 4.48
    RPM 2200 2200
    Temperature C. 407 407
  • TABLE 5
    Formulation M
    M Average Corrected (1.164)
    CH ppm 225.3 193 ppm
    CO2 % 0.104 9.02%
    Lambda 0.826 0.82
    CO % 0.059 5.10%
    O2 %
    AFR 11.96 11.96
    Run time 5.82 5.82
    RPM 2200 2200
    Temperature C. 276.3 276
  • TABLE 6
    Formulation D
    D Average Corrected (1.234)
    CH ppm 171.3 138 ppm
    CO2 % 0.1197 9.70%
    Lambda 0.89 0.896
    CO % 0.034 2.80%
    O2 %
    AFR 13.0 13.1
    Run time 6.17 6.17
    RPM 2200 2200
    Temperature C. 273 273
  • In all cases, the engine ran for significantly longer with the formulations than with gas (5.82 and 6.17 minutes compared to 4.49 minutes). Note that the air fuel ratio (AFR) and lambda were approximately the same for gas and the formulations (the results for the formulations bracket those for gas—one slightly higher and the other slightly lower), indicating that the engine was not simply running lean on the formulations. Further, the rpm was the same throughout the testing. It can be inferred, therefore that the formulations will provide better mileage than 87 octane gas. The tables show the results, which have all been corrected for a five minute run time.
  • Hydrocarbons were slightly lower for M as compared to gas. Carbon dioxide was significantly lower for M, while carbon monoxide was slightly lower (about 2% lower). The exhaust temperature was very significantly lower. Although we were unable to measure NOx, the lower exhaust temperature can be directly correlated with lower NOx emissions.
  • Hydrocarbons were significantly lower for D as compared to gas (138 ppm versus 201 ppm). Carbon dioxide was significantly lower for D (9.7% versus 12.3%), as was carbon monoxide (over 4% lower). The exhaust temperature was very significantly lower. Although we were unable to measure NOx, the lower exhaust temperature can be directly correlated with lower NOx emissions. None of the formulations were able to tolerate water—they separated into two phases.
  • Example 2
  • The following formulations were tested using the following protocol:
  • Test Procedure
    1Insert sample probe into exhaust system.
    2Tighten the 2, 14 mm nuts on the exhaust clamp.
    3Attach the yellow sample hose to the sample probe and to the analyzer.
    4Attach the magnetic pick up around a spark plug wire with
    “SPARK PLUG” towards the front of the car.
    5Turn on (plug in) gas analyzer.
    6Start car.
    7Run for a minimum of 30 minutes, using the “Extended Purge” half way
    through and “Zero” as needed.
    8Turn off car.
    9Switch transfer pump off using the electrical switch in the trunk.
    10Close main fuel delivery system return valve.
    11Close auxiliary fuel delivery system return valve.
    12Close main fuel delivery system feed valve.
    13Start car and run until it starts to run out of fuel to purge the lines.
    14Empty auxiliary fuel tank.
    15Wipe out auxiliary fuel tank.
    16Fill auxiliary fuel tank with a small, measured amount of fuel
    to flush the lines.
    17Open the auxiliary fuel tank feed valve.
    18Start car and run until fuel comes out of the return line for 30 seconds.
    19Empty auxiliary fuel tank.
    20Wipe out auxiliary fuel tank.
    21Fill auxiliary fuel tank with a measured amount of fuel for testing.
    22“Zero” the gas analyzer
    23Start data logging.
    24Start timer.
    25Run test.
    26Stop timer.
    27Stop data logging.
    28Run “Extended Purge” on the gas analyzer.
    29Measure amount of fuel remaining.
    30Close auxiliary fuel delivery system feed valve.
    31Repeat steps 13 to 30 for all fuel samples.
    Note:
    Steps 1 to 8 can be skipped if not measuring emissions
    Note:
    Steps 9 to 12 can be skipped if the car has been set to run on the auxiliary fuel delivery system.

    Additional testing involved road testing and ¼ mile drag testing to determine the torque and horsepower.
  • TABLE 7
    50N
    Petroleum distillate 50%
    Ethanol 20%
    Tetrahydrofuran 20%
    Tert-butanol 10%
  • TABLE 8
    Carbon Oxides of
    Hydrocarbons Carbon Dioxide Nitrogen Total Run Total Amount
    [ppm] Monoxide [%] [%] Oxygen [%] [ppm] RPM λ Time [s] Used [mL] LPM
    Gasoline Mean
    98 0.71 11.4 2.9 290 2839 1.13 625 925 0.0887
    50N Mean
    48 0.72 10.1 3.1 270 2837 1.17 624 448 0.0431
    Gasoline Mean
    55 0.74 13.5 1.9 279 2786 1.06 458 747 0.0979
    50:50 Mean
    62 0.87 13 2.1 267 2804 1.07 461 434 0.0565
    10:90 Mean
    53 0.74 13.2 1.9 287 2777 1.07 459 477 0.0624
    E Gas Mean
    56 0.84 12.7 2.3 269 2731 1.09 443 563 0.0763
    Gasoline Mean
    62 0.94 12.5 2.3 265 2708 1.08 448 603 0.0808
  • TABLE 9
    Gasoline Formulation
    Average Average
    RPM RPM
    Horsepower 75.2 5496 75.6 5336
    Torque 80.9 3691 79.4 4441
  • TABLE 10
    Hydro- Carbon Carbon Oxides of
    carbons Monoxide Dioxide Oxygen Nitrogen RPM λ Calculated
    Formulation Means 0 to 1000 RPM
    453 0.61 11.3 3.3 233 842 1.29
    Gasoline Means 0 to 1000 RPM
    269 1.65 12.6 2.4 206 808 1.06
    Formulation Means 1000 to 4000 RPM
    316 0.60 11.5 2.4 711 1828 1.18
    Gasoline Means 1000 to 4000 RPM
    207 1.15 12.6 2.7 674 1762 1.16
  • Example 3
  • TABLE 9
    Formulations tested:
    E Gas Husky
    25E N: 50, E: 25, THF: 15, B: 10
    30E N: 50, E: 30, THF: 10, B: 10
    15E N: 50, E: 15, THF: 25, B: 10
    50N n-butanol N: 50, E: 20, THF: 20, n-B: 10
    Formulation 1 N: 51, E: 24, THF: 15, B: 10
    Formulation 5 N: 54, E: 20, THF: 16, B: 10
    Formulation 2 N: 54, E: 20, THF: 15, B: 10, DMF: 1
    Formulation 4 N: 50, E: 30, THF: 10, B: 10
    Formulation 6 N: 50, E: 26, THF: 14, B: 10
    Formulation 7 N: 50, E: 30, THF: 10, B: 10
    Formulation 8 N: 50, E: 38, THF: 2, B: 10
    Formulation 9 N: 50, E: 20, THF: 17, B: 13

    Egas is gasoline with 10% ethanol, N ispetroleum distillate, E is ethanol, THF is tetrahydrofuran, B is tert-butanol, n-B is n-butanol, and DMF is di-methyl furan.
  • Example 4
  • Formulations were predicted to pass or fail as a fuel based on a modeling spreadsheet. A fail based on octane can be rectified by adding any octane enhancer as would be known to one skilled in the art. A fail based on vapour pressure can be rectified by adding components to raise or lower the vapour pressure. Once adjusted, these formulations will function well as fuels.
  • Examples are as follows:
  • Formulation Name Vapor Pressure [kPa] Octane
    A 38.16 81.77
  • Above is 60 N, 20 E, 15 X and 5 L X=Tetrahydrofuran
  • Fails due to Vapor Pressure being below 41.
  • Formulation Name Vapor Pressure [kPa] Octane
    A 15.59 85.28
    B 8.42 81.96
  • Above is 60 N, 20 E, 15 X and 5 L
  • X=2,5 Dim ethylfuran
  • X=2-Methyltetrahydrofuran
  • Both fail due to Vapor Pressure being below 41.
  • Formulation Name Vapor Pressure [kPa] Octane
    A 141.20 82.25
  • Above is 60 N, 20 E, 15 X and 5 L
  • X=furan
    Fails due to Vapor Pressure being over 72.
  • Formulation Name Vapor Pressure [kPa] Octane
    A 42.20 86.70
    B 145.24 87.18
  • 55N, 20 E, 15 X and 10 t-But
  • X=Tetrahydrofuran
  • X=Furan
  • Formulation A passes.
    Formulation B fails due to being over 72.
  • Formulation Name Vapor Pressure [kPa] Octane
    A 45.27 91.01
    B 42.88 89.91
  • 50N, 20 E, 20 X and 10 t-but
  • X=15 tertrahydrofuran and 5 2,5 Dimethylfuran
  • X=15 tetrahydrofuran and 5 2-Methyltetrahydrofuran
  • Both pass.
  • A 68.90 87.69
    B 87.14 90.00
  • 50N, 20 E, 20 X and 10 t-but
  • X=15 tetrahydrofuran and 5 diethyl ether
  • X=15 tetrahydrofuran and 5 furan
  • Formulation A passes.
    Formulation B fails due to the vapor pressure being over 72.
  • Formulation Name Vapor Pressure [kPa] Octane
    A 55.87 94.16
    B 98.66 98.59
  • 45N, 20 E, 25 X and 10 t-but
  • X=20 tetrahydrofuran and 5 2,5 Dimethylfuran
  • X=20 tetrahydrofuran and 5 2-Methyltetrahydrofuran
  • Formulation A passes.
    Formulation B fails due to the vapor pressure being over 72.
  • Formulation Name Vapor Pressure [kPa] Octane
    A 79.50 90.83
    B 97.74 93.15
  • 45N, 20 E, 25 X and 10 t-but
  • X=20 tetrahydrofuran and 5 diethyl ether
  • X=20 tetrahydrofuran and 5 furan
  • Both fail due to the vapor pressure being over 72.
  • Vapour pressure Octane
    A 63.39 92.99
      • 45N, 20 E, 25 X and 10 t-but
      • X=tetrahydrofuran
        • Passes.
      • Formulation Name
      • Vapor Pressure [kPa]
        • Octane
  • Vapour Pressure Octane
    A 52.79 89.84
  • 50N, 20 E, 20 X 10 T-but
  • X=tetrahydrofuran
  • Passes.
  • Formulation Name Vapor Pressure [kPa] Octane
    A 45.27 91.01
    B 42.88 89.91
  • 50N, 20 E, 20 X and 10 t-but
  • X=15 tetrahydrofuran 5 2,5 Dimethylfuran
  • X=15 tetrahydrofuran 5 2-Methyltetrahydrofuran
  • Both Pass.
  • Formulation Name Vapor Pressure [kPa] Octane
    A 68.90 87.69
    B 42.09 88.24
  • 50N, 20 E, 20 X and 10 t-but
  • X=15 tetrahydrofuran 5 diethylether
  • X=15 tetrahydrofuran+5 pinene
  • Both Pass.
  • A 52.79 89.84
    Formulation Name Vapor Pressure [kPa] Octane
    A 87.14 90.00
  • 50N 20 E 20 X and 10 t-but
  • X═X=15 tetrahydrofuran+5 furan
  • Fails due to the vapor pressure being over 72.
  • Formulation Name Vapor Pressure [kPa] Octane
    A 44.00 99.05
    B 96.05 94.61
  • 40N 25 E 25×10 t-But
  • X=15 tetrahydrofuran+10 2-Methyltetrahydrofuran
  • X=15 tetrahydrofuran+10 diethylether
  • Formulation A passes.
    Formulation B fails due to the vapor pressure being over 72.
  • Formulation Name Vapor Pressure [kPa] Octane
    A 42.16 88.16
    B 132.52 99.24
  • 40N 25 E 25×10 t-But
  • X=15 tetrahydrofuran+10 dimethyl ether
  • X=15 tetrahydrofuran+10 furan
  • Formulation A passes.
    Formulation B fails due to the vapor pressure being over 72.
  • A 42.41 95.71
  • 40N 25 E 25×10 t-But
  • X=15 tetrahydrofuran+10 pinene
  • Passes.
  • Formulation Name Vapor Pressure [kPa] Octane
    A 63.83 98.92
  • 40N 25 E 25×10 t-But
  • X=tetrahydrofuran
  • Passes.
  • The foregoing is a description of an embodiment of the invention. As would be known to one skilled in the art, variations are contemplated that do not alter the scope of the invention. These include but are not limited to, different combinations of alcohols, different alcohol isomers, and derivatives and analogues of, different water tolerance adjustors, oxygenates and terpenes. The formulation may comprise from about 44% to about 70% v/v petroleum distillate, from about 10% to about 25% v/v ethanol, from about 5% to about 15% v/v butanol as the water tolerance adjustor and from about 5% to 25% v/v oxygenate.

Claims (20)

1. A composition for use as a fuel or fuel additive, comprising a petroleum distillate, at least one alcohol having an average ratio of between about 1 to about 4 carbon atoms to 1 hydroxyl functional group, optionally, at least one lubricating oil, optionally, at least one terpene, optionally at least one water tolerance adjustor, and at least one oxygenate, wherein the oxygenate (i) has a flash point between about −10° C. and about −50° C., (ii) has at least one oxygenated functional group, and (iii) is soluble in the composition.
2. The composition of claim 1 comprising from about 44% to about 70% v/v petroleum distillate, from about 10% to about 25% v/v alcohol, from 0% to about 5% v/v lubricating oil, and from about 0.3% to 15% v/v oxygenate.
3. The composition of claim 2 wherein the oxygenate is a straight chain or cyclic ether.
4. The composition of claim 3 wherein the at least one alcohol is selected from methanol, ethanol, propanol, and isopropanol, or combinations of any of methanol, ethanol, propanol, isopropanol butanol, isobutanol and tert-butanol.
5. The composition of claim 4 wherein the petroleum distillate comprises at least about 30% v/v to about 57% v/v napthenes.
6. The composition of claim 5 further comprising a water tolerance adjustor.
7. The composition of claim 6 wherein the water tolerance adjustor is t-butanol.
8. The composition of claim 7 wherein the oxygenate is selected from tetrahydrofuran, methyl tetrahydrofuran, furan, and 2,5 dimethyl furan.
9. The composition of claim 8 wherein the terpene is selected from limonene, pinene, myrcene and farnesene.
10. The composition of claim 9 wherein the alcohol is ethanol.
11. The composition of claim 1 comprising from about 44% to about 70% v/v petroleum distillate, from about 10% to about 25% v/v ethanol, from about 5% to about 15% v/v butanol and from about 5% to 25% v/v oxygenate.
12. The composition of claim 1, wherein the petroleum distillate comprises at least about 30% v/v to about 57% v/v napthenes.
13. The composition of claim 12, wherein the petroleum distillate comprises about 45% v/v to about 53% v/v paraffins and isoparaffins and about 45% v/v to about 53% v/v napthenes with no greater than about 2% v/v aromatic hydrocarbons.
14. The composition of claim 13, further comprising gasoline.
15. A method, comprising:
(i) preparing a composition comprising composition for use as a fuel or fuel additive, comprising:
a petroleum distillate having a flash point from about 1° C. and about −15° C. and comprised of paraffins, isoparaffins and napthenes;
at least one alcohol having a ratio of between about 1 to about 4 carbon atoms to 1 hydroxyl functional group;
a water tolerance adjustor, which may be a separate component to the alcohol or may be included in the alcohol;
optionally, at least one lubricating oil;
optionally a terpene; and
at least one oxygenate;
(ii) blending the composition with about 0% to about 90% v/v gas to prepare a fuel; and
(iii) operating a motor using the fuel.
16. The method of claim 15, wherein the at least one oxygenate (i) has a flash point between about −10° C. and about −50° C., (ii) has at least one oxygenated functional group, and (iii) is soluble in the composition.
17. A method of decreasing emissions from a spark ignition, gas fueled motor, said method comprising:
(i) preparing a composition comprising a petroleum distillate, alcohol, an oxygenate, and, optionally, a water tolerance adjustor, optionally a terpene and optionally a lubricating oil;
(ii) blending said composition with about 0 to about 90% v/v gas to prepare a fuel;
(iii) fueling a motor with said fuel; and
(iv) running said motor,
thereby decreasing said motor emissions.
18. The method of claim 17 wherein said alcohol has a ratio of between about 1 to about 4 carbons to 1 hydroxyl functional group, and the oxygenate is characterized in that it:
(i) has a flash point between about −10° C. and about −50° C.;
(ii) has at least one oxygenated functional group; and
(iii) is soluble in said composition.
19. The method of claim 18, wherein the composition is further defined as comprising from about 44% to about 70% v/v of the petroleum distillate, from about 10% to about 25% v/v of the alcohol, from 10% to about 25% v/v oxygenate and optionally, up to about 17% v/v terpene and about 0.2% v/v lubricating oil.
20. The method of claim 19 wherein the composition further comprises a water tolerance adjustor.
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