WO1996040844A1 - Procede de combustion en phase vapeur et compositions ii - Google Patents

Procede de combustion en phase vapeur et compositions ii Download PDF

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Publication number
WO1996040844A1
WO1996040844A1 PCT/US1996/009653 US9609653W WO9640844A1 WO 1996040844 A1 WO1996040844 A1 WO 1996040844A1 US 9609653 W US9609653 W US 9609653W WO 9640844 A1 WO9640844 A1 WO 9640844A1
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fuel
ecs
combustion
fuels
applicant
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PCT/US1996/009653
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William C. Orr
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Orr William C
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Priority to JP9501927A priority Critical patent/JPH11504974A/ja
Priority to EP96923240A priority patent/EP0833879A1/fr
Priority to AU63806/96A priority patent/AU6380696A/en
Priority to BR9608589-4A priority patent/BR9608589A/pt
Priority to APAP/P/1998/001185A priority patent/AP9801185A0/en
Publication of WO1996040844A1 publication Critical patent/WO1996040844A1/fr
Priority to NO975746A priority patent/NO975746L/no

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/12—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/20—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/26—Organic compounds containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/30—Organic compounds compounds not mentioned before (complexes)
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B2275/00—Other engines, components or details, not provided for in other groups of this subclass
    • F02B2275/32—Miller cycle
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • This invention relates to fuel compositions for jet, turbine, diesel, gasoline, and other combustion systems. More particularly, it relates to a unique vapor phase combustion, wherein metallic fuel combinations with high heats of enthalpy are capable of improving combustion, 10 reducing combustion temperature, improving thermal efficiency, fuel economy, power and emissions.
  • I based fuels form metallic oxides in combustion.
  • such metallics when combusted in hydrocarbon fuels generate harmful heavy manganese oxides (Mn 3 0 4 and Mn 2 0 3 ) , which in turn coat engine parts, combustion systems, turbines, exhaust surfaces, emission/exhaust catalysts, etc., causing for example, early fatigue, failure, excessive wear, particulate emissions of metals, long term hydrocarbon emission degradation, and the like. See U.S. Patents 3,585,012; 3,442,631; 3,718,444; and my EPO Patent # 0235280.
  • Harmful metallic deposition is well known and heretofore the practical problem in metallic usage.
  • deposition of manganese oxide on jet engines, turbines, and the like has long been a major obstacle to manganese's use.
  • Due to the severity of manganese deposits various methods were developed just to remove such oxides from jet engines. See U.S. Patent 3,556,846; 3,442,631; 3,526,545; 3,506,488.
  • metallic usage has been virtually halted in such applications, and alternative application is limited to very low concentrations of metallic.
  • Patent 4,600,408 (issued in 1986) discloses an alkyl phenyl carbonate as an anti-knock agent. Patent 4,600,408 notes the aforementioned organo-manganese oxide problem and discloses its composition must be organo- manganese free.
  • Applicant has discovered a new class of high energy cool combustion compositions and methods, wherein a unique form of combustion occurs referred to as vapor phase combustion.
  • Such combustion represents the long awaited solution of not only correcting non-optimal combustion of fuel absent metals, but also represents the long awaited solution to the metallic oxide problem. Both are the same solution to the same problem and represent the invention's hub to which Applicant's many compositions and methods spokes attach.
  • ECS fuels may combined with more traditional fuels or co-fuels. This combination is referred to as an ECS/co-fuel.
  • Modified Fuels are stand alone fuels, which have been modified to comport with the object of Applicant's invention. These fuels have improved LHV's and/or burning velocities ("BV") . Their improvement is by substituent reformation/reformulation, including component modification and distillation temperature modification. However, modified fuels do not normally enjoy ECS and/or metallic additive.
  • Co-fuels are normally traditional fuels, which may or may not be modified prior to their addition with an ECS fuel.
  • compositions and methods employing ECS fuels, ECS/co- fuels, modified co-fuels alone, description of Drawings and Figures l through 8 are disclosed in copending International Applications No. PCT/US95/02691 and No. PCT/US95/06758, and incorporated in all respects herein.
  • Applicant's invention resides in a rare form of combustion known as vapor phase combustion.
  • Applicant's invention applies to both fuels with or without metals. But in Applicant's vastly improved combustion conditions, the use of transition metals, alkine metals, alkine earths, halogens, group IIIA elements and mixture (hereinafter "metallics") is strongly indicated, as such metals become an integral and powerful substituent in the combustion process, not merely a fuel additive. Applicant generally refers to thermal efficiency, hereinafter, in both its chemical and mechanical context, e.g. the efficiency of the combustion process and amount of useful or "net” work generated, e.g. free energy.
  • thermal and/or combustion efficiency e.g. gains in flight range, fuel economy, work potential, thrust, lift, completeness of combustion, etc.
  • thermal and/or combustion efficiency e.g. gains in flight range, fuel economy, work potential, thrust, lift, completeness of combustion, etc.
  • ASTM standards refer to published standards of the American Society for Testing and Materials, 1916 Race St., Philadelphia, Pa. 19103.
  • Applicant's invention resides in increasing i) burning velocity of a non-leaded metallic containing fuel above that of traditional fuels by a) increasing laminar burning velocity (by ECS chemical, distillation modification, and/or reformulation means) , b) increasing turbulent velocity (by chemical and/or mechanical means) and/or ii) reducing combustion temperature by chemical means e.g. increasing fuel heats of vaporization, etc. , or by mechanical means (e.g. advanced cooling systems, reducing chamber air charge temperature) .
  • chemical means e.g. increasing fuel heats of vaporization, etc.
  • mechanical means e.g. advanced cooling systems, reducing chamber air charge temperature
  • CHEMICAL MEANS Applicant's invention includes the discovery of a class of chemical compounds, which increase LHV and BV. The latter accomplished when certain free radicals are released during combustion.
  • ECS Enhanced Combustion Structure
  • Additional ECS structure include Cl, OCOO, COOH, C2H500C, CH3CO, OCH20, OCHCO, and CONH2.
  • said radicals freely form during the earliest stages of the combustion process (preferably after ignition and prior to combustion, e.g. unburnt post ignition vapors); with said radicals generally being unstable and disassociated, and having one or more free or unused valency electron(s) that can chemically bond. It is highly desireable that they act as chain carriers in the main chain reaction of combustion, particularly when in combination with metallic combustion. Preferred combustion yields significant quantities of dissociated free radicals (e.g. OH, CN, CH, NH, etc.), and/or unstable molecules, and/or atoms which subsequently reassociate and dissociate during combustion. This leads to extended combustion, acting to increase exhaust velocity and/or increase effective working fluid. Increases in exhaust velocities range from 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300 percent, or more, compared to exhaust velocities generated by traditional compositions/methods.
  • dissociated free radicals e.g. OH, CN, CH
  • Applicant's increased exhaust velocities represent a significant depart from the art, and are due to Applicant's high kinetic free radicals acting in combination with a metallic. Under Applicant's conditions, said combination results in luminous vapor phase combustion (see below) .
  • the heat of formation of said free radicals to be important. Generally, the lower heats of formation are better. Acceptable heats of formation for said free radicals typically are less than 150, 125, 100, 90, 80, 75, 70, 60, 50, 40, 30, 20, 10, 5, 2 Kcal mole" 1 . Those less than 50 Kcal mole" 1 or negative heats of formation are desired. Heats outside these ranges are also acceptable. Desireable heats of formation for free radicals include 34 (CH3) , 26 (C2H5) , 9.3 (OH), 2.0 (CH30) Kcal mole” 1 .
  • ECS compounds which yield a significant portion of CH3, CO, OH, and/or CH30 radicals as a weight percent in precombustion vapors are preferred.
  • Applicant's preferred OH, 0, CH3 and CH30 radical structure is common to methanol, dimethyl carbonate (“DMC”) , and methylal ECS compounds (see below) .
  • Reactive high kinetic energy free radicals are those radicals that generate flame velocities in excess of 47, 48, 49, 50, 51, 52, 55, 58, 60, 65, 70, 75, 80, 90 or more, cm/sec. (laminar bunsen burner flame) . As set forth herein burning velocities are measured cm/sec laminar bunsen flame.
  • the rate of flame propagation relative to unburned gas, in practical fuel-air-residual gas mixtures is a fundamental parameter that directly influences the invention's beneficial objects.
  • maximizing the elementary reactions involving free radicals that take place in the unburned gas vapors and/or flame and adapting the mass and thermal diffusivity of the various gaseous species containing said radicals (e.g. enhanced combustion structure) to yield increased combustion burning velocity is an express embodiment of this invention.
  • a high kinetic energy vapor/gaseous state free radical composition comprising: at least one disassociated radical selected from the group consisting of H, H 2 , O, 0 2 , CO, F, F2, F3, N, B, Be, BO, B2, BF, AL ALO, CH3, NH3, CH, C2H2, C2H5, Li, ONH, ON, NH, NH2, OCH 3 , OCH, OCH 2 , OH, Cl, CN, and/or optionally the group consisting of OCOO, COOH, C2H500C, CH3CO, OCH20, OCHCO, or CONH2, and mixture, wherein the selected radical's heat of formation is less than 150, 125, 100, 90, 80, 75, 70, 60, 50, 40, 30, 20, 10, 5, 2 K cal mole" 1 or negative, preferably less than 50, 40, 30, 20, 10, 5, 2 K cal mole "1 , and optionally its velocity in excess of 47, 48, 49, 50, 51, 52, 55,
  • a gaseous pre-combustion fuel vapor (“Fuel Vapor") or method, wherein the kinetic free radicals of example 1 represent 2, 5, 8, 10, 12, 15, 17, 20, 25, 30, 40, 50, 60, or more, weight percent, and preferably greater than 20%, of pre-combustion fuel vapor.
  • Example 3 The gaseous unburnt pre-combustion fuel vapor or method 1, wherein said vapor reduces the viscous drag between unburned and burned gases, optionally reduces combustion temperatures; said vapor characterized as extending the combustion interval by subsequent reassociation/disassociation of said radicals prior to final oxidation/combustion, increasing velocities of burnt/unburnt gases; when said vapor contains a transition metal, alkine metal, alkine earth, halogen, group IIIA element or mixture, luminous vapor phase burning occurs, generating oxides in the submicron range, whereby exhaust velocities of burnt gases are increased compared to burnt gases of traditional fuel vapor, absent said free radicals or metallic.
  • ECS COMPOUNDS ECS COMPOUNDS
  • ECS compounds may be solids, liquids, gases, and mixture, and may be employed in differing fuel systems. Liquid ECS compounds should be fuel soluble and are contemplated in generally all fuel state systems. Solid ECS compounds are normally employed in solid fuel systems, but may be incorporated into liquid or gaseous systems by appropriate means.
  • ECS compounds may be selected from alcohols, amines, amides, oxalates, esters, di-esters, glycols, ethers, aldehydes, ketones, glycols, glycol ethers, peroxides, phenols, carboxylic acids, acetic acids, oxalic acids, boric acids, peroxides, hydroperoxides, esters, othroesters, aldehydic acids, ketonic acids, hydroxyacids, orthoacids, anhydrides, acetates, acetyls, orthoborates, formic acids, nitrates, di-nitrates, carbonates, di- carbonates, nitro-ethers, and the like.
  • Non-limiting examples include: hydrogen, carbon monoxide, methylene di methyl ether (also ' known as methylal, dimethoxy methane) , carbonic acid dimethyl ester (also known as dimethyl carbonate "DMC"), diethyl carbonate, methyl tertiary butyl ether (MTBE) , ethyl tertiary butyl ether (ETBE) , methyl tertiary amyl ether (TAME) , methanol, ethanol, propanol, tertiary butyl alcohol, dimethyl ether, other C 3 to C 6 lower molecular weight alcohols, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dimethyl ether diethyl ether, isopropyl ether, diisopropyl ether (DIPE) , ⁇ acious.,. structuri-,- . O 96/40844
  • ECS compounds include • compounds containing carboethoxy, carbomethoxy, carbonyl, carbonyldioxy, carboxy, ethoxalyl, glyoxylyl, methoxy, methylenedioxy, glycolyl, and/or hydroxyl components and/or radicals.
  • Non-limiting examples include oxalates, carbonates, acetyl acetones, dimethyl glyoximes, ethylenediamine tetraacetic acids, and the like.
  • ECS compounds include ethylene, propylene, tertiary butylcumyl peroxide, butylene, 1,2-butadiene, 1, 3-butadiene, actetylene hydrocarbons including acetylene, allylene, butine-l, pentine-l, hexine-l; substituted hydrazines, including methylhydrazine, symmetrical dimethylhydrazine, unsymmetrical dimthylhydrazine, hydrazine,- ethane, propane, butane, diborane, tetraborane, penta bornane, hexaborane, decaborane, aluminum borohydride, beryllium borohydride, lithium borohydride, ammonium nitrate, potassiur nitrate, nitric acid, ammonium azide, ammonium.perchlorate, lithium perchlorate, potassium perchlorate, nitrogen trioxide, nitrogen dioxide,
  • ECS compounds include di-tertiary butyl peroxide, alkyl peroxides, alkyl hydroperoxides, acetyl hydroperoxides.
  • peroxides include tertiary butylcumyl peroxide, di (tertiaryamyl) peroxide, tertiary butyl hydroperoxide, di-tertiary butyl hydroperoxide, tertiary amyl hydroperoxide, acetyl tert- butyl hydroperoxide (CH3)3COOH), cyclohexyl (acetyl) hydroperoxide, ethyl (acetyl) hydroperoxide (C2H500H) , diacetyl peroxide, diethyl peroxide, dimethyl peroxide, methyl hydroperoxide (CH300H) , acetyl benzoyl peroxide, acetyl peroxide, formic acid, t
  • R may be different, same, or multiples of itself.
  • R may be 2 (R) , 3 (R) , 4 (R) , and wherein R may be a hydrogen, carbethoxy, carbomethoxy, caronyldiocy, carboxy, carbyl, ethoxalyl, ethoxy, ethylenedioxy, glycolyl, glyoxylyl, hydroxy, methoxy, methyl, ethyl, propyl, butyl, pentyl, methylenedioxy, acetonyl, acetoxy, acetyl, alkyloxy, benzoxy, or benzoyl radical.
  • ECS compounds in various systems will elicit differing response. For example, it is expected that in alcohols will elicit lower combustion and exhaust temperatures than ethers, due to differences in latent heats of evaporation. It is expected that lower molecular weight alcohols and carbonates decompose at an accelerated rate in combustion process compared to certain ethers.
  • Applicant has found a positive or low negative heat of formation for the ECS compound containing said reactive kinetic free radicals is desireable.
  • Acceptable negative ranges for heats of formation for ECS compounds include those less than approximately -200, -180, -160, -150, -145, -130, -120, -100 Kcal/mol, with more preferred being less than -90, -80, -75, -70, -65 Kcal/mol and the most preferred being less than approximately -60, -55, -50 , - 45, -40, -35, -30, -20, -10 kcal/mol, or positive in value. The closer to a positive or the higher the positive, the more preferred.
  • said vapor structure and/or the ECS compound, itself have a high latent heat of vaporization (enthalpy of vaporization) , particularly those equal to or greater than 28.0 jK mole "1 , at the compounds boiling point.
  • enthalpies of vaporization are those equal to or greater than 21, 22, 23, 24, 26, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 40, 42, 43, 45, 47, or higher, jK mole "1 .
  • said vapor structure and/or the ECS compound, itself have high flame velocity.
  • flame velocities should equal or exceed 40, 43, 45, 46, 48, 50, 52, 54, 56, 58, 60, 65, 70, 75, 80, 85, 90, 100, 110, 120, 130, 140, 150 cm/sec .
  • ECS compounds in vapor state which easily decompose and/or dissociate under temperature generating significant kinetic free radicals in compression, prior to ignition, post ignition, pre-combustion, or in combustion are desireable. Preferred is post ignition. It is also desirably decompositon occurs at below, at normal or at above normal compression pressures.
  • dissociation acts to quickly diffuse unburned vapors containing said free radicals in front of the flame front, combusting with metallic, whereby vapor phase combustion occurs.
  • Preferred boiling point temperatures of ECS compounds are those below 350°C, 325°C, 300°C, 275°C, 250°C, 225°C, 200°C, 175°C, 170°C, 160°C, 150°C, 140°C, 130°C, 120°C, 110°C, 105°C, and 100°C.
  • Preferred latent heats of vaporization of ECS compounds at 60°F are those equal to or greater than 75, 100, 110, 120, 130, 135 140, 145, 150, 155, 150, 160, 165, 170, 180, 190, 200, 210, 220, 230, 240, 250, 270, 290, 300, 325, 350, 375, 400, 425, 450, 475, 500 btu/lb, or more.
  • the latent heat of vaporization of the ESC compound be at least the same as, but more preferably 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 5.0%, 7.5%, 10%, 25%, 50%, 75%, 100%, 150%, 200%, 250%, 300%, or greater, than any unadjusted base fuel or co-fuel to which the compound might added.
  • the higher the relative difference in heat of vaporization the higher, for example, intake charges can be cooled and the greater the improvements in volumetric efficiency.
  • Flame velocities of ECS compounds herein may be measured independently or in the presence of a preferred metallic. Flame velocities of ECS compounds in the presence of a metallic are generally expected to be greater, than absent said metallic.
  • preferred laminar flame propagation velocities should exceed 30, 32, 34, 36, 37, 38, 39, 40, 41, 42, 44, 45, 47, 48, 49, 50, 51, 52, 53, 54, 55 cm/sec . The higher the better. It is preferred that the flame velocity of an any ECS compound as measured in laminar bunsen flame be at least .05% to 1.5%, 1.0% to 3.0%, 2.0% to 4.0%, 3.0% to 6.0%, 5% to 10%, 7% to 20%, 8.0% to 30.0%, 10% to 40%, 15% to 60%, 30% to 200%, 50% to 300%, or more, greater than the base fuel or co-fuel said ECS compound might be added.
  • ECS compounds rapidly decompose at temperatures slightly to moderately higher than ignition temperatures but below combustion temperatures. Decomposition at higher or even lower temperatures is contemplated, including those below ignition temperatures. However, in the case of gasolines pre-ignition should be avoided. In the case of jet turbine fuels where the fuel may act as a heat sink, thermal stability in both the liquid and vapor phase up to 165°C, 205°C, 220°C, 260°C, 280°C, 300°C, 320°C, 350°C, or more, is desireable.
  • ECS compounds not fully consumed in combustion, rapidly decompose when emitted in the atmosphere after combustion.
  • Preferred decomposition have half lives less than 20, 15, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 days and more preferred half lives less than 24, 22, 20, 18, 16, 14, 12, 10, 8, 6, 4, 2 hours or less. Most preferred half lives are less than 1.0, 0.5, 0.25 hours or less.
  • ECS compounds be thermally stable in normal handling and operating temperatures in either liquid or vapor state up to approximately 150°F, 250°F, 300°F, 350°F, 400°F, 450°F, 500°F, 550°F, 600°F, 650°F, 700°F, but readily decomposes in vapor state at approximate temperatures exceeding the above or between 300°F to 1100°F, 400°F to 1000°F, 500°F to 900°F, 650°F to 800°F, more preferably at 550°F to 900°F.
  • decomposition at temperatures outside of these and/or may occur for example during injection, compression, or prior to ignition, after ignition, and/or combustion. Optimum decomposition temperature will vary in the circumstances and is dependent upon fuel and combustion system employed.
  • Preferred ECS compounds are relatively simple in molecular structure.
  • Preferred fuel chain characteristics of Applicant's organic ECS compounds are those with limited number of carbon atoms in a chain, with 6, 5, 4, 3 or fewer preferred. 3, 2 or a single carbon are more preferred. Generally, the shorter the carbon chain the length the more preferred the ESC compound.
  • ECS compounds having flash points of -150°F, -135°F, -120°F, -115°F, -20°F, -25°F, -10°F, 0°F, 40°F, 50°F, 170°F, 280°F, more or less, are acceptable.
  • flash point temperatures above 30°C, 38°C, 40°C, 60°C, 70°C, 80°C, 90°C, 100°C, 105°C, 110°C, 120°C, 130°C or greater are desireable.
  • ECS compounds that do not adversely increase the vapor pressure or reduce flash point of a co-fuel at ambient or operating temperatures are preferred.
  • Acceptable blending vapor pressures range from 0.5 to about 50.0 psi. More desireable blending vapor pressures range from 0.5 to 15.0, 0.5 to 12.0, 0.5 to 10.0, 0.5 to 9.0, 0.5 to 8.0, 0.5 to 7.0 psi, or 0.5 to 6.0 psi, or 0.5 to 5.0 psi, or from 0.5 to 3.0, 0.5 to 1.5, 0.5 to 1.0 psi, 0.05 to 0.5, or less.
  • Individual vapor pressure ranges include 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.4, 5.6, 5.7, 5.9, 6.1,
  • Vapor pressure and flash point temperatures can be mitigated or controlled via co-solvent and/or salt practices set forth below.
  • a ECS compound comprising: a maximum carbon chain length of 5, 4, 3, 2, or 1 carbon atom(s) ; a negative heat of formation of -90, -60 kcal/mole, or less, including a positive heat of formation; a melting point of less than 20, 10, 5, 0, -10, -20, -30, -50 °C, or lower; a boiling temperature greater than 25, 30, 40, 42, 43, 44, 60, 80, 90, 100, 110, 120, 140 °C, or greater; a Bunsen burner laminar flame speed in excess of 40, 45, 48, 50, 55, 60, 65 or 70 cm/sec; a latent heat of vaporization exceeding 80, 90, 100, 120, 130, 133, 140, 143, 145, 148, 150, 152, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 230, 235, 240, 250, 300, 380, 400, 450,
  • free radicals selected from the group consisting of H, H 2 , 0, 0 2 , CO, F, F2, F3, N, B, Be, BO, B2, BF, AL ALO, CH3, NH3, CH, C2H2, C2H5, Li, ONH, NH, NH2, OCH 3 , OCH, OCH,, and OH, and mixture.
  • Example 4 wherein the ECS compound is fuel soluble and optionally contains oxygen by weight equal to 1%, 3%, 5%, 8%, 10,% 15%, 20%, 25%, 30%, 33%, 40%, 45%, 50%, 52%, 53%, 55%, 58%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 100%., more or less, ECS compounds with oxygen concentrations greater than 25% by weight are preferred. More preferred are those greater than 40% concentrations.
  • ECS compound ⁇ may less satisfactory than others, or altogether unsatisfactory.
  • Other ECS compound suffer potential health hazards.
  • MTBE has application in many fuels as an octane improver, but is now recognized as a possible carcinogen or allergen, being unfortunately rather stable in combustion with a long atmospheric half life.
  • its long term environmental utility, absent a co-ECS compound to accelerate its atmospheric . decomposition may be limited.
  • ECS compounds such as MTBE, ETBE, TAME improve ignition quality.
  • these compounds have moderate latent heats of evaporation and burning velocities.
  • ECS compound may role of ECS compound and metallic, so long as the object of invention is acheived.
  • certain ECS compounds will serve as co-solvents (see below) , or be co-ECS compounds facilitating use of one or more ECS compounds.
  • Co-ECS compounds may also be co-solvents. For example, it may necessary to increase flash point temperatures, reduce RVP, or reduce combustion temperatures of certain high BV/LHV ECS compounds by admixing a co-solvent.
  • the practice of this invention contemplates admixing an ECS compound, co-ECS compound, co-solvent, and/or co- fuel by separate means, including separate fuel injection. It is contemplated that mutual solvents may be employed to dissolve non-soluble and semi-soluble ECS compounds. However, it is preferred ECS compound ⁇ be soluble in such fuels.
  • a fuel soluble ECS compound having a melting point of less than -100°C, -80°C -55°C, -20°C, -5°C, 10°C, 50°C, -25°C -5°C, 0°C, 5°C, 10°C and a boiling point not les ⁇ than 40°C, 60°C, 75°C, 85°C, 100°C, 150°C, 275°C, 485°C, or greater.
  • those elements or compound/components wherein the above enhanced combu ⁇ tion structure exist, in high relative concentrations and/or which become intermediate and/or initial/pre-combustion and/or combustion structure/product, especially in the vapor charge and/or in the vapor of compression, post ignition, pre-combustion, and/or combustion vapor, evidenced by increased burning velocity constitute ⁇ an ECS compound herein.
  • the diffusion means of Applicant invention may additionally incorporate separate laminar and/or turbulent burning velocity increasing means, which may be mechanical or chemical. Or that such means may be absent the use of an ECS compound (see below) .
  • ECS compounds need not contain ECS structure, if their use or combination otherwise generates or causes to be generated ECS structure in the compression, ignition and/or combustion proces ⁇ .
  • any compound, which enhances the formation of ECS in the combustion proces ⁇ i ⁇ deemed to be an ECS compound any compound, which enhances the formation of ECS in the combustion proces ⁇ i ⁇ deemed to be an ECS compound.
  • Any chemical or mechanical mean ⁇ capable of causing fuel vapor fraction droplets or injected fuel particles to explode prior to combustion (including exploding outside the spray area) or to otherwise cause quick diffusion of the vapor fraction in the combustion area are preferred.
  • Such non-limiting ECS compounds capable causing fuel particle explosion include water, methanol, hydrogen peroxide, rape seed oil, and the like.
  • fuels containing water or other ECS compound by means of emulsions, additive, .co-solvent, ultra-sonic mixing or other method/combination are contemplated, such as aqueous gasoline ⁇ , die ⁇ el ⁇ , naptha ⁇ , jet aviation fuels, distillate fuels, alkylates, reformate ⁇ , and the like, are contemplated.
  • ECS compounds which are non-corro ⁇ ive and/or which do not adver ⁇ ely effect seals or elastomers are preferred.
  • corrosion inhibitor additive is contemplated.
  • a non-limiting example includes, "DC1 11" available from Du Pont used at the approximate concentrations of 20 to 30 ppm, although concentrations outside of these range ⁇ are acceptable.
  • Other known inhibitor ⁇ are contemplated.
  • ECS compounds employed in liquid fuels should have low melting points, below 32°F, -0°F, -20°F, - 40°F, -50°F, -60°F, -70°F, -80°F, -90°F, and most preferably below -100°F. Lower temperatures are contemplated if circumstances warrant.
  • Co-ECS compound and/or additives ⁇ uch as ethylene glycol monomethyl ether may be employed, if neces ⁇ ary. Again, the ECS compound' ⁇ causal increase in burning velocity and/or reduction of combustion temperature, like flash point or vapor pres ⁇ ure must be weighted against less than optimal melting point, which may be mitigated by other co-ECS compound, additive or co ⁇ solvent.
  • ECS compound not be toxic, or at least not highly toxic, or associated with adverse toxicity. It is also preferred that the compound be pumpable at low temperatures, have suitable ignition quality, and be thermally stable r although additives to correct poor thermal stability may be employed.
  • Preferred practice contemplates oxygenated ECS compounds. Maximizing oxygen of the compound is generally desirable. Oxygen contents may range from 0.0001 to 5.0, 8.0, 12.0, 15.0, 18.0, 20.0, 22.0, 25.0, 28.0, 30.0, 33.0, 35.0, 37.0, 40.0, 45.0, 50.0, 53.3, 60.0, 80.0 weight percent, or higher.
  • oxygen fuel In the preparation of ECS fuel ⁇ it is an object to also maximize oxygen fuel content. Beneficial results generally do not occur until approximately 0.05%, 1.0%, 1.5%, 2.0% or more oxygen is included. However, smaller concentrations are acceptable in co-fuel applications, including 0.001%. Desirable range is from 0.001 to 80.0% oxygen by weight.
  • ranges include 0.001 to 50.0%, 0.001 to 80.0%, 0.001 to 15.0%, 0.5% to 1.5%, 0.3% to 2.7%, 0.4% to 1.8%, 0.5% to 1.9%, 0.6% to 2.0%, 0.7% to 2.1%, 0.8% to 2.2%, 0.9% to 2.3%, 1.0% to 2.4%, 1.1% to 2.5%, 1.2% to 2.6%, 1.8% to 2.2%, 2.0% to 3.7%, 0.2% to 0.9%, 1.0% to 4%, 2.0% to 8.0%, 1.8% to 12%, 2.0% to 10.0%, 3.0% to 30%, 5.0% to 40%, 2.0% to 53%, oxygen by weight.
  • concentrations includes those greater than 0.5, 0.9, 1.4, 1.9, 2.4, 2.9, 3.4, 3.5, 4.2, 4.7, 5.2, 5.9, 6.3, 6.6, 7.4, 7.5, 7.8, 9.2, 10.1, 14.3, 18.4, 23.2, 36.3, or greater, weight percent oxygen.
  • Oxygen concentrations less than 0.1, 0.3, 0.7, 1.1, 1.2, 1.9, 2.0, 2.3, 2.7, 3.3, 3.7, 3.9, 5.1, 6.3, 8.2, 10.3, 15.3, 22.5, 32.6, 43.5, 48.3, 62.3, or less, oxygen by weight, are contemplated.
  • concentration ⁇ include both ECS fuels and ECS/co-fuel combinations.
  • oxygen concentrations will be significant. In initial co-fuel applications concentrations will be more modest. However, it is an object to include significant concentrations of oxygen which can aggressively react with the metallic, maximizing object of the invention. While desireable, ECS fuel ⁇ need not contain oxygen.
  • the preferred type and amount of metals contemplated by this invention require combustion be improved and/or pollutant ⁇ reduced. It is preferred that luminous vapor phase combustion occur, e.g. wherein 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.
  • Vapor phase burning is further characterized by the high burning rate and the presence of a luminous reaction zone that extends some distance from the metal's surface, wherein metallic oxide particles are formed in the submicron range. It is highly expansive combustion, yielding accelerated exhaust velocities.
  • the metallic is employed as a propellant or co-propellant.
  • Hydrogen content of the metallic and/or metallic containing fuel should be maximized, to the extent pos ⁇ ible. Thu ⁇ , metallic hydryl ⁇ or other ⁇ imilar compound ⁇ are de ⁇ ireable. Hydrogen containing ⁇ alts are also desireable.
  • a vapor phase method of combu ⁇ ting a metallic, ⁇ aid method comprises: introducing kinetic free radical ⁇ having enhanced combustion structure into a combustion chamber; igniting and combu ⁇ ting a flammable metallic or metal compound in pre ⁇ ence of ⁇ aid free radicals at temperature below said metal's oxide boiling point and preferably/optionally 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.
  • Example 8 The vapor phase method of example 39, wherein the exhaust ga ⁇ e ⁇ of said method travel at high velocity, exceeding 50, 52, 54, 56, 58, 60,- 62, 64, 66, 68, 70, 80, 90, 100, 120, 130, 140, 150, 160, 170, 200 cm/sec, or more ; and wherein said oxides are on average having particle sizes les ⁇ than 3.0, 2.5, 2.0, 1.5, 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.09, 0.05, 0.04, 0.02 micron ⁇ , or less.
  • the metal be introduced into the combustor a ⁇ a vapor, however solid, atomized, or particulate introduction is acceptable, ⁇ o long a ⁇ the object ⁇ of this invention are met.
  • the metallic may be introduced as a ⁇ olid.
  • hybrid application ⁇ it may be introduced as either a solid or liquid.
  • Contemplated metallics include all non-lead metal ⁇ and related compound ⁇ who ⁇ e co bu ⁇ tion product ha ⁇ negative high heat of formation. Contemplated metal ⁇ and/or metallic compound ⁇ with have high heat ⁇ of combu ⁇ tion or heating values are desired.
  • 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, pallium, rubibidium, sodium, tin, zinc, praseodymium, rhenium, salane, vanadium.
  • Applicant's metals may be organo-metallics or inorganic compounds.
  • Alkali Metals of IA, Alkaline Earths of 2A, the transition elements and metals of 3B, 4B, 5B, 6B, 7B, 8, IB, 2B, the Holgens of 7A, and 3A elements, inclusive of their compounds are contemplated.
  • - Transition metals and cyclomatic/cyclopentadienyl compounds, including carbonyls are expressly contemplated. Their preparation is set forth in U.S. Patents Nos. 2,818,416, 3,127,351, 2,818,417, 2,839,552 (incorporated by reference). Applicant has found that methyl cyclopentadienyl tricarbonyl groups to be effective.
  • Compounds including, non-limiting cyclomatic or cyclopentadienyl compounds that include metals or elements found in 4B, 5B, 6B, 7B, group 8 are particularly contemplated.
  • Metals and their non-limiting compounds found in 3A of the Periodic Table of Elements, particularly boron and aluminum are expressly contemplated.
  • Metals may be introduced into combustion with the ECS compound, or in a number of other ways, including via soluble compounds, mutual dispersents/ ⁇ olvent ⁇ , colloidal media, ⁇ u ⁇ pen ⁇ ion media, separate injection.
  • the holgens of 7A are contemplated with limitations on florine, clorine, or bromine use due to environmental and health concerns, e.g. hydroflorocarbons, etc.
  • the chalcogens of 6A, except oxygen are contemplated with limitation ⁇ on sulfur use due to environmental and health concerns.
  • Non-limiting examples of such organometallic include cyclopentadienyl methylcyclopentadienyl iron, ferrocene, methylferrocene, and butadiene iron tricarbonyl, butadiene iron tricarbonyl, dicyclopentadienyl iron and dicyclopentadienyl iron compound ⁇ ( ⁇ ee U.S.
  • a preferred cyclomatic manganese tricarbonyl is cyclopentadienyl manganese tricarbonyl.
  • a more preferred cyclomatic manganese tricarbonyl is methyl cyclopentadienyl manganese (MMT) .
  • Non-limiting examples of acceptable sub ⁇ titutes include the alkenyl, aralkyl, aralkenyl, cycloalkyl, cycloalkenyl, aryl and alkenyl groups.
  • Illustrative and other non-limiting examples cf acceptable cyclomatic manganese tricarbonyl antiknock compounds include benzyleyelopentadienyl manganese tricarbonyl; 1.2-dipropyl 3-cyclohexylcyclopentadienyl manganese tricarbonyl; 1.2- diphenylcyclopentadienyl 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- t
  • Routine te ⁇ ting will identify other metals, their compounds, and combinations meeting the criteria of
  • combu ⁇ tion temperatures also be greater than the metal's (or metallic compound's) boiling temperature.
  • Metallic concentration ⁇ will vary ⁇ ub ⁇ tantially. non ⁇ limiting examples include those varying from 0.001 to over 7.50 grams elemental metal/gal, 0.001 to over 10.00 grams elemental metal/gal, 0.001 to over 15.00 grams elemental metal/gal, 0.001 to over 20.0 grams elemental metal/gal., 0.001 to over 30.00 grams/elemental metal/gal., 0.001 to over 50.00 grams/elemental metal/gal.or more.
  • metallic concentrations equal to or greater than 1/64, 1/32, 1/16, 1/4, 3/8, 1/2, 5/8, 3/4, 1, 1.5, 2.0, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 5.0, 7.5, 10, 15, 20, 25, 26, 27, 30, 33, 35, 40.
  • elemental metal concentrations can be on the order of 100, 150, 200, 225, 250, 300, 400, 200 to 500, 600, 800 to 1000.0 grams/gal, especially in hypergolic conditions. Concentrations above these range ⁇ are al ⁇ o contemplated.
  • manganese ranges for more traditional co-fuel applications will generally range from about 0.001 to about 5.00 grams Mn/gal, 0.001 to about 3.00 grams Mn/gal, 0.001 to about 2.00 gram ⁇ Mn/gal, 0.001 to 1.00 gram ⁇ Mn/gal, 0.001 to about 0.50 gram ⁇ Mn/gal, 0.001 to 0.375 gram ⁇ Mn/gal, 0.001 to about 0.25 grams Mn/gal, 0.001 to 0.125 grams Mn/gal, 0.001 to 0.0625 grams Mn/gal, 0.034 to 0.125 grams Mn/gal of composition.
  • Other metallic or manganese concentrations include
  • manganese concentrations greater than 1.0% by weight of the fuel or approximately 25 to 33 grams/gal are al ⁇ o contemplated. In ga ⁇ olines, manganese concentrations greater than 1/64, 1/32, or 1/16 gr/gal are desireable.
  • Ranges vary depending upon the specific metallic, fuels, fuel weight, regulations, advance applications, thermodynamics, and the extent combu ⁇ tion ⁇ y ⁇ tem ⁇ are modified to enhance the accelerated low temperature high energy nature of Applicant' ⁇ invention.
  • Applicant' ⁇ metal ⁇ al ⁇ o include a full range of combu ⁇ tion cataly ⁇ ts including ferreous picrate, potas ⁇ ium ⁇ alt ⁇ , etc.
  • pota ⁇ ium salts are contemplated including those commercially mark ed by Shell Chemical, known as "SparkAid or SparkAde.”
  • Such salts may be employed in fuel ⁇ at 0.01, 0.4, 0.5, 0.75, 1.0, 2.0, 3.0, 4.0, 5.0 part ⁇ metallic per million fuel, 1.0 to 4.0 ppm metallic being contemplated, with concentration ⁇ less than 16.0 ppm metallic also contemplated.
  • potassium salt or ferrocene ranges vary from 0.10 to 8.0, 4.0 to 9.0, 5.0 to 12.0, 6.0 to 13.0, 7.0 to 14.0, 8.0 to 15.0 ppm metal per million, 9.0 to 16.0, 10.0 to 20.0, 11.0 to 22.0, 12.0 to 25.0, 13.0 to 30.0, 14.0 to 40.0, 15.0 to 50.0, 16.0 to 60.0, 17.0 to 80.0, 18.0 to 100.0 parts metallic or salt per million fuel.
  • potas ⁇ ium concentration ⁇ greater than 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0, 11.0, 12.0, 13.0, 14.0, 15.0, 16.0, 17.0, 18.0, 19.0, 20.0, 21.0, 22.0, 23.0, 24.0, 35.0, 26.0, 27.0, 28.0, 29.0, 30.0 ppm metal (or ⁇ alt) are expre ⁇ ly contemplated and desireable, and depending upon ECS chemistry and mechanical means employed, said potas ⁇ ium concentrations or greater concentrations can be employed ab ⁇ ent adver ⁇ e metallic oxide formation.
  • Applicant's fuels will contain that amount of at lea ⁇ t one Mn and/or other non-lead metallic, which con ⁇ titute ⁇ a combustion improving amount consi ⁇ tent with the fuel compo ⁇ ition, stoichiometry, EC chemisty, combustion system, efficiencies and power desired, as well as legal and/or environmental considerations.
  • Applicant's fuel also be absent metal, e.g. modified fuels. That is, Applicant's invention, by accelerating burning velocity and/or reducing combustion temperatures by fuel substituent tailoring, chemical and/or mechanical means set forth herein or in co-pending Applications, can be employed absent a metallic.
  • a composition comprised: of an ignition or combustion improving amount of a potas ⁇ ium salt (for example Shell Chemical Corporation's product markeded as SparkAid) ; and at least one organo-manganese compound; and at least one ECS compound.
  • a potas ⁇ ium salt for example Shell Chemical Corporation's product markeded as SparkAid
  • metal ⁇ herein have oxides whose heats of formation are negative, and should exceed (e.g. be more negative) about -1,000, -10,000, - 50,000, -100,000 to -150,000 gr calories/mole. More preferred are those exceeding -200,000, -225,000, -250,000, -275,000, -300,000, -325,000 -350,000, - 400,000 gr calories/mole., and greater (more negative) .
  • the metal be of a low relative molecular weight.
  • Acceptable molecular weights of Applicant's metals include those le ⁇ than 100, 80, 72, 70, 60, 59, 55, 36, 34, 32, 30, 28, 26, 24, 22, 20, 18, 16, 14, 12, 10, 8, 6, or 4; more acceptable include those less than 59, 56, 32; de ⁇ ireable molecular weights are those less than 27, 24; more desireable are those les ⁇ than 15; and even more de ⁇ ireable are those less than 14; with the most desireable being those les ⁇ than 6.
  • non-lead metallics have been set forth in the specification. Additional non- limiting examples of non-lead simple binary metallic compounds. Ternary and higher compound ⁇ including salts are contemplated. Salts of ternary hydroxy acids are contemplated. Metallic perchlorates, ⁇ ulfate ⁇ , nitrates, carbonates, hydroxides, and others, are contemplated. Metal hydroxy compounds are desireable. Contemplated ⁇ alts also include acid salts containing replaceable hydrogen.
  • oxygenated containing metallic compounds including oxygenated organo metallic compound ⁇ .
  • metallic compounds which themselve ⁇ are ECS compound ⁇ .
  • Non-limiting examples would include lithium, iodine, boron based ECS compounds.
  • Contemplated oxygenated organo metallic compounds include metallic methoxy, dimethoxy, trimethoxy, ethoxy, diethoxy, triethoxy, oxalate, carbonate, dicarbonate, tricarbonate, and similar structure, including mixture thereof.
  • Such oxygenated organo-metallic compounds may be employed with or absent additional ECS compound (e.g. DMC) .
  • this invention employs organo metallic compounds containing oxygen, including mixture of compound, as neat fuel, with additional ECS compound, a co-fuel, or additional metallic, optional.
  • a metallic compound including homologue or analogue having a structure or structure similar to M1-OCH3, wherein Ml is a metallic having a valence of one or optionally having a valence greater than one, wherein the exce ⁇ s valence is occupied by a double bond oxygen and/or one or more methyl, hydrogen, hydroxy, ethoxy, carbethoxy, carbomethoxy, carbonyl, carbonyldioxy, carboxy, methyoxy, isonitro, isonitroso, methylenedioxy1 radicals, and/or combination thereof; a metallic compound having a structure of M2-[OCH3]2, wherein M2 is a metallic having a valence of two or optionally having a valence greater than two wherein the exces ⁇ valence are occupied by a double bond oxygen and/or by one or more methyl, hydrogen, hydroxy, ethoxy, carbethoxy, carbomethoxy, carbonyl,
  • M1-M4 may contain one or multiple metals, being either the same or differing metallic.
  • Non-limiting example of said structure containing a multiple same metal includes tetramethoxydiborine [(CH30)4B2].
  • Additional contemplated oxygenated-organo metallic structure includes Ml-0(CO)0-M2, wherein Ml or M2 are the same or different metals having a valence of l or optionally valences greater than one wherein excess valence is occupied by additional metal, and/or Ml or M2 are sub ⁇ tituted for a ⁇ ingle or double bond oxygen, and/or by one or more methyl, hydrogen, hydroxy, ethoxy, carbethoxy, carbomethoxy, carbonyl, carbonyldioxy, carboxy, methyoxy, isonitro, isonitro ⁇ o, methylenedioxyl radical and/or combination thereof.
  • Ml may be ⁇ ub ⁇ ituted for single bond oxygen and/or by one or more methyl, hydrogen, hydroxy, ethoxy, carbethoxy, carbomethoxy, carbonyl, carbonyldioxy, carboxy, methyoxy, isonitro, isonitro ⁇ o, or methylenedioxyl radical.
  • Non-limiting example ⁇ include lithium carbonate [Li202 (CO) ] , pota ⁇ ium carbonate [k202 (CO) ] , ⁇ odium carbonate, cesium carbonate, copper carbonate, rubidium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potas ⁇ ium hydrogen carbonate, potassium sodium carbonate, and the like. It is contemplated that C3 and C4 plus ethers may have metallic structure.
  • M'l-CH2-CH2-0-CH2-CH2-M'2 structure is contemplated wherein M'l and M'2 may be same or different metallic or wherein M'l or M'2 may be hydrogen or atom or radical (similar to those above) with one valence.
  • contemplated structure include metallic ketone, ester, alcohol, acid, and the like.
  • Non-limiting examples include M'l-C-OH3, wherein M'l is one or more metallic comprising valence of 3;
  • Other structure include M'i-C204, wherein M'l has a valence of 2.
  • M1-C-C-0-C-C-M2 structure is also contemplated wherein Ml and M2 may be same or different metallic or wherein M2 may be hydrogen or atom of one valence.
  • said oxygenated organo ⁇ metallic compounds have the fuel properties set forth above including those for ECS compounds, e.g. higher heats of vaporization, high burning velocities, decomposition characteristic (e.g. decomposition at post ignition pre- combustion temperatures into enhanced combu ⁇ tion or free radicals structure) , be thermally stable at normal handling temperatures, etc.; and have high heat and energy releasing characteristics of metals, etc..
  • Applicant's metallics be incorporated into liquid fuel sy ⁇ tems by means of mutual solvents, as required. Or alternatively, may be introduced into the combustor/combu ⁇ tion chamber by seperate means, including liquidification or gasification. Applicant's neat oxygenated organo-metallics should be relatively inexpensive to manufacture on a mass production basis.
  • a method and composition of reduced temperature vapor phase combustion comprising: i) introducing a fuel vapor having an average particle size not exceeding 70, 60, 50, 50, 40 microns, or less, into an air breathing combustion system,- said fuel vapor containing 1) at least one fuel soluble compound or element selected from group of transition metals, alkine metals, alkine earths, halogens, group IIIA elements and mixture, whose oxide's heat of formation is negative and optionally includes or exceeds (e.g.
  • ECS compound is more negative than) about -10,000, -20,000, - 30,000, -40,000, -50,000, -100,000, -150,000, -200,000, - 225,000, -250,000, -300,000, -350,000, -400,000 gr calories/mole, and said element or compound's heating value optionally exceeds 2,000, 4,000, 4,500, 5,000, or more, Kcal/kg (see below) , and 2) at least one ECS compound characterized as having a latent heat of evaporation exceeding about 110, 120, 125, 130, 135, 140, 145, 148,
  • ⁇ aid fuel vapor optionally having a maximum ⁇ park energy of 0.3, 0.25, 0.22,0.2, 0.19, 0.18, 0.17, 0.15. 0.13, 0.10, 0.08, 0.05 mJ, or le ⁇ , and whereup ignition unburned fuel vapor decomposes into reactive high kinetic energy free radicals having a heat of formation at 25°C of less than 150, 120, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 0, or negative, Kcal.
  • said free radicals represent a gram weight .equivalent to elemental transition metal, alkine metal, alkine earth, halogen, group IIIA element or mixture, an amount equal to or exceeding the ratio of 1:20, 1:10, 1:5, 1:2, 1:1, 1.5:1, 2:1, 3:1, 5:1, 10:1, 15:1, 20:1, 30:1, 50:1, 75:1, 100:1, 150:1, 200:1, 250:1, 500:1, 1,000:1, 5,000:1, 10,000:1.
  • said free radicals optionally dis ⁇ ociated free radical ⁇ (non limiting example ⁇ include OH, CN, CH, and NH radical ⁇ with ⁇ ub ⁇ equent rea ⁇ ociation continuing combu ⁇ tion process) ; iii) diffusing said radicals ahead of the flame front in a manner sufficient to cause luminous vapor phase combustion.
  • Example 10 above wherein said combustion is characterized as increasing exhaust gas velocities at below 1400°F, 1390°F, 1375°F, 1350°F, 1325°F, 1300°F, 1275°F, 1250°F,
  • Example 10 being free or essentially free of polynuclear aromatics, lead, sulfur, barium, chlorine, or florine, and optionally free or essentially free of chlorinated solvent ⁇ , bromine and/or phosphorous, or any chemical contributing to or. causing hydrofluorocarbons, fluorocarbons, chlorofluorocarbons, hydrochlorofluorocarbons.
  • composition of example 10, wherein the ratio of ECS compound to metallic compound as mea ⁇ ured in gram ⁇ of compound or alternatively reactive radical ⁇ to gram ⁇ of elemental metal is approximately equal to or less than 1:1000 to 1:1, 1:500 to 1:1, 1:100 to 1:1, 1:50 to 1:1, 1:40 to 1:1, 1:30 to 1:1, 1:20 to 1:1, 1:10 to 1:1, 1:5 to 1:1, 1:4 to 1:1, 1:3 to 1:1, 1:2 to 1:1, 3:5 to 1:1, 2:3, 1:1, 1:1 to 3:2, 1:1 tO 5:3, 1:1 to 2:1, 1:1 tO 7:3, 1:1 to 3:1, 1:1 to 4:1, 1:1 to 5:1, 10:1, 1:1 to 15:1, 1:1 to 20:1, 1:1 to 30:1, 1:1 to 50:1, 1:1 to 75:1, 1:1 to 100:1, 1:1 to 150:1, 1:1 to 200:1, 1:1 to 250:1, 1:1 to 500:1, 1:1 to 1000:1, 1:1 to 5000:1, 1:1 to 10000:1, or other ratio optimizing the reaction.
  • ECS compound is DMC and metal optionally Mn.
  • the methods or composition ⁇ above comprising: An ECS compound (DMC) and a metal (organo-manganese) compound, whereby the ratio of grams ECS compound to grams elemental metallic range from approximately equal to or less than 100,000:1 to 1:1, 10,000:1 to 1:1, 5,000:1 to 1:1, 2,500:1 to 1:1, 2,000:1 to 200:1, 3,000:1 to 1,000:1, 2,500:1 to 500:1, 2,000:1 to 50:1; 1,500:1 to 100:1, 1250:1 to 1:1, 1000:1 to 1:1, 750:1 to 50:1, other acceptable ranges of 500:1 to 20:1, 250:1 to 15:1, 200:1 to 3:1, 50:1 to 5:1; 20:1 to 10:1; 20:1 to 1:1; and 15:1 to 1:1.
  • DMC ECS compound
  • metal organo-manganese
  • Individual concentrations include 10,000:1; 6000:1, 5500:1, 5000:1, 4800:1, 4500:1, 4000:1, 3800:1, 3600:1, 3400:1, 3200:1, 3000:1, 2800:1, 2600:1, 2400:1, 2200:1.
  • ECS to metallic ratios may be higher or lower than those set forth above.
  • An ECS fuel composition comprising: An ESC compound, preferrably dimethyl carbonate (DMC) , at least one fuel soluable metallic (preferrably a cyclomatic manganese compound) , wherein the ratio of ECS compound to elemental metal is equal to or less than 2,500 parts to one, equal to or less than 600 parts to one, equal or les ⁇ than 400:1, 300:1, 175:1, 150:1, 125:1, 100:1, 75:1, 60:1, 50:1, 40:1, 30:1, 20:1, 10:1.
  • DMC dimethyl carbonate
  • a fuel soluable metallic preferrably a cyclomatic manganese compound
  • An ECS fuel composition comprising: an ECS compound (preferrably dimethyl carbonate) ,- at least one fuel soluable transition metal, alkine metal, alkine earth, halogen, group IIIA element, or mixture, (preferrably a cyclomatic manganese compound) ,- optionally a co-fuel; wherein the ratio of grams dimethyl carbonate to grams elemental metal is within 10,000:1 to 1:500, 2,500:1 to 1:100, 1200:1 to 1:1, more preferrably less than 600:1 to 1:1 (or other ratio maximizing attributes of combustion); optionally: a salt, a VPR or FPI co-solvent or salt, an 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, anti-hydrolysi ⁇ agent, pH control additive, hydro ⁇ copic, hydroly ⁇ i ⁇ control or prevention mean ⁇ , mean ⁇ to increase flash
  • Example 17 A fuel composition, optionally of composition 15, comprising: an aviation gasoline base, a minimum octane or performance number of 87 or 130 (ASTM 909) , a distillation fraction wherein the sum of the T-10 plus T-50 ⁇ fractions are 307°F, the T-40 temperature is 167° F and the T-90 temperature is less than 250°F, with the fuel sulfur content a maximum of 0.05 wt%, or sulfur free, and a combustion improving amount of an ECS compound (preferrably DMC) ,- said resultant fuel' ⁇ latent heat of vaporization exceed ⁇ 120, 125, 130, 135, 140, 142, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 152, 152, 153, 154, 155, 156, 157, 158, 159, 160, 162, 165 BTU/lb; and whereby re ⁇ ultant fuel optionally ha ⁇ a laminar burning velocity equal to or in
  • Example 18 A fuel composition, optionally comprising of composition 15 above, comprising: an ECS compound (preferrably DMC) representing 0.01% to 10.0% oxygen by wt in the fuel, a compound or element containing a transition metal, alkine metal, alkine earth, halogen, group IIIA element or mixture in an concentration of 0.001 to about 1.0, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5,.
  • ECS compound preferrably DMC
  • DMC a compound or element containing a transition metal, alkine metal, alkine earth, halogen, group IIIA element or mixture in an concentration of 0.001 to about 1.0, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5,.
  • said fuel optionally characterized as having one or more of the following: a density ranging from about 880 to 800 kg/m 3 (optionally exceeding 880, 900, 910, 920, 930, 950, or more, kg/m 3 , visco ⁇ ity ranging from 2.5 to 1.0 cSt at 40°C, cetane index of 40 to 70, an aromatic content by vol.
  • a fuel compo ⁇ ition optionally including example 15, compri ⁇ ing: an ECS compound (preferrably DMC) repre ⁇ enting 0.01% to 40.0% or 0.01% to 2.0%, 3.0%, 4.0%, 5.0%, 7.5%, 10.0%, 15.0%, 20.0%, 25.0%, 30.0%, 35.0%, or more, oxygen by wt in the fuel, a combu ⁇ tion improving amount of compound or element containing a tran ⁇ ition metal, alkine metal, alkine earth, halogen, group IIIA element or mixture, in a concentration of 0.001 to about 1.5, 2.0, 2.5, 3.0, 4.0, 5.0, 7.5, 10.0, 15.0, 20.0, 30.0, or more, gr/gal, a die ⁇ el co-fuel; wherein ⁇ aid fuel i ⁇ optionally characterized a ⁇ having one or more of the following: an API range of about 41.1 to 45.4, optionally a ⁇ ulfur content not exceeding 500, 300, 250, 200, 150, 100,
  • IBP IBP of approximately 365°F +/- 150°F
  • 95% fraction ranging from 460°F to 540°F
  • a bunsen laminar burning velocity of at least 38 cm/sec, a latent heat of vaporization of at lea ⁇ t 105 BTU/lb
  • said method characterized in achieving reduced particulate emissions or improved fuel economy compared to co-fuel alone.
  • a fuel composition comprising for an aviation gasoline engine comprising: DMC representing 0.01% to 10.0% oxygen by wt in the fuel, at least one fuel soluble transition metal, alkine metal, alkine earth, halogen, group IIIA element or mixture in a concentration of 0.001 to about 2.5, 5.0, 10.0, 15.0, 20.0 gr/gal, an aviation ga ⁇ oline co- fuel; said fuel optionally characterized as having one or more of the following: a minimum knock octane number of 80, or 100 and minimum performance number of 87, or 130, containing lead, a max T10 distillation temperature of 75°C, a minimum T40 temperture of 75°C, a maximum T50 temperature of 105°C, a maximum T90 temperature of 135°C, a maximum end temperature of 135°C, where the sum of the T10 and T50 temperatures is a minimum of 135°C, a maximum sulfur content of 0.05 wt%, optionally a minimum net heat of combustion les ⁇ than 18,720, 1
  • a fuel composition for an aviation gasoline engine comprising: DMC representing 0.01% to 15.0%, or more, oxygen by weight of a fuel, an organo manganese representing about 0.001 to 0.5, 0.625, 0.75, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 10.0, 15.0, 20.0, or more, gr Mn/gal of fuel, and an ASTM or other aviation co-fuel having a minimum heat of combustion of about 18,000, 18,500, or 18,720 BTU/lb; wherein said resultant fuel has heat of combustion lower than 18,000, 17,950, 17,750, 17,500, 17,000, 16,500, 16,000, 15,500, 15,000, 14,500, 14,000, 13,500 BTU/lb, due to dilution effect of DMC; said composition characterized as increasing flight range of aviation engine combusting said fuel compared to higher heat of combu ⁇ tion aviation co-fuel alone.
  • a jet turbine fuel compo ⁇ ition optionally of composition 15 above, comprising: an ECS compound (preferrably DMC) representing 0.01% to 40.0% oxygen by wt in the fuel, a compound or element containing a , transition metal, alkine metal, alkine earth, halogen, group IIIA element or mixture, in a concentration of 0.001 to 5.0, 10.0, 20.0, 50.0, 100.0, 150.0, 200.0 or 250.0 gr/gal, and an aviation jet turbine co-fuel,- wherein said fuel is characterized as having a total aromatic volume concentration not exceeding 25% or 22%, a maximum sulfur content not exceeding 0.3, 0.2, 0.1 weight percent or sulfur free, a maximum T-10 temperature of 205°C, a maximum final boiling point temperature of 300°C, 280°C, or 260°C; optionally: a minimum flash point of 38°C, a density range of about 751 to 840 at 15°C, kg/m 3 , or optionally exceeding 840, 850, 860,
  • a No. 2 fuel oil compo ⁇ ition optionally of compo ⁇ ition 15 above, comprising: an ECS compound (preferrably DMC) representing 0.01% to 40.0% oxygen by wt in the fuel, a compound or element containing a transition metal, alkine metal, alkine earth, halogen, group IIIA element or mixture, a No.
  • a fuel composition comprising: an ECS fuel having lower heating value than co-fuel; said ECS fuel optionally representing at least 0.01, 0.5, 1.0, 1.5, 2.0, 2.1, 2.2, 2.5, 2.7, 3.0, 3.5, 3.7, 4.0, 4.5, 5.0, 8.0, 10.0, 12.5, 15.0, 18.0, 20.0, 22.0, 25.0, 30.0, 35.0, 38.0, 40.0, 45.0, 49.0, 50.0, 51.0, 55.0, 60,0, 65.5, 70.0, 75.0, 80.0, 85.0, 90.0, 95.0, 99.0 volume percent of the composition; a co- fuel as set forth herein or in my co-pending International Applications No. PCT/US95/02691, No.
  • co-fuel optionally comports with industry and/or ASTM specification standard ⁇ ,- optionally having T- 90, T-50, T-10, BV, or LHV modification/adju ⁇ tment a ⁇ disclosed herein or in said co-pending Applications; said ECS ⁇ co-fuel optionally containing: additive, salt, co ⁇ solvent disclosed herein or in my co-pending International Applications No. PCT/US95/02691, No.
  • PCT/US95/06758 optionally a latent heat of vaporization exceeding 100, 110, 115, 120, 125, 130, 135, 140, 142, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 152, 152, 153, 154, 155, 156, 157, 158, 159, 160, 162, 165 BTU/lb; optionally a laminar burning velocity equal to or in excess of 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 65 cm/sec; ⁇ aid ESC/co- fuel optionally having a heating value less than co-fuel alone and less than industry or ASTM fuel standard ⁇ , or le ⁇ than 43.0, 42.8, 42.5, 42.0, 41.5, 41.0, 40.5, 40.0, 39.0
  • Example 25 The Example of 24, wherein the ECS fuel represents 0.01 to 99.0% by volume of the combined ECS/co-fuel combination, an ASTM or other co-fuel representing balance,- wherein resultant fuel's heat of combustion or BTU content/lb, as measured by traditional methods, is less than the co-fuel alone,- and whereby said combined fuel's work potential, fuel economy, flight range, or thru ⁇ t is no les ⁇ than co-fuel; or optionally at least 0.5% greater than co-fuel alone.
  • ECS ⁇ co-fuel compositions characterized as being absent ECS compound, or absent ECS compound and metallic (ECS fuel component) ; said fuel being further characterized a ⁇ having elevated LHV and/or BV compared to minimum indu ⁇ try or ASTM ⁇ pecification ba ⁇ e fuel or co-fuel, alone.
  • Applicant's ECS/co-fuels may have calorific values approximately 0.01, 0.25, 0.5, 0.75, 1.0, 1.15, 1.25, 1.5, 1.75, 2.0, 2.5, 3.0, 5.0, 7.5, 10.0, 12.5, 15.0, 17.5, 20.0, 22.5, 25.0, 27.5, 30.0, 32.5, 35.0, 37.5, 40.0, 42.5, 45.0, 47.5, 50.0, 52.5, 55.0, 57.5, 60.0, 62.5, 65.0, or more, percent, below minimum existing industry, government or ASTM heat -or calorific ' standard ⁇ .
  • the calorific content of certain ECS compound ⁇ are: BTU/lb ® 60°F BTU/ ⁇ al® 60°F
  • a ⁇ can be ⁇ een ECS compound ⁇ have reduced heating capacity a ⁇ compared to ga ⁇ oline. But becau ⁇ e Applicant' ⁇ combu ⁇ tion compo ⁇ ition ⁇ and method ⁇ increa ⁇ e exhaust velocities, greater amounts of work can be accomplished with same or lower BTU fuels. This represents a very significant departure from the prior art understanding of fuel combustion.
  • Example 27 An ECS/Co-fuel combination, wherein said ECS fuel has lower BTU content than co-fuel and wherein combined ECS/Co- fuel has lower BTU content than co-fuel alone; said fuel characterized as having greater work potential, fuel economy, flight range, power, or thrust compared to co-fuel alone.
  • Applicant' ⁇ co-fuel ⁇ are generally carbonaceous or hydrogenous or other compound, or hydrocarbonaceous, and/or other compounds based, including mixture, fuels capable of combustion.
  • a detailed discription of Applicant's co-fuels is set forth in my co-pending International Applications No. PCT/US95/02691 and No. PCT/US95/06758, and incorporated herein by reference.
  • Modified Fuel modified fuels
  • ECS fuels e.g. those fuels with improved LHV, BV, distillation characteristics, and/or other structure
  • Modified fuels namely those fuels with improved LHV, BV, distillation characteristics, and/or other structure, are not necessarily contemplated in combination with an ECS compound or metallic.
  • a modified fuel may be subsituted for co-fuel.
  • co- fuels may be employed as minority, substantial minority, majority, or sub ⁇ tantial majority con ⁇ titutent in a ECS/co- fuel combination.
  • the ratio of ECS fuel to co-fuel may vary from 1000:1, 100:1, 90:1, 75:1, 50:1, 40:1, 30:1, 25:1, 20:1, 15:1, 12:1, 10:1, 8:1, 6:1, 5;1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:10, 1:15, 1:20, 1:40, 1:50, or 1:100. it is an expres ⁇ object to maximize total ESC fuel vapor ⁇ derived from the ECS/co-fuel combination.
  • the ESC vapor may repre ⁇ ent 0.001 to about 0.5, 1.0, 1.2, 1.5, 1.7, 2.0, 2.1, 2.5, 3.0, 3.4, 3.5, 3.7, 4.0, 4.2, 4.7, 5.0, 7.0, 9.0, 10.0, 12.0, 15.0, 20,0. 25.0, 30.0, 35.0, 40.0, 45.0, 50.0, 55.5, 60.0, 70.0, 80.0, 90.0, or 99.999 mass percent of the composition.
  • the ECS fuel component will repre ⁇ ent a minority component due to existing fuels, distribution and combustion system ⁇ .
  • Applicant's ECS fuel, co-fuel or ECS/co-fuels when employed in existing system ⁇ meet ASTM, government and/or industry requirements for the co-fuel, with minimum heats of combustion optional.
  • ECS/co-fuels may need adjustment or tailoring to meet minimum ASTM and/or government standard ⁇ . For example, if an ECS/co-fuel mu ⁇ t meet minimum ASTM heat ⁇ of combu ⁇ tion and DMC i ⁇ ECS compound, then high calorific components may be required. In other cases, the base co-fuel may be tailored so that the addition of ECS fuel does not avoid ASTM or government specification ⁇ .
  • Applicant's preferred co-fuels are generally traditional fuels, but include fuels constructed to enjoy high burning velocities or higher latent heats of evaporatization than conventional or reformulated fuels. See my co-pending International Application ⁇ No. PCT/US95/02691 and PCT/US95/06758 incorporated by reference and below.
  • Applicant' ⁇ co-fuel ⁇ and ECS/co-fuels may be tailored or constructed to reduce or control T-90, T-50 or T-10 distillation temperatures to reduce LHV's.
  • Applicant' ⁇ co-fuels and ECS/co-fuels are typically constructed to enjoy low or extremely low combustion emission ⁇ .
  • co-fuels be formulated, and/or ECS/co-fuel combinations be formulated or constructed to reduce to the maximum extent pos ⁇ ible emi ⁇ ion ⁇ of NOx, CO, C02, HC' ⁇ , particulate ⁇ , toxic ⁇ , reactive ozone forming precursors, polynuculear aromatics, benzene, butadiene, formaldehyde, acetaldehyde, regulated emission ⁇ , unregulated emi ⁇ ion ⁇ recognized as potentially harmful, and/or any cancer causing or environmental harming substance, either now known or identified in the future.
  • construction of base fuels need be tempered by the amerliorate emis ⁇ ion characteri ⁇ tics of ECS fuels. Thus, higher concentration of hereto beleived hazardous components may be acceptable.
  • Appliant's co-fuel ⁇ and/or ECS/co-fuel ⁇ be formulated to reduce particulate emission ⁇ to the greatest extent possible. It is desireable average particlate size be no greater than 10.0, 7.5, 6.0, 5.0, 3.0, 2.5, 2.0, 1.5, 1.0, or 0.5 microns, or smaller. It is further an object to to reduce particulates to the maximum extent pos ⁇ ible. Higher BV's reduce particulate ⁇ , NOx emis ⁇ ions. Reduced concentrations of aromatics also reduce particulates.
  • Applicant's co-fuel and ECS/co-fuels may contain reduced amounts of aromatics.
  • Aromatic volume concentrations normally will range from or less than 55, 50, 45, 42, 40, 37, 35, 30, 27, 25,- 20, 18, 17, 16, 15, 14, 13, 12, 10, 9, 8, 7, 6, 5, 4, 3, 1 volume percent, or aromatic free. Ranges less than 40, 35, 30, 27, 25, 23, 20, 19, 18 percent, or les ⁇ , are more desireable. As noted, it i ⁇ a practice to reduce aromatic concentrations when ever practical.
  • density exceeding 775 to 840, 800 to 880, or exceeding 835, 840, 850, 860, 870, 880, 885, 890, 895, 900, 950, 1,000, 1,050, 1,100, 1,150, 1,200, or more, kg/m 3 are expres ⁇ ly contemplated, Moderate, low and to very low den ⁇ itie ⁇ are also contemplated so long as the increased burning velocity object of instant invention is accomplished.
  • the visco ⁇ ity of Applicant' ⁇ co-fuel ⁇ and ECS/co-fuel ⁇ should generally meet acceptable standards. It is important that highly viscou ⁇ fuels be properly atomized to assure vapor phase combustion. Applicant's invention, however due to the vise breaking features of certain ECS compounds, particularly DMC, permits usage of highly viscous fuels, which might otherwise might be unacceptable.
  • co-fuels may have viscositie ⁇ at the upper end of industry standards or visco ⁇ ities above ASTM, government or industry requirement ⁇ .
  • Jet A co-fuel have a visco ⁇ ity greater 6.0, 7.0, 8.0, 8.1, 8.2, 8.5, 9.0, 9.5, 10.0, 12.0, 15.0, 16.0, or more, mm 2 / ⁇ L at -20°C (ASTM 445) , or greater than 13.5, 14.0, 14.5, 15.0, 15.5, 16.0, 17.0, 18.0, 19.0, 20.0, 21.0, 23.0 Cs at -30 F; or a gas oil turbine co-fuel have a maximim kinetic viscosity at 40°C exceeding 1.5, 1.7, 2.0, 2.4, 2.6, 3.0, 4.0, 5.0, 7.0, or greater, mm 2 /s (ASTM D 445) for No.
  • l-GT or exceeding 2.5, 3.0, 3.5. 3.8, 4.1, 4.2, 4.5, 5.0, 6.0, or more, mm 2 /s (ASTM D 445) for No. 2-GT; or a diesel fuel oil co-fuel have a maximum kinetic vi ⁇ cosity at 40oC exceeding 1.2, 1.8, 2.0, 2.4, 2.6, 3.0, 4.0, 5.0, 6.0, 7.0, or greater, mm 2 /s (ASTM D 445) for low sulfur or regular No. l-D, or exceeding 3.3, 3.6. 3.9, 4.1, 4.2, 4.5, 5.0, 6.0, 7.0, 8.0, 9.0, or more, mm 2 /s (ASTM D 445) for low sulfur or regular No.
  • a fuel ECS/co-fuel composition of all above examples wherein said co-fuel's visco ⁇ ity exceed ⁇ maximum permissible ASTM, indu ⁇ try or government ⁇ tandard ⁇ ; and where ECS/co-fuel combination i ⁇ characterized as meeting ⁇ ame ASTM, industry or government standards.
  • auto ignition temperatures of Applicant's ESC fuels, ECS/co-fuel combinations, and/or Applicant's reformulated co-fuels meet acceptable ASTM or industry standards. Tailoring of fuel components is contemplated as required as required to meet such standard ⁇ .
  • ECS Fuel in ECS/co-fuel combinations tends to reduce spark ignition delay.
  • Optimizing combination fuel combu ⁇ tion may require reductions in spark advances, which are expressly embodied herein.
  • a method of operating an engine employing an ECS/co- fuel combination (consistent with the example composition ⁇ herein) ,- ⁇ aid method characterized as combusting said fuel in a spark ignited engine, combustor, or other engine, including jet, turbine engine, wherein ignition delays are -68- reduced compared to co-fuel alone by about least 0.001 to 0.5, 0.01 to 2.0, 0.01 to 3.0, 0.01 to 5.0, 0.01 to 7.0, 0.01 to 8.0, 0.01 to 10.0, 0.01 to 15.0, 0.01 to 20.0, 0.01 to 25.0, 0.01 to 30.0, 0.01 to 35.0, 0.01 to 40.0, 0.01 to 45.0, 0.01 to 50.0, 0.01 to 55.0, 0.01 to 60.0, 0.01 to 65.0, 0.01 to 70.0, 0.01 to 75.0, 0.01 to 80.0, 0.01 to 85.0, 0.01 to 90.0, percent or more,- and wherein spark advance, if applicable, is adjusted accordingly.
  • Example 29 wherein the air fuel ratio is reduced by at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70%, or more, compared to co-fuel alone,- alternatively air-fuel ratios including those of approximately 5.85 to 6.45, 6.45 to 8.03, 7.55 to 10.45, 8.85 to 12.5.
  • a method of combusting an ECS/co-fuel wherein the engine is an internal combustion engine and the compression ratio of the engine is at least 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, 15.0, 15.5, 16.0, 16.5, 17.0, 17.5, 18.0, 18.5, 19.0, 19.5, 20.0, 22.0, 24.0, 25.0, 30.0, 35.0, 40.0, 50.0, or more.
  • Non-limiting examples of Applicant's co-fuels include any carbonaceous, hydrogenaceous, hydrocarbonaceous or non- hydrocarbonaceou ⁇ fuel, solid, liquid, gaseou ⁇ fuels, including alternative fuel, hydrogen, petroleum gas, liquefied petroleum gas, LPG-propane, LPG-butane, natural gas, natural gas liquids, methane, ethane, propane, n- butane, propane-butane mixture, fuel methanol, e.g.
  • M 80, M 90, or M 85 fuels fuel ethanol, biomass fuels, vegetable oil/ester fuels, rap seed methyl ester, soybean fatty acid esters, aqueous carboneou ⁇ fuel ⁇ (including aqueou ⁇ ga ⁇ olines, napthas, fuel oils, and diesels, e.g. Gunnerman A-55/D-55) , automotive gasolines (meeting ASTM standards) aviation gasoline fuels, including grade 80, grade 100, grade 10011 (meeting ASTM ⁇ tandards) , conventional automotive gasolines, reformulated gasolines (meeting U.S.
  • the vapors from an ECS fuel or a combined ECS/co-fuel powers a engine having a di ⁇ placement equal to or exceeding 150, 180, 200, 220, 270, 300, 320, 330, 350, 355, 360, 400, 444, 457, 480, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 2000, 2200, 2400, 2600, 2800, 3000, 3500, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 15000, 20000, 25000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000 cubic inch ⁇ or equivalent, or larger engine, under moderate to moderately high to high load condition ⁇ , (e.g.
  • the compo ⁇ ition ⁇ , vapor compo ⁇ itions above combusted engine or combustor selected from group consisting of rocket engine, Brayton cycle engine, gas oil turbine, aviation jet turbine, diesel (direct injection, turbo charge, lean burn, swirl, varible valve timing and lift) , marine, locomotive, aviation gas engine, gasoline/automotive engine ⁇ (non-limiting examples include low emission, ultra low emission, variable-valve timing and lift, direct fuel injection, three-way catalyst systems, lean burn engine ⁇ ) , oil burner, re ⁇ ide burner, oil furnace, high performance burner ⁇ (for example with flame envelope ⁇ with heat relea ⁇ e rates of 10,000,000 BTU/ft 3 -hr) , gas burner, gas furnace, internal compression engine, spark- ignited internal combustion engine, lean burn, fast burn, external combustion Stirling or Rankine engine, Otto cycle engine, Miller cycle, two stoke, four stroke, or catalyst system.
  • rocket engine Brayton cycle engine
  • gas oil turbine aviation jet turbine
  • diesel direct injection, turbo charge,
  • Applicant contemplates ASTM or other industry limits, if applicable. Absent such lim t ⁇ , pH level ⁇ will not exceed acceptable limits based upon fuel and combustion system constraints.
  • Applicant's modified or co-fuels contain neces ⁇ ary additives as set forth herein or in my co-pending International Applications No. PCT/US95/02691 and No. PCT/US95/06758
  • Applicant's hydrocarbon co-fuels, ECS ⁇ co- fuel ⁇ , modified fuel ⁇ be constructed or formulated to enjoy the maximum latent heats of vaporization ("LHV") practical, in light of environmental and industry considerations. It is a further embodiment that Applicant's co-fuels or modified fuels (see below) be constructed to have LHV's greater than existing ASTM, conventional, or reformulated fuels (herein unadjusted "base fuel”) . In other words, one of the bench mark of Applicant's invention is increasing LHV's above those otherwise present in fuels on date of this invention.
  • Applicant ha ⁇ di ⁇ covered that thre ⁇ hold LHV improvement ⁇ will vary greatly depending upon the fuel composition, type of combustion system.
  • Applicant' ⁇ ba ⁇ e fuels are ASTM, industry or equivalent fuels on date of this invention.
  • heavier fuels e.g. diesel, jet aviation, gas turbine fuels, etc.
  • lighter fuels e.g. diesel, jet aviation, gas turbine fuels, etc.
  • higher the boiling point temperatures of a fuel typically the lower the average LHV per unit of weight.
  • higher boiling components with latent heats of vaporization les ⁇ than approximately 40, 50, 60, 70, 80, 90, 100, 110, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180 btu/lb, or alternatively those les ⁇ than about 650, 700, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 880, 900, 905, 910, 915, 920, 925 btu/gal, or alternatively, tho ⁇ e component ⁇ lower than the average latent heat of vaporization of unadju ⁇ ted ba ⁇ e fuel, be reduced in volume concentration or removed from the compo ⁇ ition;
  • fuel components having LHV greater than base fuel's average latent heat of vaporization may increa ⁇ ed or included; such that the new formulated fuel is greater than
  • cyclanes, alkenes, alkane ⁇ in order of their ranking are preferred for purposes of achieving elevated LHV's.
  • LHV's From about 120°C- 160°C, Applicant has found aromatic hydrocarbons, alkenes, cyclanes, alkanes, in order of their ranking, to be preferred. It is noted that as boiling temperatures raise aromatic hydrocarbon LHV's decline. Between approximately 70°C to about 130°C preference between alkenes and cyclane ⁇ are about the same. Between 160 0 C-180°C to approximately 300°C, bi-cyclic hydrocarbons, aromatic hydrocarbons, and alkanes, in order of their ranking, are preferred.
  • the preferred practice of formulating base fuels to increa ⁇ e their latent heat ⁇ of vaporization i ⁇ typically by removal of higher boiling material (e.g. with low latent heat ⁇ of vaporization and/or low burning velocity) until said oxygen/metals free base hydrocarbon compo ⁇ ition ha ⁇ an average latent heat of vaporization equal or greater than 500, 550, 600, 630, 650, 680, 700, 730, 750, 780, 800, 820, 830, 840, 850, 860, 870, 880, 890, 900, 905, 910, 915, 920, 925, 930, 940, 950, 970, 990, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350 btu/gal or more. It i ⁇ desireable that it be greater than 650, 740, 790, 800, 830, 860, 880, 900, 910 btu/gal, or more.
  • the base co-fuel's latent heat of vaporization should be in excess of 100, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210 BTU/lb, or more. hile there is generally no upper limit to a modified or co-fuel's latent heat of vaporization, economic costs and other practical considerations will control. Thus, Applicant appreciates that increase above 20% to 40% may represent actual limits.
  • Construction of fuels to acheive increa ⁇ ed latent heat ⁇ of vaporization ⁇ hould be tempered by other factors, including known hazardous emission features of certain components, distillation requirements, calorific or heating requirement ⁇ , burning velocity improvement, etc.
  • those absent ECS compound and/or metallic) to acheive enhanced LHV's should be such that final formulated co-fuel be equal to or greater than approximately 55, 60, 65, 70, 75, 78, 80, 82, 85, 87, 88, 89, 90, 91, 92, 93, 94, 95, 97, 100, 103, 105, 107, 110, 113, 115, 117, 120, 122, 125, 127, 130, 131, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 163, 165, 166, 167, 170, 175, or higher, btu/lb (or equivalent) , or an amount greater than existing ASTM ba ⁇ e fuels.
  • latent heats of vaporization equal or in exces ⁇ of 115, 120, 125, 130, 133, 134, 135, 147, 140, 142, 145, 146, 147, 148, 149, 150, 151, 152, 154, 153, 155, 160, 165, 170, 175 BTU/lb, or more particularly those greater than 140, 145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 160, 165, 170 BTU/lb, to be preferred.
  • latent heats of vaporization equal to or in exces ⁇ of 100, 102, 105, 107, 110, 112, 115, 117, 120, 122, 125, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 165, 170, 175 BTU/lb, or greater, are acceptable. More desireable are those exceeding 135, 140, 145, 150, 152, 154, 155, 158, 160, 165 BTU/lb, or more.
  • latent heats of vaporization equal to or in excess of 85, 90, 95, 100, 102, 104, 105, 106, 107, 108, 109, 110, 111, 112, 115, 117, 120, 122, 125, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150 BTU/lb, are acceptable. Those in exces ⁇ of 110, 115, 120, 125, 130 BTU/lb, or more, are de ⁇ ireable.
  • LHV's should equal or exceed 30, 35, 38, 40, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 54, 55, 56, 57, 58, 59. 60, 61, 62, 63, 64, 65, 66, 68, 70, 72, 74, 76, 78, 80 cal/gram.
  • Heavy diesel and fuel oil's LHV's should exceed 45, 50, 55, 60, 65, 70, 75, 80, 82, 85, 87, 90, 95, 96, 97, 98, 100, 105, 107, 110, 112, 115, 117, 120, 122, 125, 127, 130, or more, BTU/lb. Those in exces ⁇ of 100, 102, no BTU/lb are de ⁇ ireable.
  • the fuel be constructed so that its specific heat be equal to or greater than 0.35, 0.36, 0.37, 0.38, 0,39, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52, 0.53, 0.54 BTU/lb°F, or greater. Those above 0.46 BTU/lb°F are preferred.
  • Increased LHV' s translate into reduced combustion temperatures. Desireable reductions are in range of about 10 F to 500 F. Reductions of 5°F to 50°F, or more, are also desireable.
  • combustion chamber deposit reducing composition ⁇ or other means, including deposit additives are expressly contemplated.
  • Multi-boiling point fuels benefit from end boiling, T- 90 boiling and T-50 reductions, which ⁇ imultaneou ⁇ ly increa ⁇ e LHV.
  • fuel ⁇ include aviation and automotive gasolines, gas oil turbine fuels, fuel oil ⁇ , diesel fuels, jet aviation fuel ⁇ , and the like.
  • metallic or non- metallic containing gasoline have sufficiently elevated LHV that exhaust catalyst inlet temperature ⁇ be sufficiently reduced to avoid cataly ⁇ t plugging, OBM II monitor failure, and like.
  • modification of hydrocarbon co-fuel's including T-90, T-50, or T-10 distillation temperatures and/or sub ⁇ tituent components to eliminate low burning velocity and low LHV hydrocarbons to the maximum extent possible, so .as to reduce combustion temperature and optionally insure BV above reformulated or standard fuel ⁇ , absent modification.
  • combustion temperature control alone, absent other means of Applicant's invention (e.g. ECS compounds, mechanical air charge temperature reduction, etc.), is contemplated in formulation of Applicant's modified fuel to reduce emis ⁇ ion ⁇ and/or a ⁇ a means to control wash coat deposit ⁇ from low metallic mangane ⁇ e containing fuel ⁇ , re ⁇ ulting from exce ⁇ exhaust temperature.
  • Example 35 A method of avoiding the plugging or coating of exhaust catalysts or OBD II monitors or monitoring sy ⁇ tem ⁇ with manganese oxides, said method comprising: mixing a high latent heat of vaporization ECS fuel containing 1/128 to 1/32 gr. Mn/gal of MMT in sufficient quantity with a conventional unleaded or reformulated unleaded gasoline, wherein said fuel's combustion and exhaust temperature ⁇ are sufficiently reduced that inlet exhaust ga ⁇ temperature of catalyst is less than 1400°f, more preferably less than 1350, 1300, 1250, 1200°F.
  • Example 36 A method of avoiding the oxide plugging or coating of exhaust catalysts,- said method comprising: modifying T-90 gasoline temperatures of conventional or reformulated gasoline containing up to 1/32 gr Mn/gal of MMT, whereby LHV is increased in amount sufficient to reduce exhaust inlet exhaust gas temperature to cataly ⁇ t to less than 1400°f .
  • a hydrocarbon fuel composition ⁇ elected from the group of exi ⁇ ting co-fuels or base fuels ("unadjusted base fuel”), whereby said fuel is additionally constructed, formulated, or reformulated such that its latent heat of vaporization is increased at least 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 7%, 8%, or greater; and whereby said LHV increase is made absent inclusion of an ECS compound and/or metallic compound.
  • a fuel composition comprising a conventional or reformulated gasoline, an optional oxygenate, a T-90 fraction no greater than 290°F, 280°F, 270°F, 260°F, a latent heat of vaporization above 130, 135, 140, 145, 150, 155, 160, 165, 170 btu/lb; optionally MMT up to 1/64, 1/32 gram/gal; optionally a burning velocity exceeding 48, 49, 50, 51, 52, 53, 54 cm/ ⁇ ec,- said fuel characterized as improving fuel economy (preferably at least 0.5% or more) over unadjusted fuel or adjusted T90 fuel absent minimum LHV.
  • Example 40 The method of example 39, wherein the fuel additionally comprises a charge temperature reducing amount of a combustion chamber deposit control additive.
  • Example 41
  • latent heat of vaporization and/or burning velocity of the adjusted T-90 fuel is 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0% greater than non adjusted fuel.
  • fuel T-90 temperature is les ⁇ than 310°F, more preferably le ⁇ s than 305°F, 300°F, 295°F, 290°F, 285°F, 280°F, 275°F, 270°F, 265°F, 260°F, 255°F, 250°F, 245°F, or le ⁇ ; and MMT i ⁇ included in the amount of 1/32 gr. Mn/gal; and optionally a combu ⁇ tion chamber depo ⁇ it control additive is employed in sufficient amount; whereby charge temperature is reduced; wherein fuel economy is improved over same unadjusted fuel by at least 0.2, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, or more, percentage.
  • Applicant's hydrocarbon co-fuels, ECS ⁇ co- fuel ⁇ , modified fuels (see below) be constructed or formulated to enjoy the maximumlt is also an embodiment of this invention to construct or formulate Applicant's co- fuels to acheive maximum flame velocity.
  • Applicant ha ⁇ found that C2 to C6 acetylene hydrocarbon ⁇ offer exceptional burning velocities.
  • C4 to C6 olefins and de- olefins are attractive and offer good velocities.
  • C3 cyclo paraffins and benezene are also attractive. Less attractive are paraffins, C7 plus aromatic hydrocarbons. Typically, the shorter the carbon chain length, C6, C5, C4, C3 or lower, the higher the burning velocity.
  • n- alkynes are preferred over n-alkenes over n-alkanes.
  • Burning velocity of unsaturated hydrocarbons is higher than saturated hydrocarbons of the same chain length. In unsaturated hydrocarbons with one saturated bond, burning velocity is decreased relative to the increase in molecular weight. Naphthenes and aromatic hydrocarbons have similar rates as paraffins.
  • the combustors contemplated in the practice of this invention include geometric combustors (tubular, annular, tubo-annular, spherical) , aerodynamic combu ⁇ tor ⁇ (diffu ⁇ ion flame, premixing, staged, catalytic, and application combustors (aircraft, industrial, vehicular) .
  • Applicant's invention is particularly applicable in turbine applications, e ⁇ pecially in aviation ga ⁇ turbines, industrial gas turbines, marine gas turbines, and the like.
  • the physical state of fuel ⁇ employed in thi ⁇ invention include a wide and narrow boiling range of liquid, semi- liquid, near-liquid, semi-solid, solid, and gaseous fuel ⁇ , and mixture.
  • Applicant' ⁇ neat fuel embodiment ha ⁇ exceptional propulsion and environmental attributes, which are not limiting to internal combu ⁇ tion engine ⁇ , aviation jet turbine ⁇ , gas oil turbines, furnaces, burners, air breathing propulsion systems, or rocket engines.
  • Applicant's neat fuel is a stand alone fuel, which may be used potentially in any combustion system. Albeit, modification of existing combustors may be required to accommodate the combustion maximizing and thermal dynamic aspects of such neat applications.
  • Applicant's fuel may contain at least one additional oxidizer and/or at least one addition propellant or a co-fuel.
  • RVP reduction is an express embodiment.
  • finished fuels contemplated include those whose RVP ranges from 0.01 psi to 1000.0 psi, 2.0 psi to 200.0 psi, 2.0 p ⁇ i to 40.0 psi, 1.0 psi to 20.0 psi, 1.0 to 10.0, 1.0 to 8.0 psi, 1.0 psi to 7.5 psi, 1.0 to 7.0 psi, 1.0 to 6.5 psi, 1.0 to 6.0 psi, 1.0 to 3.0 psi, 1.0 to 2.0 psi, or lower.
  • winter RVP's may range from 11.5 to 12.0 psi and summer RVP's ranging from 6.5 to 6.9 psi.
  • Olefin concentrations of approximately or less than 40, 37, 35, 33, 32, 31, 30, 29, 28, 27, 26, 25, 24, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, l volume percentage, or olefin free, are contemplated.
  • Preferred olefins are ab ⁇ ent C4 to C5 olefins.
  • an olefin range of 2.0 to 12.0, 3.0 to 10.0, 4.0 to 8.0 volume percent, or les ⁇ are contemplated.
  • Olefin free compo ⁇ ition ⁇ are al ⁇ o contemplated.
  • Applicant's invention embodies a neat, es ⁇ entially neat, majority neat ECS fuel, including compositions containing greater than 50% ECS compound(s) by volume. It also embodies a substantial majority, a minority, or sub ⁇ tantial minority application, e.g. greater than 0.5%, 1.0%, 1.5%, 1.8%, 2.0%, 2.7%, 3.0%, 3.5%, 3.7%, 4.0%, 5%, 10%, 15%, 20%, 25%, 30%, 40% by volume, or weight) of an ECS fuel, normally with a co-fuel ("Base Fuel or Co-Fuel”) .
  • the most preferred ECS fuels containing Mn include dimethyl carbonate, methanol, hydrogen, methylal, methane hydrate, hydrazine, and mixtures thereof.
  • Applicant intend ⁇ that disclosure related to any co-fuel be appropriately applied to any other co-fuel or modified fuel (e.g. anti-oxidants or detergent ⁇ of one co-fuel cla ⁇ s can be used with other co-fuel classe ⁇ , etc.).
  • beneficial environmental practice for one fuel may be applied to any other.
  • Co-fuel ⁇ or modified fuels of Applicant's invention normally will be fuels that are as environmentally attractive as po ⁇ ible, meeting regulatory ⁇ tandard ⁇ , including California Air Resources Board standard ⁇ , EPA standards, prsent and future. It is contemplated that Applicant's fuels to extend possible, including aviation turbine co-fuels or modified fuels will be lead free or essentially lead free. However, known additives consi ⁇ tent with ASTM, military, or International ⁇ tandard ⁇ may be contained in compositions. Applicant's aviation turbine fuels may meet or substantially comply with ASTM standards. Current ASTM fuel specification D 1655-93 (including future editions) , relevant prior specification ⁇ , related ASTM standards, test methods, military, and international standards are incorporated by reference.
  • Applicant' ⁇ reduced combustion temperatures are extremely useful in jet aviation applications at high altitude and/or at high mach speeds where extreme engine temperatures limit operation and de ⁇ ign of the combustion system. In practice hereof, it has been found that Applicant can reduce engine combustion temperatures significantly, on the order of 25°F to 400°F, or more.
  • a method of operating an engine employing an ECS fuel (consistent with the oxygenated example compositions herein) ,- said method characterized as combusting said fuel in a spark ignited engine or other engine, including turbine, wherein ignition delays are reduced compared to traditional fuel alone by at least 5.0, 10.0, 15.0, 20.0, 25.0, 30.0, 35.0, 40.0, 45.0, 50.0, 55.0, 60.0, 65.0, 70.0, 75.0, 80.0, 85.0, 90.0, percent, or more; and wherein spark advance, if applicable, is adju ⁇ ted accordingly.
  • Example 45 The method of Example 44, wherein the air fuel ratio is reduced by at least 25, 30, 35, 40, 45, 50, 55, 60, 65, 70%, or more, compared to traditional fuel alone (gasoline 15, jet tubine fuels 14-16, etc.); alternatively air-fuel ratios including those of approximately 5.85 to 6.45, 6.00 to 8.03, 7.55 to 10.45, 8.85 to 12.5.
  • a method of operating a jet turbine engine under temperature comprises: Mixing an ECS fuel (preferrably at least one oxygen containing ECS compound and metallic), optionally containing 0.1 to about 5.0, 10.0, 15.0, 20.0, 30.0, 40.0, 50.0, 60.0 wt percent oxygen, with an aviation co-fuel wherein said resultant fuel is thermally stable in liquid and vapor states to 220°C, 260°C, 280°C, 300°C, 320°C, 350°C, or higher temperature, said resultant fuel having LHV exceeding 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, or higher BTU/lb, acting as a primary heat sink to cool engine while in liquid or gas state, said fuel optionally containing: an antioxidant, despersant, metal deactivator and/or detergent/dispersent in such amounts to improve thermal stability,- combusting said fuel in said jet turbine engine at high mach, exceeding 1.0, 1.5, 2.0, 2.25, 2.5
  • Example 48 An aviation turbine fuel composition
  • An ECS fuel preferrably one containing at least one oxygenated ECS compound, e.g. DMC, and a metallic, e.g. MMT); optionally containing 0.1 to 95%, or about 5.0, 10.0, 15.0, 20.0, 30.0, 40.0, 50.0, 60.0 wt percent Oxygen; an aviation co-fuel; said fuel characterized as being thermally stable in liquid and vapor states to 220°C, 260°C, 280°C, 300°C, 320°C, 350°C, or higher temperature; said characterized as having LHV exceeding 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, or higher BTU/lb, and capable of absorbing heat (e.g.
  • An aviation jet turbine fuel comprising 0.01% to 40.0% by weight oxygen from DMC (more preferably 0.5% to 5.0%, 0.5% to 10.0%) and at least one manganese metallic representing 0.001 to 20.0 gr/gal (more preferably 0.01 to 7.5, 10.0 gr/gal, more preferably 0.1 to 3.0 gr/gal); said fuel having a total aromatic volume concentration not exceeding 25% (22% or less more preferred) , a maximum sulfur content not exceeding 0.3 weight percent (preferably 0.2, 0.1, 0.02, or lower, or sulfur free), a maximum T-10 temperature of 205°C, a maximum final boiling point temperature of 300°C (more preferably less than 290°C, 285°C, 280°C, 275°C, 270°C, 265°C) , a minimum flash point of 38°C, a density of 775 to 840 at 15°C, kg/m 3 , or optionally exceeding 840, 850, 860, 880, 900, or more kg/m 3 , a minimum freezing
  • a gas turbine fuel composition comprising: DMC representing 0.01% to 40.0% oxygen by wt in the fuel, at least one metallic in a concentration of 0.001 to about 7.5, 10.0, 15.0, 20.0, 40.0 gr/gal, and a gas oil turbine co-fuel selected from No. 0-GT, No. l-GT, No. 2-GT, No. 3- GT or No.
  • 4-GT gas turbine fuel oils said fuel characterized as having a flash point of 38°C to 66°C, a minimum kinetic visco ⁇ ity at 40°C ranging from 1.3 to 5.5 mm 2 /s (ASTM D 445) , optionally a sulfur content not exceeding 2500, 2000, 1500, 500, 400, 300, 200, 100, 50, 40, 20 ppm wt (or being sulfur free) , optionally a T90 temperature reduced at least 20°C compared to unadjusted co- fuel; said fuel characterized as having a bunsen laminar burning velocity of at least 32, 33, 34, 35, 36, 38, 40, 42, 43, 44 cm/sec, a latent heat of vaporization of at least 80, 85, 90, 95, 100, 105, 110, 115 BTU/lb; said fuel additionally characterized as reducing turbine inlet gas temperature to about 850°C, 800°C, 750°C or 700°C, 650°C, 625°C, 600°
  • 650°C, 625°C, 600°C or les ⁇ preferred, and/or inlet pressure is increased as compared to co-fuel alone (preferably by at least 2.0%, 3.0%, 4.0% or more; optionally harmful deposits, pollution, and corrosion on turbine blading is additionally reduced/controlled; and optionally carbon formation is reduced in the primary combustion zone during combustion of said composition; wherein free carbon formation is also reduced such that inner liner temperatures are reduced with attendant increases in turbine life up to 2, 3, 4 or more times standard lives.
  • a bio diesel fuel composition comprising: 1.0% to 95% by volume biodiesel (bio-e ⁇ ters, C18 + fatty acid methyl esters, rape seed ester ⁇ , and the like), 1.0% to 95% by volume diesel fuel oil or equivalent (conventional or reformulated, including naptha),- optionally 0.5% to 90% vol. alkylate, 1.0% to 90.0% by volume at least one ECS compound, and optionally a combustion improving amount of a metallic; under proviso all components equal 100%
  • Applicant' ⁇ diesel fuel ⁇ , co-fuels, include Swedish
  • Enviromental class 1 and 2 fuels CARB reformulated fuels, and EPA reformulated fuels, existing and future.
  • Applicant's fuels include future reformulated diesel fuels.
  • a preferred embodiment are low/no sulfur, low/no aromatic hydrotreated diesel fuels, especially those absent lubricity problems facing similar or low sulphur fuels. It is also an express embodiment to include lubricity additives in low/no sulfur fuels.
  • Applicant's preferred diesel co-fuels contemplate low sulfur concentrations including tho ⁇ e equal to or below 600, 500, 400, 300, 200, 150, 100, 60, 50, 45, 40, 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 2 ppm, or sulfur free. Preferred concentrations are 50 ppm or below.
  • Diesel co-fuels include those with low aromatic contents including those equal to or les ⁇ than 60%, 50%, 47%, 45%, 40%, 35%, 30%, 28%, 25%, 22%, 20%, 18%, 15%, 12%, 10%, 7%. 6%, 5%, 4%, 3%, 2% by vol., or an aromatic free composition. Applicant prefers that 2 and 3 ring plus aromatics be excluded to the extent feasible.
  • Preferred fuels may be nitrogen free, although in practice of invention nitrogen is expres ⁇ ly contemplated a ⁇ NOx emi ⁇ ion ⁇ are ⁇ ubstantially reduced.
  • Applicant's diesel fuel cetane number include those equal to greater than 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90 or higher. Those in excess of 45, and 55 are preferred.
  • Substituent diesel fuel formulation which operates to increase burning velocity and/or reduce combustion temperature is expressly contemplated, especially those that operate to increase burning velocities 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5%, 8.0%, 10%, 15%, 20%, or more, over the clear or unadjusted fuel.
  • Formulation that increases laminar bunsen flame speed to 39, 40, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, or greater, cm/sec i ⁇ desired.
  • Example 52 A fuel compo ⁇ ition comprising: DMC representing 0.01% to 10.0% oxygen by wt in the fuel, at least one metallic in a concentration of 0.001 to about 2.5 gr/gal, a diesel co- fuel base,- wherein combined fuel is characterized as optionally having sulfur content not greater than 250 ppm, 200 ppm, 150 ppm, 100 ppm, 75 ppm, 50 ppm, 40 ppm, 30 ppm, 20 ppm, 10 ppm, 5 ppm, or being sulfur free,- density ranging from about 880 to 800 kg/m 3 ,- viscosity ranging from 2.5 to 1.0 cSt at 40°C; cetane index of 40 to 70; an aromatic content by vol.
  • a T10 fraction temperature of about 190 to 230°C, a T50 fraction temperature of about 220 to 280°C, and a T90 fraction of about 260 to 340°C, and cloud point temperature of °C -10, - 28, or -32 (or 6°C above tenth percentile minimum ambient temperature) ,- a bunsen laminar burning velocity of at least 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48 cm/sec, a latent heat of vaporization of at least 85, 90, 95, 90, 100, 105, 110, 115, 120 BTU/lb; optionally a heating value le ⁇ s than 43, 42, 41, 40, 39, 38, 37 kj/kg.
  • Example 53 Low emis ⁇ ion diesel fuel comprising; optionally a combu ⁇ tion improving amount of an ECS compound; optionally a combu ⁇ tion improving amount of. a metallic; a die ⁇ el co- fuel; ⁇ aid fuel characterized a ⁇ having a maximum ⁇ ulfur concentration of no greater than 1100 ppm, 800 ppm, 440 ppm, 300 ppm, 250 ppm, 200 ppm, 150 ppm, 100 ppm, 50 ppm, 10 ppm, 5 ppm, or sulfur free; density kg/m 3 of 800, 805, 810, 814, 815, 839, 840, or higher,- visco ⁇ ity of cSt at 40°C 1.8, 2.4, 2.5, or lower,- cetane index of 46.2, 51.2, 52.1, 53.5, 57.5, 57.8, or higher,- aromatics by vol.% 27.1, 2.45, 14.5, l.l, 21.6, or lower, under proviso 3-ring +
  • Example 54 A reformulated diesel fuel comprising: a reformulated low emission diesel composition, wherein API ranges 41.1 to 45.4, sulfur does not exceed 10- wt ppm, or sulfur free, optionally absent nitrogen, aromatics at 20, 15, 10, 5.0% vol or less, PNA vol% 0.02 or less, or PNA free, minimum Cetane index 35, 38, 39, 40, 42, 43, 45, 47, 50, 55, an IBP Of about 215°F, 265°F, 300°F, 320°F, 345°F, 365°F, 385°F, or greater, a 95% fraction @ 545°F, 525°F, 500°F, 475°F, or more,- a combustion improving anount of a manganese or other metallic compound; optionally an ECS compound.
  • API ranges 41.1 to 45.4, sulfur does not exceed 10- wt ppm, or sulfur free, optionally absent nitrogen, aromatics at 20, 15, 10, 5.0% vol or less, PNA vol% 0.02 or less,
  • a liquid fuel comprising: a fuel soluable ECS compound at 0.01% to 5.0% by weight % oxygen (more preferably 0.5% to 2.5%); at least one manganese metallic representing 0.001 to 2.8 gr/gal (preferably 0.065 to 1.0 gr/gal, most preferably 0.1 to 0.5 gr/gal); a die ⁇ el co- fuel; wherein ⁇ aid fuel i ⁇ characterized as having sulfur content not greater than 250 ppm, 100 ppm, 50 ppm, 5 ppm, or being sulfur free; density ranging from 880 to 800 kg/m 3 ; viscosity ranging from 2.5 to 1.0 cSt at 40°C; cetane index of 40 to 60; an aromatic content by vol.
  • a T10 fraction temperature of about 190 to 230°C
  • a T50 fraction temperature of about 220 to 280°C
  • a T90 fraction of about 260 to 340°C
  • cloud point temperature of °C -10, -28, or -32
  • a bunsen laminar burning velocity of at least 34 cm/sec, or more, a latent heat of vaporization of at least 95 BTU/lb, or more.
  • a liquid fuel comprising DMC at 0.01% to 5.0% by weight % oxygen (more preferably 0.5% to 2.5%) and at least one manganese metallic representing 0.001 to 2.8 gr/gal
  • a sulfur content not exceeding 10 wt ppm (optionally sulfur, nitrogen free) , absent nitrogen, and an aromatic content of 0 to 20% by volume, PNA vol% of 0.02, or less, a Cetane index greater than 45, an IBP of 365°F, a 95% fraction ranging from 460°F to 540°F; a bunsen laminar burning velocity of at least 36 cm/sec, a latent heat of vaporization of at least 100 BTU/lb.
  • the diesel fuel compo ⁇ itions above comprising a combustion chamber deposit control/reducing additive, and optionally: an injector, intake valve deposit control, metal deactivator, or antioxidant additive.
  • Elemental concentrations of metal in diesel/distillate fuel ⁇ include those equal to or greater than 0.015625, 0.03125, 0.0625 0.125, 0.25, 0.275, 0.375, 0.50, 0.625, 0.75, 0.875, 1.0, 1.125, 1.25, 1.375, 1.5, 1.625, 1.874, 2.0, 2.125, 2.25, 2.375, 2.5, 2.625, 2.75, 2.875 gram elemental metal/gal. Higher ranges are contemplated.
  • a desireable range includes from about 0.001 to about 1.50 gram elemental metal/gal.
  • Other desireable ranges include from about 0.001 to about 0.50 gram elemental metal/gal of composition. Lower concentration ranges from .001 to about 0.25 grams/gal are also contemplated. Ranges greater than 0.0625 gr elemental metal/gal are also contemplated. Often, manganese concentrations must exceed 1/64, 1/32, 1/16, 3/32, 1/8, 5/32, 7/32, or 1/4 gr elemental metal/gal prior to noticible improvement in fuel economy or power. Elemental ranges above 3.0, 3.5, 4.0, 5.0, 7.0, 8.0, 10.0 gram ⁇ or more are contemplated.
  • cetane number of 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50 is desireable.
  • a cetane number of 40, 42, 44, 46, 48, 50, 52, 54, or greater, is preferred, especially in low sulfur No. l-D and low sulfur No. 2-D fuels.
  • An optimal cetane number in the practice of this invention is greater than 48, 50, 52, 54, 56, 58.
  • cetane numbers greater 50, 55, 60, 65, 70, 75, 80 are contemplated. hen employing low sulfur diesel fuel ⁇ Grade No. D-l and No.
  • D-2 minimum cetane index number is contingent upon amount of aromatic component ⁇ , not to exceed 40, 35, 30, 27, 25, 22, 20 percent (as measured by ASTM D 976) , alternatively an aromatic content not exceeding 35% by volume (as measure by ASTM D 1319) .
  • a composition comprising a diesel fuel meeting ASTM 975 specification ⁇ (or fuel oil, aviation turbine, or gas oil) a combustion improving amount of dimethyl carbonate and tetraethylene glycol, and a cyclopentadienyl manganese tricarbonyl compound having a concentration ranging from about 0.001 to about 2.5 gr Mn per gallon,- whereby re ⁇ ultant fuel combu ⁇ tion re ⁇ ult ⁇ in improved thermal efficiency and/or fuel economy, and meets minimum flash point temperatures.
  • a No. 2 diesel fuel composition comprising a minor portion of a combustion improving amount of dimethyl carbonate and a cyclomatic manganese tricarbonyl, and a major portion of a ba ⁇ e die ⁇ el fuel, ⁇ uch that resultant fuel has a cetane of 42 to 50 (preferably substantially greater) , an aromatic content of les ⁇ than 28 volume percent (preferably less than 20%, more preferably 15%, most preferably less than 10%) , a T-90 temperature of 560°F to 600°F (more preferably less than 540°F, 520°F, 500°F or lower), a sulfur content of 0.08 to 0.12% mass (more preferably 0.05% or sulfur free), an API gravity of 32 to 37 (more preferably higher) , and a minimum flash point of 130°F (optionally obtained via use of co-solvent or salt) .
  • a No. 1 diesel fuel composition containing a minor portion of a combustion improving amount of dimethyl carbonate and a cyclomatic manganese tricarbonyl, and a major portion of a base diesel fuel, such that re ⁇ ultant fuel ha ⁇ a cetane of 48 to 54 (preferably substantially greater) , aromatics representing 10% or less by volume, a T-90 temperature of 460°F to 520°F (more preferably les ⁇ than 425°F, or lower), a sulfur content of 0.08 to 0.12% mass (more preferably les ⁇ than 0.05% ma ⁇ s) , API gravity of 40 to 44 (more preferably higher) , and a minimum flash point of 120°F.
  • ignition promoters may be employed, individually and/or in combination with
  • ECS compounds particularly in fuels which require higher temperatures to ignite, which extend ⁇ their period of ignition.
  • a low emission No. 2 grade diesel fuel compri ⁇ ing a minimum cetane number of 52, maximum fuel ⁇ ulfur of 350 ppm (more preferred le ⁇ than 0.05% ma ⁇ ) , aromatics less than 30% volume (more preferably less than 15%) , a combustion improving amount of dimethyl carbonate and a combustion improving amount of a cyclomatic manganese tricarbonyl compound.
  • a low emission diesel fuel comprising a minimum cetane number of 52, maximum fuel sulfur less than 100 ppm, aromatic content of 12%, T-90 temperature of 475°F, bromine number of 0.10, a combustion improving amount of dimethyl carbonate ranging from 0.5 to 4.0% oxygen by weight, and a combustion improving amount of a cyclomatic mangane ⁇ e tricarbonyl compound.
  • Die ⁇ el fuel ⁇ which do not contain a pour point depressant additive, the pour point is usually from 3°C (5°F) to 15°C (25°F) below the cloud point.
  • a minimum flash point of 38°C for diesel Grades No. l-D, and 52°C for Grades 2-D and 4-D are preferred.
  • carbon residue found in the 10% distillation residue as a percentage of mas ⁇ , ⁇ hould generally not exceed 0.15 in No. l-D fuels, and 0.35 in No. 2-d fuels. However, lower mas ⁇ concentration ⁇ are more preferred.
  • the maximum percent of ash by mass is 0.01%, except for Grade No. 4-D, which is 0.10%. Lower ash percentages are preferred. However, the lower combu ⁇ tion temperature ⁇ of Applicant' ⁇ invention tend ⁇ to mitigate a ⁇ h related problems.
  • Additives are contemplated in distillate fuels include ignition quality improver, oxidation inhibitors, biocides, rust preventives, metal deactivators, pour point depre ⁇ ants, demulsifiers, smoke suppressants, detergent- dispersants, conductivity improver, dyes, de-icers and additives to reduce and/or control engine and combustion deposit ⁇ , including fuel injector, combustion chamber, and intake valve deposits.
  • combustion chamber deposit additives especially those that reduce existing combustion chamber deposit ⁇ .
  • certain depo ⁇ it additive ⁇ which control injector and valve intake depo ⁇ its, may be deleterious to combustion chamber deposition control or reduction and are therefore not as desireable.
  • Smoke suppressants including organic compounds of barium, particularly the barium carbonate overba ⁇ ed barium ⁇ ulfonate ⁇ , N-sulfinyl anilines, are contemplated, as well as others.
  • Example diesel fuel additives are shown by clas ⁇ and function in Table 1. As with any sy ⁇ tem in which a variety of additives may be used, care should be taken to avoid incompatibilitie ⁇ among additives and unanticipated interactions which may produce undesirable fuel effects.
  • Ignition quality Improver - Raise Cetane Number therebypromotingfaster start sand less whitesmoke
  • Oxidation Inhibitors Minimize oxidation Alkyl amines and amine-containingomplexmate ⁇ als and gum and precipitateformation.improve storage life
  • Rust Preventives- Minimize rust formation
  • Organicacids and amine salts A widely- usecrype is in fuels systemsand storagefacilities based on dime ⁇ zedlinoleic acid
  • Pour Point Depressants Reduce the pour Generally consist of polymeric materials such as point and improve low-temperatur ⁇ luidity polyolefins, poly acrylates poly met hacrylatesoiodified properties by modifying the wax crystal polystyrenes. ethylene-vinyhcetate copolymers, and growth structurcand/oragglomeration ethylene -vinjdhlo ⁇ de copolymers
  • Demulsifiers and Dehazers improve the Surface-activemate ⁇ als whcih increase the rate of separationof waterfrom distillatefuels and water/oikeparation Usually quite complex mixtures prevent aze
  • Smoke Suppressants - Minimize exhaust Catalyst types are generally overbased barium smoke by catalyzing more complete compounds Maintenanceof spray patternsis helped combustionof carbonaceousmate ⁇ alsor by by detergents helpingto maintainfuel spraypatterns
  • Detergent -Dispersant ⁇ Promoteenginefuel These are usuallysurface- act lvagents They are often system cleanliness help prevent nozzle polymeric materials containing amines and other deposit formation and injector sticking functionalgroups lnterferewithprecipatorygglomerationthus maintainingiptimumfiltratioirharacte ⁇ stics
  • the fuel properties most often associated with effects on exhaust emis ⁇ ion ⁇ are aromatic content, volatility, gravity, viscosity, cetane number, and the presence of specific elements (for example, hydrogen and sulfur) .
  • Increased aromatic content generates increased particulate (especially soluble organic particulate) and hydrocarbon emissions.
  • aromatics olefins, benzene, butadiene, formaldehyde, acetaldehyde, di and tri aromatics, etc.
  • aromatics, olefins, benzene, butadiene, formaldehyde, acetaldehyde, di and tri aromatics, etc. may be included in amounts now thought to be environmentally hazardous.
  • Higher distillation temperatures of the lower-vapor- pre ⁇ ure component ⁇ (for example, T-50 and T-90 point ⁇ ) generally result in higher particulate emissions, although, for typical variations in aromatics and volatility, the volatility effect is often small.
  • Fuel gravity, viscosity, cetane number, and hydrogen content usually correlate with volatility and aromatic content.
  • Example 63 Automotive gasolines contemplated in Applicant's invention include conventional unleaded, reformulated unleaded, including those meeting U.S. Clean Air Act ⁇ 211 (K) requirements, low RVP fuels, low/no sulfur, low octane, moderate octane, high octane gasoline ⁇ , high LHV and/or BV ga ⁇ oline ⁇ , advanced atomization, vaporization, injector volatilization ga ⁇ oline ⁇ , and the like, and/or any gasoline meeting ASTM and/or other regulatory standard, exi ⁇ ting and future, and combinations thereof.
  • K U.S. Clean Air Act ⁇ 211
  • a method of 63 reducing potentially carcinogenic ether concentrations from atmosphere comprising combusting an MTBE containing fuel in combination with a co-ECS compound and optionally a combustion improving metallic.
  • An improved MTBE fuel composition comprising: a low or no sulfur hydrocarbon base fuel, MTBE, and optionally an ECS compound having a burning velocity greater than MTBE
  • Example 66 A method of increasing work potential, fuel economy, reducing combustion emission ⁇ of a vehicle operating on a conventional or reformulated gasoline, oxygenate optional, comprising: Reducing the boiling temperature of ga ⁇ oline ⁇ uch that it ⁇ boiling temperature at T-90 fraction is no greater than 320°F, 315°F, 310°F, 305°F, 300°F, 295°F, 290°F, 280°F, 270°F, or 260°F, or less, while simultaneou ⁇ ly increasing the fuel's LHV to at least 130, 135, 140, 145, 150, 155, 160, 165, 170 btu/lb (or at lea ⁇ t 2.0% above unadju ⁇ ted fuel) ,- optionally admixing MMT into the compo ⁇ ition up to 1/64 or 1/32 gr mn/gal; optionally a burning velocity exceeding 48, 49, 50, 51, 52, 53, 54 c / ⁇ ec,- wherein said fuel ha ⁇ a L
  • a conventional or reformulated unleaded fuel composition comprising: sulfur at less than 300, 250, 200, 150, 100, 60, 50, 20, 10, 5 ppm, or sulfur free,- an essentially polynuclear free aromatic concentration of less than 50%, 45%, 40%, 35%, 30%, 27%, 25%, 22%, 20%, 18%, 16%, 15%, 12%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, or les ⁇ , by volume, or an aromatic free compo ⁇ ition; a non C4 to C5 olefinic concentration le ⁇ than 20%, 15%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1% including range of 3.0% to 5.0% by volume, or olefin free,- a benzene concentration of 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0% volume, or les ⁇ , including benzene free compositions;
  • At least one ESC compound preferably DMC
  • at least one combustion enhancing deposit control additive selected from combustion chamber deposit control, port fuel injector, intake valve deposit- control additive, and mixture
  • said composition has a driveability index less than 1120, 960 (les ⁇ than 930 preferred)
  • optionally a t-90 temperature equal to or le ⁇ s than 350°F, 340°F, 330°F, 320°F, 310°F, 305°F, ,300°F, 295°F, or 290°F
  • a t-50 temperature equal or exceeding 170°F, 175°F, 180°F, 190°F, 200
  • Applicant's gasoline ⁇ including reformulated, to have a driveability index as defined by (1.5 x T 10 ) + (3 x T 50 ) + (T 90 ) of less than 1370, 1330, 1300, 1295, 1275, 1236, 1200, 1190, 1180, 1170, 1160, 1155, 1150, 1140, 1130, 1120, 1100, 1090, 1080, 1075, 1050, 1000, 975, 960, 950, 945, 940, 935, 930, 925, 920, 910, 900, 875, 850, 840, 825, 800, or less.
  • T50 temperatures simultaneously equal or exceed 150, 155, 160, 165, 170, 175, 180, 185, 190, 195. degrees F.
  • An acceptable T50 range includes 190 to 210 degrees F. It is also preferred that the T-10 distillation fraction be 160, 155, 150, 145, 140, 135, 130, 125, 120, 115, 110, 105, 100, 98, 96, 95, 94, 93, 92, 91, 90, 89, 88, 87, 85, 80 degrees F, or le ⁇ .
  • An acceptable T90 range includes 280 to 300 degrees F.
  • the invention contemplates the use of a wide spectrum of fuel oils, as co-fuels, including burner fuels, fuel oils, furnace oils, petroleum and petroleum oils, and those fuel oils meeting ASTM D 396 standards, and/or fuel intended for use in various types of fuel-oil-burning equipment, under various climatic and operating conditions.
  • fuel oils as co-fuels, including burner fuels, fuel oils, furnace oils, petroleum and petroleum oils, and those fuel oils meeting ASTM D 396 standards, and/or fuel intended for use in various types of fuel-oil-burning equipment, under various climatic and operating conditions.
  • Non-limiting examples include ASTM Grades l to 5.
  • Boiling point modification is an expres ⁇ embodiment of thi ⁇ invention, e ⁇ pecially when re ⁇ ulting increa ⁇ ed LHV's and/or BV's (See my co-pending International Applications No. PCT/US95/02691 and NO. PCT/US95/06758) .
  • a No. 2 fuel oil with a kinetic velocity of no les ⁇ than 1.9 nor greater than 3.4 (mm 2 /s) measured at 40°C, a minimum T-90 temperature of 282°C, a max T-90 temperature of 338°C, a maximum ⁇ ulfur content of 0.05% ma ⁇ s, a maximum copper ⁇ trip rating of No.3, a combu ⁇ tion improving amount of an ECS compound (preferably DMC) ,- and optional metallic, fla ⁇ h point of 38°C, LHV of at least 90, 95, 100, 105, 110, 115, 120, 125, 130, 135 BTU/lb; said fuel optionally containing co-solvent and/or metallic salt.
  • ECS compound preferably DMC
  • Example 168 A No. 6 fuel oil, with a kinetic velocity of no less than 15.0 nor greater than 50.0 (mm 3 /s) measured at 100°C using ASTM D 445, and combustion improving amount of an ECS compound, optionally a metallic.
  • ASTM grade fuel oil containing a combustion improving amount of dimethyl carbonate and a combustion improving metallic, wherein expected combustion efficiency of the furnace increases in range of at least 1.0% to 20%. It i ⁇ contemplated in locomotive and marine fuel ⁇ meeting appropriate ISO DIS 8217 and BS MA 100 ⁇ tandards, containing higher concentrations of sulfur than most fuels, Applicants invention due combustion temperature object, mitigates sulfur corrosion and generation of other pollutants.
  • a method for enhanced combustion of a vapor for heavy diesel, locomotive or marine engine especially one exceeding 450, 500, 900, 1200, 3800, 20,000, or more cubic inches; wherein vapor is derived from DMC representing 0.01% to 40% oxygen by wt in the fuel, a metallic representing 0.01 to 20.0 grs of metal/gal, and a heavy diesel, locomotive or marine engine co-fuel meeting ISO DIS 8217 and/or BS MA 100 standards specification ⁇ ; wherein ⁇ aid combination contains a sulfur concentration of 0.01 to 3.0% mas ⁇ , has a visco ⁇ ity of 10 to 500 centistokes at 50°C,- whereby combu ⁇ tion of said vapors results in reduced corrosion, particulate emissions and/or improved fuel con ⁇ umption compared to co-fuel alone.
  • a rocket fuel propellant compri ⁇ ing: at least one ECS compound and a propulsion improving amount of a metallic.
  • Example 173 The example of 172, wherein composition additionally comprises an oxidizer and propellant.
  • Example 174 A rocket fuel composition comprising hydrogen peroxide and a metallic, and optionally, DMC.
  • a rocket fuel composition comprising hydrogen peroxide, an oxider and a metallic, and optionally DMC.
  • non-limiting examples of the oxidizer include oxygen, nitric acid, mixed nitric acid sulfuric acid combinations, fluorine, nitrogen tetroxide, hydrogen peroxide, potassium perchlorate, perchloryl fluoride, bromine pentafluoride, chlorine trifluoride, ON 7030, ozone, oxygen difluoride, RFNA (at various strengths) , WFNA, tetranitromethane, fluorine, chorine trifluoride, perchloryl fluoride, nitrosyl fluoride, nitryl fluoride, nitrogen trifluoride, difluorine monoxide, fluorate, chorine oxides, other known art oxidizers, and the like.
  • the oxidizer include oxygen, nitric acid, mixed nitric acid sulfuric acid combinations, fluorine, nitrogen tetroxide, hydrogen peroxide, potassium perchlorate, perchloryl fluoride, bromine pentafluoride, chlorine tri
  • a rocket fuel compo ⁇ ition comprising dimethyl carbonate, hydrazine and a cyclopentadienyl manganese tricarbonyl compound.
  • a rocket fuel composition comprising dimethyl carbonate and an oxidizer selected from the group consisting of nitric acid or sulfuric acid, inclusive or exclusive of a metallic,- and optionally a co-propellant.
  • a rocket fuel comprising dimethyl carbonate, hydrazine or a substituted hydrazine, and/or hydrogen peroxide, and/or a metallic.
  • a rocket fuel comprising dimethyl carbonate, hydrazine, and kerosine,- and optionally a metallic.
  • Example 182 A rocket fuel comprising dimethyl carbonate, hydrogen, a metallic and optionally an oxidizer.
  • Example 183 A rocket fuel comprising dimethyl carbonate, a metallic; optionally: a known oxidizer or propellant.
  • additive practice is a vital component of thi ⁇ invention. It is expressly contemplated that additive ⁇ , additive methods, lubricants, and the like, set forth in my co-pending International Applications No.
  • PCT/US95/02691 and No. PCT/US95/06758 for fuel composition ⁇ beincorporated herein by reference. It is contemplated disclo ⁇ ed additive ⁇ be interchangible between various fuel classes. However, it is appreciated art practioners certain additives lend themselve ⁇ more to one fuel group than another.
  • Appliant's invention contemplates a wide range of additive ⁇ and concentration ⁇ , including but not limited to the following (with approximate additive concentration) : anti-oxidant(s) (8-40 mg/kg), wax anti-setting (100-200 mg/kg) , anti-foam (2-5 mg/kg) , anti-valve seat rece ⁇ sion
  • contemplated additives include combustion improvers, biocides, drag reducing agents, dehazers, metallic ⁇ cavenger ⁇ , friction modifier ⁇ , antiwear additive ⁇ , anti ⁇ ludge additive.
  • Non-limiting example ⁇ of Applicant' ⁇ anti-static additives include soluble chromium materials, polymeric sulfur, nitrogen compounds, and quaternary ammonium materials. Use is generally contemplated in very cold ambient temperature ⁇ and/or in fuels ' of intermediate volatility such as aviation kerosenes .
  • Non-limiting examples of metal deactivators include 8- hydroxyquinoline, ethylene diamine tetracarboxylic acid, B- ketoesters ⁇ uch a ⁇ octyl acetoacetate, and like, N,N'- disalicylidene -l, 2 - propanediamine, such as N,N - disalicylidene-1,2-propane diamine, ethane diamine or N, N ⁇ disalicylidene- 1 , 2 - cyclohexanediamine, N,N" -disalicylidene-N' -methyl- dipropylenetriamine, 0.1 to 5.8, 7.5, 10.0, 12.0, 15.0,
  • Concentrations also range from 4 to 12, 5 to 30 ppm. Other concentrations necessary to maintain thermal stability are contemplated.
  • metal deactivators include passivator type thiadiazoles such as HITEC 314 by Ethyl Corp.
  • Non-limiting examples of drag reducing agent ⁇ include high molecular weight (1,000,000) polyi ⁇ obutenes and polyalphaolefin ⁇ .
  • Non-limiting example ⁇ of dye ⁇ include azo compound ⁇ and/or anthraquinone.
  • Non-limiting example ⁇ of demul ⁇ ifier ⁇ include complex non-ionic surfactants, alkoxylated polyglycols and aryl sulfonates, and mixture (typically at treat rates in the range of 10-20% of that of the detergent, if any) .
  • non-limiting examples include p-i ⁇ obutylphenol, p- diisobutylphenol, p-hexylphenol, p-heptylphenol, p- octylphenol, p-tripropylenephenol, p-dipropylenephenol, ammonia-neutralized sulphonated alkylphenols, oxyalkylated glycols available from BASF-Wyandotte Chemical company, proprietary products, including TALOD 286K, TALOD 286 marketed by Petrolite Corp..
  • Non-limiting examples of corrosion inhibitors include carboxylic acid, amines, and/or amine salts of carboxylic acids are used.
  • Mobile Chemical Corp. markets "Mobiladd F- 800" a combination lubricity agent and corrosion inhibitor.
  • Non-limiting examples of anti-oxidants include hindered phenols, 2,6-Di-t-butyl-4-methylphenol (15 - 40 mg/1, 25 mg/1, or more) , phenylenedimine ⁇ , aromatic diamine ⁇ , or mixture ⁇ of aromatic diamines and alkyl phenol ⁇ sterially hindered phenolic and amine groups.
  • antioxidant ⁇ in amounts up to 24.0 mg/L active ingredients (not including weight of solvent) .
  • Such antioxidant ⁇ are ⁇ elected from N,N-dii ⁇ opropylparaphenylene diamine, ⁇ eventy-five percent minimum 2,6-di-tertiary-butyl phenol plus 25% maximum tertiary and tritertiary butyl phenols, seventy-two percent minimum 2,4-dimethyl-6- tertiary-butyl phenol plus 28% maximum monomethyl and dimethyl tertiary-butyl phenols, fifty-five percent minimum 2,4-dimethyl-6-tertiary-butyl phenol plus 45% maximum mixed tertiary and ditertiary butyl phenols.
  • Additional anti-oxidants that may be employed in this invention include 2,6-di-tert-butyl-4-methylphenol, 6-tert- butyl-2,4-dimethylphenol, 2,6-di-tert-butylphenol, 75 percent min-2, 6-di-tert-butylphenol 25 percent max tert- butylphenols and tri-tertbutylphenols, 72 percent min 6- tert-butyl-2, 4-dimethylphenol
  • inhibitors whose total concentration is not greater than 1.0 lb, not including weight of solvent, per 5000 gal of fuel, of: 2, 4-dimethyl- 6-tertiary-butyl phenol, 2, 6-detertiary-butyl-4-methyl phenol, 2, 6-ditertiary-butyl phenol, 75% 2, 6-ditertiary- butyl phenol, 10-15% 2, 4, 6-tritertiary-butyl phenol, 10- 15% orthy-tertiary butyl phenol, 72% min 2, 4-dimethyl-6- tertiary butyl phenol, 28% max.
  • Additive concentrations for additive herein which is above industry ranges are expre ⁇ ly contemplated, particularly where nature or concentration of ECS or metallic compound ⁇ warrant such usage.
  • Non-limiting examples of anti-icing additives include isopropyl alcohol, hexylene glycol, dipropylene glycol, glycols, formamides, imidazoline ⁇ and carboxylic acid ⁇ .
  • Non-limiting example ⁇ of valve ⁇ eat rece ⁇ ion additive ⁇ include sodium or potas ⁇ ium long chain alkenyl ⁇ ulfonates, sodium or potassium long chain naphthenates, or microdispersions of sodium or potassium salts in oil.
  • Dispersants include ashle ⁇ succinimides or polymeric methyacrylates, including alkenyl ⁇ uccinic acid e ⁇ ters, alkenyl succinimide of an amine, methylamine, 2- ethylhexylamine, n-dodecylamine, (see U.S. Patents 3,172,892; 3,202,678, 3,219,666, 4,234,435).
  • disper ⁇ ant ⁇ include Texaco's CleanSystem 3 , high molecular weight polyisobutylene ⁇ ubstituted amine derivative TFA- 4681, fuel ⁇ oluble salts, amides, imides, oxazoline ⁇ and e ⁇ ter ⁇ of long aliphatic hydrocarbon- ⁇ ub ⁇ tituted dicarboxylic acids or their anhydrides, long chain aliphatic hydrocarbons having a polyamine attached directly thereto, a Mannich condensation product(s) formed by condensing a long chain aliphatic hydrocarbon-substituted phenol with an aldehyde, preferably formaldehyde, or similar additive is contemplated in the practice of keeping fuel injectors and valve intakes clean.
  • Texaco's CleanSystem 3 high molecular weight polyisobutylene ⁇ ubstituted amine derivative TFA- 4681, fuel ⁇ oluble salts, amides, imides, oxazoline ⁇ and
  • Applicant contemplates any commercially available dispersant, including ashle ⁇ s disper ⁇ ant ⁇ .
  • Applican ' ⁇ invention contemplates carburetor, port fuel injector and intake valve deposit control additives.
  • Non-limiting examples include amides, amines, amine carboxylates, alkenyl ⁇ uccinimde ⁇ , polybutene ⁇ uccinimides, polyalkenyl succinimide (Ethyl Petroleum Additives, Inc., HITEC 4450) , polyether amines, polyether amide amines, ployalkenyl amines, polyether amines (Oronite Chemical Co. OGA-480) , polyisobutenyl amine (Oronite Chemical Co.
  • polybuteneanine ⁇ polyetheramine ⁇
  • polyolefin amine ⁇ with or without carrier fluid.
  • Such material ⁇ may be incorporated at treat concentration ⁇ of 50 to 500 pound ⁇ per thou ⁇ and barrels, and more usally in the range of 100 to 200 lb ⁇ per thousand barrels.
  • Non-limiting example of detergent include: succinimides, Long chain aliphatic polyamines, long chain Mannich base ⁇ , ashless polymeric di ⁇ perant ⁇ , nitrogen- containing a ⁇ hle ⁇ s dispersants, especially polyolefin- substituted succinimdes of polyethylene polymine ⁇ ⁇ uch a ⁇ polyethylene tetramine ⁇ and polyethylene hexamine ⁇ are desireable. Alkenyls succinimide of an amine having at least one primary amino group capable of forming an imide group are desireable. Especially preferred are products of reaction of polyethylene polyamine with an unsaturated polycarboxylic acid or annhydride. ionic or non-ionic surfactants and detergent containing metals, including magne ⁇ ium laural salts are contemplated.
  • ashle ⁇ despersant ⁇ include alkenyl succinic acid esters and diester ⁇ of alchols containing 1-20 carbon atoms and 1-6 hydroxyl groups. See U.S. Patents # 3,331,776, 3,381,022, and 3,522,179.
  • ashless dispersant ⁇ which are an alkenyl succinic ester-amide mixture, Mannich condensates of hydrocarbyl-substituted phenols, formaldehyde or formaldehyde precusors and an amine, such as those disclosed in U.S. Patent # 3,442,808, 3,803,039 are contemplated. Applicant recognizes the art is replete with ashle ⁇ s dispersant ⁇ (see U.S.
  • Smoke suppressants including organic compounds of barium, particularly the barium carbonate overbased barium sulfonates, N- ⁇ ulfinyl aniline ⁇ , are contemplated, as well a ⁇ other ⁇ . Although environmental concerns will dictate choice and concentration levels.
  • Example diesel fuel additives are shown by class and function in Table 1, above. As with any ⁇ y ⁇ tem in which a variety of additives may be used, care should be taken to avoid incompatibilities among additives and unanticipated interactions which may produce undesirable fuel effects.
  • the fuel will contain other deposit control additives, non-limiting examples include polyether amine, polyalkenyl succinimide, or polyalkenyl ⁇ uccinimide, hydrocarbyl carbonate ⁇ , such as polybutene alcohol, polybutene chloroformate, polybutene amines formulated in mineral or other carrier ⁇ , polyisobutylene amine reformulated in polyether carriers, and one-component polyether amines, and the like.
  • polyether amine polyalkenyl succinimide
  • polyalkenyl ⁇ uccinimide hydrocarbyl carbonate ⁇
  • polybutene alcohol polybutene chloroformate
  • polybutene amines formulated in mineral or other carrier ⁇ polyisobutylene amine reformulated in polyether carriers
  • one-component polyether amines and the like.
  • Applicant's invention contemplates that acceptable deposit control additives will meet indu ⁇ try and regulatory ⁇ tandard ⁇ , including CARB's 10,000 mile BMW IVD and Chrysler PFI keep clean test ⁇ . Thu ⁇ , contempated average deposits on all valves cannot exceed 100 milligrams on said BMW test, nor no more than 5% plugging, as measured in flow lo ⁇ , in any one injector. It i ⁇ an expre ⁇ s embodiment to avoid employing IVD additives or PFI additives, which show any detrimental performance in combustion chamber deposit control or reduction.
  • Applicant notes combu ⁇ tion chamber additive ⁇ are not novel and have been u ⁇ ed to maintain fuel system cleanlines ⁇ for some time, and are contempled herein, particularly in modified, co-fuel, and ECS ⁇ co-fuel applications where the ECS fuel is a minority component. In neat ECS fuels with advanced combustion features CCD additive may not be required and is optional.
  • Non-limiting examples of desireable CCD additives include Shell's VEKTRON ORIC additive ⁇ (Octane Requirement Increa ⁇ e Control) or ORR additive ⁇ (Octane Requirement Reduction) and/or ⁇ imilar additive package, or Oronite's CCD (Combustion Chamber Deposit) additive package, Texaco's CleanSystem 3 or Ethyl's equivalent HiTec additive package.
  • Other means of controlling combustion chamber deposits optionally include lower molecular weight surfactant ⁇ and high molecular weight polymeric di ⁇ per ⁇ ants based upon polybutene. Intermittent high concentrations of polyeramines, glycol boarate ⁇ and ethylene dichloride may be employed. Additive concentration level ⁇ may range from moderate to very high, depending upon the efficacy of the additive/additive package and co-fuel employed.
  • Applicant's combustion chamber deposit control additives PFI (Port Fuel injector) and IVD (Intake Valve Deposit) additives, and concentrations thereof, be effective in controlling and preferably reducing existant combustion chamber deposits. It is an express object of instant invention to employ deposit additives inclusive of or beyond IVD and PFI additives, namely to employ additives additionally or in lieu of IVD/PFI or combustion chamber deposit (CCD) additive.
  • deposit additives inclusive of or beyond IVD and PFI additives namely to employ additives additionally or in lieu of IVD/PFI or combustion chamber deposit (CCD) additive.
  • CCD combustion chamber deposit
  • ECS compound (0.1 to 99.99% wt) ,- 2) at least one organo manganese compound (preferably MMT) and/or other combu ⁇ tion improving metallic compound (or mixture thereof) (0.01 to 99.0% wt) ; and 3) a combustion chamber deposit control/reducing additive (0.01 to 95.0% wt) , including but not limited commercially available and/or proprietary additive such as Shell's VEKTRON ORIC additive or ORR additive, Oronite Corporation's CCD additive package, Texaco's CleanSyste 3 , or Ethyl's equivalent HiTec additive; and optionally 4) a metal deactivator (0.1% to 90.0% wt) ; said package optionally characterized as having LHV exceeding 30, 50, 80, 110, 130, 135, 145, 147, 148, 150, 151, 152, 155, 157, 160, 165, 170, BTU/lb, or greater.
  • organo manganese compound preferably MMT
  • An additive package for use in hydrocarbon fuels comprising: 1) at least one ECS compound (0.1% to 99.5% wt) ; 2) at least one cyclopentadienyl manganese tricarbonyl (0.1% to 99.5% wt) ; 3) at least one metal deactivator (not limited to 8-hydroxyquinoline, ethylene diamine tetracarboxylic acid, B-ketoesters such as octyl acetoacetate, N,N'-disalicylidene -1, 2 - propanediamine, N,N'-disalicylidene-l, 2-propane diamine, N,N !
  • the additive package of 185 comprising: 1) DMC representing 1.0% to 99.0% by weight of composition; 2) cyclopentadienyl manganese tricarbonyl representing 0.01% to 40.0% weight; 3) N,N'-disalicylidene-l,2-propanediamine representing 0.001% to 15.0%; optionally: 4) 2,6-Di-t- buty1-4-methylphenol representing 0.01% to 40.0%, 5) Polyisobutenyl succinimide of tetrethylene pentamine or Mannich condensation product of p-(polyisobutenyl)-phenol, formaldhyde, and triethylene tetramine, representing 0.01% to 35% 6) di-tertiary butyl peroxide or 2-ethylhexyl nitrate, representing 0.01% to 60.0% 7) Akzo Armogard D5021 demulsifier representing 0.01% to 25.0%, 8) 4-methyl-2- pentanone representing 0.01% to 90%;
  • Example 187 A method of reducing NOx emissions comprising: mixing a combustion improving amount of a metallic and an ECS compound, and a metal deactivtor; and optionally a co-fuel; combusting said fuel, whereby NOx emissions are reduced by at least 2.0%, 5.0%, 7.0%, 10.0%, 15.0%, 20.0%, 25.0% or more, compared to co-fuel additive package.
  • Example 188 An additive package for use in hydrocarbon fuels comprising: 1) at least one ECS compound (0.1 to 99.0% wt) ; 2) at least one cyclopentadienyl. manganese tricarbonyl (0.05 to 40.0% wt) ; 3) at least one ignition promoter, e.g.
  • peroxy compounds, organic nitrates, potassium salts including those commercially marketed by Shelll Chemical, known as "SparkAid or SparkAde” (0.02 to 80.0% wt) ; said package optionally having: 4) at least one demulsifier (0.01 to 30.0% wt) , 5) at least one FPI or vapor reducing co-solvent or salt (0.0001 to 70.0% wt) , 6) at least one metal deactivator (0.1 to 40.0% wt) , 7) at least one detergent/dispersant (0.01 to 60.0%), or 8) at least one antioxidant (0.1 to 40.0% wt) ; said package optionally characterized as having LHV exceeding 20, 30, 35, 40, 45, 55, 63, 80, 90, 100, 110, 120, 133, 140, 142, 145, 147, 148, 150, 151, 152, 155, 157, 160, 165, 170, BTU/lb, or greater.
  • An additive package for use in hydrocarbon fuels comprising: 1) at least one ECS compound (0.1 to 99.0% wt) ; 2) at least one cyclopentadienyl manganese tricarbonyl (0.05 to 99.0% wt) ; 3) at least one detergent/dispersant (O.01 to 99.0%); and optionally one or more of the following: 4) at least one antioxidant (0.1 to 99.0% wt) , 5) at least one ignition promoter (0.02 to 99.0% wt) , 6) at least one demulsifier (0.01 to 99.0% wt) , 7) at least one FPI or vapor reducing co-solvent or salt (0.0001 to 99.0% wt) , 8) at least one metal deactivator (0.1 to 99.0% wt) ; said package optionally characterized as having LHV exceeding 15, 20, 25, 30, 40, 45, 50, 55, 60, 70, 80, 85, 95, 100, 120, 133, 140, 142, 145
  • Example 190 An additive package for use in hydrocarbon fuels comprising: 1) at least one ECS compound (0.1 to 99.0% wt) ; 2) at least one cyclopentadienyl manganese tricarbonyl (0.05 to 99.0% wt) ; and 3) at least one antioxidant (0.1 to 99.0% wt) ; and optionally one or more of the following: 4) at least one detergent/dispersant (O.01 to 99.0%), 5) at least one ignition promoter (0.02 to 99.0% wt) , 6) at least one demulsifier (0.01 to 99.0% wt) , 7) at least one FPI or vapor reducing co-solvent or salt (0.0001 to 99.0% wt) , 8) at least one metal deactivator (0.1 to 99.0% wt) ; said package optionally characterized as having LHV exceeding 20, 30, 35, 40, 45, 55, 63, 80, 90, 100, 110, 120, 133, 140, 142,
  • Example 191 A clean combustion additive comprising: 1) at least one ECS Compound (0.01 to 99.0 % wt) , 2) at least one organo manganese compound (preferably MMT) and/or other combustion improving metallic compound (or mixture thereof) (0.01 to 99.0% wt) ; 3) an antioxidant (0.01 to 80.0% wt) , 4) a metal deactivator (0.01 to 99% wt) , 5) a detergent or detegent/dispersant (0.1 to 99.0% wt) ; optionally 6) a stabilizer (.01 to 99.0% wt) ; said package optionally characterized as having LHV exceeding 15, 20, 30, 35, 40, 45, 55, 63, 80, 90, 100, 110, 120, 133, 140, 142, 145, 147, 148, 150, 151, 152, 155, 157, 160, 165, 170, BTU/lb, or greater.
  • this clean combustion additive package may optionally contain one or more injector and/or intake valve deposit additive(s) .
  • Concentrations of each compound or the performance features of individual additives and/or additive package, as an entirety, should meet minimum standards set by industry or requirements established by legal or regulatory standard. It is contemplated that concentrations may include those that exceed or be less than those recommended by the additive manufacture.
  • Example 192 additive and lubricating oil practice, especially in co-fuel practice that reduce or control combustion chamber deposits, are an express embodiment of this invention.
  • Example 192 is an express embodiment of this invention.
  • a composition comprised of a minor amount of at least one metallic, including, for example a cyclopentadienyl manganese tricarbonyl compound, and a major amount of a combustion chamber deposit control additive or additive package, such as Texeco's CleanSystem 3 additive.
  • a combustion chamber deposit control additive or additive package such as Texeco's CleanSystem 3 additive.
  • combustion chamber deposit control additive includes, or additionally includes, at least one ECS compound, preferably DMC.
  • composition of example ⁇ 192 additionally compri ⁇ ing an injector and/or induction valve depo ⁇ it control additive; wherein ⁇ aid additives are same or differing additives.
  • Example 195 A composition comprising at least one cyclopentadienyl manganese tricarbonyl and/or other combustion improving metallic compound, a combustion chamber deposit reducing additive, and optionally, an injector and/or induction valve deposit control additive,- wherein said additive ⁇ are ⁇ ame or differing additive ⁇ .
  • Example 196 A composition comprising at least one cyclopentadienyl manganese tricarbonyl and/or other combustion improving metallic compound, a combustion chamber deposit reducing additive, and optionally, an injector and/or induction valve deposit control additive,- wherein said additive ⁇ are ⁇ ame or differing additive ⁇ .
  • Example 196 A composition comprising at least one cyclopentadienyl manganese tricarbonyl and/or other combustion improving metallic compound, a combustion chamber deposit reducing additive, and optionally, an injector and/or induction valve deposit control additive,- wherein said additive ⁇ are ⁇ ame or differing additive ⁇ .
  • Example 197 A method incorporating the fuel compositions of Examples 192-196, where said additive package is employed in deposit reducing quantities in a fuel for combustion in an internal combustion engine,- wherein anti-knock sensors do not retard spark advance to avoid knocking, whereby fuel economy and/or power is improved by at least 0.5%, 1.0%, 1.5%, 2.0%, 3.0%, 5.0%, or more, over clear fuel.
  • composition of 197 wherein the manganese concentration is equal to an amount such that the treatment level of the additive package equals at lea ⁇ t the minimum metallic concentrations for the fuels set forth herein.
  • Example 199 The composition of 197, wherein the manganese concentration is equal to an amount such that the treatment level of the additive package equals at lea ⁇ t the minimum metallic concentrations for the fuels set forth herein.
  • composition of 197 wherein deposit control additives are in an amount such that after treatment of a fuel, combustion chamber, injector, and/or intake valve deposit ⁇ are controlled, modified, or reduced, and/or -137- wherein treated fuel meets regulatory or minimal legal standards.
  • Applicant contemplates extensive use of IVD, PFI and ORI (or CCD) control additives in the examples herein.
  • a fuel composition comprising an ECS fuel (comprising an ECS compound, preferably DMC, and at least one combustion improving metallic, preferably MMT) ; a co-fuel,- an injector deposit control additive,- an intake valve deposit control additive; and a combustion chamber deposit control additive; wherein said deposit control additive may be same or multiply compound, and/or wherein said compound or compounds change/reduce existing combustion chamber deposit ⁇ while preferably enhancing combustion efficiency (but not required) .
  • ECS fuel comprising an ECS compound, preferably DMC, and at least one combustion improving metallic, preferably MMT
  • additives including deposit control additives, operate to enhance the ECS and metallic combustion chemistry, which represent ⁇ the predominate thermodynamic and cpmbu ⁇ tion object of Applicant' ⁇ invention, a ⁇ opposed to merely enhancing the fuel and combustion characteristics of Applicant's co-fuels.
  • combustion chamber deposit ⁇ are ⁇ ub ⁇ tantially controlled when employed in combination with a co-fuel, absent need for additional additive.
  • neat ECS fuels contain deposit control additive(s), may include injector, valve intake and/or combustion chamber deposit additive(s). Lubricity, antioxidant, corrosion, and other known additive are contemplated.
  • Non-limiting examples of wax crystal modifiers (wax anti-settling agents) or middle distillate flow improvers include ashless low molecular weight co-polymer ⁇ and include ethylene vinyl acetate co-polymers.
  • Cold flow improvers are contemplated with diesel fuel ⁇ , particularly those with reduced sulphur and/or reduced aromatic concentrations, e ⁇ pecially as fuel temperatures drop.
  • Betz Process Chemicals markets a superior cold flow improver additive. In the practice of this invention cold flow improvers are expressly contemplated.
  • Non-limiting examples of antifoam agents include polysilicone based compounds.
  • Non-limiting examples of cetane improvers include peroxy compounds and organic nitrate ⁇ , including di- tertiary butyl peroxide, acetyl peroxide, benzoyl peroxide, tertiary-butylperoxyaceate, cu ene hydroperoxide, alkyl peroxides, alkyl hydroperoxides, 2.5 dimethyl 2.5 di(tertiary butyl peroxy) hexane, tertiary butylcumyl -139- peroxide, di(tertiaryamyl) peroxide, tertiary butyl hydroperoxide, tertiary amyl hydroperoxide, alkyl nitrates, cyclohexyl nitrate, methoxypropyl nitrate, mixed nitrate esters made by nitration of fusel oil, n-octyl nitrate, n- decyl nitrate, eth
  • concentrations include up to approximately 0.35, 0.40, 0.45, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5 % vol., or more, of the fuel.
  • cetane improvers include Arco's peroxide-based dialkyl peroxide improver, which may be included in the fuel composition up to approximately 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5% vol., or at greater volumes.
  • Such promoters are particularly desireable in combination with Applicant's invention, and are expres ⁇ ly contemplated in non-diesel fuels applications.
  • Multifunctional additive packages are also contemplated. Such packages may contain detergents, cetane/octane improvers, combustion chamber deposit control additives, fuel stabilizers, flow improvers, anti-foam agents, reodorants, demulifier, corrosion inhibitors, lubricity additives, and/or solvents for package stability.
  • Lubricity additives are particularly comtemplated in low/no sulfur diesel/distillate fuels, inorder to avoid equipment, elastomer, and other failure.
  • Example 194 wherein the additive optionally contains an intake deposit control additive and/or combustion chamber deposit control additive, wherein said additive or additives are employed in a compo ⁇ ition containing a diesel co-fuel, together with balance of combustion and temperature reducing amount of ECS compound( ⁇ ) and metallic(s), wherein said operation of engine results in reduction of NOx and/or particulate emissions, when compared to ⁇ aid deposit control additive(s) employed in clear diesel co-fuel alone (absent ECS compound and metallic) .
  • an intake deposit control additive and/or combustion chamber deposit control additive wherein said additive or additives are employed in a compo ⁇ ition containing a diesel co-fuel, together with balance of combustion and temperature reducing amount of ECS compound( ⁇ ) and metallic(s), wherein said operation of engine results in reduction of NOx and/or particulate emissions, when compared to ⁇ aid deposit control additive(s) employed in clear diesel co-fuel alone (absent ECS compound and metallic) .
  • Applicant notes the enhanced combustion burning and temperature reducing properties of instant invention unexpectedly enhance the operating, performance features of such PFI, IVD, CCD additive and additive packages.
  • a method of employing a CCD, IVD or PFI additive in an internal combustion chamber comprising simultaneous injection of an atomized vapor comprising a minor amount of at least one high burning velocity (and/or low combustion temperature causing) ECS compound, at least one high energy releasing metallic compound, and a minor amount of an CCD, IVD, or PFI compound, and mixture, and a low sulfur reformulated or conventional co-fuel; combusting said vapor in said combustion chamber, wherein high kenetic energy metallic vapor phase combustion occurs,- whereby existing combustion chamber deposits are modified or reduced and/or intake valve deposition is similarly avoided over time, as compared to employing said deposit control additive (s), absent said ECS compound and metallic.
  • additive packages of instant invention will be formulated to avoid intake valve sticking and crankcase oil contamination.
  • Example 205 The method of Examples above, wherein intake valve deposit, port fuel injector deposit and gum control additives are employed in sufficient concentrations, wherein intake valve deposit ⁇ are le ⁇ s than 100, 90, 80, 70, 60, 50, 40 mg under BMW 3181 te ⁇ t (BMW IVD test), and wherein port fuel injector deposits do not exceed a 10%, 9%, 8%, 7%, 6% or 5% or les ⁇ re ⁇ triction at 10,000 miles when employing a 2.2 liter Chryler engine (CRC PFI test), and wherein the maximum gum limits are 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5.0 mg/100 ml or less washed, and/or 5.0, 4.5, 4.0, 3.5, 3.0, 2.5, 2.0, 1.5, 1.0, 0.5 mg/100 ml or less unwashed.
  • intake valve deposit ⁇ are le ⁇ s than 100, 90, 80, 70, 60, 50, 40 mg under BMW 3181 te ⁇ t (B
  • Example 206 The method of Example 205, wherein the engine is a gasoline or internal combustion engine who ⁇ e compre ⁇ sion ratio is 9.6:1, 9.7:1, 9.8:1, 9.9:1, 10.0:1, 10.1:1, 10.2:1, 10.3:1, 10.4:1, 10.5:1, 10.6:1, 10.7:1, 10.8:1, 10.9:1, 11.0:1, 11.1:1, 11.2:1, 11.3:1, 11.4:1, 11.5:1, 11.6:1, 11.7:1, 11.8:1, 11.9:1, 12.0:1, 12.1:1, 12.2:1, 12.3:1, 12.4:1, 12.5:1, 12.6:1, 12.7:1, 12.8:1, 12.9:1, 13.0:1, 13.1:1; 13.2:1, 13.1:1, 13.2:1; 13.5:1, 13.6:1, 14.0:1, 14.1:1, 14.2:1, 14.3:1, 14.4:1, 14.5:1, 14.6:1, 14.7:1, 14.8:1, 14.9:1, 15.0:1, 15.5:1, 16.0:1, 16.5, 17.0:
  • the gasoline method wherein engine operation compri ⁇ e ⁇ u ⁇ e of electronic knock ⁇ en ⁇ or to retard ⁇ park and wherein spark retardation and hence combustion efficiency is improved over clear fuel by at least 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0. or 4.5 octane numbers or more, after a equalivalent of 5,000, 10,000, 15,000, 20,000, 30,000, 50,000 miles or more.
  • Example 210 The method of Example 209, wherein acceleration of engine employing Applicant's fuel compostion with combu ⁇ tion chamber depo ⁇ it control additive i ⁇ improved 1.0%, 2.0%, 3.0% to 10%, 4.0% to 15.0% or more over the clear fuel, alone.
  • ECS compound ⁇ in their neat form will contain additives, as required to avoid corrosion and maintain stability caused by peroxide formation, etc.) .
  • Non-limiting examples include phenolic-based and amine based stabilizers such as UOP 7 and UOP 5.
  • Other non-limiting stabalizers include aliphatic or cycloaliphatic amines ⁇ uch a ⁇ N- cyclohexyl-N,N-dimethyl amine. See U.S. Patent 3,909,215 and EP 188,042 for additional example ⁇ . Concentrations will vary depending upon stability concern ⁇ . For example, ETBE and diisopropyl ether have a stronger tendency to form peroxides than does MTBE and hence may require greater concentrations.
  • ECS alcohol compounds are hydroscopic and tend to phase seperate in fuel system ⁇ expo ⁇ ed to or containing water. Thu ⁇ , co-solvents that control phase separation are desireable.
  • Certain carbonates namely di-methyl and di-ethyl carbonates are prone, in certain circumstances, to hydrolyze when exposed to similar environments.
  • Lower molecular weight ECS alcohols, ethers, carbonates, ketones, and the like can adversely increase vapor pres ⁇ ure or reduce flash point temperature. Their useage can also reduce T-50 temperatures causing driveability problem ⁇ or technical enleanment. Correction of T-50 and end boiling point adjustment employing azeotroping co-solvents is known in the art, see my EPO Patent 8690642.6.
  • co-solvents be ECS compounds or have ECS combustion/temperature or BV enhancing attributes.
  • Preferred co-solvents increase LHV and/or BV.
  • FPI co-solvents will increase flash point 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 5.0, 6.0, 10.0, 15.0, 20.0, 25.0, 30.0, 35.0, 40.0°C, or more. Increases of 3.0°C, or more are preferred. It i ⁇ contemplated that FPI co-solvents will raise flash points to minimum ASTM or government specification ⁇ . VPR co-solvents will reduce RVP by 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0. l.l, 1.5, or more psi. VPR co- solvents will reduce RVP to within ASTM or government specifications.
  • Applicant's desired co-solvent ⁇ will have melting point ⁇ less than 20, 10, 0, -5, -10, -15, -20, -25, -30, - 40, -50, -60, -70, -80, -90, -100, -130. -140°C, or below. Preferred will be those with melting points les ⁇ than -5°C, more preferably le ⁇ than -40, -50, -60, -70 ,-80, -90°C, or below. It is expressly contemplated that FPI co-solvents with high melting points be combined with co-solvent or additive, including low melting point co- ⁇ olvent ⁇ , e ⁇ pecially those azeothroping temperature.
  • Alchols are intended a ⁇ well a ⁇ hydrocarbon based solvent ⁇ .
  • a preferred icing inhibitor is ethylene glycol monomethyl ether, conforming to the requirements of ASTM Specification D 4171. Preferred concentrations range from about 0.1 to 0.15 volume %. However, concentrations outside this range may be employed. Additional ant -icing additives include Phillips PFA 55 MB @ 0.15% Vol. and MIL-I-27686 @ 0.15% Vol. Max.
  • co ⁇ solvents in same or differing proportions, having different freezing points, flash points and/or vapor pressures, LHV, and burning velocities.
  • One such combination would embody combining one or more ' moderate to high freezing temperature co-solvent (s) having moderate to high flash point temperatures and a low to very low freezing point co-solvent (s) , whereby resultant mixture would have combination of moderately high to high fla ⁇ h point and low freezing point.
  • icing inhibitors may be employed, including alcohols, co-solvents, and the like, especially where the ECS compound or co-solvent doe ⁇ not have a sufficiently low melting point and/or when the finished fuel's pour point or freeze temperature is to high.
  • Applicant's co-solvent ⁇ will have boiling point ⁇ above 70, 80, 90, 100, 110, 120, 300°C, and greater. Boiling point ⁇ above 130, 160, 190, 200, 220, 240, 260, 270°C, or greater, are preferred. De ⁇ ired flash point temperatures of co-solvent ⁇ are - 80, -31, -20, -15, -10, -5, 0, 5, 10, 15, 20, 25, 30, 35, 38, 40, 50, 58, 60, 65, 70, 75, 80, 85, 90, 95, 100, 120, 130, 140, 150, 160, 170, 180, 200, 220, 250, 300, 360°C, ore or le ⁇ s.
  • Preferred flash point temperatures are -100, -80, -60, -30, 0, 40, 60, 80. 100, 120, 130, 140, 150°C, or more. More preferred are those above 80, 100, 120, 150, 170°C.
  • Co-solvents may have same flash point characteristics as ECS compounds.
  • Desireable cosolvents have a latent heat of vaporization in excess of 18, 20,. 21, 23, 24, 25, 27, 29, 30, 31, 33, 35, 37, 39, 41, 43, 45, 47, 49, 51, 53, 55, 57, 59, 62, 65 vap H(T b )/kJ mol "1 (or equivalent), or alternatively greater than 120, 123, 125, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 140, 142, 145, 147, 150, 152, 155, 157, 160, 162, 165, 170 BTU/lb.
  • co-solvent LHV' ⁇ be greater than any co-fuel to which they might by added.
  • LHV mu ⁇ t be balanced by the other a ⁇ pect ⁇ of u ⁇ age, e.g. LHV of re ⁇ ultant fuel, LHV effect of ECS compound (if any) , fla ⁇ h point and/or vapor pre ⁇ ure priority, etc.
  • Preferred BV ⁇ are equal or above 28, 30, 32, 34, 36, 38, 40, 42, 43, 44, 45, 46, 47, 48, 50, 55, 60 cm/sec (laminar bunsen flame) .
  • Preferred co-solvent temperatures at vapor pressures of l mm should exceed 20, 40, 60°C. More preferred temperatures are those that exceed 80, 29, 100, 120, 130, 140, 150, 180°C, or more.
  • the co- ⁇ olvent (s) have a vapor pre ⁇ ure of l mm, or less, at temperatures of about or greater than -20, -10, 0, 20, 30, 40, 50, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180°C. See 1969-1970, 1995 Chemical Rubber Company CRC "Handbook of Chemistry and Physics.
  • Applicant's co-solvents may be selected from a very broad class of flammable chemistry.
  • Applicant's desired co- solvents are those having less than 22, 20, 18, 16, 14, 13, 12, ii, 10 or 9 carbon atoms, with those having less than 8, 7, 6, 5, 4, 3, 2 or less atoms being preferred. While those above these ranges are contemplated and acceptable, those having 6, 5, 4, or fewer carbons in a chain are also preferred.
  • Co-solvents containing oxygen are desireable.
  • Co-solvents containing OH radicals are also desireable.
  • Applicant ha ⁇ found that co-solvents having molecular structure in part comprising CH3C02, and/or OH to be desireable. Nitrogen based compounds may be acceptable, depending upon the application. Non-carbon based co- ⁇ olvent ⁇ are contemplated.
  • Co-solvent chemical structure is not limited, and may be cyclic, bi-cyclic, aromatic, non- aromatic, branched or straight chain, or combination thereof.
  • co-solvent be thermally stable, not decompose under normal handling and operating temperatures ( ⁇ ee ECS ⁇ tandard ⁇ above) , or cau ⁇ e co-fuel deterioration, e.g. guming, corro ⁇ ion, etc. It i ⁇ additionally de ⁇ ireable that the half life of its evaporative or combustion product be very short, preferably less than days (e.g. 8, 5, 4 or less), more preferably less than hours (e.g. 24, 18, 12, 8, 4, 3, 2, 1 or less), most preferably les ⁇ than minutes (e.g. 60 ,45, 30, 15, or less) . As contemplated herein co-solvent practice need not include an ECS compound and/or metallic.
  • one or more co-solvent may be employed for phase separation control, and one or more for FPI or VPR, one or more for reducing freezing temperatures. While there is no limitation on the type, number or range ⁇ of co- ⁇ olvent ⁇ in a mixture, Applicant recognize ⁇ that differing fuel will elicit differing requirements for differing co ⁇ solvent mixture ⁇ . When practical, single component co- solvent mixtures are preferred.
  • Co-solvent practice may al ⁇ o be ⁇ upplemented or substituted by use of heavy naptha's, including aromatic naptha's.
  • heavy or moderately heavy hyrocarbons including naptha ⁇
  • co-solvent usage not increase melting/freezing point temperatures, or diminish or aggravate fuel stability, corrosion, elastermer deteriora ion, evaporative emissions, toxic emissions, hazardous combustion emissions, or diminish combustion burning velocities and LHV's.
  • co ⁇ solvent usage not to contribute to gumming or oxidation. However, in such circumstances, (e.g. for example, where freezing points are not sufficiently low) , it is contemplated an additional co-.solvent, substitute co ⁇ solvent or other additive, or means be employed.
  • Elastermer swelling or deterioration, corrosion or fuel degradaton may be corrected by employing additional agents, e.g. corrosion inhibitors, anti-oxidants, etc.
  • co-solvent be soluble with the targeted ECS compound, if employed, and optionally: co- fuel and/or water.
  • Co-solvent ⁇ having limited water soluability or insolvent are preferred.
  • Applicant has also found that nonvolitile, nonion producing co-solvents to be desireable for purposes of reducing vapor pressure and/or raising fla ⁇ h point ⁇ .
  • Applicant ha ⁇ found hydrocarbon ⁇ oluble, flammable glycol ⁇ , ketone ⁇ , and their acetate ⁇ , and esters to be desireable. Ethanoic, propanoic, butanoic, pentanoic, and hexanoic acids, including their acetates, esters and ethers are also desireable. Ethenes, butene ⁇ , propene ⁇ , hexene ⁇ , pentene ⁇ are acceptable.
  • Non-limiting example ⁇ of Applicant's co-solvent ⁇ include: alcohol ⁇ , glycols, ketones, esters, phenols, acetals, acid azides, acid halides, acids and acid derivatives (aldehydic, aliphatic dicaroxylic, alipatic monocarboxylic, aliphatic polycarboxylic, amino acids, hydroamic, hydroxyacids, imidic, ketonic, nitrolic, orthoacids, peracid, etc.), acetic acids, acetic anhydrides, acetic acid esters, aldehydes, aliphatic hydrocarbons (including high boiling point napthas) , amides, amidines, amidoximes, anhydrides, aromatic hydrocarbons, azides, azines, azelates, azo compounds, betaines, bromoactealdehyde ⁇ , bromoethanes, bromoethylenes, bromoacetic acids, bromobutanes, bromobutene
  • Additional non-limiting examples are: triethylene glycol, 3-aminopropy1 ether triethylene glycol, diacetate triethylene glycol, monobutyl ether triethylene glycol, monomethyl ether triethylene glycol, monopropyl ether triethylene glycol, te raethylene glycol, dibutoxytetraethylene glycol, diacetate tetraethylene glycol, aminopropyl ether tetraethylene glycols, monobutyl ether tetraethylene glycol, monomethyl ether tetraethylene glycol, dimethyl ether tetraethylene glycol, diethyl ether tetraethylene glycol, monoethyl ether tetraethylene glycol, monopropyl ether tetraethylene glycol, tetraethylenepentamine, tripropylene glycol, tetrapropylene glycol, dipropylene glycol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether,
  • co-solvent mixtures including mixing two or more, are expressly contemplated.
  • any two or more co-solvents may be employed jointly, in same or differing proportions.
  • high flash point co ⁇ solvent (s) with alcohol and/or other co-solvent to control hydrolysis and/or hydroscopic phase ⁇ eparation.
  • a co-solvent or mixture of co-solvents which for example act to reduce vapor pressure or elevate flash point, etc., may also act as a mutual ⁇ olvents to dissolve non-soluble or moderately mi ⁇ cible co- ⁇ olvent and/or ECS compound( ⁇ ), if employed.
  • Applicant recognizes that a wide variety of combinations and mixtures and proportions exist, which acheive the multiple objects of Applicant invention.
  • co- solvent combinations and mixture exist between individual co-solvents of any one class,- between classes of co- solvents; between classes of co-solvent(s) and classes of ECS compounds; between co-solvent (s) and co-fuels,- between co-solven (s) , ECS compound ⁇ , and co-fuel ( ⁇ ), and/or the like.
  • a moderate to high flash point fuel comprising a combustion improving amount of an ECS compound (preferably DMC) , optionally a metallic, and at least one flash point increasing flammable co-solvent.
  • ECS compound preferably DMC
  • Example 212 A co-solvent composition, or ECS compound/co-solvent composition, characterized as being soluble in liquid hydrocarbon fuels, flammable and. having a melting point less than 20, 10, 5, 0, -5, -10, -20, -30, -40, -50, -60, - 70, -80, or -90°C; a boiling temperature equal to or greater than 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 270, 280, 300°C; optionally soluble in water,- having a laminar burning velocity in excess of 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, 60 cm/sec,- a latent heat of vaporization in exces ⁇ of 23, 25, 27, 29, 31, 33, 35, 37, 39, 41, 43, 45, 47, 49, 51, 53, 55, 57, 59, 62, 65 va -
  • a fuel compo ⁇ ition comprising: a metallic and an ECS co-solvent or co-solvent package,- characterized as having a LHV exceeding 140, 143, 147, 150, 155, 160, 170, 180, 190, 200 BTU/lb, or greater, and optionally a burning velocity exceeding 38, 40, 42, 44, 46, 48, 50, 52, 54, or greater, cm/sec.
  • a high flash point, low freezing temperature co- solvent or co-solvent mixture comprising: one or more high flash point co-solvents with melting point greater than - 50, -40, -30, -20, -10, 0, 10, 20, 30, 40, 50, 60°C; and a fuel soluble, flamable, freezing point reducing agent or co-solvent selected from butyl carbitol, carbinols (including dii ⁇ opropyl, dimethylene n-propyl, i ⁇ oamyl, etc.) l-octene, 4-octene, 1-octyne, 4-octyne, glycol ether ⁇ , ethylene glycol ⁇ , diethylene glycols, dissopropyl ketone, methyl propyl, diacetone alcohol, i ⁇ opropyl acetone, di ⁇ obutyl ketone, cyclhexanone, i ⁇ ophorone, or other co- ⁇ olvent having moderate to moderately high fla ⁇ h point and low
  • one co-solvent compound is a tertraethylene glycol, triethylene glycol, l- octene, high flash point ketone, isopropyl acetone, dissopropyl acetone, disspropyl diacetone, diethylene acetate, diethylene diacetate, or ethylene acetate compound, phenol, (including derivatives thereof) or mixture; and whereby resultant fuel has an average LHV of at least 28, 30, 32, 34, 35, 38, 40, 42 va( H(T b ) /kJ mol "1 .
  • Example 214 The composition of Example 214, additionally containing an ECS compound (preferably DMC) , and optionally a metallic; whereby the composition's flash point equals or exceeds 50, 60, 70, 80, 90, 100, 130, 150°F, or more, and the freeze point is less than -40°F (-40°C) , -47°F (-44°C) , - 50°F (-46°C) , or les ⁇ ; and optionally a latent heat of vaporization equal to or exceeding 28, 30, 32, 34, 38, 40, 45 vaf p(T b )/kJ mol "1 (or equivalent) .
  • ECS compound preferably DMC
  • a metallic whereby the composition's flash point equals or exceeds 50, 60, 70, 80, 90, 100, 130, 150°F, or more, and the freeze point is less than -40°F (-40°C) , -47°F (-44°C) , - 50°F (-46°C)
  • volume ratio of ECS compound to co- ⁇ olvent ( ⁇ ) range ⁇ from 20:1, 15:1, 10:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1;1, 1:1, 1:2, 1:3, 1:4,
  • ratio's greater than 1:1 desireable ratio's of 2:1, 3:1 being desireable and those greater than 10:1, 8:1, 6:1, 5:1, 4:1 preferred
  • Example 217 Incorporating Example 217, with above examples and a co-fuel; whereby resultant fuel meets ASTM and/or government specifications, governing RVP and flash point.
  • Example 219 Incorporating Example 217, with above examples and a co-fuel; whereby resultant fuel meets ASTM and/or government specifications, governing RVP and flash point.
  • co-fuel is a conventional or reformulated gasoline, whose vapor pressure RVP exceeds 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0 psi, or more, and whereafter combination with co ⁇ solvent or mixture of co-solvent (as set forth above) , resultant fuel's RVP is equal to or less than 8.0, 7.5, 7.0, 6.5 psi, or les ⁇ .
  • An aviation jet turbine co-fuel including Jet A, A-1 or B; or a #1-D diesel, low sulfur or normal grade; or a ga ⁇ turbine fuel oil # l-GT, @ 2-GT; ⁇ aid co-fuel additionally compri ⁇ ing a combu ⁇ tion improving amount of an ECS compound (preferably DMC) having a fla ⁇ h point of les ⁇ than 38°C, and optionally at least one metallic (preferably MMT) , and a flash temperature increasing amount of a co ⁇ solvent (preferably a fuel soluble flammable polyene glycol, ketone, acetate, phenol, and/or ester having flash point in exces ⁇ of 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300°F) , wherein re ⁇ ultant fuel is characterized as having a flash point temperature of at lea ⁇ t 100°F (38°C) .
  • ECS compound preferably DMC
  • MMT metallic
  • a co ⁇ solvent preferably a fuel soluble
  • Example 221 An #2-D diesel fuel oil co-fuel, normal grade or low sulfur; said fuel additionally comprising a combustion improving amount of an ECS compound (preferably DMC) having a flash point of less than 52°C, an optionally a metallic, and a flash temperature increasing amount of a co-solvent, wherein resultant fuel is characterized as having a flash point temperature of at least 52°C,- optionally a reduced cloud or freeze point; and optionally improved viscosity.
  • ECS compound preferably DMC
  • ECS compound preferably DMC
  • a #4-GT ga ⁇ turbine fuel oil co-fuel - said fuel additonally comprising a combustion improving amount of an ECS compound (preferably DMC) having a flash point of le ⁇ s than 66°C, and optionally a metallic, and a flash temperature increasing amount of a co-solvent, wherein resultant fuel is characterized as having a fla ⁇ h point temperature of at lea ⁇ t 66°C.
  • ECS compound preferably DMC
  • An aviation ga ⁇ oline co-fuel said fuel additionally containing a combustion improving amount of DMC or other ECS compound(s) including those having blending vapor pres ⁇ ure greater than 7.0 psi (49 kPa) , and wherein said ECS optionally has laminar flame velocity exceeding aviation gasoline (reported at 44.8 cm/sec) or 45, 46, 47, 48, 49, 50 cm/sec, or greater; optionally a metallic; a vapor pressure reducing amount of a co-solvent, wherein said resultant aviation gasoline fuel is characterized as having a vapor pressure of at least 5.5 psi (38 kPa) at but not greater than 7.0 psi (49 kPa) , and wherein resultant fuel meets all ASTM D 910 specification ⁇ .
  • a marine ga ⁇ turbine co-fuel said fuel additionally comprising a combustion improving amount of an ECS compound, preferably DMC, and optionally a metallic, and a flash temperature increasing amount of a co-solvent or mixture of co-solvents, said resultant fuel is characterized as having a fla ⁇ h point temperature of at least 60°C.
  • re ⁇ ultant fuel ⁇ are additionally characterized a ⁇ meeting ASTM, indu ⁇ try or government standards present and future. It is to be appreciated the specie and compound identified herein are not limiting. Routine testing will identify co-solvent compounds meeting the structural and performance limitations of the claimed invention. It is also an embodiment of Applicant's invention to employ salt ⁇ for purposes of mitigating vapor pres ⁇ ure and/or to increa ⁇ e flash point temperatures. It is contemplated that certain salts may be employed directly in the fuel or indirectely soluble via mutual solvent (e.g. a co-solvent) .
  • mutual solvent e.g. a co-solvent
  • De ⁇ ired ⁇ alts are those that do not adversely effect combustion or the emissions of a given fuel and, which in low concentrations with Applicant's ECS fuel and optional metallic, reduce vapor pressure and/or enhance combustion.
  • Non-limiting examples include calcium salts (e.g. Ca(N03)2, CaBr2) , barium, boron salt ⁇ (e.g. H3B03) , pota ⁇ ium salts (e.g. KN03, KBr03, KN02, KHC03, K2C204, Kl, KH, K2W04, K2C03, KOH,), lithium salt ⁇ (e.g.
  • LiN03, LiBr, Lil, LiOH) iron salts, aluminum salt ⁇ , cobalt, magne ⁇ ium ⁇ alt ⁇ (e.g. Mg(N03)2, MgBr2) , sodium (e.g. NaN03, NaOH, NaN02, NaHC03, NaBR03, NaBr, Nai, Na2C03, Na2W04) , nitrogen salts (e.g. NH4N03, NH4Br, NH4I) , nickel salt ⁇ (e.g. Ni(N03)2) and zinc salts (e.g. Zn(N03)2).
  • Mg(N03)2, MgBr2 sodium
  • sodium e.g. NaN03, NaOH, NaN02, NaHC03, NaBR03, NaBr, Nai, Na2C03, Na2W04
  • nitrogen salts e.g. NH4N03, NH4Br, NH4I
  • nickel salt ⁇ e.g. Ni(N03)
  • salts containing sulfur or barium should be avoided.
  • Environmental concerns also dictate.
  • Applicant's preferred salts are those that may be added in ⁇ ufficient concentration ⁇ such that vapor pressure is reduced by 5.0, 10, 20, 30, 40, 50, 100, 150, 200, 300 mm at initial boiling temperatures of fuel composition, by the addition of 0.5, 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 8.0, 10.0 grammolecules per liter.
  • Perferred vapor pre ⁇ sure reductions are tho ⁇ e greater than 20 mm, and preferred concentration ⁇ are less than 4.0, 3.0, 2.5, 2.0, 1.5, 1.0 grammolecules per liter.
  • Other levels range from 0.001 to 30.0 grammolecules per liter (more preferred being 0.01 to 5.0 grammolecules per liter).
  • a fuel composition comprising a vapor pres ⁇ ure reducing amount of at lea ⁇ t one ⁇ alt soluble in hydrocarbon fuel or alternatively soluble in a co-solvent, wherein said salt can be treated at 0.5 grammolecules per liter of fuel, thereby reducing vapor pressure by at least 1.0, 2.0, 5.0, 7.5, 10.0, 15.0 mm at either ambient temperature or at vaporization temperatures of the fuel, which ever is higher.
  • Example 229 The Examples above, wherein said compositions additionally contain a vapor pressure reducing or flash point increasing amount of a salt..
  • Example 230 A composition of matter for use in hydrocarbons comprising: an ECS compound; a cyclopentadienyl manganese tricarbonyl; and one or more of the following: any fuel additive(s), VPR/FPI co-solvent(s) , or salt(s).

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Abstract

L'invention concerne un procédé de combustion en phase vapeur métallique à température réduite pour systèmes de combustion à injection, turbine, fuel, diesel, fuel et essence. L'invention concerne plus spécifiquement des procédés et des compositions de carburants contenant des métaux, comprenant des composés à structure de combustion renforcée, permettant d'augmenter la vitesse de combustion et de réduire la température de combustion.
PCT/US1996/009653 1995-06-07 1996-06-07 Procede de combustion en phase vapeur et compositions ii WO1996040844A1 (fr)

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JP9501927A JPH11504974A (ja) 1995-06-07 1996-06-07 蒸気相燃焼法および組成物ｉｉ
EP96923240A EP0833879A1 (fr) 1995-06-07 1996-06-07 Procede de combustion en phase vapeur et compositions ii
AU63806/96A AU6380696A (en) 1995-06-07 1996-06-07 Vapor phase combustion method and compositions ii
BR9608589-4A BR9608589A (pt) 1995-06-07 1996-06-07 Composições e processo de combustão em fase vapor
APAP/P/1998/001185A AP9801185A0 (en) 1995-06-07 1996-06-07 Vapor phase combustion method and compositions II.
NO975746A NO975746L (no) 1995-06-07 1997-12-05 Fremgangsmåte ved dampfaseforbrenning og blandinger til bruk derved

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WO1998026028A1 (fr) * 1996-12-09 1998-06-18 Orr William C Compositions de carburant caracterisees par une stabilite amelioree dudit carburant
WO2000047697A1 (fr) * 1999-02-12 2000-08-17 Exxonmobil Research And Engineering Company Formulations de carburant permettant d'etendre la limite inferieure d'inflammabilite
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NO975746L (no) 1998-02-06
JP2005272850A (ja) 2005-10-06
CN1195367A (zh) 1998-10-07
KR19990022557A (ko) 1999-03-25
RU2001134211A (ru) 2003-09-10
EP0833879A1 (fr) 1998-04-08
AP9801185A0 (en) 1998-01-31
NO975746D0 (no) 1997-12-05
BR9608589A (pt) 1999-09-14
CN101643672A (zh) 2010-02-10
AU6380696A (en) 1996-12-30
JPH11504974A (ja) 1999-05-11

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