AU2003252892A1 - Vapor Phase Combustion Method and Composition II - Google Patents

Description

P/00/011 28/5/91 Regulation 3.2

AUSTRALIA

Patents Act 1990

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT Name of Applicant: Actual Inventor Address for service is: William C Orr Willaim C Orr WRAY ASSOCIATES Level 4, The Quadrant 1 William Street Perth, WA 6000 Attorney code: WR Invention Title: Vapor Phase Combustion Method and Compositions II Details of Associated Provisional Application No(s): The following statement is a full description of this invention, including the best method of performing it known to me:- WO 96/40844 PCT/US96/09653 1/1 VAPOR PHASE COMBUSTION METHOD AND COMPOSITIONS II BACKGROUND OF TEE INVENTION Field of the Invention 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, reducing combustion temperature, improving thermal efficiency, fuel economy, power and emissions.

Description of the Prior Art The incorporation of metallics, including various organo-manganese compounds as anti-knock agents (e.g.

methylcyclopendienyl manganese tricarbonyl -MMT, et al.) in hydrocarbon fuels, is known. See U.S. Patents 2,818,417; 2,839,552; and 3,127,351 (incorporated herein by reference). Organo-manganese's use in heavier fuels such as coal, diesel and jet aviation fuels is also known and believed to help reduce smoke and solid particulate emissions. See U.S. Patents 3,927,992; 4,240,802; 4,207,078; 4,240,801.

Despite organo-manganese's anti-knock and other benefits, its use in hydrocarbon fuels produces another set of environmental and practical problems. Namely, metallic based fuels form metallic oxides in combustion. In the case of organo-manganese compounds, such metallics when combusted in hydrocarbon fuels generate harmful heavy WO 96/40844 PCr/US96/09653 -2manganese 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. For "0 example, 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. Unfortunately, due to the magnitude of this disability, metallic usage has been virtually halted in such applications, and alternative application is limited to very low concentrations of metallic.

U.S. 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 organomanganese free.

Since those skilled in the art have long since abandoned hopes of solving the fundamental oxide disability of metallic combustion, and given that manganese has been illegal in unleaded gasolines for quite some time, practitioners have long been disinclined to separate MMT WO 96/40844 PCT/US96/09653 -3from lead additive usage. See for example, European Patent Application 91306278.2 related to "Unsymmetrical dialkyl carbonate fuel additives," which recognizes this reality by disclosing tetraethyl lead, tetramethyl lead and cyclopentadienyl tricarbonyl manganese together in the same context, absent suggestion of employing them independently of each other.

Summary of Invention 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.

The essence of Applicant's invention resides in the discovery of the fundamental problem source facing traditional combustion method and compositions, e.g.

wherein less than ideal combustion occurs because combustion burning velocities and temperatures are not simultaneously optimized.

By effectively increasing the burning velocity of a fuel, while reducing combustion temperatures, Applicant not only controls or avoids the generation of most adverse emissions, but liberates the heating capacity of the fuel.

When metallics (see below) are incorporated, they become principals in a new clean "high energy" class of cooler burning propellants/fuels and combustion process, which heretofore has limited metals to mere additive or agent.

WO 96/40844 PCT/US96/09653 -4- In essence, Applicant has discovered a unique form of combustion, related processes and compositions. The various processes and compositions essentially comprise certain chemical structure/sub-structure and/or mechanical structure/sub-structure that simultaneously 1) increases burning velocity, at 2) reduced combustion temperatures, whereby a high release rate of what might be known as free energy occurs, with attendant reductions in emissions, increases in power, fuel economy, range, and the like.

Transition and alkine metals, alkine earths, halogens, group IIIA elements and mixtures (hereinafter "metals" or "metallics") are the core of Applicant's invention residing in 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.

Neat fuels containing solely Enhanced Combustion Structure compounds and metallics only, which advance this object are referred to as ECS fuels. ECS fuels may combined with more traditional fuels or co-fuels. This combination is referred to as an ECS/co-fuel.

Other neat fuels and methods include means of achieving reduced latent heats of vaporization ("LHV") and/or increased burning velocities, with or without ECS WO 96/40844 PCr/US96/09653 compounds to assist in this requirement. These fuels are referred to as "Modified Fuels," or Co-fuels. Modified fuel 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 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/cofuels, modified co-fuels alone, description of Drawings and Figures 1 through 8 are disclosed in copending International Applications No. PCT/US95/02691 and No.

PCT/US95/06758, and incorporated in all respects herein.

DETAILED DESCRIPTION OF INVENTION Applicant's invention resides in a rare form of combustion known as vapor phase combustion.

The unity of Applicant's invention is based upon this discovery and the solution to combustion's fundamental problem. This single invention impacts a multiplicity of fuels and combustion systems, flowing from the same discovery. See my co-pending International Applications No.

PCT/US95/02691, filed March 2, 1995, and No.

WO 96/40844 PCT/US96/09653 -6- PCT/US95/06758, filed May 31, 1995, incorporated herein by reference.

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.

'0 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.

Applicant's has discovered radically increased thermal and/or combustion efficiency gains in flight range, fuel economy, work potential, thrust, lift, completeness of combustion, etc.) compared to traditional or reformulated fuels.

As provided herein, industry standards, including 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) WO 96/40844 WO 9640844PCrIUS96/09653 -7reducing combustion temperature by chemical means e.g.

increasing fuel heats of vaporization, etc., or by mechanical means advanced cooling systems, reducing chamber air charge temperature).

Thus, the simplicity underlying applicant's invention unifies the multiple interrelating chemical and mechanical elements related to increasing LHV and BV.

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.

Those compounds are referred to as "Enhanced Combustion Structure" compounds or "ECS" compounds.

FREE RADICALS Applicant has discovered certain molecular forces occurring during combustion are responsible for rapid diffusion of heat and reactive centers of unburned gases.

These forces are responsible for increased burning velocities.

Certain molecular free radicals, not limited to H, H 2 0, 02, CO, F, F2, F3, N, B, Be, BO, B2, BF, AL ALO, CH3, NH3, CH, C2H2, C2H5, Li, ONH, NH, NO, NH2, OCH 3 (methoxy radicals), OCH, OCH 2 and OH (hydroxyl radicals), are believed responsible for this result. Additional

ECS

WO 96/40844 PCT/US96/09653 -8structure include Cl, OCOO, COOH, C2H500C, CH3CO, OCHCO, and CONH2.

It is an embodiment of this invention that 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 '0 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 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, 80, 90, 100, 150, 200, 250, 300 percent, or more, compared to exhaust velocities generated by traditional compositions/methods.

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).

To achieve this object Applicant has found the heat of formation of said free radicals to be important. Generally, WO 96/40844 PCT/US96/09653 -9the 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, 2 Kcal mole-'. Those less than 50 Kcal mole-' 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 2.0 Kcal mole-'.

Thus, 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 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.

It is the diffusion of pre/post ignition precombustion. gases containing said reactive kinetic free radicals that operate to increase the momentum/viscosity of the unburned gas to as close as possible to the viscosity of the burned gas. This in turn reduces the viscous drag between the burned and the unburned gases. Elimination or reduction of this drag monumentally increases burning velocity. Thus, diffusing reactive free radicals ahead of WO 96/40844 PCT/US96/09653 the flame front is accomplished by the construction of the post ignition pre-combustion vapor, which is a function of the fuel and combustion system.

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. Thus, 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 enhanced combustion structure) to yield increased combustion burning velocity, is an express embodiment of this invention.

Example 1 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 0, 02, CO, F, F2, F3, N, B, Be, BO, B2, BF, AL ALO, CH3, NH3, CH, C2H2, .0 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, 5, 2 K cal mole- 1 or negative, preferably less than 50, 20, 10, 5, 2 K cal mole' l and optionally its velocity in excess of 47, 48, 49, 50, 51, 52, 55, 58, 60, 65, 80, 90, or more, cm/sec., more preferably in excess of WO 96/40844 PCT/US96/09653 -11- 65, or 70 cm/sec., and optionally having at least one free or unused valency electron; said radical characterized as being a chain carrier in the main chain reaction of combustion, and optionally disassociating and reassociating during combustion; Example 2 A gaseous pre-combustion fuel vapor ("Fuel Vapor") or method, wherein the kinetic free radicals of example 1 0 represent 2, 5, 8, 10, 12, 15, 17, 20, 25, 30, 40, 50, or more, weight percent, and preferably greater than 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.

WO 96/40844 WO 9640844PCT/US96/0953 -12- 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, .0 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, dicarbonates, 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 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),

WO 96/40844 PCTIUS96/09653 -13nitromethane, nitroethane, nitropropane, nitrous oxide, dinitrous oxide, nitric oxide, ozone, water, gas hydrates (methane hydrate), hydrogen peroxide, hydroperoxides, oxygen, and similar compounds. Applicant believes many other compounds exist that have not yet been identified, which perform ECS function.

ECS compounds include compounds containing carboethoxy, carbomethoxy, carbonyl, carbonyldioxy, carboxy, ethoxalyl, glyoxylyl, methoxy, methylenedioxy, 0 glycolyl, and/or hydroxyl components and/or radicals.

ECS compounds containing double C=O or C=N bounds are particularly desireable. Non-limiting examples include oxalates, carbonates, acetyl acetones, dimethyl glyoximes, ethylenediamine tetraacetic acids, and the like.

Additional non-limiting examples of likely

ECS

compounds include ethylene, propylene, tertiary butylcumyl peroxide, butylene, 1,2-butadiene, 1, 3-butadiene, actetylene hydrocarbons including acetylene, allylene, butine-1, pentine-1, hexine-1; 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, potassium nitrate, nitric acid, ammonium azide, ammonium perchlorate, lithium perchlorate, potassium perchlorate, nitrogen trioxide, nitrogen dioxide, hydrazoic acid, dicyanogen, hydrocyanic acid, monethylanile, acetylene, aluminum borohydride, WO 96/40844 PCTIUS96/09653 -14ammonia, aniline, benzene, butyl mercaptan, diborane, dimethylamine, diethylenetriamine, ethanol, ethylamine, ethylene diamine, ethylene oxide, ethylenediamine, ethyl nitrate, dimethyl sulfide, furfuryl alcohol, heptene, hydrazine, hydrogen, isoethyl nitrate, isopropyl alcohol, lithium, lithium hydride, methane, methylal, methanol, methyl nitrate, methylamine, methylacetylene, methylvinyl acetylene, monoethylaniline, nitromethane, nitropropane, nitroglycerine, n-octane, propane, propylene oxide, npropyl nitrate, o-toluidine, triethylamine, trimethylamine, trimethyl trithiophosphite, turpentine, unsymmetrical dimethyl hydrazine, xylidine, 2,3-xylidine, lithium borohydride, monomethylhydrazine, pentaborane, and the like.

Other candidate ECS compounds include di-tertiary butyl peroxide, alkyl peroxides, alkyl hydroperoxides, acetyl hydroperoxides. Non-limiting examples of peroxides include tertiary butylcumyl peroxide, di(tertiaryamyl) peroxide, tertiary butyl hydroperoxide, di-tertiary butyl 0 hydroperoxide, tertiary amyl hydroperoxide, acetyl tertbutyl 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, tetramethylolmethane, n,ndiethyl formic acid, n,n-dimethyl formic acid, formamide, methyl formate, alkyl nitrates (including ethyl-hexyl nitrate and iso-propyl nitrate), 2.5 dimethyl WO 96/409" WO 9640844PCT/IJS96/09653 di (tertiary butyl peroxy) hexane, H(2)IIO CH3CHOHCHOHCH3; (CH3) 3 CHOHH3; CH2CH2 C (C3) (OH) CI3; (CH3) 2COOH; (CH3) 3COOH; CH3NO2; C3CCCOH; (CH3) 3CCH2COH; HOCH2 H2 OCH2 CH2 OH; HOCH2 CH2 OH; OCH2CEHCHO; (CH3) 3 CCO; (CH3) 3CCH(OH) CH3; C5F1402; H02CCH2CH2CO2C2H5; C3H7COCO2H; C5H802, cH3COCHO, ethonanoic acid, methyl glycolate, glyoxylic acid, phenyl glyoxylic acid, diethylene glycol ethers, methyl formiate, isoamyl formate, 1.2-ethanediol, dimethyl ether 1.2-ethanediol, ethylene nitrite, ethylene 0 nitrate, ethylene acetate, ethyl ester formic acid, formic acid, glyoxal, glyceric acid, tetraethoxymethane, triethoxymethane, trimethoxymethane, oxalic acid, oxalic ester, oxalic acid dimethyl ester, oxalic acid dipropyl ester; phenols including 2-methoxyphenol, 3-ethoxytoluene; acetyl acetone, acetic acid anhydrides, ethyl acetate, methyl acetate, methanediol diacetate, amyl acetate, acetonyl acetate, ethanoic acid, 2,4-pentadione, methanesiol diacetate, ethyl acetate, propanic acid, ethylene oxide, propylene oxide, amnonium nitrate, dinitrogen tetroxide, and like.

Applicant believes that compounds which have or become strong chelating agents in combustion are also desireable ECS candidates.

Compounds having the following structure, and which perform ECS function, are desireable: R-00, R-00-R, R- COOOCO-R, R-COOCOO-R, R-CO-R, R-COO-R, H3CO-R, C02-R, or R- CO-R, wherein any R may be void or absent structure. R may be different, same, or multiples of itself. R may be 2(R), WO 96/40844 PCT/US96/09653 -16- 3 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.

Obviously, differing ECS compounds in various systems will elicit differing response. For example, it is expected that in alcohols will elicit lower combustion and exhaust "0 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 -40, -35, -30, -20, -10 kcal/mol, or positive in value.

The closer to a positive or the higher the positive, the more preferred.

In order to reduce combustion temperature, it is desireable that said vapor structure and/or the ECS compound, itself, have a high latent heat of vaporization (enthalpy of vaporization), particularly those equal to or 01/02/98 18:33 '303 295 8261 HOLLAND AND HART 002/004 WO 96/40844 PCTnUS609653 -17greater than 28.0 jK mol0e", at the compounds boiling point.

Other enthalpies of vaporization (at the boiling point) are those equal to or greater than 21, 22, 23,.24, 26, 27, 29, 31, 32, 33, 34, 35, 36, 37, 38, 40, 42, 43, 45, 47, or higher, jK mole- 1 Generally, the higher the better.

Higher latent heats of vaporization additionally increase volumetric efficiency by. cooling intake charge as the fuel evaporates and should increase energy.density- It also is particularly desireable said vapor structure and/or the ECS compound, itself, have high flame velocity. AS a rule, when combusted in air (as a function of their own constitution and as measured in a laminar Bunsen flame), flame velocities should equal or exceed 43, 45, 46, 48, 50, 52, 54, 56, 58, 60, 65, 70, 75, 80, 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.

It is highly desireable that dissociation acts to quickly diffuse unburned vapors containing said free 2S 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 0 325 0 C, 30 0 275 0 C, 250 0 C, 225 0

C,

01/02/98 18:34 1303 295 8261 HOLLAND AND HART 003/004 WO 9640844 PCT/US96/09653 -18- 2000°C, 175C, 170°C, 16SOC, 150°C, 140 0 1300C, 120C, 1100C, l050C, and 1000°C. Preferred Latent heats of vaporization of ECS compounds at 60°? are those equal to.or greater than 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. It is generally preferred. that the latent heat of vaporization of the ESC compound be at least the same as, but more preferably 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. Normally, the higher the differences the better. Applicant has discovered, 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.

Generally, preferred laminar flame propagation velocities should exceed 30, 32, 34, 36, 37, 38, 39, 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 1.0% to to 3.0% to 5% to 10%, 7% to 20%, 8.0% to 30.0%, WO 96/40844 PCT/US96/09653 -19to 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.

It is preferred that 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 0 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 0 C, 205 0 C, 220 0 C, 260 0

C,

280 0 C, 300 0 C, 320 0 C, 350 0 C, or more, is desireable.

It is preferred 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, 0.25 hours or less.

It preferred ECS -compounds be thermally stable in normal handling and operating temperatures in either liquid or vapor state up to approximately 150 0 F, 250 0 3000F, 350 0 F, 400 0 F, 450 0 F, 500 0 F, 550 0 F, 600 0 F, 650 0 F, 700 0 F, but readily decomposes in vapor state at approximate temperatures exceeding the above or between 300 0 F to 1100 0

F,

400 0 F to 1000 0 F, 500°F to 900 0 F, 650 0 F to 800 0 F, more WO 96/40844 PCTIUS96/09653 preferably at 550 0 F to 900 0 F. However, 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 '0 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.

In liquid fuel applications, ECS compounds having flash points of -150 0 F, -135°F, -120 0 F, -115 0 F, -20 0 F, -25 0

F,

0 0°F, 40 0 F, 50°F, 170°F, 280°F, more or less, are acceptable. In jet aviation and other similar fuels, flash point temperatures above 30 0 C, 38 0 C, 40 0 C, 60 0 C, 70 0 C, 80 0

C,

0 C, 100 0 C, 105 0 C, 110 0 C, 120 0 C, 130 0 C or greater, are 0 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, to 12.0, 0.5 to 10.0, 0.5 to 9.0, 0.5 to 8.0, 0.5 to psi, or 0.5 to 6.0 psi, or 0.5 to 5.0 psi, or from to 3.0, 0.5 to 1.5, 0.5 to 1.0 psi, 0.05 to 0.5, or less.

WO 96/40844 PCT/US96/09653 -21- Individual vapor pressure ranges include 0.5, 1.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.4, 5.6, 5.7, 5.9, 6.1, 6.3, 6.6, 6.8, 6.9, 7.1, 7.2, 7.5, 7.6, 7.7, 8.1, 8.3 psi.

Blending vapor pressures less than 40, 35, 30, 25, 22, 18, 16, 15, 14, 13.5, 13.0, 12.8, 12.5, 12.4, 12.2, 12.0, 11.8, 11.5, 11.2. 11.0, 10.8, 10.5, 10.2, 10.0, 9.8, 9.4, 9.2, 9.1, 9.0, 8.8, 8.5, 8.3, 8.2, 8.1, 8.0, 7.9, 7.8, 7.7, 7.6, 7.5, 7.4, 7.3, 7.2, 7.1, 7.0, 6.9, 6.8, 6.7, 6.6, 6.4, 6.3, 6.2, 6.1, 6.0, 5.9, 5.8, 5.7, 5.6, 5.4, 5.3, .0 5.2, 5.1, 5.0, 4.9, 4.8, 4.7, 4.6, 4.5, 4.4, 4.3,4.2, 4.1, 3.9, 3.8, 3.7, 3.5, 3.3, 3.2, 3.1, 3.0, 2.9, 2.8, 2.2, 2.0, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 0.9, 0.8, 0.7, 0.5. 0.2 psi are acceptable.

Vapor pressure and flash point temperatures can be mitigated or controlled via co-solvent and/or salt practices set forth below.

Example 4 A ECS compound comprising: a maximum carbon cha-in 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 10, 5, 0, -10, -20, -30, -50 or lower; a boiling temperature greater than 25, 30, 40, 42, 43, 44, 60, 90, 100, 110, 120, 140 OC, or greater; a Bunsen burner laminar flame speed in excess of 40, 45, 48, 50, 55, 60, or 70 cm/sec; a latent heat of vaporization exceeding 100, 120, 130, 133, 140, 143, 145, 148, 150, 152, 155, WO 96/40844 PCT/US96/09653 -22- 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 230, 235, 240, 250, 300, 380, 400, 450, 500 BTU/Ib at thermally stable in either liquid or vapor state up to 200 F, 250°F, 300°F, 350°F, 400°F, 450 F, 475 0 F, 500°F, 550 F, 600OF, 650 F, 700°F, 750 0 whereinafter rapid decomposition into high kinetic energy free radicals occurs, including at least one or more free radicals selected from the group consisting of H, 0, 02, 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.

Examole Example 4, wherein the ECS compound is fuel soluble and optionally contains oxygen by weight equal to 3%, 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.

Applicant acknowledges there is great variability between possible ECS compounds, and in certain neat and/or co-fuel applications, certain ECS compounds may less satisfactory than others, or altogether unsatisfactory.

Several for example, may be very effective in non-regulated aviation, advanced jet applications, diesel applications, but unacceptable for automotive purposes.

WO 96/40844 PCT/US96/09653 -23- Other ECS compound suffer potential health hazards.

For example, 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. Thus, its long term environmental utility, absent a co-ECS compound to accelerate its atmospheric decomposition, may be limited.

Higher octane oxygenated ECS compounds, such as MTBE, ETBE, TAME improve ignition quality. However, these compounds have moderate latent heats of evaporation and burning velocities.

It is expressly contemplated multiple utility between groups, classes, and compounds exists, in the various aspects of this invention. Applicant intends duplications fill both classes or function. For example, in case of metallic ECS compound, that said compound may role of ECS compound and metallic, so long as the object of invention is acheived.

It is contemplated 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. Alternatively, it may be necessary to increase BV or LHV of an existing ECS compound such as MTBE, by admixing a co-ECS compound DMC.

WO 96/40844 PCTIUS96/0%53 -24- Certain synergies exist between individual ECS compounds, classes of ECS compounds, or individual and classes, enhancing their respective capability. Thus, a wide range of mixtures is contemplated. For example, ECS compounds in combination with alkyl nitrates, particularly in distillate fuel combinations exhibit unexpected combustion improvements.

The practice of this invention contemplates admixing an ECS compound, co-ECS compound, co-solvent, and/or cofuel 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 compounds be soluble in such fuels.

Example 6 A fuel soluble ECS compound having a melting point of less than -100 0 C, -80 0 °C -55 0 C, -20 0 C, -5° 0 C, 10°C, 50 0 C, -25 0

C

0°C, 5 0 C, 10 0 C and a boiling point not less than 40 0

C,

60 0 75 0 C, 85 0 100 0 C, 150 0 C, 275 0 C, 485 0 C, or greater.

It is also contemplated that certain mechanical structure will be required to either satisfactorily enhance an ECS compound's burning velocity and/or to reduce combustion temperature aspects e.g. enhanced atomization or injection pressure/method.

Thus, those elements or compound/components wherein the above enhanced combustion structure exist, in high WO 96/40844 PCT/US96/09653 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 constitutes an ECS compound herein.

The higher the relative gram weight or volume of kinetic free radicals as a percent of the uncombusted fuel vapor, the better.

Thus, it is an embodiment of this invention to employ a sufficient amount of enhanced combustion structure to increase the rate of diffusion between unburned and burned gases. It is contemplated that 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).

It is contemplated in the practice of this invention 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 process.

Thus, in the practice of this invention any compound, which enhances the formation of ECS in the combustion process is deemed to be an ECS compound.

Any chemical or mechanical means capable of causing fuel vapor fraction droplets or injected fuel particles to explode prior to combustion (including exploding outside WO 96/40844 PCT/US96/09653 -26the 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.

Thus, 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 gasolines, diesels, napthas, jet aviation fuels, distillate fuels, alkylates, reformates, and the like, are contemplated.

ECS compounds, which are non-corrosive and/or which do not adversely effect seals or elastomers are preferred.

However, corrosion inhibitor additive is contemplated. A non-limiting example includes, "DCl ll" available from Du Pont used at the approximate concentrations of 20 to ppm, although concentrations outside of these ranges are acceptable. Other known inhibitors are contemplated.

Preferred ECS compounds employed in liquid fuels should have low melting points, below 32°F, -0 F, -20°F, 0 -50 0 F, -60 0 F, -70 0 F, -80 0 F, -90 0 F, and most preferably below -100°F. Lower temperatures are contemplated if circumstances warrant. Co-ECS compound and/or additives such as ethylene glycol monomethyl ether may be employed, if necessary. Again, the ECS compound's causal increase in burning velocity and/or reduction of combustion temperature, like flash point or vapor pressure must be weighted against less than optimal melting point, which may WO 96/40844 PCT/US96/09653 be mitigated by other co-ECS compound, additive or cosolvent.

It is preferred practice 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, 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 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.

In the preparation of ECS fuels it is an object to also maximize oxygen fuel content. Beneficial results generally do not occur until approximately 0.05%, 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. Other ranges include 0.001 to 50.0%, 0.001 to 80.0%, 0.001 to 15.0%, 0.5% to 0.3% to 2.7%, 0.4% to 0.5% to 0.6% to 0.7% to 2.1%, 0.8% to 0.9% to 1.0% to 1.1% to 1.2% to 1.8% to 2.0% to 0.2% to 0.9%, to 2.0% to 1.8% to 12%, 2.0% to 10.0%, to 30%, 5.0% to 40%, 2.0% to 53%, oxygen by weight. Other concentrations includes those greater than 0.5, 0.9, 1.4, WO 9690844 PCT/US96/09653 -28- 1.9, 2.4, 2.9, 3.4, 3.5, 4.2, 4.7, 5.2, 5.9, 6.3, 6.6, 7.4, 7.8, 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. These concentrations include both ECS fuels and ECS/co-fuel combinations.

It is anticipated in neat fuel and rocket applications, 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 fuels need not contain oxygen.

METALS PRACTICE In the practice of this invention it is contemplated that at least one reactive'transition metal, alkine metal, alkine earth, halogen, group IIIA element or mixture, (herein ,"metal/metallic") together with an ECS compound to comprise an ECS fuel.

The preferred type and amount of metals contemplated by this invention require combustion be improved and/or pollutants 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 WO 96/40844 PCT/US96/09653 -29the 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.

In preferred practice 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 possible. Thus, metallic hydryls or other similar compounds are desireable. Hydrogen containing salts are also desireable.

ExamDle 7 A vapor phase method of combusting a metallic, said method comprises: introducing kinetic free radicals having enhanced combustion structure into a combustion chamber; igniting and combusting a flammable metallic or metal compound in presence of said free radicals at temperature below said metal's oxide boiling point and preferably/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 WO 96/40844 PCTIUS96/09653 resulting from combustion range in low to submicron range and/or remain in a gaseous state.

Examle 8 The vapor phase method of example 39, wherein the exhaust gases of said method travel at high velocity, exceeding 50, 52, 54, 56, 58, 60, 62, 64, 66, 68, 70, 100, 120, 130, 140, 150, 160, 170, 200 cm/sec, or more and wherein said oxides are on average having particle sizes less 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 microns, or less.

It is also preferred that the metal be introduced into the combustor as a vapor, however solid, atomized, or oarticulate introduction is acceptable, so long as the objects of this invention are met. In solid fuel applications, it is contemplated the metallic may be introduced as a solid. In hybrid applications, it may be introduced as either a solid or liquid.

Contemplated metallics include all non-lead metals and related compounds whose combustion product has negative high heat of formation. Contemplated metals and/or metallic compounds with have high heats of combustion 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, WO 96/40844 PCTIUS96/09653 -31pallium, 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, 43, 53, 6B, 7B, 8, 13, 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, 53, 63, 7B, group 8 are particularly contemplated. Compounds containing more than one metal and or mixture of metals and/or their compounds 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/solvents, colloidal media, suspension 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.

WO 96/40844 PCT/US96/09653 -32- The chalcogens of 6A, except oxygen are contemplated with limitations on sulfur use due to environmental and health concerns.

elements and compounds are contemplated, however phosphorous is limited due to environmental concerns.

Applicant believes those metallics or metallic compounds, which are generally fuel soluble, having melting and boiling ranges compatible with liquid hydrocarbon combustion present the best immediate option.

Non-limiting examples of such organometallic include cyclopentadienyl methylcyclopentadienyl iron, ferrocene, methylferrocene, and butadiene iron tricarbonyl, butadiene iron tricarbonyl, dicyclopentadienyl iron and dicyclopentadienyl iron compounds (see U.S. Patents 2,680,; 2,804,468; 3,341,311); nickel, cyclopentadienyl nickel nitrosyl; molybdenum hexacarbonyl, cyclopentadienyl molybdenum carbonyls (see U.S. Patent 3,272,606, 3,718,444), compounds of technetium, magnesium, rhenium (see Canadian Patent #1073207.), diborane, tetraborane, hexaborane, and mixture. It is contemplated that organo and non-organic species of these metals will be employed.

U.S. Patent 2,818,416 sets forth many such trimethylaluminum, triethylaluminum, dimethlylberyllium, boron hydrate, boron hydride, boron anhydride, triethylboron (C2H5)3B; compounds of boron with hydrogen and lithium, pentaborane, decaborane, barazole, aluminimum borohydride, beryllium borohydride, lithium borohydride, and mixtures thereof; light metals compounds WO 96140844 WO 9640844PCTIUS96/09653 -33- (CH3) 3NBH CR3)3, (CF13) 2BI, Be (C2HS) 2, C4H9BC(OH) 2, Al1(BH4) 2, Be (BH4) 2, LiBH4, B (0C2H5) 3, (30) 3(OCH3) 3; Zn (C3) 2.

Compounds with multinle metals are exoressly ccntetrplated.

A preferred cyc2.omatic manganese tricarbonyl is cyclopentadienyl manganese tricarbonyl. A more preferred cycilomatic manganese tricarbonyl is methyl cyclopenzadieny.

manganese (NM1T) Non-limiting exampl1e s off acceptable substitutes include the alkenyl, aralkyl, aralkenyl, cycJloalkyl, cycloalkenyl, aryl and alkenyl groups. illustrative and other non-limiting examples cf acceptable cyclamatic manganese tricarbonyl antiknock comounds include benzyleyelopentadienyl manganese tricarbonyl; 1. 2-dipropyl 3 -cyclohexylcyclopentadienyl manganese tri4carbonyl; 2.2diz=henylcvclomentadienylI manganese tricarbonyl; 3propenylienyl manganese tri'carbonyl; 2- tolyindeny.

manganese tricarbonyl; fluorenyl manganese tricarbonyl; 2.3.4.7 propyflourentyl manganese tricarbonyl; 3narhthvifluorenyl manganese tricarbonyl; 4.5.6.7tecrahydroindenyl manganese tricarbonyl; 3-3ethenyl-4, 7dihydroindenyl manganese tricarbonyl; 2-ethyl 3 (aphenylethenyl) 4,5,6,7 tetrahydroindenyl manganese tricarbonyl; 3 (a-cyclohex-ylenthenyl) -4.7 dihydroindenyl manganese tricarbonyl'; 1,2,3,4,5,6,7,8 octahydrofluorenyl manganese tricarbonyl and the like.

Mixtures of such compounds can also be used. The above compounds can be generally prepared by methods that are known in the art.

WO 96/40844 PCT/US96/09653 -34- Applicant has found potassium, magnesium, lithium, boran and their related high energy combustible compounds to be particularly effective, and thus desireable.

Promoters such as Li and LH are also contemplated, if circumstances require.

Routine testing will identify other metals, their compounds, and combinations meeting the criteria of Applicant's invention. Thus, any metal advancing the object of this invention is contemplated in the claims hereto.

It is preferred that combustion temperatures also be greater than the metal's (or metallic compound's) boiling temperature.

It has been found that higher oxygen weight concentrations in fuel compositions, particularly with higher concentrations of enhanced combustion properties, permit higher acceptable metallic concentrations. Higher average ECS fuel, ECS\co-fuel and/or co-fuel densities are also associated with higher acceptable metallic concentrations and higher exhaust velocities. Engine combustion thermal dynamics and stoichometry dictate upper metallic limits.

Metallic concentrations will vary substantially. nonlimiting 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 WO 96/40844 PCTIUS96/09653 over 50.00 grams/elemental metal/gal.or more. In certain applications, metallic concentrations equal to or greater than 1/64, 1/32, 1/16, 1/4, 3/8, 1/2, 5/8, 3/4, 1, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 5.0, 7.5, 10, 15, 25, 26, 27, 30, 33, 35, 40. 50, 55, 60.0, 65, 70, 80, and crams/aal may be desirable. In advance and/or rocket and/or propellant applications, 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 ranges are also contemJlated.

However, manganese ranges for more traditional co-fuel armlications 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 grams Mn/gal, 0.001 to !.00 grams Mn/gal, 0.001 to about 0.50 grams Mn/gal, 0.001 to 0.375 grams 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 1/128, 1/64, 1/32, 1/16, 3/32, 1/8, 5/32, 3/8, 1/4, 1/2, 3/4, 0.8, 0.825125, 1.0, 1.2, 1.3, 1.4, 1.5, 1.6, 1.656, 1.75, 1.875, 1.90, 2.0, 2.25, 2.3, 2.4, 2.45, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.3125, 3.4, 3.5, 3.6, 3.7, 3.75, 3.8, 3.875, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.6, 4.7, 4.75, 4.875, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.6, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.625, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.25, 7.3, 7.375, 7.4, 7.5, 7.55, WO 96/40844 PCT/US96/09653 7.6, 7.8, 7.875, 7.9, 8.0, 8.5, 8.75, 8.875, 9.0, 9.1, 9.25, 9.3, 9.375, 9.4, 9.5, 9.6, 9.7, 9.75, 9.8, 9.875, 9.9, 10.0, 10.125, 10.25, 10.375, 10.5, 10.6, 10.75, 10.875, 11.0, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.75, 11.8, 11.875, 11.9, 12.0, 12.2, 12.3, 12.375, 12.4, 12.5, 12.7, 12.75, 12.875, 12.9, 13.0, 13.1, 13.2, 13.2, 13.25, 13.3, 13.375, 13.4, 13.5, 13.6, 13.7, 13.75, 13.8, 13.875, 13.9, 14.0, 14.1, 14.2, 14.3, 14.4, 14.5, 14.6, 14.7, 14.8, 14.9. 15.0, 16.0, 17.0, 18.0, 19.0, 20.0, 21.0, 22.0 23.0, 24.0, 25.0, 26.0, 27.0, 28.0, 29.0, 30.0, 31.0, 32.0, 33.0, 34.0, 35.0, 36.0, 37.0, 38.0, 39.0, 40.0, 41.0, and ranges of 0.001 to 50.0, 100.0, 200.0, 400.0, 500.0, 700.0, 800.0, 1,200, 3,500, or 5,000, grams metal/gal, more or less. All combustion improving or stoichometric amounts of elemental metal are contemplated.

In the case of diesel fuel applications manganese concentrations greater than 1.0% by weight of the fuel or amproximacelv 25 to 33 grams/gal are also contemplated. In gasolines, 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 combustion systems are modified to enhance the accelerated low temperature high energy nature of Applicant's invention.

Applicant's metals also include a full range of combustion catalysts including ferreous picrate, potassium salts, etc. For example, potassium salts are contemplated WO 96/40844 PCT/US96/09653 -37including those commercially marketed by Shell Chemical, known as "SparkAid or SparkAde." Such salts may be employed in fuels at 0.01, 0.4, 0.75, 1.0, 2.0, 3.0, 4.0, 5.0 parts metallic per million fuel, 1.0 to 4.0 ppm metallic being contemplated, with concentrations less than 16.0 ppm metallic also concem.clated. Other 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, 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.

In the application of Applicant's invention potassium concentrations greater than 3.0, 4.0, 5.0, 6.0, 7.0, 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 salt) are expressly contemplated and desireable, and depending upon ECS chemistry and mechanical means employed, said potassium conceitrations or greater concentrations can be employed absent adverse metallic oxide formation.

Metallic concentrations that maximize combustion velocity and/or the other objects of this invention are expressly contemplated.

In accordance with this invention, Applicant's fuels will contain that amount of at least one Mn and/or other non-lead metallic, which constitutes a combustion improving amount consistent with the fuel composition, stoichiometry, WO 96/40844 PCT/US96/09653 -38- EC chemisty, combustion system, efficiencies and power desired, as well as legal and/or environmental considerations.

However, it is expressly contemplated that 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.

It is an embodiment to substitute or mix metallics to achieve synergistic improvements in heat releases, burning velocity, thermal efficiency, emission reductions, power generation, and the like.. Applicant's invention contemplates wide variation in metal substitution and mixing practice. See for example U.S. Patents 3,353,938; 3,718,444; 4,139,349. Organic metal compounds are preferred in practice of invention.

Example 9 A composition comprised: of an ignition or combustion improving amount of a potassium salt (for example Shell Chemical Corporation's product markeded as SparkAid); and at least one organo-manganese compound; and at least one ECS compound.

It is preferred practice that metals herein have oxides whose heats of formation are negative, and should WO 96/40844 PCT/US96/09653 -39exceed 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).

It desireable the metal be of a low relative molecular weight. Acceptable molecular weights of Applicant's metals include those less 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; desireable molecular weights are those less than 27, 24; more desireable are those less than 15; and even more desireable are those less than 14; with the most desireable being those less than 6.

Applicant's contemplates gaseous and solid metals and/or their related compounds. It is preferred the combustion products of the metals be environmentally friendly, e.g. low or no toxicity.

Applicant recognizes that' there is a wide number of metallics available in the practice of instant invention.

Applicant incorporates by reference the 1995 Chemical Rubber Company CRC "Handbook of Chemistry and Physics," section on Physical Constants of Organometallic Compounds (and/or other related sections). And, specifically incorporates fuel soluable metals meeting the criteria of this invention.

Other non-limiting examples of non-lead metallics have been set forth in the specification. Additional non- WO 96/40844 PCT/US96/09653 limiting examples of non-lead simple binary metallic compounds. Ternary and higher compounds including salts are contemplated. Salts of ternary hydroxy acids are contemplated. Metallic perchlorates, sulfates, nitrates, carbonates, hydroxides, and others, are contemplated. Metal hydroxy compounds are desireable. Contemplated salts also include acid salts containing replaceable hydrogen.

It is also within the scope and practice of this invention to employ oxygenated containing metallic compounds, including oxygenated organo metallic compounds.

It is an express embodiment to use metallic compounds, which themselves are ECS compounds. 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 DMC).

Thus, 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.

It is also within the practice of this invention to employ a metallic compound, including homologue or analogue having a structure or structure similar to MI-OCH3, wherein M1 is a metallic having a valence of one or optionally having a valence greater than one, wherein the excess WO 96/40844 PCT/US96/09653 -41valence. is occupied by a double bond oxygen and/or one or more methyl, hydrogen, hydroxy, ethoxy, carbethoxy, carbomethoxy, carbonyl, carbonyldioxy, carboxy, methyoxy, isonitro, isonitroso, methylenedioxyl 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 excess valence are occupied by a double bond oxygen and/or by one or more methyl, hydrogen, hydroxy, ethoxy, carbethoxy, carbomethoxy, carbonyl, carbonyldioxy, carboxy, methyoxy, isonicro, isonitroso, methylenedioxyl radicals, and/or combination thereof (an illustrative example includes trimethyl borate [BH(OCH3)2]); a metallic compound having a structure of M3-[OCH3]3, wherein M3 is a metallic having a valence of three or optionally having a valence greater than three wherein the excess valence are occupied by a single or double bond oxygen and/or by one or more methyl, hydrogen, ethoxy, carbethoxy, carbomethoxy, carbonyl, carbonyldioxy, carboxy, methyoxy, isonitro, isonitroso, methylenedioxyl radical or combination, thereof; a metallic compound having a structure of M4- [OCH314, wherein M3 is a metallic having a valence of four or optionally having a valence greater than four wherein the excess valence are occupied by a single or double bond oxygen and/or by one or more methyl, hydrogen, hydroxy, ethoxy, carbethoxy, carbomethoxy, carbonyl, carbonyldioxy, carboxy, methyoxy, isonitro, isonitroso, methylenedioxyl radical or combination, thereof.

WO 96/40844 PCT/US96/09653 -42- In the above examples, it is contemplated 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 MI-O(CO)O-M2, wherein Ml or M2 are the same or different metals having a valence of 1 or optionally valences greater than one wherein excess valence is occupied by additional metal, and/or Ml or M2 are substituted for a single or double bond oxygen, and/or by one or more methyl, hydrogen, hydroxy, ethoxy, carbethoxy, carbomethoxy, carbonyl, carbonyldioxy, carboxy, methyoxy, isonitro, isonitroso, methylenedioxyl radical and/or combination thereof. Ml may be subsituted for single bond oxygen and/or by one or more methyl, hydrogen, hydroxy, ethoxy, carbethoxy, carbomethoxy, carbonyl, carbonyldioxy, carboxy, methyoxy, isonitro, isonitroso, or methylenedioxyl radical. Non-limiting examples include lithium carbonate [Li202(CO)], potassium carbonate [k202(CO)], sodium carbonate, cesium carbonate, copper carbonate, rubidium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, potassium sodium carbonate, and the like.

It is contemplated that C3 and C4 plus ethers may have metallic structure. For example, M'1-CH2-CH2-0-CH2-CH2-M'2 structure is contemplated wherein M'l1 and M'2 may be same or different metallic or wherein M'l or M'2 may be hydrogen WO 96/40844 PCTIUS96/09653 -43or atom or radical (similar to those above) with one valence.

Other contemplated structure include metallic ketone, ester, alcohol, acid, and the like. Non-limiting examples include M'1-C-OH3, wherein M'1 is one or more metallic comprising valence of 3; Other structure include M'1-C204, wherein has a valence of 2. M1-C-C-O-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.

It is highly preferred that said oxygenated organometallic compounds have the fuel proper:ies set forth above including those for ECS compounds, e.g. higher heats of vaporization, high burning velocities, decomposition characteristic decomposition at post ignition precombustion temperatures into enhanced combustion or free radicals structure), be thermally stable at normal handling temperatures, etc.; and have high heat and energy releasing characteristics of metals, etc..

It is expressly contemplated that Applicant's metallics be incorporated into liquid fuel systems by means of mutual solvents, as required. Or altnernatively, may be introduced into the combustor/combustion 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.

WO 96/40844 PCT/US96/09653 -44- Example A method and composition of reduced temperature vapor phase combustion, said method comprising: i) introducing a fuel varor 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 l) 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 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 H10, 120, 125, 130, 135, 140, 145, 148, "150, 152; 155, 157, 160, 170, 200, 230, 250, 275, 300, 325, 350, 375, 400, 450, 500 btu/lb 60°F (preferably above 150, 151, 152, 153, 154, 155, 160 btu/lb) or alternatively exceeding about 27, 28, 29, 30. 31, or 32 !K mole- 1 at its boiling point, a laminar burning velocity exceeding about 48, 49, 50, or more, cm/sec, and optionally being thermally stable in the vapor phase uP to about 100°C. 1500 C, 200

C

250 275°C, 3000°C, 325°C, 350°C,. 400°C,. 4500°C. 500°0C, 5500°C, 6000°C, or higher, 3) optionally a co-fuel; ii) constructina said fuel vaoor ontionallv havina a maximum PCT/US96/09653 WO 96/40844 svark enercv 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 less. and whereuD ignition unburned fuel vapor decomposes into reactive high kinetic energy free radicals having a heat of formation at 25 0 C of less than 150, 120, 100, 90, 80, 70, 60, 50, 20, 10, 0, or negative, Kcal. mole whereby 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 dissociated free radicals (non limi:ing examples include OH, CN, CH, and NI radicals with subsequent reassociation continuing combustion process) iii) diffusing said radicals ahead of the flame front in a manner sufficient to cause luminous vapor phase combustion.

Examcle Examcle 10 above, wherein said combustion is characterized as increasing exhaust gas velocities at below 1400 0 F, 1390 0 1375 0 F, 1350 0 F, 1325 0 F, 1300 0 F, 1275 0 F, 1250 0

F,

1200°F, 1100 0 or 1000 0

F.

Examole 11 The composition of Example 10 being free or essentially free of polynuclear aromatics, lead, sulfur, WO 96/40844 PCT/US96/09653 -46barium, chlorine, or florine, and optionally free or essentially free of chlorinated solvents, bromine and/or phosphorous, or any chemical contributing to or causing hydrofluorocarbons, fluorocarbons, chlorofluorocarbons, hydrochlorofluorocarbons.

Examole 12 The composition of example 10, wherein the ratio of ECS compound to metallic compound as measured in grams of compound or alternatively reactive radicals to grams 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 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.

Example 12a The examples above, wherein ECS compound is DMC and metal optionally Mn.

Examole 13 The methods or compositions above comprising: An ECS compound (DMC) and a metal (organo-manganese) compound, WO 96/40844 PCT/US96/09653 -47whereby 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:l 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. 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. 2,000:1, 1850:1, 1750:1, 1550:1, 1500:1, 1450:1, 1425:1, 1400:1, 1380:1, 1350:1, 1340:1, 1325:1, 1320:1, 1300:1, 1280:1, 1260:1, 1250:1, 1200:1, 1180:1, 1150:1, 1125:1, 1100:1, 1075:1, 1050:1, 900:1, 800:1, 750:1, 650:1, 600:1, 575:1, 550:1, 500:1, 450:1, 350:1, 300:1, 250:1, 200:1, 180:1, 175:1, 170:1, 165:1, 160:1, 155:1, 150:1, 145:1, 140:1, 135:1, 130:1, 125:1, 120:1, 115:1, 110:1, 105:1, 100:1, 95:1, 90:1, 85:1, 80:1, 75:1, 70:1, 65:1, 60:1, 55:1, 50:1, 45:1, 40:1, 35:1, 30:1, 25:1, 22:1, 20:1, 18:1, 17:1, 15:1, 12:1, 10:1, 8:1, 5:1, 3:1, 2:1, 1:1, or ratio maximizing combustion attributes of method or composition. Other ranges include 4800:1 to 15:1; 1200:1 to 10:1, 600:1 to 5:1, 300:1 to 5:1, 180:1 to 50:1; 600:1 to 30:1, 500:1 to 50:1. It is contemplated ECS to metallic ratios may be higher or lower than those set forth above.

WO 96/40844 PCT/US96/09653 -48- Example 14 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 zo or less than 600 parts to one, equal or less 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.

Example 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-hydrolysis agent, pH control additive, hydroscopic, hydrolysis control or prevention means, means to increase flash point, reduce vapor press or increase WO 96/40844 PCT/US96/09653 -49front end volitility (as may be required), any other recognized additive, or other additive disclosed herein, and mixture thereof; optionally a flash point of at least 38 0 C or RVP of less than 20, 15, 12, 10, 9.5, 9.0, 8.5, 7.5, 7.0, 6.5 psi; optionally maximum vapor pressure of 21 kPa 38 0 C; optionally a minimum thermal stability meeting ASTM D 1655 standards; optionally a heat of combustion or equivalent capacity equal to or exceeding 42.8 MJ/kg; optionally a max freezing temperature of -40, -47, -50 0

C;

optionally a total max acidity of 0.1 mg KOH/g; or optionally one or more recognized ASTM, industry, or goverment fuel standard; said fuel characterized as able to acheive luminous vapor phase combustion.

Examle 16 The composition of 15 above wherein the co-fuel optionally comports with industry and/or ASTM standards, and wherein resultant ESC/co-fuel, due to dilution effect of lower heating value ECS compound has heating value less than industry or ASTM co-fuel alone, or less than 43.0, 42.8, 42.5, 42.0, 41.5, 41.0, 40.5, 40.0, 39.0, 38.0, 37.0, 36.0, 35.0 kJ/kg, or less than 18,720, 18,000, 17,900, 17,500, 17,000, 16,500, 16,000, 15,500, 15,000, or less, BTU/lb, or less than 0.1, 0.5, 1.0, 2.0, 3.0, 5.0, 10.0, 15.0, 20.0, 25.0, 30.0, 35.0, 40.0, 50.0 percent btu than co-fuel as measured -by traditional methods; said fuel characterized as having enhanced fuel economy, power WO 96/40844 PCT/US96/09653 potential, work, range, thrust or lift compared to higher heating value co-fuel alone.

Example 17 A fuel composition, optionally of composition 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 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's latent heat of vaporization exceeds 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 resultant fuel optionally has a laminar burning velocity equal to or in excess of 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52 cm/sec; optionally (unless example 25c immediately above, then required a compound or element containing a transition metal, alkine metal, alkine earth, halogen, group IIIA element or mixture; said composition optionally characterized as having a heat of combustion less than 43.0, 42.8, 42.5, 42.0, 41.5, 41.0, 40.5 kJ/kg or less than 18,000, 17,900, 17,500, 17,000, 16,500, 16,000, 15,500, 15,000 or less, BTU/lb.

WO 96/40844 PCT/US96/09653 -51- 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 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0 gr element/gal; and a co-fuel; 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 viscosity ranging from 2.5 to 1.0 cSt at 40 0 C, cetane index of 40 to 70, an aromatic content by vol. ranging from approximately 0 to 35%, 0% to 20.0%, 0% to 15%, or 0% to 10%, under proviso 3-ring aromatics not to exceed 0.16 vol%; a T1O fraction temperature of about 190 to 230 0 C, a T 50 fraction temperature of about 220 to 280 0 C, a T90 fraction of about 260 to 340 0 C, a cloud point temperature of oC -10, -28, -32 or 6 0 C above tenth percentile minimum ambient temperature, a sulfur content not greater than 250 ppm, 200 ppm, 100 ppm, 50 ppm, 40 ppm, ppm, 20 ppm 5 ppm, or being sulfur free, a bunsen laminar burning velocity of at least 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, or more, cm/sec, a latent heat of vaporization of at least 105, .110, 115, 116, 117, 118, 119, 120, 121, 121, 122, 123, 124, 125, 130, 135, or greater, BTU/lb; said composition characterized as having a heat of combustion less a conventional, reformulated, low sulfur, or any ASTM diesel WO 96/40844 PCT/US96/09653 -52fuel, or less than 43.0, 42.8, 42.5, 42.0, 41.5, 41.0, 40.5 kJ/kg or less than 18,000, 17,900, 17,500, 17,000, 16,500, 16,000, 15,500, 15,000 or less, BTU/lb.; said method characterized in achieving reduced particulate emissions or improved fuel economy compared to co-fuel alone.

It is contemplated aviation gasoline applications generally meet ASTM D 910 specifications, except heats of vaporization especially those that are lead free. However, unlike other embodiments of Applicant's invention, while less preferred aviation gasolines may contain minor amounts of lead. However, Applicant's preferred embodiment is lead free.

ExamDle 19) A fuel composition, optionally including example comprising: an ECS compound (preferrably DMC) representing 0.01% to 40.0% or 0.01% to 10.0%, 15.0%, 20.0%, 25.0%, 30.0%, 35.0%, or more, oxygen by wt in the fuel, a combustion improving amount of compound or element containing a transition metal, alkine metal, alkine earth, halogen, group IIIA element or mixture, in a concentration of 0.001 to about 1.5, 3.0, 4.0, 5.0, 7.5, 10.0, 15.0, 20.0, 30.0, or more, gr/gal, a diesel co-fuel; wherein said fuel is optionally characterized as having one or more of the following: an API range of about 41.1 to 45.4, optionally a sulfur content not exceeding 500, 300, 250, 200, 150, 100, 50, WO 96/40844 PCT/US96/09653 -53- 10, 5 wt ppm or sulfur free, optionally absent nitrogen, and optionally an aromatic content ranging from 0 to 1 to 10%, 0 to 15%, 0 to 20%, 0 to 35% by volume, or aromatic free, optionally a PNA vol% of not exceeding 0.03, 0.02, 0.01, or PNA free, optionally a Cetane index greater than 32, 34, 36, 38, 40, 43, 45, 47, 50 (or lower than 38, 36, 34, 32 or less), optionally an IBP of approximately 365 0 F 150°F; optionally a 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 least 105 BT/lb; said method characterized in achieving reduced particulate. emissions or improved fuel economy compared to co-fuel alone.

20) 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 gasoline cofuel; said fuel optionally characterized as having one or more of the following: a minimum knock octane number of or 100 and minimum performance number of 87, or 130, containing lead, a max T10 distillation temperature of 75 0

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 temperatures is a minimum of 135 0 C, a maximum sulfur content WO 96/40844 PCTrUS96/09653 -54of 0.05 wt%, optionally a minimum net heat of combustion less than 18,720, 18,000, 17,500, 17,000, 16,500, 16,000, 15,500, 15,000, 14,500, 14,000, btu/lb or less (as measured by traditional methods), a latent heat of vaporization exceeding 140, 150, 155, or 160 BTU/lb.

21) 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, 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 combustion aviation co-fuel alone.

Example 22 A jet turbine fuel composition, optionally of comoosition 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 WO 96/40844 PCT/US96/09653 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 2050C, a maximum final boiling point temperature of 3000°C, 2800°C, or 2600C; optionally: a minimum flash point of 380°C, a density range of about 751 to 840 at 15°C, kg/m 3 or optionally exceeding 840, 850, 860, 880, 900, or more, kg/m 3 a minimum freezing point of -400C, or -57°C, a minimum net heat of combustion of 42.8 KJ/kg or a heat of combustion less than 42.8, 42.0, 41.5, 41.0, 40.5, 40.0, 39.5, 39.0, 38.0, 37.0, 36.0, 35.0, 34.0, 32.0, 30.0, 28.0, 26.0, 24.0, or less, KJ/kg, a minimum latent heat of vaporization of about 110, 115, 118, 120, 125, 130, 135, 140, 145, 150, 155, or greater, BTU/lb; optionally a metal deactivator; optionally an antioxidant; optionally a detergent or dezergent/dispersent; and optionally otherwise meets ASTM 1655 finished fuel-requirements for Jet A, Jet A-1, or Jet B; whereby said composition is characterized as having increased lift, thrust and/or operating range compared cofuel alone.

Example 23 A No. 2 fuel oil composition, optionally of composition 15 above, comprising: an ECS compound (preferrably DMC) representing 0.01% to 40.0% oxygen by wt WO 96/40844 PCT/US96/09653 -56in the fuel, a compound or element containing a transition metal, alkine metal, alkine earth, halogen, group IIIA element or mixture, a No. 2 fuel oil co-fuel; said composition characterized as having a kinetic velocity of no less than 1.9 nor grea ar than 3.4 (rtmr/s) measured at 0 C, a minimum T-90 temperature of 282 0 C, a max temperature of 338 0 C, a maximum sulfur content of 0.05% mass, a maximum copper strip rating of No.3, flash point of 38 0 C, LHV of at least 90, 95, 100, 105, 110, 115, 120, 125, 130, 135 BT-U/lb, optionally containing co-solvent and/or metallic salt, and heat of combustion of about 43.0 KJ/kg or a heat of combustion less than 42.8, 42.0, 41.5, 41.0, 40.5, 40.0, 39.5, 39.0, 38.0, 37.0, 36.0, 35.0, 34.0, 32.0, 30.0, 28.0, 26.0, 24.0, or less; said fuel characterized as having greater work potential than co-fuel alone.

Example 24 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, 2.7, 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 cofuel as set forth herein or in my co-pending International Applications No. PCT/US95/02691, No. PCT/US95/06758, wherein said co-fuel optionally comports with industry and/or ASTM specification standards; optionally having T- WO 96/40844 PCT/IUS96/09653 -57- T-50, T-10, BV, or LHV modification/adjustment as disclosed herein or in said co-pending Applications; said ECS\co-fuel optionally containing: additive, salt, cosolvent disclosed herein or in my co-pending International Applications No. PCT/US95/0 2 691, 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; said ESC/cofuel optionally having a heating value less than co-fuel alone and less than industry or ASTM fuel standards, or less than 43.0, 42.8, 42.5, 42.0, 41.5, 41.0, 40.5, 40.0, 39.0, 38.0, 37.0, 36.0, 35.0, 33.0, 30.0, 28.0, 26.0 kJ/kg, or less than 18,720, 18,000, 17,900, 17,500, 17,000, 16,500, 16,000, 15,500, 15,000, 14,500, 14,000, 13,500, 13,000, 12,500 or less, BTU/lb; said composition optionally comporting with industry, government, or ASTM fuel standards (excepting heat of combustion); said ecs\co-fuel further characterized as having increased exhaust gas velocities when combusted with enhanced fuel economy, power, work potential, flight range, thrust or lift compared to higher heating value co-fuel alone.

Example WO 96/40844 PCT/US96/09653 -58- 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 thrust is no less than co-fuel; or optionally at least 0.5% greater than co-fuel alone.

Examle 26 The above example ECS\co-fuel compositions; characterized as being absent ECS compound, or absent ECS compound and metallic (ECS fuel component); said fuel being further characterized as having elevated LHV and/or BV compared to minimum industry or ASTM specification base fuel or co-fuel, alone.

It is a preferred practice of construct fuels absent ECS fuel component or absent ECS compound which enjoy LHV's and/or BV's greater than tradition fuel. This practice is accomplished by distillation temperature, combustion temperature and fuel component modifications as set herein and in my said co-pending Applications.

It is an embodiment to employ ESC/co-fuel combinations wherein their calorific/Btu contents, measured by tradition method or by simple addition of known Btu values of composition components, are below minimum ASTM, government, WO 96/40844 PCT/US96/09653 -59industry or other standards. Thus, Applicant's ECS/co-fuels may have calorific values approximately 0.01, 0.25, 0.75, 1.0, 1.15, 1.25, 1.5, 1.75, 2.0, 2.5, 3.0, 5.0, 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 standards.

The calorific content of certain ECS compounds are: BTU/lb 60°F BTU/zal@ 600F WATER 0 DMC 6,280 56,100 Methanol 8,570 56,800 Ethanol 11,500 76,000 MTBE 15,100 93,500 TAME 15,690 100,600 GASOLINE 18,000-19,000 109,000-119,000 As can be seen ECS compounds have reduced heating capacity as compared to gasoline. But because Applicant's combustion compositions and methods increase 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.

Applicant has found his lower BTU containing ECS/cofuel combinations to have approximate work equivalencies WO 96/40844 PCT/US96/09653 equal to or greater than the higher BTU containing ASTM fuels. See TABLE A below.

TABLE A BTU/HEAT OF COMBUSTION EQUIVALENCY OF EXAMPLE ECS/CO-FUEL COMBINATION PERCENTAGE ECS Compound in ECS/CofuelCombination 20% 40% 60%

APPROXIMATE

BTU OF ASTM STANDARD FUEL IN ECS/CO-FUEL COMBINATION ACHIEVING EQUIVALENT WORK 97.5% 5-90% 75-85% 70-76% 68-73% Thus, as can be seen the higher the relative concentration of ECS fuel the greater the work potential as a function of the combined fuel's heat of combustion.

Consequently, the greatest work potential of any ECS/cofuel combination is greatest with increasing amounts of ECS fuel in the combined fuel.

Example 27 An ECS/Co-fuel combination, wherein said ECS fuel has lower BTU content than co-fuel and wherein combined ECS/Cofuel 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.

SUBSTITUTE SHEET (RULE 26) WO 96/40844 PCT/US96/09653 -61- Co-Puels and ECS/Co-fuel Applicant's co-fuels 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.

As set forth herein, co-fuel practice extends to modified fuels ("Modified Fuel"). The distinction is that co-fuels are contemplated in combination with ECS fuels, whereas Modified fuels, namely those fuels with improved LEV, BV, distillation characteristics, and/or other structure, are not necessarily contemplated in combination with an ECS compound or metallic. Thus, in the description herein a modified fuel may be subsituted for co-fuel.

It is an express embodiment of this invention that cofuels may be employed as minority, substantial minority, majority, or substantial majority-constitutent in a ECS/cofuel 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 express object to maximize total ESC fuel vapors derived from the ECS/co-fuel combination. Thus, the ESC vapor may represent 0.001 to about 0.5, 1.0, 1.2, 1.7, 2.0, 2.1, 2.5, 3.0, 3.4, 3.5, 3.7, 4.0, 4.2, 4.7, WO 96/40844 PCT/US96/09653 -62- 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.

In initial application the ECS fuel component will represent a minority component due to existing fuels, distribution and combustion systems.

It is preferred that Applicant's ECS fuel, co-fuel or ECS/co-fuels, when employed in existing systems meet ASTM, government and/or industry requirements for the co-fuel, with minimum heats of combustion optional.

It is contemplated that ECS/co-fuels may need adjustment or tailoring to meet minimum ASTM and/or government standards. For example, if an ECS/co-fuel must meet minimum ASTM heats of combustion and DMC is 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 specifications.

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 Applications No.

PCT/US95/02691 and PCT/US95/06758 incorporated by reference and below.

Applicant's co-fuels and ECS/co-fuels may be tailored or constructed to reduce or control T-90, T-50 or distillation temperatures to reduce LHV's.

WO 96/40844 PCT/US96/09653 -63- Applicant's co-fuels and ECS/co-fuels are typically constructed to enjoy low or extremely low combustion emissions.

For example, it is an express object of this invention that co-fuels be formulated, and/or ECS/co-fuel combinations be formulated or constructed to reduce to the maximum extent possible emissions of NOx, CO, C02, HC's, particulates, toxics, reactive ozone forming precursors, polynuculear aromatics, benzene, butadiene, formaldehyde, ,0 acetaldehyde, regulated emissions, unregulated emissions recognized as pocentially harmful, and/or any cancer causing or environmental harming substance, either now known or identified in the future. However, construction of base fuels need be tempered by the amerliorate emission characteristics of ECS fuels. Thus, higher concentration of hereto beleived hazardous components may be acceptable.

It is the practice of this invention to avoid intentionally adding known environmentally hazardous substances, e.g. sulfur, lead, barium, chlorine, florine, etc., to Applicant's fuels, unless otherwise set forth herein.

It is also contemplated that Appliant's co-fuels and/or ECS/co-fuels be formulated to reduce particulate emissions to the greatest extent possible. It is desireable average particlate size be no greater than 10.0, 7.5, 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 possible.

WO 96/40844 PCT/US96/09653 -64- Higher BV's reduce particulates, NOx emissions.

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 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 less, are more desireable. As noted, it is a practice to reduce aromatic concentrations when ever practical.

Within practical limitations, after consideration to LHV, burning velocities, enviromentally hazardous components, calorific content (if necessary), it is desireable that Applicant's co-fuels and ECS/co-fuels have high possible densities, within ASTM, military or industry standards. Densitities greater than such standards are expressly contemplated, particularly in advanced applications. For example, 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 expressly contemplated, Moderate, low and to very low densities are also contemplated so long as the increased burning velocity object of instant invention is accomplished.

The viscosity of Applicant's co-fuels and ECS/co-fuels should generally meet acceptable standards. It is important WO 96/40844 PCT/US9609653 that highly viscous fuels be properly atomized to assure vapor phase combustion. Applicant's invention, however due to the visc breaking features of certain ECS compounds, particularly DMC, permits usage of highly viscous fuels, which might otherwise might be unacceptable.

In other words, Applicant has discovered the combination of certain ECS compounds, particularly

DMC,

tends to reduce viscous flow friction. Thus, it is contemplated that co-fuels may have viscosities at the upper end of industry standards or viscosities above ASTM, government or industry requirements.

For example it is contemplated Jet A co-fuel have a viscosity greater 6.0, 7.0, 8.0, 8.1, 8.2, 8.5, 9.0, 10.0, 12.0, 15.0, 16.0, or more, mm /s 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 exceeding 1.5, 1.7, 2.0, 2.4, 2.6, 3.0, 4.0, 5.0, 7.0, or greater, mmn/s (ASTM D 445) for No. 1-GT, or exceeding 3.0, 3.5. 3.8, 4.1, 4.2, 4.5, 5.0, 6.0, or more, mrm 2 /s (ASTM D 445) for No. 2-GT; or a diesel fuel oil co-fuel have a maximum kinetic viscosity at 40oC exceeding 1.2, 1.8, 2.4, 2.6, 3.0, 4.0, 5.0, 6.0, 7.0, or greater, mm2/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, mn/s (ASTM D 445) for low sulfur or regular No.. 2-D, or exceeding 15.0, 18.0, 20.0, 22.0, 24.0, 24.5, 25.0, 26.0, 30.0, 40.0, 45.0, 50.0, 60.0., or more, mnm/s (ASTM D 445) WO 96/40844 PCT/US96/09653 for No. 4-D; or a low emission diesel co-fuel have a viscosity exceeding 1.2, 1.5, 1.8, 2.4, 2.5, 2.8, 3.0, 3.2, 3.8, 4.2, 4.8, 5.5, or more, cSt at 40 0 C (where lmm2/s IcSt) or fuel oil co-fuel have a kinetic viscosity exceeding 1.2, 1.8, 2.1, 2.3, 2.5, 3.0, 3.4, 3.5, 4.0, 6.0, 6.5, 8.0, 10,0, or more, mm2/s at 40'C (AS"TI D 445) for No. 1, exceeding 2.2, 2.6, 3.0, 3.4, 3.5, 3.6, 5.0, 5.5, 6.0, 6.5, 8.0, 10,0, or more, am/s at (ASTM D 445) for No. 2, exceeding 3.5, 4.0, 5.0, 5.5, 5.6, 6.0, 6.5, 8.0, 10,0, 12.0, 15.0, 20.0, 25.0, or more, mm/s at 40 0 C (ASTM D 445) for No. 4 (Light), exceeding 8.0, 12.0, 15.0, 18.0, 20.0, 24.0, 25.0, 26.0, 30.0, 35.0, 40.0, or more, =17/s at 40'C (ASTM D 445) for No. 4, exceeding 6.0, 7.0, 8.9, 9.0, 9.1, 9.2, 9.3, 9.5, 10.0, 11.0, 12.0, 14.0, 14.5, 14.9, 15.0, 16.0, 18.0, 19.0, 20, 21.0, 22.0, 25.0, or more, mm 3 /s at 100 0 C (ASTM D 445) for No. (Light), exceeding 6.0, 7.5, 9.0, 11.0, 14.9, 15.0, 15.2, 15.5, 15.7, 16.0, 16.5, 17.0, 18.0, 19.0, 20, 21.0, 22.0, 25.0, 30.0, or more, mm3/s at 100 0 C (ASTM D 445) for No. (Heavy), exceeding 20.0, 25.0, 30.0, 35.0, 40.0, 45.0, 50.0, 50.5, 51.0, 5.2.0, 53.0, 54.0, 55.0, 57.0, 60, 65.0, 70.0, 75.0, 80.0, or more, mm 3 /s at 100 0 C (ASTM D 445) for No. 6 fuel oil; a heavy diesel, locomotive or marine engine co-fuel meeting ISO DIS 8217 and/or BS MA 100 standards and/or other industry specifications have viscosity exceeding 150, 200, 250, 300, 350, 400, 450, 500, 510, 520, 530, 550, 600, 650, or more, centistokes at 50 0

C.

WO 96/40844 PCT/US96/09653 -67- It is contemplated that the viscosity of Applicants ECS/co-fuel will comport with ASTM, goverment, or other standards.

Example 28 A fuel ECS/co-fuel composition of all above examples, wherein said co-fuel's viscosity exceeds maximum permissible ASTM, industry or government standards; and where ECS/co-fuel combination is characterized as meeting same ASTM, industry or government standards.

It is contemplated that 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 standards.

The addition of ECS Fuel in ECS/co-fuel combinations tends to reduce spark ignition delay. Optimizing combination fuel combustion may require reductions in spark advances, which are expressly embodied herein.

Example 29 A method of operating an engine employing an ECS/cofuel combination (consistent with the example compositions herein); said method characterized as combusting said fuel in a spark ignited engine, combustor, or other engine, including jet, turbine engine, wherein ignition delays are WO 96/40844 PCT/US96/09653 -68reduced compared to co-fuel alone by about least 0.001 to 0.01 to 2.0, 0.01 to 3.0, 0.01 to 5.0, 0.01 to 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, _ercent or more; and wherein spark advance, if applicable, is adjusted accordingly.

Example The method of Example 29, wherein the air fuel ratio is reduced by at least 5, 10, 15, 20, 25, 30, 35, 40, 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.

Example 3! 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 nonhydrocarbonaceous fuel, solid, liquid, gaseous fuels, WO 96/40844 PCT/US96/09653 -69including alternative fuel, hydrogen, petroleum gas, liquefied petroleum gas, LPG-propane, LPG-butane, natural gas, natural gas liquids, methane, ethane, propane, nbutane, propane-butane mixture, fuel methanol, e.g. M M 90, or M 85 fuels, fuel ethanol, biomass fuels, vegetable oil/ester fuels, rap seed methyl ester, soybean fatty acid esters, aqueous carboneous fuels (including aqueous gasolines, 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 1001l (meeting ASTM standards), conventional automotive gasolines, reformulated gasolines (meeting

U.S.

Clean Air Act 211 California Air Resources Board, Swedish/European EPEFET standards, or other standards), low vapor pressure gasolines, low sulfur/no-sulfur gasolines, low octane gasolines, Talbert E-gasolines, alkylate or substantially alkylate fuels (including aviation and automotive gasolines), reformate fuels, substantially reformate fuels, isooctane fuels, substantially isooctane fuels, raffinate, paraffinic fuels, substantially paraffinic fuels (including optionally n-butane, isopentane, toluene, c7-cl0 olefins), kerosine, wide range boiling fuels, gas turbine fuels, including No.0-GT, No.1- GT, No.2-GT, No.3-GT, No.4-GT (meeting ASTM standards), aviation jet turbine fuels including JP-4, JP-5, JP-7, JP- 8, JP-9, JP-10, TS, Jet A-l, Jet A, Jet B (meeting

ASTM

standards), military aviation gasolines (including JP-8, JP-8+100, a refined kerosine fuel known as JPTS for U-2/TR- WO 96/40844 PCT/US96/09653 1 aircraft), missile fuels, solid and liquid rocket fuels, monopropellant, multipropellant fuels, hypergolic fuels, gas oil turbine-engine fuels, including grades 0-4, stratified-charged engine fuels, diesel fuels, including Grade low sulfur No. 1-D, Grade low sulfur No. 2-D, Grade No. l-D, Grade No. 2-D, and Grade No 4-D (meeting ASTM standards), and older grades Type C-B, Type T-T, Type R-R, Type S-M, reformulated diesel fuels (meeting CAR3 or Swedish standards), low/no sulfur hydrotreated low/no aromatic distillate fuels, toluene fuels, substantially toluene fuels, naptha fuels, subtantially naptha fuels, fuel oils, including Grade 1, Grade 2, Grade 4 (light), Grade 4, Grade 5 (light), Grade 5 (heavy), Grade 6, heavy diesel fuels for marine or railroad, including those complying with ISO DIS 8217 and BS MA 100 standards, various distillate oils, distillate fuels, substantially distillate fuels, residual type oils, cycle oils, light cycle oils, light cycle gas oils, heavy cycle oils, heating oils, heavy cycle gas oils, vacuum oils, burner oils, furnace oils, coal liquids, SRC-II middle distillate coal fuels, near coal liquids, powdered coal, coal derivatives, coal, solid fuels, tar sand fuels, shale oil fuels, hydrazine, ammonia acetylene, any other hydrocarbon or nonhydrocarbon fuel, and/or fuel meeting ASTM specifications, military or international specifications, EPA certification standards, CARB or Swedish European standard, or meeting any industry and/or any government specification or regulation, present and future, including mixtures thereof; WO 96/40844 PCTUS96109653 -71and optionally being non-leaded and a low sulfur or no sulfur and/or low or no phosphorus containing fuel; where upon combustion luminous vapor phase combustion occurs.

ExanDle 32 The above examples, wherein the vapors from an ECS fuel or a combined ECS/co-fuel powers a engine having a displacement ea-ual 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 inChs or equivalent, or larger engine, under moderate to moderately high to high load conditions, those greater than 14.0, 15.0, 16.0, 17.0, 18.0, 19.0, 20.0, 21.0, 22.0, 23.0, 24.0, 25.0, 26.0, 27.0, 28.0, 29.0, 30.0, or 35.0 ihp, assuming a 350 cubic inch engine displacement ecuivalent, or alternatively load of exceeding 0.04, 0.043, 0.0456, 0.0514, 0.054, 0.057, 0.06, 0.063, 0.066, 0.069, 0.71, 0.74, 0.77, O.8, 0.84, 0.086, 0.10, 0.11, 0.12, 013, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.25, 0.30, 0.35, 0.40, or more, ihp/cid); whereby fuel economy and/or thermal efficiencies are increased over co-fuel operation alone by to 20.0%, or more to 30.0% preferred).

WO 96/40844 WO 9640844PCT/TJS96/09653 -72- It is an express embodiment of Applicant's invention to operate combustion systems under heavy to extreme load conditions. Applicant's invention is well suited for larger engines, under such load conditions.

Examle 33 The compositions, vapor compositions 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 engines (non-limiting examples include low emission, ultra low emission, variable-valve timing and lift, direct fuel injection, three-way catalyst systems, lean burn engines), oil burner, reside burner, oil furnace, high performance burners (for example with flame envelopes with heat release rates of 10,000,000 BTU/ft3-hr), gas burner, gas furnace, internal compression engine, sparkignited 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.

In the practice of this invention, Applicant has found that when DMC is ECS compound of choice, it is desireable to construct a fuel having a pH that is a close to nuetral as possible. Alkaline pH is acceptable, however nuetral WO 96140844 PCT/US96/09653 -73and/or a very slightly acidic pH is desireable. Higher acidity is possible, but must be tempered by ASTM fuel limitations and combustion systems, particularly those governing aviation turbine fuels which set a maximum acidity of 0.1 mg KOH/g or equivalent.

Applicant contemplates ASTM or other industry limits, if applicable. Absent such limits, pH levels will not exceed acceptable limits based upon fuel and combustion system constraints.

Exampl e 34 The above fuel compositions wherein the ECS compound is DMC, said composition being pH nuetral or slightly acidic, or optionally having a pH less than 9.0, 8.9, 8.8, 8.7, 8.6, 8.5, 8.4, 8.3, 8.2, 8.1, 8.0 (water), 7.9, 7.8, 7.7, 7.6, 7.5, 7.4, 7.3, 7.2, 7.1, 7.0 (nuetral), 6.9, 6.8, 6.7, 6.5 (water), 6.4, 6.3, 6.2, 6.1, 6.0, 5.9, 5.8, 5.7, 5.6, 5.5, 5.4, 5.3, 5.2, 5.1, 5.0, 4.5, 4.0, 3.5, 3.0, or less. pH's less than 8.0, 7.0, 6.5, and greater than 5.0, 5.5, or 6.0 are more preferred.

It is also expressly contemplated that Applicant's modified or co-fuels contain necessary additives as set forth herein or in my co-pending International Applications No. PCT/US95/02691 and No. PCT/TUS95/06758 Latent Heat of Vaporization, Enhancement It is an express object and embodiment of this invention that Applicant's hydrocarbon co-fuels, ECS\co- WO 96/40844 PCT/US96/09653 -74fuels, modified fuels (see below) be constructed or formulated to enjoy the maximum latent heats of vaporization 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.

It is a further imbodiment in multi-component fuels that such improvement occur by reformulating existing components, or adding components available in the manufacture of said fuel.

However, it is also an embodiment to incorporate

ECS

structure and/or ECS fuel into such fuels to accomplish this object.

Applicant has discovered that threshold

LHV

improvements will vary greatly depending upon the fuel composition, type of combustion system.

However, LHV increases of at least 0.5, 1.0, 1.5, 3.0, 3.5, 4.0, 4.5, 5.0, 6.0, 6.5, 7.0, 7.5, 8.0, 9.5, 10.0, 12.5, 15.0, 17.5, 20.0, 22.5, 25.0, 27.5, 30.0, 35.0, 40.0, 50.0, 55.0, 60.0 percent, or more, over unadjusted base fuel, are contemplated and desireable. For purposes of comparing LHV differences, Applicant's base WO 96/40844 PCTIUJS96/096:53 fuels are ASTM, industry or equivalent fuels on date of this invention.

It is noted, that heavier fuels, e.g. diesel, jet aviation, gas turbine fuels, etc., often have lower average latent heats of evaporation, on a per weight basis, than do the lower molecular weight gasolines. The higher the boiling point temperatures of a fuel, typically the lower the average LHV per unit of weight.

Depending upon the base fuel or co-fuel, or modified fuel, it is desireable that higher boiling components with latent heats of vaporization less than approximately 60, 70, 80, 90, 100, 110, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180 btu/7b, or alternatively those less 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, those components lower than the average latent heat of vaporization of unadjusted base fuel, be reduced in volume concentration or removed from the composition; Alternatively, fuel components having LHV greater than base fuel's average latent heat of vaporization may increased or included; such that the new formulated fuel is greater than the unadjusted base fuel.

As noted herein and in my co-pending International Applications No. PCT/US95/02691 and No. PCT/US95/06.58, Applicant has discovered that optiminal reformulating of modified fuels, co-fuels not only includes reduced end point and T-90 distillation temperatures and modification to T-50 temperacures with fuel substitutent modification WO 96/40844 PCT/US96/09653 -76reducing sulfur, aromatics, olefins, etc.), but preferrably simultaneously requires elevating average LHV and optional BV of base fuel by at least Absent simultaneously elevating LHV's and BV's the full benefit of the invention may not be acheived.

For example, in hydrocarbon fuels boiling between about 60 0 C to approximately 110°C, cyclanes, alkenes, alkanes, in order of their ranking are preferred for purposes of achieving elevated LHV's. From about 120 0

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 0 °C preference between alkenes and cyclanes are about the same. Between 160 0 C-180 0 C to approximately 300 0 bi-cyclic hydrocarbons, aromatic hydrocarbons, and alkanes, in order of their ranking, are preferred.

The preferred practice of formulating base fuels to increase their latent heats of vaporization is typically by removal of higher boiling material with low latent heats of vaporization and/or low burning velocity) until said oxygen/metals free base hydrocarbon composition has 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, 89.0, 900, 905, 910, 915, 920, 925, 930, 940, 950, 970, 990, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350 btu/gal or more. It is desireable that it WO 96/40844 PCT/US96/09653 -77be greater than 650, 740, 790, 800, 830, 860, 880, 900, 910 btu/gal, or more.

Alternatively, 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.

While 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 increased latent heats of vaporization should be tempered by other factors, including known hazardous emission features of certain components, distillation requirements, calorific or heating requirements, burning velocity improvement, etc.

For example, while benzene and xylenes have elevated L-V they are known to be environmentally harmful. As set forth herein, the reduction of aromatics has certain other environmental advantages. e.g. reduced carbon formation, etc., but also may reduce LHV. Thus, aromatic reduction should be tempered with reducing higher boiling point aromatics and not lower boiling point aromatics, which have higher LHV's.

Thus, depending upon the fuel composition and type of fuel, the tailoring/formulating of modified, co-fuel compositions those absent ECS compound and/or metallic) to acheive enhanced LHV's should be such that WO 96/40844 PCT7US96/09653 -78final 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 base fuels. Latent heats of vaporization outside this range are also acceptable.

However, in the case of automotive gasolines, Applicant has found that latent heats of vaporization equal or in excess 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 BTUJ/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.

In the case of aviation gasolines latent heats of vaporization equal to or in excess 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.

In the case of diesel fuels, latent heats of vaporization equal to or in excess of 85, 90, 95, 100, 102, WO 96/40844 PCT/US96/09653 -79- 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 BTUJ/lb, are acceptable. Those in excess of 110, 115, 120, 125, 130 BTUTJ/lb, or more, are desireable.

in the case of jet aviation turbine fuels, LEV'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.; alternatively they should equal or exceed about 55, 60, 75, 80, 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, 155, 160, 165 B3U/lb. Those in excess 85, 90, 95, 100, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165 BTU/lb. are more desireable. Those in excess of 120, 125, 130, 135, 140, 145, 150, 155, 160, 165 BTU/lb. are preferred.

Heavy diesel and fuel oil's LHV's should exceed 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 excess of 100, 102, 110 BTU/lb are desireable.

In the construction or reformulation of Applicant's modified or co-fuels and depending upon the individual base fuel, it is also desireable that 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, WO 96/40844 PCT/US96/09653 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52, 0.53, 0.54 BTTJ/lb°F, or greater. Those above 0.46 BTU/lb°F are preferred.

Increased LEV's translate into reduced combustion temperatures. Desireable reductions are in range of about F to 500 F. Reductions of 5°F to 50°F, or more, are also desireable.

It is an express embodiment to reduce combustion temperatures by constructing compositions to avoid or reduce combustion chamber deposits. Thus, combustion chamber deposit reducing compositions, or other means, includina deposit additives are expressly contemplated.

Applicant has discovered that work potential is not lost due to reductions in end -point and/or temperatures, if LHV is simultaneously increased.

Multi-boiling point fuels benefit from end boiling,

T-

boiling and T-50 reductions, which simultaneously increase LHV. Such fuels include aviation and automotive gasolines, gas oil turbine fuels, fuel oils, diesel fuels, jet aviation fuels, and the like.

It is an express embodiment that metallic or nonmetallic containing gasoline have sufficiently elevated

LHV

that exhaust catalyst inlet temperatures be sufficiently reduced to avoid catalyst plugging, OBM II monitor failure, and like. Catalyst inlet temperatures of about 1400°F or less, including 1350 0 F, 1300 0 F, 1250 0 F, 1200 0 F, 1150 0

F,

1100°F, 1050 0 F, or less, other temperature sufficient to assure acceptable catalyst activity while avoiding the WO 96/40844 PCTIUS96/09653 -81likely hood of manganese oxide plugging, are contemplated and an embodiment of this invention.

Thus, it is an embodiment that modification of hydrocarbon co-fuel's, including T-90, T-50, or distillation temperatures and/or substituent 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 fuels, absent modification.

Thus, such combustion temperature control alone, absent other means of Applicant's invention

ECS

compounds, mechanical air charge temperature reduction, etc.), is contemplated in formulation of Applicant's modified fuel to reduce emissions and/or as a means to control wash coat deposits from low metallic manganese containing fuels, resulting from excess exhaust tererature.

Example A method of avoiding the plugging or coating of exhaust catalysts or OBD II monitors or monitoring systems 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 temperatures are sufficiently reduced that inlet exhaust gas temperature of WO 96/40844 PCT/US96/09653 -82catalyst is less than 1400 0 f, more preferably less than 1350, 1300, 1250, 1200 0

F.

Examle 36 A method of avoiding the oxide plugging or coating of exhaust catalysts; said method comprising: modifying 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 catalyst to less than 1400°f.

It is expressly contemplated that formulating fuels for higher latent heats of vaporization be'an independent embodiment of this invention. However, the preferred practice of this invention contemplates simultaneous use of ECS structure and/or metallics in said high LHV modified or co-fuels.

Example 37 A hydrocarbon fuel composition, selected from the group of existing 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 3%, or greater; and whereby said LHV increase is made absent inclusion of an ECS compound and/or metallic compound.

WO 96/40844 PCT/US96/09653 -83- Example 38 The example of 37, wherein the latent heat of vaporization of resultant composition is greater than original unadjusted base line composition, and wherein said additionally reformulated composition (,,LHV Enhanced Cofuel Composition") is blended with at least one ECS compound and/or a metallic, whereby the resultant combined composition meets ASTM, government and/or industry standards.

Example 39 A fuel composition comprising a conventional or reformulated gasoline, an optional oxygenate, a 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, 51, 52, 53, 54 cm/sec; said -fuel characterized as improving fuel economy (preferably at least 0.5% or more) over unadjusted fuel or adjusted T90 fuel absent minimum

LIHV.

Examnle The method of example 39, wherein the fuel additionally comprises a charge temperature reducing amount of a combustion chamber deposit control additive.

WO 96/40844 PCT/US96/09653 -84- Exan=me 41 The method of example 39, wherein fuel economy is improved over the clear fuel containing same amount of metallic but not having reduced T-90 temperatures and elevated LHV.

Examole 42 The examples above, wherein latent heat of vaporization and/or burning velocity of the adjusted fuel is 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, greater than non adjusted fuel.

Example 43 The examples above, wherein fuel T-90 temperature is less than 310 0 F, more preferably less than 305°0, 300 0

F,

295 0 F, 290 0 285 0 280 0 275 0 F, 270 0 F, 2 65°F, 260 0 F, 255 0

F,

250 0 F, 245 0 F, or less; and MMT is included in the amount of 1/32 gr. Mn/gal; and optionally a combustion chamber deposit 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, 1.0, 1.5, 2.0, 2.5, 3.0, or more, percentage.

BURNING VELOCITY ENHANCEMENT It is an express object and embodiment of this invention that Applicant's hydrocarbon co-fuels, ECS\cofuels, modified fuels (see below) be constructed or WO 96/40844 PCT/US96/09653 formulated to enjoy the maximumIt is also an embodiment of this invention to construct or formulate Applicant's cofuels to acheive maximum flame velocity. Applicant has found that C2 to C6 acetylene hydrocarbons offer exceptional burning velocities. C4 to C6 olefins and deolefins 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, CS, C4, C3 or lower, the higher the burning velocity.

In terms of carbon atoms of the same chain length, nalkynes 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.

It is also contemplated that Applicant's modified fuels or co-fuels will have low and extremely evaporative emissions and thus low vapor pressures.

FUELS AND COMBUSTION SYSTEMS GENERALLY The combustors contemplated in the practice of this invention include geometric combustors (tubular, annular, tubo-annular, spherical), aerodynamic combustors (diffusion WO 96/40844 PCTIUS96/09653 -86flame, premixing, staged, catalytic, and application combustors (aircraft, industrial, vehicular).

It is preferred in the practice of this invention to employ a diffusion flame combustor, wherein Applicant's combustion flames are further propagated by gaseous jet diffusion, advanced droplet evaporation,. accelerated burning, and/or spray diffusion.

Thus, it is an embodiment to employ a diffusion flame combustor in combination with ECS fuels; whereby combustion emissions are improved, combustion is accelerated and/or there is a reduction of combustion temperatures.

Applicant's invention is particularly applicable in turbine applications, especially in aviation gas turbines, industrial gas turbines, marine gas turbines, and the like.

The physical state of fuels employed in this invention include a wide and narrow boiling range of liquid, semiliquid, near-liquid, semi-solid, solid, and gaseous fuels, and mixture.

Applicant's neat fuel- embodiment ECS compound and metallic) has exceptional propulsion and environmental attributes, which are not limiting to internal combustion engines, aviation jet turbines, 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 WO 96/40844 PCT/US96/09653 -87accommodate the combustion maximizing and thermal dynamic aspects of such neat applications.

It is also an embodiment of this invention to incorporate advanced combustion systems, capable of better converting higher amounts of free energy under higher pressures and/or improved thermal efficiencies resulting from the usage of Applicant's fuels. It is anticipated, system modifications and new design will be made to maximize the advantage of the neat, near neat, majority neat, or minority neat ECS fuels of Applicant's invention.

Hence, it is an embodiment of this invention to incorporate such advanced combustion systems with Applicant's fuels.

It is also an express embodiment of Applicant's invention to employ an ECS compound, or mixture, solely by itself, with or without a combustion improving amount of non-lead metallic. However, it is a preferred embodiment to employ an ECS compound, or mixture, together with at least one non-leaded metallic ("ECS Fuel"). It is also an embodiment that Applicant's ECS fuel may contain at least one additional oxidizer and/or at least one addition propellant or a co-fuel.

In co-fuel practice, e.g. where ECS fuel is combined with hydrogen and/or a hydrocarbonaceous based fuel, RVP reduction is an express embodiment. However, 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 psi to 40.0 psi, WO 96/40844 PCT/US96/09653 -88psi 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, to 3.0 psi, 1.0 tO 2.0 psi, or lower.

In the case of reformulated gasolines, for example, winter RVP's may range from 11.5 to 12.0 psi and summer RVP's ranging from 6.5 to 6.9 psi.

It is also an express embodiment to optimize flash point in fuels that specify minimum flash point temperatures, e.g. aviation, turbine and marine applications, etc. It is also anticipated that co-solvent practice, tailoring of hydrocarbon fractions (so as to increase flash point), salts, soaps, and other additives will be employed as required to reduce RVP and/or increase flash point. See Mitigation Practice.below.

As noted, reduced concentrations of aromatics are expressly contemplated in Applicant's co-fuels. Reduced concentracions of olefins are also contemplated.

l0efin concentrations of approximately or less than 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, 4, 3, 2, 1 volume percentage, or olefin free, are contemplated. Preferred olefins are absent C4 to olefins. In the case of reformulated gasoline an olefin range of 2.0 to 12.0, 3.0 to 10.0, 4.0 to 8.0 volume percent, or less, are contemplated. Olefin free compositions are also contemplated.

Thus, Applicant's invention embodies a neat, essentially neat, majority neat ECS fuel, including WO 96/40844 PCT/US96/09653 -89compositions containing greater than 50% ECS compound(s) by volume. It also embodies a substantial majority, a minority, or substantial minority application, e.g. greater than 3.7%, 10%, 15%, 20%, 25%, 30%, 40% by volume, or weight) of an ECS fuel, normally with a co-fuel ("Base Fuel or Co-Fuel").

In the practice of Applicant's invention, the most preferred ECS fuels containing Mn include dimethyl carbonate, methanol, hydrogen, methylal, methane hydrate, hydrazine, and mixtures thereof.

However, with greater concentrations of ECS fuels as a volume percent of the finished fuel, combustion and emission properties increase dramatically.

In the more specific co-fuel or modified fuel applications herein or in co-pending Internation Applications, Applicant intends that disclosure related to any co-fuel be appropriately applied to any other co-fuel or modified fuel anti-oxidants or detergents of one co-fuel class can be used with other co-fuel classes, etc.). Likewise, beneficial environmental practice for one fuel may be applied to any other.

Co-fuels or modified fuels of Applicant's invention normally will be fuels that are as environmentally attractive as possible, meeting regulatory standards, including California Air Resources Board standards,

EPA

standards, prsent and future.

WO 96/40844 PCT/US96/09653 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 consistent with ASTM, military, or International standards 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 specifications, related ASTM standards, test methods, military, and international standards are incorporated by reference.

Applicant's 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 design 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 0 F, or more.

Examcle 44 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, WO 96/40844 PCT/US96/09653 -91- 75.0, 80.0, 85.0, 90.0, percent, or more; and wherein spark advance, if applicable, is adjusted accordingly.

Example The method of Example 44, wherein the air fuel ratio is reduced by at least 25, 30, 35, 40, 45, 50, 55, 60, or more, compared to traditional fuel alone (gasoline 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.

Example 46 The method of 44, wherein the compression ratio of the engine is a- 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.

Example 47 A method of operating a jet turbine engine under temperature, said method comprises: Mixing an ECS fuel (preferrably at least one oxygen containing ECS compound and metallic), optionally containing 0.1 to about 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 0 C, 260 0

C,

280 0 C, 300 0 C, 320 0 C, 350 0 C, or higher temoerature, said WO 96140844 PCT/US96/09653 -92resultant 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, 2.75, 3.0, 3.25, 3.75, 4.0, 4.25, 4.5, 4.75, 5.0, 5.25, 5.5, 5.75, 6.25, 6.5 or under extreme temperature, and/or optionally at high or extreme altitude of 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000, 100,000, 110,000, 120,000, 130,000, !50,000, 170,000, 200,000, 250,000, 300,000, 350,000 feet above sea level, wherein engine and combustion temperature is reduced 25°f to 300°, 50°f to 350°F, 75°f to 375°F, 100°f to 400°F, 125°f to 450°F, 150°f to 500°F, 175°f to 550°F, 200°f to 600°F, 225°f to 750°F, 250°f to 900°F, or alternatively where gas inlet turbine temperature does not exceed about 1500°K., 1400°K., 1300°K., 1200°K., 1150°K., 1100°K., 1050°K., 1000°K., 950°K. 900°K. 850°K., 800°K., 750°K., 700°K., 650°K., 600°K., or less (with less than 1200°K. preferred), or at least by 0.5% to 25.0% over best presently known method for temperature reduction; whereby turbine inlet pressure in increased by 0.5% to 80.0%, or more.

Example 48 WO 96/40844 PCT/US96/09653 -93- An aviation turbine fuel composition comprising: 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 0 C, 260 0

C,

280 0 C, 300 0 C, 320 0 C, 350 0 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 heat capacity) to act as a primary heat sink to cool engine; said fuel optionally containing an antioxidant, despersant, metal deactivator and/or detergent/dispersent in such amounts to improve thermal stability; optionally meeting ASTM or military fuel specifications (optionally excepting heat of combustion) Example 49 An aviation jet turbine fuel comprising 0.01% to 40.0% by weight oxygen from DMC (more preferably 0.5% to to 10.0%) and at least one manganese metallic representing 0.001 to 20.0 gr/gal (more preferably 0.01 to 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 temperature of 205 0 C, a maximum final boiling point WO 96/40844 pCT/US96/09653 -94temperature of 300 0 C (more preferably less than 290 0 C, 285 0

C,

280OC, 275 0 C, 270 0 C, 265 0 C) a minimum flash point of 38 0

C,

a density of 775 to 840 at 15 0 C, kg/m 3 or optionally exceeding 840, 850, 860, 880, 900, or more kg/rn, a minimum freezing point of -40 0 C, a net heat of combustion of about 35.0, 36.0, 37.0, 38.0, 39.0, 40.0, 41.0, 42.0, 42.8, 43.0, 44.0 KJ/kg, a latent heat of vaporization exceeding 90, 100, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175 BTU/lb; whereby combined fuel meets ASTM 1655 finished fuel requirements for either Jet A, Jet A-1, or Jet

B;

Examtole 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 10.0, 15.0, 20.0, 40.0 gr/gal, and a gas oil turbine co-fuel selected from No. 0-GT, No. I-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 0 C to 66 0 C, a minimum kinetic viscosity at 40 0 C ranging from 1.3 to mM/s (ASTM D 445), optionally a sulfur content not exceeding 2500, 2000, 1500, 500, 400, 300, 200, 100, 20 ppm wt (or being sulfur free), optionally a temperature reduced at least 20 0 C compared to unadjusted cofuel; said fuel characterized as having a bunsen laminar burning velocity of at least 32, 33, 34, 35, 36, 38, 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 WO 96/40844 PCT/US96/0953 additionally characterized as reducing turbine inletgas temperature to about 850°C, 800°C, 750°C or 700°C., 650°C, 625°C, 600°C or 550°C., or less, with 650°C, 625°C, 600°C or less preferred, and/or inlet pressure is increased as compared to co-fuel alone (preferably by at least 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.

Example 51 A bio diesel fuel composition comprising: 1.0% to by volume biodiesel (bio-esters, C18 fatty acid methyl esters, rape seed esters, and the like), 1.0% to 95% by volume diesel fuel oil or equivalent (conventional or reformulated, including naptha), optionally 0.5% to 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's diesel fuels, co-fuels, include Swedish Enviromental class 1 and 2 fuels, CARB reformulated fuels, and EPA reformulated fuels, existing and future.

WO 96/40844 PCTIUS96/09653 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 exoress embodiment to include lubricity additives in low/no sulfur fuels.

Applicant's preferred diesel co-fuels contemplate low sulfur concentrations including those equal to or below 600, 500, 400, 300, 200, 150, 100, 60, 50, 45, 40, 30, 20, 15, 10, 9, 8, 7, 6, 5, 2 ppm, or sulfur free. Preferred concentrations are S0 ppm or below.

Diesel co-fuels include those with low aromatic contents including those equal to or less than 60%k, 47%, 45%, 40%, 35%, 30!k, 28%, 25!k, 22%, 20%k, 18!k, 152k, 12%, 10%, 71k. 6!k, 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 expressly contemplated as NOx emissions are substantially 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 WO 96/40844 PCT/US96/09653 -97temperature is expressly contemplated, especially those that operate to increase burning velocities 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, 56, 57, 58, 59, 60, or greater, cm/sec is desired.

Example 52 A fuel composition 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 cofuel 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, ppm, 10 ppm, 5 ppm, or being sulfur free; density ranging from about 880 to 800 kg/m3; viscosity ranging from to 1.0 cSt at 40 0 C; cetane index of 40 to 70; an aromatic content by vol. ranging from approximately 0 to 35%, 0 to 20.0%, 0% to 15%, 0 to 10%, or less, on priviso 3-ring aromatics not to exceed 0.16 vol%; a TI0 fraction temperature of about 190 to 230 0 C, a T50 fraction temperature of about 220 to 280 0 C, and a T90 fraction of about 260 to 340 0 and cloud point temperature of oC -10, 28, or -32 (or 6 0 C above tenth percentile minimum ambient temperature); a bunsen laminar burning velocity of at least 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48 cm/sec, a latent heat of vaporization of at least 85, WO 96/40844 PCT/US96/09653 -98- 90, 100, 105, 110, 115, 120 BTU/lb; optionally a heating value less than 43, 42, 41, 40, 39, 38, 37 kj/kg.

Example 53 Low emission diesel fuel comprising; optionally a combustion improving amount of an ECS compound; optionally a combustion improving amount of a metallic; a diesel cofuel; said fuel characterized as having a maximum sulfur concentracion of no greater than 1100 ppm, 800 ppm, 440 ppm, 300 ppm, 250 ppm, 200 ppm, 150 ppm, 100 ppm, 50 ppm, ppm, 5 ppm, or sulfur free; density kg/m 3 of 800, 805, 810, 814, 815, 839, 840, or higher; viscosity of cSt at 40 0

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, 1.1, 21.6, or lower, under proviso 3-ring aromatics are 0.16, 0.02, or less; a distillation fraction where,

°C

IBP ranges from 188.5, 213, 153, 215, 195, less than 180 preferred, and T1O fraction temperatures range from 221, 215.5, 198, 227, 210, T50 fraction temperatures range from 272.5, 247.5, 249, 249, 227, T90 fraction temperatures range from 321, 272.5, less than 285, 336, 271, 273 preferred, and FBP temperatures range from 348.5, 299, 360, 285, 300 0 C; cloud point oC -10, -28, -32; CFPP oC -11, -34, 34; optionally a caloric value, Mj/kg 42.8, 43.3, 43.3, or lower; optionally a bunsen laminar burning velocity is at least 37, 40, 42, 45, 47 cm/sec, or higher (or alternatively, having a burning velocity higher than the base conventional or reformulated diesel); and wherein the WO 96/40844 PCT/US96/09653 -99latent heat of vaporization is in excess of 80, 85, 90, 100, 105, 110, 115, 120, 125, 130 btu/ib.

Exammle 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, 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 0 F, 265°F, 300 0 320 0 345°F, 365 0 F, 385 0 F, or greater, a 95% fraction 545°F, 525 0 F, 500 0 F, 475 0 F, or more; a combustion improving anount of a manganese or other metallic compound; optionally an ECS compound.

ExamPle A liquid fuel comprising: a fuel soluable

ECS

compound at 0.01% to 5.0% by weight oxygen (more preferably 0.5% to at least one manganese metallic representing 0.001 to 2.8 gr/gal (preferably 0.065 to gr/gal, most preferably 0.1 to 0.5 gr/gal); a diesel cofuel; wherein said fuel is 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 0 C; cetane index of 40 to 60; an aromatic content by vol. ranging from approximately 0 to 20.0%, (inclusive 3-ring aromatics not exceeding 0.16 vol%); a T10 fraction temperature of about WO 96/40844 PCT/US96/09653 -100- 190 to 230 0 C, a T50 fraction temperature of about 220 to 2800°C, and a T90 fraction of about 260 to 3400°C, and cloud point temperature of oC -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.

Example 56 A liquid fuel comprising DMC at 0.01% to 5.0% by weight oxygen (more preferably 0.5% to and 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 gr/gal), and a diesel co-fuel base; wherein combined fuel is characterized as having an API range of about 41.1 to 45.4, 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 0 F, a fraction ranging from 460°F to 540 0 a bunsen laminar burning velocity of at least 36 cm/sec, a latent heat of vaporization of at least 100 BTU/lb.

Example 57 The diesel fuel compositions above comprising a combustion chamber deposit control/reducing additive, and optionally: an injector, intake valve deposit control, metal deactivator, or antioxidant additive.

WO 96/40844 PCT/US96/09653 -101- Elemental concentrations of metal in diesel/distillate fuels 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 grams or more are contemplated.

As noted above, the greater the 02 concentrations contained in the fuel composition with superior ECS compounds, the greater the permissible elemental metal concentrations. Also with heavier fuel compositions, which enjoy improve burning velocities and/or reductions in combustion temperature, manganese concentrations may be increased.

A synergism occurs complimenting the usage of ECS compounds and elemental metal, particularly when temperature are reduced. Differing fuel specifications, operating conditions, environmental requirements, and WO 96/40844 PCT/JS96/09653 -102combustion systems will dictate final compositional construction.

In the practice of this invention a cetane number of 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. In advanced reformulated diesel fuels cetane numbers greater 50, 55, 60, 65, 70, 75, 80 are contemplated. When employing low sulfur diesel fuels Grade No. D-1 and No. D-2 minimum cetane index number is contingent upon amount of aromatic components, 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).

It is noted the practice of employing an ECS based diesel fuel normally improves ignition quality, which in turn positively influences cold starting, warmup, combustion roughness, acceleration, deposit formation under idle and light load operation, and exhaust smoke density.

Example 58 A composition comprising a diesel fuel meeting

ASTM

975 specifications (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 WO 96/40844 PCTIUS96/09653 -103about 0.001 to about 2.5 gr Mn per gallon; whereby resultant fuel combustion results in improved thermal efficiency and/or fuel economy, and meets minimum flash point temperatures.

Example 59 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 base diesel fuel, such that resultant fuel has a cetane of 42 to 50 (preferably substantially greater), an aromatic content of less than 28 volume percent (preferably less than 20%, more preferably most preferably less than a T-90 temperature of 560°F to 600°F (more preferably less than 540 0 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).

Examole A No. 1 diesel fuel composition containing a minor pocrion of a combustion improving amount of dimethyl carbonate and a cyclomatic manganese tricarbonyl, and a major portion of a base diesel fuel, such that resultant fuel has a cetane of 48 to 54 (preferably substantially greater), aromatics representing 10% or less by volume, a temperature of 460 0 F to 520 0 F (more preferably less WO 96/40844 PCT/US96/09653 -104than 425°F, or lower), a sulfur content of 0.08 to 0.12% mass (more preferably less than 0.05% mass), API gravity of to 44 (more preferably higher), and a minimum flash point of 120°F.

In the practice of this invention ignition promoters may be employed, individually and/or in combination with ECS compounds, particularly in fuels which require higher temperatures to ignite, which extends their period of ignition.

Example 61 A low emission No. 2 grade diesel fuel comprising a minimum cetane number of 52, maximum-fuel sulfur of 350 ppm (more preferred less than 0.05% mass), aromatics less than volume (more preferably less than a combustion improving amount of dimethyl carbonate and a combustion improving amount of a cyclomatic manganese tricarbonyl compound.

Examnle 62 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 4750F, 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 manganese tricarbonyl compound.

WO 96/40844 WO 9640844PCTIUS96/09653 -105- Diesel fuels which do not contain a pour point depressant additive, the pour point is usually from 3 0

°C

0 to 15 0 °C (25 0 below the cloud point.

In the practice of this invention a minimum flash point of 38 0 C for diesel Grades No. and 52 0 C for Grades 2-D and 4-D are preferred. However, in the practice of this invention flash points outside these temperatures are contemplated.

In the practice of the instant invention sulphur content of 500 pares per million is acceptable, however concentrations lower are more preferred. Most preferred concentrations are those of 50 parts per million or less.

Sulfur weight percentage of 0.05% or less are also preferred. Sulfur concentrations of 0.05% mass or. less is required in Grade low sulfur 1-D and 2-D.

In the practice of this invention, carbon residue found in the 10% distillation residue, as a percentage of mass, should generally not exceed 0.15 in No. 1-D fuels, and 0.35 in No. 2-d fuels. However, lower mass concentrations are more preferred.

In the practice of this invention the maximum percent of ash by mass, using ASTM D 482, is 0.01%, except for Grade No. 4-D, which is 0.10%. Lower ash percentages are preferred. However, the lower combustion temperatures of Applicant's invention tends to mitigate ash related problems.

WO 96/4844 PCT/US96109653 -106- Additives are contemplated in distillate fuels include ignition quality improver, oxidation inhibitors, biocides, rust preventives, metal deactivators, pour point depressants, demulsifiers, smoke suppressants, detergentdispersants, conductivity improver, dyes, de-icers and additives to reduce and/or control engine and combustion deposits, including fuel injector, combustion chamber, and intake valve deposits.

However, it is an express embodiment to etploy combustion chamber deposit additives, especially those that reduce existing combustion chamber deposits. it is contemolated that certain deposit additives, which control injector and valve intake deposits, 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 overbased barium sulfonates, N-sulfinyl anilines, are contemplated, as well as others.

Examole diesel fuel additives are shown by class and function in Table 1. As with any system 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.

TABLE 1 COMMRCIAL DIESEL FUEL ADDITIVES FUNCTION AND TYPE PCTIUS96/09653 WO 96/40844 -107- Class or Fu~ctiofl Ccrmn Additive Type 1. Ignition quality Improver Raise Cetane Number therebypromotingfaster startsand less white smoke.

2. Oxidation Inhibitors Minimize oxidation .0 and gumn and precipitateformlat ion.im prove storage life.

3. Biocides- lnhibitthe growthof bacteriaand fungi which feed on hvdrocarbors. help prevent filter-clogging caused by these organisms.

4. Rust Preventives- Minimize rust formation in fuels svstemsand storage facilities.

S. Metal Deactivator- Deactivatexopper ions whichare powerful ox ida t ioncatalysts.

6. Pour Point Depressants- Reduce the pour 2 5 point and improve low- temnperaturtluidity properties by modifying the wax crystal growt h.st ructure.and /oragglomeratiofl.

Alkyl nitrates.

Alkyl amines and amine-coltaii2gomplex materials.

Boron cornpoundsrt hersof et hyleneglycolquaterflary amine cornpounds.

Organicacids and amine salts. A widely- usedypeis based on dimerizedlinoleic acid.

Generally consist of polymeric materials such as polyolerins. polvacrylatespolyrmethacrylatemodiicd polystyrenes.ethylene- vinvykcetate copolymers. and ethylene- vin~dhloride copolymers.

PCr/US96109653 WO 96/40844 -108- 7. Demulsifiers and Dehazers improve the separationof waterfromn distillatefueis and preventhaze.

8. smoke Suppressnts Minimize exhaust smoke by catalyzing more complete combust zonof carbonaccousflaterialsor by helping to maintainfuel spray patterlis.

9. Detergent Dispersant4promateengine fuel system cleanliness, help prevent nozzle deposit formation and injector sticking.

intefrw prc tatglmrtin u mnaintainiiptimurriltratiorcharactristics.

Conduct ivit improver- lmproved issipat ion of ciectrostaticcharge.

11. Dyes -Various identification purposes includingtax status.

12. De- icers- Reduce t he freezingpoiftt of small amounts of water to prevent fuel line plugging.

Surf act- activernaterials whcih increase the rate of water/ oi~eparat ion Usually quite compleC-1i tures.

Catalyst types are generally overbased barium compounds. Maintenanceof spray patternsis helped by detergents.

These are usuallysurface-activagents. Theyare often polymeric materials containing amines and other funct ionalgroups.

Amine salts. metallicsalts. and polymericcotmpounds.

Oil-solizolesolid and liquid dyes.

Low molecular weight alcohols (ethanol. isopropanol.

and/or met hanol). and ethylene glycol monomethyl ether or diet hyleneglycol monomet hylether.

Note: Some materialsmay also be marketedas multitunctionabr multipurposeadditivespeformingmnore than one of the functions.

The f uel properties most of ten associated with ef fects on exhaust emissions are aromatic content, volatility, gravity, viscosity, cetane numiber, and the presence of specific elements (for example, hydrogen and sulfur).

Increased aromatic content generates increased particulate WO 96/40844 PCT/US96/09653 -109- (especially soluble organic particulate) and hydrocarbon emissions.

However, by increasing burning velocity and/or reducing combustion temperatures, the problematic nature of aggravating hydrocarbon components, i.e. aromatics, etc.

are substantially mitigated. Thus, it is expressly contemplated aromatics, olefins, benzene, butadiene, formaldehyde, acetaldehyde, di and tri aromatics, etc., may be included in amounts now thought to be environmentally hazardous.

Mitigation of diesel hydrocarbon emissions is an express object, as Applicant does not believe those in the art are fully aware of the photochemical reactivity of diesel HC emissions.

Higher distillation temperatures of the lower-vaporpressure components (for example, T-50 and T-90 points) 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.

It has also been found desireable to keep the local carbon/oxygen ratio below 0.5, as an effective means of additionally controlling particulate emissions.

It is now believed NOx and CO emissions are generally unaffected by modifications to diesel fuel. Due to improved burning velocities and reduced combustion temperatures, significant reductions of both NOx and CO emissions result.

WO 96/40844 PCTIUS96/09653 -110- This is yet another substantial departure from the prior art.

Examn 1 e 63 Automotive gasolines contemplated in Applicant's invention include conventional unleaded, reformulated unleaded, including those meeting U.S. Clean Air Act 211 requirements, low RVP fuels, low/no sulfur, low octane, moderate octane, high octane gasolines, high LHV and/or BV gasolines, advanced atomization, vaporization, injector volatilization gasolines, and the like, and/or any gasoline meeting ASTM and/or other regulatory standard, existing and future, and combinations thereof.

Examole 64 A method of 63 reducing potentially carcinogenic ether concentrations from atmosphere; said method comprising combusting an MTBE containing fuel in combination with a co-ECS ccmpound and optionally a combustion improving metallic.

Examole 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 (preferably 20%, 30%, 40%, 50%, 60%, or more, with DMC preferred); total oxygen by weight of the fuel does not exceed 2.25%, WO 96/40844 PCT/US96/09653 -111optionally a burning velocity improving amount of a metallic, (MMT and/or potassium salt marketed by Shell Chemical Corporation known as SparkAid) and/or optionally a combustion improving amount of a manganese metallic compound; said fuel additionally characterized as having a LHV exceeding 133, 135, 140, 142, 145, 146, 147, 148, 149, 150, 151, 152, 153, 154, or greater, btu/lb and a BV exceeding 44, 46, 48, 50, 52, or more, cm/sec; optionally a max. T-90 temperature of 320, 310, 300, 295°F, or less; optionally a T-50 temperature equal or exceeding 170, 175, 180, 185, 190, 195, 200° 0

F.

Example 66 A method of increasing work potential, fuel economy, reducing combustion emissions of a vehicle operating on a conventional or reformulated gasoline, oxygenate optional, comprising: Reducing the boiling temperature of gasoline such that'its 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 simultaneously increasing the fuel's LHV to at least 130, 135, 140, 145, 150, 155, 160, 165, 170 btu/lb (or at least 2.0% above unadjusted fuel); optionally admixing MMT into the composition up to 1/64 or 1/32 gr mn/gal; optionally a burning velocity exceeding 48, 49, 50, 51, 52, 53, 54 cm/sec; wherein said fuel has a LHV and/or BV greater than an unadjusted convention or reformulated gasoline, and WO 96/40844 WO 9640844PCr/US96/09653 -112optionally greater than same unadjusted fuel containing to or 2.0% to 5.0% weight oxygen of MTBE; combusting said composition in a gasoline powered vehicle; whereby fuel economy is improved over unadjusted fuel alone, or unadjusted co-fuel with manganese, or co-fuel with same T90 absent LHV increase, or manganese containing co-fuel with same T90 absent LHV increase (preferred increases are 0.5, 1.0, 1.5, 2.0, or more).

Examole 67 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%, 12%, 10%, or less, by volume, or an aromatic free composition; a non C4 to C5 olefinic concentration less than 20%, 15%, 13%, 12%, 11%, 10%, 1% including range of 3.0% to by volume, or olefin free; a benzene concentration of volume, or less, including benzene free compositions; an RVP of less than 12.0, 11.5, 11.0, 10.0, 9.0, 8.5, 7.5, 7.0, 6.9, 6.5, 6.0, 5.5 psi and ranges of 11.5 to 12.0 psi or 6.5 to 6.9 psi; oxygen at 0.5% to 5.0% or 3.7% wt., 0.6 to 3.0% wt, 0.7% to 2.7% wt., 1.8% to 2.2% weight, provided in part or wholly by at least one ESC compound WO 96/40844 PCT/US96/09653 -113- (preferably DMC) a combustion improving amount of at least one metallic, including a cyclomatic manganese tricarbonyl having an Mn concentration of 1/128 to 3/8 gr./gal (1/128 to 1/8 preferred) or up to 1/64, 1/32, 1/16, 1/8, 1/4, 3/8; at least one combustion enhancing deposit control additive selected from combustion chamber deposit control, port fuel injector, intake valve deposit control additive, and mixture; optionally antioxidant or other additive provided herein; said composition has a driveability index less than 1120, 960 (less than 930 preferred); optionally a temperature equal to or less than 350°F, 340 0 F, 330° 0 F, 320°F, 3100F, 305 0 F, .300°F, 295°F, or 290°F; a t-50 temerature eual or exceeding 170°F, 175°F, 180°F, 190°F, 200°F, or 210°F; whose T-10 temperature is less than 160°F, 140°F, or 120°F; a latent heat of vaporization equal to or greater than 130, 135, 140, 143, 145, 147, 150, 151, 152, 155, 160, 165 btu/lb or alternatively greater than 860, 900, 910 btu/gal; a miminum laminar bunsen flame burning velocity of 40, 43, 48, 49, 50, 51, 52, 53, 54, 53, 56, 58, 60, 65, 70, 80, 90 cm/sec (preferably 45, 48, 50, 60 cm/sec., or greater); optionally a maximum heating value less than 44, 43, 42, 41, 40, 39, 38, 37, 36 Kj/kg; It is object to improve burning velocity/combustion temperatures by modifying T-90 and/or end-boiling point distillation fractions as taught herein.

It is an object that Applicant's gasolines, including reformulated, to have a driveability index as defined by WO 96/40844 PCTIUS96/09653 -114- 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. It is preferred that temperatures simultaneously equal or exceed 150, 155, 160, 165, 170, 175, 180, 185, 190, 195 degrees F. An acceptable TSO 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 less. 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.

Non-limiting examples, include ASTM Grades 1 to Boiling point modification is an express embodiment of this invention, especially when resulting increased LHV's and/or BV's (See my co-pending International Applications No. PCT/US95/026 9 1 and No. PCT/US95/06758) Examole 167 A No. 2 fuel oil, with a kinetic velocity of no less than 1.9 nor greater than 3.4 (nu/s) measured at 40°C, a WO 96/40844 PCT/US96/09653 -115minimum T-90 temperature of 282°C, a max T-90 temperature of 338°C, a maximum sulfur content of 0.05% mass, a maximum copper strip rating of No.3, a combustion improving amount of an ECS compound (preferably DMC) and optional metallic, flash 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.

ExamDle 168 A No. 6 fuel oil, with a kinetic velocity of no less than 15.0 nor greater than 50.0 (mm3/s) measured at 100°C using ASTM D 445, and combustion improving amount of an ECS compound, optionally a metallic.

Examole 169 The example of 167, 168, wherein end boiling point and/or T-90 fraction temperatures are reduced at least employing boiling point modification; whereby LHV are imroved.

ExamDle 170 The operation of burners in a furnace, employing an 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 WO 96/40844 PCT/US96/09653 -116- It is contemplated in locomotive and marine fuels meeting appropriate ISO DIS 8217 and BS MA 100 standards, containing higher concentrations of sulfur than most fuels, Applicants invention due combustion temperature object, mitigates sulfur corrosion and generation of other pollutants.

Examole 171 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 specifications; wherein said combination contains a sulfur concentration of 0.01 to mass, has a viscosity of 10 to 500 centistokes at 50 0

C;

whereby combustion of said vapors results in reduced corrosion, particulate emissions and/or improved fuel consumption compared to co-fuel alone.

Example 172 A rocket fuel propellant comprising: at least one ECS compound and a propulsion improving amount of a metallic.

Example 173 WO 96/40844 PCT/US96/09653 -117- 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.

Examole 175 A rocket fuel composition comprising hydrogen peroxide, an oxider and a metallic, and optionally

DMC.

Examle 176 The rocket fuel composition of 175, wherein the metal is selected from the group consisting of cyclopentadienyl manganese tricarbonyl, technetium, rhenium, aluminum, beryllium or boron compound, including pentaborane, decaborane, barazole, aluminimum borohydride, trimethylaluminum, beryllium borohydride, dimethlylberyllium, lithium borohydride, homologues thereof, and mixtures.

Example 177 The examples of 173, 175, wherein 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 WO 96/40844 PCTIUS96/09653 -118various strengths), WFNA, tetranitromethane, chorine trifluoride, perchloryl fluoride, fluoride, nitryl fluoride, nitrogen trifluoride, monoxide, fluorate, chorine oxides, other oxidizers, and the like.

fluorine, nitrosyl difluorine known art Example 178 A rocket fuel composition comprising dimethyl carbonate, hydrazine and a cyclopentadienyl manganese tricarbonyl compound.

Examole 179 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.

Example 180 A rocket fuel comprising dimethyl carbonate, hydrazine or a substituted hydrazine, and/or hydrogen peroxide, and/or a metallic.

Examole 181 A rocket fuel comprising dimethyl carbonate, hydrazine, and kerosine; and optionally a metallic.

Examople 182 WO 96/40844 WO 9640844PCT/US96/09653 -119- 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.

The propellants of rocket fuel claims are set forth in my co-pending Applications. The JET AVIATION TURBINE FUELS AND RELATED TURBINE SYSTEMS, GAS TURBINE FUEL OILS AND SYSTEMS, GAS TURBINE FUEL OILS AND SYSTEMS, DIESEL FUEL OILS AND SYSTEM, EXAMPLE TESTS, EXAMPLE TEST FUELS, TEST METHODOLOGY, Analysis of Tables/Figures, DESCRIPTION

OF

TEST TWO "FIGURES 1 THROUGH SUMMARY OF FIGURE 1-6, 7, 8, GASOLINE COMPOSITIONS, Mechanical Means, Aviation Gasoline, Fuel Oils, Rocket Fuel Applications, Combustion Temperature Modification Practice Sections and all other sections of my co-pending International, Applications No.

PCT/US95/02691 and No. PCT/US95/06758 are incorporated by reference.

ADDITIVE PRACTICE As set forth herein additive practice is a vital component of this invention. It is expressly contemplated that additives, 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 compositions WO 96/40844 PCT/US96/09653 -120beincorporated herein by reference. It is contemplated disclosed additives be interchangible between various fuel classes. However, it is appreciated art practioners certain additives lend themselves more to one fuel group than another.

Appliant's invention contemplates a wide range of additives and concentrations, 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 recession (100-200 mg/kg), pipe-line drag reducing agents (2-20 mg/kg), diesel detergents (10-300 mg/kg), gasoline detergents, demulsifiers (3-12 mg/kg), diesel flow improvers (50-1000 mg/kg), deposit control additives 3000 mg/kg), lubricity improvers (25-1000 mg/kg), antistatic (2-20 mg/kg), stabilizers (50- 200 mg/kg), antiicing agents vol), corrosion inhibitor (4-50 mg/kg), combustion chamber deposit modifiers (50-3000 mg/kg), metal deactivator (4-12 mg/kg), dyes (.2-20 mg/kg), cetane/octane improvers (200-2000 mg/kg). Other contemplated additives include combustion improvers, biocides, drag reducing agents, dehazers, metallic scavengers, friction modifiers, antiwear additives, antisludge additive.

Non-limiting examples of Applicant's anti-static additives include soluble chromium materials, polymeric sulfur, nitrogen compounds, and quaternary ammonium materials. Use is generally contemplated in very cold WO 96/40844 PCT/US96/09653 -121ambient temperatures and/or in fuels 'of intermediate volatility such as aviation kerosenes.

Non-limiting examples of metal deactivators include 8hydroxyquinoline, ethylene diamine tetracarboxylic acid, Bketoesters such as octyl acetoacetate, and like, N,N'disalicylidene 2 propanediamine, such as N,N 1 disalicylidene-1, 2-propane diamine, N, N-disalicylidene-l, 2ethane diamine or N,Nl-disalicylidene-1, 2 cyclohexanediamine, N,N"-disalicylidene-N' -methyldipropylenetriamine, 0.1 to 5.8, 7.5, 10.0, 12.0, 15.0, 18.0, 22, or more, mg/L, or 1.0 to 8.0 mg/l, 2.0 to 10.0, to 15.0 (not including weight of solvent).

Concentrations also range from 4 to 12, 5 to 30 ppm. Other concentrations necessary to maintain thermal stability are contemplated.

Other non-limiting examples of metal deactivators include passivator type thiadiazoles such as HITEC 314 by Ethyl Corp.

Non-limiting examples of drag reducing agents include high molecular weight (1,000,000) polyisobutenes and polyalphaolefins.

Non-limiting examples of dyes include azo compounds and/or anthraquinone.

Non-limiting examples of demulsifiers 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). Other non-limiting examples include p-isobutylphenol, p- WO 96/40844 PCTIUS96/09653 -122diisobutylphenol, p -hexyiphelol, p-heptylphenOl. poctyJlphenol, p-tripropyleiephenol, p-dipropylenephencl, ammonia -neutralized suJlphoflated alkylphelols, oxyalkylated glycols available from BASF-Wyandotte Chemical. company, proprietary products, including TALOD 286K, TALOD 286 marketed by Petro2.ite 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 agenc and corrosion inhibitor.

Non-imiting e-xampl es of anz-.-oxiLdants include hindered phenols, 2,-itbt-14Mtypec (15 mg/i, 25 mg/l, or more), phenylenedimines, aromatic diamines, or mixtures of aromatic- diamines and alkyl phenols szerially hindered phenolic and amine groups.

Other anti-oxidants in amounts up to 24.0 mg/L active ingredients (not including weight of solvent) Such antioxidants are selected from N, N-diisopropylparaphenylene diamine, sevent ,-:ive percent minimum 2, 6-di-tertiary-butyl phenol plus 25%k maximum tertiary and tritertiary butyl phenols, seventy-two percent minimum 2,4-dimethyl-6tertiary-butyl phenol plus 28%r maximum monomethyl and dimethyl tertiary-butyl phenols, f ifty-f ive 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,-d-etbtl4mhycen, 6 -tertbutyl-2,4-dimethylmhenol, 2,6-di-tert -butylphenol, WO 96/40844 PCT/US96/09653 -123percent min-2, 6-di-tert-butylphenol 25 percent max tertbutylphenols and tri-tertbutylphenols, 72 percent min 6tert-butyl-2, 4-dimethylphenl 28 percent max tert-butyl-methylphenols and tert-butyldimethylphenals, 55 percent min 6-tert-butyl-2, 4dimethylphenol 45 percent max mixture of tert-butylphenols and ditert-butylphenols, 60 to 80 percent 2,6-dialkyphenols to 40 percent mixture of 2,3,6-trialkylphenOls and 2,4,6-trialkylphenols, 35 percent min 2,6-di-tert-bUtyl-4methylphenol 65 percent max mixture of methyl-, ethyl-, and dimethyl-tert-butylphenols, 60 percent min 2, 4-di-tertbutylphenol 40 percent max mixture of tert butylphenols, percent min mixture of 2,3,6-trimethylphenol and 2,4,6trimethylphenol 70 percent max mixture of dimethylphenols, 55 percent min butylated ethylphenols 45 percent max butylated methyl- and dimethylphenols, 45 percent mix 4,6di-tert-butyl-2-methylphenol, 40 percent min mixture of 6tert-butvl-2-methylphenol 15 percent max mixture of other butylated phenols. Also 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-ditertiarybutyl phenol, 10-15% 2, 4, 6-tritertiary-butyl phenol, 15% orthy-tertiary butyl phenol, 72% min 2, 4-dimethyl-6tertiary butyl phenol, 28% max. monemethyl and dimethyl tertiary butyl phenol, 60% min 2, 4-ditertiary-butyl phenol, 40% max, mixed, tertiary-butyl phenol, 2,4,6-tri- WO 96/40844 PCTIUS96/09653 -124tert-butylephenol; 4-methyl-2,6 di-tert-butylephenol; 2tert-butylphenol, and mixtures thereof; 2,6-di-tert-butylp-cresol; and phenylenediamines such as N-N'-di-sec-butylp-phenylenediamines; N-isopropylphenylene diamine; and N,N'-disalicylidene-l, 2-propanediamine; and mixtures of tertiary butylated phenols, and/or aromatic amine antioxidants. Concentrations levels are those necessary to maintain or assure thermal stability.

Additive concentrations for additive herein, which is above industry ranges are expressly contemplated, particularly where nature or concentration of ECS or metallic compounds warrant such usage.

Non-limiting examples of anti-icing additives include isopropyl alcohol, hexylene glycol, dipropylene glycol, glycols, formamides, imidazolines and carboxylic acids.

Non-limiting examples of valve seat recession additives include sodium or potassium long chain alkenyl sulfonates, sodium or potassium long chain naphthenates, or microdispersions of sodium or potassium salts in oil.

Dispersants include ashless succinimides or polymeric methyacrylates, including alkenyl succinic acid esters, alkenyl succinimide of an amine, methylamine, 2ethylhexylamine, n-dodecylamine, (see U.S. Patents 3,172,892; 3,202,678, 3,219,666, 4,234,435). Other dispersants include Texaco's CleanSystem 3 high molecular weight polyisobutylene substituted amine derivative

TFA-

4681, fuel soluble salts, amides, imides, oxazolines and esters of long aliphatic hydrocarbon-substituted WO 96/40844 PCT/US96/09653 -125dicarboxylic 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. Applicant contemplates any commercially available dispersant, including ashless dispersants.

Applicant's invention contemplates carburetor, port fuel injector and intake valve deposit control additives.

Non-limiting examples include amides, amines, amine carboxylates, alkenyl succinimdes, polybutene succinimides, 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. OGA- 472), polybuteneanines, polyetheramines, and polyolefin amines, with or without carrier fluid. Such materials may be incorporated at treat concentrations of 50 to 500 pounds per thousand barrels, and more usally in the range of 100 to 200 lbs per thousand barrels.

Non-limiting example of detergent include: succinimides, Long chain aliphatic polyamines, long chain Mannich bases, ashless polymeric disperants, nitrogencontaining ashless dispersants, especially polyolefinsubstituted succinimdes of polyethylene polymines such as polyethylene tetramines and polyethylene hexamines are WO 96/40844 PCT/US96/09653 -126desireable. 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 magnesium laural salts are contemplated.

Other ashless despersants include alkenyl succinic acid esters and diesters 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.

Other non-limiting ashless dispersants, 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 ashless dispersants (see U.S. Patents 3,957,845; 3,'697,574; 3,413,347; 3,533,945; 4,857,214; 3,666,730; 3,909,215) and proprietry dispersants, including Chevron OFA 425B, and contemplates their usage in the practice of this invention. Any .commercially available detergent, detergent/dispersant is within the scope of this invention.

Similar additive is contemplated in the practice of keeping fuel injectors and valve intakes clean.

Smoke suppressants, including organic compounds of barium, particularly the barium carbonate overbased barium sulfonates, N-sulfinyl anilines, are contemplated, as well WO 96/40844 PCT/US96/09653 -127as others. 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 system 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.

It is contemplated the fuel will contain other deposit control additives, non-limiting examples include polyether amine, polyalkenyl succinimide, or polyalkenyl succinimide, hydrocarbyl carbonates, such as polybutene alcohol, polybutene chloroformate, polybutene amines formulated in mineral or other carriers, polyisobutylene amine reformulated in polyether carriers, and one-component polyether amines, and the like. Several others have been set forth elsewhere in the specification and are contemplated in gasolines, and other co-fuels.

Applicant's invention contemplates that acceptable deposit control additives will meet industry and regulatory standards, including CARB's 10,000 mile BMW IVD and Chrysler PFI keep clean tests. Thus, contempated average deposits,on all valves .cannot exceed 100 milligrams on said BMW test, nor no more than 5% plugging, as measured in flow loss, in any one injector.

It is an express embodiment to avoid employing

IVD

additives or PFI additives, which show any detrimental performance in combustion chamber deposit control or reduction.

WO 96/40844 WO 9640844PCT/US96I09653 -128- Applicant notes combustion chamber additives are not novel and have been used to maintain fuel system cleanliness 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 additives (Octane Requirement Increase Control) or ORR additives (Octane Requirement Reduction) and/or similar 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 surfactants and high molecular weight polymeric dispersants based upon polybutene. Intermittent high concentrations of polyeramines, glycol boarates and ethylene dichloride may be employed. Additive concentration levels may range from moderate to very high, depending upon the efficacy of the additive/additive package and co-fuel employed.

Applicant expressly contemplates employing new classes of additives which control or reduce combustion chamber deposits, and which in the case of gasoline reduce octane requirement increases (ORI), particularly those additives which can reduce existing deposits and/or reduce the ORI below clear base fuel absent said additive, over time.

WO 96/40844 PCT/US96/09653 -129- It is contemplated that certain deposit additives, which control manifold, injector and valve intake deposits, may be deleterious to combustion chamber deposition control and are therefore not as desireable.

However, given nature of increased burning velocity and temperature reducing aspects of Applicant's invention, less desireable conventional additives can be employed, absent significantly deleterious adverse combustion chamber deposition.

Thus, it is preferred that 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.

Set forth below are various additive packages increasing burning velocity and/or improving LHV and simultaneously facilitating amelimorative characteristics of co-fuels.

Example 184 A clean combustion additive package comprising: 1) an ECS compound (0.1 to 99.99% wt); 2) at least one organo manganese compound (preferably MMT) and/or other combustion improving metallic compound (or mixture thereof) (0.01 to WO 96/40844 WO 9640844PCT/US96109653 -130- 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 CleanSystem 3 or Ethyl's equivalent HiTec additive; and optionally 4) a metal deactivator to 90.0% wt); said package optionally characterized as having LHV exceeding 30, 50, 80, 110, 130, 135, 145, 147, 148, 150, 0 LO 151, 152, 155, 157, 160, 165, 170, BTU/lb, or greater.

Example 185 An additive package for use in hydrocarbon fuels comprising: 1) at least one ECS compound to 99.5% wt); 2) at least one cyclopentadienyl manganese tricarbonyl 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 2 propanediamine, N,N'-disalicylidene-1,2-propane diamine, N, Ndisalicylidene-1,2-ethane diamine or N,NI-disalicylidene- 1,2-cyclohexanediamine, N,N"-disalicylidene-N'-methyldipropylenetriamine) to 99.5% wt); and optionally 4) at least one antioxidant to 99.5% wt), 5) at least one detergent/dispersant to 99.5% wt), 6) at least one ignition promoter (peroxy compounds, organic nitrates, potassium salts including those commercially marketed by Shell Chemical, known as "SparkAid or SparkAde," to WO 96/40844 PCTIUS96/09653 -131- 99.5% wt), 7) at least one demulsifier to 99.5% wt), or 8) at least one Flash Point Improving (PFI) or vapor pressure reducing co-solvent or salt to 99.5% wt) said package optionally characterized as having LHV exceeding 10, 20, 25, 30, 43, 48, 50, 60, 65, 72, 80, 95, 100, 110, 130, 133, 135, 140, 142, 145, 147, 148, 150, 151, 152, 155, 157, 160, 165, 170, BTU/lb, or greater.

Example 186 The additive package of 185, comprising: 1) DMC 0 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-1,2-propanediamine representing 0.001% to 15.0%; optionally: 4) 2,6-Di-tbutyl-4-methylphenol representing 0.01% to 40.0%, 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-2pentanone representing 0.01% to 90%; under proviso all components equate to 100% weight; 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 WO 96/40844 PCT/US96/09653 -132at least 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 or 8) at least one antioxidant (0.1 to 40.0% wt); said package optionally characterized as having LHV exceeding 20, 30, 35, 40, 63, 80, 90, 100, 110, 120, 133, 140, 142, 145, 147, 148, 150, 151, 152, 155, 157, 160, 165, 170, BTU/lb, or greater.

Example 189 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 (0.01 to and optionally one or more of the following: 4) at least one antioxidant (0.1 to 99.0% wt), WO 96/40844 PCT/US96/09653 -133at 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, 100, 120, 133, 140, 142, 145, 147, 148, 150, 151, 152, 155, 157, 160, 165, 170, BTU/lb, or greater.

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 (0.01 to 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 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.

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) WO 96/40844 PCT/US96/09653 -134- (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, 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.

It is further contemplated this clean combustion 3J 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.

In the practice of this invention Applicant has found that certain halogen scavengers in combination with certain metallics, notably potassium, may aggravate valve sticking.

Thus, it is vital that compatibility of additive and ECS metallic containing fuels be determined prior to use.

However, additive and lubricating oil practice, especially in co-fuel practice that reduce or control combustion chamber deposits, are an express embodiment of this invention.

WO 96/40844 PCTUS96/09653 -135- Examole 192 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.

Example 193 The composition of example 192, wherein the combustion chamber deposit control additive includes, or additionally includes, at least one ECS compound, preferably

DMC.

Example 194 The composition of examples. 192, additionally comprising an injector and/or induction valve deposit control additive; wherein said 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 additives are same or differing additives.

Example 196 A method incorporating the fuel compositions of Examples 192-195, where said additive package is employed WO 96/40844 PCTIUS96/09653 -136deposit reducing quantities in a fuel for combustion in an internal combustion engine; wherein said compression ratio is increased to a compression ratio beyond average conventional compression ratios, or compression ratio's equal to greater than 8.6:1, 8.7:1, 8.8:1, 8.9:1, 9.0:1, 9.1:1, 9.2:1, 9.3:1, 9.4:1, 9.5:1, 9.6:1, 9.7:1, 9.8:1, 9.9:1, 10.0:1, 10.2:1, or greater.

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 or more, over clear fuel.

ExamPle 198 The composition of 197, wherein, the manganese concentration is equal to an amount such that the treatment level of the additive package equals at least the minimum metallic concentrations for the fuels set forth herein.

Example 199 The 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 deposits are controlled, modified, or reduced, and/or WO 96/40844 PCT/US96/09653 -137wherein 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.

Example 200 A fuel composition comprising an ECS fuel (comprising an ECS compound, preferably DMC, and at least one .0 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 deposits while preferably enhancing combustion efficiency (but not required).

It is preferred that additives, including deposit control additives, operate to enhance the ECS and metallic combustion chemistry, which represents the predominate thermodynamic and combustion object of Applicant's invention, as opposed to merely enhancing the fuel and combustion characteristics of Applicant's co-fuels.

Thus, given the extremely attractive combustion characteristics of ECS metallic containing fuels, alone, combustion chamber deposits are substantially controlled WO 96/40844 PCT/US96/09653 -138when employed in combination with a co-fuel, absent need for additional additive.

Greater concentrations of ECS metallic fuels as a percentage of total fuel, when in combination with cofuels, reduces combustion chamber deposition.

However, as noted it is contemplated that 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-polymers and include ethylene vinyl acetate co-polymers. Cold flow improvers are contemplated with diesel fuels, particularly those with reduced sulphur and/or reduced aromatic concentrations, especially 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 nitrates, including ditertiary butyl peroxide, acetyl peroxide, benzoyl peroxide, tertiary-butylperoxyaceate, cumene hydroperoxide, alkyl peroxides, alkyl hydroperoxides, 2.5 dimethyl di(tertiary butyl peroxy) hexane, tertiary butylcumyl WO 96/40844 PCT/US96/09653 -139peroxide, 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, ndecyl nitrate, ethyl-hexyl nitrate, iso-propyl nitrate, of which 2 ethyl hexyl nitrate is desireable, and mixture, with concentrations of 0.01, 10, 25, 50, 75, 100, 150, 200, 250, 500, 750, 800, 900, 1000, 1100, 1200, 1250, 1300, 1400, 1500, 1600, 1750, 1900, 2000 ppm or greater .0 concentrations acceptable. Other 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.

Other 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 expressly contemplated in non-diesel fuels applications.

Several proprietary ashless long chain polar compounds are currently marketed, which are contemplated in the practice of this invention. 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, WO 96/40844 PCT/US96/09653 -140corrosion 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.

The operation of lower combustion temperatures in the practice of Applicant's invention unexpected serves to reduce the formation of port fuel injector deposits.

.0 ExamPle 201 A method of operating an engine at combustion temperatures at least 50°F below same fuel absent ECS compound, metallic, and PFI deposit control additive, wherein said reduced temperature operation after said operation, results in a reduced temperature transfer to fuel remaining in or near the pintle tips of port fuel injector subject to otherwise high soak temperature transfer; wherein the formation of free radicals capable of combination in auto-oxidation, chemical rearrangement and/or degradation of remaining fuel are reduced; and/or wherein sticky deposits and/or degraded fuel acting as deposit precurors are reduced; wherein Port Fuel Injector deposits are controlled and/or flow restriction is less than 10.0%, or less; or alternatively employing a Peugeot XUD-9A/L test for diesel fuel measuring injector coking, shows an air flow rating in excess of 180, 190, 200, 210, 220, 230, 250, 260 ml/minute when needle lift is 0.3 mm.

WO 96/40844 PCTIUS96/09653 -141- Applicant's invention also unexpectedly reduces the increase in NOx emissions and particulates typically occuring from use of such additives in diesel fuel systems.

Example 202 The method of 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 composition ,0 containing a diesel co-fuel, together with balance of combustion and temperature reducing amount of ECS compound and metallic wherein said operation of engine results in reduction of NOx and/or particulate emissions, when compared to said- 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.

ExamPle 203 A method of employing a CCD, IVD or PFI additive in an internal combustion chamber: said method 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 WO 96/40844 PCT/US96/09653 -142one 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.

.0 It is further contemplated that the additive packages of instant invention will be formulated to avoid intake valve sticking and crankcase oil contamination.

Example 204 The method of 203, wherein said engine passes a laboratory test or other test wherein measured combustion chamber deposits or equivalent show less than 300, 250, 220, 200, 180, 160, 140, 120, 100, 80, 60, 40, 20, 10, 3.0, 2.5, 2.0, 1.75, 1.5, 1.25, 1.0, 0.75, 0.6, 0.5, 0.4, 0.3, 0.25, 0.2, 0.15, 0.125, 0.11, 0.10, 0.09, 0.08, 0.075, 0.06, 0.05, 0.002, 0.0.01 grams of deposition, or less.

Preferred deposition weight is less than less 1.5, 0.9, 0.6, 0.3, 0.15, 0.10 grams, or less, per combustion chamber or equivalent.

Example 205 WO 96/40844 PCTIUS9/09653 -143- 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 deposits are less than 100, 90, 70, 60, 50, 40 mg under BMW 3181 test (BMW IVD test), and wherein port fuel injector deposits do not exceed a 6% or 5% or less restriction 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, .L0 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, mg/100 ml or less unwashed.

Example 206 The method of Example 205, wherein the engine is a gasoline or internal combustion engine whose compression 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, 17.0:1, 17.5:1, 18.0:1, 18.5.1:1, 19.0:1, 19.5:1, 20.0:1, 20.5:1, 21.0:1, 21.5:1, 22.0:1, 22.5:1, 23.0:1, 23.5:1, 24.5:1, 25.0:1, 30.0:1, 35.0:1, 40.0:1, 50.0:1, 70.0:1 and compression ratios therein and/or greater.

WO 96/40844 PCT/US96/09653 -144- Examole 207 The methods and gasoline compositions above, wherein the octane of the composition is 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107.

Example 208 The gasoline method, wherein the engine is designed to 0 operate on a gasoline whose octane is equal to or exceeds 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 100, 101, 102, 103, 104, 105, 106, 107, 108 (R+M)/2 or greater.

Example 209 The gasoline method, wherein engine operation comprises use of electronic knock sensor to retard spark and wherein spark retardation and hence combustion efficiency -is improved over clear fuel by at least 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.

Examole 210 The method of Example 209, wherein acceleration of engine employing Applicant's fuel compostion with combustion chamber deposit control additive is improved WO 96/40844 PCT/US96/09653 -145- 3.0% to 10%, 4.0% to 15.0% or more over the clear fuel, alone.

ECS compounds 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 such as N- _0 cyclohexyl-N,N-dimethyl amine. See U.S. Patent 3,909,215 and EP 188,042 for additional examples. Concentrations will vary depending upon stability concerns. For example,

ETBE

and diisopropyl ether have a stronger tendency to form peroxides than does MTBE and hence may require greater concentrations.

In the case of carbonates, especially DMC, when exposed to water for extended periods, due to hydrolysis, decomposition into methanol may occur, hense leading to corrosion concerns. Thus, water reducing agents, salts, cosolvents, demulsifiers, anti-oxidants, stabilizers, corrosion inhibitors, and the like are expressly contemplated.

Mitigation Practice It is contemplated that Applicant's neat ECS fuels, neat co-fuels (absent ECS and/or metallics), and/or ECS\ co-fuel combinations, standard fuels, modified fuels, will employ certain mitigation practices, to for example reduce WO 96/40844 PCT/US96/09653 -146vapr pressure or vapor pressure reduction (VPR), increase flash point temperature or flash point increase (FPI), avoid hydroscopic/phase separation, and the like.

Lower molecular weight ECS alcohol compounds are hydroscopic and tend to phase seperate in fuel systems exposed to or containing water. Thus, 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 pressure or reduce flash point temperature. Their useage can also reduce T-50 temperatures causing driveability problems 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.

In the practice of this invention a different and unicque class of co-solvents and means are contemplated to mitigate vapor pressure and flash point problems, particularly in fuels heavier than gasoline, e.g. jet turbine, gas oil turbi.ne, diesel fuels, and the like.

It is generally preferred that co-solvents be ECS compounds or have ECS combustion/temperature or BV enhancing attributes. Preferred co-solvents increase LHV and/or BV.

WO 96/40844 PCT/US96/09653 -147- Applicant's preferred co-solvents, while not required, should be flamable. Both inorganic and/or organic compounds are contemplated.

It is contemplated preferred FPI co-solvents will increase flash point 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 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 is contemplated that FPI co-solvents will raise flash points to minimum ASTM or government specifications.

VPR

co-solvents will reduce RVP by 0.1, 0.2, 0.3, 0.4, 0.6, 0.7, 0.8, 0.9, 1.0. 1.1, 1.5, or more psi. VPR cosolvents will reduce RVP to within ASTM or government specifications.

Applicant's desired co-solvents, will have melting points less than 20, 10, 0, -10, -15, -20, -25, -30, -50, -60, -70, -80, -90, -100, -130. -140 0 C, or below.

Preferred will be those with melting points less than -5 0

C,

more preferably less than -40, -50, -60, -70 -90 0 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-solvents, especially those azeothroping temperature. Alchols are intended as well as hydrocarbon based solvents. 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 WO 96/40844 PCT/US96/09653 -148employed. Additional anti-icing additives include Phillips PFA 55 MB 0.15% Vol. and MIL-I-27686 0.15% Vol. Max.

Thus, it is an embodiment to employ multiple cosolvents, 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 \0 freezing point co-solvent(s), whereby resultant mixture would have combination of moderately high to high flash point and low freezing point.

In cases where FPI co-solvents have high melting point, In the practice of this invention icing inhibitors may be employed, including alcohols, co-solvents, and the like, especially where the ECS compound or co-solvent does 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-solvents will have boiling points above 80, 90, 100, 110, 120, 300 0 C, and greater. Boiling points above 130, 160, 190, 200, 220, 240, 260, 270 0 C, or greater, are preferred.

Desired flash point temperatures of co-solvents are -31, -20, -15, -10, 0, 5, 10, 15, 20, 25, 30, 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 0

C,

WO 96/40844 PCT/US96/09653 -149more or less. Preferred flash point temperatures are -100, -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, 31, 33, 35, 37, 39, 41, 43, 45, 47, 49, 51, 53, 55, 57, 59, 62, 65 va (Tb)/kJ mol' 1 (or equivalent), or L0 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. It is preferred that co-solvent LHV's be greater than any co-fuel to which they might by added. However, LHV must be balanced by the other aspects of usage, e.g. LHV of resultant fuel, LHV effect of ECS compound (if any), flash point and/or vapor pressure priority, etc. Preferred BV's are equal or above 28, 30, 32, 34, 36, 38, 40, 42, 43, 44, 46, 47, 48, 50, 55, 60 cm/sec (laminar bunsen flame).

Preferred co-solvent temperatures at vapor pressures of 1 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.

In FPI or VPR applications, especially when an ECS compound, it is preferred that the co-solvent(s) have a vapor pressure of I mm, or less, at temperatures of about or greater than -20, -10, 0, 20, 30, 40, 50, 60, 65, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, WO 96/40844 PCT/US96/09653 -150- 180 0 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 cosolvents are those having less than 22, 20, 18, 16, 14, 13, 12, 11, 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 has 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-solvents are contemplated.

Solid co-solvents, which may be dissolved by mutual solvent, are contemplated. Co-solvent chemical structure is not limited, and may be cyclic, bi-cyclic, aromatic, nonaromatic, branched or straight chain, or combination thereof.

It is preferred that the co-solvent be' thermally stable, not decompose under normal handling and operating temperatures (see ECS standards above), or cause co-fuel deterioration, guming, corrosion, etc. It is additionally desireable that the half life of its evaporative or combustion product be very short, preferably WO 96/40844 PCT/US96/09653 -151less than days 8, 5, 4 or less), more preferably less than hours 24, 18, 12, 8, 4, 3, 2, 1 or less), most preferably less than minutes 60 ,45, 30, 15, or less).

As contemplated herein co-solvent practice need not include an ECS compound and/or metallic.

It is desireable that a synergistic relationship exist between the ECS compound(s), and co-solvent(s). Thus, wide variability in mix of co-solvents is expressly contemplated. Differing requirement can be satisfied with differing co-solvents, and mixtures thereof, optionally in with or without an ECS compound.

In other words, 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 ranges of cosolvents in a mixture, Applicant recognizes that differing fuel will elicit differing requirements for differing cosolvent mixtures. When practical, single component cosolvent mixtures are preferred.

Co-solvent practice may also be supplemented or substituted by use of 'heavy naptha's, including aromatic naptha's. Thus, it is an embodiment to employ heavy or moderately heavy hyrocarbons, including napthas, in lieu of or in addition to co-solvent(s), as means for FPI and VPR.

It is also preferred that co-solvent usage not increase melting/freezing point temperatures, or diminish or aggravate fuel stability, corrosion, elastermer WO 96/40844 PCTIUS96/09653 -152deterioration, evaporative emissions, toxic emissions, hazardous combustion emissions, or diminish combustion burning velocities and LHV's. It is also preferred cosolvent usage not to contribute to gumming or oxidation.

However, in such circumstances, for example, where freezing points are not sufficiently low), it is contemplated an additional co-solvent, substitute cosolvent 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.

However, Applicant's preferred co-solvents do not cause such problems.

It is desireable that the co-solvent be soluble with the targeted ECS compound, if employed, and optionally: cofuel and/or water. Co-solvents 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 flash points.

Applicant has found hydrocarbon soluble, flammable glycols, ketones, and their acetates, and esters to be desireable. Ethanoic, propanoic, butanoic, pentanoic, and hexanoic acids, including their acetates, esters and ethers are also desireable. Ethenes, butenes, propenes, hexenes, pentenes are acceptable.

Non-limiting examples of Applicant's co-solvents include: alcohols, glycols, ketones, esters, phenols, WO 96/40844 PCT/US96/09653 -153acetals, 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, bromoactealdehydes, bromoethanes, bromoethylenes, bromoacetic acids, bromobutanes, bromobutenes, bromobutylenes, bromo ethers, di bromo compounds, butyric acids, butanoic acids, butanoic esters, esters, orthoesters, ethers, glycols, ethylene glycols, di-ethylene glycols, diethylene glycol ethers, diethylene glycol acetates, propylene glycols, propylene glycol esters/ethers, di-propylene glycols, glycol ethers, triethylene glycols (including acetates, diacetates, esters, ethets, and amines thereof), tetraethylene glycols (including acetates, diacetates, esters, ethers, and amines thereof), tripropylene glycols, tetrapropylene glycols, dibutylene glycols, tributylene glycols, tetrabutylene glycols, pentaethylene glycols (including acetates, diacetates, esters, ethers, and amines thereof), glyceric acids, glycerols, formates, carbinols, carbitols, nitriles, acetates, ethylene acetates, esters, hydrates, hydrides, hydroperoxides, hydroxamic acids, hydroxyacids, imides, imidic acids, imines, ketenes, lactams, lactones, glycolic WO 96/40844 PCT/US96/09653 -154acids, butyric acids, heptic acids, valeric acids, isocaproic acids, nitrolic acids, nitrosolic acids, octanoic acids, esters of octanoic acids, onium compounds, orthoacids, ortho borates, octynes, octenes, octanones, oximes, esters of oxalic acid, oxalic acids, ethanoic acids, esters of ethanoic acids, esters of nonanoic acids, propanoic acids, esters of propanoic acid, pentanoic acids, propanediones, propanones, ethenes, propenes, butenes, pentanes, petenes, hexenes, esters of pentanoic acids, butanoic acids, oxalic esters, esters of butanoic acids, pentaneoic acids, esters of pentaneoic acids, pentanedioic acids, esters of pentanedioic acids, 2- or 3-pentanones, hexanoic acids, esters of hexnoic acids, heptanoic acids, esters of heptanoic acids, esters of- formic acid, glycol esters, octenes, octanone(s), oxalic acids, esters of oxalic acids, esters of hexanoic acid, hexanones, toluene bromides, toluene cresols, toluene dimethyl amino compounds, toluene ethers, toluene oxyls, pentanedials, peroxides, furans, esters of 2-furancarboxylic acids, furfurals, propenes, propenoic acids, esters of propenoic acids, ethers, butenedioc acids, bromo-alcohols, ethanetriols, propanetriols, butanetriols, pentanetriols, naphthalenes, hexanetriols, septanetriols, octanetriols, nitrobenzene, iodobenzene, 2-nitrophenol, and the like.

Additional non-limiting examples (to also include homologues and analogues thereof) are: triethylene glycol, 3-aminopropyl ether triethylene glycol, diacetate triethylene glycol, monobutyl ether triethylene glycol, WO 96/40844 PCTIUS96/09653 -155monomethyl ether triethylene glycol, monopropyl ether triethylene glycol, tetraethylene 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 monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol -monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol, ethylene glycol, hexylene glycol, dipropylene glycol, diethylene glycol, triproylene glycol, tetraethylene glycol, tetramethylene glycol, tetrapropylene glycol, polyethylene glycol (200, 300, 400, 600, 1000, 1500, 1540, 4000, 6000 Ashland Chemical), polyethylene glycol 3350 (Spectrum), polypropylene glycol (P400, P1200, P2000, P4000 Ashland Chemical), cyclohexylamine, dibutylamine, diethylamine, diethylenetriamine, diethylethanolamine, diisopropanolamine, morpholine, triethylamine, triethylenetetramine, triisopropanolamine, toluene, amino methyl propanol, propylene oxide, propylene glycol, 1,2 propanediol carbonate, salicylic acid, succinic WO 96/40944 WO 9640844PCT/US96/09653 acid, tartaric acid, tannic acid, 2,2,4-trimethylpentale, dimethylbenezenes, dimethyl formaride, n-methyl-2 pyrrolidone, amyl alcohol (primary), cyclohexano-, 2ethyihexanol, methyl amyl alcohol, tetrahydrofurfury.

alcohol, TEXANOL ester alcohol (Eastman Chemical) tTCAR Filmer IBT (Uinion Carbide Corp.) amyl acetate, dibase ester, ester solvent EEP (Ashland Chemical), 2-ethylexyl acetate, glycol ether acetates (DE, DE, DPM, EB, EE, PM, Ashland Chemical), isobutyl acetate, isobutyl isobutyrate, n-penty. propionate, cyclohexanole, 2 -hexanone, 3 -hexanone, 2-methyl-3 -pentanone, 3 -methyl-2-pentanone, 4-methyl-2pentanone, 3,3 -dimethyl -2 -butanone, diactone alcohol, diisobutyl ketone, ethyl methyl ketone, pinacolone, methone, 3,3-diphenyl 2-butanone, 1-hydroxy 2-butanone, 3hydroxy-(dl) 2-butanone, 3-methyl 2-butanone, oxime 2butanone, 2-butanone, 2-methyl proponoic acid, cyclopentanone, cyclopropyl methyl ketone, 2tetrahdrofurylmethanol, cyclohexanone, isophorone, methyl amyl ketone, methyl isoamyl ketone, acetonylacetone, acetic anhydride, benzyl alcohol (a-hydroxytoluene) and variations, triisobutylene, tetraisobutylene, allylidene diacetate, acetol, 1 (4-methyoxyphenyl) propanone, isobutyrophenone, acetonylbenzene, butyl acetate, C-4, C- 4+ aliphatic alcohols, n-butylbutyrate, cetyl alcohol, cyclohexane, cyclohexanol, cyclohexanone, diethylphthalate, dimethoxytetrahydofuran, p-dioxane, 1, 3-dioxane, 1,4dioxane, 5-hydroxy-2-methyl-l, 3-dioxane, glycol methylene ether, propylene carbonate, isopropylene carbonate, WO 96/40844 PCT/US96/09653 -157glycerin, 1,2,3-propanetriol, heptane, n-hexane, 2methylpentane, 3-methylpentane, methycyclopentane, 1,4benzenediol, isopentyl alcohol, methyl ethyl ketone, 4methyl-2-pentanone, methyl propyl ketone, diisopropyl ketone, 1- or 3- or 4- or 5 hydroxy 2- pentanone, diisopropyl ketone, methyl propyl ketone, diacetone alcohol, isopentyl phenyl ketone, 2-pentanone, diacetone alcohol, isopentyl phenol ketone, n-butyl phenol ketone, ibutyl phenol ketone, 2-butyl phenol ketone, isopropyl -0 acetone, 2- or 3- or 4-methoxy phenol, dihydrate oxalic acid, pentane, phenol, 3-methoxy phenol, 1,2 or 1,3 or 1,4 or 2,4 or 2,5 or 2,6 or 3,4 or 3,5 dimethyphenol, 1-octene, isobutyl 2-methylpropanate, 2-phenoxyethanol, diethyl carbitol, methyl carbitol, butyl carbitol, methyl ethyl carbinol, ethylene glycol, ethylene acetate, ethyl acetate, acetonphenone, benzyl acetate, 1,3 or 1,4 or 2,3 butanediol, formaldehyde, formamide, triethyl ester orthoacetic acid, trimethyl ester orthoacetic acid, oxalic ester (diethyl ester oxalic acid), methyl hydroperoxide, ethyl hydroperoxide, acetyl peroxide, ethyl peroxide, di(tert-butyl) peroxide, acetic anhydride, 2-ethyl butyl ester acetic acid, cresyl acetates, methylglycolate, methylester phenoxy acetic acid, nitrile acid, butyric acid, butanoic acid, 2-butyl butanoic acid, 2-ethyl butanoic acid, tert-butyl butanoic acid, butyl nitril, propyl ester butanic acid, diethyl acetic acid, acetonacetic acid, allyl acetoneacetate, diacetylacetone, acetylacetone, ethyl ester benzoic acid, butanic methyl WO 96/40844 WO 9640844PCTIUS96/09653 -158ester, butanic ethyl ester, butanic propyl ester, isoamyl butyrate, propyl ester butanoic acid, hexyl ester butanoic acid, 2-methyl-(d) butanoic acid, 2-methyl-(dl) butanoic acid, ethyl ester 3-methyl butanoic acid, methyl ester 3methyl butanoic acid, isopropyl ester 3-methyl butanoic acid, 2, 2-dimethyl butanoic acid, allyl ester butanoic acid, amide butanoic acid, N,N-dimethyl butanoic acid, anhydride butanoic acid, butyl ester butanoic acid, pentyl ester butanoic ester, propyl ester butanoic acid, _0 diethylacetic acid, 2-methyl-(d) butanic acid, methyl acetoacetate, ethyl acetoacetate, diethyl acetal, acetate,' acetyl acetone, 2,2-dimethyl ether ester propanoic acid, 2oxo ethyl ester propanoic acid, 2-oxo methyl ester propanoic acid, 2-oxo isobutyl propanoic acid, 2-oxoiso-propyl propanoic acid, methyl ester propanoic acid, ethyl ester propanoic acid, propyl ester propanoic acid, propanoic acid, glyceric acid, 1, 2 dimethoxethane, 1,2 ethanediol, 1,3 butanediol, 2,3 butanedione, 1,2,3 butanetriol, 1,2,4 butanetriol, glutaric acid, glutaric anhydride, glutaronitrile, 1, 5 pentanedial, glutaraldehyde, 2,4 pentadione (CH3COCH2COCH3), pentanic acid, levulinic acid, (CH3COCH3COC02H) dimethyl suberate, octanedioc acid, 1,2,3 pentanetriol, 2,3,4 pentanetriol, formamide, bromoacetic acid, acetamide, pyruvic acid, methyloxyacetic acid, propionamide, allyl bromide, diethyl acetal propenal, diacetate propenal, propenal, 1,2 propanediol, 1,3 pro-panediol, glycerol, trimethyl ether glycerol, acetylpropionyl, acetylacetone, propionic acid, WO 96/40844 WO 9640844PCTIUS96/0%653 9methyloxyacetic acid, propionanide, rnaleic anhydride, eiscrotofliC- acid, dimethyl oxal~ate, isobutyric acid, hydroxyisobutyriC acid, ethylene glycol., diethylene glycol, diacetate diethylele glycol, diethyl. ether diethyJlene glycol, dioleate diethylele glycol, tnonobutyl ether diethylene glycol, mono (2 hydroxyipropyl) ether diethylene glycol, monobutyl ether diethylele glycol., monopropy. ether diethylene glycol, monomethyl ether diethylenle glycol, monomethyl ether acetate diethylene glycol., monoethyl ether diethylene glycol, ethanetriols, propanetriols, butanetriols, pentafletriols, hexanetriols, septanetriolS, 1,2,3 butanetriol, 2,3,4 pentanetriol, 1,2,3 pentanetriol, 1,2,3 propanetriol, dioxypeitale, 2,4-dioxypeitale, hexantriols, monobutyl ether triethylene glycol, propanoi.c acid, anhydride propanoic acid, butyl ester propanoic acid, ethyl ester propanoic acid, pentyl ester propanoic acid, octyl ester propanoic ester, pimelic acid, suberic acid, azelaic acid, methacrylic acid, dibromobutales 1,2; dl-2,3; 1,4; meso-2,3; etc), tribromobutanes 1,1,2; 1,2,2; 2,2,3; etc.), diacetamide, di(2-bromoethyl) ether, 2-ethyihexalol, furfuryl alcohol, 2-propanone, 2-propen-1ol, ethyl methanate, methyl ethanate, pentadioic acid, pentadicic acid diethyl ester, pentadioic acid dimethyl ester, pentadicic acid dinitril, 2,3-pentaediole, 2,4pentadione, 1,2,3-pentanetriol, pentanoic acid, pentanoic acid methyl ester, pentanoic acid butyl ester, pentanoic acid ethyl ester, pentanoic acid furfuryl ester, pentanoic acid hexyl ester, pentanoic acid nitrile, pentanoic acid WO 96140844 WO 9640844PCT/US96/09653 -160octyl ester, pentanoic acid pentyl ester, carbinol, butyl carbinol, diethyl carbino., methyl n-propyl carbinol, dimethyl isobutyl carbinol, ethyl isopropyl carbinol, ethyl isopropyl methyl carbinol, diisopropyl carbinol, triethyl carbinol, isoamyl carbinol, dimethyl n-propyl carbinol, 2butyl methyl carbinol, methyl isobutyl carbinol, diethyl methyl carbinol, methyl propyl ketone, methyoxacetic acid, acetoacetic acid, methyl acetate, tert-amryl acetate, ethyl acetate, glycol diacetate, 1,2-propendiol carbonate, 1,2- -i propanediol, 1, 3-propanediol, adiponitrile, 2-amino-2methyl-i -propanol, triethylenetetramine, benzaldehyde, benzin, benzene, toluene, benzl alcohol, butyl acetate, dimethylaniline, di-n-propylaniline, methyl isobutyl ketone, n-amyl cyanide, di-n-butyl carbonate, diethylacetic acid, diethyl formamide, diisobutyl ketone, ethyl benzoate, ethyl phenylacetate, heptadecanol, 3-heptanol, n-heptyl acetate, n-hexy ether, methyl isopropyl ketone, 4-methyln-valeric acid, o-phenetidine, tetradecanol, triethylenetetramine, 2,6, 8-trimethyl 4-nonanone, ethanedial, carbonate 1,2-ethanediol, diacetate 1,2ethanediol, dimethyl ether 1,2-ethanediol, dinitrate 1,2ethanediol, n,n-di-methyl formic acid, n,n-di-ethyl formic acid, butyl ester formic acid, isoamyl formiate, octyl ester formic acid, pentyl ester formic acid, propyl ester formic acid, isobutyl ester formic acid, propargl acetate, 2methoxyethanol, cyclopentanone, cyclopropyl methyl ketone, ethyl propenoate, 3-methyl-2-butanone, phenol, 2-or 3-or 4methoxyohenol, propanoic anhydride, cyclohexanone, 4- WO 96/40844 PCT/US96/09653 -161methyl-3-penen-2-one, 2- or3- Hexanone, 3 or 4] -methyl- [2 or3]-pentanone, 2-heptanone, methyl phenyl ketone, diethyl benzene, and azulene.

Wide ranges of co-solvent mixtures, including mixing two or more, are expressly contemplated. Thus, any two or more co-solvents may be employed jointly, in same or differing proportions.

It is an embodiment to combine high flash point cosolvent(s) with alcohol and/or other co-solvent to control hydrolysis and/or hydroscopic phase separation. It is also an embodiment that 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 solvents to dissolve non-soluble or moderately miscible co-solvent and/or ECS compound(s), if employed.

Applicant recognizes that a wide variety of combinations and mixtures and proportions exist, which acheive the multiple objects of Applicant invention. Thus, it is an express embodiment of this invention that cosolvent combinations and mixture exist between individual co-solvents of any one class; between classes of cosolvents; between classes of co-solvent(s) and classes of ECS compounds; between co-solvent(s) and co-fuels; between co-solvent(s), ECS compounds, and co-fuel(s), and/or the like.

Example 211 A moderate to high flash point fuel: comprising a combustion improving amount of an ECS compound (preferably WO 96/40844 WO 9640844PcT/us96/0953 -162- DMC), optionally a metallic, and at least one flash point increasing flammable co-solvent.

ExamDle 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, -10, -20, -30, -40, -50, -60, -80, or -90 0 C; a boiling temperature equal to or greater jk0 than 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 270, 280, 300 0 C; optionally soluble in water; having a laminar burning velocity in excess of 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, cm/sec; a latent heat of vaporization in excess of 23, 25, 27, 29, 31, 33, 35, 37, 39, 41, 43, 45, 47, 49, 51, 53, 57, 59, 62, 65 va (Tb)/kJ mol 1 (or equivalent); optionally a vapor pressure of 1 mm at a temperature greater than -30, -25, -20, -15, -10, 0, 20, 30, 40, 70, 80, 90, 100, 110, 120, 130, or 140 0 C; and optionally a flash point temperature of at least 40, 60, 80, 100, 120, 130, 150, 170, 180, 200, 220, 250 0 or greater; and optionally a freeze point equal to or less than 30, 20, 0, -10, -20, -30, -40 (-40 0 -50, -60, -80, -90 0 or less; said composition characterized as raising hydrocarbon fuel flash point.

Example 213 A fuel composition comprising: a metallic and an ECS co-solvent or co-solvent package; characterized as having WO 96/40844 PCT/US96/09653 -163a 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.

Examole 214 A high flash point, low freezing temperature cosolvent 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 0 C; and a fuel soluble, flamable, freezing point reducing agent or co-solvent selected from butyl carbitol, carbinols (including diisopropyl, dimethylene n-propyl, isoamyl, etc.) 1-octene, 4-octene, l-octyne, 4-octyne, glycol ethers, ethylene glycols, diethylene glycols, dissopropyl ketone, methyl propyl, diacetone alcohol, issopropyl acetone, dissobutyl ketone, cyclhexanone, isophorone, or other co-solvent having moderate to moderately high flash point and low to extremely low freezing point, or mixture thereof; whereby the composition's flash point exceeds 100 (38 0 120, 140, 160, 180, 200, 220, 240, 260 0

F,

and whereby freezing temperature is equal to or less than -20, -30, -40 (-40 0 -50, -60, -80, -90 0 F, or less.

Examole 215 The example 214, wherein at least one co-solvent compound is a tertraethylene glycol, triethylene glycol, loctene, high flash point ketone, isopropyl acetone, WO 96/40844 WO 9640844PCT/US96/09653 -164dissopropyl 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 v,,(Tb)/kJ mol'.

Example 216 The composition of Example 214, additionally containing an ECS compound (preferably DMC), and optionally £0 a metallic; whereby the composition's flash point equals or exceeds 50, 60, 70, 80, 90, 100, 130, 150 0 F, or more, and the freeze point is less than -40 0 F (-40 0 -47 0 F (-44 0 C) (-46 0 C) or less; and optionally a latent heat of vaporization equal to or exceeding 28, 30, 32, 34, 38, 45 ,aP(Tb)/kJ mol-1 (or equivalent).

Example 217 The example 216, wherein the volume ratio of ECS compound to co-solvent(s) ranges 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, 1:6, 1:8, 1:10 with 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).

Examole 218 Incorporating Example 217, with above examples and a co-fuel; whereby resultant fuel meets ASTM and/or government specifications, governing RVP and flash point.

WO 96/40844 WO 9640844PCT/US96109653 -165- Examle 219 The example of 218, wherein the 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 cosolvent or mixture of co-solvent (as set forth above), resultant fuel's RVP is equal to or less than 8.0, 6.5 psi, or less.

Example 220 An aviation jet turbine co-fuel, including Jet A, A-i or B; or a #1-D diesel, low sulfur or normal grade; or a gas turbine fuel oil 1-GT, 2-GT; said co-fuel additionally comprising a combustion improving amount of an ECS compound (preferably DMC) having a flash point of less than 38 0 C, and optionally at least one metallic (preferably MMT), and a flash temperature increasing amount of a cosolvent (preferably a fuel soluble flammable polyene glycol, ketone, acetate, phenol, and/or ester having flash point in excess of 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 3000F) wherein resultant fuel is characterized as having a,flash point temperature of at least 100 0 F (38C) Examole 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 0 C, an optionally a metallic, WO 96/40844 PCT/US96/09653 -166and a flash temperature increasing amount of a co-solvent, wherein resultant fuel is characterized as having a flash point temperature of at least 520C; optionally a reduced cloud or freeze point; and optionally improved viscosity.

Example 222 An #4-D diesel fuel oil co-fuel, normal grade or low sulfur; or #5 light or #5 heavy fuel oil; or 3 GT gas turbine fuel oil; said fuel additonally comprising a combustion improving amount of an ECS compound (preferably DMC) having a flash point of less than 55 0 C, a metallic, and 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 550C.

Example 223 A #4-GT gas turbine fuel oil co-fuel; said fuel additonally comprising a combustion improving amount of an ECS compound (preferably DMC) having a flash point of less than 66 0 C, and 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 66 0

C.

Example 224 An aviation gasoline co-fuel; said fuel additionally containing a combustion improving amount of DMC or other WO 96/40844 PCT/US96/09653 -167- ECS compound(s) including those having blending vapor pressure 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 j0 resultant fuel meets all ASTM D 910 specifications.

Example 225 A marine gas 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 flash point temperature of at least 60 0

C.

Examnle 226 The above examples wherein the co-solvent is comprised of at least one fuel soluble, flammable triethyelene glycol, tetraethylene glycol, including mixtures.

Example 227 The above examples, wherein the resultant fuels are additionally characterized as meeting ASTM, industry or government standards present and future.

WO 96/40844 PCT/US96/09653 -168- 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 salts for purposes of mitigating vapor pressure and/or to increase flash point temperatures. It is contemplated that certain salts may be employed directly in the fuel or indirectely soluble via mutual solvent a co-solvent).

Most salts are soluble in aqueous solutions and Applicant's invention includes method of employing such solutions directly into fuel, either by separate injection, emulsions, or co-solvent.

However, direct soluability is the more preferred practice. Mutual soluability via ketones, glycols, ethers, alcohols, and the like, is also contemplated.

Desired salts 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 salts H3B03), potassium salts KNO3, KBr03, KN02, KHCO3, K2C204, KI, KH, K2W04, K2C03, KOH,), lithium salts LiN03, LiBr, Lil, LiOH), iron salts, aluminum salts, cobalt, magnesium salts Mg(N03)2, MgBr2), sodium NaN03, NaOH, NaN02, NaHCO3, NaBR03, NaBr, Nal, Na2C03, Na2WO4), nitrogen WO 96/40844 PCT/US96/09653 -169salts NH4NO3, NH4Br, NH4I) nickel salts (e.g.

Ni(NO3)2) and zinc salts Zn(N03)2).

Applicant has found fuel soluable Al, Mg, Li, Mn, Na, Sr, salts to be desireable. Other salts capable of reducing vapor pressure or increasing flash point are contemplated in the claims below.

At higher concentration levels, salts containing sulfur or barium should be avoided. Environmental concerns also dictate.

Applicant's preferred salts are those that may be added in sufficient concentrations 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, 10.0 grammolecules per liter. Perferred vapor pressure reductions are those greater than 20 mm, and preferred concentrations are less than 4.0, 3.0, 2.5, 2.0, 1.5, 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).

Example.228 A fuel composition comprising a vapor pressure reducing amount of at least one salt 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, 10.0, 15.0 mm at either ambient temperature or at WO 96/40844 WO 9640844PCrIUS96/09653 -170vaporization 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).

Those skilled in the art will appreciate that many variations and modifications of the invention disclosed herein may be made without departing from the spirit and scope thereof. The 170/1 Throughout this specification, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers.

Claims (1)

1. 3. A composition of matter for use in hydrocarbons substantially as hereinbefore described with reference to the examples. Dated this TENTH day of OCTOBER 2003 WILLIAM C ORR Applicant Wray Associates Perth, Western Australia Patent Attorneys for the Applicant