CA2194572A1 - Vapor phase combustion methods and compositions - Google Patents

Abstract

Method of reduced temperature metallic vapor phase combustion for jet, turbine, diesel, fuel oil, and gasoline combustion systems. More particularly, it relates to methods and composition of metal-containing fuels comprised of enhanced combustion structure capable of increasing combustion burning velocity and reducing combustion temperature.

Description

w095/33022 21 9 4 5~ 2 r~l~u~ 0~758 ~ VaPOR P~A8B _ Jf NETlIOD8 ~D _ .~

P~ _ OF T~B l~v Fiel~ of the Invention Thi6 invention relates to methods and fuel ~ compositions capable of vapor phase combustion for use in ~et, turbine, diesel, fuel oil, g~--l;n~ and other combustion systems. More particularly, it relates to metallic vapor phase fuel combinations with high heats of enthalpy capable of major free energy i _ u~. while simul~An~ol~ 1y reducing combustion , ~Lur~.

De~cription of the Prior Art The incuL~uL~tion of - 11 ;CF, in~ ing various organo , n~e ' as anti-knock agents (e.g.
methylcyclop~n~i~nyl r~ngAn~e tricarbonyl -MMT, et al.) in hydL~aLLu-- fuel~, is known. See U.S. Patents 2,818,417;

2,839,552; and 3,127,351 (incuL~u~ated herein by reference1. Organo - ngAn~Fe~s use in heavier fuels ~uch as coal, diesel and jet aviation fuels is also known and believed to help reduce smoke and solid particulate e~;~sinn~. See U.S. Patents ~ 3,927,992; 4,240,802;
4,207,078; 4,240,801.
Despite organo - ng~np~e~s anti-knock and other 25 benefits, its use in l.ydLocaLLufuels produces another set of envi~ ~al and practical problems. Namely, Al 1 i~
based fuels form lliC oxides in combustion. In the case of organo ngAn~e _ '-~ such metallics when combusted in hydLOu~LLu-l fuels generate harmful heavy W095/33022 2 1 9 4 5 7 2 P~

r~ng~nP~e oxides (Mn304 and Mn203), which in turn coat engine parts, combustion systems, turbines, exhaust surfaces, s;.-n/exhaust cataly6ts, etc., causing for example, early fatigue, failure, excessive wear, particulate _~iccinnc of metals, long term hydrocarbon _n;Ccirn degradation, and the like. See U.S. Patents 3,585,012;

3,442,631; 3,718,444; and my EP0 Patent ~ 0235280.
Harmful metallic deposition is well known and heretofore the practical problem in metallic u6age. For example, deposition of r-~J_I.P~e oxide on jet engines, turbines, and the like, has long been a major obstacle to rcn~ Pce~ use. Due to the severity of r-ng~n-ce deposits, various methods were developed just to remove suoh 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 flic~hility~ metallic usage has been virtually halted in such applications, and alternative application is limited to very low ~-,n~ tions of ~ l l i r .
U.S. Patent 4,600,408 (issued in 1986) ~iCcl~-~-- an alkyl phenyl carbonate as an anti-knock agent. Patent 4,600,408 notes the aforementioned organo , -e oxide problem and AicclocPc its composition must be organo-r-ng_n-~e free.
Since those skilled in the art have long since ~h_n~r;-Pd hopes of solving the fnn~ L~l oxide ~ic~hility of metallic combustion, and given that ~-n~nFRa is illegal in l~n~ P~ g~colinpc~ practitioners have long been ~icinrlinPd to separate MNT from lead additive usage. See woss/33022 2 1 9 4 ~72 ~ C7~8 ~ -3-for example, European Patent Application 91306278.2 related to ~U~y LLical dialkyl carbonate fuel additives," which rerogni~ this reality by ~i~closin~ tetraethyl lead, t~LL yl lead and cyclopentadienyl tricarbonyl , ~
~ 5 together in the same context, absent suggestion of employing them ;n~r~n~ntly of each other.

8ummary of Invontion ApplicAnt has disc~v~L~d a new class of high energy cool combustion compositions and ~Locesses, which i8 additionally taught in ~i~n Application PCT/U595/02691, filed 3/2/95 and inc~r~v~ted by reference in all regards to instant claimed invention.
The essence of ArplicAnt's invention resides in the discovery of the source of heavy metal oxidation problem, which occurs in a less than ideal combustion process wherein co~bustion burning velocities and t~ _ ~tuLes are not optimized.
By effectively increasing the burning velocity of the fuel, while ideally reducing combustion t~ _ ~LUL~8 with Applicant's fuel compositions and process, Applicant not only controls or avoids the generation of adverse metallic oxides, but liberates metallics to become prin~irAl~ in a new "clean high energy" class of propellAnt~/fuels and combustion process. Applicant is also able to beneficially apply this discovery of the problem source to n~ llic fuels and systems.

.~.................. . . . _ w095/33022 2 l 94 572 P~ 758 In essence, Applicnnt has diocovered a combustion process that comprises certain oh~m; c~l structure/sub-~tructure and/or mechanical structure/sub 6LLU~LUL~ that simult~nPol~aly 1) increases burning velocity while 2) reducing combustion t~ aLuu~6~ in a vapor phase combustion, whereby a high release rate of what might be known as "free energy" occurs.
In the practice of this invention, methods of in~oL~Lating this new class of propellants into existing fuels and systems, e.g. mitigating flash point, vapor p~esDuLe, and the like, i5 ~iaol~a~.

BRIEF DBo~ OF ~%~ D~
Figure 1. Combu~tion ~ _ Lu._ Dirr~
compares differences in combustion t~ aLu~ ~s of differing fuel compositions measured via exhaust gas temperatures at different engine loads.
Figure a. t ~ ~ion T~mp-rature~ and ~ydrocarbon F~ - es combustion t~ UL~ differences and their relationship to the generation of hyd~ bon~
~m;aai~na.
Figure 3. combu~tion Temperature~ and NO~ P~
compares combustion temperature differences and their rela~ionahir to the generation of NOx ~miaai~na.
Figure 4. Indicat-C Burning ~olocity, ~8 the burning velocity of different fuels under differing loads.

W0 95133022 2 1 9 4 5 7 2 . ~ '758 ~ --5--Figure 5. Burning Veiocity and HC T~io~ , compares burning velocity to the generation of HC D~;cSirne Figure 6. Burning Velocity and NOY T~;~n~
compares burning velocity to the generation of NOx emissions.
Figure 7. Comparat$ve Distillation Curv-s shows distillation ranges for MTBE a,nd DMC containing fuels, achieving object of Applicant's invention.
Figure 8. T~ T~lf - Duo to Di~tillation Dopre~ion shows warm driveability, emission and combustion ~ ntS of MTBE/oxygen containing g~eolinQc, due to maintaining minimum distillation t~ ~ ~LuLas for fuel containing oxygenated -.

nR~TTRn D~ OF ~VL~
Appl; cA~t~s discovery is discovery of the original source of the heavy metallic oxide problem and its attendant solution, e.g increasing burning velocity and/or reducing combustion t~ ~LUL~5.
Accordingly, Applicant ~ir~losDe herein multiple methods and compositions that increase burning velocity and reduce combustion t ~O~LUL~, which solve this problem.
The unity of Applicant's invention is based upon the discovery of the problem's source, and that the solution has many aspects.
In Applicant's i ~v~d combustion conditions, the r~ llir., itself (in preferred but not required practices), becomes an integral and powerful agent in the combustion W095/33022 2 1 9 4 5 7 2 ~ ~l/u~ ~cE758 process, itself, and ~ e~e~ly i u~5 combustion thermal efriciencies, fuel economy, net available work, power generation, thrust, and the like; while simultaneously reducing hazardous pollutants.
Applicant expects significant combustion and energy conversion ; ~. Ls at altitude in the case of aviation jet systems, aviation gA~ol;n~ engines. Similar ; u~c ts are contemplated for a wide range of applications, e.g. diesel, gA~Ol ;n~, fuel oils, gas oil turbines, etc.
In the context of this invention, Applicant generally refers to thermal efficiency, hereinafter, in both its rh~;rAl and ~ -n;~Al context, e.g. the efficiency of the combustion process and a~ount of useful work generated in the system, e.g. free energy.
~rrl;cAnt has found in virtually every case, thermal efficiency, particularly as measured as a function of net useful work generated by the system i5 increased. Often very substantially. SimultAnPo~ly, due to the cool nature of the combustion t~ aLu-~s, combustion systems will enjoy extended useful life, ease of operation, and improve performance.
For example, Applicant's has lln~Yr~teAly discuv~l~d thermal and/or combustion efficiency te.g. complet~n~ of combustion, etc.) over existing fuels and combustion systems to be on the order of 2.0% to 20~. And, ~r~n~;ng upon the ciluu~wL~nces average ; u~ ~ can range from 2.0% to 5.0%, 5.0% to 10.0% or higher, modest ; u~ Ls woss/33022 2 1 9 ~ 5 7 2 . ~I/U~ C.'C '758 range from 0.05% to 1.0~ to 2.0%. Exceptional i u~. ts will range from 10%, 25% to 40%, 30% to 80%, or more.
Additionally, Applicant ultimately expects ~, u~. L8 on the order of 5% to 25%, or more, due to ~ 5 modifications of combustion and fuel injection systems ~c;qn~ to optimize the unique combustion features of Applicant's invention.
The invention flln~ Lally resides in increasing 1) burning velocity of a non-leaded r ' 11; C containing fuel by a) increasing laminar burning velocity (by ECS rhPm;cAl, distillation modification, and/or reformulation means), b) increasing turbulent velocity (by rh~-;cAl and/or -n;cAl means) and 2) reducing combustion t~ ~LUL~
(by rh~m;cAl means, e.g. increasing latent heats of vaporization or - -h~n;cAl means e.g. advanced cooling systems, reducing chamber air charge t atuLe).
Thus, applicant's invention inauL~urd-es multiple interrelating chemical and - ~hAnirAl elements, all vital to the practice of the invention.
The use of ~ / Ls and/or rh~m;cAl and/or merhAnical, processes, methods, formulations, reformulations, rh~m;cAl and non l- ;cAl means, ;nr~ ;ng combinations and sub c 'inAtionc thereof, which operate to increase combustion burning velocity and/or reduce combustion temperature (especially simultaneous velocity increases and t~ ~Lu-u reductions), are expressly contemplated.

W095/33022 2 1 9 4 5 7 2 ~ 7~8 ~

In the practice of the invention, should an oxygenated _ be employed, m~Yimi7ing oxygen content is generally desirable. Oxygen contents may range from 0.0001 to 80.0% by weight, or higher, of the composltion.
Fuel composition, combustion systems, legal C~IIC~LIID
dictate. However, beneficial results do not tend to occur until 1.0%, 1.5%, 2.0% or more oxygen is included. More preferred c~nc~llLL~Lions are 2.0% or more. However, smaller c~ll~llL-~Lions are acceptable in co-fuel applications. A
desirable range is from 0.001 to 30.0% oxygen by weight.
Additional weight cullcel-L.~tions of oxygen include 0.001 to 15.0%., 0.5% to 1.5%, 0.3% to 2.7%, 0.4% to 1.8%, 0.5% to 1.9~, 0.6% to 2.0%, 0.7% to 2.1%, 0.8% to 2.2%, 0.9% to 2.3%, 1.0% to 2.4%, 1.1% to 2.5%, 1.2% to 2.6%, 1.8% to 2.2%, 2.0% to 3.7%, 0.2% to 0.9%, 1.0% to 4%, 2.0% to 8.0%, 1.8% to 12%, 2.0% to 10.0%, 3.0%, 5.0% to 40%, 2.0% to 53%
It is anticipated in neat fuel and rocket applications, oxygen oollc~,-LL~tions will be significant. In initial co-fuel applications c~llcel.LL~tions will be more modest. However, it is an object to include significant c~n~cllLL~tions of oxygen which can aggressively react with the metallic, maximizing object of the invention.
In the practice of this invention, acceptable increases in the rate of the fuel's burning velocity over an ulladjuDLed fuel or combustion system will range from 1.0% to approximately 800%, or more. Velocity increases of 0.2%, 0.5%, 1.0%, 2.0%, 3.5%, 5% to 10.0%, 7.0% to 15.%, 9.0% to 25%, 5.0% to 20%, 12% to 30%, 15% to 40%, 20% to 21. ~4572 WO 9S/33022 1~ 3''D~758 _g_ 50~ are desirable. More desireable increases range from 5%
to 60%, 10% to 80%, 20% to 100%, 30% to 150%. Other increases are from about 100% to 200%, 100% to 300%.
Increases of 200% to 400%, 300~ to 600%, 400% to 800%, 500%
~ 5 to 900% are also contemplated and desireable. Increases of 300%, or more, are highly d_sireable, QspeciAlly in ~rplir~nt~s advance fuel and combustion systems. Increases outside these ranges are contemplated and desireable.
New knock sensor te~hnol~gy will be employed in ~njul~Lion with higher O~sion spark ignited engines nQcQ~cAry to practice Applicant's preferred ' '; Ls.
New clean and super clean engine combustion design is contemplated as further ~ L T, ~d and new catalytic conversions of exhaust ~mi ~ion~ are also contemplated.
Advanced fuel formulation, Q~rQc~ y co-fuel formulation or reformulation, which substantially reduces hazardous Qmi~ n~ known or later learned to be hazardous are contemplated. Reformulation optimizing Applicant's preferred . -~i Ls are Q-peci~lly contemplated.
Other advance applications include operation of large and very large engines under moderate to heavy load.
It is contemplated that many applications of the invention will not be fully appreciated until certain thresholds of operation have been achieved.
For example, and as will be ~et forth in more detail below, the benefits of i ~_d fuel economies are not be fully enjoyed until engine is operated under moderate, W095/33022 2 1 9 4 5 7 2 P~ 7~8 moderately heavy to heavy load conditions. Thus, new engine design with taking advantage of greater thermal effi~ riPc under load are contemplated.
Furth~ e, absent other adj~L ts, e.g. reductions S in NBT spark advance, Pnh~nred air-fuel ratio's, turbocharging, increased es~ion, the full benefit of Applicant's invention will not be fully enjoyed.
In the practice of Applicant's invention, i ,,~ Ls in ignition and spark timing, combustor design, power plant, and the like, which Pnhlnr~c the unique combustion in engines employing Applicant's new class of fuels is an express ~
Additionally, close stoi~hi LL1C air-fuel ratio a3ju~; -t employing, for example computer PnhAnrPd electronics, is expre6sly contemplated.
Increases in the pre-ignition or post-ignition partial - ~res~u,~ of the vaporized fraction is particularly effective in inflll-nring i ~ Ls in burning velocity.
Thus, the character of t_e pre-ignition/post-ignition vaporized fraction and those features related to the diffusion of heat and active reaction centers in l~nhnrnP~
gases, and the like, are ~PtPrmin~tive and are intended to be optimized as an object of this invention.
It is an object of Applicant's invention that the diffusion of pre/post ignition pL~ ion gases operate to increase the Lu~/viscosity of the unburned gas to as close as p~C5,ihlp to the viscosity of the burned gas, in order to reduce the viscous drag between the burned and the WO95133022 2 l 9 ~ 5 72 P~ C7!58 unburned gases. It is the elimination of this drag, where Lal increases in burning velocity are achieved.
The rate of flame propaga1:ion relative to unburned gas, in practical fuel-air-residual gas mixtures i5 a ~ 5 r, ~ L~ 1 paL 0~ that directly influences the invention's beneficial object~. Thus, r - ~ i m i 7 i ng the el~ Lary reaction6 that take place in the flame and adapting the mass and thermal diffusivity of the various gaseous species comprising the composition of enhAnred combustion (see below), to yield increased combustion burning velocity, is an express Pmho~ir-nt of this invention.

_ TEMPERAT~R~ MODIFICATION PRACTICE
r - -ing combustion f~ a-u~e8 and improving burning vQlocities are expressly contemplated. One such means iD by reducing or eliminating higher boiling point hydLuuaLbulls having lower relative latent heats of vaporization ("1HV"), as compared to the average LHV of the fuel. For example, Applicant has diDscuv~l~d that by reducing or eliminating higher boiling point alkanes from gasoline boiling fuels, work potential is not lost despite the rPdnr~ion in fuel end point and T-90 tempeLaLuLes.
Applicant has unexpectedly dibcuv~l.d that fuel economy ; u~ -ntc occur in such circumstances.
Thus, it is an express object to CUIIDLLUUL or tailor fuel fractions that increase latent heat of vaporization ("LHV") and/or increase the average burning velocity of the W0 95/33022 2 19 ~ 5 7 2 rc.,~ 758 fuel, when reducing or modifying T-go, T-50, T-10 tr ~Lu,as.
Thus, it is an : - i- L that modification of hydrocarbon co-fuel's, including T-90, T-50, or T-10 distillation , aLuL~s and/or sub6tituent -nts eliminate low burning velocity and low LHV hyd~aLb~..s to the maximum extent possible.
Thus, by reducing boiling t~ a~u,as, e.g. end boiling and T-90 temperatures and simultaneously increasing the fuel's average LHV, combustion t- _ ~tuLe are reduced.
Wide boiling fuels benefit from end boiling, T-90 boiling and T-50 reductions, which simult~n~ol~cly increase LHV, ;nrlu~ing aviation and automotive g~olin~, gas oil turbine fuels, fuel oils, diesel fuels, jet aviation fuels, and the like.
In gasoline boiling range fuels ~pplin~nt~s preferred practice i nrl ~ elimination of higher boiling point alkanes over aromatic hydrocarbons, over cyclanes, over alkenes of the same boiling temperature. In fuels, whose initial boiling point is in excess of 160~C (e.g. diesel, aviation jet, fuel oils, gas oil turbine fuels, etc.), the preferred practice generally includes elimination of higher boiling temperature alkanes over aromatics over bi-cyclic hydLo~a~bons of the same boiling temperature.
Thus, it is an : ~ i- L in wide boiling petroleum fractions, e.g. diesel, heavy diesel, gas oil turbine fuels, wide cut jet fuels tJet B, JP 4), fuel oils, gasolines, etc., to reduce the fuel's distillation boiling 2l q4572 W095/33022 r ~ . c -758 temperatures, ~Cpe~iAlly end point and/or T 90 ~ ~LuLe by 5~F to 20~F, 10~F to 30~F, 20~F to 50~F, 25~F to 60~F, 40~F
to 70~F, 50~F to 80~F, 60~F to 90~F, 70~F to 100~F, 80~F to 120~F, 40~F to 150~F, 75~F to 175~F, 60~F to 200~F, 70~F to 225~F, 80~F to 250~F, 90~F to 275CF, 100~F to 280~F, 110~F to 300~F, 120~F to 320~F, 140~F to 350~F, or more. It is preferred this practice simul~An~oll~ly increase the fuel's inherent latent heat of vaporization.
It is a specific 'i-- L of this invention to io reduce end point and T-90 boiling t~ _ aLUL~8 of co-fuels, which may used either in combination with ECS fuels, or as stand alone fuels.
It is an express : ~ ;~ L of this invention that fuel's, with reduced end point and/or T-90 fraction~, having increased LHV's be used in combination with a high energy metallic _ ' (as set forth below), and optionally with a ECS _ _- ' (as set forth below);
whereoy reductions in the formation of free carbon in primary combustor zones, reductions in hazardous exhaust e~ni c8irmc~ in-~ln~ling NOx, rP~nltinnC or control of e oxides on exhaust catalyst beds, and the like, occur. In the case of automotive fuels, this T-90 reduction tends to reduce harmful VOC, hydrocarbon and/or NOx ~ni ~ci~-nc .
Quite nn-Yrectetlly, Applicant has discovered that when reducing gACOl ine t-90 t~ ~Lur,cs to less than 270~F while increasing LHV above the unadjusted fuel, a material combustion advantage occurs in combination with minor W095/33022 21 ~ 4 5 7 2 ~ 7s8 amount6 of Mn. Applicant has dis~v~Led that $uel economy and/or mileage u~ e~edly ; ~v~s, even though higher heating value c ~nnPnts had been eliminated in the T-90 reduction.
obviously, this effect is sensitive to the fuel and the ~ that are eliminated and those that remain after ~-90 reduction.
In the examples set forth below, ~ppl~r~nt intends they be logically cnnn~cted to Applicant's single invention, namely an advanced form of combustion resulting from reduced combustion ~ ~-u~e and/or increased burning velocity. For example, Applicant's initial ~ losllre below relate6 primarily to t-, ~-ULe re~ t;nn obtained by intrinsic fuel modification. Later examples amplify b~n~f~ combustion effect by adding additional burning velocity and combustion temperature reductions by extrinsic means.
This unity of invention becomes more obvious as one und~L~ar.d~ the source of the problem has solved. Thus, despite the plethora of fuels, combustion systems and method, they all tie back to a single hub--a single invention.
Certain examples may at first blush appear ~;~cnnn~nted, but should later become logically connected once the problem source is fully appreciated. Thus, it is Applicant's intent the structure or substructure of his various examples, which may or may individually deal with W09sl33022 2 1 q4 572 ~ 758 the same fuel, the same aspect of the problem, or even same combustion system, may non-the-less be ~inD~.
However, due to the scope and multiplicity of examples, Applicant has not attempted to combine all such ~ 5 possibilities in this specification, but believes the ~pecification is self evident as to their combination(s).

r le 1 A method of increasing work potential, fuel economy, reducing combustion emissions of a vehicle operating on a conventional or reformulated gasoline, uAyyenate optional, comprising~ n~ing the boiling t ~tu~e of q~o~;n~
such that its boiling temperature at T-90 fraction i8 no greater than 300~F, 295~F, 290~F, 280~F, 270~F, or 260~F, or less, while simult~n~o~l~ly increasing the fuel's LHV to at least 130, 135, 140, 145, 150, 155, 160, 165, 170 btu/lb;
- optionally ~miYing MMT into the composition up to 1/64 or 1/32 gr mn/gal; combusting said composition in a gasoline powered vehicle; whereby fuel economy is i uv~d over unadjusted fuel alone, or unadjusted co-fuel with m~ng~n~e/ or co-fuel with T90 absent LHV increase, or m-ngineFe containing co-fuel with T90 absent LHV increase (preferre~ increases are 0.5, 1.0, 1.5, 2.0, 2.5% or more).

E ~e la A fuel composition comprising a conventional or reformulated gasoline, an optional oxygenate, a T-90 fraction no greater than 290~F, 280~F, 270~F, 260~F, a latent . ~ , W09~33022 2 1 q 4 5 7 2 . ~ 7S8 heat of vaporization a~ove 130, 135, 140, 145, 150, 155, 160, 165, 170 btu/lb; optionally MMT up to l/64, l/32 gram/gal; optionally a burning velocity ~Yr~e~;ng 48, 49, 50, 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 LHV.

r le 2 The method of example l, wherein the fuel additionally comprises a charge t~ ~tuLe reducing amount of a combustion chamber deposit control additive.

E le 3 The method of example 1, wherein fuel economy is i _ ~v~d over the clear fuel containing same amount of metallic but not having reduced T-90 t~ , ~Lu~as and elevated LHV.

~Y~r~le 4 The ~ above, wherein latent heat of vaporization and/or burning velocity of the adjusted T-90 fuel is 0.5, l.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0 greater than non adjusted fuel.

r le 5 The examples above, wherein fuel T-90 t~ , ~LULe is less than 310~F, more preferably less than 305~F, 300~F, 2l 94572 w095l33022 Pe~ clla~

295~F, 290~F, 285~F, 280~F, 275~F, 270~F, 265~F, 260~F, 255~F, 250~F, 245~F, or less; and NNT is included in the amount of l/32 gr. Nn/gal; and optionally a combustion chamber deposit control additive i5 employed in sufficient amount;
whereby charge t~ ~LUL~ is reduced; wherein fuel economy is ; ~._d over same unadjusted fuel by at least 0.2, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, or more, percentage.

~Y~ le 6 The composition of example 5, wherein toxic, C0, HC, and/or NOx PmiRcionC are also reduced.

r le 7 The example of 5, wherein NMT is contained in a quality of up to 1/32 gram mn per gallon, wherein fuel economy is ; ~v_d over unadjusted clear fuel.

Examrle 8 The example of 7, where an ~y~ ated ECS _ ' is employed in excess of 0.5~ by weight in the fuel, and wherein the gasoline's mid-range - ~Lu~e is from 170~F, 175~F to approximately 205~F.

r le 9 The eYample of 8, wherein the composition comprises an ECS ~ ' in a sufficient c~ ..LL~Lion to increase average burning velocity of composition by an additional .. ~ .................. ..

W09~33022 2 1 q ~ 5 7 2 rCll~_ C758 ~

5.0~, or more, over clear composition as measured by laminar bunsen burner.

r le 10 The example of 9, wherein the addition of the ECS
~ _ ' is sufficient to reduce average combustion t~ ~, LUL ~.s by 25~F, as measured under load of at least 20 indicated horse power (ihp) (using the equivalent of 350 CID engine).
Applicant notes this aspect of his invention (e.g.
nddition of ECS .ul-d with/or without metallic) as applied to gasoline is r~peci~l]y beneficial when T-90 t-r, aLUL~s are equal to or below approximately 300~F, 280~F, 270~F, 260~F, and optionally when T-50 t~ tule6 are in the range of approximately 160~F to 205~F or 170~F
to 205, 180~F to 205~F; or alternative 160~F to l90oF or 160~F to 180~F (particularly in later date applications).
The application of mid-range t~ _ ~tULe control is generally applicable to all wide boiling fuels.

TEMPERATURE ~ ATION
In the practice of this invention, preferred reductions in combustion t~ ~lLuLes range from 10~F to 500~F. Reductions of 25~F to 50~F, or more, are desireable.
Rr~ rtirnP: of 100~F, or more, are desireable. Reductions of 5~F to 15~F, 10~F to 25~F, 15~F to 30~F, 20~F to 40~F, 25~F to 45~F, 30~F to 50~F, 35~F to 60~F, 40~F to 55~F, 45~F to 60~F, 50~F to 65~F, 55~F to 75~F, 65~F to 75~F, 70~F to 95~F, 85~F to ~ WO95/33022 2 1 94 5 72 ~ 758 105~F, 100~F to 120~F, 110~F to 140~F, 100~F to 130~F, 110~F
to 150~F, 120~F to 160~F, 150~F to 250~F, 250~F to 450~F, 200~F
to 500~F, 300~F to 600~F, 200~F to 800~F, 400~F to 1000~F, 300~F to 900~F, 500~F to 2000~F, 600~F to 2500~F, or more, are preferred, ~spe~i~lly with simultaneous increases in burning velocity. Reductions outside above ranges are fully evL~ pec;Ally as the cv.l~.lLL~tion of the ~rpli~nt~s ~nh~r ~~ L combustion _ '- (see below) increase as a percent volume of the fuel composition.
In the case of gasoline, reduced exhaust temperature translates into increased power and/or reductions of exhaust catalyst inlet temp~L~tuL~s. It is an express c'; -t of this invention th,at exhaust catalyst inlet t~ ~Lu-e8 be reduced to avoid catalyst plugging. Hence it is an express object to reduce catalyst inlet temperatures to about 1400~F or less, 1350~F, 1300~F, 1250~F, 1200~F, 1150~F, 1100~F, 1050~F, or less, other temperature sufficient to assure acceptable catalyst activity while avoiding the likely hood of ~-ng~n~e oxide plugging.
It is also an express ~mho~;r-nt to reduce combustion Ules by constructing fuel compositions and/or operating engines to avoid or reduce combustion chamber deposits. Increased combustion chamber deposition is attributed to increased charge t ~Lu.~. Thus, combustion cha_ber reducing deposit additives are expressly t contemplated.
Thus, combustion t ~LUL~ control, absent any other aspect of Applicant's invention, is contemplated to reduce , ~

W095/33022 2 l 9 4 57 2 P~ c 758 ~ml cci~nc and/or a5 a means to control wa5h coat deposits from low mn concentrations r le 11 A method of avoiding the plugging or coating of exhaust catalysts or OBD II monltors or monitoring systems with r-ng~ncce oxides, said method comprising mixing a high latent heat of vaporization ECS fuel in sufficient guantity with a conventional nnl~ or reformulated nnl ~ d gasoline (preferably formulated to increase L~V) containing 1/64, 1/32 gr or more Mn/gal of ~MT, wherein said fuel's combustion and exhaust temp~L~tuLas are sufficiently reduced that inlet exhaust gas t~ ~Lu-~ of catalyst is less than 1400~f, more preferably less than 1350~ 1300~ 1250~ 1200~F.

r lç 17 A method of avoiding the plugging or coa~ing of çxhaust catalysts with r~ng~n~ce oxides, said method comprising modifying T-90 gasoline t~ -ntuLas to reduce combustion t~ ~LuLa of a low mn containing fuel, wherein said fuel's comoustion and exhaust t~ ~Lu.as are sufficiently reduced that inlet exhaust gas tr GLuL~ of catalyst i5 less than 1400~f Applicant has found t~ ~Lu-~ reductions to be more significant in higher t~ ~LuLa systems WO 9S/33022 . ~ 758 C~RMT~T N_AN8 Applicant 1 8 invention includes the discovery of a class of ~h~m;c~ , which reduce combustion temperature and/or contain certain free radicals, which are ~ 5 released during the combustion process to perform the object of accelerating burning velocity of Applicant's invention.
The lec~ r or chemical structure yielding high latent heat and/or accelerated burning velocity, etc., to wit, that ~LL~Lure causing the i_mediate high kinetic diffusion of the unburnt co_bustion vapor, etc., and/or otherwise acting in the combustion process to increase burning velocity (and exhaust velocity), and/or reduce combustion (and/or exhaust) t~ ~LUL~ is hereinafter referred to as ~'~nh~n~ Combustion SLLU~LULe or ECS."
Those ~ - which contain such DLLu~LuLe and/or are otherwise capable of performing the object of this invention are referred to as ECS _ - , e.g. those compounds containing ECS and that perform the object of ~rplic~nt~s invention Applicant has dis~eLed that certain - lec~ r features during combustion are r~cp~ncibl~ for the rapid diffusion of heat and active reaction centers in unburned gases, including the rapid diffusion of unburned gases in front of the flame front, responsible for increased burning velocities.
As a conseguence of this discovery, Applicant has identified certain molecular free r~ic~lc, but not limited ~ ~ _ _ _ _ _ _ _ _ _ _ _, . . ..... _ .

WO9~/33022 2194572 rc~ o~7~8 ~

to H, H2, ~, ~2~ CO~ F, F2, F3, N, B, Be, BO, B2, BF, AL
ALO, CH3, NH3, CH, C2H2, C2H5, Li, ONH, NH, NH2, OCH3 (methoxy radicals), OCH, OCH2, and OH (hydroxyl radicals), believed to be rpspnncihle for this result. Additional rho~i~ LU~-ULe believed capable of achieving similar result include Cl, OCOO, COOH, C2H500C, CH3CO, OCH20, OCHCO, and CONH2.
It is an : '; L of this invention that said radicals freely form during the earliest stages of the combustion process (preferably after ignition); with said radicals being unstable and having a free or unused valency electron that can chemically bond. It is highly desireable that they act as chain carriers in the main chain reaction of combustion, particularly in combination with - Allic combustion.
It is additionally preferred that as a c~nqo~-onre of said radical combustion activity or other means, that combustion yields diccoci ited and unstable molecules and atoms (e.g. OH, CN, CH, NH, etc.) with s~lhco~ont re~csoci~tion, leading to c~ntim~ing combustion, increasing exhaust velocity.
Applicant has found the heat of formation of his preferred free radicals to be relatively low. Acceptable heats of formation for said free radicals typically are less than 150, 100, 75, or 50 R cal mole1. Other heats of formation include 34 (CH3), 26 (C2H5), 9.3 (OH), 2.0 (CH30) Rcal mole~1. It is contemplated that negative heats of formation are also acceptable.

~ w095133022 2 1 9 4 ~ 72 ~ 7s8 A positive or low negative heat of formation for the ECS - c~ntAining said free radicals is desireable.
Acceptable negative ranges for heats of formation for ECS
~ _ '- include those less than approximately -200, -180, - 5 -160, -150, -145, -130, -120, -100 Kcal/mol, with more preferred being less than -90, -80, -75, -70, -65 Kcal/mol nd the most preferred being less than approximately -60, -55, -50 ,- 45, -40, -35, -30, -20, -10 kcal/mol, or positive in value. The closer to a positive or the higher the positive, the more preferred.
ECS __ '-, which easily ~ Fe and/or ~;rcc~lAte generating significant free radicals in compression, early and/or regular ignition or combustion, are desireable. It is desirably that ~iccoc;Ation occurs below normal or normal combustion, ~ssion, or at or near ignition t~ _ ~LUL~S (above if pre-ignition is a concern). It is desireable that rl i ccociAtion acts to quickly diffuse unburned vapors in front of the flame front, whereby burning velocity is increased.
It also is particularly desireable that said vapor ~LLU~LUL~ and/or the ECS L _ ', itself, have high latent heats of vaporization (enthalpy of vaporization), particularly those equal to or greater than 28.0 jK mole~1, at the c __ c boiling point. Other enthalpies of vaporization (at the boiling point) are those equal to or greater than 21, 22, 23, 24, 26, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 40, 42, 43, 45, 47, or higher, jK mole~
1. Generally, the higher the better.

W095/33022 2 l 9 4 5 7 2 r~ r ~c758 Preferred boiling point temperatures of ECS __ -C
are those below 350~C, 325~C, 300~C, 275~C, 250~C, 225~C, 200~C, 175~C, 170~C, 160~C, 150~C, 140~C, 130~C, 120~C, 110~C, 105~C, and 100~C. Preferred latent heats of vaporization of ECS _ __ -c at 60~F are those equal to or greater than 75, 100, 110, 120, 130, 135 140, 145, 150, 155, 150, 160, 165, 170, 180, 190, 200, 210, 220, 230, 240, 250, 270, 290, 300, 325, 350, 375, 400, 425, 450, 475, 500 btu/lb, or more. It i5 generally preferred that the latent heat of vaporization of the ESC -_ ' be at lea6t the same as, but more preferably 1.0%, 2.0%, 5.0%, 10%, 25%, 50%, 75%, 100%, 150%, 200%, 250%, 300~, or greater, than any unadjusted base or co-fuel to which the - ' might added. Normally, the higher the differences the better.
Applicant has dis~u~_red, the higher the relative difference in heat of vaporization, the higher, for example, intake charges can be cooled and the greater the i ~v ts in VQ1 LL ic efficiency.
Another feature of Applicant's ECS - _ ' is their superior flame propagation velocity features. 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 be equal to or greater than 40, 43, 45, 46, 48, 50, 52, 54, 56, 58, 60, 65, 70, 75, 80, 85, 90, 100, 110, 120, 130, 140, 150 cm/sec. Flame velocities of ECS _ -c herein may be measured inA~p~n~ntly or in the presence of a preferred metallic. Flame velocities of ~ Woss/33022 21 ~4572 ~ 758 ECS ,ou.lds in the presence of a metallic are generally expected to be greater, than absent said lli r..
Generally, preferred laminar flame ~Lu~ay~tion velocities should exceed 55 cm/sec. The higher the better.
It is preferred that the flame velocity of an any ECS
_ ' as measured in laminar bunsen flame be at least .05% to 1.5%, 1.0% to 3.0%, 2.0% to 4.0%, 3.0% to 6.0%, 5 to 10%, 7% to 20%, 8.0% to 30.0%, 10% to 40%, 15% to 60%, 30% to 200%, 50% to 300%, or more, than unadjusted co-fuel.
It is preferred that ECS _ '~ rapidly ~ ~e at temperatures slightly to moderately higher than ignition t _ LUL ~5 but below combustion temp~L ~ LUL ~s.
~e - 6 ition at higher or even lower t~ tUL ~8 is contemplated, including those below ignition tr Lures.
However, in the case of gasolines pre-ignition should be avoided.
It is preferred that ~ ;nin~j ECS ' , which nre not c _ ' in combustion, rapidly ~P. -6e when emitted in the A; - ~re after combustion. Preferred d-~~ ;tion have half lives less than 20, 15, 12, ll, lO, 9, 8, 7, 6, 5, 4, 3, 2, l days and more preferred half lives less than 24, 22, 20, 18, 16, 14, 12, lO, 8, 6, 4, 2 hours or less. Most preferred half lives are less than l.0, 0.5, 0.25 hours or less.
It preferred that ECS . '- be ~hPrr-lly stable in normal hAn~l inj and operating t~ ~LuLes up to approximately 150~F-300~F, but readily ~e_ ?~ at approximately temperatures approaching 300~F to 800~F, 300~F

~ 9~,, WO95/33022 2 1 9 ~ 5 7 2 A ~ i ~ ~ _. 0~758 to 500~F, more preferably at 400~F to 500~F. However, ~r _ ition at tL~eL~LuL_s outside of these and/or may occur for example during injection, ession, or prior to ignition, after ignition, and/or combustion.
Preferred fuel chain characteristics of Applicant's organic ECS ~ _ '- are those containing limited number of carbon atoms in chain with 6, 5, or 4 or fewer atoms preferred. 3 or 2 carbon atoms or a single carbon are more preferred. Generally, the shorter the carbon chain the length the more preferred the ESC

r le 13 A ECS _ ~__ ' comprising: a maximum carbon chain length of 5, 4, 3, 2, or 1 carbon atom(s); a negative heat of formation of -90, -60 kcal/mole, or less, ;nr~ ;ng a positive heat of formation; a melting point of less than 20, 10, 5, 0, -10, -20, -30, -50 ~C, or lower; a boiling t~ u~e greater than 25, 30, 40, 42, 43, 44, 60, 80, 90, 100, 110, 120, 140 ~C, or greater; a Bunsen burner laminar flame speed in excess of 40, 45, 48, 50, 55, 60, 65 or 70 cm/sec; a latent heat of vaporization ~yrr~e~;ng 80, 90, 100, 120, 130, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 230, 235, 240, 250, 300, 380, 400, 450, 500 BTU/lb at 60~F; th~-r~lly stable up to 200~F, 250~F, 300~F, 350~F, 400~F, 450~F, 475~F, 500~F, 600~F, whereinafter rapid O_ -toition into high kinetic energy free radicals occurs, including at least one or more free radicals selected from the group consisting of 2~ 94~72 wos~330zz ~ ,~0-758 H, H2, ~~ ~2~ CO, F, F2, F3, N, B, Be, BO, B2, BF, AL ALO, CH3, NH3, CH, C2H2, C2H5, Li, ONH, NH, NH2, OCH3, OCH, OCH2, and OH, and mixture.
-- 5 xample 14 Example 13, wherein the composition i5 fuel soluble and contains oxygen by weight in excess of 15%, 20%, 25%, 30%, 33%, 40%, 45%, 50%, 52%, 55%, 58%, 60% or more.
Non-limiting examples of ' that Applicant has initially identified that contain ECS structure and that are likely to be effective in accomplishing this object, include: 1IYdLUYen~ carbon ~ ~ , methylene di methyl ether (also known as methylal, ~ oYy 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, methanol, ethanol, propanol, tertiary butyl alcohol, dimethyl ether, other C3 to C~ lower molecular weight alcohols, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dimethyl ether diethyl ether, isopropyl ether, diisopropyl ether, ni~L~ n~
nitroethane, nitropropane, nitrous oxide, dinitrous oxide, nitric oxide, ozone, water, gas hydrates (methane hydrate), hydrogen peroxide, hydLu~u~ides and similar _ -.
Applicant believes many other . __ '- exist that have not yet been identified, which perform ECS function.
~pplic~nt acknowledges there is great variability in performance and characteristics between possible ECS

wo gs/33022 2 1 9 4 5 7 2 P~ 'C758 _ ' , and that in certain neat and/or co-fuel applications, certain ECS _ '~ 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 ~uL~o~es. Other ECS _ suffer potential health hazards. For example, NTBE has application in many fuels, but is now rAroqni~A~ as a possible carcinogen or allergen, having a long al A' iC
half life.
It is further rA~ogni ~A~ that differing ECS ~-will be employed in different fuel 6ystems, and that liquid fuel soluble ECS _ ' are contemplated in generally all ~uel state systems. Solid ECS __ ~- are normally employed in solid fuel systems, but may be incorporated into liquid or gaseous systems by ~L~Iiate means.
Obviously, differing ECS __I.ds in various systems will elicit differing response. For example, it is expected that in alcohols will elicit lower combustion and exhaust t~ ~LUL~5 than ethers, due to differences in latent heats of evaporation. It is also expected that lower molecular weight alcohols and carbonates, de :e at an accelerated rate, when compared to ethers.
ECS compounds may be solids, liquids, gases, and mixture, and may be selected from alcohols, amines, amides, oxalates, esters, di-esters, glycols, ethers, aldehydes, ketones, glycols, glycol ethers, peroxides, phenols, carboxylic acids, acetic acids, oxalic acids, boric acids, 2l q4572 wossl33022 rc~ c ~7s8 peroxides, hy~Lu~elu~ides~ esters, ~LhLue~Lers, aldehydicacids, ketonic acids, hydLu~yacids~ orth~Aci~, anhydrides, acetates, acetyls, orthoborates, formic acids, nitrates, di-nitrates, carbonates, di-carbonates, nitro-ethers, and the like.
ECS __ ~- include ~ '~ containing carbethoxy, ~a~b Lhoxy, carbonyl, carbonyldioxy, carboxy, ethoxalyl, glyoxylyl, methoxy, methyl~n~ioYy~ glycolyl, and/or hydroxyl -ntS and/or radicals.
ECS _ - containing double C=0 or C=N bounds are particularly desireable. Non-limiting examples include oxalates, ~Lbu-lates, acetyl Aret~n~, dimethyl glyoximes, ethylPn~;Amin~ tetraacetic acids, and the like.
Additional non-limiting ~xamples of likely ECS
~ include ethylene, propylene, tertiAry butylcumyl peroxide, butylene, 1,2-butadiene, 1, 3-butadiene, actetylene hydrocarbons in~ ing acetylene, allylene, butine-l, pentine-l, hexine-1; substituted hydrazines, in~ ing methylhydrazine, ~y LLical dimethylhydrazine, ~l~y LLical dimthylhydrazine, hydrazine; ethane, propane, butane, diborane, tetraborane, penta bornane, hexaborane, decaborane, aluminum bo~uhydLide~ beryllium bu~ uhy dL ide, lithium buLullydLide~ m nitrate, potassium nitrate, nitric acid, a_monium azide, inm perchlorate, lithium perchlorate, potassium perchlorate, nitrogen trioxide, nitrogen dioxide, hydrazoic acid, dicyanogen, hydLuuyanic acid, monethylanile, acetylene, Alll~imlm bu~ollydLide~
ammonia, aniline, benzene, bul:yl - ua,uLan, diborane, Wo 95/33022 2 1 q 4 5 7 2 .~ C 7S8 dimethylamine, diethylenetriamine, ethanol, ethylamine, ethylene diamine, ethylene oxide, ethylPnPAiAmin~ ethyl nitrate, dimethyl sulfide, furfuryl alcohol, heptene, hydrazine, hydLu~ll, isoethyl nitrate, isopropyl alcohol, lithium, lithium hydride, methane, methylal, methanol, methyl nitrate, methylamine, methylacetylene, methylvinyl acetylene, monoethyl~ni 1 i nP, nitromethane, niLLu~i vjuane, nitroglycerine, n-octane, propane, propylene oxide, n-propyl nitrate, o-toluidine, triethylamine, trimethylamine, trimethyl trithiorhn6l?hite, turpentine, Uilc.y ical dimethyl hydrazine, xylidine, 2,3-xylidine, lithium bOLUIIYd; ide, monomethylhydrazine, pentaborane, and the like.
Other candidate ECS, ---n~lc include di-tertiary butyi peroxide, alkyl peroxides, alkyl hy-lLu},eLu~.ides, acetyl hy-lLup~Loxides. Non-limiting ~ 1PC of peroxides include tertiary butylcumyl peroxide, di(tertiaryamyl) peroxide, tertiary butyl hydroperoxide, di-tertiary butyl hydLuj~:Luxide~ tertiary amyl hy-lLuj,eru,,ide, acetyl tert-butyl hylLu}~Lu,.ide tCH3~3COOH), cyclohexyl (acetyl) hy.lLu~Lu..ide, ethyl (acetyl) hydroperoxide (C2H500H), diacetyl peroxide, diethyl peroxide, dimethyl peroxide, methyl hy-lLu~eIuxide (CH300H), acetyl benzoyl peroxide, acetyl peroxide, formic acid, tetramethylnlr L'~nP, n,n-diethyl formic acid, n,n-dimethyl formic acid, formamide, methyl formate, alkyl nitrates (including ethyl-hexyl nitrate and iso-propyl nitrate), 2.5 dimethyl 2.5 di(tertiary butyl peroxy) hexane, OHC(CH2)4CHO;

~ W095133022 21 94572 r~ 0~758 CH3r~0~c~r~; tcH3)3C~wouc~; CH2CH2C(CH3)(OH)CH3;
(CH3)2COOH; (CH3)3COOH; CH3N02; CH3CCCOH; (CH3)3CCH2COH;
HOCH2CH20CH2CH20H; HOCH2CH20H; OCH2CHCHO; (CH3)3CCHO;
(CH3)3CCH(OH)CH3; C5H402; H02CCH2CH2C02C2H5; C3H7COC02H;
C5H802, CH3COCHO, ethonAn~i~ acid, methyl glycolate, glyoxylic acid, phenyl glyoxylic acid, diethylene glycol ethers, methyl formate, isoamy] formate, 1.2-e~hAnPAiol~
dimethyl ether 1.2-ethanediol, ethylene nitrite, ethylene nitrate, ethylene acetate, ethyl ester formic acid, formic acid, glyoxal, glyceric acid, tetraethoxymethane, trieth~y hAnP, trl y tlane, oxalic acid, oxalic ester, oxalic acid dimethyl ester, oxalic acid dipropyl ester; phenols including 2 ,y~henol, 3-ethoxytoluene;
acetyl acetone, acetic acid a22hydrides, ethyl acetate, methyl acetate, me~hAnPAinl diacetate, amyl acetate, acetonyl acetate, ethanoic acid, 2~4-pont~Ainnp, me~hAnP~i nl diacetate, ethyl acetate, propanic acid, ethylene oxide, propylene oxide, 2 i nitrate, dinltrogen tetroxide, and like.
Applicant believes that ~ Js which have or become strong chelating agents in combustion are also desireable ECS candidates. C _I-ds having the following structure, and which perform ECS function, are desireable: R-OO, R-OO-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 ~LLu~Lu.a. R may be different, same, or multiples of itself. R may be 2(R), 3(R), 4(R), and wherein R may be a hydL~y~ carbethoxy, carbomethoxy, caronyldiocy, carboxy, w09s/33022 21 94 572 r~ c-7S8 ~

carbyl, ethoxalyl, ethoxy, ethylenedioxy, glycolyl, glyoxylyl, hydroxy, methoxy, methyl, et-h-yl~ propyl, butyl, pentyl, methylenedioxy, acetonyl, acetoxy, acetyl, alkyloxy, benzoxy, or benzoyl radical. Applicant's S preferred OH combustion ~nh~r- L ~L~ULULe is common to his alcohols, most notably methanol.
Appllcant also rocogni 7~ that certain duplication exists between various classes in this invention. For example, ECS chemistry may contain certain metals, certain metals may contain ECS chemistry and/or be propellant fuels, ect. It is expressly contemplated that such ~ will have multiple utility, and may, for ~uL~o~eb of this ~icclosllre~ ~ey e6ellL both the ' 1 1 ir and ECS
- _ ', as set forth herein.
Applicant expects a small number of ECS - ' will actually be commercially suitable and elicit optimum performance. It is additionally contemplated that certain ECS c - will be co-ECS ; ~- (e.g. co-solvents) and be re~uired to assist the ussage of one or more ECS
__ . Co-ECS ~c may also be co-solvents. For example, it may nPc~ccAry to increase flash point temper~LuLès~ reduce RVP, or reduce combustion t~ ~tuLe6 of certain high velocity ECS ~ul~ds by A~ ;ng a ECS
co-solvent (see below). It is also ~Ypected that certain 25 synergies exist between individual(s) or classes of ECS
~nh~nring their respective c~r~h;1;ty.

~ WO 95133022 2 1 9 4 5 7 2 ~ 758 The practice of this invention also contemplates ~mi~ing water and/or co-ECS _ ' by separate means, including separate fuel injection.
It i8 contemplated that mutual solvents may be e_ployed to dissolve non-soluble and semi-soluble ECS
~ into the intended fuel composition. However, it is preferred that ECS _ '- intended for liquid fuel application by fully soluble in such fuel5.

E le 14a A fuel soluble ECS ~ ' having a melting point of less than -50~C, -25~C -5~C, 0~C, 5~C, 10~C, and a boiling point not less than 40~C, 60~C, 75~C, 85~C, or greater.
It is also contemplated that certain r- '~nicAl structure will be required to either satisfactorily enhance an ECS _ _ ''s burning velocity and/or to reduce co_bustion t~ _ ~Luue aspects e.g. Pnh~n~Pd atomization.

r le 15 A post-iynition, ~L~ ~ ~ Lion composition containing a diffusion increasing amount of ECS, whereby combustion burning velocity is in~L

E le 16 A pre-ignition vapor composition containing a diffusion increasing amount of ECS, whereby a minimum flame propagation of 60 cm/sec is achieved by a maximum spark energy of 0.2 J, preferably 0.15, 0.10 or less mJ.

W0 95/33022 2 19 4 5 7 2 r.~ 5~0~758 ~

~34--r ~lc 17 The vapor composition of examples 15 and 16, wherein the diffusion increasing ECS vapor is derived from the de -~ition product of dimethyl carbonate.

r le 18 The composition of ~ le~ 15 and 16, wherein the composition is a combustion composition.

Thus, those elements, ECS _ __ '/ L~ wherein the above enhanced combustion ~LL~u~uLa exist, in high relative cuncel.LL~tions and/or which become intD 'iAte and/or initial/~re ~ ction and/or combustion ~LLuuLul~/product, ~Cp~CiAlly in the vapor charge and/or in the vapor of ~ assion and/or combustion, and which causes rapid diffusion of the flame front, and/or rapid diffusion of , Led vapors and/or otherwise accelerates and/or ; uv~s combustion are most preferred.
The higher the relative volume of onhAnr~A combustion structure as a percent of the volume of , - ' Led vapor fraction, the better.
Thu6, it is an ~mho~;r L of this invention to employ a sufficient amount of ~nhAnr~d combustion ~LLuuLuLa in the vapor fraction to increase the rate of diffusion. It is contemplated that the diffusion means of Applicant invention additionally inuuL~uLaLe separate laminar and/or turbulent burning velocity increasing means.

~ W095133022 2 1 94 572 P~ C-7~8 ECS ~ ds preferably should be soluble in the fuel composition to which it i8 added. However, di~yeL ~IlLs or other means, ;n~ Aing mutual solvents, may be employed.
Alternatively, insoluble or partially soluble ECS~
~ 5 may be employed in emulsions and/or by other means, inr~ ;ng by separate injection, and/or by hybrid means.
It is contemplated in the practice of this invention ECS _ need not contain ECS ~LuuLu.~, if their use or combination otherwise generates or causes to be generated ECS ~LL ~U~UL -_ in the - es~ion, ignition and/or combustion process. Thus, in the practice of this invention a - .ul.d, which ~nh~nr~ the formation of ECS in the combustion process is deemed to ~be an ECS _ Higher octane u~y~cn~Led ECS _ '- tend to improve ignition quality. ECS '- with higher latent heat~ of evaporation, which reduce~ ession, post ignition (pre-ignition) and/or reduce combustion t~ ~tUL~s, are particularly preferred.
r l~i~n~ or other combination, inrll~ing those 20 containing ECS, are also desireable, particularly those capable of causing vapor fraction droplets to explode or to explode outside the spray or to otherwise cause quick diffusion of the vapor fraction. Such non-limiting ECS
~ n ,_ '~ include water, methanol, hydLog~
25 peroxide, rape seed oil, and the like.
Thus, fuels containing water are contemplated, such as aqueous gasolines, diesels, jet aviation fuels, distillate fuels, and the like.

W095/33022 2 ~ 9 4 ~7 2 . ~ 'C7s8 Preferred ~cs c __ are relatively simple in molecular ~LLuuLuLc. In the case of liquid fuels, ECS
'~ that do not adversely increase the vapor pL~8~ULC
or flash point of the base fuel at ambient or operating temp~LuLuLcs are more preferred. Acceptable blpn~in7 vapor ~reS~uLeS range from 0.5 to about 50.0 psi. More desireable hlPn~ing vapor prcs~uLcs range from 0.5 to 15.0, 0.5 to 12.0, 0.5 to 10.0, 0.5 to 9.0, 0.5 to 8.0, 0.5 to 7.0 psi, or 0.5 to 6.0 psi, or 0.5 to 5.0 psi, or from 0.5 to 3.0, 0.5 to 1.5, 0.5 to 1.0 psi or less. Individual vapor ranges include 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.
Vapor ~Les~uLe and flash point t~ -~UL~S can be mitigated or controlled via practice set forth below.
It is preferred that ECS ~ employed directly (as opposed to for example separate injection) in liquid co-fuels do not adversely increase the flash point of such base fuels. In liquid fuel applications, ECS
having flash points of -10~F, 5~F, 10~F, 15~F, 20~F, 25~F, 30~F, 40~F, 50~F, 60~F, 70~F, 80~F or greater are acceptable.
In jet aviation and other applications, flash point t~ ~LULeS above 30~C, 38~C, 40~C, 60~C, 70~C, 80~C, 90~C, 100~C, 105~C, 110~C, 120~C, 130~C or greater, are acceptable.
However, like vapor pressure, an ECS ~ __ "5 propensity to reduce flash point temperatures may be mitigated or i ovcd by a~yLu~Liate means te.g. co-solvents, salts, co-fuel tailoring, ect.), which is contemplated in this ~ Wog~/3302~ 2 1 ~ 4 ~ 7 2 l~l/u~ 758 invention (see Mitigation Practice, below). Thus, the - ''s causal increase in burning velocity and/or rPdn~inn of combustion temperature must be weighted cost of flash point and vapor ~Laa~u~ c ts attributed to mitigation means.
ECS - '-, which are non _oLL~sive andtor which do not adversely effect seals or elastomers are preferred.
However, corrosion inhibitors are contemplated, if nPcP~Ary. For an example, a suitable inhibitor is "DCl 11"
available from Du Pont. It is contemplated that this inhibitor should be used at the approximate c~ cl.LL-tions of 20 to 30 ppm.
Preferred ECS o A '- employed in liquid fuels ~hould have low melting points, below 32~F and preferably below -0~F, or more preferably below -40~F or below -50~F, and most preferably below -80~F. Lower tempa~tuL~s are also preferred. However, t~ u~c reducing additives such as ethylene glycol ~ hyl ether may be employed, if nP~ y. Again, the ECS _ ''s cau~al increase in burning velocity and/or reduction of combustion temperature must be weighted against less than desireable melting points.
It is preferred, though not required, that the ECS
' not be toxic, or at least not highly toxic, or associated with adverse toxicity. It is also preferred that the _ ' be ~, -hlP at low t~ ~uLa6, have suitable ignition quality, and be thPrr-lly stable as a fuel Woss/33o22 2 1 94 572 P~l/u~ 7~8 ~

additive, although additive~ to correct poor thermal stability may be employed.
ECS ~ ds need not contain oxygen. However, ECS
~ containing oxygen are preferred. Those containing at least 5%, 10%, 15%, 20%, 25%, 30~, 35%, 40%, 45%, or 50%
or more oxygen by weight are desireable. Oxygen cu..ce..~L~Lions greater than 25% by weight are preferred.
Most preferred are greater than 40% cu..c~,.LL~tion6.
The amount of oxygen introduced into the system of critical import in advanced high velocity applications. It is contemplated that higher velocity, higher oxygen containing ECS ~ _ ~-, particularly those with high latent heats of vaporization, represent the more preferred u _ - in advanced applications.
In the case of preferred metallic usage, it is noted the nucleus of Applicant's invention resides in vapor phase combustion, ~r~s~llLing the hub to which the many fuel spokes which are attached.

Example 1~_ A method of creating vapor phase combustion, said method comprising: vaporizing or injecting a fuel of an nverage particle size not ~rDe~;ng 70, 60, 50, 40, 30, or less, microns under suitable ~LeS~UL~ into an air breathing combustion system; said fuel vapor solely comprised of at least one fuel soluble non-leaded metallic whose oxide's heat of formation is negative and exceeds about -200,000, -225,000, -250,000, -275,000, -300,000, -325,000 or -350,000 ~ w095/33022 21 94572 .~ .C:7~8 gr calories/mole, and at least one ECS . __ ' having latent heat of evaporation PYnePr77ng about 150, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 240, 250 btu/lb, or greater, @ 60~F and a laminar burning velocity PYnPPn7;ng 40, 42, 43, 44, 45, 46, 47, 48, 49, 50, 52, 54, 56, 58, 60 cm/sec; introducing sufficient r~ _ atuL~ to the vapor to cause ignition whereinafter ~ unburned vapor ~ into reactive high kinetic energy free radicals; diffusing said ra,dicals ahead of the flame front containing said metallic; wherein lnm;nn--~ vapor phase burning occurs; and/or whereupon combustion s~ C
oxide particles are formed in the submicron range.

r le l9a The composition of 19, additionally containing an oxidant.

'.~YA~le 20 A composition of matter comprising at lea~t one ECS
_ ' having a latent heat of vapuL~ion PY~ePr'in~ 200 btu/lb Q 60~F and a laminar burning velocity ~Y~Per7;ng 48 cm/sec, and a combustion improving amount of at lea6t one fuel soluble high heating value non-leaded metallic whose t oxide's heat of formation is negative and exceeds about -200,000 or -350,000 gr calories/mole, said metal or metallic containing _ _ ', i8 sPl P~t~'7 from the metals consisting of aluminum, boron, bromine, bismuth, beryllium, calcium, cesium, u~ ;nm, cobalt, copper, francium, _ _ _ _ _ _ W095/33022 ' 21 94572 r~ r~7~8 gallium, g~rr-nillm~ iodine, iron, indium, lithium, ~-gn~ r~ n~ce~ molybden, nickel, niobium, rh~crh~rus, potassium, pallium, rubibidium, sodium, tin, zinc, praseodymium, rhenium, salane, vanadium, and mixture;
said metallic fuel characterized as capable of (vapor phase) combustion at reduced t~ ~Lul~ having increased power generation capacity.

r le 21 The composition of Example 20, additionally comprising a substantial majority, majority, substantial minority, or minority of at least one co-fuel; said combination characterized as having latent heat o~ vaporization and burning velocity greater than co-fuel alone; whereby combustion t~ _ ~LuLe of, '-in~ fuel i8 reduced at least 5~F, 10~F, 20~F, 30~F, 40~F, 50~F, 60~F, 70~F, 80~F, 90~F, 100~F, 120~F, 140~F, 150~F, 160~F, 175~F, or lower, ed to co-fuel alone.

r le 22 The method of 19, wherein at least one oxygenated ECS
_ _ ' is contained in the fuel vapor, and wherein the u..vu~u,ized fuel's latent heat of vaporization exceeds 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, or 38 kJ mol at its boiling temperature, not to exceed about 40~C, 60~C, 70~C, 80~C, 90~C, 95~C, 100~C, 105~C, 110~C, 115~C, 120~C, 130~C, 140~C, 150~C.

~ W0 95133022 2 l 9 4 ~ 7 2 . ~ '0~7!!i8 E le 23 The method of Example 19, wherein the metallic vapor is derived from a - llic ' having a high heating value e~ee~;ng 4,000, 4,500, 5,000, 5,500, 6,000, 6,500, 7,000, 7,500, 8,000, 8,500, 9,000, 9,500, 10,000, 10,500, 11,000, 11,500, 12,000, 12,500, 13,000, 13,500, 14,000, 14,500, 15,000, 15,500, 16,000, 16,500, 17,000 Kcal/kg, selecte~ from the metals group consisting of aluminum, boron, bromine, bismuth, beryllium, calcium, cesium, chromium, cobalt, copper, francium, gallium, gerr-n;llm, iodine, iron, indium, lithium, magnesium, r-nqAn~ce, molybden, nickel, niobium, rhnsrl-nrus, potassium, pallium, rl~h;h;~ sodium, tin, zinc, pI -- 'y~ium, rhenium, ~alane, vanadium, and mixture.
~xam~ple 24 The method of 21, wherein the ~L _ .- ' Lion vapor is a product derived from dimethyl carbonate and a cyclomatic r~ngAneRe _ and wherein the ratio of dimethyl carbonate to organo r~n~An~e is less than 2,500 parts to one.

Example 25 The methods of 19-24, wherein the pre-ignition vapor is exclusively a combination of an ECS _ __ ' (preferably DMC) and at least one organo - ng~n~e C ,_ ' (referrably MMT), whereby the parts ratio of DMC to r-ng~n~ce, range8 from those equal to or less than 100,000:1 to 1:1, 10,000:1 _ _ _ _ _ _ _ _ W09~330~ 2 l q4 572 P~ .;758 ~

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; and 15:1.
Individual cullcenLLations include 2,000:1, 1750:1, 1550:1, 1250:1, 1050:1, 900:1, 800:1, 750:1, 650:1, 550:1, 500:1, 450:1, 350:1, 300:1, 250:1, 200:1, 150:1, 125:1, 100:1, 85:1, 75:1, 70:1, 65:1, 60:1, 55:1, 50:1, ~5:1, 40:1, 35:1, 30:1, 25:1, 20:1, 15:1, or 10:1. Rato's will vary ADpDnAing upon application.
In mo5t application'5 where DMC and MMT (and/or other organo - ll;c) are employed as neat ECS fuel, it is preferred that the DMC to metal ratio be le~s than 5,000:1, 4,500:1, 4,000:1, 3,500:1, 3,000:1, 2,500:1, 2,000:1, 1,500:1, 1,000:1, 950:1, 900:1, 850:1, 800:1, 750:1, 700:1, 650:1, 600:1, 550:1, 500:1, 450:1, 400:1, 350:1, 300:1, 250:1, 200:1, 150:1, 100:1, 90:1, 80:1, 75:1, 65:1, 60:1, 55:1, 50:1, 45:1, 40:1, 35:1, 30:1, 25:1, 20:1, or lower.

~Q--FIlDl c Applicant'5 co-fuels are generally carbnnlrDol~c or MydLuy~lluus or other __ ', or hydLuu~Lb~ reollc~ and/or other _ '~ ba8ed, inclllAing mixture, fuels capable of combustion. It is an express '~'i L of this invention that co-fuels may be employed a8 minority, substantial minority, majority, or 5Ubstantial majority ~ _ Ls of a ECS/co-fuel combination. The ratio of ECS to co-fuel may ~ Wos~33022 2 1 9 4 5 72 P~ 7~8 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, 1:100.
However, it is an express object of this invention to r-~im; 7e total ESC vapor in the vapor derived from the ECS/co-fuel combination. Thus, it i8 an object the ESC
vapor be a substantial minority or majoritarian -n~nt of any ECS/co-fuel combination, such that said ECS vapor, on a mass/volume basis, is a substantial minority or the majoritarian vapor.
However, in initial application of Applicant's invention it is contemplated the ECS fuel _ _ ent will represent the minority _ -nt, ultilizing existing fuels and distribution systems and combustion system.
It is preferred that Applicant's initial co_binations - (e.g. ECS fuel + co-fuel) meet all the particularities of ASTN, government and/or industry requirements regarding the co-fuel employed.
Thus, it is contemplated that resultant 'inpd fuel may need adjustment or reformulation to meet minimum ASTM
and/or u,~v~ L standards. For example, the ~;nPd fuel prior to reformulation may not meet heats of combustion requirements due to the lower heats of certain ECS
, 5c. Thus, additional high calorific material may need to be added. or, alternatively, the base co-fuel may be tailored so that the addition of ECS fuel does not avoid ASTM or guv~ L specifications.

W09~33022 2 1 9 4 ~ 7 2 ~ c~7~8 ~ rplic~nt's preferred co-fuels are generally those which enjoy high burning velocities, and higher latant heats of evaporatization than convention or current reformulated fuels. Applicant' 6 co-fuels typically enjoy low or e~L.~ -ly low combustion emissions.
For example, it is an express object of this invention that co-fuels be formulated to reduce to the maximum extent pn#~;hl~ ~m;~jnn~ of NOx, CO, C02, HC's, toxics, reactive ozone forming precursors, polynuculear aromatics, benzene, butadiene, formaldehyde, acetaldehyde, and/or any cancer causing or envi~ t~l harming substance, either now known or identified in the future.
It is also contemplated that ,appliant's co-fuel's be formulated to reduce particulate ~ ;nn~ to the greatest extent poR~;hl~. It is expressly contemplated that such fuels be formulated (or as a result of the addition of ECS
fuel and metallic) have particulate emissions of a particle size less than 10.0, 7.5, 6.0, 5.0, 3.0, 2.5, 2.0, 1.5, 1.0, 0.5 microns, or smaller, and/or reduced to the maximum extent po~;hl~
arpl; cAnt's co-fuels can contain reduced amounts of aromatics. ,~romatic volume cu..n~..L,~tions normally will range from or less than 55, 50, 45, 42, 40, 37, 35, 30, 27, 25, 20, 18, 17, 16, 15, 14, 13, 12, 10, 9, 8, 7, 6, 5, 4, 3, 1 volume percent, or aromatic free. ~anges less than 40, 35, 30, 27, 25, 23, 20, 19, 18 percent, or less, are more desireable.

~ w09sl33022 2 1 94 j 72 rc.,~ c~7s8 r ~e 26 The method of 19, wherein the ~L e c ' ction vapor additionally comprises a vapor derived from a co-fuel; said co-fuel characterized as being an alternative fuel, hyd~vgell, petroleum gas, liquefied petroleum gas, LPG-propane, LPG-butane, natural gas, natural gas liquids, methane, ethane, propane, n-butane, propan~ buLane mixture, fuel methanol, e.g. M 80, M 90, or M 85 fuelfi, fuel ethanol, biomas6 fuelfi, vPget~hle oil/ester fuels, rap seed methyl ester, soybean fatty acid esterfi, aqueous ~a~bv.levus fuels (inrln~ln7 aqueous gA~olin~ and diesels, e.g.
GnnnPrr n A-55/D-55), automotive gasolines (meeting ASTM
standards) aviation gasoline fuels, inrlllA;ng grade 80, grade 100, grade 10011 (meeting ASTM standards), conventional automotive gasolines, reformulated gasolines (meeting U.S. Clean Air Act ~ 211 (k), California Air ReE~u~es Board, Swedish/European EPEFET ~Landa~ds), low vapor ~L~6DULe glCOl in~s~ low sulfur/no-sulfur g~~olinps~
low octane gasolines, Talbert E-gasolines, alkylate or substantially alkylate fuels (inrlll~ing aviation and automotive gasolines), reformate fuelfi, fiubstantially reformate fuels, ~ooct~nP fuelfi, substantially i~oo~ P
fuels, paraffinic fuels, substantially paraffinic fuels (inrlll~ing optionally n-butane, isopentane, toluene, c7-clO
olefins), kerosine, wide range boiling fuels, gas turbine fuels, including No.0-GT, No.1-Gl', No.2-GT, No.3-GT, No.4-GT (meeting ASTM standards), aviation jet turbine fuel 1nrln~ing JP-4, JP-5, JP-7, JP-8, JP-9, JP-10, TS, Jet A-1, wosS/33o~ 2 l 9 4 5 7 2 ~ ,'C758 ~

Jet A, Jet B (meeting ASTM standards), military aviation gasolines, missile fuels, solid and liquid rocket fuels, , upellant, multipropellant fuels, hypergolic fuels, gas oil turbine-engine fuels, including grades 0-4, stratified-charged engine fuels, diesel fuels, innlnAing Grade low sulfur No. 1-D, Grade low sulfur No. 2-D, Grade No. 1-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 CARB or Swedish standards), low/no sulfur l~lLuLL~aLed low/no aromatic distillate fuels, toluene fuels, substantially toluene fuels, naptha fuels, subtantially naptha fuels, fuel oils, inrlllAing Grade 1, Grade 2, Grade 4 (light), Grade 4, Grade 5 (light), Grade 5 (heavy), Grade 6, heavy diesel fuels for marine or railroad, inrl~lA;ng those complying with IS0 DIS 8217 and BS MA 100 ~LandaLls, 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, and/or any fuel meeting ASTM
specifications, EPA certification standards, CARB or Swedish European standard, or meeting any industry and/or any yuv~L ~-L specification or regulation, present and future, including mixtures thereof; and optionally being ~ wo95/33022 2 1 9 4 5 72 ~ 7~

non-leaded and a low sulfur or no sulfur and/or low or no rhn~rhnrus containing fuel.

~YA le 27 The above example, where the combination composition ~rom which the vapor i8 derived is characterized as meeting all ASTM, yuv~ L, and industry specifications and standards of said co-fuel, including minimum distillation t~ _ ~LUL~, flash point, additive, vapor ~L~UL~, composition ranges, ingredients, emissions, heats of combustion, and the like as set forth in the specification.

Exa~le 28 The method 26, wherein latent heat of vaporization of said co-fuel was increased to an amount greater than 1.5~
of the unadjusted co-fuel prior to its combination with the ECS fuel.

Example 2~
The method 26, wherein pre combustion vapor additionally comprises at least one additive or detergent, gPlPcted from additives which control combustion chamber deposits, valve intake deposits, fuel injector deposits, or other additive as set forth in the specification.
~ 25 r le 30 The above examples, wherein the vapors from ~ d ECS/co-fuel powers a large engine under moderate to W095/33022 2 1 q ~ 5 7 2 . ~ 758 ~

moderately high to high load conditions, (e.g. 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, 2g.0, 30.0, or 35.0 ihp, ~ ;ng a 350 cubic inch engine displ~r ("CID") equivalent, or alternatively load of 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, 0.8, 0.84, 0.086, 0.10 ihp/cid); whereby fuel economy and/or thermal effiri~nries are increased over co-fuel operation alone by 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0% to 20.0%, or more (2.0% to 30.0% preferred).
It is an express . 'i ~ of Applicant's invention to operate combustion systems under load conditions, ~perlllly moderate to heavy load. ~rpl;r~nt~s invention is well suited for larger engines, under such load conditionr.

r le 31 A method of operating an engine, particularly larger engines, having disp~ equal to or greater than approximately 1.0, 1.5, 2.0, 3.0, 4.0, 4.5, 5.0, 5.7, 6.0, 6.5 (400 cubic inchs) 7.0, 8.0, 10.0, 12.0, 14.0, 15.0, 16.0, 17.0, 18.0, 20.0, 21.0, 22.0, 23.0, 24.0, 25.0, 26.0, 27.0, 28.0, 29.0, 30.0, 35.0, 40.0, 50.0, 60.0, 75.0, 100.0, 150.0, 200.0, 250.0, 300.0, 500.0, 1,000.0 cubic liters, and larger displnt ts; wherein said engine combusts a fuel containing a combustion improving amount of an ECS __ ' and suitable r '~ll;c~ and optionally combusting said fuel in combination with a co-fuel;

~ WO9S133022 2 1 9 4 5 72 P.~ 758 operating said engine under moderate to heavy load;
whereby combustion t ~Lu~es are reduced and/or fuel economy is ; ~Yed over co-fuel operation alone.

~ 5 Exa_~le 32 The method of Example 33a, wherein said engine is a heavy duty diesel (including Volvo TD 163 ES, TD 123 ES, TD
63 ES, D 12 engines), truck, locomotive, marine, heavy industrial, o} similar engine.

E le 33 The method of 19, 26, wherein said vapor additionally contains at least one vapor from an engine, ca~bu.èLv~
and/or induction/injection and/or combustion chamber deposit system rleAn;ng agent or detergent/dispersant (non-limiting examples include commercially available long-chain dibasic acid derivatives (e.g. 5llrcinimid~c such as HiTec 4450), long-chain aliphatic polyamines (e.g. polyisobutenyl polyamine), or long chain Mannich bases, and/or an ashless detergents, including a polyether amine, polyalkenyl amine, alkenyl surcinimi~e, poly ether amine, polyether amide amine, and mixture), and/or an an~irYi~nt~ d~ lc;fer, emulsifer corrosion inhibitor, aromatic solvent, scavenger, diluent oil, mutual solvent, metal deactivator, anti-static, dehazer, drag reducing, anti-foam, re-odorant, sfAh;li7~r, flow i VV~L, wax crystal modifier, cetane or octane ~nh~nr~r/ i _ vv_L, combustion i vvel, lubricity ;, vVeL additive, and/or mixture.

W095/33022 21 9 ~ 5~2 r~ 758 ~

r le 34 The method of example 19-27, wherein said vapor i8 combusted in an engine or combustor selected from group con6isting of rocket engine, 8rayton 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, ~olinplautomotive engines (non-limiting examples include low ~ ion, ultra low emission, variable-valve timing and lift, direct fuel injection, thL.e u_y 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 _ ession engine, spark-ignited internal combustion engine, lean burn, fast burn,external combustion Stirling or Rankine engine, Otto cycle engine, Miller cycle, two stoke, four stroke, or catalyst system.

T-~tent Heat of Va~orization It is an express object and : ;- L of this invention that Applicant's hydrocarbon co-fuels be constructed or formulated such they enjoy the maximum latent heats of vaporization ("LHV") practical, in light of enviI~ L~l and industry considerations.
It is a further ~ L that Applicant's co-fuels have individual LHV's higher than a normal unadjusted ~1 945~2 WO 95/33022 P~,11L.,,.,.r /a~

conventional or reformulated fuel (base line) at the date of this invention.
Applicant has dis~uv~I~d that threshold i ~ ~
will vary greatly ~p~n~ing upon the unadjusted base line 5fuel composition, type of fuel, and amount of LHV increase.
However, LEV increases of at least 0.5, 1.O, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 6.0~ 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 12.5, 15.0, 17.5, 20.0, 22.5, 25.0, 27.5, 30.0 percentage, or more, compared to unadjusted base line 10fuel (conv~nti~nAl or reformulated), are contemplated and desireable. For ~u~05a5 of comparing LHV differences, ~pplicAnt~5 base line fuels are ASTN, industry or equivalent fuels on date of this invention.
It is noted, that heavier fuels, e.g. diesel, jet 15aviation, gas turbine fuels, etc., often have lower average latent heats of evaporation, on a per weight basis, than do the lower r-lPc~ r weight gasolines. The higher the boiling point ~ ~LuLes of a fuel, typically the lower the average LHV per unit of weight.
20~p~n~ing upon the co-fuel, it is desireable that higher boiling~ Ls with latent heats of vaporization of less than approximately 40, 50, 60, 70, 80, 90, 100, 110, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180 btu/lb, or alternatively those less than 650, 700, 25750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 880, 900, 905, 910, 915, 920, 925 btu/gal, or alternatively, those lower than the equivalent average latent heat of vaporization for an unadjusted fuel, w09~33022 2 19 ~ 5 7 2 rcllu~ c-7~8 be reduced or removed from the fuel compo6ition, whereby average latent heat of vaporization for the new formulated fuel is greater than the unadjusted base line fuel.
As noted, Applicant has disco~Lad that optiminal reformulating of co-fuels not only inrlll~Q~ reduced end point and T-90 distillation t ~el~Lu.~s and modification to T-50 t~ LULeS, etc., together with fuel substitutent modification (e.g. reducing sulfur, aromatics, olefins, etc.), but additionally requires elevating average LEV, by at least 2.0~ (5%, 10~ more preferred), or more, over the unadjusted base line fuel. Absent simultAn~nucly elevating ~HV's, one may not acheive the full benefit of the invention.
Thus, in the practice of this invention reducing T-90 and end boiling temp~l~Lur.s additionally requires reducing or eliminating low LHV c ~ while similtaneously increasing high LHV c~ L~, such that resultant co-fuel enjoys QnhAn~d LHV. This is a significant depaILuL~ from the prior art.
For example, in hydrocarbons boiling between about 60~C
to approximately 120~C-160~C, Applicant has found aromatic hydrocarbons, alkenes, cyclanes, alkanes, in order of their ranking, to be preferred for purposes of achieving elevated IHV's. It is noted that as boiling t~ ~LUL~8 raise aromatic LHV's decline. Between approximately 70~C to about 130~C preference between alkenes and cyclanes are about the same. Between 160~C-180~C to approximately 300~C, bi-cyclic ~ wossl33o22 2 1 9 4 5 7 2 P~ . 758 hydrocarbons, aromatic hydrocarbons, and alkanes, in order of their ranking, are preferred.
Construation of fuels to acheive increased latent heats of vaporization should be t-~ ed by other factors, ~ 5 in~ln~in~ known hazardous r~ml~ion features of certain t~, minimum energy, calorific or heating requirements, buring velocity i ~. t, etc. For example, while benzene and certain xylenes have elevated LEV they are also known to be environmentally harmful. As set forth herein, the reduction of aromatics has certain other envil, - L~l 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.
Thus, A~p~n~ing upon the fuel composition and type of fuel, the tailoring/formulating of co-fuel compositions (e.g. absent ECS _ ' and/or ~ lic) to acheive Pnh~nrr~ LHV~s should be such that final formulated co-fuel be equal to or greater than approximately 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, or higher, btu/lb (or equivalent), or higher than the unadjusted base line fuel.
Applicant's co-fuels may also have latent heats of vaporization outside this range and be 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, 135, 140, 145, 150, 152, 153, ~1 94~72 W095/33022 1~ 758 155, 160, 165, 170, 175 BTU/lb, or greater, to be desireable. More preferred LHV's are equal to or in excess of 152, 155, 160, 165, 170 BTU/lb.
In the case of aviation gasolines latent heats of vaporization equal to or in exce~s of 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175 BTU/lb, or greater, are acceptable. More desireable are those PY~ee~ing 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, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150 BTU/lb, are acceptable. Those in excess of 110, 115, 120, 125, 130 BTU/lb, or more, are desireable.
In the case of jet aviation turbine fuels, LHV's should exceed 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165 BTU/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's LHV's should exceed 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 100, 105, 110, 115, 120, 125, 130, or more, BTU/lb. Those in excess of 100, 102, 110 BTU/lb are desireable.
In the construction or reformulation of Applicant's co-fuels and ~PpPn~ing upon the individual co-fuel, it is also desireable that the fuel be constructed so that its ~ wossl33o22 2 l 9 ~ 5 7 2 F~l/~ 3!'1~7~8 specific heat be equal to or yreater than 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52, 0.53, 0.54 BTU/lb~F, or greater. Those above 0.46 BTU/lb~F are preferred.
It is further desireable that the co-fuel be constructed such that its density is r~imi 7ed. For example, hydrocarbons boiling ~Erom about 60~C to about 110~C, cylcanes, alkenes, alkanes, in order of their ranking are preferred. From about 110~C to about 160~C, aromatic hydrocarbons are ranked the highest. From about 160~C to about 280~C, bi-cyclic hydrocarbons are ranked the highest.
It i5 expressly contemplated that formulating fuels with elevated latent heats of vaporization be an in~r~n~nt practice of this invention. However, the preferred practice of this invention cnnt~ ~te6 use of ECS structure and/or ~ llic~ in said new formulated co-fuels (conventional or reformulated).

Exam~le 35 - A hydL~LL~Il fuel composition, selected from the group of co-fuels ~i~closed above, comprising otherwise a conventional or reformulated composition thereof, whereby said fuel is additionally formulated/reformulated such that its latent heat of vaporization is at least 1%, 1.5%, 2%, 2.5%, 3~, 4%, 5%, 6%, 7%, 8%, or greater, compared to the unadjusted base fuel, and whereby said fuel is free of ECS
structure and/or metallic r ~ ~.

w09~33022 ' 2 ~ 9 4 5 7 2 ~ C7~8 r le 36 The example of 35, whereby the additionally reformulated hydLu~LLul- fuel composition is a conventional or reformulated gasoline having a latent of heat of vaporization of at least 0.5%, 1.0%, 1.5%. 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5~, 5.0%, 6.0%, 6.5%, 7.0%, 7.5%, 8.0%, or more, greater than an unadjusted conventional or reformulated composition at the date of this invention.

o r le 37 The example of 35, wherein the latent heat of vaporization of the additionally reformulated hydrocarbon composition is greater than original unadjusted base line composition, and wherein said additionally reformulated composition ("LHV ~nhAnred Co-fuel Composition") i8 blended with at least one ECS _ _ ' and/or a r ' 11; r~ whereby the resultant 'inPd composition meets ASTM, and/or industry standards.
Out side of cul.DLLu~Ling the fuel to meet minimum industry and ~uv~ L specifications, ArplicAnt's co-fuels should meet be Cull LL~Led to acheive maximum rP~117~hle latent heats of vaporization.
It is also an : ':'i r L of this invention to construct or formulate Applicant's co-fuels to acheive maximum flame velocity. Applicant has found that C2 to C6 acetylene hydLu~-bullD offer exceptional burning velocities. C4 to C6 olefins and de-olefins are attractive and offer good velocities. C3 cyclo paraffins and bPnPzPnP

~ wosst33o22 2 1 9 4 5 7 2 I~l/u~ 7s8 are also attractive. Less attractive are paraffins, C7 plu6 aromatic IlYdLO~LbUII~. Typically, the shorter the carbon chain length, C6, C5, C4, C3 or lower, the higher the burning velocity. In terms of carbon atoms of the same chain length, n-alkynes are preferred over n-alkenes over n-alkanes. Burning velocity of u,.~ Lu~ted hYdLO~LbUIIS is higher than saturated hydrocarbons of the same chain length. In ul.~LuL~ted hy~uu~Lulls with one ~aturated bond, burning velocity is decreased relative to the increase in molecular weight. Naphthenes and aromatic hydrocarbons have ~imilar rates as paraffins.

r le 38 A co-fuel having elevated latent heat of vaporation of at least 1%, 2%, 3~, 4%, 5%, 6%, 7%, 8%, 10%, 12%, or more, compared to unadjusted base fuel (employing fuels as of date of this Application), and a combustion improving ECS
' and/or - llir. ~LLU~LULe.
The preferred practice of formulating base fuels to increase their latent heats of vaporization is typically by removal of higher boiling material (e.g. 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 780, 800, 820, 830, 840, 850, 860, 870, 880, 890, 900, 905, 910, 915, 920, 925, 930, 940, 950, 970, 990, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350 btu/gal or more. It is ,,j:

W09~33022 2 1 ~ 4 5 7 2 ~ 758 o desireable that it be greater than 860, 880, 9oo, slo 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 i8 no upper limit to said base tco-fuel) composition's latent heat of vaporization, e i~ costs and other practical considerations will control.
It is contemplated that Applicant's co-fuels will have low and ~xLL~ -ly ~v~poL~Live emissions and thus low vapor pl~ ~:S=i UL ~8 .
It i5 also expressly contemplated that co-fuels contain nPc~sR~ry additives to reduce existing and/or control future combustion chamber, injector, induction system, and other fuel or combustion related deposits (see below), which directly interfere or inhibit combustion and/or cause ~mi ~ n degradation.
It is expressly contemplated that gasoline co-fuels contain elevated octane value (R+M)/2 over current convention fuels and that diesel fuels contain elevated cetane value over conventional fuels.
It is expressly contemplated that Applicant's co-fuels be formulated with greatest reductions, and if po~ihl~, be free of sulfur, benzene, polyml~llleAr aromatics, and any substance now known or later learned to be hazardous to the environment or human health. For example, limitations of di W095/33022 _59_ r~ o7s8 and tri aromatics and particulate natter causing and/or ozone forming aromatics are contemplated.
As noted above, Applicant's co-fuels contemplate distillation fractions, which reduce hazardous emissions and/or cancer causing It is generally contemplated that Applicant's co-fuels will be free of lead, rhnsrhnrous, sulfur, silicon and/or other harmful l l; C or non ~ d.

O MR~T.C ~RACTIC~
The preferred amount of metals contemplated by this invention re~uires that combustion be ; _ uved and/or pollutants reduced. Thus, A~p~n~;ng upon fuel composition, combustion system, combustion t ~Luues and combustion burning velocities, fuel injection factors, carbon, hydLuy~ oxygen contents, and the like, - L ll;cs and their respective ~u--~ L~Lions can vary greatly.
In the practice of Applicant's invention the metallic may itself be employed as a propellant or co ~L u~ellant.
Thus, the hy~ruy~ll content of the metallic and/or metallic containing fuel should be ~Y;m;zed, to the extent poR~;hle. Thus, metallic hydryls or other similar '-are desireable. HYdLOYell containing salts are al o desireable.
It is an express ~ho~; L of this invention that the combustion of the r ' 11; r be by means of vapor phase burning, e.g. wherein combustion does not take place on the . , . ~. -, woss/3302z 2 1 9 4 5 7 2 P~ 7S8 o surfnce of the metal, or on and/or within a molten layer of oxide covering the metal, typical of metallic combustion.
Applicant's vapor phase burning object i6 a very uni~ue aspect of Applicant's invention and characterized by high burning rate and the ~Les~ e of a luminous reaction zone that extends some distance from the metal's surface, where lli~ oxide particles are formed in the submicron range. Vapor phase burning is also characterized has being highly expansive combustion, which yield the thermal and other i ~ Ls of Applicant's invention.

Example 39 A method of combusting a r ' Al 1 ;C. wherein said method comprise6: introducing a sufficient amount of free radicals having ~nh~n~ed combustion ~LLUULULe into a combustion chamber; igniting and combusting a metal containing ~ __ ' in presence of said free radicals at ~ ~LULe below said metal' 8 oxide boiling point (and preferably above said metal or metallic "s boiling point);
combusting said metal at an accelerated burning rate wherein vapor phase burning occurs, evidenced by a brillant luminous reaction zone extending some distance from the metal's surface; wherein combustion ~ oxide particles are formed in the submicron range and/or remain in the gaseous state.

~ wos~l33o22 -61- ~1 q 4 5 72 Y~ c -758 r le 40 The method of example 39, wherein the formed metallic c oxides travel at high velocity and their particulate size is less than 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.05 microns, or less.
As a . ~ of ~ppl;rAnt~s invention, in order to achieve the above object, while not required, Applicant prefers the metal's oxide boiling point should be qreater than the boiling point of the metal. It is also preferred that the metal be introduced into the combustor as a vapor, however solid, atomized, or particulate i..L,~du~Lion is acceptable, 80 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.
- While not required, it is preferred that combustion t~ ~L4L~8 also be greater than the metal's (or metallic ~ .d~s) boiling t~ ~L4L~.
It has been found that higher weight oxygen c~..c~-.LL~tions in fuel compositions, particularly with higher c~-.c~--LL~tions of ~nhAnred combustion properties, permit higher acceptable metallic ~..c~.,LL~tions. Higher average ECS and/or co-fuel densities are often associated with higher acceptable - All;c c~nc~nfrations and higher heat release.
Applicant has found that higher Mn col,cenLL~tions generally translate into higher heat releases. But that is W095/33022 2 19 ~ 5 7 2 ra~ 758 O

not to ~ay there is no upper metallic limit. Fuel and engine combustion thermal dynamics and sto;~l L~y dictate upper -- Al 1 i r limits.
Metallic or r-nqAn~ce conaenLL~tions will vary substantially. non-limiting examples include those varying from 0.001 to over 7.50 grams Mn/gal, 0.001 to over 10.00 grams Mn/gal, 0.001 to over 15.00 grams Mn/gal, 0.001 to over 20.0 grams Mn/gal., 0.001 to over 30.00 grams/Nn/gal., 0.001 to over 50.00 grams/Mn/gal.or more. In certain application6, metallic cu~.ue..L.~Lions equal to or greater than 1/64, 1/32, 1/16, 1/4, 3/8, 1/2, 5/8, 3/4, 1, 1.5, 2.0, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 5.0, 7.5, 10, 15, 20, 25, 26, 27, 30, 33, 35, 40. 50, 55, 60.0, 65, 70, 80, and 90 grams may be desirable. In advance and/or rocket and/or propellant applications, metallic/Mn col.ael-LL~tions can be on the order of 100, 150, 200, 225, 250, 300, 400, 200 to 500, 600, 800 to 1000.0 grams/gal, ~p~c;Ally in hypergolic conditions. COnc~..LLdtions above these ranges are also contemplated.
~owever, r~nqAn~ce ranges for more traditional co-fuel applications will generally range from about 0.001 to about 5.00 grams Mn/gal, 0.001 to about 3.00 grams Mn/gal, 0.001 to about 2.00 grams Mn/gal, 0.001 to 1.00 grams Mn/gal, 0.001 to about 0.50 grams Mn/gal, 0.001 to 0.375 grams Nn/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.

~ WO~sl33022 21 94572 rc~ 758 Other metallic or r-n7~n~ee cunc~ r~Lions 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, 5~ 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, 4.5, 4.6, 4.7, 4.75, 4.875, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 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, 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 grams/gal.
In the case of diesel fuel applications r~ng In~ce culluellLL~tions greater than 1.0% by weight Or the fuel or ~ approximately 25 to 33 grams/gal are also contemplated. In gasolines, r-ng~n~ce cu.. ~-e.. LL~tions greater than 1/64, 1/32, or 1/16 gr/gal are desireable.
Ranges vary ~pen~ing upon the specific metallic, fuels, fuel weight, regulations, advance applications, =

wossl33o22 21 9 4 57 2 r~ 0~7s8 O

thP :yllamics, and the extent combustion systems are modified to enhance the accelerated low t~ _ ~tUL~ high energy nature of Applicant's invention.
Applicant's metals also include a full range of combustion catalysts in~ln~ing ferreous picrate, potassium salts, etc. For example, potassium salts are contemplated including those commercially r~rketed by Shell rhP
known as '~spArkAi~ or SpArk~P."
Such salts may be employed in fuels at 0.01, 0.4, 0.5, 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 c~l.c~llLr~tions less than 16.0 ppm metallic al60 contemplated. Other potassium salt or f~Ll~c~l.e ranges vary from 0.10 to 8.0, 4.0 to 9.0, 5.0 to 12.0, 6.0 to 13.0, 7.0 to 14.0, 8.0 to 15.0 ppm metal per million, 9.0 to 16.0, 10.0 to 20.0, 11.0 to 22.0, 12.0 to 25.0, 13.0 to 30.0, 14.0 to 40.0, 15.0 to 50.0, 16.0 to 60.0, 17.0 to 80.0, 18.0 to 100.0 parts r ' 11 i ~ or salt per million fuel.
In the application of Applicant's invention potassiu_ concentrations greater than 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0, 11.0, 12.0, 13.0, 14.0, 15.0, 16.0, 17.0, 18.0, 19.0, 20.0, 21.0, 22.0, 23.0, 24.0, 35.0, 26.0, 27.0, 28.0, 29.0, 30.0 ppm metal (or salt) are expressly contemplated and desireable, and ~PpPn~ing upon ECS chemistry and 25 -- -nirAl means employed, said potassium c~.-c~LL~tions or greater c~..cel-LL~tions can be employed absent adverse metallic oxide formation.

~ w095133022 -65- 2 1 ~ 4 5 7 2 . ~I/U~ 758 Netallic c~..c~.-LL~tions that m-Yimi 7e combustion velocity andlor the other objects of this invention are expressly contemplated.
In accordance with this invention, ~rrlicAnt's fuels will contain that amount of at least one Nn and/or other non-lead metallic, which constitutes a combustion i_proving amount consistent with the fuel composition, stoirhi~ y, EC chemisty, combustion sy~tem, eff i ciPnri DC and power desired, as well as legal and/or environmental crnCi~Ql-ations.
However, it is expressly contemplated that ~pplic~nt~s fuel may be absent any r llic at all, e.g. be metal free. That is, Applicant's invention, by accelerating burning velocity and/or reducing combustion t~ _ ~Lul~s by employing rhPmic~l and/or ~ h~nir~l means set forth herein, can be employed absent a metallic. That is, fuels which due to their combustion chemistry, and/or the operating conditions require re8ll~ti~nc in hazardous combustion emissions and/or i ~ Ls in fuel economy, may employ Applicant's invention absent ~ llicc.
It is an . ~ i- L of this invention to substitute or combine various metallics (e.g. mix them), including substituting or mixing similar and/or different ~ 5 of different _ ' groups or with the same or similar ~ _ ' group, or substituting or mlxing metals of the same group or subgroup, with each other or any other metallic _. ' group or metal. Thus, Applicant's invention contemplates substantial variation in metal 21 ~4~72 Woss/33022 ~ 'C758 o substitution and/or metal mixing, inr~ ng variation inmix ratios, mix ingredients, metal ~ ' , etc. See for example U.S. Patents 3,353,938; 3,718,444; 4,139,349.
Thus, it is expressly contemplated that any non-lead metal, or any non-lead organo - lli r, non-lead inorganic ~- ' ~lllr~ oAyyenate~ ~Lyano ~ ' llir or u~yy~llaLed inorganic-metallic ~ , and/or any of their related high heat r~leA~in~ and/or combustion improving metallic _ ___ '-, may be employed, mixed in varying proportions, and/or substituted for each other and/or replaced by any non-lead lliC or n~ allic (organic or inorganic) Al li~hing the object of this invention.

Exam~le 41 A combustion improving amount of a potassium salt and at least one uLy~no n~Anese ~ __ , together with a - fuel amount of at least one ECS ~ __ '.
It is contemplated that Applicant's metals may be blended with one or more metals or n~ in varying proportions to achieve synergistic ~ ~. in heat releases, burning velocity te.g. vapor phase burning), thermal efficiency, emission rP~n r~ion~ power generation, and the like.
Contemplated metallics include all non-lead metals and related _ __ '- whose combustion product has negative high heat of formation. As noted above, contemplated metals and/or metallic ~ '- should have high heats of combustion or heating values. Preferred negative heats of ~ wossl33o22 2 ? 9 4 5 7 2 ~ C-7s8 formation, for example of related metallic oxides, should exceed -100,000 to -150,000 gr calories/mole. ~ore preferred are those ~re~ing -200,000, -225,000, -250,000, -275,000, -300,000, -325,000 -350,000, - 400,000 gr ~ 5 calories/mole., and greater.
It desireable that the ele_ental metal be of a lower --lecnlAr weight, if practical. Acceptable molecular weights of Applicant's metals include those le6s than 36;
more acceptable include those less than 32; desireable molecular weights are those less than 26; 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.
Non-limiting 1PC of acceptable metals include Alnm;n-lm, boron, bromine, bismuth, beryllium, calcium, cesium, ~L~ illm, cobalt, copper, francium, gallium, germanium, iodine, iron, indium, lithium, r~gnDc m-ng~n~Fe, molybdenum, nickel, niobium, p~ u~, potassium, pallium, rnhihi~i , sodium, tin, zinc, praseodymium, rhenium, salane, V~nA~i Applicant's metals may be organo - lli rC o]~ inorganic _ ' .
Transition metals and metals found in lA, lB, 2A, 2B, 3B of the periodic table of elements and their cyclomatic inr]n~ing cyclopentadienyl carbonyls are expressly desireable. Their preparation is set forth in U.S. Patents Nos. 2,818,416, 3,127,351, 2,818,417, 2,839,552 (incuL~u~uted by reference). Applicant has found W095/33022 r~l,s~ u,~ o that methyl cyclopentadienyl tricarbonyl groups to be effective.
Cyclomatic ; ,-nn~c that include metals found in 4B, 5B, 6B, 7B, group 8 are also contemplated. Cyclomatic ~ _ ' containing more than one metals are contemplated.
Netals and their _ -c found in 3A of the Periodic Table of ~ , particularly boron and Alnm;nnm are expressly contemplated. Metals may be introduced into combustion with the ECS r ,_ ', or in a number of other ways, ;n~ ;ng via soluble _ '-, mutual dispersents/solvents, colloidal media, sllcr~nC;~n media, separate injection.
~rrl;c~nt believes that those r t ~ s or - ll;c _I~ds~ which are generally fuel soluble, having melting and boiling ranges compatible with liquid hydrocarbon combustion present the best immediate option.
Because Applicant's invention also contemplates gaseous and solid ECS '- and gaseous and solid co-fuels, metals and/or their related _ ' that are gaseous and/or solid are also contemplated.
Applicant generally prefers elemental metals of low lecul ~r weight and their ~ _ , although their heating value and the nature of any co-fuel and combustion system will also dictate choice. It is also preferred the combustion products of element and/or its - be environmentally friendly, e.g. low toxicity.
Applicant recognizes that there is a wide number of metallics available in the practice of instant invention.

~ w09sl~022 2 1 ~ 4 ~ 7 2 PCT~595/06758 Non-limiting examples include cyclopentadienyl methylcyclopentadienyl iron, f~LLocel.e, methylferrocene, and butA~ien~ iron tricarbonyl, butadiene iron tricarbonyl, dicyclopentadienyl iron and dicyclopentadienyl iron ~ 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~ of technetium, r-gn~ri--~, rhenium (see CAn~iAn Patent ~1073207.), diborane, tetraborane, hexaborane, and mixture. It is contemplated that organo and non Oly~lliC 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; '- of boron with 11YdLOY~II and lithium, pentaborane, decaborane, barazole, A~ in; bulohydLlde~ beryllium b~L~hydLide, lithium boI~hydLide, and mixtures thereof; light metals (CH3)3NBH(CH3)3, (CH3)2BI, Be(C2H5)2, C4H9B(OH)2, Al(BH4)2, Be(BH4)2, LiBH4, B(OC2H5)3, (BO)3(0CH3)3; Zn(CH3)2.
C __I.ds with multiple metals are expressly contemplated.
A preferred cyclomatic r-ngAnPre tricarbonyl is cyclopentadienyl ~ny-~ese tricarbonyl. A more preferred cyclomatic r-ngAn~ce tricarbonyl is methyl cyclopentadienyl ~-ngAn~e (NMT).
Non-limiting examples of acceptable substitutes include the alkenyl, aralkyl, aralkenyl, cycloalkyl, cycloalkenyl, aryl and alkenyl groups. Illustrative and W095/33022 2 1 ~ 4 5 7 2 F~ 75~ ~

other non-limiting examples of acceptable cyclomatic r9n~An~ce tricarbonyl antiknock ~ _ ~c include benzyleyelopentadienyl r-ngAn~ce tricarbonyl; 1.2-dipropyl 3-cyclohexylcyclopentadienyl rqnqAne~e tricarbonyl; 1.2-diphenylcyclopentadienyl r-ngAn~-~ tricarbonyl; 3-propenylienyl ~ J~r~pce tricarbonyl; 2-tolyindenyl r~ngAn~ce tricarbonyl; fluorenyl r-ngAn~ce tricarbonyl;
2.3.4.7 - propyflourentyl r~ngAn~ce tricarbonyl; 3-naphthylfluorenyl r-ngAn~ce tricarbonyl; 4.5.6.7-tetrahydroindenyl rqngAn~ce tricarbonyl; 3-3ethenyl-4, 7-dihydroindenyl rqng,qn~e tricarbonyl; 2-ethyl 3 (a-phenylethenyl) 4,5,6,7 tetrahydroindenyl r-ngAn~qce tricarbonyl; 3 - (a-cyclohexylenthenyl) -4.7 dihydroindenyl m-ngAn~ce tricarbonyl; 1,2,3,4,5,6,7,8 -octahydrofluorenyl r-"~A"~e tricarbonyl and the like.
Mixtures of such _ ~c can also be used. The above _I.ds can be generally prepared by methods that are known in the art.
Applicant has found potassium, rqg"~ci~, lithium, boran and their related high energy combustible -c to be particularly effective, and thus desireable.
Promoters such as Li and ~H are also contemplated, if circumstances require.
All such metallics, which advance the object of this invention and/or benefited from the practice of this invention, are a specific ~ '-'i L and contemplated in the claims hereto.

WO gS/33022 2 1 9 4 5 7 2 ~ r~7~8 Other non-limiting examples of non-lead metallics have been set forth in the specification. Additional non-limitlng examples of non-lead simple binary metallic c ~__rlds. Ternary and higher ~c ;n~lu~ing salts are ~ 5 contemplated. Salts of ternary hydroxy acids are contemplated. M~llir. perchlorates, sulfates, nitrates, carbonates, hydroxides, and others, are contemplated. Metal hydroxy '- are desireable. Contemplated salts also include acid salts containing rep~c~hl~ IlYdLUg~ll.
It is also within the scope and practice of this lnvention to employ u~yg~nated containing metallic ~-, in~ A;ng uAyu~-ated organo metallic _ '~.
It is an express ~ L to use - 11; n _ , _ ~-, which themselves are ECS _ ' . Non-limiting examples would include lithium, iodine, boron based ECS _ Contemplated oxygenated organo - ~ll;c - _ ':
include r ' lli~ methoxy, ~i- L y, trimethoxy, ethoxy, diethoxy, triethoxy, oxalate, ~L bunate, dicarbonate, tricarbonate, and similar ~L~U~LuL~, including mixture thereof. Such oxygenated organo-metallic _ '- may be employed with or absent additional ECS _ _ ' (e.g. DMC).
Thus, it is in the practice of this invention to employ oxygenate organo metallic -_ ' , in~ln~;ng ~ mixture, as neat fuel, with or absent additional ECS
~ _ ', with or absent a co-fuel, with or absent an additional metallic. It is within the practice of this invention to employ a - ~ll;c , _ ', including homologue or analogue having a ~LLUULULe or structure woss/33oz2 2 ' q4 57 2 ~ 758 0 ~imilar to Ml-OCH3, wherein M1 i8 a metallic having a valence of one or optionally having a valence greater than one, wherein the excess valence is occupied by a double bond oxygen and/or one or more methyl, hydLo~ , hydroxy, ethoxy, carbethoxy, ~CL~ Lhoxy, carbonyl, carbonyldioxy, carboxy, methyoxy, isonitro, isonitroso, methylenedioxyl radicals, and/or combination thereof; a metallic ~
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, hydL~y~ hydroxy, ethoxy, carbethoxy, CdL' '' y, carbonyl, carbonyldioxy, carboxy, methyoxy, isonltro, isonitroso, methyl~n~Ai~yl radicals, and/or combination thereof (an illustrative example in~lnA~c trimethyl borate tBH(OCH3)2]); a '~lliC __ ' having a structure of N3-tOCH3]3, wherein M3 is a T' ' llic 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, h~dLO~ ethoxy, carbethoxy, ~L} Lhoxy, carbonyl, carbonyldioxy, carboxy, '~ methyoxy, isonitro, isonitroso, methyl~n~ yyl radical or combination, thereof; a metallic , having a structure of M4-tOCH3]4, wherein M3 is a metallic having a valence of four or optionally having a valence greater than four wherein the excess valence are occl~pied by a single or double bond oxygen and/or by one or more methyl, h~dLOgeII~
hydroxy, ethoxy, carbethoxy, ~L1 '' Y, carbonyl, W09~3302~ P~ 7~8 carbonyldioxy, carboxy, methyoxy, isonitro, isonitroso,methylPn~inYyl radical or combination, thereof.
In the above examples, it is contemplated N1-M4 may contain one or multiple metals, being either the same or ~ 5 differing - ~llic Non-limiting example of said structure containing a multiple same metal includes tet thoxydiborine [tCH30)4B2].
Additional contemplated u~yy~nated u~y~no metallic ~Lu~LuLe in~ AP~ M1-O(C0)0-M2, wherein M1 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 M1 or M2 are substituted for a 6ingle or double bond oxygen, and/or by one or more methyl, h~1LOYe~I~ hydroxy, ethoxy, carbethoxy, 15 U~L~ 'hnxy, carbonyl, carbonyldioxy, carboxy, - yuAy, isonitro, isonitroso, methylPne~inYyl radical and/or combination thereof. M1 may be subsituted for single bond oxygen and/or by one or more methyl, l-ylL~gell~ hydroxy, ethoxy, carbethoxy, ~.} ' y" carbonyl, carbonyldioxy, carboxy, methyoxy, isonitro, isonitroso, or methylP~P~inYyl radical. Non-limiting examples include lithium carbonate [Li202(Co)]~ potassium carbonate [k202tC0)], sodium carbonate, cesium c~LLv..a~e, copper u~Lbun~te, rubidium ~ carbonate, lithium hylLOy~ll carbonate, sodium hY1LOg~II
25 carbonate, potas6ium }.ylLugen carbonate, potassium sodium ~-Lb~nate~ 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 W0~5/33022 2 1 9 ~ ~ 7 2 A ~~ s 0~758 o uLLu~LuL~ is contemplated wherein M'l and M'2 may be same or different metallic or wherein M'l or N'2 may be hydL~n or atom or radical (similar to those above) with one valence.
Other contemplated ULLU~LUL_ include metallic ketone, ester, alcohol, acid, and the like. Non-limiting examples include M'l-C-OH3, wherein N'l i6 one or more metallic comprising valence of 3; Other structure include M'l-C204, wherein M'l has a valence of 2. Nl-C-C-O-C-C-M2 ULLU~LUL~
is also contemplated wherein Ml and M2 may be same or different metallic or wherein M2 may be h~dL~Yen or atom of one valence.
It is highly preferred that said ~y~e.,ated organo-r ~ ll;C ~ _ '~ have the fuel properties set forth above including those for ECS ~ , e.g. higher heats of vaporization, high burning velocities, de_ sition characteristic te.g. dc ;tion at post ignition pre-combustion t~ ~Lu.~s into Pnh~nred combustion or free radicals ~LLU~LU ~), be thPrr-lly 6table at normal h~n~l;ng ~ ~LUL~8, etc.; and have high heat And energy releasing characteristics of metals, etc It is expressly contemplated that Applicant's r ' ~ c be incuL~L~ted into liaAuid fuel systems by mean6 of mutual solvents, as reaAuired. or altnernatively, may be introduced into the combustor/combustion chamber by seperate means, in~ ;ng li~i~;fication or gasification.
-~ W095/33022 2 1 q 4 5 7 2 r~a,~ 0~7s8 Applicant's neat oxygenated organo-metallics should be relatively ;no~ron~;ve to manufacture on a mass production basis.

MFr~NTf~at, Mra~ n It is contemplated that multiple r- ~ -n;~Al means will be employed to enhance burning velocity and/or reduce combustion t~ ~uL~B of Applicant's ECS based fuels. See ~ppl;cAnt~g International Application No. PCT/US95/02691, filed 3l2/95, for detailed description of - -n;~Al means contemplated herein.
The Application of these systems has the beneficial result of improving the combu3tion, om;~s;~n, thermal efficiency, fuel economy and other adv~ of ~rrl;cAnt's ECS fuels, beyond that which is intrinsic to the ECS fuel alone. Thus, these systems are synergistic, and i ~ s to ECS fuels go beyond those found for co-fuels alone.
It is ~n~ic;rated that the r- ~n;~Al means of Applicant's invention will vary d~ponAing upon the fuel and the combustion system contemplated. For example, neat ECS
fuel applications, having higher burning velocities, will inco~oL~Le differing -r;c~l means (e.g. higher ,- ~s~ion ratio), than co-fuels alone having a lower burning velocity in lower _ assion ratio combustion systems. Such system are characterized as increasing fuel economy, burning velocity and,/or reducing combustion t~ _ aLuLe of an ECS based fuel, greater than amount w095/33~22 2 1 9 4 5, 2 ~ s~-7s8 0 attributable to ECS based fuel alone in unmodified system.
Applicant appreciates the r--h~n;c~l means of this invention, which are synergistic to ECS based fuels, are many. Non-limiting examples include: fuel injection systems, ~p~ri~lly those capable of directing a fine uniform atomized spray of vapors at Pnh~nred dynamic flow rates and ~L~-U1eS at desirable angles into combustion chambers (combustors, burners, etc.) advanced evaporators, combustor designs PnhAnring combustion t~rhlllenre, higher combustion chamber inlet PLe6~ULeS (e.g. higher ~ssion ratios), high swirl rh; ' ~s, swirl combustors, spherical U ' LULD, divided rh; ' ~ combustors ~nh~nr;ng combustion efficiency, combustor design Pnh~nr;ng fuel-air mixing, combustion chamber (combustor) design Pnh~nring turbulence and/or fuel-air mixing, engine design r-Y;m;~ing ~- ession (inlet ~Le~ULe) advantages, engine design r-Y;r;~;ng increaged power combustion ~L~ (pt~S~ULe densities), engine design maximizing lower combustion t~ ~~LULe5~ and/or the other advantages of Applicant's invention.
Additional ~ n;r~l means, which may be employed and/or adapted, include lean burn systems, catalytic combustors/combustion systems, pre-mixed combustor, diffusion flame combustors, lean premixed pre-evaporizing ~5 combustor, ple ~v~puLizing premixing combustor, variable ~sion ratio engines, direct injection, direct injection stratified charge engines, ~IL~S ~_Y catalytic systems, high swirl ratio to lean-air ratio systems ~ WO95133022 2 1 9 1 ~ 7 2 P~ 7s8 (particularly during ignition to warm up), varible-valve timing technology (e.g. Honda VTEC tenhnnlogy)~ turbo-chargers, port fuel injection systems, tuned intake and exhaust, multiple valves, knock sensors, electronic feed-back control, and adaptive learning computer ~nhAnre~systems, after-cooling systems, ~L ~.ILL~lL combustion rh~ S, ~L~ . ' Lion , '- ~, re-matched inlet port swirl systems, reduced ~l~nrh i ng systems, reduced heat transfer systems, onh~nred fuel-air mixing systems, enhAnred spray atomizer kinetic energy systems, injector designs onhAnr;ng fuel-air mixing, water injection systems, computer ~nhAnred systems, combinations thereof, and the like.
In the practice of this invention lean-burn and/or fast burn combustion systems are desireable for ~uL~oses of onh~nrin~ ArplirAnt's object, particularly with advanced higher oxygen cnnt~ining fuels.
Mechanical systems employing combustion rh~ ~ D/combustorS~ which enhance turbulence are preferred. Non-limiting examples include tumble air motion systems, four valve pent roof combustion rhAr~ D, swirl combustion rh: ' D, indirect injection combustion rh~ '~ D, indirect injection swirl combustion rh: ' D, direct injection combustion chambers, and combustion chambers where , L~y, hole diameter, spray angle, compression ratio, and the like, act to enhance tnrhlllonre are preferred.

W09~l33022 2 1 9 ~ 5 7 2 P~ o Injection timing, ~uel metering, injection ~.es~u,G5, injection p~es~u e drop, nozzle design, inlet air temperatures, inlet air pLe~uLG, droplet size, velocity, ~.es~uLe and t ~LULG of injected droplets, and t combustion chamber ~ L y are among the influential ~actors in --Y;mi~in~ the benefits of ~pplic~nt~s invention, and are incuL~ Led as an express ~mhoAin L of this invention.
For example, by varying the nozzle angle, nozzle throat angle, nozzle jet spray centerline eccG.ILLicity~
spray radius (sphere radius~ in a ~1G C ~ Lion (swirl chamber), and by modifying injection timing, rate, duration, and the like, Applicant can m-Yi m i 7e the beneficial attributes of his invention. It is noted, g~~olinn, diesel fuel, jet turbine, gas oil turbine, fuel oil burner applications are expressly contemplated.
Thus, application, in~ln~;n7 the injection of highly atomized vapors into the combustion chamber/combustor, and the like, is a particularly desireable object of this invention, especially in turbine, diesel, and fuel oils.
Applicant contemplates a multiplicity of injection and atomization means. Differing fuels, fuel systems, combustion stems require differing injection, at i~ln7 systems, P~G~ULG8~ tempGL~LuLGs, and the like. Obviously, gasoline systems are different than, for example, Grade No.
4-6 fuel oils, which in the practice of this invention, require devices to atomize higher viscosities, and to inject them into burner or combustion cha_bers at greater WO95/33022 21 ~4572 r~ S758 pL~C~ule6. The gasoline sy6tems of Applicant invention contemplate injection manifold sy6tem6, wherea6 the diesel systems contemplate direct/indirect injection cylinder sy6tem6, etc.
With Applicant's high latent heat of vaporization fuels, a vacuum effect can occur when introducing the charge into a cylinder. CnnCp~lpntly~ in such conditions varying fuel injection P1~6DULe6~ in~lllAing low and very low ~Le~DuLe6 are contemplated.
Heavy die6el fuel, fuel oil, and related combustion sy6tem6 require higher amounts of pLeanuLe~ load sensing capability, and i ~v~d atomization features, when compared to gasoline systems. Jet aviation fuels have similar, yet differing requirememts and must, for example, ~nnc;~P~ fuel flow ranges of 50:1.
For example, in the practice of this invention, contemplated optimum gasoline fuel injection ~.~snuL~s are on the order of 1 to 5, 3 to 15, 5 to 20, 10 to 30, 15 to 45, 20 to 50, 25 ~o 70 psi.
Optimal diesel fuel injection p.~anuLes are on the order of 1500 to 30,000 p8i. 1~YPPCtP~ diesel injection ~L~S~UL~6 in the practice of this invention include 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10,000, 11,000, 12,000 to 18,000, 13,000 to 20,000, 14,000 to 25,000, 15,000 to 30,000, 17,000 to 30,000, 18,000 to 30,000, 18,000 to 35,000, 17,000 to 40,000 p6i. Lower injection pLe6DuL~6, due to the vacuum effect of Applicant'6 invention is al60 expressly contemplated.

t Woss/~o22 2 1 945~2 P~ 7~8 ~

~ xamples of Applicant' 8 non-limiting atomization systems include: single fluid and multifluid and/or fluid/gas atomizer jets, twin-fluid atomization, internal-mixing atomizers, ~L e~u~e atomizer, Y-jet atomizers, ~pinning disk systems, air sprays systems, spray atomizers, vaporizing systems, airblast atomizers, ;nrl~lAing plain-jet, prefilming, flat air blast atomizer , centrifugal injectors, rotary atomization, rotary wheel injection, ultrasonic, acoustic atomizers and other existing and/or future systems. Air blast atomizers are desireable in the preferred practice of this invention. Applicant's invention anticipates substantial i~LU~ in atomizer technology and in~uL~uL~tes said i _ u~. Ls herein.
Thus, it is a desired and an express ' ';- L of this invention that the particle (drop size) of injected or vaporized fuels in the combustion chamber be 1 to 70 microns. Preferable average particle sizes are 40 to 60 microns or less, more preferably from 30 to 50 microns, 20 to 40 microns, 5 to 30 microns, or less, inrl-l~ing 1 micron or submicron. There is no limitation to the r~ tion of vapor particle size so long as fuel vapor distribution characteristics are not adversely effected. Average particle sizes greater than 30, 40, 50, or 70 microns are acceptable if rapid diffusion of the vapor fraction occurs by other means, e.g. rh~micAl means, and/or if smaller particle sizes hinder proper fuel distribution characteristic. However, believes that certain applications ~ wo95/33022 -81- 21 q4572 r~ 7s8 will require a miminum particle size of not greater than 5, 10, 20, 30, 40, 50, or 60 microns.
Cold air induction systems, whereby air intake temperature are reduced are contemplated.
- 5 In the practice of heavy diesel fuels and _-ninn engines, higher injection ~L~b~L_b with retarded timing under full load conditions yields maximum mixing energy and ~nh~n~c the burning velocity object of Applicant's invention and i5 thus preferred.
It has been found that lower injection ~Le8~uL~8 for heavier diesels fuel applications under high speed, but light load conditions, tends to mi n i m i 7e over-mixing and redUCe8 hYdL~U~LL~ ;R8;~nC and is also a preferred practice.
Simultaneous fuel injection, by adequate means employing one or more injection systems te.g. a dual fuel injector), of similar or dissimilar physical state fuels, e.g. gas with a liquid, solid with a liquid, etc., is within the scope of this invention and expressly contemplated. Such application is expressly contemplated where the mixing of an ECS ' with a base co-fuel that may not be pocRihl~ prior to fuel injection and/or to optimize combustion, which best occurs via separate injection. Separate injection i_ also contemplated when fuel mixing can not be achieved by other means prior to fuel injection and/or combustion.
For example, the introduction of a liquid llydLou~Loll co-fuel and a gaseous ECS fuel, such as hydrogen into a W095133022 2 1 9 4 5 72 P~ .758 ~

combustion chamber or - ~UL would be accomplished by ~eparate injection, tailored to the specific characteristics of the fuel, and combustion system, d~iqn~d to ~Yiri 7e combustion burning velocity.
~hus, it i8 contemplated that diR~imilAr state fuel ingredients may be injected into a combustion system, simultAneo~ly, by singular and/or separate means.
Various mixing and injection combinations of ~rrl ir~nt~g BCS fuelg, co-fuels, are contemplated in the context of advanced fuel injection systems and methodology.
In the case of jet aviation turbine applications, rate tailoring for fuel flow adju~i L~ at altitude i8 9 --;A11Y preferred, as variations in combustion e~iciency occur due to lower ambient ~ ULU~.
T _ v~d pump line nozzle injection systems, unit injector systems, and/or other systems with high ~Las~u~a çArAhility, injection rate control, timing control, and/or other sensing controls are ~r~CiAlly desirable. Injection systems which can control injection ~ as-uLa, timing, rate metering, and/or combustion pL~58UL~5 are expressly contemplated.
In the practice of this invention, direct and indirect fuel injection systems are acceptable. However, direct injection systems are more desireable, ~per;~lly for diesel applications. Direct fuel injection systems are also more desireable in view of r-Yi~i7ing the higher burning velocities of ArplirAnt's ECS fuels.

~ woss~3u22 2 1 q 4 5 72 r~l" Cr758 - A further ~ nt, as noted above, is turbocharging and supercharging, which is highly preferred practice of this invention, PcpeciAlly in g~anlinP and diesel applications. Advanced air breathing, air pLe~ULe ~ 5 dp~a~aLUs, and/or tl-rbo~h~rge systems, increasing intake air pLas~uLas, operate in conjunction ERG systems, are particularly desireable, and Dub~ lly enhance the object of this invention.
Advanced cooling, after cooling, and/or coolant systems may also be employed. For example, combustion temperatures can be reduced by reductions in engine coolant temperatures, inlet air tempeLaLuLas reductions, and/or intake manifold heat inputs. All such means are within the scope of this invention.

r le 42 A method of reducing combustion tempeLa~uLas and/or increasing burning velocity employing ECS based fuels; said means in~ Ap~ use of at least one system selected from the group consisting advanced evaporators, combustor designs enhancing combustion turbulence, swirl or high swirl combustors or nh~ , spherical ~ UL~, divided chambers, PnhAnn~d engine design r~;m;~ing increased power combustion pLaSDULa (~ra~uLe densities), engine design maximizing lower combustion t~ a~uLe8, lean burn systems, catalytic combustors/combustion systems, pre-mixed combustor, diffusion flame combustors, lean premixed pre-evaporizing combustor, p~ e~apuLizing premixing combustor, WOgsl33022 ~ 7~8 o variable compression ratio engines, indirect injection methods, direct injection methods, direct injection stratified charge engines, tl~ac __y catalytic systems, high swirl ratio to lean-air ratio systems (particularly during ignition to warm up), varible-valve timing ~erhnnlogy ~e.g. Honda VT~C technology), LUL~O _I.argers, port fuel injection systems, tuned intake and exhaust, multiple valves, knock sensors, oxygen sensors, electronlc feed-back control, adaptive learning computer PnhAnr9~
systems, re _.IL~nt combustion rhiit~ D, ple ~ ' Lion chambers, re-matched inlet port swirl systems, reduced gu~h;ng sygtems, reduced heat transfer systems, Pnhi~nrQ~
fuel-air mixing systems (inrl-~;ng computer Pnhi~nned systems), Pnhi~nnP~ spray atomizer kinetic energy systems, injector designs Pnh~nr;ng fuel-air mixing, water injection systems, computer Pnhi~nred systems, fuel-air a~JuDi L
system (;nrln~;n~ computer enhance systems), lean-burn and/or fast burn combustion systems, tumble air motion systems, four valve pent roof combustion chambers, indirect injection combustors or rh~ S~ indirect injection swirl combustors or chambers, direct in~ection combustors or rh~ '~ D, turbulence Qnh~nning combustor or rhi ' ~L~
advanced cooling, after-cooling, coolant systems or air intake systems reducing inlet air t~, ~LUL~S, fuel injection systems (~crPcii~lly those capable of directing a fine uniform atomized spray of vapors at Pnh~nred dynamic flow rates and pressures at desirable angles into combustion chambers, combustors, and burners), and/or other , . . _ _ _ _ _ _ ~

WO 95133022 2 1 9 4 ~72 . ~./ L~, ., ~758 nic~l means set forth in the specification; said use characterized as increasing the burning velocity and/or reducing the combustion t~ rl~UUe of an ECS based fuel a amount greater than a co-fuel alone.
r le 43 In combination, a combustion improving fuel containing a high latent heat of vaporization oxygenated based ECS
' and a combustion improving amount of a metallic, a combustion system, and an exhaust gas recirculation (ERG) system, wherein said fuel is combusted and exhaust gases are recirculated back into the combustion system; whereby combustion t~ aLUL~ are reduced by at least 10, 20, 30, 40, 50, 100, 150, 200, 250, 300~F, or more.

E le 44 The examples of 43, wherein the ERG system is a closed loop system.

r le 45 The example of 43, wherein the fuel enjoys an increased burning velocity, and thermal PfficiPnry of the system is improved; whereby fuel economy is increased by at ; least 0.5%, 1.0%, 2.0%, 5.0%, 10~ or more.
Applicant's invention also contemplates use of exhaust after treatment systems, with non-limiting examples including ceramic liners, filters, trapg, trap-~Yifli7Pr8, regenerative particulate filters, and exhaust catalysts, _ _ _ _ _ _ _, . _ _ _ _ _ _ _ _ wos5/33o22 2 1 9 4 5 7 2 r ~11~ 758 o including three-way catalyst heated by direct electrical power or engine control or other means. The practice of this invention expressly contemplates employing ~;RRi~n control exhaust catalyst, ~RpeciAlly in automotive application.
In the practice of this invention it is contemplated, pe~i~lly in automotive applications to employ an exhaust emissions catalyst (three way catalysts, preferably monolithic catalysts) and to simultaneously employ an on board oxygen sensor, which in part measures the efficiency of the catalyst.
In sum, it is the combination of Applicant's advance combustion improving fuels with Appli~Ant~s mechanical and related systemR, which ~oge~hQr, r~ E~ significant 15 d~aL LULe from art.
Thus, it i6 an : --ir L of this invention to vary and/or adapt the above -- ~ni~Al meang to achieve the highest utility of this invention.

F~EL8 AND _ _ 8Y8TENB ~T"~T~y The combustors contemplated in the practice of this invention include g~ ic combustors (tubular, annular, tubo-annular, spherical), aerodynamic combustors (diffusion flame, premixing, staged, catalytic, and application combustors (aircraft, industrial, v~hicnl~r).
It is preferred in the practice of this invention to employ a diffusion flame combustor, wherein Applicant's combustion flames are further ~lu~a~ted by gaseous jet _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ~, W095/33022 -87- 21 94572 P~ C~758 diffusion, advanced droplet ~va~u~a~iOn, accelerated burning, and/or spray diffusion.
Thus, it is an : ' 'i to employ a diffusion flame combustor in combination with ECS fuels; whereby combustion ~ 5 P~icci~nc are i _ ~ved, combustion is accelerated and/or there is a reduction of combustion t~ _ aLULe8.
Applicant's invention i8 particularly applicable in turbine applications, Pcpeci~lly in aviation gas ~nrhinPc, industrial gas turbine6, marine gas turbines, and the like.
The physical state of fuels employed in this invention include a wide and narrow boiling range of liquid, semi-liquid, near-liquid, semi-solid, solid, and gaseous fuels, and mixture.
Applicant's neat fuel : ' 'i- (e.g. ECS
and metallic) has exceptional prop~lci~n and enviI~ 1 attributes, which are not limiting to internal combustion engines, aviation jet tllnhinps~ gas oil turbines, furnaces, burners, air breathing proplllci~n 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 combuEtors may be required to ~ e the combustion ~-Yi~i~ing and thermal dynamic ~ aspects of such neat application~.
It is also an r-~o~ of this invention to incoL~uLa~e advanced combustion systems, capable of better converting higher amounts of free energy under higher ~uLes and/or i ~v~d thermal effir-iPn~i~c resulting Wos~33022 2 1 9 4 572 P~ C7~8 ,~

from the usage of Arp~ nt'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 ~ ~ -;r L of this invention to incorporate such advanced combustion systems with Applicant's fuel6.
It is also an express ~ho~; L of Applicant's invention to employ an ECS ~ ', or mixture, solely by itself, with or without a combustion improving amount of non-lead metallic. However, it is a preferred : ' ';- L to employ an ECS ~ _ , or mixture, together with at least one non-leaded metallic ("ECS Fuel"). It is also an e - ; that Applicant's ECS fuel may contain at least one additional ~v;~ and/or at least one addition propellant or a co-fuel.
In co-fuel practice, e.g. where ECS fuel is h;n~d with hydruy~ll and/or a carknn~r~ fuel, RVP r~AI-~1 i~n i6 an express - ~ir L. However, finished fuels contemplated include those whose RVP ranges from 0.01 psi to 1000.0 psi, 2.0 psi to 200.0 p8i~ 2.0 psi to 40.0 psi, 1.0 pBi to 20.0 psi, 1.0 to 10.0, 1.0 to 8.0 psi, 1.0 psi to 7.5 psi, 1.0 to 7.0 psi, 1.0 to 6.5 psi, 1.0 to 6.0 psi, 1.0 to 3.0 p8i, 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.

~1 94572 woss/33022 P~~ 758 It i5 also an express ~ '_'i r L to optimize flash point in fuels that specify minimum flash point temperatures, e.g. aviation, turbine and marine applications, etc. It is also ~ntj~irated that co-solvent ~ 5 practice, tailoring of hydrocarbon fractions (so as to increase flash point), saltc, soaps, and other additives will be employed as reguired to reduce RVP and/or increase flash point. See ~itigation Practice below.
As noted, reduced concentrations of aromatics are expressly contemplated in Applicant's co-fuels. Reduced c~- -nl~tions of olefins are also contemplated.
Olefin ~I,cenL~tions of approximately or less than 40, 37, 35, 33, 32, 31, 30, 29, 28, 27, 26, 25, 24, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 volume percentage, or olefin free, are contemplated. Preferred olefins are absent C4 to C5 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.

r le 46 The method of Example 19, wherein a co-fuel is - employed so]~c~ed from a CARB reformulated diesel fuel, a Swedish/European EPEFET environmental class 1 or 2 diesel fuel, an EPA reformulated diesel fuel, present and future.
Thus, Applicant's invention ~ c a neat, essentially neat, majority neat ECS fuel, in~ Ainq W095l~022 2 l 9 4 5 7 2 --so--composition~ containing greater than 50% ECS __ '(S) by volume. It also ~ a substantial majority, a minority, or substantial minority application, e.g. greater than 0.5%, 1.0%, 1.5%, 1.8%, 2.0%, 2.7%, 3.0%, 3.5%, 3.7%, 4.0%, 5%, 10%, 15%, 20%, 25~, 30%, 40% by volume, or weight) of an ECS fuel, normally with a co-fuel ("Base Fuel or Co-Fuel").
In the practice of Applicant's invention, the most preferred neat ECS fuels containing Mn include dimethyl 10 ~,bvate, methanol, hydLuy~, methylal, methane hydrate, hydrazine, and mixtures thereof.
It i6 initially contemplated Applicant' 8 ECS fuels will likely be incv,~vl~ted in minority volumes into co-fuels cvnvuL~..Lly in the market.
However, with greater c- r~ Lions of ECS fuels as a volume percent of the finished fuel, combustion and P~ inn properties increase dramatically.
In the more specific co-fuel applications below, ~pplic~nt intends that his di~rlos--re of one co-fuel be ap~lv~Liately applied to any other co-fuel, where application is appropriate (e.g. anti-oxidants or detergents of one co-fuel class can be used with other co-fuel classes, etc.). Likewise, beneficial envi~ - L~l practice for one fuel may be applied to any other.
Co-fuels of Applicant's invention normally will be fuels that are as envi ~ Al ly attractive as pc~sihle, meeting regulatory standards, inrlll~ing California Air ~ WO 95/33022 2 t 9 ~ 5 7 2 . ~ 758 Resource6 Board standards, EPA 6tandard6, prsent and future.
Thus co-fuels will generally low in sulfur or be absent sulfur, low or absent carcin~g~nir polynuclear aromatics, low or absent lead, P1~O~UL~S~ benzene, toxics, and/or other known or to be dis~u~crad carcin~g~n~.
Co-fuels will be formulated (e.g. reformulated) to increase combustion burning velocities and reduce comhustion temperature to the maximum extent po~sihle. They will be additionally formulated to acheive maximum environmental advantage. Again practices of one class of fuels (e.g. reformulated gasolines~ may be applied in any other class of fuels (e.g. diesel, gas/oil turbine fuels, etc.) to advance the objects of this invention.

~3T AVIATION T~RBINE F~3L8 A~D R~3~AT13D T~RBINE 8Y8TEN8 This invention expressly contemplates jet aviation turbine fuel application and co-fuel application. Applicant anticipates wide application in a wide range of jet fuels, aviation turbine engine fuels, in~lnAing fuels for propulsion and lift engines, starters and ~nYili~ry units.
The practice of this invention expre~gly ~ ~oAie~
aviation turbine, resultant aviation turbine fuels (ECS
- fuel and co-fuel) or aviation turbine co-fuels, which meet ASTM D 1655 standards, in~lnAing Jet A, Jet A-l (a relatively high flash point di6tillate of the kerosine type), and Jet B-A (a relatively wide boiling range volatile distillate). Other jet turbine grades are woss/33022 2 ~ 9 4 5 7 2 PCT~S95106758 ~

contemplated, including those meeting IATA guidance manual specifications and military aviation turbine specifications, such as NIL-T-5624, MIL-T-83133, and MIL-P-87107. Thus, Applicant ir.~u~u~ates by reference the uas specifications of aviation and gas turbine fuel's incll~Ain~ ASTN 1655 Specifications and Chapter 2, "Gas Turbine Fuels," L. Gardner and R.B. Whyte, Desi~n of Nodern Tllnbine Combustors, ~rA~A~m;~- Press, 1990 (pages 81-227).
The aviation turbine fuels of this invention, except as otherwise specified herein, consist of blends of refined hydrocarbons derived from crude petroleum, natural gasoline, or blends thereof with synthetic hyl uu~LLul.D.
They are generally a mixture of hyl~uu~rbulls (i.e.
paraffins, cycloparafins, aromatics, and olefins, plus trace levels of h~ruat such as sulfur _ -) and blended from straight run distillate fractions, which have been subjected to some form of additional proc~sing.
Aviation turbine fuels, consisting of minor and major portions of ECS material, as disclosed herein are specifically contemplated.
Applicant's invention expressly contemplates gas turbines and air-breathing pr~p~ n systems. Such non-limiting systems include turbojet, LuLLu~Lu~, ducted fan, ram jet, scram jets, ducted jet, pulse jet systems, and their many variations. These systems are contemplated in the instant practice of aviation turbine fuels.
For example, non-limiting gas turbine configurations include basic, one intercooling, two intercooling, ~ wO9S/33~22 2 1 945 72 ~ s 7s8 isothermal intercooling, one reheating, two reheating, isothermal reheating, one intercooling and one reheating, two intercooling and two reheatin,g, isothermal intercooling and isothermal reheating, L egen~Lation, I ey~ L~tion with basic gas turbine, regeneration with one intercooling, ~ g~ L~tion with one reheating, regeneration with one intercooling and one interheating, L~gLll~L~tion with two intercooling and two reheating, and regeneration with isothermal intercooling and isothermal reheating.
10Non-limiting ~ 1~5 of "turbo jet" air breathing propulsion systems include: basic, intercooling, reheating, intercooling and reheating, after-burning, intercooling and reheating. Non-limiting examples of "turbo prop" systems include; basic, intercooling, reheating, intercooling and 15reheating, regeneration, intercooling and reheating with regeneration, basic ducted fan, intercooling and reheating ducted fan, ducted fan with afterburing, basic ram jet, scream jet, li~uid metal cycle nuclear turbo-jet, liquid metal cycle nuclear LuLLo pL~p, ducted rocket and the like.
20Arpl; c~nt has found that ram jet and pulse jet operation represent a particular]Ly preferred : ; ~ of this invention. Thus, Applicant incuL~L~tes by reference the thermal dynamics of the pulse jet. See, "Jet, Rocket, - Nuclear, Ion and Electric Propl~lRi~n: Theory and Design,"
25Edited and Authored by W.H.T. LOH, 1968, p 191.
The desired combustion chambers of Applicant's turbine combustors include tubular, tubo-annular, annular type, and spherical.

wogsl33022 21 9 4~72 r~ c-7s8 ~

Applicant's invention has particular application with the above turbine combustion configurations and systems in that it u..~ecLedly and significantly reduces the formation of free carbon in the primary combustion zone. It has also been found that the reduction of free carbon in the primary combustion zone, in turn reduces flame radiation, which in turn reduces combustion liner t~ _ ~LuLes. Thus, reducing liner heat loads and increases engine life.
Furthermore, Applicant's reduced combustion t~ ~LUL~8 are ~LL~ -ly useful for high altitude and high mach applications where extreme engine t~ ~LUL~S
limit the operation and design of the combustion system. It has been found that Applicant can reduce engine combustion t- _ ~LUL~S significantly, on the order of 25~F to 400~F, or more.

Exam~le 47 A method of operating hiqh altitude, high maoh or other jet engine exposed to high operating t~ ~Lu~
wherein said method comprises: Mixing an ECS fuel (containing an ECS __ ' and ~Lu~Liate metallic) in such proportions with an aviation co-fuel that combustion at high mach, exceeding 1.0, 1.5, 2.0, 2.25, 2.5, 2.75, 3.0, 3.25, 3.5, 3.75, 4.0, 4.25, 4.5, 4.75, 5.0, 5.25, 5.5, 5.75, 6.0, 6.25, 6.5 or higher mach, and/or 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, ~ W09~33022 2 1 9 4 5 7 2 ~ 7~8 150,000, 170,000, 200,000, 250,000, 300,000, 350,000 feet above sea level or higher a~titudes, is at reduced temperature; operating jet engine at said high mach and/or at high or extreme altitude; wherein engine and combustion t~ __L~Lu~ is reduced 25~f to 300~F, 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 more.
It has also been found that Applicant's invention increases useful work, thrust, engine thermal efficiency ~rom 0.5% to 2.0%, 0.5% to 5.0%, 1.0% to 10.0%, 5.0% to 20~, 10% to 40%, 25~ to 50%, 35% to 75~, or more, and d~penAing upon character and concentration of the ESC fuel, composition of the co-fuel, alld the specific engine operation.
~rpli~~nt~s invention, in the application of ~et turbines, also ha~ particular advantage in reducing hazardous exhaust co~r~ tion~ of C0, NOx and HC
~iRRion~s, which are typically associated with idle condition.
As noted above, problematic turbine coating r-ng~n~8~
oxides, which have in the past plagued the usage of r-ng~n~ge in turbine fuels are now quite u-le~e~Ledly controlled. ~rpliC~nt~s reduction of combustion t- ~LUL~8 also beneficially reduces the coating of other _ ' to turbine surfaces and reduces corrosion.
In the practice of this invention, a preferred rh~ic~l means employing an ECS _ _ ' comprises a _ _ _ _ _ W09~/33022 2 1 94 572 ~ 758 ~

combustion improving amount of dimethyl carbonate in combination with a combustion improving amount of a cyclomatic r-ngAnD~e tricarbonyl ' in a base aviation jet turbine fuel. It is preferred that the final combination fuel be Cull LL u~Led to meet minimal ASTM
~~pec;flc~tions, including fla6h point, pour point, thermal stability, distillation, aromatic, density, freezing point, viscosity, net heat of combustion, and the like.
The hydrocarbon portion of the turbine fuel composition (co-fuel) comprises paraffins, naphethenes, olefins, nnd aromatics in order of their preference.
It is contemplated that the oxygen derived from ECS
~ fuels will be incoL~L~ted into aviation turbine fuels in varying c~..cel.Ll~tions, with optimal amounts ~_p_n~Pnt upon average flight altitudes, speed, lirt/thrust requirements, combu6tion system configurations, combuOtion efricl_nri_~, base fuel hydrocarbon composition, r-ngAn~-q concentrations, and the like.
AA~llm~ ng an ECS oxygenated means of improving combustion, the L~_ ' ' ~2 weight pe~
c~l.cellLr~tion of the resultant fuel at sea level to 10,000 feet is from 0.1% to 5.0%, with 3.0% to 5.0% preferred; at 20,000 feet, the re: -n~~d 0~ weight pe,~llLdge 0.1% to 10.0~, with 3.0% to 8.0% being preferred; at 30,000 feet the ~ ~2 weight percentage concentration is from 0.1% to 16.0%, with 5.0% to 7.0% I~ and 5% to 16.0% preferred; at 40,000 feet the r~- ~'~' ~2 weight percentage c~llcel.LL~tion is from 0.1% to 30.0%, with 11.0%

~ WO9S/330~2 2 1 94 ~ 72 1~ U~ 758 to 30.0% preferred. Rr -n~d average ~2 weight peLc~lltage uu..uenLL~tion of the resultant fuel may greatly exceed the upper limit of 30.0% or more, particularly in adva--~d fuel applications, high or extreme high altitudes, with fuel mixes containing alternative oxidants.
R~ average ~2 weight puLue~ ge c ~ r~ atiOtl8 of aviation turbine compositions for general distribution, involving co-fuel application, is from about 0.01~ to about 50.0~, 1.0~ to about 40%, 1.0% to about 20%, 1% to 15~, 1%
to 7% oxygen by weight of resultant fuel. 2.0~ oxygen by weight is an acceptable collc~llLration. However, 4.5~ weight percent is an average preferred ~ ILr~tion. Specific weight peIce..L~y~s of 02, in co-fuel applications, will vary with any particular fuel, its combustion system, flash point cnnAi~rations, and operating conditions.
MAng~n-ee ~., e..LLations will range from o.ool grams to 10.0 grams per gallon for aviation jet turbine fuel.
However, cu.lu~l-LLa~ions subst~nt~ y above this range is anticipated in advanced minority, majority, and/or neat ECS
fuel applications. Hypergolic a]?plications also dictate higher cu--ù~llLLations of Mn.
It also appears the higher the altitude of operation, the greater the indicated cullcel.LLation levels of Nn.
Higher uoncenLLation level6 of r-ng~nr-~e are permissible with higher concentrations of oxygen in the composition. As noted, higher concentrations of Oxygen are also indicated at higher altitudes. For example, operating at approximately 40,000 to 50,000 feet above sea level, _ _ _ _ _ _ _ _ , W095/33022 2 1 9 ~ 5 7 2 F~ 758 O

acceptable Mn conce..LL~tions can range from about 0.001 to 4.00 grams/gal. At lower altitudes of approximately 5,000 to 20,000 feet above sea level, de6ireable Mn c~...e..LL~tions range from about 0.001 to 0.50 grams per gallon (those ranging from about 0.125 to 0.50 grams Mn/g being more desireable). However, c~ e..LLctions outside these ranges are expressly contemplated, ~cpec;~lly in more advance operations.
As in the practice of this invention else where, metallic and oxygen concel.LL~tions are det~rm; n~ by optimizing the combustion of the composition, in the operating environment of the system.

r le 48 An aviation jet turbine fuel meeting ASTM 1655 specification6, diisopropyl ether or dimethyl carbonate, and mixture, le~Lesel-Ling 0.5% to 4.5%, 1.0% to 2.0% oxygen weight percent of the composition, and 1/64 to 1/8 g/gal Mn of a cyclopentadienyl rsng~n~ce tricarbonyl ~ '.

le 4~
An aviation jet turbine fuel comprising 0.01% to 40.0%
by weight oxygen from DMC (more preferably 0.5% to 5.0%, 0.5% to 10.0%) and at least one ~sn~_n~gce - Alli~
le~Lese.. Ling 0.001 to 20.0 gr/gal (more preferably 0.01 to 7.5, 10.0 gr/gal, more preferably 0.1 to 3.0 gr/gal); said fuel having a total aromatic volume conce..LL~tion not ~gY~ 1ng 25% (22% or less more preferred), a maximum ~ WO95/33022 2 1 9 4 5 72 .~ 758 _99_ ~ulfur content not PY~eP~;ng 0.3 weight percent (preferably 0.2, 0.1, 0.02, or lower, or sulfur free), a maximum T-10 temperature of 205~C, a maximum final boiling point t~ ~tUl~ of 300~C (more preferably less than 290~C, 285~C, 280~C, 275~C, 270~C, 265~C), a minimum flash point of 38~C, a density of 775 to 840 at 15~C, kg/m3, a minimum freezing point of -40~c, a minimum net heat of combustion of 35.0, 36.0, 37.0, 38.0, 39.0, 40.0, 41.0, 42.0, 42.8, 43.0, 44.0 RJ/kg, a latent heat of vaporization PY~Pe~ing 90, 95, 100, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175 BTU/lb; whereby ~inPA fuel meets ASTM 1655 finichP~ fuel re~uirements for either Jet A, Jet A-1, or Jet B;

~x~amEl~ 5-~
A method of employing the fuel of Example 49, in a jet combustor, whereby said method is characterized as increasing the lift and/or operating range of jet employing said fuel, _ ~d to jet aviation co-fuel alone.
E le 51 A method employing the fuel of Example 49 above, wherein combustion occurs at an altitude in excess of 10,000 feet above sea level, whereby thermal, combustion efficiency or lift is i _ ~ved compared to co-fuel alone.

- 21 ~572 WO 95/33022 A ~, i / ~ . C 758 O

r le 52 A method employing fuel of Example 49, wherein inlet turbine t~ ~u,~ and ~L~6~ULe, and turbine outlet ~L~S~UL~ operate jet in excess of mach 3, 4, 5, or 6.

r le 53 An aviation jet turbine fuel meeting ASTM 1655 specifications comprising, dimethyl u~Lbu..~e, a flash point increasing co-solvent, jointly L~ e..Ling 0.5~ to 40.0% oxygen weight percent of the composition, and 0.001 to 5.0 g/gal Mn of a cyclopentadienyl r-ng~n~ce tricarbonyl , _ .

r le 54 Same as ~ c 49, except that fuel is combusted in an aviation jet engine operating at 5,000 feet altitude above sea level.

r le 55 Same as example 49, except the composition is combusted in an aviation jet engine which is operating at 10,000, 20,000 feet altitude above cea level with thermal or combustion efficiency improving at least 1%, 2%, 3%, 4%
or more.

r le 56 5ame as example 49, except dimethyl carbonate is in the composition at 25% oxygen weight percent and the ~ w095/33022 2 1 9 4 5 72 ~ lC-758 cyclopentadienyl r-ng~n~se tricarbonyl _ ' has a Mn weight in excess o~ 1.0 gr/gal.

E le S7 Same as example 49, except the composition i6 combusted in an aviation jet engine which is operating at 40,000 feet altitude above sea level.

E le 5~
The ~ of 49, wherein the dimethyl carbonate is in the composition at an oxygen weight of about 0.1 to about 3.0 percent.

E le 58a The example~ o~ 56, 58, wherein the composition contains a flash point increa~ing amount of tetraethylene glycol, triethylene glycol, co-solvent or salt.

E le 59 The ~ of 49, wherein said operation is at altitudes in excess of 60,000 feet above sea level, wherein 02 wt of DMC is 3.0~ to 15.0~ and metallic is a oonc~"LL~tion of 0.5 to 10.0 grams/gal; whereby engine - temperatures are by 10~F to 400~F, or more, over known aviation methods.

.. . . .

WO95r33022 2 1 9 4 572 ~ C~758 jo E le 60 A method of operating a high altitude jet engine comprising: mixing an aviation jet fuel with an ECS
L representing 0.01 to 30.0% oxygen by weight of the composition toqeth~ with a combustion improving amount of a high energy releasing metallic; operating said engine at altitude in excess of 40,000 feet, preferably 60,000 to 100,000 feet or more; exhausting combustor gases into inlet of a turbine; whereby gas inlet t ~Lu~ is reduced below 1200qK., 1150~X., 1100~., 1050qK., lOOOqK., 9SOqK., or at least by 0.5$ to 25.0% over best known me~hod for t~ ~-Ul~ reduction; and/or turbine inlet ~eS~ULe is increased over existing methods by 0.5S to 40.0%; and/or thermal efficiency is ; ~v~d by at least 0.5% to 20S, or more, over existing methods.

r le 61 An avlation jet turbine fuel meeting ASTM 1655 specifications containing an oAygen~Led ECS ', wherein resultant fuel composition contains 0.5 to 4.0%
oxygen weight percent, and at least one cyclopentadienyl rqngqn~ce tricarbonyl ' at 1/8 gr Mn/gal.

r le 62 In combination, an aviation jet turbine engine and a jet turbine fuel meeting AST~ 1655 specifications containing an oxygenated ECS ~, wherein resultant fuel composition contains 0.5 to 5.0% oxygen weight 2~ 94572 W0 9S133022 P~ 758 percent, and at least one cyclopentadienyl r-ng~n~e tricarbonyl compound at 1/8 gr Nn/gal, whereby the formation of free carbon in the primary combustion zone is reduced and inlet , ~LuLes are substantially reduced.

r le 63 The combination of example 62, whereln comlDustion temperatures are reduced, or liner heat loads are reduced and/or turbine engine life is extended.
Thus, it is an ~ L of this invention to employ Applicant' 8 advanced ECS based fuel in combination with advance combustors having ~horter combustor length to casing ~ tQ~ ratios than convention combustors; reduced specific fuel ~ _Lions with Bmaller ~i~ L~r casting;
~maller casing ~i; ters with lower PL~ULa losOes~ at higher combustion pt eS~ULeS; higher combustion PL~ OUL~
combustors absent in~L~ased turbine inlet or liner temp~L~LuLe3; reduced flame tubes sizes that do not sacrifice combustion efficiency, lift, or fuel economy; low ~L~UL~ lift combustors of reduced flame tubes sizes that do not sacrifice combustion efficiency, lift, or fuel economy; larger diameter combustor casings that enjoy 1 ~v~d lift; larqer diameter combustor casings with shorter flame tubes enjoying ; _ ~ved combustion efficiencies; reduced casing ~i~T' t~s absent increasing p~es~uLe losses; combustors having reduced pr~s~uL~ losses;
lower c _ eOsion ratio engines; lower _ ession ratio lift engines; higher ~33ion ratio engines, absent W095/330z2 2 1 9 4 572 ~ 758 jo adverse flame tube wall ~ atuLe increases (hence reducing film air cooling requirements); combustors wherein primary zone combustion efficiency is higher than conventional effiri~nrie~; combustors wherein primary sone is lean or for fuel weak combustion; and the like.

r le 64 In combination, an ECS based aviation jet turbine fuel and a jet engine, the combination characterized by: the combustion of said fuel in a low ~ es~La lift engine, wherein said engine's flame tube length has been decreased by at least 10~, absent impairing lift or combustion efficiency.

r le 65 In combination, an ECS based aviation jet turbine fuel and a jet engine, the combination characterized by: the combustion of said fuel in a high ~ssion engine, wherein said engine's turbine flame tube wall temperatures are reduced and thermal efficiency is increased by at least 5%.
It is an express ~ L of this invention to employ Applicant's combustion improving fuel compositions in combination with traditional or advanced aviation jet tur~ines combustors, which at high altitudes, inrlllA;ng those in excess of 40,000 feet, enjoy i ~.~d combustion effi~i~nries 5% or better, than the co-fuel operating at the same altitude and/or at sea level.

~ Wo9s/33022 2 1 9 4 ~ 7 2 1 _I/rJ~ ~ -758 It is an additional r~mho~ir L of this invention to reduce the total distance of the combustor's dilution zone, while simultaneously reducing the outlet stream t- _ aLuL-s. Thus, in the practice of this invention r ~ 5 desirable dilution zone length is equal to 1.5 to 2.0 times the flame tube width, ~p~ci~lly in engines intended for high altitude cruise. Other desireable dilution zone lengths are egual to 0.9 to 1.5, 1.2 to 1.6, 1.3 to 1.7, 1.4 to 1.6, times the flame tube width.
Thus, it is an : - -ir-nt of thi~ invention to employ combustors whose dilution zone length is 1.4 to 1.6 time6 the total flame tube width, ~hile at the same time improving combustion efficiencies at high altitudes.
Contemplated combustion effici~nries are greater than 2% at altitudes in excess Or 20,000 feet.
In order to prevent local da~age to turbine blades, it is a further '_~ir-nt of this invention to ~oll~LLu~L ECS
fuel and operate jet combustor such that the outlet stream t~ _ a~ULr S (turbine inlet t~ _ aLuLas) be less than 1200~K.
Thus it is a further : -'i L to operate such systems at turbine inlet temperatures no greater than approximately 1200~, 1100~, 1050~, 1000'~, 950~, 900~, 850~X, or less. It is al50 an : ' i L to operate said 6y~tem at t- _ a~u~dS below 800qR, or less, if practical.
However, to rqYimi~e the benefits of Arplic~qnt's invention, it is desireable that maximum outlet stream t _ a~ures of the combustor (e.g. maximum turbine entry _ _ _ _ _ _ _ WO 95/33022 2 1 9 ~ 5 7 2 ~ 7S8 ~i~

t~, ~LULeS) not exceed 1100~. It is also preferred that the average/mean gas f' _ ~LULe6 approximate the maximum turbine entry t-, ~LUL~, in order to maintain affective power out put of the engine.

E.xample 66 A method of reducing fipecific fuel ~nl ,Lion, comprising combusting an ECS fuel and/or an ECS plus co-fuel combination in an annular, tubular or tubo-annular combustor whose dilution zone length is about 1.5 times the flame tube width; whereby specific fuel ~ ~ion is reduced.

Exam~le 67 The method of example of 66, wherein annular combustor length to casing ~ is reduced with lift and/or fuel efficiency i ~v~d.

r le 68 The examples of 66, 67, wherein the ECS fuel comprises an majority ASTM aviation jet fuel and a minority comprised of dimethyl carbonate together with a combustion improving amount of at least one non-leaded -- -llic r le 71 The examples of 66, 67, wherein the combustor operates on a hydrocarbon fuel composition containing a majority fuel I -nt hydrocarbons and a minority comprising of 0 Woss/33022 2 1 9 4 ~ 7 2 r~l~u~. /a~

dimethyl ~L~IaLe and a combustion improving amount of at least one cyclomatic ~-ngAn~e tricarbonyl, wherein outlet ~ stream t~, ~Lur~8 are less than llO0~.

~ 5 Example 72 The examples of 66, 67, wherein the combustor operates on essentially a neat fuel composition comprising dimethyl carbonate and a combustion improving amount of at least one non-leaded metaliic or.

r le 73 The example of 72, wherein the fuel composition additionally comprises a commercial jet aviation fuel co-fuel.

E le 74 The ~ of 66, 72, wherein usable work is increased and combustor life is ~Yt~n~Ad by at least 10~.

r 1 e 75 The combustor of ~ _les 64, 74, wherein combustion efficienrie~ at altitudes in excess of 30,000 feet are at least 2i greater than current engines.

ExamDle 76 The combustor of ~ _le~ 74, 75, wherein pL~8~UL_~
realized and/or turbine rotational speeds achieved are at least 5~ to 20~ greater than existing engines.

_ WO g5/33022 2 1 q ~ 5 7 2 . ~ 'C 758 ~

TABI~ 1 r r- of Aviation lbrbine Fuel~
Jet A or ASTM Test Propeny Jet A-1 Jet B Method cn ~1 l l~JN
Acidiy, totai mg KOH/g ma~ 0.1 ... D3242 A}omadcs, vol % mal~ 22C 22C D1318 Suh~r, mercaptan, weight % max 0.003 0.003 D3227 Sulfur, total weight % max 03 0.3 D1266 or D1662 or D2622 or D4284 VOLATJLITY
Disdliadon i , , oC
10% recovered, temp max 205 ... D86 20% recovered, temp max ... 145 50% recovered, temp man repon 190 90% recovered, temp max repon 245 Fmai boiling point, temp max 300 ...
Disdlladon residue, % mal~ 1.5 1.6 Distiiiadon lois, % mas 1.6 L5 Flash point, ~C min 38 ._ D56 or D3828!
Density at 15OC, I~g/m~ 775 to 840 761 to 802 D1298 or D4052 Vapor pressure, 38OC, l~Pa max ... 21 D323 EI,U}DITY
Fhezing point, oC ma~ -40 Jet A~ -50~ D2388 ~7 Jet A-1~
Viscosity-20OC, mmG/sL ma~ 8.0 D445 C~ 1 l~N
Net heat of combusdon, MJ/~g mm 42.8G 42.8G D4529, D3338 or D4809 One of the foliowing . ~ shaii oe met:
(1) i numoer, or min 45 45 D1740 (2) Smol~e point, mm, or min 25 25 Di322 (3) Smol~e point, mm, and min 191' 19~' D1322 N .' 5, vol, % max 3 3 D1840 T P~l~'T~N
Copper strip, 2 h at 100~C max No. 1 No. 1 D130 SlABlLll'Y
Thermai:
Fiiter pressure drop, mm Hg max 25~ 25r D3241N
Tube deposit les~s than Code 3 Code 3 No Peacock or Abnormai Color Deposits CONTAMINANTS
Esistent gum, mg/100 mL max 7 7 D381 Water reacdon:
Interface radng max lb lb D1094 ADDITIV~ See 5.2 See 5.2 Electrical c ~,, pSlm D2524 21 9~572 V095/33022 . _ I / L~ 758 The rlr~tA; l~d description and practice of preparing Applicant's jet aviation turbine fuels of this invention are set forth in my _-n;r~n International Application No.
PCT/US95/02691, which is incu.~or~-~ed by reference.
~ 5 The fuel specifications of Applicant's jet aviation turbine fuels shall generally comport to requirements of TABLE 1.
As noted, it is desireable to construct Applicant's fuel to reduce combustion temperature as means for increasing LHV. Desired LHV of fuel after adjuDi ~ is equal to or above 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. Preferred IIHV's exceed 67, 68, 69, 70 (125 BTU/lb), 71, 72, 73, 74 cal/gr.
As noted, it i5 an '- i ~ that Applicant's resultant reformulated jet turbine fuel's latent heat of vaporization be higher than those provided by typical ASTN
standards.
It i8 an express i ~ to modify Jet A or Jet A-1 fuels to have acheive minimum ASTM freeze and Flash points, if required due to presence of ECS fuel.
The use of aromatics and other means, presented ~ herein, to modify distillation and volatility, while having certain applicability, are generally limited in the case of Jet A and Jet A-1 fuels. But, non-the-less may be applied in warranted circumstances.

W095l33022 2 1 9 4 5 7 ~ 758 ~

Illustrative example of Applicant' 6 ECS turbine aviation jet fuel combination iB as follows:
Properties Limits Limits Test Method Gravity, deg AFI37 57 ASTM D287 Distillation Temp., 10% ev-~vLatedmax 4000F
(204.4OC) 50% evaporated190.20C 4500F
(232.20C) End Point max 5720F
t3000C) Loss, % max 1.5 Residue, % max 1.5 Sulfur, ~ by weight max 0.30 ASTM D1266 captan Sulfur,max 0.005 ASTM D1323 by weight or D1219 (See Note 1) Net Heat of Combustion BTU/lb 18,400 min ASTM D240 J/Kg 42.8 x 10~ min Freezing Point, C max -40 Jèt A
tSee Note 2)-47 Jet A-l Reid Vapor Pressure, lb m 3 ASTM D323 Aromatic Content, 5.0-22 20 ASTM D1319 % by volume tSee Note 3) Burning Quantity Ll-~ir t~r # 45 min ASTM D1740 t5ee Note 4) Copper Strip Corrosion, Classification max 40 ASTM D130 Temp: lOOoC = o 2120F - 1.80 Time: 2 hrs.
Viscosity, Cs at -300F
t-34.40C) max 15 ASTM D445 Water Reaction, Volume Change, ml max 1 ASTM Dl094 Water Reaction, Interface Rating max 1-b A5TM Dl094 ECS Fuel/C
t02 wt~, dimethyl carbonate) 0.5-20.0% 0.5-5.0 CMT tg./gal) l/64-5.0 1/64-2.5 tContinued) W095133022 r "~ a~

Latent Heat of Vaporization (BTU/lb) min 130 125 ~ 5 Flash Point, ~C min 38 66 Laminar burning velocity cm/sec min 48 52 11~
Note 1. Mercaptan sulfur ~QtQrminAtion may be omitted provided Doctor test per ASTM D484 i8 c~n~l~rt and results are neqative.
1~
Note 2. The freezing point shall be at least 60C b_low the minimum engine fuel inlet temperature.
Note 3. May contain aromatic up to 25% by volume.
Note 4. Fuels will be acceptable provided they meet one of the following alternative requirements or combination of requirements:
-a. Smoke point of not less than 25 mm when d~tQrminQd per ASTM Method Dl322.
b. Smoke point of not less than 20 mm when detQrminQd per ASTM Nethod D1322 provided fuel does not contain more than 3.0 percent by volume of napthalene as ~Qt~rm1nQd per ASTM D1840.
c. Due to occasional difficulties meeting the reguirement of item b., minimum smoke point may be relaxed down to 18 mm, as nD~P- r y ~
when detQmminQd per ASTM method D1322, provided fuel does not contain more than 3.0 percent napthalene as detQrminQ~ per ASTM
Dl840.
ArplicAnt notes, that while aromatic have particular advantage in maintaining fuel stability and/or in modifying fuel volatility, their application in Jet A or Jet A-l fuels for ~uL~03es of modifying t~ aL4L~s are limited, because T-10 and end-boiling temperatures for said fuels vary only about 100~C. While adverse conditions generally associated with aromatic usage, e.g. free carbon formation, are largely controlled by the practice of this WO95133022 2 1 9 4 ~ 7 2 Ic~ ,C0758 ~

invention, such aromatics, otherwise tend to a~y.Qvate flame radiation, smoke, and erode elastomers.
Consequently, their usage to the extent possible, should be limited or avoided. However, it is an express ~ ~1 L to employ aromatics at cul.~el.LLations outside those preferred, while still achieving measurable reduction~ in flame radiation, emissions, etc.

~q In~RTN~ FUE~ OIL8 AND 8Y8~EVQ
Applicant' 5 invention expressly contemplates gas turbine fuel oils and co-fuel application of gas turbine fuel oils, and the like, including those meeting suitable requirements of industry, gas oil turbine manufactures, ASTM D 2880 standards, and the like. ASTN fuel specifications D 2880-92, D 396 and D 975 tinrlll~ing future editions), relevant prior specifications, related ASTM
standards, test methods, military, and international standards are incuL~uLated by reference. Applicant's ~ n International Application No. PCT/US95/02691, filed 3/2/95~ Bets forth Gas Turbine Oils and Systems and is incuL~uLQted herein by reference.
A principal object of this invention employing Applicant's solution is the i _uvc - L of gas oil turbine thermal efficiency, r~ductirn of harmful deposits, pollution, and control of corrosion on turbine blading.

~ W095133022 2 1 94572 J~ s :758 ~le 77 The method wherein an ~nhAnred combustion vapor is ~ co_busted in a gas oil turbine combustor; and is derived from DMC repre~nting 0.01% to 40.0% oYygen by wt in the fuel, at least one metallic in a ~"~nL~Lion of 0.001 to about 7.5 gr/gal, and a gas oil turbine co-fuel selected from No. 0-GT, No. l-GT, No. 2-GT, No. 3-GT or No. 4-GT gas turbine fuel oils; wherein , '~nod fuel is characterized as having a flash point of 38~C to 66~C, a minimum kinetic viscosity at 40~C ranging from 1.3 to 5.5 2mm/s (ASTM D
445), optionally a sulfur content not ~Y~e~ing 2500, 2000, 1500, 500, 400, 300, 200, 100, 50, 40, 20 ppm wt (or being sulfur free), optionally a T90 t~ ~LuLa reduced at least 20~C ed to unadjusted fuel, a bunsen laminar burning velocity of at least 32, 33, 34, 35, 36, 38, 40, 42, 43, 44 cm/sec, a latent heat of vaporization of at lea~t 80, 85, 90, 95, 100, 105, 110, 115 BTU/lb; whereby turbine inlet gas t~ _ ~t4~ is less than 650~C, 625~C, 600~C or 550~C., and/or whereby inlet pL~4'e is increased as compared to co-fuel alone (preferably by at least 2.0%, 3.0%, 4.0~ or more; optionally harmful deposits, pollution, and corrosion on turbine blading is additionally reduced/controlled; and optionally carbon formation is reduced in the primary ; co_bustion 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.

W09~l33022 2 1 q ~ 572 J~ 7~8 ~

e 78 The method of Example 77, wherein said combustor' 6 flame tube has a dilution zone length of approximately 1.4 to 1.6 times the total flame tube width.

EYample 7g A gas turbine fuel oil composition comprising a 0.01 to 30.0% oxygen by weight DMC and combustion improving amount of a r~ng~nP~e tricarbonyl or other non-leaded fuel soluble metallic polln~, and a majority portion of a ga6 oil turbine fuel, whereby resultant composition meets applicable ASTM D 2880, D 396, and D 975 ~L~nda~ds, present and future.

r le 80 The example of 77, wherein the cyclomatic r-ng~nD~e - __ ' iB present in the composition in an amount from about 0.0625 to 3.00 gram Mn/gal, with 0.25 to 1.50 g Mn/gal preferred, with 0.125 to 0.375 g Mn/gal also preferred; and wherein the oxygen content of the resultant fuel does not exceed 4.5% oxygen weight percent.

le 81 The composition of example 62, wherein said composition's end boiling point, T 90, and T-50 ~ _ ~LuLas are reduced at least 10~F or 50~F and latent heat of vaporization is increased, whereby combustion t~ _ ~LUL~S are reduced.

W09~330~ Fc~ a~

In the practice of this invention, different gas turbine fuels pL~pared to different specifications and sold under different names are acceptable. However, those that meet the requirements of fuels specified under ASTM
Specification D 2880, are preferred.
Desireable gas turbine co-fuels of this invention are ~, -, - mixtures of hydrocarbon oils, free of inorganic acid, and free of exces~ive amounts of solid or fibrous ~oreign matter, which would otherwise make f~u~..L
cle~ning of suitable strainers n~c~s~ry. It is preferred that all grades of turbine fuel oil remain h~ e~US in normal storage and not separate by gravity into light and heavy oil _ _ ~s outside the viscosity limits for the grade.
Applicant' 8 turbine fuel oils should be primarily hydL~ b~nO, but may include bio material and/or coal derivatives. It is also preferred that Applicant's co-fuel turbine fuel oils be free of contaminants. In the present context, contaminants are considered to be foreign materials that make the fuel less suitable or even unsuitable for the intended use. For preferred preparation of turbine co-fuels, see International Application No.
PCT/US95/02691.
The various grades of gas turbine fuel oil contemplated in Appl i r~nt~s invention shall conform to the limiting requirements shown in Table 2. The requirement for Grade No., l-GT and 2-GT conform in most respects to the CU~L~ ;ng Grade Nos. 1 and 2 fuels of ASTM

W095/33022 2 1 q 4 ~ 7 2 I~ 0758 ~

Specification D 396, and to Grade Nos. l-D and 2-D in ASTM
Specification D 975.
The viscosity range of Grade Nos. 3-GT and 4-GT fuel brackets the Grade Nos. 4, 5, and 6 of ASTM Specification D 396 and Grade No. 4-D of ASTM Specification D 975. It is the intent of this invention that fuels meeting ASTM
Specification D 396 and D 975 requirements may be employed.
Non-limiting ~ 1P~ of acceptable fuels include fuels meeting the requirements of Table 2.
~i~s~l Fu~l 0~1B A - 8Vs1 ~
As noted, this invention contemplates a wide range of diesel fuel oils and related system applications. Non-limiting examples of diesel co-fuels and resultant fuels, include, synthetic diesel, bio diesel (bio esters, soybean, e.g. C18 + fatty acid methyl esters, rap seed, see IFP
EsterFip process), etc., fuels meeting ASTM D 975 standards (inuuL~uLated by reference), industry, international specifications, including CA~3, EPA, European EPEFP
specifications, certification standards and/or regulations, present and future. See TABLE 3.

2~ 94572 Wo95/33022 1~ ,, 5.'/~-758 TABLE ;2 DETAILED FIFm l , '-''TS FOR GAS TURBIINE FUEL OILS AT TiME AND PLACE
OF CUSTODY TRANSFER TO USER~
ASTM Gr~laD
Property Test No. No. No. No. No.
MethodC O-GT 1-GT 2-GT 3-GT 4-GT
FLASH POINT D 93 F 38 1100~ 3a 1100) 55 1130~ 66 1150) - oC (oF) min WATER AND
SEDIMENT D 1798 0.05 0.05 0.05 1.0 1.0 % vol max DISTILLATION

oC (oF) 90% VOL. RECOVERED
min ... ... 282 ... ...
max ... 288 338 ... ...
KINEMATIC VISCOSITY
2 mm/of D 445 AT40OC (104OF) min G 1.3 1.9 5.5 5.5 max 2.4 4.1 ... ...
AT 100 o C (212 o F) max ... ... 50.0 50.0 RAMSBOTTOM
CARBON RESIDUE D 524 0.15 0.16 0.35 ... ...
on 10% DISTILLATION
RESIDUE
% mass, max ASH
% MASS, max D 482 0.01 0.01 0.01 0.03 ...
DENSITY at 15OC k~/m' max ... 850 876 ... ...
POUR POINTF D 97 ... -18 -6 ... ...
oC (oF) A To meet special operatino conditions, " of individual limitino - .
may be aoreed upon between purchaser, seller, and ~
' Gas turbines with waste heat recovery equipment may require fuel sulfur limits to 40 prevent cold and corrosion. Cr. :.u-- ' limits may also apply to fuel sulfur in selected areas in the United States and in other countries.
c The test methods indicated are the approved referee methods. Other acceptable methods are indicated in ô.1.
D No. O-GT includes naphtha, Jet B fuel and othar volatile h,-. . ~ Iiquids. No. 1-GT
c.,.. . ' in oeneral to ~, '' D 396 Grade No. 1 fuel and D 975 Grade 1-D diesel fuel in physical properties. No. 2-GT c~... ' in oeneral to '' D 396 No. 2 - fuel and D 975 Grade 2-D diesel fuel in physical properties. No. 3-GT and No. 4-GT
viscosity ranoe brackets " D 396 Grades No. 4, No. 5 (lioht), No. 5 (heavy), andNo. 6, and D 975 Grade No. 4-D diesel fuel in physical properties.
50 ~whentheflashpointisbelow38oc(loooF)orwhenkinemabcviscosityisbelowl~3 mm'/s at 40 o C (104 o F) or when both conditions exist, the turbine manufacturer should be consulted with respect to safe handlino and fuel system desion.
F For cold weather operation, the pour point should be specified 6 o C below the ambient ~ at which the turbine is to be operated except where fuel heatino facilities are 55 provided. When a pour point less than -18 o C is specified for Grade No. 2-GT, the minimum viscosity shall be 1.7 mm3/s and the minimum 9096 recovered i . _ shall be waived.

W09s/33022 21 ~4 572 r~ oc758 ~

r le 82 A bio diesel fuel composition comprising: 1.0% to 50%
by volume biodiesel (bio-esters, C18 + fatty acid methyl Qsters, rape seed esters, and the like), 1.0% to 95% by volume diesel fuel oil (conventional or LefuL l~ted)~
optionally 0.5% to 90% alkylate, 1.0% to 90.0% by volume at least one ECS ', and optionally a combustion improving amount of a - t~ ~; under the proviso that total volume of hio~;~cpl~ diesel fuel oil, alkylate, and ECS ' be equal to 100% of the composition's volume (less ll; r ~..c~.lLL~tion, if any).
Applicant's diesel fuels include Swedish Enviromental class 1 and 2 fuels, CARB reformulated fuels, and EPA
reformulated fuels, existing and future.
Non-limiting examples of diesel fuel engines contemplated in Applicant's invention include: indirect injection, i v._d indirect injection and advanced ignition assisted diesel engine systems, direct injection, ~uLLo _I-arge direct injection, existing and future advance swirl chamber engines, existing and future.
Applicant's invention also cont~ tes exhaust gas LLeai -~t via catalyst, trap, and/or other system.
It is an express : '--'i L of this invention that Applicant's fuel5 include future reformulated diesel fuels of the calibre to be defined either by industry or y~. L. A preferred : ~_'ir t are low/no sulfur, low/no aromatic l-yd-~L~eated diesel fuels, absent normally ~ w09~33022 PCT~S9SJ06758 associated lubricity problems facing similar or low sulphur fuels.
It is also an express : --i L to include lubricity additives in low/no sulfur fuels.
r le 83 A fuel composition comprising at least one ECS
_ _ ~ and a combustion improving amount of at least one metallic; a low/no sulfur and/or low/no aromatic reformulated diesel composition; and a lubricity additive;
wherein the gum ou~ lLr~Lion i6 approYimately 5.0, 4.5, 4.0, 3.5, 3.0, 2.5, 2.0, 1.5, 1.0, 0.5 mg/lOOml.

r le 84 The fuel composition of Example 83, additionally comprises combustion chamber, induction valve, or injector deposit control additive, or additive package.

Exam~le 85 The fuel composition of Example 83, wherein the dieael fuel has a sulfur content of 0.05 wt% or less, a color standard of less than 2, 1 under ASTM 1500, an aromatic c~ llLL~tion of 25%, 20%, 15%, 10%, or less, a gum ~o.lcellLL~Lion of 1.5 to 2.0, or less, mg/lOOml.
r ~ , .

TABI ~ 3 ASIM D g75 D~TAII~D K~ . POR D113SI~ PUI~ O~

ASTM Test Grade Low Grade Low Property Method~ Sulfur No. 1-D Sulfur No. 2-D Grade No. I-DC Grade No. 2-DC Grade No. 4 Dc Flash Point, ~C, min. D93 38 52 38 52 55 Water ~ Sediment, % vol, ma~L D1796 0.05 0.05 0.05 0.05 0.50 Distillation T . , ~C 90% % vol. D86 Recovered ~_ min 282D 282 ......... o ma~ 288 338 288 338 Kinematlc Viscosity, mm2/S at 40~C D445 ~
min 1.3 1.9 1.3 1.95.5 ~~
ma~ 2.4 4.1 2.4 4.124.0 Ash % mass, ma~ D482 0.01 0.01 0.01 0.01 0.10 Sulfur, % mass, ma~F D2622~ 0.05 0.05 ... ... ...
D129 . ... 0.50 0.50 2.00 r~
Copper strip corrosion rating ma~ 3 h D130 No.3 No3 No.3 No.3 ...
at 50~C
Cetane number, minG D613 40N 40N 40N 40N 30N
One of the following properties must be met:
(1) Cetane inde2c, min. D976~t 40 40 ... ... ...
(2) Aromaticity, % vol, ma~ D1319~ 35 35 ... ... ...
.

(conti~uod) DI~TAII~D h~U ' . ~ OR DILSEL l~[~L O~
,~
ASTM Test Grade Low Grade Low Property Method~ Sulfur No. l-D Sulfur No. 2-D Grade No. l-DC Grade No. 2-DC Grade No. 4-DC

aoud point, ~C, ma~L D25W 1 r r r ~ cubon resldue on 10% D524 0.15 0.35 0.15 0.35 ...
I - distillation residue, % mass, ma~
To meet spedal operating conditions, ~ of individual limiting ., may be agreed upon between purchaser, seller and The test methods indicated are the approved referee methods. Other acceptable methods are indicated in 4.1. ~
c Grades No. 1-D, No. 2-D und No. 4-D ue required to contain a suffident umount of 1,4-dialkyl amino - . ~ (blue dye) so its presence is visually ?
apparent.
D When 8 cloud poln: less l'u~ -12 ~ is sped-led, -.he minimum fiash poini shaii be 3X~C, the minimum viscoshy at iO' shall be 1.7 mm2/s and the minimum 90% r~
' recovered temperature shall be waived.
~ Otber sulfur limits c~n appb in selected ueas in the United States and in other countries.
P These test methods ue specified in a~R 40 Put 80.
G Where oetane number by Test Method D 613 is not availahle, Test Method D 4737 can be used as an A I ' '' n Low amblent i , as well as engine operation at high altitudes may require the use of fuets with higher oetane ratings.
I It is unrealistic to spedfy low temperature properties that will ensure satishctoq operadon at all ambient conditions. However, satisfactory operation should be achieved in most cases if the cloud point (or wa~ appearanoe point) is spedfied at 6~C above the tenth peroentile minimum ambient temperature for the area in which umbient i , for U.S. Iocations ue shown in Appendb~ X2. This ~uidanoe is generaL Some equipment designs or operation may allow higher or requirc lower cloud point fuels. Appropriate low temperature operability properties shoutd be agreed upon between the fuel supplier and purchaser for the intended use and eupected ambient i t Editorialb corrected.

W095/33022 2 1 9 ~ 572 P~ C/~758 O

Applicant'~ 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, 25, 20, 15, 10, 9, 8, 7, 6, 5, 2 ppm, or sulfur free. Preferred ~v..ce~,L~ions are 50 ppm or belcw.
Applicant's diesel co-fuels include those with low aromatic contents including those equal to or less than 60%, 50%, 47%, 45%, 40%, 35%, 30~, 28%, 25%, 22%, 20%, 18%, 15%, 12%, 10%, 7%. 6%, 5~, 4%, 3%, 2% by vol., or an aromatic free composition. Arrl;c~nt prefers that 2 and 3 ring plus aromatics be excluded to the extend feasible.
Preferred fuels should be nitrogen free.
Applicant's diesel fuel cetane number include those e~ual 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.
Applicant rero~ni 7~C that an upper limit exists, if cetane is achevied solely via cetane additive enh~nr~r(5).
It is desired that cetane be acheived via fuel formulation, to the extent pocsihle. Thus, the desired fuel subsitutents would include n-parafins, cycl~h~Y~n~ and benzene, in order of their prefernce. ~owever, benzene ~un~enLL~Lions should be strictly limited to less than 15, 10, 9, 8, 7, 6, 5.5, 5.4, 5.2, 5, 4.9, 4.5. 4.2, 4, 3.9, 3.7, 3.5, 3.5, 3, 2.5, 2, 1.5, 1.0, 0.5 volume percent (benzene free compositions are desireable), or limited to o W09~33022 2 1 9 4 ~ 7 2 r~ sc758 c~l.ce.lLL~Lions provided by regulation. Benzene concentrations of less than 5.0, 3.0, 2.5, 1.0, 0.5, 0.0 volume percent are preferred.
Polynuclear aromatics (PNA) should be reduced to maximum extent possible and not exceed 7.0, 6.0, 5.0, 4.0, 3.0, 2.5, 2.0, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.2, 0.02, 0.01, 0.001 weight percent.
PNA's less than 0.3 wt percent and/or compositions Qssentially free of polynuclear aromatics are most preferred.
API should equal to or exceed 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 41.1, 42, 43, 44, 45, 45.4, 46.0, 47, 48, 49, 50.0, 51.0, 52.0, 53.0, 54.0, 55.0, or greater.
Densities should range from 800-820 kg/m3. Densities outside this range are also desireable, ;n~ ing 780, 785, 790, 800, 805, 810, 815, 820, 825, 830, 840, 850 kg/mg3.
Substituent diesel fuel formulation, which operates to increase burning velocity and/or reduce combustion ~ ~LuLe is expressly contemplated, ~peci~lly those that operate to increase burning velocities 0.5%, 1.0%, 1.5S, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5%, 8.0%, 10%, 15~, 20%, or more, over the clear or unadjusted fuel.
Formulation that increases laminar bunsen flame speed to 39, 40, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, or greater, cm/sec is desired.
Similar formulation, which operates to reduce combustion t~ ~LULe i5 contemplated, e.g. formulation that increases latent heat of vaporization equal to or Wo9s/33022 2 l 9 4 5 7 2 r~ . C~7~8 o above 30, 35, 38, 40, 4z, 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, or greater, i5 desireable. It is an express ' ;r L that Applicant's diesel and diesel based compositions be constructed whereby latent heat of vaporization ("LHV") exceeds at least 40, 43, 45, 46, 50, 54 (100 BTU/lb), 56 cal/gram for heavy diesel, and 50, 53, 56, 59, 62, 64 (115 BTU/lb), 66, 68 cal/gram for light diesels.
As noted, it is an -- i L that Applicant's resultant reformulated fuel's latent heat of vaporization be higher than conventional or reformulated base diesel fuels, including low aromatic, low or now sulfur fuels, etc.
In the case of achieving maximum Dm;Cci~ reductions, an acceptable minimum IBp temperature of a reformulated diesel fuel i n~l nA~c 356~F and a 95~ distillation t~ ,lLu.a of 545~F to 563~F max.
r le 86 A method wherein said an ~nh~n~ed combustion vapor is combusted in a diesel engine; and is derived from DMC
representing 0.01~ to 10.0~ oxygen by wt in the fuel, at least one metallic in a conce,-L.~tion of 0.001 to about 2.5 gr/gal, a diesel co-fuel base; wherein ~ in~d fuel is characterized as optionally having sulfur content not greater than 250 ppm, 200 ppm, 150 ppm, 100 ppm, 75 ppm, 50 ppm, 40 ppm, 30 ppm, 20 ppm, 10 ppm, 5 ppm, or being sulfur free; density ranging from about 880 to 800 kg/m3; viscosity W09~33022 .~ J~758 ranging from 2.5 to 1.0 cSt at 40~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 (inclusive 3-ring + aromatics not to exceed 0.16 vol%); a T10 fraction temperature of about 190 to 230~C, a T50 fraction t~ _ a~ULe of about 220 to 280~C, and a T90 fraction of about 260 to 340~C, and cloud point ~ LULa of ~C -10, -28, or -32 (or 6~C above tenth percentile minimum ambient temperature); a bunsen laminar burning velocity of at least 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46 cm/sec, a latent heat of vaporization of at least 85, 90, 95, 90, 100, 105, 110, 115, 120 BTU/lb.

r le 87 A method where an ~nh~nred combustion vapor is combusted in a diesel engine; and is derived from DNC
asellLing 0.01% to 10.0% oxygen by wt in the fuel, at least one metallic in a concentration of 0.001 to about 2.5 gr/gal, a diesel co-fuel base; wherein ~ ;n~ fuel is characterized as having an API range of about 41.1 to 45.4, optionally a sulfur content not GY~e~Aing 300, 250, 200, 150, 100, 50, 40, 20, 10, 5 wt ppm or sulfur free, absent nltrogen, and an aromatic content ranging from 0 to 5%, 1 to 10%, 0 to 15%, 0 to 20%, 0 to 35% by volume, PNA vol% of 0.03, 0.02, or less, a Cetane index greater than 45, an IBP
of approximately 365~F, 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 _ _ _ _ _ _ _ _ , . . .

W095/33022 2 1 9 ~ ~ 7 2 . ~ 7~8 o B~U/1~; 6aid method characterized in achieving reduced particulate emissions or ; ~v~d fuel economy compared to co-fuel alone.

r le 88 Low emission diesel fuels comprising; a maximum sulfur o~l.ce,.~L~Lion of no greater than 1100 ppm, 800 ppm, 440 ppm, 300 ppm, 250 ppm, 200 ppm, 150 ppm, 100 ppm, 50 ppm, 10 ppm, 5 ppm, or less (incl~ g sulfur free); density kg/m3 of 800, 805, 810, 814, 815, 839, 840, or higher;
viscosity of cSt at 40~C 1.8, 2.4, 2.5, or lower; cetane index of 46.2, 51.2, 52.1, 53.5, 57.5, 57.8, or higher;
aromatics by vol.~ 27.1, 2.45, 14.5, 1.1, 21.6, or lower, (including 3-ring + aromatics of 0.16, 0.02, or less); a distillation fraction where, ~C IBP ranges from 188.5, 213, 153, 215, 195, less than 180, and at T10 fraction t aLU~L range from 221, 215.5, 198, 227, 210, at T50 fraction t~ ~tuLeS range 272.5, 247.5, 249, 249, 227, and at T90 fraction temperatures range from 321, 272.5, less than 285, 336, 271, 273, and at FBP t~ ~LuLes ranges 348.5, 299, 360, 285, 300; cloud point ~C -10, -28, -32; CFPP ~C -11, -34, -34; caloric value, Mj/kg 42.8, 43.3, 43.3; optionally a burning velocity improving and/or combustion temperature reducing amount of an ECS ';
optionally a combustion improving amount of a metallic;
optionally a bunsen laminar burning velocity i8 at least 37, 40, 42, 45, 47 cm/sec, or higher (or alternatively, having a burning velocity higher than the base conventional 21 ~4572 Woss/33022 ' P~ 758 or r~ ted diesel); and ~herein the latent heat of vaporization is in excess of 80, 85, 90, 95, 100, 105, llO, 115, 120, 125, 130 btu/lb.

r le 89 A reformulated diesel fuel comprising a diesel composition, wherein API ranges 41.1 to 45.4, sulfur does not exceed 10 wt ppm (preferably sulfur free), absent nitrogen, aromatics at 20, 15, 10, 5.0% vol or less, PNA
vol% 0.02 or less (preferably PNA free), Cetane index 45, 47, 50, 55, an IBP of 365~F, a 95% fraction ~ 545~F, 525~F, 500~F, 475~F, or more; a combustion improving anount of a r-ng in~e or other r ~ 1 1 i E le 90 A liquid fuel comprising DMC at 0.01% to 5.0% by weight % oxygen (more preferably 0.5% to 2.5%) and at least one r-ng~r~-e metallic representing 0.001 to 2.8 gr/gal (preferably 0.065 to 1.0 gr/gal, most preferably 0.1 to 0.5 gr/gal), and a diesel co-fuel blse; wherein in~d 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/m3; viscosity ranging from 2.5 to 1.0 cSt at 40~C; cetane index of 40 to 60; an aromatic content by vol. ranging from approximately 0 to ~20.0%, (inclusive 3-ring + aromatics not PYr~ing 0.16 vol~); a T10 fraction t~ ~Lula of about 190 to 230~C, a T50 fraction t~ ~LuLa of about 220 to 280~C, and a T90 W09~33022 21 94 3 72 r~l~v~ 7~8 ~

fraction o~ about 260 to 340~C, and cloud point t~ ~LuLe of ~C -10, -28, or -32; a bunsen laminar burning velocity of at least 34 cm/sec, a latent heat of vaporization of at least 95 BTU/lb.

E le 91 A li~uid fuel comprising DMC at 0.01% to 5.0% by weight % oxygen (more preferabiy 0.5% to 2.5%) and at least one r-ngAn~e metallic representing 0.001 to 2.8 gr/gal (preferably 0.065 to 1.0 gr/gal, most preferably 0.1 to 0.5 gr/gal), and a diesel co-fuel base; wherein ~inP~ fuel is characterized as having an API range of about 41.1 to 45.4, a sulfur content not PYree~ing 10 wt ppm (preferably sulfur free), absent nitrogen, and an aromatic content of 0 to 20% by volume, PNA vol% of 0.02, or less, a Cetane index greater than 45, an IBP of 365~F, a 95% fraction ranging from 460~F to 540~F; a bunsen laminar burning velocity of at least 36 cm/sec, a latent heat of vaporization of at least 100 BTU/lb.

le 92 The example of 91, additionally comprising a burning velocity increasing and/or temperature reducing ECS
~ ' in c~"~enLL~tion of 0.5 to 1.0, 0.5 to 1.2, 0.5 to 1.3, 0.5 to 1.5, 0.5 to 1.8, 0.5 to 2.0, 0.5 to 2.2, 0.5 to 3.0, 0.5 to 3.5, 0.5 to 4.0, 1.0 to 3.0, 1.0 to 5.0, 1.0 to 7.0, 2.0 to 8.0 volume percent oxygen in the composition.

~ W095/33022 2 1 9 4 ~ 7 2 ~ s c-758 EY~ 1e 93 The example of 91, 92, additionally compri~ing a combustion chamber deposit control/reducing additive, and optionally an injector or intake valve deposit control ~ 5 additive.
Thus, it is an : '-'i L to inCoL~U' ~te an ECS fuel and a diesel co-fuel, such that the resultant fuel meets ASTM, industry and/or g~v~ L specifications, present and future. In the practice of this invention, Mn or metallic operating ranges in the resultant diesel composition may range from 0.001 to about 10.00 gr Mn/gal, 0.001 to 7.0, .001 to 5.0, .001 to 4.0, 0.001 to 3.5, 0.1 to 2.6, 0.1, 2.2, 0.1 to 2.0, 0.1 to 1.9, 0.1 to 1.6, 0.1 to 1.4, 0.1 to 1.2, 0.1 to 1.0, 0.1 to 0.9, 0.1 to 0.7, 0.1 to 0.5, 0.001 to 0.375, 0.1 to 0.25, 0.1 to 0.18, 0.001 to 0.125, 0.1 to 0.0625 Nn/gal, or equivalent, if an alternative r ' 11 ic _ is employed (including combination).
It appears optimum Mn leve]Ls are less than 5 gr./gal, with those less than 3.0 or even 2.5 gr. Nn/gal being acceptable. However, cu--c~--L~tions greater than 10, 12, 15, 20, 22, 25, 26, 27, 28, 29, 30, 31, 32, 35, 40, 50 grs Mn/gal are also contemplated, particularly in advance applications. For purposes of improving combustion, a desireable concentrations include 0.03125, 0.0625, 0.09375, 0.125, 0.15625, 0.21875, 0.25, 0.28125, 0.3125, 0.34375, 0.375, 0.5, 1.0, 1.5, 2.0, 2.2, 2.3, 2.5, 2.7 gr Mn/gal, including concentrations within these ranges. Desireable , ~
_ _ _ _ _ , _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ . . . _ _ _ _ _ _ _ _ _ _ _ _ , _ . _ _ _ _ ~ _ _ _ _ _ .
_ _ _ 2t q4572 Wo9~/330~ ~ 758 ranges in~ c from about 0.001 to about 3.00, 0.001 to 2.9, 0.001 to 2.8, 0.001 to 2.7, 0.001 to 2.6, 0.001 to 2.5 gram Mn/gal. Ranges outside these are acceptable.
Other ~-n~Ane~e cv..~..LL~Lions 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 Mn/gal. A desireable range in~ln~
from about 0.001 to about 1.50 gram Mn/gal. Other desireable ranges include from about 0.001 to about 0.50 gram Mn/gal of composition. Lower vu..c...L,~tion ranges from .001 to about 0.25 grams/gal are also contemplated. Ranges greater than 0.0625 gr Mn/gal are also contemplated.
However, as noted above, the greater the 02 ov..c~..LL~tions contained in the fuel composition, ~periAlly with superior ECS _ ' , the greater the permissible Mn cv..~e..L-~tions. Also with heavier fuel compositions, which enjoy improve burning velocities and/or reductions in combustion t~ _ ~LUL~, r~ng~n~e 20 cvl.v~LL~tions may be increased.
Often, r-ng~n~e c~n~ tions must exceed 1/64, 1/32, 1/16, 3/32, 1/8, 5/32, 7/32, 1/4 gr Mn/gal prior to noticible 1 v~. L in fuel economy or power.
A synergism occurs - _li- Ling the usage of ECS
~- and ~n, particularly when T-90 t~ ~LuL~ are reduced. Differing fuel specifications, operating conditions, envi~l L~l requirements, and combustion systems will dictate final compositional construction.

21 9~572 WO9s/33022 PCT~S951067~8 Applicant notes the desira~Dle oxygen of his ECS
t by weight in diesel compositions, which yields good results normally exceeds at least 1.0% by weight, and those equal to or ~Y~eo~ing 1.5%, 1.75%, 2.0% are ~ 5desireable. However, in the practice of this invention lower 02 con~el.L.~tions are contemplated, in~ln~ing to a low as 0.01 weight P~LCell~ag~.
In the practice of this invention oxygen col,c~l,L.a~ions ranging from 0.01 to 0.5% weight are 10acceptable. Oxygen conc~l,LL~tions from 0.01 to 1.5~ weight percent is desireable. 02 concentrations from about 0.5 to 5.0%, and those greater than 1.5% slightly more preferred.
Other oxygen ranges include 0.5 to 1.0, 0.5 to 1.2, 0.5 to 1.3, 0.5 to 1.5, 0.5 to 1.8, 0.5 to 2.0, 0.5 to 2.2, 0.5 to 153.0, 0.5 to 3.5, 0.5 to 4.0, 1.0 to 3.0, 1.0 to 5.0, 1.0 to 7.0, 2.0 to 8.0 volume percent oxygen in the composition.
Acceptable oxygen ranges, when the ECS fuel constitutes a significant minority or su~Ds~An~ ly greater percentage of the composition i n~ln~ oxygen weight 20col,cenLL~tions of 5.0%, 10%, 15%, or 20%, or greater. In larger diesel fuel engines, ;nrlu~ing locomotive, marine and large stationary industrial applications, it is anticipated that the fuel compositions will contain 02 cu..ce..LLations of 2~, 3%, 5% weight, or more.
25There are no maximum limit anticipated in advanced applications. Hence, in the practice of this invention, 02 c~nce..~.ations m~Yimi~ing the advantages of Applicant's ,, ,~ ~

w095/33022 2 1 9 4 5 7 2 r~ 758 ~

invention are eYpressly contemplated, Q~peci~lly those that r-Y;mi7e advance combustion of the metallic.
Arplic~nt has u.lex~euLedly discovered that diesel ~mi~ n~, including particulates, HC, C0 and NOx DmiA~
are materially reduced in the practice of Applicant's invention. Combustion chamber deposits, absent additives are also reduced. Such reductions appear to be closely tied to the invention's increases in burning velocities and reductions in combustion t~ _ ~LUL~8.
Applicant has also unexpectedly di~cuvel~d that due to increases in burning velocities and lower combustion temperatures that diesel engine noise can be controlled, without sacrificing economy and emi~ci~n~.
The properties of - uial distillate diesel fuels depend on the refinery practices employed and the nature of the crude oils from which they are derived. Thus, they may - differ both with and within the region in which they are r~nl-factllred. Such fuels generally boil over a range between 163 and 3710C (325-7000F). Their makeup can l~ 3_,~t various combinations of volatility, ignition quality, viscosity, sulfur level, gravity, and other characteristics.
The properties and preferred practice of Applicant's diesel co-fuels are set forth in International Application No. PCT/US95/02691.
Applic~nt~s preferred diesel co-fuels enjoy high cetane numbers, Q~reci~lly those QY~ee~ing 40 cetane, and ~ woss/33022 2 l 94572 r~l,u~ 758 can be ~L udu~ed where arom,atics are converted to naphthlenes and paraffins.
The diesel co-fuel6 of Arpl ir~ntls invention include all ASTM grades, including Grade low sulfur No. l-D, which 5 iB a special purpose, light distillate fuel for automotive diesel engines requiring low sulfur fuel and requiring higher volatility than that provided for Grade low sulfur No 2-D, and is met to comply with 40 CFR Part 80 regulations. Grade Low Sulfur No. 2-D, which is a general purpose middle distillate fuel for automotive diesel engines requiring low sulfur fuels. It is also suitable for use in non-automotive applications, e~r~C;~lly in conditions of varying speed and load. This grade is also in conformity with 40 CFR Part 80 regulations. Grades No. l-D
and No. 2-D, which are similar in purpose to their low sulfur counter parts, except that their sulfur contents are not as strictly regulated. Grade No. 4-D, which is a heavy distillate fuel, or a blend of distillate and residual oil, for low and medium speed diesel engines in non-automotive applications involving p~ n~tely uO~ dn~ speed and load.
Type C-B - Diesel fuel oils for city-bus and similar operations Type T-T - Fuels for diesel engines in trucks, tractors, and similar service. Type R-R - Fuels for railroad diesel engines Type S-M - Heavy-distillate and residual fuels for large stationary and marine diesel engines.

WO95133022 ~ 2 1 9 4 5 7 2 1 ~/IJ . c /a~ o It i~ anticipated the base co-fuel hYdL~1LOn composition of Applicant's diesel co-fuels will be tailored to maximize the beneficial aspects of ignition quality, heating value, volatility, gravity, oxidation stability, burning velocity, latent heat of vaporization, etc., to positively effect combustion, power, economy, ~ sion~
fuel economy, wear, deposit formation, starting, warm starting, driveability, noise, particulate generation and smoke performance of Applicants diesel engines.
In the practice of this invention a cetane number of 30 is desireable. A cetane number of 40 or greater i5 preferred, e~rer;~lly in low sulfur No. 1-D and low sulfur No. 2-D fuels. An optimal cetane number in the practice of this invention i8 greater than 48. However, in advanced reformulated die~el fuels cetane numbers greater 50, 55, 60, 65, 70, 75, 80 are contemplated. It i~ also a preferred practice, when employing low sulfur diesel fuels Grade No. D-1 and No. D-2 to have a minimum cetane index number, a limitation on the amount of high aromatic ~ ~nts, of 40 (as measured by ASTM D 976) or an aromatic content not PYree~ing 35~ by volume (as measure by ASTN D 1319).

Example 94 A composition comprising a diesel fuel meeting ASIM
975 specifications (or fuel oil, aviation turbine, or gas oil) a combustion improving amount of dimethyl ~Londte, a co-solvent, and a cyclopentadienyl r-ng~n~e tricarbonyl ~ Woss/33022 2 1 ~ 4 5 7 2 ~ . 7s8 ' having a conc~l.LLdtion ranging from about 0.001 to about 2.5 gr Mn per gallon; whereby resultant fuel combustion results in i ~v~d thermal efficiency and/or fuel economy, and meets minimum flash point ~ ~LUL~S..

E 1~ 95 A No. 2 diesel fuel composition comprising a minor portion of a combustion improving amount of dimethyl carbonate and a cyclomatic r-nq~n~se tricarbonyl, and a major portion of a base diesel fuel, such that resultant fuel has a cetane of 42 to S0 (preferably substantially greater), an aromatic content of less than 28 volume percent ~preferably less than 20%, more preferably 15~, most preferably less than 10%), a ~-90 t~ ~Lu~e of 560~F
to 600~F (more preferably less than 540~F, 520~F, 500~F or lower~, a sulfur content of 0.08 to 0.12% mass (more preferably 0.05% or sulfur free), an API gravity of 32 to 37 (more preferably higher), and a minimum flash point of 130~F (optionally obtained via u~e of co-solvent or salt).

E le 96 A No. 1 diesel fuel composition containing a minor portion of a combustion improving amount of dimethyl carbonate and a cyclomatic r-nq~n~e 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 T-90 t~ ~tu~ of 460~F to 520~F (more preferably less W095/~022 21 9 4 572 r~ J758 0 than 425~F, or lower), a sulfur content of 0.08 to 0.12~
mass (more preferably less than 0.05~ mass), API gravity of 40 to 44 (more preferably higher), and a minimum flash point of 120~F.

E le 97 The above ~ ~c, wherein fuel meets ASTM D 975 specifications.

Exam~le 98 A method for operating a diesel engine, said method comprising injecting the fuels of examples of 88-90 ( i n~lnA i ng a gub8tituted No. s-heavy) by means of high pLeS~UL~ direct fuel injection system, employing pres~ures ranging from 30 MPa to 120 NPa, wherein the average vapor particle size is less than 70, 60, 40, 30, 20, 10, 5 micron~, more preferably 40-60 microns; whereby burning velocity is increased.

xam~le 99 The methods above, wherein the combustion system additionally comprises a turbocharger, an ERG system, and wherein the fuel injection ~ystem employs sensor input means to regulate fuel injection rate and/or timing.

~le lO0 A method incuL~uL~ting the above r l~, wherein ~ w095l33022 21 94572 rc~ 7s8 an engine i5 operated under a moderate to heavy load, of at least 16, 17, 18, 20, 22, 24, 28, or more, ihp (employing equivalent of 180hp to 280 hp engine); whereby fuel economy is ; v._l.
S

FY~mnle 101 The method examples above, wherein resultant exhaust emissions meet U.S. EPA and Clean Air Act regulations, ~n~lllA;ng 42 USC 7545 et seq.
In the practice of this invention ignition promoters may be employed, individually and/or in combination with ECS _ , particularly in fuels which require higher temperatures to ignite, which extends their period of ignition. Such promoters include di-tertiary butyl peroxide, alkyl peroxides, alkyl hylLv~ ides~ alkyl nitrate additives, ;n~ A;ng ethyl-hexyl nitrate and iso-propyl nitrate, 2.5 dimethyl 2.5 di(tertiary butyl peroxy) hexane, tertiary butylcumyl peroxide, di(tertiaryamyl) peroxide, tertiary butyl hY1LV~r oAide, tertiary amyl 21) I.~lLv~e~v~ide, and mixtures thereof.

r le 102 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 30~ volume (more preferably less than 15%), a combustion improving amount of dimethyl carbonate and a combustion W095/33022 ~l 94 5 72 r~ 7~8 O

improving amount of a cyclomatic r-ng~n~-o tricarbonyl r le 103 A low emission diesel fuel comprising a minimum cetane number of 52, maximum fuel sulfur less than lO0 ppm, aromatic content of 12%, T-90 t~ a~uL~ of 475~F, bromine number of 0.10, a combustion improving amount of dimethyl carbonate ranging from 0.5 to 4.0% oxygen by weight, and a combustion improving amount of a cyclomatic r~ng~no~e tricarbonyl _-nn~ .

E le 104 A low emission diesel fuel comprising a minimum cetane number of 62, maximum fuel sulfur less than 0.01% weight, 10~ aromatic content, olefin by weight les6 than 30%, 25%, 20.0%, 15.0%, 10~, 7.0%, 6.0%, 5.0%, 4.0%, 3.0%, or less, in~ ing olefin free, T-90 temperature of 514~F, bromine number of 0.10, aniline point less than 145~F, a combustion improving amount of dimethyl ~b~-.a~e and/or optionally triethylene glycol or tetraethylene glycol; and a combustion improving amount of a cyclomatic r~ng~no~e tricarbonyl ~ '.

r le 105 The composition of Example 104, wherein said composition is combusted in a heavy duty truc~ engine and ~ W09~33022 2 1 9 4 ~ 7 2 . ~ s.r~758 HC, C0, Nox, and particulate ~mi~sinn~ are 1.3, 15.5, 4.0, o.IO gmtbhp-hr, respectively.
It i8 an ~ L of this invention that the emissions of Applicant'fi fuels, ASTM, CAA, CAR8, ~ 5 Swedish/European, and all international requirements and/or other y~v~L --L~l regulations, current and future.

[TABLE 4 lh~ T.T.Y OMITTEID]

An additional ~mho~i- L is the reduction of PM 10 (particulate matter of 10 microns or more), which is believed to be caused by heavier aromatics. It is also an ~ ho~i- L to reduce particulate matter to 5.0, 4.0, 3.0, 2.5, 2.0, 1.5, 1.0 mircrons or lower. Applicant's invention is particularly effective to reducing such particulate matter.

A method of operating a diesel engine, comprising:
introducing into the combustion chamber via direct fuel injection under ~L ~ur , an atomized ECS - ~ of sufficiently high burning velocity and latent heat of vaporization, together with a combustion improving metallic, and a reformulated diesel co-fuelj combusting said fuel at e~LL. ly high efficiency and rate, whereby particulate combustion emissions are ~ubstantially avoided, and if formed are gaseous submicron particles of high kenetic energy.

W095l33022 21 9~572 r~ 758 ~

In the practice of this invention all fuels and co-fuels are contemplated to be combusted in engines employing as required advanced lubricating oils and technologies, as an additional means for reducing combustion temperatures and increasing burning velocities.
Contamination of lubricating medium can cause or advance combustion chamber and/or other deposits. The elimination of combustion chamber deposits (CCD) is an express object of Applicant's invention, as said CCD
interfere with combustion an increase combustion t~ ~uLe, in turn exascerbating NOx Qmicsi~nc and the like.
Thus, advanced lubricating oils, ~Q~ignQA to avoid such contamination and/or designed to improve lubricity under accerlerated combustion is expressly contemplated.
Non-limiting examples of contemplated lubricating oils include those meeting API CG-4, API CF-4/SG, API CF-4/SH, future PC-7 standards, SAE J300, and/or other standards that operate to minlmi~e piston deposition on operation with low/no sulfur fuels. It is known that piston deposition operates to increase other deposits and hazardous êmissions and therefore should be avoided.
Other advanced lubrication technologies, such as those ~;CC1OSQ~ in U.S. Patent ~4,204,968, ~3,001,941 which i ~veS combustion efficiency and/or burning velocity (noted by increases in fuel economy), and/or which tend to reduce operating temperatures are also contemplated in the various aspects of this invention.

21 94~72 Woss/33022 1~ C-758 See International Application No. PCT/U595/02691 for analysi6 of Example tests and Figures 1 to 7, incvL~uL~ted herein by reference.

~ 5 [T~3LE 5 T~T~TI ~T.~.Y O~ITTDD]

FIG~RE L
Figure 8 shows t~hnicAl ~nle: L of oxygen containing fuels, which have not been adjusted to elevate d~Lessed T-15 to T-70 regions. As Applicant disclosed in his 770,836 Application, lower molecular weight alcohols and ethers depress distillation , ~L~LeS due to azeuLLu~hing effect and adversely impact warm driveability, particularly warm engince start up.
Figure 8 shows that by adjusting di6tillation curve, preferably by tailoring underlying hydLou~LLull base, or by the addition of higher l e~ r weight co-solvent, particularly C4, C5, C6 plus alcohols, while maintaining a constant level of oxygen, that an adjusted distillation curve can be acheived, which is above the te~hn;~Al Qnl PA L region. Hence capable of avoiding warm operational driveability problems.
~rPl; CAn~ notes the addition of higher molecular weight llydLu~Lbu-- material boiling above 220~F, 250~F, 270~F, 300~F, 320~F, 370~F, and therewithin, can be added to the fuel to elevate noted depression. It is normally desireable, while not required, that said hyd~oc~Lbull w095/33022 Zl 9 4 ~ 7 2 P~ ~ ,'C-758 ~

material have some aromaticity and/or azeotrophing property.
Thus, Figure 8 shows that tailoring of the base hydrocarbon fuel, wherein a hYdLO~LbVI- fraction elevates T-60 to T-70 or higher distillation temperature, can be - essed into the mid-range fractions, due to addition of C1 to C3 ~lcnhnl~ and .~TBE or ETBE. Thus, the higher molecular weight hydrocarbons elevating T-60, T-70 plus fractions are offset by .~TBE, ETBE and C1 to C6 alcohols, which depress the T-20 to T-50 fractions.

a~r77..TN7Z ,r l-V~l'l'.,_ _ See International Application No. PCT/US95/02691 for additional practice disclosure on gasoline compositions.
Automotive gasolines contemplated in ~ppl i C~nt ~ 8 invention include conventional nnlp7~7~pd~ reformulated 17nl P~7r7.P~7~, low RVP fuels, low sulfur, no sulfur gasolines, low octane g~Rol;np~ moderate octane gasolines, high octane gasolines, advanced atomization, vaporization, injector volatilization gACOl inPC, and the like, and/or any gasoline meeting AST.~ and/or other regulatory ~tandard, existing and future, and com~inations thereof.
Non-limiting examples of the gasoline engine/fuel systems include, ~LbUl ~tor~ 7 , ~d gasoline, manifold feed/injected, direct injection, direct injected 6tratified charge, advanced stratified charge, and the like. It is contemplated that Applicant's automotive gS7col;n~ will be in combustion systems employing exhaust catalysts ~ woss/33022 2 1 94 572 ~ 758 (including three way systems), regulated emission control systems, and the like.
One of the particular objects of Applicant's invention is the inou-~u.~tion of emission catalysts, OBD II catalyst Pffi~i~nry monitors, related Pn;~ion control systems in method6, where upon their operation in the ~.ese..ce of a Mn containing combustion exhaust gas, is not impaired.
Another object is the operation of gasoline engines operating under minimum threshold loads, where upon the 10benefits of Applicant's invention become beneficial. For example, ~pplic~nt has discuv~led that when employing ECS
_ ' and minor amounts of metallic, e.g. Mn, that optimum fuel economy and t~ ~ ~t4Le reduces do not start to occur until loads are at leaGt 12.5 ihp to 16.0 ihp.
15An object of instant invention is to employ and make g~ol;nP~ having superior combustion, emission and operational features with a very wide range of octane value tR + M)/2), 8, inrltl~in~ e~LL~ ~y low (e.g. 5 to 30, 10 to 35, 15 to 40), to low (e.g. 40 to 60, 50 to 70, 60 to 75), 20to moderately low (e.g. 75 to 80, 75 to 85), to average (85 to 88, 86 to 90), to high (e.g. 90 to 95, 93 to 100, 95 to 105) to ~L.~ -ly high 105 to 115, or higher.
Another object of this invention is ; ~ u~d combustion of gasolines and the operation of i nt~n~ 1 25comoustion engines at altitude. At altitudes above sea level, particularly those greater than 1,500, 2,000, 2,500, 3,000, 3,500, 4,000, 4,500, 5,000, 5,500, 6,000, 6,500, 7,000, 7,500, 8,000, 8,500, 9,000, 9,500, 10,000, 10,500, , .. .

w09~33022 2 1 ~ 4 S72 ~ c-7s8 ~

11,000 feet above sea level in combustion in gasoline and diesel engines show ;--- lete combustion and elevated C0, particularly in older engines.
It is still another object to employ faster burning velocity, higher LHV ECS _ '- (e.g. DMC, methanol, ethanol) with lower burning velocity LHV ECS a_ (e.g. MTBE, ETBE), PCpeciAlly in circumstances where the later , _ a~ have long photooxidation periods, due not readily d~- -se, and are s~crPrtcAd as being carrinog~n;c.
Employing Applicant's fuel compositions and method at altitudes wherein a~ ric ~-as~uL~s are reduced on the order of 0.5 psi to 8.0 psi, 0.5 to 1.0 psi, 0.5 to 2.0 psi, 0.5 to 3.0 p5i, 0.5 to 2.5 psi, 0.5 to 3.5 psi, 0.5 to 4.0 psi, 0.5 to 4.5 psi, 0.5 to 5.0 psi, 0.5 to 5.5 p8i, 0.5 to 6.0 psi, or more, effectively PnhAn~c combustion, whereby reducing the emissions of incomplete combustion, including C0, particulates, hydrocarbons, NOx, etc., ecp-A~AiAlly C0 _~;ccionc which are othewise elevated compared to clear fuel at sea level.

r le 157 A method of operating an internal combustion engine at an altitude ~Yr~An;n~ 1,000, 2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000, 9,000, 10,000, or more feet above sea level and/or wherein a~ - ,'-Aric pLasDuLa is 0.5 to 8.0 psi below that of sea level, said method comprising: mixing an ECS and metallic containing gasoline or diesel co-fuel;
wherein resultant fuel has an increased burning velocity ~ WO 95/33022 2 1 9 4 5 7 2 1 ~, /IJ~ r,~o7s8 and/or reducèd combustion temperature (e.g. compared to clear co-fuel or an MTBE containing co-fuel); injecting ; resulting fuel into combustion chamber of said engine, wherein ambient yLes~u~ is 0.5 to 8.0 psi below sea level;
~ 5, combusting said fuel; wherein C0 and/or other emissions associated with incomplete combustion due to lower ambient yLds~u.e are reduced (e.g. over clear fuel combusted at same altitude).
An additional object of this invention is the i u.~d combustion, ~ ;tion and general deposition of MTBE
and/or other known car~i nog~n; ~ ethers into more benign or benign ~ , as to avoid contamination of ground and surface water.
~rplir~nt has discuv~led that certain high octane ethers, namely MTBE and ETBE, are found in high relative c ~ r~tions in the evaporative and/or combustion exhaust emissions of ~TBE or ETBE containing fuels. The increase of said _ '- into air and water supply, ~r~r;~lly at altitude, now constitutes the beg; n; ng of a major hazard.
Applicant has discvvlLed MTBE to be rather stable once emitted into the ai ~ e, and appears to be rather solubility in ~ ric water ~apor. Thus, MTBE as a fuel L is now and will continue to be found in ever increasing cul.cel-LL~tions in ambient air and ground water, constituting a potential hazard, due to its carr;n~gPnic attributes. Thus, a need exists to enhance the -Eition of MTBE combustion to reduce total ambienrt cu~.cellLL~tions of MTBE in the ai ,'~~e.

W095/33022 21 94 572 r~ . 758 0 Applicant has discovered that by employing a combustion accelerating ECS ~ p~ciAlly one whose burning velocity and/or heat of vaporization i8 greater than MTBE'6, e~p~ci~lly an ECS , a releasing high amounts of free radicals, and optionally together with at least one combustion improving amount of a metallic te.g.
Shell Ch~mic~l ~s SparkAid or a potassium salt and/or a ~-ng~nP~e ~ or other useful ~ , in combination with an NTBE or ETBE containing fuel, the MTBE/ETBE containing fuel enjoys better combustion and MTBE
~e~ at an accelerated rate, ~d to MTBE
containing fuel alone.

ExAmple 10~
An ameliorative fuel composition characterized as an aviation/automotive gasoline, diesel, turbine, fuel oil, or other fuel containing MTBE, ETBE, TAME, or mixture; said fuel additionally containing a combustion improving amount of an ECS _ ' tpreferably DMC) having a burning velocity and/or a latent heat of vaporization greater than MTBE; and optionally a combustion improving amount of at least one metallic; whereby enhAn~fl attributes of combustion accelerate d~ sition of carcingenic ether prior to its ~ n into ai r le 109 A method of 108 reducing potentially carcinogenic ether o... ~ ion5 from ai ~h~e; said method ~ w09~/33022 2 1 9 ~ 5 72 ~ 7s8 comprising combusting an NTBE containing fuel in combination with DMC and optionally a combustion improving metallic.

r le 110 A fuel compostion of Example 108, wherein the fuel is a reformulated ga~oline and contains NTBE, ETBE, TANE, or mixture, said ether or mixture comprising an amount equal to or less than 2.7, 2.5, 2.2, 2.1, 2.0, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3 weight percent oxygen of the fuel; and a ECS
_ ' having a burning velocity and a heat of vaporization greater than said ether and a minimum oxygen weight content of at least 0.02%, ~uch that total fuel oxygen by weight i8 less than 6.0%, 5.0%, 4.0%, 3.7%, 3.0~, 2.7~, 2.5%, 2.2~, 2.0%, 1.9~, 1.5%, 1.2%, 1.1%, 1.0%, or less; and optionally, a combustion improving amount of at least one - llic _ '.

r le 111 An ; ~v~d NTBE fuel composition comprising: a low or no sulfur hydrocarbon base fuel, MTBE, and an ECS _ _ ' having a burning velocity grea.ter than NTBE (preferably ,- 20%, 30%, 40%, 50%, 60%, or more, with DNC preferred), wherein total oxygen by weight of the fuel does not exceed 8.0%, 6.0%, 5.0%, 4.5%, 4.0%, 3.7%, 3.5%, 3.0%, 2.7%, 2.5%, 2.25%, 2.2%, 2.0%, 1.9%, 1.8%, 1.5%, 1.2%, 1.1%, 1.0%, 0.8%, 0.7%, 0.5%; and a burning velocity improving amount W09S/33022 2 l 9 4 57 2 r~ C-758 ~

of a metallic, including a pota~sium salt r-rk~te~ by Shell Chemical Corporation known as SparkAid; and/or optionally an anti-knock or combu~tion improving amount of a ~~ng~nQ~e metallic ~ ' (in lieu of or in addition to the potassium salt).

r-- le 117 The Composition of Example 111, wherein the fuel composition is unleaded, containing less than 400, 350, 300, 250, 200, 150, 100, 50, 40, 30, 20, 10, 5, 0 ppm sulfur, and comprised of 10:1, 9:1, 8:1, 7:1, 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, 1:9, 1:10 parts oxygen/or parts MTBE (or parts MTBE/ETBE/TA~E
and mixture) to part ECS : '; and/or wherein the ~ C~...... c~.. LL~tion of metallic potassium or potassium salt is less than 3.0, 5.0, 6.0, or 1.0 to 4.0, 1.0 to 10.0, 2.0 to 15.0, 2.0 to 20.0, 3.0 to 30.0, 4.0 to 35.0, or greater, ppm of the fuel; and/or wherein the r~ng~no~e ~..ce..LL~tion i~ at least 1/64, 1/32, 1/16 gram Mn/gal of the fuel composition.

FY~mrle 113 A method employing the fuel compositions of 111, wherein said composition is supplied to and combusted in a spark-ignited internal combustion engine, wherein MTBE
Qmi~inn~ are reduced by 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, or more, compared to same fuel Woss/33022 2 1 945 72 P~ 67~8 .

containing same conce..LL~tion of MTBE, absent ECS
and metallics.
Another object is a combustion - ~ll ;r containing gasoline absent an u~yyG.Iate, which has ; u~_d buring velocity and/or reduced combustion ~ ~LULG~. Thus, Applicant's invention includes fuel compositions, wherein combustion burning velocities are increased over typical base compositionc. This may be accomplished by formulating a co-fuel composition to include hYdLU~bUII substitutents having increased burning velocities, and/or by inrlll~;ng combustion catalysts or combustion improving r ' 11;Cc such as Shell~s potassium salt.

~ le 114 A combustion composition comprising: an low or no sulfur gasoline or diesel co-fuel; cu..DLLu~Led to have increased burning velocities over typical base fuel; and an organ ~ _ '; and optionally a burning velocity improving amount of additional metallic.

r le 115 The composition of Example 114, wherein constructed/lecu..~Llu~Led co-fuel hac a burning velocity at least 2.0%, 3.0%, 5.0%, 7.5%, 9.0%, 10%, 12%, 15%, 17%, 20%, 25%, 30%, 40%, 50%, or 60% or higher than unmodified base fuel; and a r-"g~n~ce cu--cG~.LL~tion PYreeA;ng or equal to 1/128, 1/64, 1/32, 1/16, 3/32 gr Mn/gal; and wherein said fuel optionally contains a burning velocity amount of WO95/33022 2 l 9 4 ~ 7 2 P~ 758 ~

a comhustion acceleration amount of separate metallic, preferably a potassium salt in a ~u.l~el,LL~tion not ~YrDP~in~ 25, 20, 18, 16, 14, 12, 10, 8, 7, 6, 5, 4, 3, 2, or 1 ppm (-- 1l ir. or metallic __ '); and the composition optionally contains means of reducing combustion t~ ~LUL~ (a8 Bet forth in the specification herein), but not limited to distillation modification and/or employing a combustion chamber deposit control additive in a cu.,-~--LL~tion of 50 to 400, 100 to 600, 150 to 800, 150 to 1000, 200 to 1500 mg/kg or other amount sufficient to avoid combustion chamber deposits; whereby combustion t~ aLULeS are reduced.
Applicant's co-fuel g~o1inD~ should be constructed to min;mi 7e hazardous pollutant6 to the maximum extent pr~iblP Thus, sulfur c .~ tions should approach sulfur free levels, if pn~sihle~ harmful heavy aromatics (while their effect is substantially mitigated in the practice of this invention) should be reduced as much as practical. To the extent possible, co-fuels should be formulated to reduce volatile organic _ ~- tVOC's), NOx, benzene, butadiene, formaldehyde, acet~ hyde, polycyclic organic material. Reformulated g~ClinD~
constructed under the complex model are expre6sly contemplated.
An important : ~o~i- L of Applicant's invention is its capacity towards ultra clean combustion emissions, due to the nature of its combustion. ~n~DTlontly~ in addition to the reduction of most hazardous Dmi~ir~n~, it is an ~ w095/33022 2 I q4 ~ 72 ~ 7s8 ~ to avoid combustion chamber deposits, which now be caused by the use of detergents to keep intake valves clean.
An additional ~ho~ is the reduction of PM 10 (particulate matter of 10 microns or more), which i6 believed to be caused by heavier aromatics. It is also an : -~; L to reduce particulate matter to 10.0, 9.0, 8.0, 7.0, 6.0, 5.0, 4.0, 3.0, 2.5, 2.0, 1.5, 1.0, 0.5, 0.25 mircrons or lower. Applicant's invention is particularly effective to reducing such particulate matter (PM) in both gasolines and fuels heavier than gasolines (e.g. diesel).

r le 116 A method of reducing the ~ize of particulate matter incu~ ing an ECS/n ~ fuel composition in combination with a co-fuel, preferably a co-fuel e~ual to or heavier than gasoline, wherein said fuel is combusted in an engine; emitting combustion ~ Si~r~ from said engine, whereby particulate matter is less than 10 PM, 5 PM, or 2.5 PM; and particulate emissions are reduced ed to co-fuel, absent ECS/metallic fuel.

e 117 The method of Example 116, wherein the fuel composition contains aromatic cunc~llLl~tions of 30%, 27%, 25%, 22%, 20%, 19%, 18%, 17%, 16%, 15%, or less by vol.

WO95/33022 2 1 q 4 572 ~ 758 o FY~r~le 118 A conventional or reformulated unleaded fuel compo6ition comprising: sulfur at less than 300, 250, 200, 150, 100, 60, 50, 20, 10, 5 ppm, inrll-Aing range of 5 ppm to 50 ppm or 15 to 25 ppm sulfur or sulfur free; a polynllrnlPAr free aromatic cu-.c~.lLL~tion of less than 50%, 45%, 40%, 35~, 30%, 27%, 25%, 22%, 20~, 18%, 16%, 15%, 12%, 10%, 9~, 8%, 7%, 6%, 5%, 4%, or less, by volume, ;nr~ ing ranges therein, or aromatic free composition; a none C4 to C5 olefinic cu.. u~l.LL~tion less than 20~, 15~, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1% including range of 3.0% to 5.0% by volume (also inrlll~1ng olefin free concentrations); a benzene cu..ce..LL~tion of 0.2~, 0.3%, 0.4~, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0% volume, or less, inrll-~ing benzene free compositions; an RVP of less than 12.0, 11.5, 11.0, 10.0, 9.0, 8.5, 8.0, 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 p5i; oYygen 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 ~ _ ' ~preferably DMC~; a combustion improving amount of at least one metallic, i nrl n~ i ng a cyclomatic r~ng~n~e 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 Pnh~nri ng deposit control additive selected from combustion chamber deposit control, port fuel injector, inta~e valve deposit control additive, and mixture; and wherein said composition has a driveability wossl33o22 rc~ 7s8 index less than 1120, 960 (less than 930 preferred); whose t-50 mid range f' - ~LuLe exceeds 170~F, 175~F tpreferably ranging from 190~F to 210~F); whose T-10 temperature is less than 160~F (preferably less than 140~F, 120~F); and wherein the composition has an average latent heat of vaporization equal to or greater than 130, 135, 140, 145, 150, 155, 160, 165 btu/lb or alternatively greater than 860 btu/gal (preferably greater than 900, 910 btu/gal); and wherein the composition optionally has a miminum laminar bunsen flame 10burning velocity of 40, 43, 45, 48, 50, 60, 65, 70, 75, 80, go cm/sec (preferably 45, 48, 50, 60 cm/sec., or greater nre preferred).

r le ll9 15The vapor composition of method Example 118, absent metallic.

Exam~le 120 A method of operation an internal gasoline combustion engine, said method comprising: mixing a convention, non-convention, or reformulated gasoline with a combustion improving amount of an ECS - ' and a combustion improving amount of MNT and/or other r ~ ( including the fuel of Example (im abv); combusting said fuel in said engine, wherein engine is under load of at least 12.5 ihp (more preferably at least 16.0, 20.0 ihp), wherein fuel economy is increased.

,~ ,~ ;,, ~ .

W095/33022 2~1 ~4572 : P~" ~758 ~

e 171 The method of 120, wherein the load i8 approximately 20 ihp and fuel ec~ c are i ~v~d 0.5%, 1.0%, 2.0%, 3.0%, 5~, or 2.0% to 30%, and/or combustion t~ _ t~tUL~ i5 reduced ~ad to conventional fuel, including temperatures from 2~F to 10~F, 5~F to 20~F, 10~F to 50~F, 15~F
to 60~F, 20~F to 100~F, 25~F to 125~F, 25~F to 150~F, 50~F to 200~F, 25~F to 225~F, 25~F to 250~F, 50~F to 300~F, or more.
It is another object of instant invention is improving burning velocity/combustion tempe.~LuLes by modifying T-90 and/or end-boiling point distillation fractions c~nh~nrlng combustion, improving mileage, driveability and/or reducing hazardous combustion emissions.
It is an object that Applicant's gasolines, inr]llAin1 RFG, have a driveability index as defined by (1.5 x T~o) +
(3 x T50) + (T90) 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 T50 t~ ,lLuL~s simulf~nt~ol~cly equal or exceed 150, 155, 160, 165, 170, 175, 180, 185, 190, 195 degrees F. An acceptable T50 range includes 190 to 210 degrees F. It is also preferred that the T-10 distillation fraction be 160, 155, 150, 145, 140, 135, 130, 125, 120, 115, 110, 105, 100, 98, 96, 95, 94, 93, 92, 91, 90, 89, 88, 87, 85, 80 degrees F, or less. An acceptable T90 range in~lnA~c 280 to 300 degrees F.

~ W09~33022 2I 9 ~572 r-a~ of758 r le 177 An l-nl P~ d reformulated gasoline composition whose driveability index i8 less than 1160, 1150, 1140, 1130, 1120, 1110, 1100, 1080, 1050, 1040, 1020, 1000, 995, 990, 985, 982, 980, 978, 975, 973, 970, 968, 967, 965, 964, 960, 950, 945, 940, 935, 930, 927, 925, 922, 920, 915, 910, 905, 900, 895, 890, 885, 880, 875, 870, 865, 860, or less; whose t-50 mid range exceeds 170~F, 175~F; whose t-10 is less than 130~F, 125~F, 120~F, 115~F, 110~F, 100~F, 95~F, 90~F, 85~F, 80~F, 75~F, 70~F; said composition containing a combustion improving amount of a metallic; a burning velocity improving and/or combustion t- _ ~Luu~ amount of an ESC

C _ _-- ;

lS r le 123 The llnl~A~ed reformulated gasoline of example tim abv), whose driveability index i6 less than 1120, 1050, 1000, 970, 940, 930; and whose T-10 temperature is 100~F to 90~F; RVP is 9.0, 8.7, 8.5, 8.2, 8.1, 8.0, 7.9, 7.8, 7.7, 2[~ 7.6, 7.5, 7.3, 7.0, 6.9, 6.8, 6.7, 6.6, 6.5, 6.4, 6.2, 6.0, 5.9, 5.8, 5.6, or less;

Thus, it is an object to improve combustion by controlling mid-range distillation t~ _ ~LULeS. still another is T-10 adjustment to enhance combustion properties of this invention. RVP reductions, which are tied to reductions in T-10, are contemplated and it is preferred that Applicant's gasolines generally be lower RVP fuels 4.0 W095/3302z 2l q4572 rc.,~ c~7ss o to 12.0 psi, more preferred are those 4.0 to 9.0 psi, 4.0 to 8.0 psi, 4..0 to 7.5 psi, 6.0 to 7.0 p5i, 6.0 to 6.5 psi, 1.0 to 6.0 psi, l.0 to 3.0 psi, 1.0 to 2.0 psi, or lower. Contemplated RVP's include 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 7.8, 6.9, 7.0, 7.1, 7.2 tmax), 7.3 (max), 7.4 (max), 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1 (max), 8.2 (max), 8.3 (max), 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0 psi. Winter RVP's may range from 11.5 to 12.0 psi, or higher. Summer RVP's may range from 6.5 to 6.9 psi.

r le 1~4 The reformulated fuel composition of example 122, wherein t-10 temperature is less than 125~F, 120~F, 115~F, 110~F, 100~F, 95~F, 90~F, 85~F, 80~F; and RVP is 6.4, 6.5, 6.6, 6.7, 7.8, 6.9, 7.0, 7.1, 7.2 (max), 7.3 (max), 7.4 (max), 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1 (max), 8.2 (max), 8.3 (max), 8.4, 8.5 psi, or less.
In the T-10, T-50, T-90 t~ uLe reducing or control practices of this invention, eliminating gasoline Ls having low latent heats of evaporation and/or low burning velocities is expressly contemplated.
It i8 preferred the finich~ hydrocarbon portion of the gasoline composition (e.g. absent oxygenates and metals, etc.), particularly reformulated fuels, including automotive and aviation gasolines, have an average latent heat of vaporization greater than 130 btu/lb or 830 btu/gal. More preferred are 135, 140, 145, 150, 155, 160, ~ wossl3302z 2 1 9 4 5 7 2 PCT~S95106758 165, 170, 175, 180, 185, 190, 195, btu/lb, or greater, if practical.
Applicant has discvvc~ed compositional/ - L
substitution and/or modification leading to a higher latent heat of evaporization can be normally be accomplished absent losses in the fuel's heating. Often, heating values increase.
In the practice of this invention, it i8 acceptable that reductions of end point and~or T-90 t-, ~LUL~CS be in such an amount that the average latent heat of evaporization of the adjusted fuel (e.g. the reduced fuel), ~uch that its latent heat of vaporization i5 0.5% to 10.0%, or greater, than the unadjusted base fuel. Increases of 1.0%, 2.0%, 3.0%, 4.0% to 20%, 5.0% to 25%, 6.0% to 40%, or greater, are also desireable.
In the preferred practice of this invention, Arrlir~n~
has dis~uvcLcd that acceptable T-90 t~ _ ~Lulcs will range from 240~F, 250~F, 255~F, 260~F, 265~F, 270~F, 275~F, 278~F, 280~F, 285~F, 290~F, 292~F, 293~F, 294~F, 295~F, 296~F, 297~F, 298~F, 299~F, 300~F, 305~F, 310~F, 315~, 320~F, 325~F, 330~F, 335~F, 340~F, 345~, and ranges therein, i nr 1~-~ i ng 280~F to 300~F, 265~F to 295~F. To ~LuLrc8 outside these ranges are also contemplated. T~ ~LULC8 below 280~F are also ~ desireable.
Final T-90 t~ Lu~e is function of i _ u~cd latent heat of vaporization and/or ; _ uvcd combustion velocities, elicited by the ra~ tinn, which in turn is ~ an~ L upon the base fuel. Modifying differing fuels land hydruc~rL

W09s/33022 2 1 9 4 5 7 2 . ~ 758 o streams) will elicit differing respon6e. Thu6, variability in actual amount of T-90 r~ ti~n is anticipated.

r le ~7~
A conventional or reformulated gasoline compo6ition wherein higher boiling point fuel fraction is cut such that end point and/or T-90 boiling t~ - ~LuLas of the gasoline are reduced; and whereby the cut clear fuel's (e.g. reduced t-90 fuel's) average latent heat of vaporization is at least 0.5% and more preferably 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 7.0%, 8.0%, 9.0%, 10~, 12.0%, 15.0%, 20.0%, 25.0%, 30.0%, or 2.0% to 50.0%, or greater, than the clear uncut fuel.

~Y~mnle 176 The composition of 125, additionally comprising sufficient quantity of a combustion chamber deposit control/modification additive or additive package (such as Texeco's CleanSystem~); and a minor amount of Mn; and optionally an ~nh ln~;n7 injector and/or intake valve deposit control additive; whereby adverse hydrocarbon emissions are controlled.

Yam~le 127 The composition of 126, wherein after the inclusion of deposit control additive, or additive packace, combustion ~LuLas are reduced.

~IWO95l33022 2 1 ~ 4 5 7 2 ~ c ~7S8 r le 128 The example of 125, wherein said adjusted and unadjusted T90 gasolines both comprise 1.0% to 2.0% oxygen by wt of MTBE and a cyclomatic r nq~nPse tricarbonyl having a Mn col.ce.,LL~Lion from 0.001 to 0.03125 gr. mn/gal, ~uch that fuel economy of the reduced boiling temperature fuel i8; ~ ~v~d over the unadjusted fuel.

Example 12~
The example of 125, wherein T-90 tempe,~LuLes of the adjusted reformulated fuel is approximately 260~F to 280~F, or less, and/or the driveability index is less than 1160, 1155.

It is also contemplated that toluene will constitute a greater compositional role, and exist in greater volume ..c~..LL~tions in future gasoline compositions, inrln~;nq aviation fuels. Contemplated toluene volume percent include 0.2, 0.5, 1.0, 2.0, 2.5, 3.0, 5.0, 5.5, 6.0, 7.0, 8.0, 10.0, 12.0, 15.0, 16.0, 18.0, 20.0, 25, 30.0, 35.0, 40.0, 50.0, 60.0, 70.0, 80.0, 90.0, 100.0 pelcenL~ge.
FUrth~ ~, limitation on Reid Vapor PL~SDUL~8 (RVP) are contemplated to for example egual to or less than 9.9, 9.5, 9.o, 8.7, 8.5, 8.2, 8.1, 8.0, 7.9, 7.7, 7.5, 7.0, 6.8, 6.5, 6.2, 6.0, 5.8, 5.6 PSI, or less. Limitations on sulphur c~ .LL~tions are contemplated, including those less than 550, 500, 450, 400, 350, 300, 250, 200, 150, 100, 75, 50, 25, 20, 15, 10, 5 ppm, or less than 0.002 wt %, W095/33022 2 1 9 4 5 7 2 1 ~lIU~,_.'C'758 ~

~n~ln~ing sulfur free compositions, and naphtenes at les6 than 7~ (or le6s than 0.5%, if practical) by volume are contemplated.
Emis6ion6 of paramount concern is toxic ~ ion~, which this invention u~le~,ueoLedly reduces, on a mass basis, on the order of 5%, or more, over conventional and other reformulated gasolines. This is a most unexpected dev~ . For example, it has been found that the levels of 1,3-butadiene (a regulated toxic) increase in the presence of MTBE when reducing olefins and T-90 temperatures. Furth~ ~, it has been found that formaldehyde exhaust ~mi ~fi; nn actually increase when aromatics are reduced and/or when NTBE is added.

r le 130 An lln~ d, ph~Dll~Lu8 free, reformulated gasoline composition having a max of 8.5, 8.0, 7.5, 7.8, 7.7, 7.6, 7.5, 7.4, 7.4, 7.3, 7.2, 7.1, 7.0, 6.9, 6.8, 6.7, 6.6, 6.5, 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, 5.2, S.0 psi RVP; a max of 5.0S to 10.0% vol olefins (6.0% to 9.0%, 6.0% to 10.0%, 5.0% to 8.0%), a max of 27, 25, 20, 19, 18% vol aromatics (preferably 15%, 10%, or lower), a max of 1.1, 1.0, 0.9, 0.8% benzene (preferably less than 0.7%, 0.6%, 0.5%, 0.4~, 0.3%, 0.2% or benzene free~, a max of 100 ppm sulfur (preferably 50 ppm or less or sulfur free), an 02 cu..c~ ,ation ranging from 1.8% to 2.2%, 2.0% to 2.7%, 3.5%, 3.7%, 4.0% 02 wt of dimethyl carbonate, MTBE, ETBE, TAME, ethyl tertiary amyl ether, ~ wOgsl33022 ' 2 1 9 4 5 7 2 ~ 758 diisopropyl ether or ethanol, or mixture, a cyclomatic ~-n~ In~e tricarbonyl compound at 1/64 to 3/16 gr. Mn/gal tl/32 gr mn/gal preferred), a max T-90 t- ~tuLe of 260~F
to 280~F, or less, a T-50 t ~LULe of approx. 160~F to 230~F tl70~F to 205~F, 175~F to 210~F, 175~F to 225~F, 180~F
to 210~F), maximum T-50 t~ ~LULe equal to or less than 100, liO, 120, 130, 140, 145, 150, 155, 160, 170 degree F;
a driveability index number equal to of less than 1200, 1190, 1180, 1170, 1160, 1155, 1150, 1140, a bromine number of not greater than 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, or less; an average latent heat of vaporization of 890, 900, 905, 910, 915, 920, 925, 930, 910 to 930, 915 to 940, 915 to 950, 920 -to 960, 925 to 970, 930 to 980 BTU/gal, or greater.
r le 131 The Example of 130, wherein the fuel contains an ashless dispersant, in~lrt;s-n control/deposit control additive tinrlll~;ng combustion chamber, port fuel injector, and intake valve deposit additive) in conformity with S 211 (l~ and a~L~.iate regulationfi of the Clean Air Act; and optionally containing a minor amount of a co-solvent to enhance water solubility, such as hexanol.

r le 133 The Example of 130, 132, wherein the injected fuel particle has an approximate injected ~L~UL~ of approximately 15 to 45 psi.

W09St33022 2 1 9 4 5 7 2 . ~ r ~ /aO ~

r le 134 Method of combustion example 130, wherein the temperature of combustion i6 sufficiently reduced that under for example a load of 20 indicated horse power exhaust gas temperatures are reduced by at least 10~F to 50~F (or more), whereby the average exhaust gas temperature entering the exhaust gas inlet is less than 1400~F (or such other temperature that r-n;An~e oxide coating of the catalyst wash coat and/or monitor does not appreciably occur).

E le 135 A method for controlling the combustion formation of hazardous heavy ~ J~ e oxides comprising: Mixing an nnleAded h~dL~aLb~n fuel base, re~ormulated gasoline base, diesel base, or leL~ lated diesel (in~ln8i~; those set forth herein) with a burning velocity increasing and/or combustion t~ ~ atuL ~ reducing amount of an ECS ~
including one selected from the group consisting of carbonic acid dimethyl ester, methyl tertiary butyl ether, ethyl tertiary butyl ether, methylene di methyl ether, tertiary methyl amyl ether, diisopropyl ether, Cl to C6 alcohols, and mixture; and a combustion improving amount of at least one r ~ preferably a cyclomatic rongAnP~e tricarbonyl - _ '; combusting said fuel in an engine operating under load equal to or in exess of approximately 16.0 ihp; whereby combustion tempe~a~u,~s are reduced; exhausting engine out gas through an _mi ~i nn ~I W0 9~/33022 ' 2 1 9 4 5 7 2 J ~ 7~8 control system employing a reduction cataly6t, particulate trap, or three way exhaust catalyst system; wherein said method avoids deposition of harmful heavy rqngAn~e oxides and/or other deposits upon combustion chamber, fuel in;ectors, or intake valves; emitting resultant exhaust into the a~ re; whereby hazardous ~mi ~Si ~n~ are reduced.

r le 13~ =
The method of Example 135, additionally comprising via the illLL~du~Lion of an ESC . ' into said fuel, igniting said fuel, wherein H, H2, OCH3, or OH free radicals are formed in sufficien,t quantity as int~ te combustion product to increa6e said resultant fuel 1 8 1~ burning velocity over burning velocity of base fuel alone, absent ESC ' and/or - L llic.

r le 137 The method of Example 135, wherein said engine is operated under a load of 20 ihp, or greater, whereby ~Yp~fPd engine out combustion exhaust/gas t~ ~LUL~r- or combustion t~ ~LuL~6 are reduced by up to approximately 15~F to 59~F, or more, and/or where fuel economy is i uv~d.

r le 138 The method of Example 137, wherein said resultant fuel has a combustion chamber deposit reducing/control additive W095l33022 ' 2 1 9 4572 ~ 758 ~

and/or a mid-range and/or T-90/end-boiling distillation fraction temperature lower than existing conventional g~ol in~ or diesel (or as otherwise set forth herein~.

E le 139 A method, wherein reduced t- ~Lu~~ engine exhaust gases are from an nnlP~d g~Clin~ system and are vented through an exhaust emissions catalyst, whereby ~mi ~ n system's onboard catalyst monitoring does not fail due to false catalyst oxygen storage capacity readings and/or oxide desposition upon the monitor.

r ~e 140 The above methods or compositions, wherein they can qualify for an EPA waiver under S 211 (k) of the Clean Air Act.

r le 141 A low toxic fuel economy improving composition comprising an nnle~d fuel composition comprising pho5rhoru8 free hydrocarbons, having a max of 8.0, 7.0, 6.5, or 6.0 psi RVP; a max of 6.0%, 5.0% vol olefins, a max of 25%, 20% vol aromatics (preferably 15%, 10%, or lower), a max of 0.8% benzene (lower or benzene free) a max of 40 ppm sulfur (lower or sulfur free), a total 02 concentration ranging of 1.0 to 2.7~ wt or 3.5~ 02 wt of dimethyl u~Lbu,.aLe, NTBE, ETBE, TAME, or ethanol, a cyclomatic r-ng~n~e tricarbonyl ' at 1/64 to 3/16 gr. Mn/gal ~ Wo95/33022 ''' ~ 2 ~ 9 ~ 5 7 ~ 7~8 ~preferably 1/32 gr. Mn), a max T-90 t~ _ ~LULe of 300~F, 280~F (preferred), a T-50 temperature of approx. 170~F to 230~F., a minimum (R+M)/2 octane of 87, a bromine number of 20 or less, an average latent heat of vaporization of 900, 910, 920 or more BTU/gal at 60~F; a heating value greater than 106,000 btu/gal at 60~F (more preferably greater than 108,000, 114,000 btu/gal); whereby toxic 1,3-butadiene, fnr~ hyde~ or ~cet~ hyde emis6ions are reduced and/or fuel economy 16; _ uv~d.
E le 142 The Example of 141, wherein the o~yy~l.aLe is MTBE at 2.0% wt and the average latent heat of vaporization of the fuel exceeds 900 }3TUjgal Q 60~F and is preferably greater than 905 BTU/gal Q 60~F; MMT u - lr~tion is 1/32 gr./gal;
and average heating value of the composition exceeds 106,000 btu/gal at 60~F; has an average laminar burning velocity of at ambient conditions greater than 48 cm/sec.

r le 143 The MTBE composition of example 142, wherein the MMT
concentration is greater than 1/32 gr mn/gal.

E le 144 The examples above, wherein the oxygenate is DMC and - the MMT cu.,ce.. LL~tion is greater than 1/32 gr mn/gal.

, . . = . ~ , l wo gs/330z2 2 l 9 4 5 7 2 PCT~S95/06758 ~

r le 145 The composition of examples 141, wherein RVP is 6.8, 6.5, 6.0, 5.5 p5i or lower.
In the practice of this invention, in view of reducing regulated emissions, preferred g~rol inP compositions include, but are not limited to those which have the following specifications:

TABL~ 6 T.P~ FP~ ~n~r.
~ ,~ C
Reid Vapor Pressure (max psi) 8.7 .o 3.0-6.0 Olefin (max volume ~) 9.2 8.0 .0-8.0 Aromatics (max volume %) 32.0 20.0-25.0 .0-10.0 Benzene (max volume %) 1.5 1.0 .0-0.5 Sulphur (max parts/million) 339 100 0.0-lO
Oxygen (weight ~) 0.0 2.0-2.7 2.0-5.0 T-90 tMax ~ ~Lu~ ~F) 330.0 320.0 300-330 (R & M)/2 (min) 87.0 87.0 87.0-95.0 DMC (optional) 02 wt .8-2.1 2.0 2.7 LXV btu/lb 152 153 156 Burning velocity optional cm/sec (min) 49 51 50 Netallic (NNT) 1/64 1/32 1/30 E le 145a A composition of matter comprising; an nnl r~
conventional or reformulated g~rol i n~ composition (the later comforming with 211(k) of Clean Air Act), said ~ w095l33022 ? 1~45~2 P~

composition additionally characterized as having a minimum latent heat of vaporization at 145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156 btu/lb e 60~F, and optionally a minimum laminar flame burning velocity of 45, 46, 47, 48, 49, 50, 51 cm/sec.

Exam~le 146 The Example fuels of 145a, B and C of TABLE 6 above, wherein 1) said fuels contain Applicant'~ oxygenated means and a 2) combustion improving amount of r n~nDce~ and 3) wherein the _ ~;nDA ev~puL~tive emissions of said fuels' ~torage and its delivery to a combustion chamber, and emitted ~L ~'-~ric combustion emi6sions, are 4) such that in the year 1995 said fuel's volatile organic Dm;~ nc and toxic air pollutants, on a mass basis, are 15% lower than the h~cDl;nP g~Qol;np as defined under S 211 (k) of the Clean Air Act, and are 5) such that in the year 2000 said fuel's volatile organic _ _ ~ D~;ccj~nc and toxic air pollutants, on a mass basis, are 25% lower than said h~c~l;ne gasoline.

r le 147 An nn1P~D~, phocrh~rus free, reformulated gasoline composition fuelc having a max of 8.0, 7.2, 7.0, 6.5 psi RVP, a max of 8.0%, 6.0% vol olefins, a max of 20-25~ vol aromatics, a max of 1%, 0.8% benzene (preferably less), a max of 300-40 ppm sulfur (preferably lower or sulphur free), an 02 c~..c~.,LL~tion ranging from 2.0 to 2.7% wt or 21 94~72 W095/33022 ~ rc~ c:7~ o 3.5~ 02 by weight of dimethyl carbonate, a cyclomatic r~nq~nP~e tricarbonyl ' or mixture at 1/64 to 3/16 gr. Mn/gal (preferably greater than 1/32 gr/gal), a max T-9o temperature of 300~F to 320~F ~preferably 280~F or lower), a preferred T-50 temperature of approx. 170~F to 220~F; a minimum latent heat of vaporization of 900, 905 BTU/gal Q
60~F (preferably greater than 920 BTU/gal Q 60~F ); a minimum heating value of the composition A~llm;nq 2.0~ 02 weight of 106,000, 110,000, 113,000, 116,000 BTU/gal Q 60~F, and a minimum average laminar burning velocity at ambient condition6 of 48 cm/sec (50 to 52 cm/sec or more preferred).

r le 148 The above example wherein the composition additionally contains deposit control additives in conformity with S 211 (1) and related Sections/regulations of the Clean Air Act.

~y~nle 149 Example 147, wherein the composition optionally contains at least one C4 to C6 alcohol or other additive assuring hydroscopic stability (water solnhility).

Example 150 A fuel injection system that injects the fuel vapor of Example 19, under acceptable pressure into a combustion chamber, wherein average vapor particle sizes are less than 60 microns, and wherein computer Pnh~nred EGR, an onboard ~ wog~l33022 2 1 9 4 5 72 P~ 7~8 oxygen sensor, injection sensors, air inlet cooling system or turbocharger i5 employed; whereby fuel synergi6m exists.
Applicant notes that said - -nir.~l systems are ~ynergistic to Applicant's invention in they show a greater - 5 in~L. L~ L for ECS fuels than clear co-fuels.
Thus, the in~L~ L~ . t for ECS fuels divided by the in~L- Lal i ~, L for co-fuel tabsent ECS
, L) i5 greater than one.

r le 151 A system, wherein the fuel injection system injects a fuel vapor under optimum pressure into a combustion chamber, wherein average vapor particle sizes are 10, 20, 30, or 40, wherein a turbocharger, EGR system, an onboard oxygen sensor, and injection sensors are simul~n~ollcly employed; whereby fuel economy is i ~v~d by at least 2~.

F le 152 A method, wherein the combustion chamber is ~iqn~d to increase turbulent burning velocity, and wherein the ~ ~ssion ratio is 2.0:1 to 6.5:1; 7.5:1, 8.0:1, 8.5:1;
9.0:1; 9.5:1, 10:1, 10.5:1, 11 0:1, and more preferable 11.5:1.

~Y le 153 [Omitted]

W09~33022 ' 2 1 ~ 4 5 7 2 P~ ,5.~758 ~

e 154 The above examples, wherein the - es6ion ratio ranges from 9.5:1 to 12.5:1.

E~r~le 155 The examples above, wherein the combustion chamber i5 ~;5n~A to increase turbulent burning velocity, and wherein the e~sion ratio exceeds 17:1.

E le 156 The examples above, wherein the combustion system operates in conjunction with a regulated exhaust/emission control system employing an Pm;~io~ catalyst and an on-board oxygen sensor.

r le 157 A method of operation, wherein at least 30% of the ~.s. automotive fleet operates on said fuels, whereby total reference ~o--c~llLL~tions of air borne r-ng~n~se emitted from such operation, does not exceed 0.05 ug/m3 or EPA
standards, which ever is lower.
Applicant's gasoline compositions expressly contemplate reductions in emissions and compositional characteristics as set forth in Tables 7 and 8, below.

~ W09~33022 - 2 1 9 4 ~ 72 P~ 7~8 TABLE 7 COMPL~Y u~m~T. 8T~ND~PnQ FOR RFG

P~aSE 1 P~ASE 2 P~h.l~ 1995 2000 and after VOC REDUCTION t%)/GAL(1) - Class B 35.1 27.5 Class C 15.6 25.9 NOx k~ ON (%)(1) Summer 0-1.5 5.5-6.8 Winter 0-1.5 o 1.5 TOXICS REDUCTION(l) 15.0-16.5 20.0-21.5 OXYGEN (WT%) 2.0-2.1 2.,0-2.1 BENZENE (vol%) 0.0-1.0 0.0-1.0 Note 1 Reduction~ are ~rom the h~l ;n~
gasoline defined under S 211 (k) (10) (B) WO 9Sl33~22 2 1 9 4 5 7 2 ~ '758 ~

EYANPLE FUEL8 COMPLYI~G WITH CLA88 C RFG ~rT ~ -PRU~h,lhS PHASE 1 PHASE 2 1995-2000 2000 and After REDUCTION % (1) VOC'S 17.3 27.6 N0X 1.6 6.9 TOXICS 25.4 27.6 15 ~O~K~l~S
RVP (psi) 8.0 6.6 OXYGEN (WT%) ( 2) 2.1 2.1 AROMATICS (VOL~) 25.0 24.0 BENZENE (VOL%) 0.95 0.95 OLEFINS (VOL %) 9. 2 9.2 SULPHUR (ppm) 339 185 E200 41.0 45.0 E300 83.0 87.0 MAngAnP5e (Gr. Mn/g) (3) 1/32 1/32 ~0 Note 1 r-~nrtinn~ are from the bA~plinp gasoline defined under S 211 (k) (10) (B) Note 2 In the form of dimethyl carbonate.
Note 3 ~qn~Anp~e ~ LLations may range from 1/64 to 1/4 gr. Mn/gal.

An example of a reformulated gasoline comprises a gasoline base with less than 0.01~ wt 6ulfur, MTBE 7% max.
by vol., benzene 5.0% or less by vol., kerosene 4.0% or less by vol., existent gum 5 mg/100 ml max, unwashed gum 20 mg/100 ml max, RON 96.0 to 89.0, density at 15~C 0.783 max, T10 70~C max, T50 125~C max, T90 180~C max, F.B.P. Z20~C max, Re6idue 2% max, copper corr. max 1, RVP 44-78 kPa, induction time min. of~ 240 min ' - 2194572 w095l33022 ~ 758 In the practice of this invention, when formulating gasoline compositions to meet RF~ standards, tailoring may be required to accomplish the objects of this invention. It has been found that various ~, which have the ~ 5 largest effect in reducing specific target emissions may be tailored: For example, VOC's are effected mostly by RVP, Aromatics, Sulphur. NOx are effected mostly by sulphur~
Aromatics, Olefins; and Toxics are effected mostly by Benzene, Aromatics, oxygen.
10International Application No. PCT/U595/02691 presents ref~ l~t~nn practice, which ig incu~uL~-ed by reference.
RQ~n~ nR in sulfur content linearly influence reductions in NOx, toxic, and VOC Qmi~inn~ (in order of their relative ~ Qmi ~si~n reductions). For example, a 15reduction in sulfur from 340 ppm to approximately 50 ppm causes a rQ~n~ n of NOx, toxic, and VOC QmiRsi~n~ of about 11.0%, 8.5~, and 3.5~, respectively. It appears that reductions in NOx Qmi~ion~ are strongly influenced by reductlons in sulfur content. In the practice of this invention sulfur cu-lc~l-LL~tions less than 40 ppm are particularly preferred. Sulfur content 30 ppm or less (or sulphur free) is even more preferred. Again, the operation of this invention will permit envi~ lly acceptable NOx, Toxics, and VOC's even at sulfur cu,-cenLL~tions higher than currently permitted under the regulations.
However, sulfur ~u-.~..Ls~tions on the order of 200 ppm or more Appear to be acceptable, due the increased burning velocity and reduced co_bustion temperatures of instant ,, ,, , , ~

W09s~3022 21 94 572 r~ 75~ 0 invention, which appear to inhibit sulfur's adverse NOX and Toxic ~;RRi~n characteristics.

~viation 4aBol; r -The invention also contemplates aviation gasoline co-fuel applications and resultant fuel6 meeting ASTN D 910 ~pecifications (see TABLE 9), ~RperiAlly those that are lead free. However, unlike other ~hoAi ' R of Applicant's invention, while less preferred aviation gasolines may contain minor amounts of lead. However, Applicant's preferred ~ -nt is lead free.
Applicant's invention contemplates a broad application in aviation gasolines for civil and military uge, inrll-Aing those applications, which do not comply with ASTN
standards. Thus, TABLE 9 is intended to define aviation gasoline suitable for most types of spark-ignition aviation engines; however, certain equipment or conditions of use may re~uire fuels having other characteristics.
A major problem with aviation gasolines and related combustion resides in the substantial incompleteness of combustion at altitude. Combustion i n' , l~teness is a function of the fuel's composition, air/fuel ratio's, altitude of operation, and generally the amount of air passing through the engine.
The principal advantage of Applicant's invention is that it radically improves the thermal efficiency or useful amount of work available from a given amount of fuel under operation at altitude, --~d to traditional fuels.

.

~ W0 95/33022 2 1 9 4 5 7 2 ~ '758 In today 1 6 aviation gasoline engines the completeness of combustion under altitude conditions approaches 85% (see M. Scott, R Stansfield, T. Tait, J. Tn~t. Petrol~lm. 37, 487 tl951)).
~ 5 Quite uneYpectedly, in the practice of ~pplic~nt's invention complet~n~ss of combustion and thermal efficiancy at altitude increase6 over 2.0%, 5.0%, 7.5%, 10.0%, or more. Thus, the flight range of an aviation gasoline powered aircraft employing Applicant 15 composition and method should be eYtended 2%, 3~, 4~, 5% to 30%, or more, ~op~n~;ng upon application.

r le 158 A aviation fuel boiling meeting ASTM specifications comprising: an ESC fuel (cont~;n;ng preferably MMT at 0.25 to .75 Mn gr/gal of finished fuel and DMC ranging from 0.5%
to 10.0% of f;n;~h~ fuell, a aviation co-fuel comprised substantially of hydrocarbons; such that resultant fuel meets strict ASTM standards; and is characterized as having a latent heat of vaporization ~Y~oe~;ng 120, 130, 140, 150, 155, 160, 165, 170 BTU/lb; and whereby said fuel when combusted in an internal combustion engine at altitude of at least 5,000 feet above ground level increases the complet~n~s of combustion to amount greater than 85%, 86%, 87%, 88%, 89%, 90%, or alternatively increases thermal engine ~ffici~nr-y by at least 2.0i! 3.0%, 5.0%, 7.5%, 10.0%, or more, over the unadjusted aviation co-fuel.

., ~.. , ; -..... .

WO 95/33022 2 1 9 4 5 7 2 1 ~ r 0C758 0 AsrM D 910 S AVIATION GASO~SN

ASTM
Grade 80 Grade 100 Grade 100LL Test MethodJ
Knock Yalue, min, octane number, lean rating 80 100 100 D 2700C
Knoclr value, min, rich rating:
Minimum octane number 87 D 909 1~ Minimum F r number~~ 130 130 D 909 C,blorD red green blue D 2392 Dye content:
Pern11ssible blue dye,l' ma~l, mg/gal 05 4.7 5.7 Permissible yeUow dye,a ma~, mg/gal none 5.9 none Permisslble red dye,~ma~4 mg/gal 8.65 none none T~ ' 5,'ma~,mUgal o.s~ 4.0 2.0 D2559OrD3341 r . for aU Grades DistiUation i , ~, ~F (~C):
10 % evaporated, max temp 167 (75) D 86 40 % evaporated, min temp 167 (75) 50 % evaporated, ma~ temp 221 (105) 90 % evaporaled, ma~ temp 275 (135) Final boiling point, max, ~F (~C) 338 (170) Sum- of 10 and 50 % evaporated i . 307 (135)~
min, ~F (~C) DistiUation recovery, min, % 97 DistiUation residue, ma~, % 15 DistiUation loss, ma~, % 15 Net heat of combustion,~ n~in, Btu/lb 18 720 D 1405 or D 3338 Vapor pressure:
min, psi (I~Pa) 55 (38) D 323 or D 7551 mau, psi (I~Pa) 7.0 (49) D 323 or D 2551 Copperstrip corrosion, ma~ No. 1 D 130 Potential gum (5-h aging gum),~ max, mg/100 mL 6 D 873 Visible lead precipitate,L ma~;, mg/100 mL 3 D 873 Sulfur, wt ma~, % 0.05 D 1266 or D 2622 Free~ing point, mal~, ~F (~C) -72 (-58) D 2386 Water reaction volume change not to D 1094 e~ceed +2 mL
Perntissible ~ ~ v max, 4.2 lb/1000 bbl (42 gal) So ~ . contained herein are absolute and are not subject to correction for tolerarce of the test methods. If multiple J~are made, average results shaU be used.
' The test metbods indicated in this table are referred to in Section 9.
c The values shown in Table 1 represent Aviation Method Ratings. Motor octane ratings obtained by Test Method D 2700 should be converted to aviation tatings by Conversion Table 2.
55 D These colors bave been approved by the Medical Director Chief, Division of O
Health, US. Department of Health, Education and Welf~re.

~ WO 95/33022 21 9 4 5 7 2 r~ n. ~ o( ~
-1~511-~ABLe 9 (con~nuod~
~ ASrM D 910 ~ AVIATION GAS4I~

65 ~ If mutuaLty agreed upon between the purchaser and the suppLer, Gracte 80 may be required to be free from i '1~ ' In such a case, the fuel shaLt not contain any dye and the color as determined in accordance with Test Method D 156 shall not be darl~er than +20.
r The onty blue dye whtch shaD be present tn tho finished gasoLine shaLt be essentiaLty 1,4 "' '~, ' '' ' The onty yeLtow dyes which shaLt be present in thc finished gasoLne shaLt be cssentiaDy p-~ (colortndel~No-ll02l)u~l t,a7'-[3,3'-dimethyl][l,l' ! '.- ,~; ~,4 dlyl]bis(azo) bis [4-nonyl] (Color tnden Solvent YeLtow No. 107), or 1,3 P 1, 2,4-bis [(~, i ,I)P '']
~ The onty red dyes which shaLt be present in the finished gasohne shaLt be cssentiaLty methyl derivatives of ~ ~ 2-naphthol (methyl derivatives of Color Inde~c No. 26105) or aLltyl derivatives of ~ 1 r7A 2- ~ .
~ The i '1~ ~- ' shaLt be added in the form of an antitcnocl~ millture containing not less than 61 weight % of i ~ ' and sufficient ethyleno dibromide to provide two bromine atoms per atom of lead. The batance shaL contain no added ingredients other than tterosine, and an approved inhlbitor, and blue dye, as specilied, herein.
~ Use the value calcutated rrom Table 1 in Test Method D 14,)5. Test Method D 2382 may be used as an alternative method. Ln case of dispute, Tcst Method D 2382 must be used. Ln tbis latter case, the minimum vatues for the net hea, of combustion in Btu's per pound shaLt be 18 700 for Grades 80, 100, and 100LL
~ Note that the temperature conversion for the sum is Cl + C2 = 5/9 (Fl - 32 + F2 - 32).
~ If mutuaLty agreed upon between the purchaser and the suppLier, aviation gasohne r~ay be rcquired to meet at 16-h aghg gum test (Test method D 873) instead of the 5-h aging gum tesL
In such a case, the gum content shaLt not e~cceed 10 mg per 100 Mt and the vis~ble lead procipitate shaLt not enceed 4 mg per 100 mL Ln such fuel L~le permisslbLe antioxidants shaLt not cnceed 8.4 Ib per 1000 bbl (42 gal).
L The vislble lead precipitate requirement appLes onty to leaded fueLs.
Y Permisslble antionidlmts are as foLtows:
N,N"' . .
N,N' ~' . ~ ! ~1,- 1 ~ . ..
7~ 6 t~
76-ditertiary 1 ~, ~ ~ ~, 'j ~
?,fi :'' ' ~ butylphenol 75% min ?,~ :'" li~,~ butylphenol plus 25% 1~ tertiary and tritertiuy butylphenols 75% min di- and tri-isopropyl phenols plus 25% mal~ di- and t~ ,- phenoLs 100 These inhlbitors may be added to the gasohne separately or in ! ~' ', in total not to e~eed 4.2 Ib of inlubitor (not inctuding weight of solvent) per 1000 bbl (42 gat).

W095/33022 2 ~ 94572 r ~ 758 0 Three principal grades of aviation gasoline contemplated by this invention, which meet ASTM ,Land~ldD, include: Grade 80, Grade 100 and Grade lOOLL.
Grades 100 and lOOLL represent two aviation ga601ines identical in anti-knock cIuality but differing in maximum lead content and color. The color identifies the difference for engines that have a low tolerance to lead.
Although the grade designations show only a single octane rating for each grade, each grade must meet a minimum lean mixture aviation rating and a minimum rich mixture super-charge rating.
Aviation gasoline has traditionally been comprised of substantial cIuantities of isoo~Lane and/or alkylated material. Applicant contemplates his aviation gasoline co-fuels may consist of blends of refined h~drv~ 01l3 derived from crude petroleum, natural gasoline, alkylates, blends thereof from synthetic hydru~LLùn~ or aromatic hydrocarbons, or both. Aviation gasolines has may derived in whole or part from bio-substituents.
As thermal efficiency i ~ are a principal object of this invention, aside from c~..,LLu~ing fuels to acheive the maximum latent heats of vaporization and to meet strict ASTM standards (;nrln~ing heat of combustion, etc.), Applicant's preferred order of fuel ~c _ ts (in order of their preference) are: paraffins, monocyclic napthenes, cyclo-olefins, bicyclic n~rhPnP~, aromatic monocyclic with side chains, aromatic monocyclics and aromatic bicylics.

~w095l33~22 2 I q 4 5 7 2 ~ r-7s8 Applicant has found that by prioritizing his fuel Ls, after meeting his LHV object aDd ASTM
standards, that Applicant is further able to improve thermal efficiency.
- 5 Additional avaition gasoline practice is ~i~cl~ in International Application No. PCT/U595/02691 and incuL~u~ted by reference.
Additives other than tetraethyl lead, dyes, and an~Y;~Ants specified in Table 9 are permitted under 5.1 and Section 7 of ASTM ~p~;fication D 910. These include fuel system icing inhibitor and special purpose additives.
Additional avaition gasoline practice is ~i~rlosed in International Application N~a. PCT/US95/02691 and in~uL~L~ted by reference.
In ~ppl;c~nt~s preferred practice DNC is employed as the ECS _ _ ' of choice. Due to the high relative cu..c~,.LLations of oxygen (e.g. 53S by weight), smaller volume quantities of DMC need be employed to acheive the ~ame oxygen cu-.~e~-LL~tions as MFr3E (e.g. 18.2% by wt), TAME
(e.g. 15.7~ by wt).
Thus, on a heat of combustion basis, while DMC has lower total heat per gallon (e.g. approx. 57,000 btu/gal) t ad to MTBE's (e.g. approx 94,200 btu/gal), TAME
(100,600 btu/gal), DMC has superior heat of combustion on a per oxygen weight basis. Consequently, a co-fuel can ~ maintain a greater proportion of its heat of combustion, given the same amount of oxygen, when said oxygen is added by DMC as ~ d MTBE, ETBE or TAME. Thus, the addition wog~33022 2 1 94572 ~ 7S~ O

of DMC reduces the amount of additional high heating material nec~sAry to acheive minimum heats of combustion.

r le 159 A method wherein a ~nh~nr~d combustion vapor is combusted in a aviation g~olin~ engine; and is derived from DMC lep~s~ ing 0.01~ to 10.0~ oxygen by wt in the fuel (more preferably 0.1 to 5.0%), at lea8t one r ' 11;~
in a c~ncG..L-~tion of 0.001 to about 2.5 gr/gal (preferably 0.001 to 1.5 gr/gal, more preferably 0.001 to 0.75), an aviation gasoline co-fuel; wherein combined fuel is characterised as having a minimum knock octane number of 80, or 100 and minimum performance number of 87, or 130, optionally cnntAining lead, a max T10 distillation t~ ~-UL~ of 75~C, a minimum T40 t ~uLe of 75~C, a maximum T50 temperature of 105~C, a maximum T90 t~ ~LULG
of 135~C, a maximum end t~ _ ~LULG of 135~C, where the sum of the T10 and T50 ~ ~uLes is a minimum of 135~C, a maximum sulfur content of 0.05 wt~, optionally a minimum net heat of combustion of 17,500, 18,000, 18,500, 18,720, 19,000, 19,500 BTU/lb, a latent heat of vaporization ~Yr~ing 125, 130, 135, 140, 145, 150, 155, or 160 BTU/lb;
whcreby when combusted in said aviation engine at altitude of at least 5,000, 10,000, 15,000 feet above ground level combustion let~n~ or thermal efficiency (as reflected in range) is greater than unadjusted aviation co-fuel alone (preferably at least 2.0~ or more).

~W09~33022 2 1 ~ ~ 5 7 2 P~ 758 E~m~le 160 A method of operating a gasoline aviation engine on an ~nhAn~d combustion vapor, wherein said vapor is combusted in an aviation gasoline engine; and is derived from an ECS _ ' representing 0.01% to 15.0% oxygen by weight of a fuel, an organo r-~g~n~e le~L~s~ ing about 0.001 to 3.0 gr Mn/gal of fuel, and an ASTN or other aviation co-fuel having a minimum heat of combustion of 18,720 BTU/lb; whereby said : ~;n~ fuel has heat of combustion lower than 18,720 BTU/lb due to dilution effect of DMC; said method characterized in that aviation engine combusting lower heat of combustion vapor has increased flight range compared to higher heat of combustion vapors from co-fuel alone (preferably greater than 2.0S).

r le 161 A method above, wherein said engine is u~L~ted on an air-fuel ratio of 30, 35, 40, 45, 50, 55, 60 (preferably 35 to 60, more preferably 40 to 60; wherein said operation employing DMC ~Lesel.ts an incL~ 'Al thermal efficiency ~ L for ECS fuel over same i _ u~. ~, if any, for co-fuel alone.

r le 162 An llnl~ d aviation fuel composition meeting ASTM
standards comprising 2.0% oxygen by weight in form of an ECS _ ' (preferably DMC), a combustion ~h~nr; ng amount of a metallic (preferably r-~g~n~se in a , ~ ~,, .: . . , '.

W095/33022 2 1 q 4 5 7 2 r~~ E758 o concentration of 1/4 to 5/8 gr/gal), and a minimum heat of combu~tion of 18,720 BTU/lb; whereby the in~L~ ~ Al lost heat of combustion of the composition due to addition of ECS ,_ ' is less 1500, 1000, 750, 500, 300 BTU/gal or 250, 160, 120, 80, or 50 btu/lb.

RYAr~le 163 A liquid aviation g~col ;nQ fuel comprising DMC at 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5%, or more, oxygen by weight in the fuel and at least one r-ngAnDce metallic lepLes~--Ling 0.001 to 1.5 gr/gal, and an aviation co-fuel base; wherein , ~;nQd fuel is characterised as having a minimum knock octane number of 80, 100, 100, and minimum ~f~L~nce number of 87, 130, 130, a max T10 distillation f~ _ ~tuLe of 75~C, a minimum T40 t~ Lu~ of 75~C, a maximum T50 t~ ~Lu~ of 105~C, a maximum T90 t~ ~uLe of 135~C, a maxi~um end ~ ~LULe of 135~C, where the sum of the T10 and T50 t~ _ aLuL~8 is a minimum of 135~C, a maximum sulfur content of 0.05 wt%, a minimum net heat of combustion of 18,720 BTU/lb, a latent heat of vaporization QYreQ~ing 120, 130, 140, 150, 155, or 160 BTU/lb.

E le 164 The example of 162, wherein fuel originally meets ASTM
D 910 heat of combustion standards; and wherein 2.0% oxygen by weight in form of DMC is added, together with r-ng~n~ce in a c~ tion from about 1/4 to 5/8 gr/gal; said O wossl330~ Zl 94~72 rS~ 7s8 resultant CODposition is not adjusted for 1088 of heat due to addition of DMC; operating said aviation engine on lower heat of combustion fuel, whereby flight range i5 increased by at least 2.0% greater over original ASTM clear aviation - 5 co-fuel.

le 165 An ASTM aviation gasoline comprising a hyd~ u~ar Lu-ba~e, 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 t~ atuL~ is 167~ F and the T-90 temperature is less than 250~F, with the fuel sulfur content a maximum of 0.05 wtS (preferably less~, and a combustion improving amount of an ECS
__ '; whereby the 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 egual to or ~Yr~e~ing 40, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52 cm/sec.

E le 166 The example of 165, wherein the aviation gasoline composition is nnl~8~ and comprises a blend of llyJlo ~ a combustion improving amount of CMT ranging from 0.001 to 3.00 gr. Nn/gal, more preferably 0.001 to 2.0 gr. Mn/gal, 0.001 to 0.1 gr. mn/gal, 0.001 to 0.8 gr W095/33022 2 1 ~4572 ~ . 758 O

mn/gal, 0.001 to 0.6 gr mn/gal, 0.125 to 0.5 gr mn/gal (minimum amounts greater than 1/4, 3/8 gram/gal preferred), a combustion improving amount of DNC ranging from 0.01% to 20.0% 02 by weight (1.5% to 5.0% preferred, 1.5% to 2.5%
more preferred), whereby the octane rating number as t~rmin~ by ASTM D 2700 is at least 100, with the balance of the fuel's specifications strictly conforming to strict ASTM standards; and whereby the fuel's LHV exceeds 145, 144, 145, 146, 147, 148, 149, 150, 152, 153, 154 BTU/lb.

~xam~le 167 The nnl~Dd composition of 165, wherein CNT i6 greater than 1/16, 1/8/, 1/4, 1/2, or 5/8 gram Nn/gal, and the combustion improving amount of DNC is greater than 1.0%
02 by weight, preferably qreater than 1.5%, and the minimum net heat of combustion of composition i8 approximately 18,500 BTU/lb, 18,720, 18,800 BTU/lb., or more preferably greater than 19,000 BTU/lb, and flight range is increased over clear fuel alone.

ample 168 The nnl~ d composition of 165, wherein CMT is greater than 1/16, l/8/, l/4, 1/2, or 5/8 gram Nn/gal, and the combu6tion improving amount of DMC is greater than 1.0%
02 by weight, preferably qreater than 1.5%, and the net heat of combustion is approximately 16,500 to 18,500 BTU/lb, wherein flight range is increased at least 5% over the clear fuel.

O Wos~/33022 2 1 q 4 5 7 2 . ~ s8 ~le 169 A method of operating a aviation gasoline power aircraft; said method characterized: by mixing a fuel of eYample 165, supplying said fuel to an injection or - 5 vaporization system, wherein said fuel is injected into an engine manifold or combustion chamber, wherein average fuel droplet particles is less than 80, 70, 60, 50 microns;
whereby combustion of said fuel results in an increase in power, thermal or combustion efficiency greater than clear fuel preferably 2.0% or more.

r le 170 A method above, wherein the fuel is COIIDL' ucLed employing DMC such that combustion t~ ~Lu.~s are reduced by at least 25~F, and whereby thermal efficiency is ; ~v~d by 5% to lOS and/or the operation of aviation gasoline - engine life is extended by at least 5.0%

E le 171 2() ~he example of 169-170, wherein the fuel additionally haD an end boiling t~ _ ~LUL of less that 300~F, (or alternatively a T-90 temperature less than 250~F), and an average latent heat of vaporization increased over base fuel by at least 2.0S, preferably 5.0%, or more.

, ~

W095/33022 2 1 9 ~ ~ 7 2 r~ 758 o r le 172 The examples above, wherein the fuel's aromatic content is less than 20 volume percent, and wherein benzene is less than 1.0% by volume.

FY le 173 The examples of 169-170, wherein the fuel is combusted in a spark ignited internal combustion engine, equipped with fuel injection or manifold, and/or other means, wherein fuel particles averaging 70, 60 microns, or les6, are c ;cated/injected into the combustion chamber; and wherein said combustion is occurring at an altitude of at 5,000 to 10,000 feet above sea level, or more; and wherein combustion efficiency is increased by at least 5.0~.

r le 174 The aviation gasolines o~ the above examples meeting ASTM D 910 specifications, and a combustion improving amount of dimethyl carbonate and CMT in a col.~e.lLL~Lion from about 0.001 grams to about 0.125 grs per gallon.

Example 175 In combination, an aviation gasoline meeting ASTM D
910 specifications, a spark ignited aviation gasoline engine, wherein said combination is characterized in that:
said fuel contains a combustion improving amount of dimethyl carbonate up to 5.0% oxygen wt/gal, and a least one CMT __ ' in a c~o)c~ tion from about 0.001 grams 21 ~4~72 W095/33022 ~ C758 to about 1.00 grs ~n/per gallon, wherein said fuel L~
to ASTM requirements; and whereby improved engine thermal ~f f; ci~n~y i8 2.0%, or more.

Fuel n~ 1 ~
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 0118 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 through 5, which are found at TABLE 10.
International Application No. PCT/U595/02691 sets forth in detail Applicant's Fuel oil practice, which i5 incuL~L~ted herein by reference.
As noted, boiling point modification of fuels oils is an express '_'; L of this invention, ~p~;Ally that resulting increased LHV' 8 . It is expressly contemplated that T-90 t~ ~LuLas herein be reduced to maximum extend practical, but not below minimum required specification t~ _ ~Lu~a8. For example, T-90 t-~ ~LuLas may be reduced 20~ C below max ASTM specification temperatures. Reductions of 50~ C are al60 preferred so long as, as in the case of 2~ Grade No. 2 fuel oils, T-90 is not reduced ~elow 282~ C.

~ . . . ~ ~

DE~TAlLeD h~ ' . ~;~ POR PUeL Oll~

ASTM Test Grade No. 4 No. 5 No.
Proper~r Methodi3 No. 1 No. 2 (L4ht) No. 4 (Light) (Hea~) No. 6 Flash Point ~C, min. D 93 38 38 38 55 55 55 60 Water and sediment, % ~rol. max D 17% Q05 0 05 (0 50)C (0 50)C (l~oo)c ~Loo~C (2 00)C
Distillation temperature ~C D 86 10 % vol recovered, max 215 ... ... ... ... ... ... ~, 90 % vol recovered, min ... 282 ... ... ... ... ... ~~
max 288 338 ... ... ... ... ...
Kinematic viscosity at 40~C, mm2/s D 445 min 13 1.9 1.9 >55 ... ... .
ma~ 2.1 3.4 5,5 24 0 Kinematic vlscosit~ at 1~C, mm3/s min ... ... ... ... 5.0 9.0 15.0 U I
max ... ... ... ~ 8 gD 14,9 50.0 P carbon residue on 10% D 524 0.15 0.35 ... ... ... ... ...
distillation residue % mass, max Ash, % mass, max D 482 ... ... 0.05 0.10 0.15 0.15 ...
Sulfur, % mass maf D 129 0.50 0,50 ... ... ... ... ...
Copper strip corrosion rating, ma~, D 130 No. 3 No. 3 ........ ... ... ... ... ~-3 h at 50~C

.

(c~trn~ed) ~SIM D 396 DPTAlLeD hc~ FOR FUEL OILS~

ASTM Test Grade No. 4 No. 5 No.
- Property Method~ No. 1 No. 2 (Light) No. 4 (Light) (Heavy) No. 6 Density at 15~C, kpJm3 D 1298 min ... ... >876~ ... ... . ..
- ma~ 850 876 ........... ... ... ..
Pour Point ~C, malcG D 97 -18 -6 -6 -6 ... ...

~ It is the intent of these ~ that hilure to meet any requirement of a given grade does not lh, place an oil in the ne~ct lo wer grade unless ~
in fact it meets all . I . of Ihe lower grade. However, to meet special operating conditions ~ of individual limiting I , - m ay be a~reod 1~) u~on among the purchasor, seller and The test methods indicated are the approved referee methods. Other acreptable methods are indicated in Section 2 and 5.1. ~
c The amount of water by distiiiation by Test Method D 95 plus the sediment by e~action by Test Method D 473 shall not ~ceed the value shown in the table. r--For Grade No. 6 fuel oil, the amount of sediment by eatraction shall not e~ceed 0.50 mass %, and a deduction in quantity shali be made for all water and sediment ~n~
in e~ ess of 1.0 mass %.
D Where low suifur fuel oii is require4 fuel oii hiling in the viscosiq range of a iower numb~ed grade down to and inciuding No. 4 can be supplied by agreement between the purchaser and supplier. The v~cosity range of the initial shipment shali be identified and advanoe notice shaU be required when changing from one viscosity range to another. This notice shali be in sufficient time to permit the user to make the necessary adjustments.
6 Other suifur limits may appiy in selected areas in the United States and in other countrien ~ ' This iimit assures a minimum heating value and also prevents I and ,, of this product as Grade No. 2.
G Lower or higher pour points can be specified whenever required by cl)nditions of storage or use. When a pour point less than -18~C is specified, the minimum viscosity at 40~C for grade No. 2 shaii be 1.7 mm2k and the minimum 90 % recovered temperature shali be wa}vcd ~ Where low sulfur fuel oil is required, Grade No. 6 fuel oii wili be ciassified as Low Pour (+ 15~C max) or High Pour (no max). Low Pour fuel oii shouid be used uniess tanks and lines are heated.

w095/33022 ~1 9 ~ J 72 . .,~ _ 758 o There i8 gener~lly no limit on T-lo or T-50 r~l~t;~n~, nor T-90 reduction (except for No. 2 fuels) so long as the fuel i8 easily vaporized and operates efficiently, particularly in vaporizing type burners.
A minimum T-90 f', ~Lu~e limitation for Grade No. 2 heating oil is intended to maintain compatibility with at~ l~i ng type household heating burner applications.
otherwise, distillation limits are not specified for fuel oils of Grade Nos. 4, 5, and 6, and T-90 t~ -1 atULeS may be reduced to the extent practical, in order to improve combustion and/or reduce pollutants.

~mnle 176 A No. 2 fuel oil, with a kinetic velocity of no less than 1.9 nor greater than 3.4 (mmZ/s~ measured at 40~C, a minimum T-90 t~ ~Lu~ of 282~C, a max T-90 ~ ~LuLe 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 ' (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.

r le 177 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 ASTN D 445, And combustion improving amount of an ECS
_.-d, optionally a '~llir ~I woss/33022 ~ 2194572 r~ 00758 r le 178 The example of 176-177, wherein end boiling point r and/or T-90 fraction t~ ~LUL~ are reduced at least 30~C, employing boiling point modification; whereby LHV are - 5 ; uv~d.

Example 179 The operation of burners in a furnace, employing an ASTM grade fuel oil, containing a combustion improving amount of dimethyl u~-bu--aLe and a combustion improving metallic, wherein PYp~rta~ combustion efficiency of the furnace increases in range of at least 1.0% to 20%.

It is contemplated in locomotive and marine fuels meeting ~-u~-iate IS0 DIS 8217 and BS MA 100 standards, containing higher cu..~,.L.~tions of sulfur than most fuels, Arpl; ~Ant8 invention due combugtion temperature object, mitigates sulfur corrosion and generation of other pol l~tAnt-:.
E le 180 A method for ~nhAnr~ combustion of a vapor for heavy dlesel,locomotive or marine engine; wherein vapor is derived from DMC repr~C~nt;ng 0.01% to 40% oxygen by wt in the fuel, a r ' 11;~ repr~nt;ng 0.01 to 20.0 grs of metal/gal, and a heavy diesel, locomotive or marine engine co-fuel meeting IS0 DIS 8217 and/or BS NA 100 standards specifications; wherein said combination contains a sulfur W095/33022 2 ~ 9 ~ 5 ~ 2 , 11~ ~r~7ss o -~89-c~ tion of o.o1 to 3.0S mass, has a viscosity of 10 to 500 centistokes at 50~C; whereby combustion of said vapors results in reduced corrosion, particulate Dmi~si~
and/or ; vv~d fuel vv.,_ Lion ed to co-fuel alone.

E le 181 The method of 180, wherein said operation of said heavy diesel, locomotive or ~arine engine is under load (moderate to high load conditions~; whereby fuel con~, Lion is i vv=d by at least 0.5% to 5.0~, or more, over fuel absent ECS fuel.

r le 182 The fuel composition of example 180, additionally contains an ashless dispersant, which may be selected from an alkenyl s~cin;~ acid esters, alkenyl sl~cinim;~D of an amine, methylamine, 2-ethylhexylamine, n-dodecylamine, and the like (see U.S. Patents 3,172,892; 3,202,678, 3,219,666, 4,234,435) and/or a combustion chamber deposition control additive.

r le 183 The fuel composition of example 180-181, wherein the ECS fuel contains dimethyl carbonate from 0.01 to about 30.0% volume and a combustion improving amount of CNT.

~ W095/33022 2 l q 4 5 7 2 F~l/~,~.758 E le 184 A method of improving thermal efficiency in the operation of a locomotive or marine engine, wherein said method comprise6: injecting ln ECS based heavy fuel ~ 5composition into a combustion chamber, wherein combustion occurs at an accelerated, more Dff1CiDnt rate, and combustion tA _ ~LULe6 are reduced; whereby thermal Af f i ciDn~y increased by at least 5%.

l~D~nnTTIV~ PRACTICE
As set forth herein additive practice is a vital _ L of this invention. It is expressly contemplated that additives, additive methods, lubricants, and the like, set forth above in the various co-fuel applications be 15interchangible between co-fuels and neat fuel applications.
It is an express object of this invention to ~-Yiml~e the durability of fuel system _ An~c, prevent intake valve sticking, minimize combu~tion chamber deposit6 and the like.
20Appliant's invention contemplates a wide range of additives and ~uno ..L,~tions, inoln~inq but not limited to the following (with approximate additive c~ e,.L,~tion):
anti-oxidant~s) (8-40 mg/kg), wax anti-setting tlO0-200 mg/kg), anti-foam (2-5 mg/kg), anti-valve geat recDcsion 25(100-200 mg/kg), pipe-line drag reducing agents ~2-20 mg/kg), diesel detergents (10-300 mg/kg), ~ ifiers (3-12 mg/kg), diesel flow i ~V~L~ (50-1000 mg/kg), deposit control additives (50-3000 mg/kg), lubricity i uv~I~ (25-WO9S/33022 2 1 94 572 ~ _ 758 ~

looo mg/kg), anti-static (2-zo mg/kg), stsh;li~Qrs (50- 200 mg/kg), anti-icing agents (0.1-2.0% vol), corrosion inhibitor (4-50 mg/kg), combu6tion chamber deposit modifiers (50-3000 mg/kg), metal deactivator (4-12 mg/kg), dyes (2-20 mg/kg), cetane/octane i ~V~L_ (200-2000 mg/kg). Other contemplated additives include combustion ; _ ~V_LD, hjori~c, drag reducing agents, dehazers, r ' llir scavengers, friction modifiers, antiwear additives, anfi R ll~ge additive.
Non-limiting examples of Applicant' 5 anti-static additive6 include soluble ~I.r i materials, polymeric sulfur, nitrogen ~ _ ' , and quaternary il~
materials. Use is generally cnnt ~ ted in very cold ambient t~ _ ~LUL~8 and/or in fuels of int~ ste volatility such as aviation kero~enes.
Non-limiting examples of metal deactivators include N,N'-disalicylidene -1, 2 - prop~nP~i~rinp~ and its basic ' sni F~ ig to chelate dissolved copper, mitigating surface formation of - L llir. salts/deposits, etc. Non-limiting examples of drag reducing agents include high molecular weight (1,000,000) polyisobutenes and polyalphaolefins.
Non-limiting examples of dyes include azo __ '-and/or ~l.LhLa~uinone. Non-limiting examples of d lcifiers include complex non-ionic surfactants, alkoxylated polyglycols and aryl sulfonates, and mixture (typically at treat rates in the range of 10-20% of that of the detergent, if any). Non-limiting ~ lec~ of corrosion ~ W095l33022 2 1 9 4 ~ 7 2 rc~ . .r~7ss inhibitors include carboxylic acid, amines, and/or amine salts of carboxylic acids are used. Mobile rh~mic~l Corp.
markets "M~b;l~AA F-800" a combination lubricity agent and corrosion inhibitor. Non-limiting examples of anti-oxidants ~ !5 include hindered phenols, phenylanDAimin~ aromatic ~iAmin~, or mixtures of aromatic Ai~m;n~A and alkyl phenols,. Disperants could be ashless s-t~cin;m;A~ or polymeric methyacrylates, Non-limiting examples of anti-icing additives include isopropyl alcohol, hexylene glycol, dipropylene glycol, glycols, f~mr~miA~, imidazolines and carboxylic acids.
Non-limiting examples of valve seat rec~ion additives include sodium or potassium long chain alkenyl sulfonates, sodium or potassium long chain n&pl,U-ena-es, or microdispersions of sodium or potassium salts in oil.
Applicant's invention cont.emplates ~b~Letor, port fuel injector and intake valve deposit control additives.
Non-limiting examples include amides, amines, amine carboxylates, alkenyl s~l~cini-~ polybutene 5nc~in;m~
polyalkenyl s~rinimiA~ (Ethyl Petroleum Additives, Inc., HITEC 4450), polyether amines, polyether amide amines, ployalkenyl amines, polyether antines tOronite Chemical Co.
OGA-480), polyisobutenyl amine (Oronite Chemical Co. OGA-472), polybuton~nin~c~ polyetheramines, and polyolefin amines, with or without carrier fluid. Such material6 may be incuL~ ted at treat c~ e..LL~tions of 50 to 500 pounds per ~hou~nA barrels, and more usally in the range of 100 to 200 lbs per thousand barrels Other examples include woss/33o2z ~ 9 4 ~ 7 2 P~ 'C:7~8 o Additional detergent/dispersants, include high Ir 1 e~ m weight polyisobutylene substituted amine derivative TFA-4681, fuel soluble salts, amides, imides, oxazolines and esters of long aliphatic h~1L~ bOI~
substituted dicarboxylic acids or their anhydrides, long chain aliphatic hydrocarbons having a polyamine attached directly thereto, a Mannich cnn~Pncation product(s) formed by con~nqing a long chain aliphatic hydrocarbon-substituted phenol with an aldehyde, preferably forr~ hyde~ or qimilar additive is contemplated in the practice of keeping fuel injectors and valve intakes clean.
As noted, it is an express '- '; L to employ combustion chamber deposit additives (except where deleterious to ~nhAnreA combustion feature of invention), ~qpeciAlly those that reduce existing combustion chamber deposits. It is contemplated 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 ~u~pLe~sa..Ls, ;nc~ n~ organic _ _ ~ of barium, particularly the barium ~Lo..ate overbased barium sulfonates, N-sulfinyl in; 1 ;n~q, are contemplated, as well as others.
Additional deposit control additives include, a polyether amine sold by Oronite rh~m;r~l as OGA-480, a polyalkenyl sll~c;n;mi~e sold by ~thyl Corp as HITFC 4450, ~I W095/33022 2 1 9 4 5 7 2 F~ /an a polyisobutenyl amine sold by Oronite Chemical as OGA-472, and the like.
Example die6el fuel additives are shown by class and function in Table 4. As with any system in which a variety - !5 of additives may be used, care should be taken to avoid i- __tibilities 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 succin;mi~e, or polyalkenyl gnrcinimi~, hydLuu~LLyl carbonates, such as polybutene alcohol, polybutene chloroformate, polybutene amines formulated in mineral or other carriers" polyisobutylene amine reformulated in polyether caLriers, and ul,e -polyether amines, and the like. Several others have been - set forth ~l~e~h~re in the specification and are contemplated in gasolines, and other co-fuels.
~pplic~nt'5 invention contemplates that acceptable deposit control additives will meet industry and regulatory standards, inrll~Aing 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 1088, in any one injector.
It is an express '-'i L to avoid employing IVD
additives or PFI additives, which show any detrimental performance in combustion ch~mber deposit control or reduction.

WO9~/33022 2 1 q 4 5 7 2 ~ 5 -758 0 Applicant's invention expressly incuL~L~Les a combustion chamber deposit control additive. It is an express object o~ instant invention to employ deposit additives beyond IVD and PFI additives, namely to employ Sadditives additionally or in lieu of IVD/PFI a com'oustion control deposit (CCD) additive.
It is an express ~ ' 'i r L to employ additive or other means to reduce and/or control combustion chamber deposition, so as to improve combustion and/or reduce 10combustion temperature.
Applicant notes that combustion chamber additives are not nPcpcsArily novel and have been used to maintain fuel ~ystem ~1PAn1 inQCc for some time. In the practice of Applicant's invention, qCpeciAlly with higher performing lSneat FCS ~uels, CCD additive is optional.
However, additive and lubricating oil practice, ~cpe~lly in co-fuel practice that reduce or control com'oustion chamber deposits, are sn express '- ~i L of this invention.
20Thus, Arpl;cAnt's invention expressly cont~ ~lAtes the use of combustion cham'oer deposition control/deposit modifier additive or additive PA.~AgP~ especially those absent carrier fluid, and which have the effect of reducing octane number increase (ORI) of engines with combustion 25chamber deposits and/or which reduce and/or are capable of ~hAnging the characteristic of combustion chamber deposits.
Applicant's preferred combustion chamber deposit control additives exclude lower -~ler~ r weight ~ woss/33022 2 1 9 4 5 7 2 r~ 5 /a~

surfactants and high ~ nl~r weight polymeric di~ a.lL~
based upon polybutene. Applic~nt expressly contemplates employing new classes of additive6 which control or reduce combustion chamber deposit6, 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.
Non-limiting examples of desireable CCD additives include Shell's VEKTRON ORIC additives (Octane Requirement Increase Control) or ORR additive6 (Octane Requirement Reduction) and/or similar additive package, or Oronite's CCD (Combustion Chamber Deposit) additive package, Texaco's CleanSystem~ or Ethyl's eguivalent HiTec additive package.
It is ~Ypecte~ other combustion control additives and p~k~g~ will be developed. Additive ounc~..L.~Lion levels may range from moderate to very high, ~pon~;ng upon the efficacy of the additive/additive package and co-fuel employed. Other means of controlling combustion chamber deposits include intermittent high ~..ce..LL~tions of polyeramines. glycol boarates and ethylene dichloride may be employed.
~ owever, given nature of increased burning velocity and t~ _L~LuL~ reducing aspects of Applicant's invention, less desireable conv~n~ion 1l additives can be employed, absent significantly deleterious adverse combustion chamber deposition.

W095/33022 2l94572 r~.",~ 'C'758 0 Thus, it is preferred that Applicant's combustion chamber deposit control additives, PFI (Port Fuel In~ector) and IVD (Intake Valve Deposit) additives, and concentrations thereof, be effective in controlling and preferably reducing existant combustion chamber deposits.
It is also preferred that said deposit control additives be in amounts able to enhance the ~Les~nce of ~pplic~nt's ECS
~ 6 and/or - ~llic5, which may be cw.~-el.L-~Lions above or below those ~ -n~P~.
It is an express QmhO~i L of this invention that a clean combustion additive package be incuL~uL~Led into any co-fuel and/or ESC fuel composition. It is further contemplated that said combustion additive package incuL~u~dLe at least one organo r-nq~nP~e (preferably MNT) and/or other combustion improving metallic ~ _ ' (or mixture thereof), and a combustion chamber deposit control/reducing additive (e.g. Shell's VEKTRON
ORIC Octane Requirement Increase Control or ORR additive, Oronite's CCD additive package, Texaco's CleanSystem~, or Ethyl's eguivalent HiTec additive package).
It is further contemplated this clean combustion additive package may optionally contain one or more injector and/or intake valve deposit additive(s).
Concentrations of each or the performance features of individual additives and/or additive package, as an entirety, should meet minimum standards set by industry or requirements es~hli~hPd by legal or regulatory standard. It is contemplated that ~uncel~Ll~tions may 21 9~572 ~I WO9S/33022 P~ 7~8 include those that exceed or be less than those I~
by the additive manufacture.
In the prnctice of this invention Applicant has found that certain halogen s~v~l.g~,s in co_bination with certain - 5 metallics, notably pota6sium, may __ a-v~te valve sticking.
Thus, it is vital that compatibility of additive and ECS
- L 11i~ containing fuels be dp~prm; nP~ prior to use.

Exa~Dle 1~5 A composition comprised of a minor amount of at least one m ~llic, inrlu~;ng~ for example a cyclopQn~iPnyl ~-ng~nP~e tricarbonyl ~_ ', and a major amount of a combustion chamber deposit control additive or additive package, such as Texeco's CleanSystem3 additive.

r le 186 The composition of example 185, wherein the combustion chamber deposit control additive inrl~l~P~ or additionally includes, at least one BCS ~ ', preferably DMC.
le 187 The compo6ition of examples 185, additionally comprising an injector and/or induction valve deposit control additive; wherein said additives are same or differing additives.
-. . .
.

Woss/33o22 2 1 q4572 ~ Cl~758 o r le 188 A composition comprising at least one cyclopentadienyl ~-ng~n~e tricarbonyl and/or other combustion improving metallic _ ', a combustion chamber deposit reducing additive, and optionally, an injector and/or ;n~llrt~n valve deposit control additive; wherein said additives are same or differing additives.

.

RY~mnle 189 A method incoL~uL~ting the fuel compositions of Examples 185-189, where said additive package is employed deposit reducing quantities in a fuel for combustion in an internal combustion engine; wherein said es6ion ratio is increa6ed to a c ~es6ion ratio beyond average conventional _ a6~ion ratios, or ~ssion 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.

r le l90 A method incur~ul~ting the fuel compositions of Examples 185 - 189, where said additive package i8 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 kn~k~ng, whereby fuel economy and/or power is i uv~d by at least 0.5%, 1.0%, 1.5%, 2.0~, 3.0%, 5.0%, or more, over clear fuel.

~ WO 95/33022 2 1 9 ~ 5 7 2 . ~ 758 EYA~ 1e 191 The composition of 190, wherein the r~ng~n~~e ll~e.lLL~Lion i8 egual to an amount ~uch that the tLea, L
level of the additive package equals at least the minimum 5 ~ ' 11; r c~--ce--Lr~tions for the fuel~ set forth herein.

EX_~1e 192 The composition of 190, wherein deposit control additives are in an amount such that after LL~ai L of a fuel, combustion chamber, injector, and/or intake valve deposits are controlled, modified, or reduced, and/or wherein treated fuel meets regulatory or minimal legal standards.
Thus, ~rpl;oAnt contemplated additive par~g~ will incorporate IVD, PFI and ORI (or CCD) control additives, additive p~r~Ag~ and/or mixture thereof.

Exam~le 193 A fuel composition comprising an ECS fuel (comprising an ECS _ _I.d, preferably DMC, and at least one combustion improving metallic, preferably MMT); a co-fuel;
an injector deposit control additive; an intake valve deposit control additive; and a combustion chamber deposit ~ control additive; wherein said deposit control additive may be same or multiply ~ ', and/or wherein said -or : _ - change/reduce existing combustion chamber deposits while preferably ~nh~ncing combustion efflciency (but not required).

. ., ~ , ~

Wogs/330~ 2 1 9 4 5 7 2 1 11~ c ~-758 o It i5 preferred that additives, including deposit control additives, operate to enhance the ECS and - lli r.
combu6tion chemistry, which represents the predominate th- - y~.a~ic and combustion object of ~rpl;c~nt's invention, as opposed to merely Pnh~n~ing the fuel and combustion characteristics of Applicant's co-fuels.
Thus, given the ~L-~ ly attractive combustion characteristics of ECS metallic containing fuels, alone, combustion chamber deposits are substantially controlled when employed in combination with a co-fuel, absent need for additional additive.
Greater COnUe~l~L ations of ECS - lli~ fuels as a percentage of total fuel, when in combination with co-fuels, 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~. ~ubricity, anti~Y;~nt, corrosion, and other known additive are contemplated. Non-limiting 1P~ of wax crystal modifiers (wax anti-settling agents) or middle distillate flow i _ UV~D include ashless low molecular weight co-polymers and include ethylene vinyl acetate co-polymers. Cold flow ; vvel~ are contemplated with diesel fuels, particularly those with reduced sulphur and/or reduced aromatic cul.u~llL.ations, P~pP~ y as fuel t~ aLuLes drop. Betz Process ~hPm;c~l~ markets a superior cold flow ; uv~r additive. In the practice of ~ W095/33022 2 ~ ~ 4 5 7 ~ c c-758 this invention cold flow i ~_L~ are expressly contemplated.
Non-limiting examples of antifoam agents include poly~1l1 cnnP based '-. Non-limiting examples of - 5 detergents include sl~cinim;~O, ashless polymeric disperants.
Non-limiting examples of ;cetane i _ ~V~l~ include alkyl nitrates of which 2 ethyl hexyl nitrate is desireable with c~l.ce,.L~tions 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 aonc~ L~tions acceptable. Other ~ c~ tions 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 i u.~, D include Arco' 8 peroxide-based dialkyl peroxide i _ ~ , which may be inn~ od 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.
6everal proprietary ashless long chain polar~ '-are currently m-rket~8, which are contemplated in the practice of this invention. Multifl~nr~ inn~l additive p~n~go~ are also contemplated. Such pan~ges may contain detergents, cetane/octane i ~V~LS, combu~tion chamber deposit control additives, fuel st~hi 1 i 70rS, flow ~ _LD, anti-foam agents, reodorants, demulifier, W09~33~2Z 21 q4~72 rc~ c:7~8 o corro~ion inhibitor~, lubricity additives, and/or solvents for package stability.
Lubricity additives are particularly comtemplated in low/no sulfur diesel/distillate fuels, inorder to avoid e~l1 L, elastomer, and other failure.
The operation of lower combustion t~ ~Lul~s in the practice of ~ppl i r~nt ~ 6 invention ""~ le~ serves to reduce the formation of port fuel injector deposits.

r le 194 A method of operating an engine at combustion t~ ~LUL~S at least 50~F below same fuel absent ECS
_ ', metallic, and PFI deposit control additive, wherein said reduced to~ 7tUl~ operation after said operation, results in a reduced t~ _ ~Lu.~ transfer to fuel r~--ining in or near the pintle tips of port fuel injector subject to otherwise high soak t ~Lu~e transfer; wherein the formation of free radicals capable of combination in auto-oxidation, chemical rearr~ , L
and/or degradation of 1~ lnin~ fuel are reduced; and/or wherein sticky deposits and/or degraded fuel acting as deposit ~L~urO~S are reduced; wherein Port Fuel Injector deposits are controlled and/or flow restriction is less than 10.0%, 9.0%, 8.0%, 7.0%, 6.0%, 5.0%. 4.0%, 3.0%, 2.0%, 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.

~ w095133022 2 1 q 4 5 ~ 2 ~ 758 Applicant's invention also ~ e~-~e~ly reduces the increase in NOx r~mi ccionc and particulate6 typically occuring from use of such additives in diesel fuel systems.

c ~ 5 E le 195 The method of Example 194, wherein the additive optionally contains an intake deposit control additive and/or combustion chamber deposit control additive, wherein ~aid additive or additives are enployed in a composition 10 containing a diesel co-fuel, togethD~ with balance of combustion and t~ _ c~u~ reducing amount of ECS
, '(8) and - ~ 11;Qt8) ~ wherein said operation of engine results in re~ ti nn of NOx and/or particulate r~m; ccir~nc~ when compared to said deposit control 15~ additive(s) employed in clear diesel co-fuel alone (absent ECS ,_ ' and metallic).

Applicant notes the r~nh~nrr~ CO_ bustion burning and temperature reducing propertie6 of instant invention ~l~e~Ledly enhance the operating performance features of such PFI, IVD, CCD additive and additive p~r~ c.

ExamDle 196 A method of employing a CCD, IVD or PFI additive in an internal combustion chamber: said method comprising simultaneous injection of an atomized vapor compri6ing a minor amount of at least one high burning velocity tand/or low combustion temperature causing) ECS ,-I.d, at least W095/33022 : 2 1 9 4 5 7 2 r~l/~ 758 ~

one high energy releasing metallic _ -ol~A, and a CCD, IVD, or PFI _ ', 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 c _ a and metallic.
It is further contemplated that the additive packages of instant invention will be formulated to avoid intake valve sticking and crankcase oil contamination.
It is further contemplated that Applicant's IVD, PFI
and/or ORI (Combustion Chamber Deposit) control additives meet minimal industry and ~ve. tests and/or regulations.

F l~ 1~7 A method of avoiding CCD deposits employing an ECS/co-fuel combination; said method comprising: mixing a co-fuel with combustion improving amount of a - t llic and a ECS
_ ' (preferably DMC); a combustion chamber deposit (CCD) control additive; and a co-fuel; combusting said fuel in an engine for the equivalent of 5,000, 10,000, 15,000, 20,000, 30,000, 50,000, 75,000, or 100,000 miles, or more;
wherein the octane requirement for engine operating on ECS/co-fuel combination does not exceed, or is less, than ~ WO95/33022 ' 2 ~ ~57 ~ I~,",~ 758 -ao6-the octane requirement of same engine operating on clear co-fuel alone (but containing same CCD additive).

-E~am~le 198 - 5 The method of Example 197, wherein the octane requirement as ~ d in (R+M)/2 of said fuel is at least 0.5, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or more numbers les6 than clear co-fuel alone (2 number or greater preferred).

Exam~le 199 The method of Example 198, wherein said engine has operated the equivalent of 15,000, 20,000, 30,000, 50,000, 100,000 miles or more.
r le 200 The method of 199, wherein said engine passes a laboratory test or other test wherein measured combustion chamber deposits or equivalent show le~s than 300, 250, 220, 200, 180, 160, 140, 120, 100, 80, 60, 40, 20, 10, 5.0, 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, 0.001 gram~ of deposition, or less.
Preferred deposition weight i6 less than le~s 1.5, 0.9, 0.6, 0.3, 0.15, 0.10 grams, or less, per combustion chamber ~ or equivalent.

- t ~

W09S133022 2 1 ~ 4 5 7 2 rc~ Of758 o r le 201 The method of Example 199-200, wherein intake valve deposit, port fuel injector deposit and gum control additives are employed in sufficient aonc~l,LL~ions, wherein intake valve deposits are less than 100, 90, 80, 70, 60, 50, 40 mg under BMM 3181 test (BMW IVD test), and wherein port fuel injector deposits do not exceed a 10~, 9%, 8%, 7%, 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, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5.0 mg/100 ml or less washed, and/or 5.0, 4.5, 4.0, 3.5, 3.0, 2.5, 2.0, 1.5, 1.0, 0.5 mg/100 ml or less I RhPd.

E le 202 The method of Example 201, wherein the engine is a glROl ;n~ or internal combustion engine whose , , ~sion ratio is 9.6:1, 9.7:1, 9.8:1, 9.9:1, 10.0:1, 10.1:1, 10.2:1, 10.3:1, 10.4:1, 10.5:1, 10.6:1, 10.7:1, 10.8:1, 10.9:1, 11.0:1, 11.1:1, 11.2:1, 11.3:1, 11.4:1, 11.5:1, 11.6:1, 11.7:1, 11.8:1, 11.9:1, 12.0:1, 12.1:1, 12.2:1, 12.3:1, 12.4:1, 12.5:1, 12.6:1, 12.7:1, 12.8:1, 12.9:1, 13.0:1, 13.1:1; 13.2:1, 13.1:1, 13.2:1; 13.5:1, 13.6:1, 14.0:1, 14.1:1, 14.2:1, 14.3:1, 14.4:1, 14.5:1, 14.6:1, 14.7:1, 14.8:1, 14.9:1, 15.0:1, 15.5:1, 16.0:1, 16.5, 17.0:1, 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, ~ WogS/33022 2 ~ 9 4 5 7 2 ' ~ 7~8 24.5:1, 25.0:1, 30.0:1, 35.0:1, 40.0:1, 50.0:1, 70.0:1 and ~ es~ion ratios therein and/or greater.

r le 203 - 5 The methods and gasoline compositions above, wherein the (R~M)/2 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.

r le 204 The gasoline method, wherein the engine is designed to operate on a gasoline whose octane i6 equal to or exceeds 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 9S, 96, 97, 98, 100, 101, 102, 103, llD4, 105, 106, 107, 108 or greater.

r le 205 The g~ol in~ method, wherein engine operation comprises use of electronic knock sensor to retard spark and wherein spark le~dation and hence combustion efficiency is ; _ uved over clear fuel by at least 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4Ø 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.
- r le 206 The method of Example 205, wherein acceleration of engine employing ~pplic~nt~s fuel compostion with WOgsJ33022 2 1 9 4 5 ~ 2 ~ 5C758 ~

co~bu6tion chamber deposit control additive is ; ~v~d 1.0%, 2.0%, 3.0% to 10%, 4.0% to 15.0% or more over the clear fuel, alone.

r le 207 A method of reducing NOx emissions comprising: mixing a combustion improving amount of a metallic with an ECS
' and optionally with a co-fuel, toge~hPr with a combustion chamber deposit reducing additive; combusting said fuel, whereby NOx ~mi~sionc are reduced by at least 5.0%, 7.0%, 10.0%, 15.0%, 20.0%, 25.0% or more, compared to co-fuel absent metallic, ECS _ _ ' and combustion chamber deposit control/reducing additive.
It is additionally contemplated that ECS '- in their neat form will contain additives, as required. For example, to avoid corrosion and maintain stability, caused by peroxide formation, phenolic-based and amine based st~h11i7~r6 such as UOP 7 and UOP 5 may be employed in the storage and use of neat ECS ~ _ ~ or fuels.
Cv..ce..LLation6 will vary dQpon~ing upon stability c-n -- ~.
For example, ETBE and diisopropyl ether have a stronger tendency to form peroxides than does MTBE and hence re~uire greater c~..ce..L ~tions.
In the case of carbonates, ~cp~ lly DMC, when exposed to water for extended periods, due to hydrolysis, ~ 1tion into r ' ' -n~l may occur, hense leading to corrosion ~u..ceL..s. Thus, water reducing agents, salts, co-solvents, d l~ifiers, anti-oxidants, 8t~hili7~rs~

~ w09~/33022 2~ 9~ 7 2 r~ ,s,.~7ss corrosion inhibitors, and the like are expressly contemplated.

Mi tiaation Practice It is contemplated that Applicant's neat ECS fuels, neat co-fuels (absent ECS and/or metallics), and/or ECS
and/or r 11; r co-fuel combinations, will employ certain mitigation practices, as required. ~itigation practices include vapor ples~uLe re~ tinn (VPR), flash point temperature increase (FPI), l.yd.~b~ic/phase separation control, and the like. Co-solvent usage is also contemplated to reduce ~va~oL~tive ~ si~n~
Lower ~olecular weight ECS alcohol ~_ ' are hydL~sc~ic and tend to phase~seperate in fuel systems ~xposed to or containing water. Thus, co-solvents that control phase separation are desireable.
Certain ~L L~.lates, namely di-methyl and di-ethyl carbonates are prone, in certain CiL~ Lal.ces, to hydrolyze when exposed to similar enviL L~. Lower 20 molecular weight ECS alcohols, ethers, ~Lb~ates, ketones, and the like, can adversely increase vapor ~l~S-ULe or reduce flash point ~ aLuL~. Their useage can also reduce T-50 tl ~ LUL~S causing driveability problems or te~hnicA1 ~nl~: L. Correcticn of T-50 and end boiling point adjustment employing azeotroping co-solvents is known in the art, see my EP0 Patent 8690642.6.
In the practice of this invention a different and unique class of co-solvents and means are cont~ l~ted to 21 9~572 W09s/33022 I~ t758 mitigate vapor pressure and flash point problems, particularly in fuels heavier than gaDoline, e.g. jet turbine, gas oil turbine, diesel fuels, and the like.
It i8 generally preferred that co-solvents be ECS
, -c or have ECS combustion/t~ ~tuL~ Rnh~nring attributes. Thus, It is preferred that Applicant's co-solvents (in~rPn~ent of ECS and/or metallic effect) generally increase the resultant fuel's LHV and/or burning velocity, ~creci~lly in co-fuel applications.
It is contemplated that Applicant's co-solvents include inorganic and/or organic _ -. In FPI or VPR
applications, e~peci~lly when an ECS ~_ ~ is present (or ~lternatively in fuels absent ECS or - llir)~ it is preferred that the co-solvent(s) have a vapor PLa~DUL~ of 1 mm, or less, at t~ ~u~as of -20, -10, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140~C, or greater.
It i5 also desireable that Applicant's co-solvent(s), Rcperi~lly when employed for FPI, have flash point ~ ~LUL~ of at least 60, 80, 100, 110, 120, 130, 140, 160, 180, 200, 210, 230, 240, 260, 280, 300, 320, 330, 350, or 360~F.
It is desireable that Applicant's co-solvents be fl; hle. It is prefered that they be preheated before ignition, or moderately heated and exposed to high ambient temperature, or easily ignited under almost all ambient temperature conditions. Complete or substantially compete ~ ition at combustion and pLe ,~ ction t~ ULa ~ WO95133022 2 ~ ~4 5 72 ~ . 7~8 is preferred. It i8 desireable the co-solvent have as many of the combustion burning velocity and temperature reducing ; features of ECS ~ a as pcssible.
In certain applications, the co-solvent should not be ~ 5 water soluble. However, when hydrolysis and/or phase separation occur due to pLesen~ of water or acidity, a water soluble co-solvent can be advantageous.
It i5 desireable that a synergistic relation~hip exist between the ECS __ '(s) when employed, and the co-solvent(s~. It is expressly contemplated that multiple co-solvent mixtures be employed.
In other words, differing requirements can be satisfied with differing co-solvents, and mixtures thereof.
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 t~ ~LuLeg. While tbere is no limitation on the number or ranges of co-solvents in a mixture, Applicant rGCogni 7~~ that differing fuels requirements will elicit differing co-solvent mixtures. When practical single ~ _ co-solvent mixtures are preferred.
Co-solvent practice may also be sl~ppl ~ed or substituted by use of heavy napha's, inrl~ ng aromatic napha's. Thus, it is an ~ho~ i r ~ to employ heavy or moderately heavy hYLO~Lb~ll5~ in~ ing naphas, in lieu of or in addition to co-solvent(s), as means for FPI and VPR.
It is an express ~ o~ this invention that use of Applicant's co-solvents in fuel combinations will Wo95l33022 2 1 9 4 572 ~ s8 ~

provide increases in fl~sh point or reductions ln vapor pres6ure that are arithmetic and those greater than the arithmetic effect of their combination. cO-solvent cost, ease of use, cnnCi~rations of toxicity, av~ hility~ ECS
properties, and the like, must be weighted in such cnn~:id~rations.
Therefore, while not required, it i6 an ~mhn~;- L
that vapor pL~s~uLa r~n~tinnC and/or increases in flash point t- _ ~Lu~, and/or re~ tinnC in average fuel melting t~ ~Lules exceed the sum of the individual co-solvent, ECS _ ' (if employed), and/or co-fuel _ ~8.
It is an express : ~ -ir L to employ ~rPl ic~nt~s co-solvents in neat ECS and/or r ~ c fuels, alone. It is also an : ' 'i- L to employ such co-solvents in clear fuels (co-fuels), which are absent ECS _ _ ' or metallic; or employ such co-solvents in co-fuels, which may contain ECS ' and/or - llic.
It iB also preferred that co-solvent usage not increase melting/freezing point t~ ~Lu.ds, or ~im;ni~h or aggravate fuel stability, corrosion, elastermer deterioration, evaporative emissions, toxic ~mic~jon~, hazardous combu8tion ~miccinnc, or combustion burning velocities and combustion t~ ~Lu~ds. It i6 also preferred the co-solvent usage not contribute to gumming or oxidation.
~ owever, in such circumstances, (e.g. for example, where freezing points are not sufficiently low), it is ~ w09~33022 ' 2 1 ~4572 P~l/. C~7S8 contemplated an additional co-solvent, substitute co-solvent, additional additive, or other means may be r employed.
Co-solvents that cause elastermer ~wellinq or - 5 deterioration, corrosion or fuel degradaton may be corrected by employing additional agents, e.g. corrosion inhibitors, anti-oxidants, etc. ~owever, Applicant's preferred co-solvents do not cause such problems.
Applicant 16 desired co-solvents will have melting points less than 20, 10, 0, -5, -10, -15, -20, -25, -30, -40, -50, -60, -70, -80, -90, -100, -130. -140~C, or below.
Preferred will be those with melting points less than -5~C, more preferably less than -40, -50, -60, -70 ,-80, -90~C, or below.
Applicant's co-solvents will have boiling points above 70, 80, 90, 100, 110, 120, 300~C, and greater. Boiling points above 130, 160, 190, 200, 220, 240, 260, 270~C, or greater, arè preferred.
Desired flash point ~ ~tUL~ of co-solvents are greater than --0, -31, -20, -15, -10, -5, 0, 5, 10, 15, 20, 25, 30, 35, 38, 40, 50, 58, 60, 65, 70, 75, 80, 85, 90, 95, 100, 120, 130, 140, 150, 160, 170, 180~C, or greater.
Preferred flash point ~ ~tUL~s are those in excess of 40, 60, 80. 100, 120, 130, ~40, 150~C, or more. Nore preferred are those above 80, 100, 120, 150, 170~C.
; ~ppliC~ntl deBireable cosolvents have a latent heat of vaporization in excess of 18, 20, 21, 23, 24, 25, 27, 29, 30, 31, 33, 35, 37, 39, 41, 43, 45, 47, 49, 51, 53, 55, 57, WosS/33022 2 l 9 4 5 7 2 ~ c -758 o 59, 62, 65 ~V.pH(Tb)/kJ mol~1 (or equivalent). It is preferred that co-solvent LHV's be greater than any co-fuel to which they might by added. However, LHV must be bAl~nred by the other aspect6 of usage, e.g. LHV of resultant fuel, LHV
effect of ECS _ (if any), flash point and/or vapor p~DDuLa priority, etc. Applicant's preferred LHV's are equal or above 28, 30, 32, 34, 38, 40, 45, 50, 55, 60 H(Tb)/kJ mol~1 (or equivalent~.
Applicant's desired co-solvents, ~peciAlly for vapor lO pL~DDuLa reduction and/or flash point ; u~, will have moderate, to very low, to exceptionally low vapor pLes~uLa8. Albeit moderate vapor p-asDuLa may be acceptable in certain cil~u~_L~nces.
It is desireable that Applicant's co-solvent have a vapor ~LasDu.a of 1 mm at temperature greater than -20, -10, 0, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 160, 180~C, or greater. Preferred co-solvent t~ UL~ at vapor p.~s-u.es of 1 mm should exceed 20, 40, 60~C. More preferred t~ ~uLas are those that exceed 80, 100~C, or more.
~9~ LL~hing co-solventts) may be employed, however in cases where flash point i ~v, ~ is sought, azeotrophing i6 less preferred. Thus, the co-solvent lower molecular weight alkyl alcohols, are generally less preferred.
~pplir~nt has found hYdLV~1b~I~ soluble, fl hle glycols, ketones, and their acetates, and esters to be desireable. Ethanoic, propanoic, butanoic, pentanoic, and h~Y~noic acids, inrltl~ing their acetates, esters and ethers 2~ ~4~7~
W0 95/33022 1 ., ~ 7:!i8 are also desireable. Ethenes, butenes, plopel.es, hexenes, pentenes are acceptable.
~ The specie or ~ n~ classifications found herein are not intended to be limiting. Arrl;c~nt contemplates co-solvents, which may be out6ide any disclosed herein, and further ~ l~tes his preferred co-solvents may include any species, 5~hcperies or homologue or analogue of any ~ccloced species, __ ~, or group herein, under the proviso said co-solvent(s) meet the fnn~inn~l requirements set forth herein.
It is desireable that the co-solvent be soluble with the taly~ed ECS _ ', if employed, and optionally with water.
Applic~nt~8 co-golvents may be selected from a very broad class of fl -hl~ chemistry. Applicant's desired co-solvents 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 single carbon atoms being preferred.
While those above these ranges are cnnt~ ted and acceptable, those having 7, 6, 5, 4, or fewer carbons in a chain are also preferred. Co-solvents containing oxygen are desireable. Co-solvent6 containing OH radicals are al50 desireable. Applicant has found that co-solvents having _ ~-]~cnl~ ru~-uL~ in part comprising CH3C02, and/or OH to be desireable. Applicant has al~o found that nonvolitile, ~ nonion producing co-solvents to be desireable for ~uL~ ~-of reducing vapor pLesDuLa and/or raising flash points.

W095/33022 2 I q 4 5 7 2 r ~ 1/~ 758 o Non-limiting examples of Applicant's co-solvents include: A1 cnh n1~ g lycols, ketones, esters, phenols, acetals, acid azides, acid halides, acids and acid derivatives (aldehydic, aliphatic dicaroxylic, alipatic L~ylic, aliphatic polycarboxylic, amino acids, hydroamic, hyd~uAy~cids, imidic, ketonic, nitrolic, or~hn~ c, peracid, etc.), acetic acids, acetic anhydrides, acetic acid esters, aldehydes, aliphatic hydL~LL~ns (including high boiling point napthas), amides, Am;Ain~ Ami~nYi~ anhydrides, aromatic hydroc~-bnn~, azides, azines, azelates, azo ' , betaines, bromoactealdehydes, bromoethanes, L~ hylenes, bromoacetic acids, bromobutanes, bromobutenes, Ll. -'_Lylenes, bromo ethers, di _romo _ ' , 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 ester6/ethers, di-propylene glycols, glycol ethers, triet_ylene glycols (inrlnAing acetates, diacetate~, esters, ethers, and amines thereof), tetraethylene glycols (inrlllA;ng acetates, diacetates, ester6, ethers, and amines thereof), tripropylene glycols, teLL~ ~ylene glycols, di-butylene glycols, tributylene glycols, tetrabutylene glycols, pentaethylene qlycols (incln~ing acetates, diacetates, esters, ethers, and amines thereof), glyceric acids, glycerols, formates, carbinols, carbitols, nitriles, acetates, ethylene acetates, esters, hydrates, hydrides, ~I W095/33022 2~ 9~572 rc~ .7~8 l.ylLvp~Lv~ides, ~IylLvx~mic acids, ~1~1LV~yaCids~ imides, imidic acids, imines, ketenes, lactams, lactones, glycolic ~ acids, butyric acids, heptic acids, valeric acids, isocaproic acids, nitrolic acids, nitrosolic acids, octanoic acids, esters of octanoic acids, onium ' , or1ho~ R~ ortho borates, octynes, octenes, octanones, oximes, esters of oxalic acid, oxalic acids, ethanoic acids, esters of e~h~n~ic acids, esters of nonanoic acids, propanoic acids, esters of propanoic acid, pentanoic acids, propanediones, prop~nnn~C, ethenes, ~rv~nes, butenes, pentanes, petenes, hexenes, esters of pentanoic acids, butanoic acids, oxalic esters, esters of butanoic acids, pentaneoic acids, esters of p~ oic acids, pent~n~inic acids, esters of pentanedioic acids, 2- or 3 p~ "~, 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 h~Y~n~i~ acid, h.. _r.. rR~ toluene bL. id~C~ toluene cresols, toluene dimethyl amino ' , toluene ethers, toluene oxyls, p_.,~ lc, peroxides, furans, esters of 2-furAn-~rhv~ylic acids, furfurals, ~L~nes, propenoic acids, esters of propenoic acids, ethers, buten~;oc acids, bromo-alcohols, ethanetriols, propanetriols, butanetriols, pentanetriols, 25 naphth~l~n~c~ hexanetriols, septanetriols, octanetriols, nitr~b~n7en~, io~ n7~n~, 2-nitrophenol, and the like.
Nitrogen based _- ~c are also acceptable, d~p~n~ing upon the application. However, Florine, ~ _ _ _ _ _ _ wos~/33o22 2 1 9 4 ~7 2 P ~ 7~8 0 chlorine, surphur, phocrh~rou6 ~ased, and other toxlc ~ , now known or later ~PtPrm;nP~, should be avoided. Non-carbon based co-solvents are also expressly contemplated. Solid co-solvents, which may be dissolved by mutual solvent, are contemplated. Co-801vent nhP~in~l structure is not limited, and may be cyclic, bi-cyclic, aromatic, non-aromatic, branched or straight chain, or combination thereof.
It is preferred that the co-solvent be ~hPr~ y stable, not dP e under normal hAn~l ;ng and operating t ~UL~, and not cause co-fuel deterioration, e.g.
guming, corrosion, etc. It is additionally desireable that the half life of its evaporative or combustion product be very short, preferably less than days (e.g. 8, 5, 4 or less), more prefera_ly less than hours (e.g. 24, 18, 12, 8, 4, 3, 2, 1 or less), most preferably less than minutes (e.g. 60 ,45, 30, 15, or less).
Non-limiting 1PC (to also include homologues and An~lo~-PC thereof) are: triethylene glycol, 3-aminopropyl ether triethylene glycol, diacetate triethylene glycol, - -'_Lyl ether triethylene glycol, - Lllyl ether triethylene glycol, monopropyl ether triethylene glycol, tetraethylene glycol, dibutoxytetraethylene glycol, diacetate tetraethylene glycol, aminopropyl ether tetraethylene glycol6, ~ yl ether tetraethylene glycol, monomethyl ether tetraethylene glycol, dimethyl ether tetraethylene glycol, diethyl ether tetraethylene glycol, - ~_~ yl ether tetraethylene glycol, -~ w09~33022 2 ~ 94 5 72 r~ 7s8 ether tetraethylene glycol, tetraethyl~ ..L~mine, tripropylene glycol, teLL~p~u~ylene glycol, dipropylene glycol, propylene glycol hyl ether, ethylene glycol monomethyl ether, ethylene glycol , up~l ether, J 5 propylene glycol r , u~yl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol t -hLLyl ether, tripropylene glycol monomethyl ether, propylene glycol, ethylene glycol, hexylene glycol, dipropylene glycol, diethylene glycol, triproylene glycol, tetraethylene glycol, tetramethylene glycol, t~L~plopylene glycol, polyethylene glycol t200, 300, 400, 600, 1000, 1500, 1540, 4000, 6000 Ashland ~h~m;c~l ), polyethylene glycol 3350 (Spectrum), polypropylene glycol (P400, P1200, P2000, P4000 Ashland Chemical), cyclohexylamine, dibutylamine, diethylamine, diethylenetriamine, diethyleth~nnlAminp~
diisopropanolamine, morpholine, triethylamine, triethylenetetramine, triisopropAnnlAmin~, toluene, amino methyl propanol, propylene oxide, propylene glycol, 1,2 prop~nP~iol carbonate, salicylic acid, su~cini~ acid, tartaric acid, tannic acid, 2,2,4-trimethy1pPntAnD, dimethylhenPzP~P8, dimethyl formamide, n-methyl-2 pyrrolidone, amyl alcohol (primary), cyclohPYAno1, 2-ethylhexanol, methyl amyl alcohol, tetral.yd~uruuru~yl alcohol, TEXANOL eater alcohol (Eastman rhPmin~ UCAR
Filmer IBT (Union Carbide Corp.), amyl acetate, dibase ester, ester solvent EEP (Ashland ~hPmiCAl), 2-ethylexyl ,~

W09s/33022 2 1 q 4 572 ~ 7~8 o acetate, glycol ether acetates (DB, DE, DPM, EB, EE, PM, Ashland Ch~mirAl), isobutyl acetate, isobutyl iaobuLyLate, n--pentyl propionate, cynlnh--YAnnn~, 2--h~YAnnn~, 3--hPYAnnn~, 2-methyl-3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 3,3-dimethyl-2-butanone, ~iiActon~ alcohol, diisobutyl ketone, ethyl methyl ketone, pinacolone, methone, 3,3-diphenyl 2-butanone, 1 hy-lL~ay 2-butanone, 3-hydroxy-tdl) 2-butanone, 3-methyl 2-butanone, oxime 2-LuL~ ..e, 2 buLa-lcne, 2-methyl proponoic acid, cyclopentanone, cyclopropyl methyl ketone, 2-tetrahdrofurylmethanol, cyclnh~YAnnn~, isu~h~.one, methyl amyl ketone, methyl isoamyl ketone, acetonylacetone, acetic anhydride, bensyl alcohol ta-l-y~,ay~oluene~ and variations, triisobutylene, tetraisobutylene, allylidene diacetate, acetol, 1 t4-metl,yuay~l.e.. yl)-2- pl~,y-~l.one, isoba~y~ h~ . ~", acetonylhDn7 n~ ~
butyl acetate, C-4, C-4+ aliphatic alcohols, n-butylbutyrate, cetyl alcohol, cyclnh~An~-, cyrlnh~Y:~nnl, cyclohexanone, diethylphthalate, 2,5 dimethoxytetrahydofuran, p-dioxane, 1,3-dioxane, 1,4-dioxane, 5-hydroxy-2-methyl-1,3-dioxane, glycol methylene ether, propylene ~:aL L~..ate, isopropylene Ca~ L~,nate, glycerin, 1,2,3-propanetriol, heptane, n-hexane, 2-methylpentane, 3-methylp~nlAn~, methycyclopentane, 1,4-~h/~n7~n~ isopentyl alcohol, methyl ethyl ketone, 4-methyl-2-pentanone, methyl propyl ketone, diisopropyl ketone, 1- or 3- or 4- or 5 hydroxy 2- pentanone, diisopropyl ketone, methyl propyl ketone, diacetone ~ W09a/33022 2 1 9 4 ~ 7 2 ~ /aM

alcohol, isopentyl phenyi ketone, 2-pentanone, diAcet~nP
alcohol, isopentyl phenol ketone, n-butyl phenol ketone, i-butyl phenol ketone, 2-butyl phenol ketone, isopropyl acetone, 2- or 3- or 4-methoxy phenol, dihydrate oxalic ~ 5 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 d; r tl.y~l.~l,ol, 1-octene, isobutyl 2-methyl~u~an~, 2-phc..v~y~lanol, diethyl carbitol, methyl carbitol, butyl carbitol, methyl ethyl carbinol, ethylene glycol, ethylene acetate, ethyl acetate, ~ ~nrhPn~ne~ benzyl acetate, 1,3 or 1,4 or 2,3 butanediol, ethylene glycol, fnr~ hyde~ f~rr-ml~
triethyl ester orthoacetic acid, trimethyl ester orthoacetic acid, oxalic ester (diethyl ester oxalic acid), methyl hydLu~e~uAide~ ethyl hydroperoxide, acetyl peroxide, 15~ 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, -~et~n~cetic acid, allyl acetoneacetate, diacetylacetone, acetylacetone, ethyl ester benzoic acid, butanic methyl ester, 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 3-methyl butanoic acid, isopropyl ester 3-methyl butanoic acid, 2, 2-dimethyl butanoic acid, allyl ester butanoic - ' 21 q~ 72 Wos5/33o22 ~ SC758 acid, amide butanoic acid, N,N-dimethyl butanoic acid, anhydride butanoic acid, butyl ester butanoic acid, pentyl ester butanoic ester, propyl ester butanoic acid, diethylacetic acid, 2-methyl-td) butanic acid, methyl acetoAcetAte, ethyl acetoacetAte, diethyl acetal, acetate, acetyl acetone, 2,2-dimethyl ether ester propanoic acid, 2-oxo ethyl ester propanoic acid, 2-oxo methyl ester propanoic acid, 2-oxo isobutyl propanoic acid, 2-oxo-isopropyl propanoic acid, methyl ester propanoic acid, ethyl ester propanoic acid, propyl ester propanoic acid, propanoic acid, glyceric acid, 1, 2 dimethrY~thAn~, 1,2 eth~n~iQl, 1,3 butanediol, 2,3 butAn~ione, 1,2,3 butanetriol, 1,2,4 butanetriol, glutaric acid, glutaric anhydride, glutaronitrile, 1,5 pen~n~;Al, glutaraldehyde, 2,4 pentadione (CH3COCH2COCH3), p~ntAnir acid, levulinic acid, (CH3COCH3COC02H), dimethyl suberate, oct~nD~ioc acid, 1,2,3 pentanetriol, 2,3,4 pentanetriol, fom-~mide, bL~ -aAetic acid, Acet~mi~, pyruvic acid, methyloxyacetic acid, propionamide, allyl bromide, diethyl acetal propenal, diacetate propenal, propenal, 1,2 propAn~ ll 1,3 prop~n~iol, glycerol, trimethyl ether glycerol, acetylpropionyl, acetylacetone, propionic acid, methyloxyacetic acid, propionamide, maleic anhydride, eis-crotonic acid, dimethyl oxalate, isobuLyLic acid, I-~lL~yisobutyric acid, ethylene glycol, diethylene glycol, diacetate diethylene glycol, diethyl ether diethylene glycol, dioleate diethylene glycol, ~ yl ether diethylene glycol, mono (2 hydroxylpropyl) ether diethylene ~ W09a-133022 21 9 ~ 5 7 2 p~ n la~

..
glycol, r ~~ Lyl ether diethylene glycol, , ~yl ether diethylene glycol, monomethyl ether diethylene glycol, ~ monomethyl ether acetate diethylene glycol,~ ~ yl ether diethylene glycol, ethanetriols, propanetriols, butanetriols, pentanetriols, hexanetriols, septanetriol~, 1,2,3 butanetriol, 2,3,4 pentanetriol, 1,2,3 p~ e~Liol, 1,2,3 LJL~dll~ lol, diG~y~llL~ne~ 2,~-dio~y~_.-Lane, hexantriols,~ ,~bu~yl ether triethylene glycol, propanoic acid, anhydride propanoic acid, butyl ester propanoic lo acid, ethyl ester propanoic acid, pentyl ester propanoic acid, octyl ester propanoic ester, pimelic acid, 6uberic acid, azelaic acid, methacrylic acid, dibromobutanes (e.g.
1,2; dl-2,3; 1,4; meso-2,3; etc), tribL -hu~nc8 (e.g.
1,1,2; 1,2,2; 2,2,3; etc.), diacetamide, di(2-bl yl) ether, 2-ethylhexanol, furfuryl alcohol, 2-propanone, 2-propen-1-ol, ethyl methanate, methyl ethanate, pPnt~inic acid, pentadioic acid diethyl ester, pQnt~ioic acid dimethyl ester, pentadioic acid dinitril, 2,3-pen~e~inn~
2,4-pentadione, 1,2,3-pentanetriol, pentanoic acid, pentanoic acid methyl ester, pentanoic acid butyl ester, pentanoic acid ethyl ester, pentanoic acid fur~uryl ester, pentanoic acid hexyl ester, pentanoic acid nitrile, pentanoic acid octyl ester, pentanoic acid pentyl ester, carbinol, butyl carbinol, diethyl carbinol, methyl n-propyl carbinol, dimethyl isobutyl carbinol, ethyl isopropyl ; carbinol, ethyl isopropyl methyl carbinol, diisopropyl carbinol, triethyl carbinol, isoamyl carbinol, dimethyl n-propyl carbinol, 2-butyl methyl carbinol, methyl isobutyl W095/33022 2 1 9 4 572 P~ C 7~8 o~

carbinol, diethyl methyl carbinol, methyl propyl ketone, - y~ C~Ptic acid, acetoacetic acid, methyl acetate, tert-amyl acetate, ethyl acetate, glycol diacetate, 1,2-propPn~linl carbonate, 1~2-prop~np~in~ 3-~L~ r1;n1~
adiponitrile, 2-amino-2-methyl-1-propanol, triethylenetetramine, bPn7~ Phyde~ benzin, benzene, toluene, benzl alcohol, butyl acetate, dimethylAnilinp~ di-n-propylAnil1np~ methyl isobutyl ketone, n-amyl cyanide, di-n-butyl carbonate, diethylacetic acid, diethyl fnrr-mlrlP, diisobutyl ketone, ethyl benzoate, ethyl phenylacetate, hept;~PcAnnl, 3-heptanol, n-heptyl acetate, n-hexy ether, methyl isopropyl ketone, 4-methyl-n-valeric acid, o-phenetidine, tetrA~l~rAnnl, triethylPnPtetramine~
2,6,8-trimethyl 4 -nnnAnnnP ~ ethAnPrl i A 1, carbonate 1,2-eth~nP~lio~, diacetate 1,2-e1h:~nP~iol, dimethyl ether 1,2-ethAnPrl101, dinitrate 1,2-ethAnPrllol~ n,n-di-methyl formic acid, n,n-di-ethyl formic acid, butyl ester formic acid, isoamyl formate, octyl ester formic acid, pentyl ester ~ormic acid, propyl ester formic acid, isobutyl ester formic acid, propargl acetate, 2 - yethanol, cyclopentanone, cyclopropyl methyl ketone, ethyl propenoate, 3-methyl-2-butanone, phenol, 2-or 3-or 4-methoYyphenol, propanoic anhydride, cynl~hPYAnonP, 4-methyl-3-penen-2-one, 2- or3- T~PYAnnnP, [2, 3 or 4]-methyl-[2 or3]-pentanone, 2-heptanone, methyl phenyl ketone, diethyl benzene, and azulene.
Wide ranges of co-solvent mixtures, inrln~ing mixing two or more, are expre6sly contemplated. Thus, any two or ~ WO9~/33022 21 945 72 r~ 7~8 more co-solvents may be employed jointly, in same or differing proportions.
Varying proportions of different co-solvents will often elicit differing 1 ~ollse. For example, it is an ~ 5: ' '; nt of this invention to employ the 6ame or varying proportions for individual co-solvents of the same general class, or for different classes.
It is an : ~o~i- L to employ multiple co-solvents, in same or differing proportions, having different freezing 10points, flash points and/or vapor ~LesDuze6, LHV, and burning velocities. One such combination would embody '~ln;ng one or more moderate to high freezing t~ -c LUL e co-solvent(s) having moderate to high flash point t~ _ -LULeS and a low to very low freezing point co-15solvent(s), whereby resultant mixture would have combination of ' ct~ly high to high flash point and low freezing point.
It is an : 'i- to combine high flash point co-solvent(s) with alcohol and/or other co-solvent to control 20hydrolysis and/or hydroscopic phase separation. It is also an o~ho~;- L that a co-solvent or mixture of co-solvents, which for example act to reduce vapor ~LesDuLe or elevate flash point, etc., may also act as a mutual solvents to dissolve non-soluble or moderately ~i~; hl o co-solvent 25and/or ECS __ '(s), if employed.
Applio~nt rocogn;~-~ that a wide variety of combinations and mixtures and proportions exist, which acheive the multiple objects of Applicant invention. ~hus, .

wo~/33022 2 1 ~ ~ 5 ~ c 7~8 ~

it i6 an express ~ L of this invention that co-solvent combinations and mixture exist between individual co-aolvQnts of any one class; between classes of co-solvents; between classes of co-solvent(s~ and classes of ECS '-; between co-solvent(s) and co-fuels; between co-solvent(s), ~CS _--ds, and co-fuel(s), and/or the like.

.

r le 208 A moderate to high flash point fuel: comprising an ECS
_ ' (preferably DMC), optionally a metallic, and at least one flash point increasing fl~ hl ~ co-solvent selected from $uel soluble polymethylene glycols, polyethylene glycols (including tetraethylene glycols, triethylene glycols, propylethylene glycols, diethylene glycols), acetates, glycol acetates, ketone acetates, ethylene acetates, ethylene diacetates, di-ethylene acetates, benzyl Al~nh~lR, acetic anhydrides, phenol, and/or other nonvolitile, nonion producing co-solvent, homologues, analogues, or mixture thereof; and optionally a co-fuel; under the proviso that if co-fuel is employed the resultant fuel meets co-fuels ASTM or yuv_L
specifications, including minimum flash point t~ ~Lu,~.

r le 20~ =
A co-solvent composition, or ECS/co-solvent composition, characterized as being soluble in liquid hydrocarbon fuels, flammable and having a melting point ~ Woss/33o22 ' 2 1 ~ ~ 5 72 P~ 758 less than 20, 10, 5, 0, -5, -10, -20, -30, -40, -50, -60, -70, -80, or -90~C; a boiling temperature equal to or greater than 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 270, 280, 300~C; optionally soluble t 5 in water; having a laminar burning velocity in exce~s of 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, 60 cm/sec; a latent heat of vaporization in excess of 23, 25, 27, 29, 31, 33, 35, 37, 39, 41, 43, 45, 47, 49, 51, 53, 55, 57, 59, 62, 65 ~V~H(Tb)/kJ mol~1 (or equivalent); a vapor ~Las~uLa of 1 mm at a t~ ~ aLuLa greater than -30, -25, -20, -15, -10, 0, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, or 140~C; and optionally a flash point t- ~Lur~
of at least~40, 60, 80, 100, 120, 130, 150, 170, 180, 200, 220, 250~F, or greater; and optionally a freeze point egual to or les~ than 30, 20, 10, 0, -10, -20, -30, -40 (-40~C), -50, -60, -80, -90~F, or less.

r le 210~
A high flash point, low freezing t ~LUL~ co-solvent composition comprising one or more fuel ~oluble and flamable triethylene glycol ~ _I.ds~ tetraethylene glycol c _ -, or other high flash point co-solvent(s), or mixture thereof; and a fuel soluble, flamable, freezing point reducing agent or co-solvent sPlected from butyl carbitol, carbinols (in~n~;n7 diisopropyl, dimethylene n-; propyl, isoamyl, etc.) 1-octene, 4-octene, 1-octyne, 4-octyne, glycol ethers, ethylene glycols, diethylene glycols, dis6u~L~yl ketone, methyl propyl, d;acetnnP

.. , 7 .

wos~l33o22 2 1 9 4 ~ 7 2 . ~ C -7~8 o alcohol, i~yL~y 1 acetone, dissobutyl ketone, cyrlh~YAn~n~, isophorone, or other co-solvent having moderate to moderately high flash point and low to ekLL~ ly low freezing point, or mixture thereof; whereby the composition's flash point exceeds 60, 80, loo (38~C), 120, 140, 160, 180, 200, 220, 240, 260~F, and whereby freezing t~ ~uLe is equal to or less than -10, -20, -30, -40 (-40~C), -50, -60, -80, -90~F, or less.

~ le 211 The example 210, wherein at least one co-solvent _ ' is a tertraethylene glycol, triethylene glycol, 1-octene, high flash point ketone, isopropyl acetone, diss~ ~yl acetone, disspropyl Ai~etnn~, diethylene acetate, diethylene diacetate, or ethylene acetate ~ , phenol, (inrlnA;ng derivatives thereof) or mixture; and whereby the resultant fuel has an average LHV
of at least 28, 30, 32, 34, 35, 38, 40, 42 Qv.pH(Tb)/kJ mol1.

xamDle 212 The composition of Example 210, additionally containing an ECS __ ' (preferably DMC), and optionally a lli~; whereby the composition's flash point equals or exceeds 100, 130, 150~F, or more, and the freeze point is less than -40~F (-40~C), -47~F (-44~C), -50~F (-46~C), or less; and optionally a latent heat of vaporization equal to r or ~reeAing 28, 30, 32, 34, 38, 40, 45 QV~pH(Tb)/kJ mol1 (or equivalent).

Wos~33022 ~ 72 P~ C758 r le 213 The example 211, wherein the volume ratio of ECS
' 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, ljl, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:8, 1:10 with ratio's greater than 1:1 desireable (ratio's of 2:1, 3:1 being desireable and ~hose greater than 10:1, 8:1, 6:1, 5:1, 4:1 preferred).

Exa~ple 214 The example 213, wherein the above example fuels additionally comprise a co-fuel; whereby resultant fuel meets all ASTM and/or guv~ L specifications, lnrln~in~
fuel volitility, e.g. RVP
and flash point.

FY~rle 215 The example of 214, wh,erein the co-fuel is a conventional or reformulated gaEoline, whose vapor p~e~8u.
RVP exceeds 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0 psi, or more, and whereafter combination with co-solvent or mixture of co-~olvent (as set forth above), resultant fuel's RVP is equal to or less than 8.0, 7.5, 7.0, 6.5 psi, or less.

E 1~ 216 An aviation jet turbine co fuel, inrln~ng Jet A, A-l or B; or a ~1-D diesel, low sulfur or normal grade; or a gas turbine fuel oil ~ l-GT, Q 2-GT; said co-fuel W09s/33022 21 ~4572 r~l,u~,~r~7s8 o additionally comprising a combustion improving amount of an ECS _ ' ~preferably DMC) having a flash point of less than 38~C, and optionally at least one metallic (preferably MNT), and a flash t- ~LULe increasing amount of a co-.olvent (preferably a fuel soluble fl: hle polyeneglycol, ketone, acetate, phenol, and/or ester having flash point in excess of lO0, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300~F), wherein resultant fuel is characterized as having a flash point temperature of at least 100~F t38~C).

r le 217 - ~ ~
An J2-D diesel fuel oil co-fuel, normal grade or low sulfur; said fuel additionally comprising a combustion improving amount of an ECS _ ' (preferably DMC) having a flash point of less than 52~C, an optionally a metallic, and a flash t~ _ ~Lul~ increasing amount of a co-solvent, wherein resultant fuel is characterized as having a flash point t~ ~tUL~ of at least 52~C; optionally a reduced cloud or freeze point; and optionally i ~v~d viscosity.

Exam~le 218 An #4-D diesel fuel oil co-fuel, normal grade or low sulfur; or ~4, ~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 __ ' (preferably DMC) having a flash point of less than 55~C, a metallic, and optionally a metallic, and a flash t~ ~Lu~ increasing mount of a co-solvent, wherein resultant fuel is ~ W09~33022 2 1 945 72 P~ '1J0 characterized as having a flash point t~ aLuLe of at least 55~C.
c ~xa~le 219 A ~4-GT gas turbine fuel oil co-fuel; said fuel additonally comprising a combu~tion improving amount of an ECS _ ' (preferably DMC) having a flash point of less than 66~C, and optionally a metallic, and a flash t~ a~ULe increasing amount~of a co-solvent, wherein resultant fuel is characterized as having a flash point t- ~u~e of at least 66~C.

r ~e 220 An aviation gasoline co-fuel; said fuel additionally containing a combustion improving amount of D~C or other ECS ~ _ '(s) inrlll~ing tho~e having hlpn~;ng vapor ~Le~U~e greater than 7.0 psi (49 kPa), and wherein said ECS optionally has laminar flame velocity ~Yre~ing aviation gasoline (re~ ~ed at 44.8 cm/sec) or 45, 46, 47, 48, 49, 50 cm/sec, or greater; optionally a metallic; a vapor p'e6~urè reducing amount of a co-solvent, wherein said resultant aviation gasoline fuel is characterized as having a vapor pressure of at least 5.5 psi (38 kPa) at but not greater than 7.0 psi (49 kPa), and wherein resultant fuel meets all ASTM D 910 specifications.

W095/33022 2 1 9 4 5 7 2 rc~ c c -7~8 ~

r le 221 ~
A marine gas turbine co-fuel; said ruel additionally comprising a combustion improving amount of an ECS
_ ', preferably DMC, and optionally a - ll;c, And a flash t ~Lu~e 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~C.

o r le 222 The above examples wherein the co-solvent is comprised of at least one fuel aoluble, flammable triethyelene glycol, tetraethylene glycol ~ ; n~ i ng mixtures.

r le 223 The above examples, wherein the resultant fuels are additionally characterized as meeting ASTM, industry or ~U.~L L standards present and future.
It i6 also An Q~hO~ of Applicant's invention to employ salts for purposes of mitigating vapor pL~ULe and/or to increase flash point temp~L~tuL~s. It is contemplated that salts may be employed where they are soluble directly into the fuel or indirectely soluble via mutual solvent (e.g. a co-solvent). Most salts are soluble in aqueous solutions and Applicant's invention ~ ncl n~Qc method of employing such solutions directly into fuel, either by separate injection, : lcinnc, or co-solvent.

~I W095/33022 2 1 9 4 5 72 . ~ o la~

However, mutual solvents are the more preferred practice. For example, many vapor pressure reducing salts are soluble in ketones, inrln~ing acetone, glycols, ethers, A 1 r~h~l ~, and the like.
Desired aalts are those that do not adversely effect combustion or the Pmi ~ n~ of}a given fuel and, which in combination with Applicant's ECS fuel and optional - ' ~lir~ operate to reduce vapor ~Las~uLe and/or enhance com~ustion .
Acceptable salts are wide ranging. Non-limiting examples include calcium salts te.g. CatN03)2, CaBr2), barium, boron salts te.g. H3B03), potassium salts te.g.
KN03, XBrO3, XN02, XHC03, R2C204, XI, XH, K2W04, X2C03, KOH,), lithium ~alts te.g. LiNo3, LiBr, LiI, LioH), iron salts, ~ mimlm salts, cobalt, r~gnPcillm salts te.g. MgN03, MgBr2), sodium te.g. NaN03, NaOH, NaN02, NaHC03, NaBR03, NaBr, NaI, Na2C03, Na2W04), nitrogen salts te.g. NH4N03, NH4Br, NH4I), nickel salts te.g. Ni(No3)2) and zinc salts te-g- ZntN03)2).
Applicant has found that calcium, barium, boron, potassium, magnesium, nickel, and lithium salts to be desireable, P~pDciAlly those soluble directly into hydrocarbons fuels, indirectly via a mutual solvent tco-solvent, e.g ketones), and which can be added to the composition in sllffir-iPnt quantities to reduce vapor pressure.
ApplirAnt~5 pl~feLL~d sal1:s are those that may be added in sufficient cu..ce..LL~tions such that vapor p es~uL~

wogsl33022 2 1 9 4 ~ 7 2 l c~ r~7s8 ~

is reduced by 5.0, 10, 20, 30, 40, 50, 100, 150, 200, 300 mm at initial boiling t~ ~LuLas of fuel composition, by the addition of 0.5, 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 8.0, 10.0 grammolecules per liter. Perferred vapor p~e~u reductions are those greater than 20 mm, and preferred c~ ..L~tions are less than 4.0, 3.0, 2.5, 2.0, 1.5, 1.0 grammolecules per liter.

~y~mrle 224 A fuel composition comprising a vapor pL~s~uLa reducing amount of at least one salt soluble in hydrocarbon fuel or alternatively soluble in a co-solvent, wherein ~aid ~alt can be treated at 0.5 grammolecules per liter of fuel, thereby reducing vapor p~ UL e by at least 1.0, 2.0, 5.0, 7.5, 10.0, 15.0 mm at either ambient t~ ~LuLa or at vaporization t~ _ ~LuLas of the fuel, which ever is higher.

E le 225 Method wherein treatment levels range from 0.001 to 30.0 grammolecules per liter (more preferred being 0.01 to 5.0 grammolecules per liter).

r le 226 The Example of 212-223, wherein said compositions additionally contain a vapor ~asDuLa reducing or flash point increasing amount of a salt.

~ W09~33022 2 1 9 ~ 5 72 . ~ 5~758 ~t Fuel ~nrlication~
Rocket engine propulsion is a particularly desireable ob~ect of this invention and has been set forth in detail in my c ni on International Application No PCT/US95/02691, incu-~u.~Led herewith by reference r le 227 A rocket fuel propellant comprising an BCS
s~lPct~d from the group of dimethyl u~Lbu.~te, acetylene, aluminum bu~olylLide, ammonia, Aniline, benzene, butyl - u~L~ , diborane, diethylenetriamine, ethane, ethanol, ethylamine, ethylene, ethylene diamine, ethylene oxide, ethyl nitrate, furfuryl alcohol, gasoline, heptene, hydrazine (;nrl~ ng su~stituted hydrazines), hydLoy-n~
isopropyl alcohol, lithium, lithium hydride, methane, methylal, methanol, meth,ylamine, nitromethane, nit.u~-u~ne, n ouL~ne, propane, n-propyl nitrate, o-toluidine, triethylamine, trimethyl tri~hinph~phite, turpentine, un~y Lrical dimethyl hydrazine, 2,3-xylidene, lithium bu-uh~lLide, 'ylhydrazine~ pentaborane, and mixture; and a prop~ ion impro~ing amount of a metallic r le 228 The example of 180, wherein composition additionally comprises a known ~Yi~i7Gr, ~ cted from the group consisting of liquid oxygen, nitric acid, mixed nitric acid sulfuric acid combinations, fluorine, nitrogen tetroxide, l-yd~uyel- peroxide, potassium perchlorate, perchloryl .

WO9S/3302Z 21 9~ 572 r ~ 758 0 rluoride, bromine pentafluoride, chlorine tri~luoride, ON
7030, ozone, oxygen difluoride, RFNA (at various ellyUls) ~ WFNA, tetrani~LI '-nD, fluorine, chorine trifluoride, perchlory1 fluoride, nitrosyl fluoride, nitry1 fluoride, nitrogen trifluoride, difluorine - ~Yi~D, fluorate, chorine oxides, and the like.

r le 229 A rocket fuel composition comprising hy-ll-,lJei. peroxide and a metallic, such as cyclopentadienyl r-ng~n~e tricarbonyl _ _ ', and optionally, D15C.

Exa~Dple 2 3 0 A rocket fuel composition comprising hy~
peroxide, an oxider, a metallic, and optionally DNC.

E le 231 The rocket fuel composition of 230, wherein the metal is selected from the group consisting of cyclopentadienyl r~ng~nD~e tricarbonyl, technetium, rhenium, illnm;m-m, beryllium or boron -, in~ ing pentaborane, decaborane, barazole, alnminimllm borohydride, trimethylaluminum, beryllium borohydride, dimethlylberyllium, lithium LuL~hydLide, lnomologues thereof, and miYtures.

~ Wo95/33022 2 i 9 ~ ~ 7 2 r~ 1/~ ~ J7S8 ~_~ple 232 A rocket fuel for air breathing systems comprising dimethyl carbonate, a r ' llir; and optionally a rocket co-fuel; and optionally an oxidizer.

E le 233 Example 232, wherein non-li_iting examples of a rocket co-fuel include ll~dLU~I, hydrazine and kerosene.

EY~mnle 234 A rocket fuel composition comprising l,ilLù~en peroxide, CMT, and a co-propellant selected from the group consisting of dimethyl carbonate, acetylene, aluninum buLu~,ydLlde, ammonia, aniline, benzene, butyl diborane, diethylenetriamine, ethane, ethanol, ethylamine, ethylene, ethylene diamine, ethylene oxide, ethyl nitrate, furfuryl alcohol, gasoline, heptene, hydrazine (inn~ ing substituted hydrazines), }~ydLu~ell~ isopropyl alcohol, lithium, lithium hydride, methane, methylal, r ~'onol, methylamine, nitromethane, ni~u~ru~ane, n ouL~ne, propane, n-propyl nitrate, o-toluidine, triethylamine, trimethyl trithinrhn~rhite, turpentine, u~y ical dimethyl hydrazine, 2,3-xylidene, lithium borohydride, - ~I hylhydrazine~ pentaborane, and _ixture; and a propulsion improving amount of a cyclomatic m-ng~n~e tricarbonyl .

W09~/33022 2 t ~4 572 r~ ..r 75~ o r le 235 A method for onh~noQ~ vapor phase combustion of a metallic, wherein said vapor is combusted in a rocket engine; and is derived from and ECS ~ L~s~,-Ling 0.01% to 50~ oxygen by wt in the fuel, a - ~ lli r ese,.Ling O.ol to lOOO.o grs of metal/gal, and optionally a co-propellant and/or nYi~i70r.

Those skilled in the art will appreciate that many variations and modifications of the invention disclosed ~erein may be made without departing from the spirit and scope thereof.

Claims (10)

1) A method of reduced temperature vapor phase combustion, said method comprising: introducing a fuel having a particle size not exceeding an average of 70 microns into an air breathing combustion system; said fuel containing at least one fuel soluble non-leaded metal, halogen, or group IIIA element or compound, whose oxide's heat of formation is negative and exceeds about -200,000 gr calories/mole, and at least one ECS compound as provided in the specification and characterized as having a latent heat of evaporation exceeding about 200 btu/lb @ 60°F and a laminar burning velocity exceeding about 48 cm/sec; introducing sufficient temperature to cause ignition wherein unburned fuel vapor decomposes into reactive high kinetic energy free radicals; whereby said radicals diffuse ahead of the flame front in a manner sufficient to cause luminous vapor phase burning.

2) The method of 1, wherein the ECS compound is an oxygenated compound with a latent heat of vaporization exceeding about 31 kJ
mol -1 at its boiling temperature not exceeding about 110°C.

3) The method claim 1), wherein the fuel soluble non-leader metal, halogen, or group IIIA element or compound contains aluminum, boron, bromine, bismuth, beryllium, calcium, cesium, chromium, cobalt, copper, francium, gallium, germanium, iodine, iron, indium, lithium, magnesium, manganese, molybden, nickel, niobium, phosphorus, potassium, pallium, rubibidium, sodium, tin, zinc, praseodymium, rhenium, salane, or vanadium, and/or mixture; and optionally has a heating value exceeding 9,500 Kcal/kg.

4) A method of reduced temperature vapor phase combustion, said method comprising: introducing a fuel having a particle size not exceeding an average of 70 microns into an air breathing combustion system; said fuel containing at least one fuel soluble non-leaded metal, halogen, or group IIIA element or compound, whose oxide's heat of formation is negative and exceeds about -200,000 gr calories/mole, and at least one ECS compound as provided in the specification and characterized as having a latent heat of evaporation exceeding about 200 btu/lb @ 60°F and a laminar burning velocity exceeding about 48 cm/sec; and a co-fuel; introducing sufficient temperature to cause ignition wherein unburned fuel vapor decomposes into reactive high kinetic energy free radicals;
whereby said radicals diffuse ahead of the flame front in a manner sufficient to cause luminous vapor phase burning.

5) The method of 1, 3, or 4, wherein the unburned vapor prior to decomposition contains dimethyl carbonate, and at least one fuel soluble non-leaded metal, halogen, group IIIA element or compound selected from the group consisting of alumina, boron, magnesium, manganese, lithium, potassium, iodine, and mixture.

6) The method 4, wherein the co-fuel is selected from the group of fuels consisting of alternative fuel, hydrogen, petroleum gas, liquefied petroleum gas, LPG-propane, LPG-butane, natural gas, natural gas liquids, methane, ethane, propane, n-butane, propane-butane mixture, fuel methanol, e.g. M 80, M 90, or M 85 fuels, fuel ethanol, biomass fuels, vegetable oil/ester fuels, rap seed methyl ester, soybean fatty acid esters, aqueous carboneous fuels, including aqueous gasolines and diesels, aviation fuels, including grade 80, grade 100, grade 100ll aviation gasolines, conventional automotive gasolines, reformulated gasolines, low vapor pressure gasolines, low sulfur/no-sulfur gasolines, low octane gasolines, Talbert E-gasolines, alkylate or substantially alkylate fuels, reformate fuels, substantially reformate fuels, isooctane fuels, substantially isooctane fuels, paraffinic fuels, substantially paraffinic fuels, kerosine, wide range boiling fuels, gas turbine fuels, including No.0-GT, No.1-GT, No.2-GT, No.3-GT, No.4-GT, aviation jet turbine fuels including JP-4, JP-5, JP-7, JP-8, JP-9, JP-10, TS, Jet A-1, Jet A, Jet B, military aviation gasolines, 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. 1-D, Grade No. 2-D, and Grade No 4-D, and older grades Type C-B, Type T-T, Type R-R, Type S-M, reformulated diesel fuels, low/no sulfur hydrotreated low/no aromatic distillate fuels, toluene fuels, substantially toluene fuels, naptha fuels, substantially 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, 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, and mixtures thereof; said co-fuel optionally containing low concentrations of sulfur or no sulfur and/or low amounts or no phosphorus; said co-fuel characterized as representing substantial majority, majority, equal, substantial minority or minority concentration of the final fuel.

7) The method of 4 or 6, wherein said final fuel or co-fuel is characterized as meeting ASTM, government, or industry specifications.

8) The method of 1, 4, 6, or 7, wherein said fuel particle size does not exceed an average of 60, 50, 40, or 30 microns.

9) The method of claim 1, 4, 5, 7, or 8, wherein said fuel or pre-combustion vapor contains dimethyl carbonate and a fuel soluble non-leaded metal, halogen, or group IIIA element or compound containing aluminum, boron, bromine, bismuth, beryllium, calcium, cesium, chromium, cobalt, copper, francium, gallium, germanium, iodine, iron, indium, lithium, magnesium, manganese, cyclopentadienyl manganese tricarbonyl, molybden, nickel, niobium, phosphorus, potassium, pallium, rubibidium, sodium, tin, zinc, praseodymium, rhenium, salane, or vanadium, and/or mixture; wherein the ratio of dimethyl carbonate to fuel soluble non-leaded metal, halogen, or group IIIA element or compound is less than 2,500, 2,000, 1,500, 1,000, 800, 600, 500, 400, 300, 200, 100, 80, or 60 parts to one.

10) The method of 1, 4, 6, 7, or 8, wherein the air breathing combustion system is a large internal combustion engine exceeding 6.5 liters or 400 cubic inch displacement (or equivalent); and said engine is operated under heavy load; whereby combustion temperatures are reduced and/or fuel economy is improved over co-fuel operation alone.

11) The method of claim 1, 3, 4, 6, 7, or 8, wherein the air breathing combustion system is an engine or combustor selected from group consisting of rocket engine, Brayton cycle engine, gas oil turbine, aviation jet turbine, diesel engine, including direct injection, turbo charge, lean burn, swirl, variable valve timing and lift, marine, locomotive, aviation gas engine, gasoline/automotive engine, including 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, gas burner, gas furnace, internal compression engine, spark-ignited internal combustion engine, lean burn, fast burn, external combustion Stirling or Rankine engine, Otto cycle engine, Miller cycle, two stoke, four stroke, or catalyst system;
whereby the thermal or combustion efficiency of said engine operation is increased over usage of co-fuel alone.

12) The method of 11, wherein said combustion system additionally comprises mechanical means for reducing combustion temperatures and/or increasing burning velocity; characterized as increasing fuel economy or range, and/or reducing combustion temperature greater than an amount attributable to said fuel alone, absent said mechanical means, and/or greater than amount attributable to mechanical means and co-fuel alone.

13) The method of claim 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, wherein the exhaust emissions of said method are characterized as meeting or exceeding governmental standards.

14) The method of 1, 3, 4, 6, or 11, wherein the method additionally comprises introducing an oxidizer into said air breathing combustion system.

15) The method of Claim 4, 6, 7 or 11, wherein said air breathing combustion system is a jet turbine combustor; and said fuel contains DMC representing 0.01% to 40.0% oxygen by wt in the fuel, at least one metal, halogen, or group IIIa element or compound in a concentration of 0.001 to 5.0, 10.0, 20.0, 50.0, 100.0, 150.0, 200.0 or 250.0 gr/gal, and an aviation jet turbine co-fuel; wherein said fuel is characterized as having a total aromatic volume concentration not exceeding 25% or 22%, a maximum sulfur content not exceeding 0.3, 0.2, 0.1 weight percent or sulfur free, a maximum T-10 temperature of 205°C, a maximum final boiling point temperature of 300°C, 280°C, or 260°C; and whereby said method is characterized as increasing the lift and/or operating range of jet employing said combustor and combusting said fuel compared to jet turbine co-fuel alone.

16) The method of claim 15, wherein said fuel optionally has: a minimum flash point of 38°C, a density range of about 751 to 840 at 15°C, kg/m3, a minimum freezing point of -40°C, -5°C, or -57°C, a minimum net heat of combustion of 42.8 KJ/kg, a minimum latent heat of vaporization of about 115 BTu/lb, meets ASTM 1655 finished fuel requirements for Jet A, Jet A-1, or Jet B; and wherein combustion optionally occurs at an altitude in excess of 10,000 feet above sea level, whereby thermal, combustion efficiency or lift is improved over co-fuel alone.

17) The method of Claim 15 and 16, additionally comprising inlet turbine temperature, pressure, or turbine outlet pressure sufficient to provide thrust to operate said jet at a speed in excess of mach 3, 4, 5, or 6.

18) The method of Claim 6, 7 or 11, wherein the air breathing combustion system is a diesel engine; and said fuel contains DMC
representing 0.01% to 10.0% oxygen by wt in the fuel, at least one metal, halogen, or group IIIa element or compound in a concentration of 0.001 to about 1.0, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0 gr/gal, and a diesel co-fuel; wherein said fuel is optionally characterized as having one or more of the following: a density ranging from about 880 to 800 kg/m3; viscosity ranging from 2.5 to 1.0 cSt at 40°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 T10 fraction temperature of about 190 to 230°C, a T 50 fraction temperature of about 220 to 280°C, a T90 fraction of about 260 to 340°C, a cloud point temperature of °C -10, -28, -32 or 6°C
above tenth percentile minimum ambient temperature, a sulfur content not greater than 250 ppm, 200 ppm, 100 ppm, 50 ppm, 40 ppm, 30 ppm, 20 ppm 5 ppm, or being sulfur free, a bunsen laminar burning velocity of at least 40 cm/sec, a latent heat of vaporization of at least 110 BTU/lb; said method characterized in achieving reduced particulate emissions or improved fuel economy compared to co-fuel alone.

19) The method of Claim 4, 6, 7 or 11, wherein said air breathing combustion system is a diesel engine; and said fuel contains DNC
representing 0.01% to 2.0%, 3.0%, 4.0%, 5.0%, 7.5%, 10.0%, 15.0%, 20.0%, 25.0%, 30.0%, 35.0%, or more oxygen by wt in the fuel, at least one fuel soluble metal, halogen, or group IIIA element or compound, in a concentration of 0.001 to about 1.5, 2.0, 2.5, 3.0, 4.0, 5.0, 7.5, 10.0, 15.0, 20.0, 30.0, or more, gr/gal, a 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, 40, 20, 10, 5 wt ppm or sulfur free, absent nitrogen, and an aromatic content ranging from 0 to 5%, 1 to 10%, 0 to 15%, 0 to 20%, 0 to 35% by volume, or aromatic free, PNA vol% of not exceeding 0.03, 0.02, 0.01, or PNA free, a Cetane index greater than 45, an IBP of approximately 365°F, a 95% fraction ranging from 450°F to 540°F; a bunsen laminar burning velocity of at least 38 cm/sec, a latent heat of vaporization of at least-105 BTU/lb; said method characterized in achieving reduced particulate emissions or improved fuel economy compared to co-fuel alone.

20) The method of Claim 4, 6, 7 or 11, wherein said air breathing combustion system is an aviation gasoline engine; and said fuel contains is DNC representing 0.01% to 10.0% oxygen by wt in the fuel, at least one fuel soluble metal, halogen, or group IIIA
element or compound in a concentration of 0.001 to about 2.5, 5.0, 10.0, 15.0, 20.0 gr/gal, an aviation gasoline co-fuel; said fuel optionally characterized as having one or more of the following:
a minimum knock octane number of 80, or 100 and minimum performance number of 87, or 130, containing lead, a max T10 distillation temperature of 75°C, a minimum T40 temperture of 75°C, a maximum T50 temperature of 105°C, a maximum T90 temperature of 135°C, a maximum end temperature of 135°C, where the sum of the T10 and T50 temperatures is a minimum of 135°C, a maximum sulfur content of 0.05 wt%, a minimum net heat of combustion of 18,720 BTU/lb, a latent heat of vaporization exceeding 140, 150, 155, or 160 BTU/lb.

21) The method of claim 4, 6, 7 or 11, wherein said air breathing combustion system is an aviation gasoline engine; and said fuel contains DMC representing 0.01% to 15.0% oxygen by weight of a fuel, an organo manganese representing about 0.001 to 2.0, 2.5, 3.0, 3.5, 10.0, 15.0, 20.0 gr Mn/gal of fuel, and an ASTM or other aviation co-fuel having a minimum heat of combustion of 18,720 BTU/lb; wherein said fuel has heat of combustion lower than 18,720 BTU/lb due to dilution effect of DMC; said method characterized in that aviation engine combusting said fuel has increased flight range compared to higher heat of combustion co-fuel alone.

22) The method of Claim 4, 6, 7 or 11, wherein said air breathing combustion system is a gas oil turbine-combustor; and said fuel contains DMC representing 0.01% to 40.0% oxygen by wt in the fuel, at least one fuel soluble metal, halogen, or group IIIA element or compound representing a concentration of 0.001 to about 3.5 7.5, 10.0, 15.0, 20.0, or more gr/gal, and a gas oil turbine co-fuel;
said turbine co-fuel may be selected from No. 0-GT, No. 1-GT, No.
2-GT, No. 3-GT or No. 4-GT gas turbine fuel oil, or other oil;
wherein said fuel is optionally characterized as having one or more of the following: a minimum flash point of 38°C to 66°C, a minimum kinetic viscosity at 40°C ranging from 1.3 to 5.5 2mm/s (ASTM D
445), optionally a sulfur content not exceeding 1500, 500, 400, 300, 200, 100, 50, 40, 20 ppm wt, or being sulfur free, a T90 temperature reduced by at least 20°C below the conventional co-fuel, or equivalent, a bunsen laminar burning velocity of at least 35, 36 cm/sec, a latent heat of vaporization of at least 100 BTU/lb; and optionally whereby turbine inlet gas temperature is less than 650°C, 600°C, or 550°C and/or whereby inlet pressure is increased compared to co-fuel alone.

23) The method of Claim 15 or 22, wherein said combustor's flame tube has a dilution zone length of approximately 1.4 to 1.6 times the total flame tube width.

24) The method of Claims l, 4, 5, 6, 7, 15, 18, 19, 20, 21, or 22 wherein said fuel additionally contains a co-solvent, co-solvent mixture, salt, and/or other means as set forth in the specification to increase flash point or reduce vapor pressure.

25) A composition of matter comprising; at least one ECS compound having, a latent heat of evaporation (LHV) exceeding 200 btu/lb @

60oF, optionally being an oxygenated compound with its LHV
exceeding about 31 KJ mol-1 at its boiling temperature not to exceed about 110°C, and a laminar burning velocity exceeding 48 cm/sec;
and a combustion improving amount of at least one fuel soluble high heating value non-leaded metal, halogen, or group IIIA element or compound whose oxide's heat of formation is negative and exceeds about -200,000 gr calories/mole, said element or compound containing an element selected from the group consisting of aluminum, boron, bromine, bismuth, beryllium, calcium, cesium, chromium, cobalt, copper, francium, gallium, germanium, iodine, iron, indium, lithium, magnesium, manganese, molybden, nickel, niobium, phosphorus, potassium, pallium, rubibidium, sodium, tin, zinc, praseodymium, rhenium, salane, vanadium, and mixture; and optionally a co-fuel; said composition characterized as being able to achieve luminous vapor phase combustion in an air breathing combustion system.

26) The composition of claim 25, wherein said composition contains DMC and at least one co-fuel; said composition characterized as having latent heat of vaporization and/or burning velocity greater than co-fuel alone; whereby thermal efficiency, fuel economy, or combustion temperature of combined fuel is superior to co-fuel alone.

27) The composition of Claims 25 or 26, additionally comprising a co-solvent, co-solvent mixture, salt, and/or other means as set forth in the specification to increase flash point or reduce vapor pressure .

28) The method of Claim 7 or 11, wherein said air breathing combustion system is a gasoline automotive engine; and said fuel contains DMC representing 0.01% to 1.0%, 2.0%, 3.5%, 4.0%, 4.5%, 5.0%, 7.0%, 10.0%, or more, oxygen by wt in the fuel, at least one fuel soluble high heating value non-leaded metal, halogen, or group IIIA element or compound in a concentration up to 1/64, 1/32, 1/16, 1/8, 1/4 or 3/8, 1/2, 5/8, 3/4, 7/8, 1.0, 1.5, 2.0, 2.5, 3.0 gr/gal, and a conventional or reformulated gasoline co-fuel; said fuel optionally characterized as having one or more of the following: a sulfur content less than 500, 400, 300, 200, 100, 20, or 10 ppm, or sulfur free; a polynuclear free aromatic concentration of less than 35%, 27%, 20%, 15%, 10%, or aromatic free; an olefin concentration (excluding C4-C5 olefins) less than 15%, 10%, 8%, 5%, or olefin free; a benzene concentration of less than 3.0%, 2.0%, 1.0%, 0.9%, 0.8%, 0.7% volume, or benzene free;
an RVP of less than 12.0, 10.0, 8.5, 8.0, 7.5, 6.9, 6.5, 6.0 psi, or less; a minimum octane (R+M)/2 of 102, 100, 98, 95, 94, 93, 92, 91, 90, 89, 88, 87, 86, 85; at least one deposit control additive selected from combustion chamber deposit control, port fuel injector, or intake valve control additives; a driveability index less than 1120, 960, or 930 (preferred); a T 90 temperature less than 350°F, 340°F 330°F, 320°F 310°F, 305°F, 300°F, 295°F, 290°F, 285°F, 280°F, 275°F, 270°F, 265°F, or less; a t-50 temperature greater than 170°F, 175°F, 180°F, 185°F, 190°F, 195°F, 200°F, or 205°F; a T-10 temperature less than 140°F,130°F, 120°F, 110°F, or 100°F; a heat of vaporization equal to or greater than 140, 145, 150, 152, 155 btu/lb; a miminum laminar burning velocity of 48, 49 cm/sec.

29) The method of Claim 4, 7, or 11, wherein said air breathing combustion system is a heavy diesel, locomotive or marine engine;
and said fuel contains DMC representing 0.01% to 40% oxygen by wt in the fuel, a non-leaded metal, halogen, or group IIIA element or compound representing 0.01 to 20.0, 30.0, 40.0, 50.0, 75.0, 100.0, 150.0, 200.0 grs/gal, or more, and a heavy diesel, locomotive or marine engine co-fuel, optionally meeting ISO DIS 8217 and/or BS
MA 100 standards specifications; said fuel characterized as optionally having one or more of the following attributes: being sulfur free or having a sulfur concentration of 0.01 to .05%, 0.1%, 0.5%, 1.0%, 2.0%, 3.0%, 4.0%, 5.0% mass, or greater, a viscosity of 10 to 500 centistokes at 50°C; whereby the combustion of said fuel in said engine in said method results in reduced corrosion, particulate emissions and/or improved fuel consumption compared to co-fuel alone.

30) A method of enhancing a multiple boiling range hydrocarbon fuel base; said method comprising: increasing said fuel's LHV by at least 0.5%, 1.0%, 2.0%, 3.0%, or more; and/or increasing said fuel's burning velocity by at least 0.5%, 1.0%, 2.0%, 3.0%, or more; combusting resultant fuel, whereby fuel economy, range or efficiency is increased compared to the unadjusted base fuel alone.

31) The method of Claim 1, 4, 7 or 11, wherein said air breathing combustion system is a rocket engine; and said fuel contains an ECS compound representing 0.01% to 50%, or more, oxygen by wt in the fuel, a non-leaded metal, halogen, or group IIIA element or compound representing 0.01 to 1000.0 grs, or more, of metal/gal, and optionally a co-propellant and/or optionally an oxidizer.

32) A method of increasing work potential, fuel economy, or reducing emissions of a gasoline vehicle operating on conventional or reformulated gasoline, said method comprising: Reducing the boiling temperature of gasoline such that its T-90 fraction is no greater than 300°F, 295°F, 290°F, 285°F, 280°F, 275°F, or 270°F, or less; optionally increasing its latent heat of vaporization above 155, 160, 165, or greater, btu/lb; optionally increasing its burning velocity in excess of 49, 50, 51, or more, cm/sec;
optionally admixing MMT up to 1/64, 1/32 gr mn/gal; combusting said composition in a gasoline powered vehicle whereby fuel economy is improved over unadjusted fuel.

33) The composition of 25, 26 or 30, wherein said fuel or pre-combustion vapor contains dimethyl carbonate and a fuel soluble non-leaded metal, halogen, or group IIIA element or compound containing aluminum, boron, bromine, bismuth, beryllium, calcium, cesium, chromium, cobalt, copper, francium, gallium, germanium, iodine, iron, indium, lithium, magnesium, manganese, cyclopentadienyl manganese tricarbonyl, molybden, nickel, niobium, phosphorus, potassium, pallium, rubibidium, sodium, tin, zinc, praseodymium, rhenium, salane, or vanadium, and/or mixture; wherein the ratio of dimethyl carbonate to fuel soluble non-leaded metal, halogen, or group IIIA element or compound is less than 2,500, 2,000, 1,500, 1,000, 800, 600, 500, 400, 300, 200, 100, 80, or 60 parts to one.

34) The fuel compositions of 25, 26, 30, 32, or 33, wherein said compositions meet or exceed ASTM, CARB, U.S. Clean Air Act, Swedish European, EEC or other government fuel standards.

35) A fuel composition comprising: a conventional or reformulated aviation/automotive gasoline, diesel, turbine, fuel oil, or other co-fuel; an ether selected from the group consisting of MTBE, ETBE, TAME, DIPE, and mixture; at least one non-ether ECS compound having a burning velocity and/or a latent heat of vaporization greater than MTBE; and optionally a combustion improving amount of at least one fuel soluble non-leaded metal, halogen, or group IIIA element or compound; whereby combustion of said fuel accelerates decomposition of said ether(s) prior to its emission into atmosphere, or increases fuel economy compared to fuel containing said ether but absent ECS compound and/or optional metal, halogen, or group IIIA element or compound 36) A composition of matter comprising; an unleaded conventional or reformulated gasoline composition conforming with Clean Air Act requirements under ~ 211(k), said composition additionally characterized as having a minimum latent heat of vaporization of about 153, 154 btu/lb @ 60°F, and optionally a minimum laminar flame burning velocity of 49, 50, 51 cm/sec.

37) A method of avoiding CCD deposits, said method comprising:
mixing combustion improving amount of a fuel soluble non-leaded metal, halogen, or group IIIA element or compound, an ECS compound, a combustion chamber deposit (CCD) control additive, and a co-fuel;
combusting said fuel in an engine for the equivalent of 5,000,

10,000, 15,000, 20,000, 30,000, 50,000, 75,000, or 100,000 miles;
wherein the octane requirement for engine operating on said fuel does not exceed, or is less, than the octane requirement of same engine operating on clear co-fuel alone containing same CCD
additive.