Fuel compositions

Abstract

Improved fuel compositions and fuel additive packages which serve to prolong stability at various ambient conditions and to increase fuel efficiency and fuel economy while also significantly reducing the level of multiple emissions constituents generated upon combustion of the fuels including CO.sub.2, NO.sub.X, SO.sub.X, Particulate Matter PM2.5, PM10 and Black Carbon. The fuels may include the hydrocarbon fuels gasolines, diesel fuels, biodiesel fuels, biomass diesel fuels, renewable fuels, synthetic fuels, algae-based fuels, kerosene fuel or heavy fuel oils, or may alternatively be hydrosols, and include an additive package having a sorbitan oleate, a polyoxyethylene alcohol, an alkylene glycol, and an amine. The fuels are mixed with an additive and are emulsified with clean, soft water having a water quality of 1 micron or less.

Claims

1. A fuel composition comprising a combustible hydrocarbon-based fuel and an additive package mixed with said fuel, said additive package being present at a level for reducing the amount of CO.sub.2, NO.sub.X, SO.sub.X, PM2.5, PM10 and Black Carbon emissions generated upon combustion of the fuel composition as compared with an otherwise identical fuel composition in the absence of said additive package, said additive package including respective quantities of synthetic surfactants, sorbitan oleate, a polyoxyethylene alcohol, an alkylene glycol, and an amine, and said additive package containing soft water purified by filtration to approximately 1 micron or smaller.

2. The fuel composition of claim 1, said hydrocarbon-based fuel selected from the group consisting of gasolines, diesel fuels, biodiesel fuels, biomass diesel fuels, renewable fuels, synthetic fuels, algae-based fuels, kerosene fuel or heavy fuel oils, or may alternatively be hydrosols containing a substantial fraction of water with a hydrocarbon fuel.

3. The fuel composition of claim 1, said hydrocarbon-based fuel being a hydrosol and comprising a hydrocarbon fuel and an amount of soft water purified by filtration to approximately 1 micron or smaller.

4. The fuel composition of claim 3, said hydrosol containing from about 5-30% by weight soft water purified to approximately 1 micron or smaller, based upon the total weight of the fuel composition taken as 100% by weight.

5. The fuel composition of claim 1, including individual quantities of synthetic or organic surfactants, sorbitan monooleate and sorbitan sesquioleate.

6. The fuel composition of claim 1, said fuel composition of said additive package including respective quantities of synthetic or organic surfactants, for which the surfactants being about 1.8-5.00% by weight, based upon the total weight of the fuel composition taken as 100% by weight.

7. The fuel composition of claim 1, said fuel composition being essentially water-free, said sorbitan oleate being present at a level of from about 1.8-5.00% by weight, based upon the total weight of the fuel composition taken as 100% by weight.

8. The fuel composition of claim 1, said polyoxyethylene alcohol comprising POE (6) tridecyl alcohol.

9. The fuel composition of claim 7, said fuel composition being essentially water-free, said polyoxyethylene alcohol being present at a level of from about 3.00-8.00% by weight, based upon the total weight of the fuel composition taken as 100% by weight.

10. The fuel composition of claim 1, said alkylene glycol comprising hexylene glycol.

11. The fuel composition of claim 1, said fuel composition being essentially water-free, said alkylene glycol being present at a level of from about 0.25-0.75% by weight, based upon the total weight of the fuel composition taken as 100% by weight.

12. The fuel composition of claim 1, said amine being a primary amine having the formula R—NH.sub.2, where R is selected from the group consisting of C1-C18 straight or branched chain alkyl, alkenyl, and alkynyl groups, aryl groups, and organic heteroatom groups containing an O, S or N.

13. The fuel composition of claim 11, said amine selected from the group consisting of C1-C12 alkyl amines.

14. The fuel composition of claim 1, said fuel composition being essentially water-free, said amine being present at a level of from about 0.05-5.00% by weight, based upon the total weight of the fuel composition taken as 100% by weight.

15. The fuel composition of claim 1, said additive package further including individual quantities of toluene and xylene.

16. The fuel composition of claim 14, said additive package including equal quantities of toluene and xylene.

17. The fuel composition of claim 15, said fuel composition being essentially water-free, said quantities of toluene and xylene together totaling from about 0.10-10.00% by weight, based upon the total weight of the fuel composition taken as 100% by weight.

18. The fuel composition of claim 1, said fuel composition being essentially water-free, said additive package including naptha present at a level of from about 0.5-10.00% by weight, based upon the total weight of the fuel composition taken as 100% by weight.

19. The fuel composition of claim 1, said additive package being present at a level of from about 0.16-0.64 fluid ounces/gallon of hydrocarbon-based fuel.

20. The fuel composition of claim 18, said fuel being a gasoline, said additive package being present at a level of from about 0.16-0.48 fluid ounces/gallon of gasoline.

21. The fuel composition of claim 18, said fuel being selected from the group consisting of diesel fuel, biodiesel fuel, biomass diesels fuel, or algae-based diesel fuel, kerosene and heavy fuel oils, said additive package being present at a level of from about 0.32-3.00 fluid ounces/gallon of said fuel being selected from the group consisting of diesel fuel, biodiesel fuel, biomass diesel fuels, or algae-based diesel fuel, kerosene and heavy fuel oils.

22. The fuel composition of claim 1, said fuel composition being a hydrosol, said sorbitan oleate being present at a level of from about 0.45-3.00% by weight, based upon the total weight of the fuel composition taken as 100% by weight.

23. The fuel composition of claim 1, said fuel composition being a hydrosol, said polyoxyethylene alcohol being present at a level of from about 0.15-0.60% by weight, based upon the total weight of the fuel composition taken as 100% by weight.

24. The fuel composition of claim 1, said fuel composition being a hydrosol, said alkylene glycol being present at a level of from about 0.10-0.30% by weight, based upon the total weight of the fuel composition taken as 100% by weight.

25. The fuel composition of claim 1, said fuel composition being a hydrosol, said amine being present at a level of from about 0.05-2.50% by weight, based upon the total weight of the fuel composition taken as 100% by weight.

26. The fuel composition of claim 15, said fuel composition being a hydrosol, said quantities of toluene and xylene together totaling from about 0.20-5.00% by weight, based upon the total weight of the fuel composition taken as 100% by weight.

27. An additive package for mixing with a hydrocarbon-based fuel and operable to reduce CO.sub.2, NO.sub.X, SO.sub.X, Particulate Matter PM2.5, PM10 and Black Carbon emissions generated upon combustion of the fuel, said additive package including respective quantities of a sorbitan oleate, a polyoxyethylene alcohol, an alkylene glycol, and an amine, and said additive package containing soft, submicron purity filtered water.

28. The additive package of claim 27, including individual quantities of sorbitan monooleate and sorbitan sesquioleate.

29. The additive package of claim 27, said polyoxyethylene alcohol comprising POE (6) tridecyl alcohol.

30. The additive package of claim 27, said alkylene glycol comprising hexylene glycol.

31. The additive package of claim 27, said amine being a primary amine having the formula R—NH.sub.2, where R is selected from the group consisting of C1-C18 straight or branched chain alkyl, alkenyl, and alkynyl groups, aryl groups, and organic heteroatom groups containing an O, S or N.

32. The additive package of claim 31, said amine selected from the group consisting of C1-C12 alkyl amines.

33. The additive package of claim 27, said additive package further including individual quantities of toluene and xylene.

34. The additive package of claim 32, said additive package including equal quantities of toluene and xylene.

35. The additive package of claim 27, said additive package further including a compound selected from the group consisting of 2-ethyl hexyl nitrate, methanol and ethylene glycol.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) As noted above, the fuel compositions of the present invention broadly include a combustible hydrocarbon-based fuel and an additive package mixed with the fuel. The fuels may be traditional, essentially water-free hydrocarbon fuels such as gasolines, diesel fuels, biodiesel fuels, biomass diesel fuels, renewable fuels, synthetic fuels, heavy fuel oil, kerosene fuel, biofuels, and algae-fuels or, alternatively, hydrosols comprising such hydrocarbon fuels with added water and containing a substantial fraction of water with a hydrocarbon fuel. In all instances, the additive package is present in relatively small amounts, normally on the order of from about 0.16-3.00 fluid ounces of additive package/gallon of hydrocarbon-based fuels. It will be appreciated, however, that the amount of additive package used is based upon the exact makeup of the package, the desired fuel performance, the cost of the additive package, and the duration of emulsification stability required. Further, the fuel-water and additive package will obtain enhanced shelf life stability and performance characteristics with the use of clean (purified) water. Soft water should be used and the water should be purified to 1 micron or less, and bacteria should be eliminated by methods such as UV lighting.

(2) The additive package of the invention has slightly different makeups when used with essentially water-free fuels, versus hydrosols. In all instances though, the additive package includes respective quantities of a sorbitan oleate, a polyoxyethylene alcohol, an alkylene glycol, and an amine.

(3) The sorbitan oleate component is preferably made up of individual quantities of sorbitan monooleate and sorbitan sesquioleate, with a total sorbitan oleate fraction being used set forth in the following Tables. The oleates are useful as coupling and dispersing agents in the improved fuels of the invention.

(4) The polyoxyethylene alcohol component can be variable, but in most preferred cases it compromises a combination of 3 and 6 molar ethoxylates of a C6-C22 alcohol (e.g., tridecyl alcohol), i.e., POE(3) and POE(6)alcohols. The overall alcohol content of the fuels, and the preferred contacts of the POE(3) and POE(6) are set forth below.

(5) The additive packages also contain an alkylene glycol, which serve as a source of hydrogen radicals. Preferably, the glycols are C2-C8 glycols, most preferably hexylene glycol.

(6) The amine component of the additive packages can be in the form of a primary, secondary (e.g., ethoxylated fatty acid amines), or tertiary amine or amine derivative. For reasons of cost, the primary amines are preferred, these having the formula R—NH2, where R is selected from the group consisting of C1-C18 straight or branched chain alkyl, alkenyl, and alkynyl groups, aryl groups, and organic heteroatom groups containing an O, S or N ion. Most preferably though, the primary amines are selected from the group consisting of C1 C12 alkyl amines. More specifically, the following alkylamines are particularly useful: isopropylamine, CAS #75-31-0, ethylamine, CAS #75-04-7, diethylamine, CAS #109-89-7, and triethylamine, CAS #121-44-8. Alkanolamines are also useful, e.g., monoethanolamine, CAS #141-43-5, diethanolamine, CAS #111-42-2, triethanolamine, CAS #102-71-6.

(7) The following Table 1 sets forth additional operative amines useful in the invention.

(8) TABLE-US-00001 Alternative Product CAS CAS Name number CAS Name Number CAS Name E-14-2 68478- Poly(oxy-1,2- 218141- Poly(oxy-1,2- 95-5 ethanediyl), 23-2 ethanediyl),a,a.sup.1- a,a.sup.1-(iminodi-2,1- (limiodi-2,1- ethanediyl)bis]w- ethanediyl)bis[w- hydroxy-, hydroxy-,N-[2-(C9-11- N-[3-(branched isoalkyloxy)propyl] decyloxy)propyl] derivs., derivatives. C10 rich E-14-5 68478- Poly(oxy-1,2- 218141- Poly(oxy-1,2- 95-5 ethanediyl), 23-2 ethanediyl),a,a.sup.1- a,a.sup.1-(iminodi-2,1- (limiodi-2,1- ethanediyl)bis]w- ethanediyl)bis[w- hydroxy-, hydroxy-,N-[2-(C9-11- N-[3-(branched isoalkyloxy)propyl] decyloxy)propyl] derivs., derivs. C10 rich E-17-2 68478- Poly(oxy-1,2- 223129- Poly(oxy-1,2- 96-5 ethanediyl), 76-8 ethanediyl),a,a.sup.1- a,a.sup.1-(iminodi-2,1- (limiodi-2,1- ethanediyl)bis]w- ethanediyl)bis[w- hydroxy-, hydroxy-,N-[2-(C13- N-[3-(branched rich, 11-14 tridecyloxy)propyl] isoalkyl)oxy]propyl] derivs. derivs. E-17-5 68478- Poly(oxy-1,2- 223129- Poly(oxy-1,2- 96-6 ethanediyl), 76-8 ethanediyl),a,a.sup.1- a,a.sup.1-(iminodi-2,1- (limiodi-2,1- ethanediyl)bis]w- ethanediyl)bis[w- hydroxy-, hydroxy-,N-[2-(C13- N-[3-(branched rich, 11-14 tridecyloxy)propyl] isoalkyl)oxy]propyl] derivs. derivs. E-S-15 61791- Amines, soya alkyl, 24-0 ethoxylated E-S-2 61791- Amines, soya alkyl, 24-0 ethoxylated E-S-3.5 61791- Amines, soya alkyl, 24-0 ethoxylated E-S-5 61791- Amines, soya alkyl, 24-0 ethoxylated

(9) The additive packages may also have a number of optional ingredients, such as individual quantities of toluene and xylene, the latter normally being in equal quantities. Where an essentially water-free fuel is being supplemented, the additive package may also include VMP naphtha. Other optional ingredients may include alkyl benzene, and an alpha olefin (e.g., decene-1). The alkyl benzene aids in the lubricity of the fuels and cleavage of hydrocarbon molecules. The alpha olefin increases the power factor of the complete fuels.

(10) The following tables 2-5 set forth ranges of use for the components of water-free and hydrosol fuels in accordance with the invention, as well as additive packages for incorporation into water-free fuels and hydrosols; the tables include information respecting generic components as well as preferred components. In Table 2 and 3 relating to complete fuels, the ranges are expressed as percentages by weight, based upon the total weight of the fuels taken as 100% by weight. In Tables 4 and 5 to the additives per se, the ranges are expressed as percentages by weight, based upon the total weight if the additive packages taken as 100% by weight.

(11) TABLE-US-00002 TABLE 2 WATER-FREE FUELS FUEL BROAD CONSTITUENT CAS NO. RANGE PREFERRED Hydrocarbon-based fuel n/a 67.50-97.90% 84.50% Total additive package n/a  2.10-12.50% 15.50% Total sorbitan oleate n/a  1.80-6.00%  3.75% a. Sorbitan monooleate 1338-43-8  0.90-2.50%  1.25% b. Sorbitan sesquioleate 8007-43-0  0.90-3.50%  2.50% Total POE alcohol n/a  3.00-8.00%  5.00% a. POE(3) tridecyl 78330-21-9  2.00-5.00%  1.66% alcohol     b. POE(6) tridecyl 78330-21-9  1.00-3.00%  3.34% alcohol     Alkylene glycol n/a  0.25-0.75%  0.30% Amine n/a  0.05-5.00%  3.00% Toluene 108-88-3  0.05-5.00%  0.75% Xylene 1330-20-7  0.05-5.00%  0.75% VMP naptha 68410-97-9  0.50-10.00%  1.50% Alkyl benzene 68855-24-3  0.05-5.00%  0.50%

(12) TABLE-US-00003 TABLE 3 HYDROSOLS BROAD FUEL CONSTITUENT CAS NO. RANGE PREFERRED Hydrocarbon-based fuel n/a 67.80-93.40% 75.50% Soft Water with 1 micron or less purity n/a  5.00-25.00% 20.00% Total additive package n/a  0.75-6.00%  4.50% Total sorbitan oleate n/a  0.45-3.00%  0.90% a. Sorbitan monooleate 1338-43-8  0.30-2.0%  0.60% b. Sorbitan sesquioleate 8007-43-0  0.15-1.00%  0.30% Total POE alcohol n/a  0.15-0.60%  0.60% a. POE(3) tridecyl 78330-21-9  0.10-0.40%  0.40% alcohol     b. POE(6) tridecyl 78330-21-9  005-0.20%  0.20% alcohol     Alkylene glycol n/a  0.10-0.30%  0.20% Amine n/a  0.05-0.50%  0.40% Toluene 108-88-3  0.10-0.50%  0.35% Xylene 1330-20-7  0.10-0.50%  0.35% Alkyl benzene 68855-24-3  0.10-0.40%  0.20%

(13) TABLE-US-00004 TABLE 4 ADDITIVE PACKAGES FOR WATER-FREE FUELS ADDITIVE PACKAGE BROAD CONSTITUENT CAS NO. RANGE PREFERRED Total sorbitan oleate n/a 0.45-3.00%  1.50% a. Sorbitan monooleate 1338-43-8 0.15-1.00%  0.50% b. Sorbitan sesquioleate 8007-43-0 0.30-2.00%  1.00% Total POE alcohol n/a 0.10-3.00%  1.50% a. POE(3) tridecyl 78330-21-9 0.05-2.00%  1.00% alcohol   b. POE(6) tridecyl 78330-21-9 0.05-1.00% 0.50% alcohol   Alkylene glycol n/a 0.05-1.00%  0.50% Amine n/a 0.05-5.00%  3.00% Toluene 108-88-3 0.05-5.00%  1.50% Xylene 1330-20-7 0.05-5.00%  1.50% VMP naptha 68410-97-9 67.80-95.00% 90.00% Alkyl benzene 68855-24-3 0.50-1.00%  0.50%

(14) TABLE-US-00005 TABLE 5 ADDITIVE PACKAGES FOR HYDROSOLS ADDITIVE PACKAGE BROAD CONSTITUENT CAS NO. RANGE PREFERRED Total sorbitan oleate n/a 4.00-25.00% 18.00% a. Sorbitan monooleate 1338-43-8 1.00-10.00%  6.00% b. Sorbitan sesquioleate 8007-43-0 3.00-15.00% 12.00% Total POE alcohol n/a 1.50-15.00%  9.00% a. POE(3) tridecyl alcohol 78330-21-9 1.00-10.00%  6.00% b. POE(6) tridecyl alcohol 78330-21-9 0.50-5.00%  3.00% Alkylene glycol n/a 0.50-3.00%  2.00% Amine n/a 1.00-10.00%  5.00% Toluene 108-88-3 5.00-40.00% 32.50% Xylene 1330-20-7 5.00-40.00% 32.50% Alkyl benzene 68855-24-3 0.05-2.00%  1.00%

(15) Although not wishing to be bound by any theory, it is believed that the presence of the amine in the improved additive packages, the soft water purity quality of approximately 1 micron or less, and the submicron nano-emulsification, as well as the improved fuels of the invention, aid in decreasing CO.sub.2, NO.sub.X, SO.sub.X, PM2.5, PM10 and Black Carbon emissions upon combustion of the fuels. That is, the amine reacts catalytically with hydrogen present in the fuel mixture by virtue of the glycol fraction to generate ammonia. The ammonia then reacts with CO.sub.2 to form ammonium carbamate, which is in turn dehydrated during combustion to yield urea and water. These reactions are exemplified by the following, where use is made of a primary amine. The remaining constituents are reduced by a combination of the chemical reaction taking place during the combustion process as well as, in the case of the hydrosols, a natural reduction on account of the hydrocarbon fuel displacement by the quantity of soft water used in the emulsification.

(16) ##STR00001##

(17) As can be seen, this reaction scheme is both simple and environmentally benign, yielding only water and urea as end products. However, significant quantities of CO.sub.2, NO.sub.X, SO.sub.X, PM2.5, PM10 and Black Carbon are taken up, resulting in lessened emissions thereof. The fuels of the invention should exhibit up to 90% reduction in emissions, as compared with present-day conventional fuels.

(18) TABLE-US-00006 TABLE 6 ASTM D-975 Ultra Low Sulfur Diesel Scenario Test Procedure Min Max Hydrosol Invention Flash Point PMCC ASTM D93 52 — 61.1° C. Density ASTM D4052 0.820 0.860 0.850 g/cm3 API Gravity @ 15° C. ASTM D4052 — — 35.2 Deg. API Viscosity - Kinematic @ 40° C. ASTM D445 1.9 4.1 2.63 mm2/s Ash ASTM D482 — 0.010 <0.001 Mass % Copper Corrosion @ 50° C. ASTM D130 — 3 1 A 3 hr Cetane Index ASTM D976 40 — 45 Lubricity by HFRR @ 60.sup.eC ASTM D6079 — 520 330 um Distillation 90% Recovered ASTM D86 282 338 326.6° C. Conductivity ASTM D2624 25 — >2000 pSm Cold Filter Plugging Pt. ASTM D6371 — — −28° C. Pour Point ASTM D97 — — −18° C. Cloud Point ASTM D2500 — — −0.5° C. Sediment and Water (free water) ASTM D2709 — 0.05 0.00% Vol Aromaticity by FIA ASTM D1319 — 35 11.3% Vol

(19) Any fossil fuel, including gasoline, can be emulsified, although diesel fuel works best. Emulsification of water in hydrocarbon-based and other fuels, such as hydrosols, creates micelles. Cavitation processes at high pressure and relatively constant temperature will produce appropriately small fuel micelles for use in fuels and additives according to the invention. Cavitation processes will reduce the size of fuel micelles.

(20) It has been discovered that an inline high pressure multi-cavitation force emulsion process, not requiring recirculation of mixture provides enhanced submicron emulsification and low nano-emulsification, resulting in prolonged stability at various ambient conditions and also resulting in increased fuel efficiency (work output enhancements) and fuel economy while also significantly reducing the level of multiple emissions constituents generated upon combustion of the fuels.

(21) As a nonlimiting example, Table 6 shows test results for the enhanced submicron emulsified technique with ASTM D-975 Ultra Low Sulphur Diesel Fuel in an inline high pressure multi-cavitation force emulsification process not requiring recirculation of mixture, according to the invention that has been tested under relevant standard test methods. Enhanced submicron emulsification using ultra-filtered soft water substantially improved test results over that of fuels that had been emulsified without the use of soft, ultra-filtered (filtered to submicron level) water and/or non-enhanced submicron emulsification.

(22) Likewise, engines using fuels or additive packages prepared with emulsifications of ultra-filtered, soft water according to the present invention had substantially reduced emissions of CO.sub.2, NO.sub.X, SO.sub.X, Particulate Matter PM2.5, and PM10.