KR20060054204A - Novel hydrocarbon fuel additives and fuel formulations exhibiting improved combustion properties - Google Patents

Abstract

Fuel additives, fuel formulations, and processes for their preparation and use are provided. The additives improve the combustion properties of hydrocarbon fuels. The enhanced combustion indicates reductions in certain emissions.

Description

NOVEL HYDROCARBON FUEL ADDITIVES AND FUEL FORMULATIONS EXHIBITING IMPROVED COMBUSTION PROPERTIES}

The present invention relates to novel and useful additives, fuel formulations, preparation methods and uses for hydrocarbon based fuels. More specifically, the present invention relates to compounds, materials and methods for improving the combustion characteristics of fuels in order to reduce undesirable pollutant emissions produced during combustion.

The present invention generally relates to compositions and methods for improving combustion and reducing pollutant emissions in fuels.

Interest in improving fuel efficiency has become important as our natural resources shrink and fuel costs rise. Fuel efficiency and improved emission characteristics can be improved by adding fuel additives to hydrocarbon fuels. Some existing fuel additives are known to increase fuel efficiency, for example US Pat. Nos. 4,274,835, 5,826,369 and 6,193,766 disclose fuel additives that improve combustion. Despite the success of these inventions, there is still a need for fuel additives that improve combustion.

When hydrocarbon-based fuels are burned, various contaminants are produced. These combustion products include particulates, carbon monoxide, nitrogen dioxide, sulfur dioxide, and lead (combustible fuels are still used). Ozone is also a contaminant from unburned hydrocarbons (but not directly). The US Department of Environment (EPA) and the California Air Resource Board (CARB) have adopted air quality standards for these pollutants. Both also adopted specifications for low-emission gasoline and diesel fuels.

For these legislative efforts, producers of hydrocarbon fuels, such as gasoline, diesel, jet, and the like, have attempted to re-regulate refinery processes to produce base fuels that meet these more stringent specifications. Such an approach involves many disadvantages, including the high costs involved in rearranging the purification method, reduced production of refineries, and the like. Therefore, fuels free of these and other related economic disadvantages are highly desirable.

Hydrocarbon fuels generally contain a mixture of complex hydrocarbons, depending on the particular application, including but not limited to gasoline, diesel, jet, fuel oil, coal fuel, residual oil fuel, kerosene, and the like. Fuels generally may also contain surfactants, antifreezes, emulsifiers, corrosion inhibitors, dyes, precipitation modifiers, ignition modifiers and other additives including non-hydrocarbons such as oxygenates to improve fuel emission characteristics. have.

It would be desirable to find compounds that have a positive effect on reducing the emission characteristics of burned hydrocarbon fuels. Improvements in combustion (such as in jet, diesel or gasoline engines) and emission characteristics may be relevant for some fuel combustion test procedures. Smoke points of some fuels, including additives, can be tested using standard methods for smoke point of ASTM Test D 1322-90 aviation turbine fuels. This test procedure is included in this specification by reference. Specifically, A, 1, JP-4 or JP-8 (hereafter referred to as "jet"), which represents a smoke-free flame of a reproducible height when burned in the wick-feed lamp of the ASTM test using the test of smoke point and The same can be used to show the effect of additives on standard jet engine fuels. This test qualitatively relates to the potential radiant heat transfer from the combustion products of the fuel. Improving fuel properties, completing combustion, and the additives included in the fuel show higher smoke points. This effect may be synergistic and may not be expected for some additives previously unknown as additives to hydrocarbon fuels for this purpose. If an improvement in the smoke point is found, this correlates positively with the reduction of pollutant emissions to the environment. Since emission reductions are desirable, there is a continuing need for HC fuels containing novel useful additives to achieve this. Accordingly, the present invention addresses the problem of contaminant emissions from various internal combustion devices, for example automotive engines, diesel engines (so-called piston engines), coal combustion plants, aero-engines, jet engines, two-stroke cycle engines, and the like. By providing a solution, the aforementioned limitations in the field of hydrocarbon fuel formulations are overcome.

Summary of the Invention

The present invention relates to additives for hydrocarbon fuels which, when added in small amounts, improve combustion and reduce emissions. Hydrocarbon fuels can be considered to include, but are not limited to, gasoline, diesel, oil fuels, coal, and the like, which, when combined in the presence of oxygen and ignition sources, provide for the production of radiant heat. These fuels are useful in cars, motorcycles, trucks, generators, and power plants.

The present invention includes fuel additives for hydrocarbon fuels that include molecules having a system of from 2 to about 11 (or more) conjugated carbon-carbon double bonds. For the purposes of the present invention, the term "conjugated" includes aromatic species, for example biphenyl in preferred embodiments. Conjugated groups may further comprise one or more end groups comprising cyclic linear or branched C ₅ -C ₈ saturated, unsaturated or aromatic moieties. If the additive comprises two or more aromatic moieties, a single double carbon bond between them is optional. The additive may further be substituted with an oxygen containing group such as hydroxyl or keto group. Other substituents include branched or linear, one or more C ₁ -C ₆ containing groups, end group moieties, or a combination of the two which may be substituted in a system of conjugated carbon-carbon double bond containing groups. The fuel additive may be a molecule consisting of at least 12 carbon atoms and up to about 40 to 50 carbon atoms.

Fuel additives according to the above may comprise a mixture of cis and trans beta-carotene. These compounds may be derived from natural and / or synthetic sources. In the case of mixtures of cis and trans beta-carotene they may be in the form of precursors from the process for producing pure trans beta-carotene. The fuel additive may be an astaxanthin or astaxanthin derivative obtained from a synthetic or natural source. In addition, the additive may comprise a mixture of cis and trans beta-carotene and astaxanthin and / or astaxanthin derivatives obtained from synthetic or natural sources. Preferred aromatic group containing compounds are, for example, cis- stilbene, trans-stilbene, 1,6 diphenyl-1,3,5-hexatriene, 1,4-diphenyl-1,3-butadiene, 1 , 4-diphenyl-2-methyl-1,3-butadiene, 1,4-diphenyl butadiene, a mixture with or without bibenzyl and carotene, astaxanthin or lutein derived compounds.

In other embodiments, the fuel additive may further include solubilizers such as surfactants having a hydrophobic-lipophilic balance to increase the solubility of the fuel additive in hydrocarbon fuels. Particularly useful solubilizers are those comprising an ethoxylated or propoxylated moiety having from about 6 to about 25 or 30 ethoxylated or propoxylated moieties derived from ethylene oxide and / or propylene oxide units. For example, there is an ethoxylated macadamia nut oil having an ethoxylation of about 12-16.

It has been found that oxygen can reduce the effect of the additive when an additive with conjugated groups is used. Thus, in some additives it may be important to exclude oxygen from the start of the manufacturing process of the fuel additive during manufacture and from addition to the fuel. In addition, in other embodiments of the invention, antioxidants such as quinoline compounds or derivatives or equivalents may be included. In another embodiment, a method of preparing a fuel composition comprising one or more additives of the present invention is provided, the method comprising obtaining a fuel additive prepared or synthesized in a low oxygen or oxygen free environment; Removing a substantial portion of dissolved oxygen from the fuel solvent or diluent; Mixing the solvent or diluent with a fuel additive under reduced oxygen prior to addition to the fuel to produce an added solution and adding it to the fuel.

In another embodiment of the present invention, a phytic acid (inositol hexaphosphoric acid) based fuel additive is provided. The phytic acid may be an aqueous solution, salt or mixture. Effective amounts of antioxidants such as surfactants such as macadamia nut oil based surfactants and quinoline compounds may be added to increase oxidation resistance.

The foregoing has outlined rather broadly the features and technical advantages of the present invention in order that the detailed description of the invention that follows may be better understood. Further features and effects of the present invention will be described below. It will be understood by those skilled in the art that the disclosed concepts and specific embodiments may be readily utilized as a basis for designing modifications or other structures for carrying out the same purposes of the present invention. It should also be appreciated by those skilled in the art that such equivalent constructions do not depart from the spirit and scope of the invention disclosed herein. With regard to its organization and method of operation, the novel features believed to be characteristic of the invention will be better understood from the following description when considered in conjunction with the accompanying drawings, with further objects and effects. However, it is clearly understood that each figure is provided for the purpose of illustration and description only and is not intended to define the limits of the invention.

Brief description of the drawings

1 illustrates a smoke point apparatus used herein to obtain a smoke point.

2 illustrates an experimenter using a head rest and a smoke point apparatus.

Detailed description of the invention

The following description and examples illustrate some embodiments of the invention and include preferred embodiments for each of the various types of fuel additives, formulations, and methods. It will be appreciated by those skilled in the art that variations and modifications of the disclosed invention are possible and therefore that disclosure of the embodiments should not be seen as limiting the scope of the invention.

Without being bound by any particular theory regarding the mode of operation of the presently disclosed fuel additives, additives that improve the combustion properties of hydrocarbon-based fuels and thus the emission properties of burned fuels are molecules with structural parameters that have not been recognized as particularly useful until now. It is thought to be improved by including some groups of the structure. In particular, it is believed that extended pi-bond systems, molecules comprising multiple hydrocarbon rings, provide improved combustion properties. Such molecules with the aforementioned properties often show improved combustion properties when formulated in hydrocarbon fuels when added in the ppm to ppt range. It is also contemplated to use solubilizers such as surfactants (eg, PET-type surfactants) that may include oxygen atoms in their structure in combination with the foregoing, further improving combustion efficiency.

In view of the foregoing, it is contemplated that molecules having an expanded pie or double bonded structure of about 2 to 11 or more conjugated double bonds thereof will improve combustion characteristics and lower pollution when properly included in fuels such as jets or diesel. The moiety comprising the double bond structure may be terminated by one or more end groups comprising an aromatic, cyclic branched C ₅ -C ₈ moiety which may be further saturated or unsaturated. Examples include cyclo-pentane, cyclo-pentene, cyclo-hexane, cyclo-hexene, cyclo-heptane, cyclo-heptene, isopentane or isopentene and the like. Aromatic structures are also considered extended pi structures. Unsaturated / aromatic moieties and terminal groups may further include various other substituents such as hydroxyl groups, keto groups, alkyl groups, alkenyl groups and combinations of these groups. In addition, the additive molecule may comprise 12 to about 40 or 50 carbon atoms. Such molecules are found in mixtures of synthetic carotenoid precursors. One such mixture is a product called "iso-mixten" which is an intermediate used in the formulation of synthetic trans beta carotene. Iso-Mixten is a product of DSM Chemical (Texas) (formerly Roche Vitamin, Inc.) and is a mixture of about 89 to about 98% trans β carotene and about 1.4 to 11% cis β carotene isomer. . These can be obtained from natural or synthetic sources. Carotenoids and / or carotenoid precursors may also be those disclosed in German Patent No. 954,247, issued in 1956.

In another embodiment of the invention, the compounds in the above description are astaxanthin or astaxanthin derivatives obtained from synthetic or natural sources, or lutein or lutein derivatives obtained from synthetic or natural sources. Other embodiments include derivatives having cis and trans stilbenes, bibenzyl or hydroxyl groups, or molecules having two aromatic end groups such as alkyl or alkenyl groups substituted on the phenyl ring; Or substituted or unsubstituted 1,6 diphenyl-1,3,5-hexatriene as described above. In a preferred embodiment, the additive may be added to the fuel at a concentration of at least 1 ppm or more to provide improved combustion and reduced contamination.

One embodiment of the present invention involves adding a solubilizer, such as a surfactant with a hydrophobic-lipophilic balance, to increase the solubility of the fuel additive in HC. If higher molecular weight additives contemplated by the present invention are included to improve combustion properties, there may be solubility limits that can be overcome upon addition of solubilizers such as surfactants or surfactant systems. These solubilizers may further comprise ethoxylated or propoxylated moieties, such as polyethylene- or polypropylene glycol modified oils, which may synergistically improve the combustion of the fuel when included with oxygen-containing species such as additives. Can be. These materials can be used in amounts sufficient to provide the desired degree of solubilization as can be determined by one skilled in the art. Generally they can be added in amounts up to 10 to 100 times the excess of the present additive molecules.

Another aspect of the invention relates to a method for preparing additives and fuels in the absence of oxygen and optionally in the presence of antioxidants. Some compounds can act as both antioxidants and heat stabilizers. Thus, it is possible to prepare formulations containing a single compound that provide both thermal stabilizing and antioxidant effects. Examples of compounds known in the art to provide some degree of oxidation resistance and / or thermal stability include substituted or unsubstituted diphenylamines, dinaphthylamines, and phenylnaphthylamines, for example N , N'-diphenylphenylenediamine, p-octyldiphenylamine, p, p-dioctyldiphenylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, N- (p -Dodecyl) phenyl-2-naphthylamine, di-1-naphthylamine, and di-2-naphthylamine; Phenothiazines such as N-alkylphenothiazines; Imino (bisbenzyl); And 6- (t-butyl) phenol, 2,6-di- (t-butyl) phenol, 4-methyl-2,6-di- (t-butyl) phenol, 4,4'-methylenebis (-2 Hindered phenols such as, 6-di- (t-butyl) phenol) and the like. In a preferred embodiment, there are compounds such as quinoline and especially 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline ("EDTMQ") or other equivalent agent. Various compounds known for use as oxidation inhibitors can be used in fuel formulations of various embodiments. These include phenolic antioxidants, amine antioxidants, sulfurized phenolic compounds, and organic phosphites. For best results, antioxidants are mainly or wholly (1) 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert- Butylphenol, 4,4'-methylenebis (2,6-di-tert-butylphenol), and mixed methylene crosslinked polyalkyl phenols, or (2) cycloalkyl-di-lower alkyl amines, and phenylenediamine Aromatic amine antioxidants such as or combinations of such phenolic antioxidants with one or more such amine antioxidants. Especially preferred are combinations of tertiary butyl phenols such as 2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol and o-tert-butylphenol. N, N'-di-lower-alkyl phenylenediamines, such as N, N'-di-sec-butyl-p-phenylenediamine, and analogs thereof and combinations of such phenylenediamines with such tertiary butyl phenols useful.

In addition, fuel manufacturing methods capable of removing a substantial portion of oxygen from an additive or solvent or diluent that will contain the additive include pumping under partial vacuum or sonication under an inert atmosphere and are preferred prior to addition to the fuel. Particular preference is given to combinations of materials and process steps.

These materials can usually be added in amounts of 1 to 100 ml per gallon of solvent or diluents such as toluene, cyclohexene, xylene and the like. In one preferred embodiment, the additive concentration is added in ppm amount, in an amount from about 1 to about 1000 ppm. For example, the ppm amount can be gradually increased in steps of 1, 3, 5, 7, 9 ppm and the like. The diluted range in the solvent or diluent may be 500 to 10,000 ppm of the base additive. In another preferred embodiment the additive is added in about 500 ppm increments, for example in amounts of about 1000, 1500, 2000, 2500 to about 10,000 ppm. In another preferred embodiment, the additive is added in an amount of about 1000 to 1100 ppm, 2000 to 2200 ppm, 3000 to about 3500 ppm and 4000 to about 4500 ppm. In another preferred embodiment the additive is added in an amount of about 1057 ppm, 2114 ppm, and 4227 ppm.

In the case of diesel fuel compositions, it may contain cetane improvers or ignition accelerators. Ignition accelerators are preferably organic nitrates different from the nitrates or nitrate sources described above and are used in addition to those described above. Preferred organic nitrates are substituted or unsubstituted alkyl or cycloalkyl nitrates having up to about 10 carbon atoms, preferably 2 to 10 carbon atoms. Alkyl groups may be linear or branched. Specific examples of nitrate compounds suitable for use in the preferred embodiments include, but are not limited to: methyl nitrate, ethyl nitrate, n-propyl nitrate, isopropyl nitrate, allylnitrate, n-butyl Nitrate, isobutyl nitrate, sec-butyl nitrate, tert-butyl nitrate, n-amyl nitrate, isoamyl nitrate, 2-amyl nitrate, 3-amyl nitrate, tert-amyl nitrate, n -Hexyl nitrate, 2-ethylhexyl nitrate, n-heptyl nitrate, sec-heptyl nitrate, n-octyl nitrate, sec-octyl nitrate, n-nonyl nitrate, n-decyl nitrate, n- Dodecyl nitrate, cyclopentylnitrate, cyclohexyl nitrate, methylcyclohexyl nitrate, isopropylcyclohexyl nitrate, and 1-methoxypropyl-2-nitrate, 1-ethoxypropyl Esters of alkoxy substituted aliphatic alcohols such as -2 nitrate, 1-isopropoxy-butyl nitrate, 1-ethoxylbutyl nitrate and the like. Preferred alkyl nitrates are ethyl nitrate, propyl nitrate, amyl nitrate, and hexyl nitrate. Another preferred alkyl nitrate is a mixture of primary amyl nitrate or primary hexyl nitrate. Primary means that the nitrate functional group is attached to a carbon atom attached to two hydrogen atoms. Examples of primary hexyl nitrates include n-hexyl nitrate, 2-ethylhexyl nitrate, 4-methyl-n-pentyl nitrate and the like. The preparation of nitrate esters can be accomplished by any of the commonly used methods such as, for example, esterification of suitable alcohols, or reaction of a suitable alkyl halide with silver nitrate. These additives may be present in the same or different amounts as the present additives and in preferred embodiments particularly preferred cetane improvers are added in an amount equal to or several times the ppm amount of the additive.

Embodiments based on phytic acid are also contemplated. In one embodiment, a fuel additive is provided comprising ethoxylated nut oils such as phytic acid, (inositol hexaphosphoric acid), and ethoxylated macadamia nut oil. In a particularly preferred embodiment, an effective amount of EDTMQ can be used to provide improved oxidation resistance. The phytic acid may be a disodium salt commercially available from Aldrich Chemical, mixed in 450 ml of toluene at a concentration of about 1 to about 5, preferably about 1.5 to about 3 g. About 40 to about 60, preferably about 50 ml of ethoxylated macadamia nut oil-an ethoxylated moiety with an average of 16 ethylene glycol repeat units can be added to this solution. An antioxidant such as EDTMQ may be added to this solution in an amount of about 0.5 to about 3 or more, preferably about 1.0 ml. In a particularly preferred embodiment, the additive is added to 50 ml of jet A fuel and burned in an ASTM smoke point apparatus. The formulations exhibited ASTM smoke points of 22.0 to 22.5.

In another embodiment of the present invention, a fuel additive and a method of making a fuel include adding the additive directly to the fuel; Mixing, dissolving, or blending additives in a diluent or solvent and the resulting solution finally comprises dilution in fuel and variations thereof are disclosed. Particularly preferred methods of preparing fuel compositions include obtaining fuel additives prepared in a low oxygen or oxygen free environment; Removing a substantial portion of dissolved oxygen from the fuel solvent or diluent; Mixing the solvent or diluent with the fuel additive under reduced oxygen conditions prior to fuel addition to produce the added solution and adding the fuel.

In other embodiments, methods of using the fuels and additives of the present invention include, but are not limited to, adding additives directly to the fuel and burning the fuel in an internal combustion engine, gas turbine, or other such apparatus. In addition, methods of using additives include preparing intermediate solutions of additives, mixing them into fuel at an effective ratio and combusting the additive-enhanced fuel in a suitable apparatus.

Formulated fuel compositions of preferred embodiments may contain additives other than those disclosed. These additives include, but are not limited to, one or more octane improvers, surfactants, antioxidants, demulsifiers, corrosion inhibitors and / or metal deactivators, diluents, cold flow improvers, heat stabilizers, and the like.

To test the radiant heat transfer capability of a fuel additive, the fume point lamp disclosed in ASTM D 1322-90 is used: The disclosure of this test method is incorporated herein by reference. The apparatus comprises a housing defining a base, a candle socket mounted on the base, a candle socket mounted on the base, a housing defining a so-called "gallery" guided on a candle on the base, a wick burner parallel to the wick burner in the housing. It consists of a transparent quartz window that is a cover for the housing attached to the scale portion for viewing, a chimney for driving the burned product out of the top of the gallery and an ASTM wick through which the flame can be seen. This device is shown in FIG. 1 in the test procedure bultin.

To improve the accuracy of the basic smoke point combustion test, the lamp is mounted on a large, rigid test base with an adjustable stand to position the head of the tester in a manner to reduce reading errors on the scale in the smoke point device. The stand is mounted perpendicular to the lamp and mounted in such a way that the eyes of the investigator observing the flame test are in a constant position with respect to the distance from the flame and constant with respect to the height of the smoke point lamp housing. In summary, this improvement in the test apparatus and method allows the tester to place the head in position relative to the flame in the housing. Thus, more consistent and accurate data is obtained for the smoke point.

The test prepares a fuel sample, adds fuel to the lamp, burns the fuel through a known smoke point composition, in this case a wick feed ramp calibrated for so-called standard jet A or 1, and obtains it as a test fuel without smoke. It consists of observing on the scale the exact height of a spark that can be set. The flame height is estimated to be the nearest millimeter. All values in the following examples are estimated to be the closest 0.5 mm and this considerable number is made possible using the experimenter's headrest shown in FIGS. 1 and 2.

When used as disclosed, this test is also a measure of combustion efficiency and pollution reduction when using standard methods for testing jet fuel, as will be appreciated by those skilled in the art. The test indicates that if the base scale millimeter reading is lower than the additive-treated fuel observed in the mm reading, the fuel additive is useful for reducing the different pollutant emissions produced during the combustion of the hydrocarbon fuel.

Example  One

DSM Chemical, which is an intermediate in the synthesis of pure trans-beta-carotene and is a mixture of isomeric forms of 89-98% trans beta carotene with 1.4 to 11% cis beta carotene (the mixture is synthesized and packaged in an inert environment before use) A fuel additive of so-called "iso-mixten", formerly manufactured by Roche (formerly Roche Vitamin, Inc.), is prepared with sufficient 6-ethoxy-1,2-dihydro-2 to reduce the oxidative effect of dissolved oxygen in the fuel. , 2,4-trimethylquinoline, EDTMQ, was added at 1.0 ml per gallon and mixed in a standard jet fuel aliquot and burned in the smoke point test apparatus described above. This fuel additive showed an ASTM smoke point reading of 22.5 mm when formulated in standard jet A or 1 fuel. In contrast, the jet used as a reference point for the smoke point generally exhibited a smoke point of 19.0. The jet fuel used meets the established standards of Seybolt Laboratories of Carlson California.

Example  2

Astaxanthin from Mera Pharmaceuticals, 3,3'-dihydroxy-4,4 'diketo-beta-carotene is mixed at a concentration of about 1.5 g per gallon of toluene and the solution is then poured into a 50 ml standard jet. Mix at a concentration of 0.25 ml. A combustion point of 21.0 was observed when burned in the ASTM smoke apparatus and was an improvement over Jet A.

Example  3

Example 2 was repeated with astaxanthin but this compound was added at 3 g per gallon of toluene and the solution was then mixed with 50 ml of Jet A fuel at 0.25 ml. This fuel, and the additive, showed an ASTM smoke point reading of 22.0, which is an improvement over standard jet A. The results demonstrate positive concentration dependence of combustion improvement and emission reduction with increasing astaxanthin concentration.

Example  4

Myo-inositol hexakis (dihydrogen phosphate) as isodium salt, phytic acid, commercially available from Aldrich Chemical, was mixed with 450 ml of toluene at a concentration of 1.5 g. To this solution was added 50 ml of ethoxylated macadamia nut oil-an ethoxylated moiety with an average of 16 ethylene glycol repeat units. 1.0 ml of EDTMQ was mixed into this solution. 0.4 ml of this additive was added to 50 ml of Jet A fuel and burned in an ASTM apparatus. The formulations exhibited ASTM smoke points between 22.0 and 22.5.

Example  5

Cis-Stilbene, 96% pure and commercially available from Aldrich Chemical, was mixed in 50 ml of Jet A fuel at a concentration of 0.25 ml and burned in an ASTM smoke point apparatus. A value of 21.0 was obtained. In contrast, jet A represents a reference value of 19.0.

Example  6

Bibenzyl, 99% pure and commercially available from Aldrich Chemical, was mixed in 500 ml of toluene in an amount of 8 g of bibenzyl. 1.0 ml of EDTMQ was added to complete the test fuel. Eight drops of 0.4 ml were added to 50 ml of Jet A and tested for smoke point. This fuel had an ASTM smoke point of 22.0.

Example  7

Control samples of toluene and jet A fuel were prepared using 0.5 ml toluene in 50 ml jet fuel. A smoke point of 19.0 was observed.

Example  8

A control sample of EDTMQ was prepared by mixing 5.0 ml of EDTMQ with 500 ml of toluene and 0.25 ml of this solution was mixed with 50 ml of Jet A fuel and the smoke point was tested. A value of 19.0 was obtained.

Example  9

1,6 diphenyl-1,3,5-hexatriene is added in 3 g to 3785 ml toluene with 1 ml EDTMQ. This additive solution is tested at 0.25 ml in 50 ml of jet fuel. Smoke point readings ranging from 20.0 to 21.0 are observed.

Example  10

The fuel additive based on Example 1 is 2170 ppm of the first solution containing 500 ml of toluene, 12 drops of EDTMQ (Santoquin ^TM ), 1.12 g of isomicsten and 2-ethyl hexyl nitrate (cetan improver) 3170 per gallon Prepared by mixing ppm. The base diesel fuel is an EPA-certified diesel fuel with 19.1% total aromatics, 48.7 cetane (by ASTM D-613), a distillation endpoint of 662.4 (ASTM D-86), and 62 ppm sulfur (ASTM D-5453) and 65/35 blend of a second diesel fuel with 30.2% total aromatics, 46.2 cetane (according to ASTM D-613), distillation endpoint 666.1 (ASTM D-86), and 416 ppm sulfur (ASTM D-5453). Basic and added fuels were tested for emissions (NO _x , hydrocarbons, particulate matter and carbon monoxide) using a 1992 Detroit Diesel Series 60, 350 HP turbocharged engine, and the test protocol was based at West Virginia University in Morgantown, West Virginia. Designed to verify fuel for diesel fuel certification in Texas. The burnt, added fuel showed a 4.5% reduction in total NO _x , 8.1% reduction in hydrocarbon content, 4.1% increase in particulate matter, and 12.4% reduction in carbon monoxide over the same diesel fuel mixture under the same conditions.

Claims (39)

A fuel additive for a hydrocarbon fuel comprising an additive molecule having a conjugated system of carbon-carbon double bonds having 2 to 11 double bonds. The fuel additive of claim 1, further comprising at least one end group comprising a cyclic C ₅ -C ₈ aromatic, cycloaliphatic, saturated or unsaturated moiety. The fuel additive of claim 2, further comprising at least one oxygen containing group substituted on at least one cyclic end group. 4. The fuel additive of claim 3, wherein the oxygen containing group is selected from the group consisting of hydroxyl groups or keto containing groups bound on a cyclic aliphatic saturated or unsaturated moiety. 4. The fuel additive of claim 3, further comprising at least one methyl group bonded on a conjugated carbon-carbon double bond containing group, a cyclic end group, or a combination thereof. The fuel additive of claim 3, wherein the molecule comprises at least about 12 to about 50 carbon atoms. The fuel additive of claim 1 comprising a carotenoid, a mixture of carotenoids and / or a carotenoid precursor. The fuel additive of claim 1, wherein the additive is a mixture of crude synthetic cis and trans beta-carotene isomers. The fuel additive of claim 8 wherein the mixture contains a mixture of about 89% to about 98% trans beta-carotene isomer and about 1.4% to about 11% cis beta-carotene isomer. The fuel additive of claim 1, wherein the additive comprises astaxanthin obtained from a synthetic or natural source. The fuel additive of claim 1, wherein the additive comprises a mixture of trans beta-carotene isomers, cis beta-carotene isomers, and astaxanthin. The fuel additive of claim 1, further comprising a solubilizer with a hydrophilic-lipophilic balance that increases the solubility of the fuel additive in the hydrocarbon fuel. The solubilizer according to claim 12 further comprising an ethoxylated or propoxylated group containing moiety. The solubilizer according to claim 13 wherein the portion comprises macadamia nut oil. The solubilizer according to claim 13 wherein the number of ethoxylated or propoxylated is from about 6 to about 25. The solubilizer according to claim 15 wherein the number of ethoxylated or propoxylated is from about 8 to about 16. The fuel additive of claim 1 further comprising an antioxidant. 18. The fuel additive of claim 17 wherein the antioxidant is 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline ("EDTMQ") or a derivative thereof. 9. The fuel additive of claim 8 further comprising a cetane improver containing nitrate groups. The fuel additive of claim 19 wherein the cetane improver is 2-ethyl, hexyl nitrate. The fuel additive of claim 9 when formulated into standard jet fuel with a 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline antioxidant, exhibiting an ASTM smoke point reading of about 22.5. . The method of claim 1, comprising astaxanthin fuel additive in the solvent at a concentration of about 0.5 g to about 4 g per gallon exhibiting an ASTM smoke point of about 21.0 when mixed with 50 ml of standard jet fuel at about 0.25 ml. Fuel additives. The fuel additive of claim 22 wherein the 3 g astaxanthin-based compound additive per gallon exhibits an ASTM smoke point reading of 22.0. Hydrocarbon fuel additive comprising phytic acid. The additive of claim 24 wherein the phytic acid is in the form of an aqueous solution, salt or mixture thereof. The fuel additive of claim 25 further comprising a surfactant. The fuel additive of claim 26 further comprising an ethoxylated surfactant. 27. The phytic acid fuel additive of claim 26 wherein the surfactant is a polyethylene glycol derivative of macadamia nut oil, wherein the ethoxylation degree is on average 6-20. 29. The fuel additive of claim 28 wherein the degree of ethoxylation is from 8 to 16. The fuel additive of claim 24 further comprising an antioxidant. 31. The fuel additive of claim 30 wherein the antioxidant compound is 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline. A fuel additive comprising an aromatic compound having two or more aromatic rings. 33. The fuel additive of claim 32, wherein the aromatic compound is selected from the group of cis- stilbene, trans-stilbene, and bibenzyl or mixtures thereof. 34. The fuel additive of claim 33, wherein the aromatic compound is mixed into 50 ml of jet fuel at a concentration of 0.25 ml, resulting in an ASTM smoke point of 21.0. 34. The fuel additive of claim 33 comprising 8 g of benzyl mixed in 500 ml of toluene and 1.0 ml of EDTMQ exhibiting an ASTM smoke point of 22.0 when mixed at about 0.4 ml in 50 ml of jet fuel. . 33. The compound of claim 32, wherein 1,6 diphenyl-1,3,5-hexatriene, 1,4-diphenyl-1,3-butadiene, 1,4-diphenyl-2-methyl-1,3- A fuel additive comprising butadiene, and 1,4-diphenyl butadiene or mixtures thereof. 37. The fuel additive of claim 36 comprising 3 g of 1,6 diphenyl-1,3,5-hexatriene and 1.0 ml of EDTMQ in 3785 ml of toluene. 1 to 5 ppm / gallon of a first mixture containing, as a diesel fuel, a mixture of about 89% to about 98% of all trans beta-carotene isomers and about 1.4% to about 11% cis beta-carotene isomers, and 2- When added to 3170 ppm / gallon of ethyl hexyl nitrate and burned in a diesel engine, 4.5% reduction in total NO _x , 8.1% reduction in hydrocarbon content and 4.1% increase in particulate matter compared to combusted diesel fuel without additives And diesel fuel showing a 12.4% reduction in carbon monoxide. As a method for producing a fuel additive, Obtaining an additive prepared under substantially an oxygen free environment; Blending the fuel additive into the substantially oxygen free diluent or solvent in a reduced oxygen atmosphere; And Adding to fuel Method of producing a fuel additive comprising a.

Images