Non-petroleum sourced aviation fuel blends including blending components directly sourced from turpentine having enhanced seal swell, reduced sooting, and enhanced density

Abstract

Materials and methods for forming a non-petroleum sourced aviation fuel blend are described. A non-petroleum sourced base fuel is combined with aromatic and / or cyclic molecules sourced from turpentine as a blending component that provides a non-petroleum sourced aviation fuel blend meeting applicable standards for an aviation fuel. The aromatic and cyclic molecules sourced from turpentine may be directly sourced from the turpentine, through distillation, fractionation, vapor recovery, and the like from wood or wood products, or by hydrogen-alteration of molecules directly sourced from the turpentine. The aromatic and cyclic molecules sourced from the turpentine used in the blending component have from 6 to 14 carbon atoms, preferably 9 to 11 carbon atoms, and more preferably 10 carbon atoms.

Description

Non-Petroleum Sourced Aviation Fuel Blends Including Blending Components Directly Sourced from Turpentine Having Enhanced Seal Swell, Reduced Sooting, and Enhanced DensityREFERENCE TO RELATED APPLICATIONS

[0000] This application claims the benefit of U.S. Provisional Application No. 63 / 637,050 entitled “Non-Petroleum Sourced Aviation Fuel Blends Including Blending Components Directly Sourced from Turpentine Having Enhanced Seal Swell, Reduced Sooting, and Enhanced Density” filed April 22, 2024, which is incorporated by reference in its entirety.BACKGROUND

[0001] Presently, non-petroleum sourced aviation fuels have difficulty meeting the ASTM standards for general aviation fuel. For example, ASTM D7566 is the Standard Specification for Aviation Turbine Fuel Containing Synthesized Hydrocarbons and ASTM D 1655 is the standard for petroleum sourced aviation fuel. Conventional non-petroleum sourced base fuels include Hydroprocessed Esters and Fatty Acids Synthetic Paraffinic Kerosene (HEFA-SPK), Alcohol to Jet Synthetic Paraffinic Kerosene (ATJ- SPK), Fischer Tropsch Synthetic Paraffinic Kerosene (FT-SPK), Hydroprocessed Fermented Sugars to Synthetic Isoparaffins (HFS-SIP), Fischer Tropsch Synthetic Paraffinic Kerosene with Aromatics (FT-SPK / A), Catalytic Hydrothermolysis Synthesized Kerosene (CH-SK, or CH J), Hydroprocessed Hydrocarbons, Esters and Fatty Acids Synthetic Paraffinic Kerosene (HHC-SPK or HC-HEFA-SPK), Alcohol to Jet Synthetic Kerosene with Aromatics (ATJ-SKA), and the like. Conventional processes provide non-petroleum sourced base fuels via initial fermentation, gasification and / or hydroprocessing of sugars, starches, cellulosic feedstocks, fats, oils,CAPT_0002_WOand / or greases followed by additional hydroprocessing, hydroisomerization, dehydration, synthesis, and / or oligomerization steps.

[0002] Petroleum sourced aviation fuel (Jet-A, Jet-Al, JP8, and the like) contains many different aromatic molecules, including benzene, alkyl benzenes, toluene, xylene, indenes, and naphthalenes. These aromatic molecules have from approximately six to twelve carbon atoms and make up about 15% of the aviation fuel by volume - with the primary constituents being paraffins at 60% and cycloparaffins at 25%. A key benefit provided by these aromatic molecules in aviation fuels is that the aromatics cause swelling of the seals, such as gaskets, O-rings, and the like, of the jet engines, thus preventing or reducing the jet engines from leaking fuel and lubricants during operation.

[0003] Most conventional non-petroleum sourced base fuels lack a significant concentration of aromatic molecules when made (in some instances <0.5%), and hence cannot meet the applicable standards for aviation fuel at least because these fuels do not cause sufficient swelling of the elastomeric seals during use to prevent leakage of fuel and lubricants from the jet engine. Hence, having the appropriate type / s and concentration of aromatic molecules in jet fuel is critical, whether the fuel is petroleum or non-petroleum sourced.

[0004] To meet the applicable standards for aviation fuel, such non- petroleum sourced base fuels are combined with a blending component or “blendstock” to provide an acceptable fuel. The most used blending component is petroleum sourced aviation fuel. However, while the resulting blended fuel may meet the applicable standard for aviation fuel, only 50% or less of this blended fuel is non-petroleum sourced after sufficient petroleum sourced aviation fuel is added to meet the applicable standards for aviation fuel and provide sufficient seal swell.CAPT_0002_WO

[0005] To eliminate the need to blend the non-petroleum sourced base fuel with petroleum sourced aviation fuel to meet applicable standards, nonpetroleum sourced aromatic molecules could be added to the non-petroleum sourced base fuel as the blending component. This is because a primary deficiency in the non-petroleum sourced base fuels regarding meeting the applicable standards is an insufficient aromatic component. However, considerations other than seal swell performance also exist, including the amount of soot produced by the fuel after combustion in the jet engine and the density of the fuel. Such non-petroleum sourced aromatics conventionally used include benzene, toluene, ethyl benzene, and xylene.

[0006] Such non-petroleum sourced aromatics do not occur naturally in nature in useful quantities, thus, are conventionally synthesized from other non-petroleum sourced compounds, and do not all provide aromatic molecules having 8 to 16 carbon atoms per molecule as desired for aviation fuels. Such non-petroleum sourced compounds include starches, alcohols, and sugars. Non-petroleum sourced fuel synthesis may also proceed through steps where the molecules having fewer or greater than the desired 8 to 16 carbon atoms, including molecules containing two or fewer carbon atoms, such as carbon oxides and ethanol, are converted to lower or higher carbon count molecules, respectfully. However, to undertake the conversion synthesis (whether decreasing or increasing the number of carbon atoms per molecule) of such non-petroleum sourced organic compounds into the desired non-petroleum sourced aromatics generally requires a dedicated production line costing in the hundreds of millions of dollars and relatively large amounts of energy to operate - thus making the resulting non- petroleum sourced aviation fuel impractical due to cost.

[0007] While aromatic molecules have a positive effect on seal swell, they often have the disadvantage of causing sooting resulting fromCAPT_0002_WOincomplete combustion when burned and the resultant undesired production of contrails. The production of soot, or “sooting” occurs when the fuel creates too much black particulate matter or “soot”, which is primarily carbon, as a combustion product of burning the fuel in the jet engine. Thus, while aromatics can have a desirable seal swelling effect, they can also lead to the need to clean the engines more often, undesirable particulate emissions, especially at high altitudes, and the resulting contrails.

[0008] Cyclic molecules have the advantage of potentially having a positive effect on seal swell without the sooting characteristics attributed to aromatics. Testing with various aromatics versus cyclic molecules has established that the more unsaturated, thus the more hydrogen-deficient the molecule, the greater the propensity for the molecule to generate soot when burned.

[0009] Three specific examples of non-aromatic cyclic molecules are alpha-pinene, beta-pinene, and delta-3-carene, with alpha-pinene and betapinene having the most economic value. Turpentine also may contain dipentenes, which are ten carbon atom molecules having a six-carbon ring and two double carbon-carbon bonds. Dipentenes and delta-3 -carene generally are of lower economic value than alpha- and beta- pinene.Terpenes are found in the sap of pine trees and are a primary component of the gaseous “wastes” in the process air exhausted from commercial wood drying processes and paper making.

[0010] As can be seen from the above description, there is an ongoing need for simple and efficient methods for producing backward, thus JetA, compatible non-petroleum sourced aviation fuel that includes the aromatic content, density, energy density, material compatibility, dielectric constant performance, lubricity, and like properties comparable to petroleum sourcedCAPT_0002_WOaviation fuels. The materials and methods of the present invention overcome at least one of the disadvantages associated with conventional non-petroleum sourced aviation fuels.SUMMARY

[0011] Fossil fuels used in aviation today pull carbon out of the earth and release it into the air which increases atmospheric carbon. Using nonpetroleum sourced fuels, sometimes referred to as Sustainable Aviation Fuels (SAF), has the potential to address this issue by lowering life-cycle carbon (CO2) emissions. SAF can be used today whereas other technologies such as electric and hydrogen remain decades away. According to some estimates, 100% SAF can reduce flight carbon emissions by up to 80% compared to petroleum sourced aviation fuel and in certain circumstances has the potential to be net carbon negative.

[0012] In one aspect, the invention provides a non-petroleum sourced aviation fuel blend, for meeting at least a subset of the applicable standards for aviation fuel, the fuel blend comprising a non-petroleum sourced base fuel; and a blending component comprising molecules sourced from turpentine and chosen from aromatic molecules and cyclic molecules, where the molecules sourced from the turpentine have from 6 to 14 carbon atoms, and where the fuel blend comprises from 8% to 60% of the blending component by volume.

[0013] Other systems, methods, features, and advantages of the invention will be, or will become, apparent to one with skill in the art upon examination of the following figures and detailed description. It is intended that all such additional systems, methods, features, and advantages be included within this description, be within the scope of the invention, and be protected by the claims that follow. The scope of the present invention isCAPT_0002_WOdefined solely by the appended claims and is not affected by the statements within this summary.BRIEF DESCRIPTION OF THE FIGURES

[0014] The invention can be better understood with reference to the following drawings and description. The components in the figures are not necessarily to scale and are not intended to accurately represent molecules or their interactions, emphasis instead being placed upon illustrating the principles of the invention.

[0015] FIG. 1 represents the combination of a non-petroleum sourced base fuel with a blending component including aromatic and / or cyclic molecules sourced from turpentine.

[0016] FIG. 2 represents a dipentene directly sourced from turpentine undergoing hydrogen-alteration to form aromatic para-cymene and the cycloalkane menthane, both having ten carbon atoms per molecule.

[0017] FIG. 3 represents the terpene pinene undergoing hydrogenalteration to form a cycloalkane, the terpane pinane, having ten carbon atoms per molecule.

[0018] FIG. 4 represents the molecular structures of aromatic molecules sourced from turpentine that are potentially useful in the blending component.

[0019] FIG. 5 represents the molecular structures of cyclics sourced from turpentine that are potentially useful in the blending component.

[0020] FIG. 6 represents volume percent ratios of aromatics and cyclics in relation to the non-petroleum sourced base fuel that when blended provide the non-petroleum sourced aviation fuel blend.CAPT_0002_WO

[0021] FIG. 7 provides smoke points for multiple aromatic and cyclic molecules sourced from turpentine that may be used in the blending component.

[0022] FIG. 8 provides smoke points for blends 1-4 prepared from the combination of a blending component with the non-petroleum sourced base fuel to produce the non-petroleum sourced aviation fuel blend.

[0023] FIG. 9 compares the seal swell performance by optical dilatometry after approximately 40 hours for nitrile rubber O-rings (N0602- 70) submerged at room temperature in blends 0, 1, or 2 as prepared from the combination of the blending component with the non-petroleum sourced base fuel to produce the non-petroleum sourced aviation fuel blend versus the non-petroleum sourced base fuel alone and petroleum sourced aviation fuels.

[0024] FIG. 10 establishes that the non-petroleum sourced aviation fuel blends 1, 2, and 3 prepared from the combination of a blending component and the non-petroleum sourced base fuel to produce the non- petroleum sourced aviation fuel blend meeting a subset of the applicable standards of ASTM D 1655.

[0025] FIG. 11 establishes that the non-petroleum sourced aviation fuel blend 1 , prepared from the combination of a blending component and the non-petroleum sourced base fuel, produces the non-petroleum sourced aviation fuel blend meeting the applicable standards of ASTM D 1655.CAPT_0002_WODETAILED DESCRIPTION

[0026] Materials and methods for forming a non-petroleum sourced aviation fuel blend are described. A non-petroleum sourced base fuel (NPSBF) is combined with aromatic and / or cyclic molecules sourced from turpentine as a blending component that provides a non-petroleum sourced aviation fuel blend (NPSAFB) meeting applicable standards for an aviation fuel. The aromatic and cyclic molecules sourced from turpentine may be directly sourced from the turpentine, through distillation, fractionation, vapor recovery, and the like from wood or wood products, or by hydrogenalteration of molecules directly sourced from the turpentine. The aromatic and cyclic molecules sourced from the turpentine used in the blending component have from 6 to 14 carbon atoms, preferably 9 to 11 carbon atoms, and more preferably 10 carbon atoms.

[0027] FIG. 1 represents the combination of a NPSBF 100 with a blending component 101 including aromatic and / or cyclic molecules sourced from turpentine. The presently preferred NPSBFs 100 are HEFA- SPK and ATJ-SPK, however, other NPSBFs may be used. The blending component 101 is not synthetically prepared from isoprene, starches, or sugars and is not produced from fermentation.

[0028] The resulting combination provides a NPSAFB 102 that preferably meets a subset of the applicable standards for a non-petroleum sourced aviation fuel, and more preferably meets the applicable standards for a non-petroleum sourced aviation fuel. The NPSAFB 102 includes from 8% to 60% of the blending component 101 by volume, preferably from 10% to 50%, and more preferably from 20% to 30% of the blending component 101 by volume. In another aspect, the NPSAFB 102 includes from 30% to 50% or from 8% to 20% of the blending component 101 by volume.CAPT_0002_WO

[0029] Any combination technique that is compatible with hydrocarbons may be used, including stirring, shaking, shear mixing, suspension mixing, agitation, and the like. Combination may occur in an open, sealed, or partially sealed vessel and may be equipped with heating or cooling coils to facilitate the combination in addition to a vapor recovery system. While not required, combination may occur under an inert atmosphere. Preferably, the combination technique provides a homogenous combination of the NPSBF 100 and the blending component 101.

[0030] FIG. 2 represents a dipentene directly sourced from turpentine undergoing hydrogen-alteration to form aromatic para-cymene and the cycloalkane menthane, both having ten carbon atoms per molecule. The terpene in this instance is limonene, but other terpenes directly sourced from turpentine may be used. Having ten carbon atoms as directly sourced from the turpentine, only hydrogen-alteration is used to produce a ten- carbon atom blending component.

[0031] FIG. 3 represents the terpene pinene directly sourced from turpentine undergoing hydrogen-alteration to form a cycloalkane. Both the pinene starting molecule and the hydrogen-altered pinane molecule have the most preferred ten carbon atoms per molecule.

[0032] As represented in FIG. 2 and FIG. 3 hydrogen-alteration may be hydrogenation, where hydrogen atoms are added to the starting molecule, or dehydrogenation, where hydrogen atoms are removed from the starting molecule. For example, regarding FIG. 2, the dipentene molecule is dehydrogenated to form the two aromatic para-cymene molecules and hydrogenated to form the cyclo-alkane menthane. Regarding FIG. 3, the pinene is hydrogenated to remove the unsaturation (lack of possible hydrogen atoms) to form the saturated pinane.CAPT_0002_WO

[0033] While either hydrogenation or dehydrogenation may be used to hydrogen-alter the molecules directly sourced from the turpentine, dehydrogenation is the preferred form of hydrogen-alteration, as it is through dehydrogenation that the preferred aromatic para-cymene is produced. A hydrogen-alteration is essentially dehydrogenation when no more than 10% by weight of the reaction products produced from the reaction are hydrogenated in relation to the starting material. As the molecules directly sourced from the turpentine have ten carbon atoms, neither condensation nor cracking are necessary to provide the desired ten carbon molecules.

[0034] The hydrogen-alteration process may be controlled to provide the desired ratio of aromatics to cyclics when being used to alter the molecules directly sourced from the turpentine. Preferably, the blending component 101 is at least 80% by weight ten carbon molecules, more preferably, the blending component 101 is at least 90% by weight ten carbon molecules, most preferably, the blending component 101 is at least 95% by weight ten carbon molecules. Preferably, the blending component 101 is at least 90% by volume, more preferably, at least 95% by volume cyclic and / or aromatic molecules.

[0035] While a palladium / silica heterogenous catalyst system as used in FIG. 2 or a palladium on carbon catalyst system as used in FIG. 3 may be used for hydrogen-alteration as represented in the figures, other reagents, reaction conditions, and heterogeneous catalyst systems may be used to affect the desired hydrogen-alteration that converts the molecules directly sourced from turpentine into aromatics, cycloalkanes, and / or mixtures thereof.

[0036] Useful catalyst systems for hydrogen-alteration include (1) oxide catalysts, such as y-Al2O3, TiO2, and SiO2; (2) moderate acidity catalysts,CAPT_0002_WOsuch as silica, alumina, silica-alumina mixed oxides, zeolites, natural clays, and active carbon as generally modified / promoted by metals such as Pd, Ag, Pt, Ni, Na, Fe, and Mn; (3) chromium and tin mixture on silica; and (4) silica supported palladium (as represented in FIG. 2) assisted by alpha-olefins, e.g. 1 -decene, as hydrogen acceptor, Zn(II)-Cr(III) mixed oxide as efficient bifunctional catalyst for dehydroisomerisation of a-pinene to para-cymene, and the like. Reaction temperatures may range from 100 to 400 degrees Celsius. Preferably, the catalyst system converts the directly turpentine sourced molecules into the aromatics, cyclics, and / or mixtures thereof at a 90% and greater conversion rate by weight, more preferably at a 95% and greater conversion rate.

[0037] FIG. 4 represents the molecular structures of aromatic molecules sourced from turpentine that may be useful in the blending component 101. The represented molecules are para-cymene, metacymene, ortho-cymene, benzene, ethylbenzene, xylene, and toluene. Formally, these molecules are also cyclic in addition to being aromatic - but it is the aromatic nature of the molecules that is most important for their use in the blending component 101. Para-cymene (p-cymene) is the most preferred at present turpentine sourced aromatic molecule for use in the blending component 101, in one aspect this preference is attributable to the relatively high yield of para-cymene that may be obtained from turpentine. Para-cymene preferably constitutes from 5% to 98% of the blending component 101 by volume, more preferably from 30% to 98% of the blending component 101 by volume.

[0038] FIG. 5 represents the molecular structures of cyclics sourced from turpentine that are potentially useful in the blending component 101. The represented molecules are delta-3-carene, alpha-pinene, menthane, beta-pinene, dipentene, pinane, and eucalyptol. These molecules are notCAPT_0002_WOaromatic and have either two degrees (limonene), one degree (delta-3-carene, alpha-pinene, and beta-pinene), or zero degrees (menthane, pinane, and eucalyptol) of unsaturation. Having zero degrees of unsaturation means that the molecule is saturated as there are no additional sites for hydrogen atoms to be added to the molecule.

[0039] Pinane and menthane are the preferred at present turpentine sourced cyclics for use in the blending component 101 as these molecules have zero degrees of unsaturation and are thus saturated - with pinane being the more preferred at present. Also preferred is delta-3-carene having only one degree of unsaturation and being of much lower economic value than alpha- or beta-pinene. The dipentene limonene is preferably hydrogen- altered to form para-cymene and menthane as opposed to being included in the blending component 101. The blending component 101 may comprise greater than 50% cyclic molecules by volume.

[0040] Gum turpentine, a form of turpentine, while not represented in FIG. 4 or in FIG. 5 as it is a combination of molecules, is also a preferred for use in the blending component 101, preferably with the higher value constituents, such as alpha-pinene and beta-pinene, substantially removed to reduce the cost of the blending component 101. While there is variance in the specific constituents of gum turpentine from different pine trees, generally gum turpentine is composed of mainly alpha- and beta-pinene with lesser amounts of carene, camphene, dipentene, and the like. When the constituents of gum turpentine are hydrogen altered to para-cymene the blending component 101 may include approximately 98% para-cymene, 1% menthane, and less than 1% dipentene by volume. Hence, including two of the preferred cyclic molecules, para-cymene and menthane, with paracymene being the significant primary constituent. The blending component 101 may comprise greater than 90% para-cymene by volume.CAPT_0002_WO

[0041] FIG. 6 represents volume percent ratios of aromatics and cyclics in relation to the NPSBF 100 that when blended provide the NPSAFB 102. NPSAFBs 0-4 and the fuel blends found within the trapezoid formed by the 5 fuel blends will all provide the desired NPSAFB 102 meeting at least a subset of the applicable standards for an aviation fuel. However, fuel blends 0, 1, and 2 and the fuel blends found within the triangle formed by these three fuel blends are preferred, with fuel blends 1 and 2 and the fuel blends on a “line” joining fuel blends 1 and 2 internal to the trapezoid being most preferred at present. The “line” between fuel blends 1 and 2 includes fuel blends 1 and 2 in addition to fuel blends having plus and minus approximately 40% by volume above and below a straight line drawn between the points representing fuel blends 1 and 2.

[0042] The volume percentages of the aromatic versus cyclic molecules in the fuel blends as represented in the figure are provided in Table I below.Table I

[0043] The aromatic used in this instance was para-cymene, however, additional or different aromatics as described above also may be used. The cyclics used in this instance were delta-3 -carene and the saturated cyclic pinane, however, additional, or different cyclics as described above also may be used. The blending component 101 may include greater than 90% by volume aromatic molecules, with the remainder being cyclic and / orCAPT_0002_WOmolecules that do not substantially alter the burn or physical properties of the NPSAFB 102. Preferably, a ratio of aromatics to cyclics by volume in the blending component 101 is from 1:9 to 1:0.01, preferably from 1:6 to 1:0.1, and more preferably from 1:4 to 1:0.5 by volume. More preferably, a ratio of aromatics to cyclics by volume in the blending component 101 is from 1:9 to 1: 1, preferably from 1:6 to 1: 1.5, and more preferably from 1:4 to 1:2 by volume.

[0044] None of the NPSAFBs 0- 1 include greater than 0.3% total sulfur by weight and none of the NPSAFB blends 0-1 include greater than 0.003% mercaptan sulfur, which has the foul odor of rotten eggs. Fuel blends 2-4 are expected to have similar sulfur and mercaptan sulfur contents. An advantage of using the NPSBF 100 with aromatic and / or cyclic molecules sourced from turpentine as the blending component 101 is that sulfur containing molecules are not a significant component of either the NPSBF 100 or the blending component 101. Sulfur compounds in fuels are highly undesirable due to their ability to cause mercaptan sulfur attack on elastomeric materials, to form sulfur oxides during combustion that can be corrosive to turbine metal parts, and to result in the emission of sulfur oxides upon combustion that are converted in the atmosphere to fine particulate matter.

[0045] FIG. 7 provides smoke points for multiple aromatic and cyclic molecules sourced from turpentine that may be used in the blending component 101. As shown in the figure, pinane has the highest smoke point, thus being the most preferred molecule to reduce sooting when used in the blending component 101. Similarly, while not tested, menthane would be expected to have a similar smoke point to pinane due to also being saturated. Hence, pinane and menthane are the more preferred cyclics when less sooting is desired as both molecules are saturated.CAPT_0002_WO

[0046] However, the smoke points of the aromatic para-cymene, dipentenes, delta-3-carene, and gum turpentine may also be high enough to be useful in the blending component 101. This is especially true when one or more of these molecules are used in combination with the pinane and / or menthane. NPSAFBs 1-4 of FIG. 7 met the applicable standard for smoke point for an aviation fuel, even though fuel blend 1 lacked pinane. This is attributed to the smoke point of the NPSBF 100 being above the smoke point specification such that the blend of the two meets the specification.

[0047] FIG. 8 provides smoke points for NPSAFBs 1-4 prepared from the combination of a blending component 101 with the NPSBF 100 to produce the NPSAFB 102. As shown in the figure, fuel blend 4 containing the most pinane had the highest smoke point, thus making pinane the most preferred molecule to reduce sooting when used in the blending component 101.

[0048] FIG. 9 compares the seal swell performance by optical dilatometry after approximately 40 hours for nitrile rubber O-rings (N0602- 70) submerged at room temperature in NPSAFBs 0, 1, or 2 as prepared from the combination of the blending component 101 with the NPSBF 100 to produce the NPSAFB 102 versus the NPSBF 100 alone and petroleum sourced aviation fuels. Petroleum sourced aviation fuels with aromatic concentrations of 8-25% have been shown to swell nitrile O-rings by an average of 6.9%, ranging from 3.4% to 10.5% by volume. NPSAFB 1 provided an approximate 5-30% enhancement in seal swell in relation to petroleum sourced aviation fuels, while NPSAFB 0 provided approximately 50% less seal swell than the petroleum sourced aviation fuels. As previously mentioned, the seal swell performance of the NPSBF 100 is insufficient to meet the applicable standards for seal swell.CAPT_0002_WO

[0049] The seal swell performance of the NPSAFB 102 meets or exceeds the applicable standard for seal swell, with the blending composition 101 providing significantly enhanced seal swell over the NPSBF 100. Preferably, the NPSAFB 102 provides at least 5% increased seal swell by volume than the petroleum-sourced aviation fuel, more preferably the NPSAFB 102 provides at least 15% increased seal swell by volume than petroleum-sourced aviation fuel. Preferably, the NPSAFB 102 provides at least 50% increased seal swell by volume than NPSBF, more preferably the NPSAFB 102 provides at least 70% increased seal swell by volume than NPSBF.

[0050] The percentage seal swell values on a volume expansion basis (v / v) as represented in the figure for three test trials with average values provided in Table II. The table also includes average seal volume expansion data for Jet-A and an industry accepted average value for the petroleum sourced aviation fuel JP8.Table II

[0051] As aromatics may be required under the applicable standard and generally are the most effective at producing seal-swell, but cause sooting, the ratio of aromatics to cyclics in the blending component 101 may be altered to produce the desired seal swell and sooting properties for the NPSAFB 102. The blending component 101 preferably includesCAPT_0002_WOsufficient aromatic molecules to provide an aromatic content in NPSAFB 102 from 5% to 30%, preferably from 8% to 25% by volume.

[0052] Surprisingly, the cyclic delta-3 -carene was found to synergistically provide seal swell volumes approaching aromatics when combined with the NPSBF 100. While delta-3 -carene was the only cyclic tested regarding seal swell, other cyclics, such as pinane, would be expected to have comparable performance. The ratio of aromatic to cyclic molecules in the blending component 101 may be designed to have the minimum of aromatics required to meet the desired applicable standard, thus reducing sooting of the fuel during combustion to the absolute minimum, while using cyclics that improve the seal swell performance of the NPSAFB 102 beyond what could be achieved with the minimum of aromatics required by the applicable standard.

[0053] The blending component 101 preferably includes sufficient cyclic molecules to provide a cyclic content in the NPSAFB 102 from 10% to 45%, preferably from 20% to 30% by volume. In fuels with low or no aromatics required to meet applicable standards or with sufficient existing aromatic molecule content, cyclics including delta-3 -carene and / or pinane may constitute at least 70% by volume of the blending component 101, preferably at least 80% or more of the blending component 101 by volume.

[0054] Applicable ASTM standards for a non-petroleum sourced aviation fuel specify a fuel density from approximately 775 kg / m3to 840 kg / m3. NPSBF 100 has a density of approximately 760 kg / m3, thus does not meet the applicable standard. NPSAFB 1 had a density of779.5 kg / m3, NPSAFB 2 had a density of 778.4 kg / m3, and NPSAFB 3 had a slightly higher density of 805.5 kg / m3. Hence, each of these NPSAFBs met the applicable density standards.CAPT_0002_WO

[0055] Preferably, the blending component 101 has a density from 830 kg / m3to 890 kg / m3, more preferably from 840 kg / m3to 880 kg / m3, and most preferably from 850 kg / m3to 870 kg / m3. Hence, when the blending component 101 is combined with the NPSBF 100, NPSAFB 102 meeting the applicable standard for density is produced.

[0056] Turbidity (cloudiness) when exposed to water is an important consideration for an aviation fuel. Excess turbidity in the presence of contaminating water can be an indicator of the fuel’s propensity to plug fuel filters and deposit unwanted solids in the fuel system of the aircraft.NPSAFB 102 demonstrates a similar turbidity (Nephelometric Turbidity Units (NTU) of 7 or less, preferably of 5 or less) to petroleum sourced base fuel when a preferred combination of aromatic and cyclic molecules is used in the blending component 101.

[0057] Table III provides NTU units from blending components of and the NPSAFB 102 in comparison to fuel blends lacking the blending component 101. As seen from the table, the aromatic para-cymene demonstrated an unpredicted ability to reduce the turbidity of a HEFA and dipentene (cyclic) mixture by about 60%. Hence, in addition to the previously discussed benefits of using the para-cymene aromatic in the blending component 101, the molecule also has the unexpected ability ofCAPT_0002_WOsignificantly reducing turbidity that otherwise results from using the cyclic dipentene in combination with the NPSBF 100 to provide the blending component 101 and thus the NPSAFB 102.Table III

[0058] FIG. 10 establishes that the NPSAFBs 1, 2, and 3 prepared from the combination of a blending component 101 and the NPSBF 100 to produce the NPSAFB 102 meeting a subset of the applicable standards of ASTM D 1655. As there are many different tests to meet all the applicable standards, this figure provides what are believed to be the most relevant subset of tests in relation to the applicable standard to isolate NPSAFBs meeting the applicable standard.

[0059] FIG. 11 establishes that the NPSAFB 1, prepared from the combination of a blending component 101 and the NPSBF 100, produces NPSAFB 102 meeting the applicable standards of ASTM D1655. Similar performance is expected for the blends included by the “line” between fuel blends 1 and 2 within the trapezoid as described in relation to FIG. 6.

[0060] In addition to the non-petroleum sourced fuel 100 and the blending component 101, the NPSAFB 102 may include a biocidal additive.CAPT_0002_WOFor example, BIOBOR™ JF, as available from Sky Mart, Miami, FL could be used as a “curative treatment” to kill and control microorganisms in the NPSAFB 102. However, such additives provide no fuel value, and the blending component 101 inherently functions as a biocide as it is sourced from trees. Hence, preferably, the inclusion of the blending component 101 in NPSAFB 102 reduces or eliminates the need for an additional biocide and other types of additives lacking fuel value. Hence, NPSAFB 102 preferably does not include sufficient biocidal additive to alter the burn or physical properties of NPSAFB 102 in relation to a NPSAFB 102 lacking biocidal additive.

[0061] NPSAFB 102 may include other additives at a concentration of 10% or less by volume. Such other additives may be selected from the group including electrical conductivity additives, oxygenates, antioxidants, thermal stability improvers, stabilizers, cold flow improvers, combustion improvers, an anti-foam additives, anti-haze additives, corrosion inhibitors, lubricity improvers, icing inhibitors, injector cleanliness additives, smoke suppressants, drag reducing additives, metal deactivators, dispersants, detergents, de-emulsifiers, dyes, markers, static dissipaters, odorants, and the like. However, a purpose of the invention is to reduce or eliminate the need for such other additives due to the inherent properties of the blending component 101.

[0062] While not preferred due to the inclusion of petroleum-sourced fuel, petroleum-sourced aviation fuel may be blended with NPSAFB 102 to provide a hybrid aviation fuel with the desired physical characteristics. This hybrid aviation fuel ensures the resulting fuel would better meet the applicable standards than a petroleum-sourced fuel blended with the nonpetroleum sourced aviation fuel 100 alone. In this instance, a higher ratioCAPT_0002_WOof cyclic to aromatic molecules may be preferred than when petroleum- sourced fuels are excluded.

[0063] To provide a clear and more consistent understanding of the specification and claims of this application, the following definitions are provided.

[0064] Unless the context clearly dictates otherwise, where a range of values is provided, each intervening value to the tenth of the unit of the lower limit between the lower limit and the upper limit of the range is included in the range of values.

[0065] The terms “a”, “an”, and “the” used in the specification claims are to be construed to cover both the singular and the plural, unless otherwise indicated or contradicted by context. No language in the specification should be construed as indicating any non-claimed element to be essential to the practice of the invention.

[0066] While the present general inventive concept has been illustrated by description of several example embodiments, and while the illustrative embodiments have been described in detail, it is not the intention of the applicant to restrict or in any way limit the scope of the general inventive concept to such descriptions and illustrations. Instead, the descriptions, drawings, and claims herein are to be regarded as illustrative in nature, and not as restrictive, and additional embodiments will readily appear to those skilled in the art upon reading the above description and drawings. Additional modifications will readily appear to those skilled in the art. Accordingly, departures may be made from such details without departing from the spirit or scope of applicant's general inventive concept.CAPT_0002_WO

[0067] Meeting applicable standard or standards means that the NPSAFB meets the ASTM D7566 standard and / or the ASTM D1655 standard, and / or the ASTM D4054 standard, even though the D 1655 standard is intended for petroleum-based aviation fuels. Similarly, meeting a subset of the applicable standard or standards means that the NPSAFB meets a subset of the D4054, D7566, and / or D 1655 standards.

[0068] Crude sulfate turpentine means turpentine that contains more sulfur than gum turpentine and often is produced as a byproduct of paper manufacture.

[0069] Turpentine means turpentine that naturally includes or has been purified to include no more than 0.3% by weight total sulfur.Naturally occurring turpentine is obtained from plants, generally being distilled from the resin of pine trees. Turpentine includes much less sulfur than crude sulfate turpentine and also may be obtained through fractionating (purifying) crude sulfate turpentine. Turpentine includes a mixture of different terpene molecules primarily composed of terpene molecules having ten carbon atoms that are generally referred to as monoterpenes.

[0070] While various aspects of the invention are described, it will be apparent to those of ordinary skill in the art that other embodiments and implementations are possible within the scope of the invention.Accordingly, the invention is not to be restricted except considering the attached claims and their equivalents.CAPT_0002_WO

Claims

CLAIMS1. A non-petroleum sourced aviation fuel blend, for meeting at least a subset of the applicable standards for aviation fuel, the fuel blend comprising: a non-petroleum sourced base fuel; and a blending component comprising molecules sourced from turpentine and chosen from aromatic molecules and cyclic molecules, where the molecules sourced from the turpentine have from 6 to 14 carbon atoms, preferably from 9 to 11 carbon atoms, and where the fuel blend comprises from 8% to 60% of the blending component by volume.

2. The fuel blend of claim 1, where the non-petroleum sourced base fuel is selected from the group consisting of Hydroprocessed Esters and Fatty Acids Synthetic Paraffinic Kerosene (HEFA-SPK), Alcohol to Jet Synthetic Paraffinic Kerosene (ATJ-SPK), Fischer Tropsch Synthetic Paraffinic Kerosene (FT-SPK), Hydroprocessed Fermented Sugars to Synthetic Isoparaffins (HFS-SIP), Fischer Tropsch Synthetic Paraffinic Kerosene with Aromatics (FT-SPK / A), Catalytic Hydrothermolysis Synthesized Kerosene (CH-SK, or CH J), Hydroprocessed Hydrocarbons, Esters and Fatty Acids Synthetic Paraffinic Kerosene (HHC-SPK or HC-HEFA-SPK), Alcohol to Jet Synthetic Kerosene with Aromatics (ATJ-SKA), and combinations thereof3. The fuel blend of any one of the preceding claims, where the blending component is not synthetically prepared from isoprene, starches, and sugars and is not produced from fermentation.CAPT_0002_WO4. The fuel blend of any one of the preceding claims, where the fuel blend comprises from 10% to 50%, from 30% to 50%, from 20% to 30%, or from 8% to 20% of the blending component by volume.

5. The fuel blend of any one of the preceding claims, where the molecules sourced from the turpentine are directly sourced from the turpentine or are hydrogen-altered directly turpentine sourced molecules.

6. The fuel blend of any one of the preceding claims, where the blending component comprises at least 90% or at least 95% by volume ten carbon molecules.

7. The fuel blend of any one of the preceding claims, where the blending component comprises 90% by volume the molecules sourced from the turpentine.

8. The fuel blend of any one of the preceding claims, where the aromatic molecules are selected from para-cymene, meta-cymene, ortho-cymene, benzene, ethylbenzene, xylene, toluene, and combinations thereof.

9. The fuel blend of any one of the preceding claims, where the blending component comprises from 5% to 98% para-cymene by volume.

10. The fuel blend of any one of the preceding claims, where the cyclic molecules are selected from delta-3-carene, alpha-pinene, menthane, betapinene, dipentenes, pinane, eucalyptol, and combinations thereof11. The fuel blend of any one of the preceding claims, where the blending component comprises the volume percents of aromatic and cyclic molecules included by and within the trapezoid of FIG. 6, the volume percents of aromatic and cyclic molecules included by and within the triangle formed byCAPT_0002_WOfuel blends 0, 1, and 2 of FIG. 6, or the volume percents of aromatic and cyclic molecules included by the line joining fuel blends 1 and 2 of FIG. 6.

12. The fuel blend of any one of the preceding claims, where the blending component comprises a ratio of aromatics to cyclics from 1:9 to 1:0.01, preferably from 1:9 to 1: 1, by volume.

13. The fuel blend of any one of the preceding claims, where the fuel blend is configured to provide an at least 15% enhancement in seal swell volume in relation to the non-petroleum sourced base fuel without the blending component.

14. The fuel blend of any one of the preceding claims, where the blending component has a density from 830 kg / m3to 890 kg / m315. The fuel blend of any one of the preceding claims, where the fuel blend comprises a combination of the aromatic molecules and the cyclic molecules and the fuel blend is configured to provide a turbidity less than 5 NTU when the fuel blend is exposed to water.

16. A non-petroleum sourced aviation fuel blend, for meeting at least a subset of the applicable standards for aviation fuel, the fuel blend comprising: a non-petroleum sourced base fuel; and a blending component comprising molecules sourced from turpentine and chosen from aromatic molecules and cyclic molecules, where the molecules sourced from the turpentine have from 6 to 14 carbon atoms, and whereCAPT_0002_WOthe fuel blend comprises from 8% to 60% of the blending component by volume.

17. The fuel blend of claim 16, where the aromatic and cyclic molecules sourced from turpentine have from 9 to 11 carbon atoms.

18. The fuel blend of claim 16, where the non-petroleum sourced base fuel is selected from the group consisting of Hydroprocessed Esters and Fatty Acids Synthetic Paraffinic Kerosene (HEFA-SPK), Alcohol to Jet Synthetic Paraffinic Kerosene (ATJ-SPK), Fischer Tropsch Synthetic Paraffinic Kerosene (FT-SPK), Hydroprocessed Fermented Sugars to Synthetic Isoparaffins (HFS-SIP), Fischer Tropsch Synthetic Paraffinic Kerosene with Aromatics (FT-SPK / A), Catalytic Hydrothermolysis Synthesized Kerosene (CH-SK, or CH J), Hydroprocessed Hydrocarbons, Esters and Fatty Acids Synthetic Paraffinic Kerosene (HHC-SPK or HC- HEFA-SPK), Alcohol to Jet Synthetic Kerosene with Aromatics (ATJ-SKA), and combinations thereof.

19. The fuel blend of claim 16, where the non-petroleum sourced base fuel is selected from the group consisting of Hydroprocessed Esters and Fatty Acids Synthetic Paraffinic Kerosene (HEFA-SPK), Alcohol to Jet Synthetic Paraffinic Kerosene (ATJ-SPK), Fischer Tropsch Synthetic Paraffinic Kerosene (FT-SPK), Catalytic Hydrothermolysis Synthesized Kerosene (CH-SK, or CH J), and combinations thereof.

20. The fuel blend of claim 16, where the non-petroleum sourced base fuel is selected from the group consisting of Hydroprocessed Esters and Fatty Acids Synthetic Paraffinic Kerosene (HEFA-SPK), Alcohol to Jet Synthetic Paraffinic Kerosene (ATJ-SPK), and combinations thereof.CAPT_0002_WO21. The fuel blend of claim 16, where the blending component is not synthetically prepared from isoprene, starches, and sugars and is not produced from fermentation.

22. The fuel blend of claim 16, where the fuel blend comprises from 10% to 50% of the blending component by volume.

23. The fuel blend of claim 16, where the fuel blend comprises from 30% to 50% of the blending component by volume.

24. The fuel blend of claim 16, where the fuel blend comprises from 20% to 30% of the blending component by volume.

25. The fuel blend of claim 16, where the fuel blend comprises from 8% to 20% of the blending component by volume26. The fuel blend of claim 16, where the fuel blend is homogeneous.

27. The fuel blend of claim 16, where the molecules sourced from the turpentine are directly sourced from the turpentine.

28. The fuel blend of claim 16, where the molecules sourced from the turpentine are hydrogen-altered directly sourced molecules.

29. The fuel blend of claim 28, where hydrogen-alteration comprises dehydrogenation.

30. The fuel blend of claim 28, where hydrogen-alteration consists essentially of dehydrogenation.CAPT_0002_WO31. The fuel blend of claim 16, where the blending component comprises at least 90% by volume ten carbon molecules.

32. The fuel blend of claim 16, where the blending component comprises at least 95% by volume ten carbon molecules.

33. The fuel blend of claim 16, where the blending component comprises 90% by volume the molecules sourced from the turpentine.

34. The fuel blend of claim 16, where the blending component comprises 95% by volume the molecules sourced from the turpentine.

35. The fuel blend of claim 16, where the aromatic molecules are selected from para-cymene, meta-cymene, ortho-cymene, benzene, ethylbenzene, xylene, toluene, and combinations thereof.

36. The fuel blend of claim 16, where the blending component comprises from 5% to 98% para-cymene by volume.

37. The fuel blend of claim 16, where the cyclic molecules are selected from delta-3-carene, alpha-pinene, menthane, beta-pinene, dipentenes, pinane, eucalyptol, and combinations thereof.

38. The fuel blend of claim 16, where the cyclic molecules are selected from delta-3-carene, menthane, pinane, and combinations thereof.

39. The fuel blend of claim 16, where the cyclic molecules are selected from menthane, pinane, and combinations thereof.

40. The fuel blend of claim 16, where the cyclic molecules comprise pinane.CAPT_0002_WO41. The fuel blend of claim 16, where the blending component comprises greater than 50% by volume cyclic molecules.

42. The fuel blend of claim 16, where the blending component comprises greater than 90% para-cymene by volume.

43. The fuel blend of claim 16, where the blending component comprises the volume percents of aromatic and cyclic molecules included by and within the trapezoid of FIG. 6.

44. The fuel blend of claim 16, where the blending component comprises the volume percents of aromatic and cyclic molecules included by and within the triangle formed by fuel blends 0, 1, and 2 of FIG. 6.

45. The fuel blend of claim 16, where the blending component comprises the volume percents of aromatic and cyclic molecules included by the line joining fuel blends 1 and 2 of FIG. 6.

46. The fuel blend of claim 16, where the blending component comprises greater than 90% by volume aromatic molecules.

47. The fuel blend of claim 16, where the blending component comprises a ratio of aromatics to cyclics from 1:9 to 1:0.01 by volume.

48. The fuel blend of claim 16, where the blending component comprises a ratio of aromatics to cyclics from 1:4 to 1:0.5 by volume.

49. The fuel blend of claim 16, where the blending component comprises a ratio of aromatics to cyclics from 1:9 to 1: 1 by volume.CAPT_0002_WO50. The fuel blend of claim 16, where the blending component comprises a ratio of aromatics to cyclics from 1:4 to 1:2 by volume.

51. The fuel blend of claim 16, where the blending component does not comprise greater than 0.3% total sulfur by weight.

52. The fuel blend of claim 16, where the fuel blend is configured to provide an at least 5% enhancement in seal swell volume in relation to petroleum sourced aviation fuels.

53. The fuel blend of claim 16, where the fuel blend is configured to provide an at least 15% enhancement in seal swell volume in relation to the non-petroleum sourced base fuel without the blending component.

54. The fuel blend of claim 16, where the fuel blend is configured to provide an at least 50% enhancement in seal swell volume in relation to the non-petroleum sourced base fuel without the blending component.

55. The fuel blend of claim 16, comprising from 5% to 30% aromatic molecules by volume.

56. The fuel blend of claim 16, comprising from 8% to 25% aromatic molecules by volume.

57. The fuel blend of claim 16, comprising from 10% to 45% cyclic molecules by volume.

58. The fuel blend of claim 16, comprising from 20% to 30% cyclic molecules by volume.CAPT_0002_WO59. The fuel blend of claim 16, where the blending component comprises a cyclic chosen from menthane, pinane, and combinations thereof at a volume percentage of at least 70%.

60. The fuel blend of claim 16, where the blending component has a density from 830 kg / m3to 890 kg / m3.

61. The fuel blend of claim 16, configured to have a lower turbidity when mixed with water than the non-petroleum sourced base fuel.

62. The fuel blend of claim 16, where the fuel blend comprises a combination of the aromatic molecules and the cyclic molecules and the fuel blend is configured to have a turbidity less than 5 NTU when the fuel blend is exposed to water.

63. The fuel blend of claim 16, where the fuel blend lacks a biocidal additive.

64. The fuel blend of claim 16, where the fuel blend lacks sufficient biocidal additive to alter the burn or physical properties of the nonpetroleum sourced aviation fuel blend in relation to a non-petroleum sourced aviation fuel blend lacking any biocidal additive.

65. The fuel blend of claim 16, where the fuel blend lacks petroleum sourced aviation fuel.

66. Each and every novel feature herein disclosed.CAPT_0002_WO

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