# Patent

## Title
High octane unleaded aviation gasoline

## Abstract

High octane unleaded aviation fuel compositions having high aromatics content and a CHN content of at least 97.2 wt %, less than 2.8 wt % of oxygen content, a T10 of at most 75° C., T40 of at least 75° C., a T50 of at most 105° C., a T90 of at most 135° C., a final boiling point of less than 190° C., an adjusted heat of combustion of at least 43.5 MJ/kg, a vapor pressure in the range of 38 to 49 kPa, freezing point is less than −58° C. is provided.

## Background
This present application claims the benefit of U.S. Provisional Patent Application No. 61/898,244 filed Oct. 31, 2013, 61/991,888 filed May 12, 2014, and 62/021,249 filed Jul. 7, 2014, the entire disclosures of which are hereby incorporated by reference


FIELD OF THE INVENTION
The present invention relates to high octane unleaded aviation gasoline fuel, more particularly to a high octane unleaded aviation gasoline having low-oxygen content.
BACKGROUND OF THE INVENTION
Avgas (aviation gasoline), is an aviation fuel used in spark-ignited internal-combustion engines to propel aircraft. Avgas is distinguished from mogas (motor gasoline), which is the everyday gasoline used in cars and some non-commercial light aircraft. Unlike mogas, which has been formulated since the 1970s to allow the use of 3-way catalytic converters for pollution reduction, avgas contains tetraethyl lead (TEL), a non-biodegradable toxic substance used to prevent engine knocking (detonation).
Aviation gasoline fuels currently contain the additive tetraethyl lead (TEL), in amounts up to 0.53 mL/L or 0.56 g/L which is the limit allowed by the most widely used aviation gasoline specification 100 Low Lead (100LL). The lead is required to meet the high octane demands of aviation piston engines: the 100LL specification ASTM D910 demands a minimum motor octane number (MON) of 99.6, in contrast to the EN 228 specification for European motor gasoline which stipulates a minimum MON of 85 or United States motor gasoline which require unleaded fuel minimum octane rating (R+M)/2 of 87.
Aviation fuel is a product which has been developed with care and subjected to strict regulations for aeronautical application. Thus aviation fuels must satisfy precise physico-chemical characteristics, defined by international specifications such as ASTM D910 specified by Federal Aviation Administration (FAA). Automotive gasoline is not a fully viable replacement for avgas in many aircraft, because many high-performance and/or turbocharged airplane engines require 100 octane fuel (MON of 99.6) and modifications are necessary in order to use lower-octane fuel. Automotive gasoline can vaporize in fuel lines causing a vapor lock (a bubble in the line) or fuel pump cavitation, starving the engine of fuel. Vapor lock typically occurs in fuel systems where a mechanically-driven fuel pump mounted on the engine draws fuel from a tank mounted lower than the pump. The reduced pressure in the line can cause the more volatile components in automotive gasoline to flash into vapor, forming bubbles in the fuel line and interrupting fuel flow.
The ASTM D910 specification does not include all gasoline satisfactory for reciprocating aviation engines, but rather, defines the following specific types of aviation gasoline for civil use: Grade 80; Grade 91; Grade 100; and Grade 100LL. Grade 100 and Grade 100LL are considered High Octane Aviation Gasoline to meet the requirement of modem demanding aviation engines. In addition to MON, the D910 specification for Avgas have the following requirements: density; distillation (initial and final boiling points, fuel evaporated, evaporated temperatures T10, T40, T90, T10+T50); recovery, residue, and loss volume; vapor pressure; freezing point; sulfur content; net heat of combustion; copper strip corrosion; oxidation stability (potential gum and lead precipitate); volume change during water reaction; and electrical conductivity. Avgas fuel is typically tested for its properties using ASTM tests:
Motor Octane Number: ASTM D2700
Aviation Lean Rating: ASTM D2700
Performance Number (Super-Charge): ASTM D909
Tetraethyl Lead Content: ASTM D5059 or ASTM D3341
Color: ASTM D2392
Density: ASTM D4052 or ASTM D1298
Distillation: ASTM D86
Vapor Pressure: ASTM D5191 or ASTM D323 or ASTM D5190
Freezing Point: ASTM D2386
Sulfur: ASTM D2622 or ASTM D1266
Net Heat of Combustion (NHC): ASTM D3338 or ASTM D4529 or ASTM D4809
Copper Corrosion: ASTM D130
Oxidation Stability—Potential Gum: ASTM D873
Oxidation Stability—Lead Precipitate: ASTM D873
Water Reaction—Volume change: ASTM D1094
Electrical Conductivity: ASTM D2624
Aviation fuels must have a low vapour pressure in order to avoid problems of vaporization (vapor lock) at low pressures encountered at altitude and for obvious safety reasons. But the vapor pressure must be high enough to ensure that the engine starts easily.
The Reid Vapor pressure (RVP) should be in the range of 38 kPa to 49 kPA. The final distillation point must be fairly low in order to limit the formations of deposits and their harmful consequences (power losses, impaired cooling). These fuels must also possess a sufficient Net Heat of Combustion (NHC) to ensure adequate range of the aircraft. Moreover, as aviation fuels are used in engines providing good performance and frequently operating with a high load, i.e. under conditions close to knocking, this type of fuel is expected to have a very good resistance to spontaneous combustion.
Moreover, for aviation fuel two characteristics are determined which are comparable to octane numbers: one, the MON or motor octane number, relating to operating with a slightly lean mixture (cruising power), the other, the Octane rating. Performance Number or PN, relating to use with a distinctly richer mixture (take-off). With the objective of guaranteeing high octane requirements, at the aviation fuel production stage, an organic lead compound, and more particularly tetraethyllead (TEL), is generally added. Without the TEL added, the MON is typically around 91. As noted above ASTM D910, 100 octane aviation fuel requires a minimum motor octane number (MON) of 99.6. The distillation profile of the high octane unleaded aviation fuel composition should have a T10 of maximum 75° C., T40 of minimum 75° C., T50 maximum 105° C., and T90 of maximum 135° C.
As in the case of fuels for land vehicles, administrations are tending to lower the lead content, or even to ban this additive, due to it being harmful to health and the environment. Thus, the elimination of lead from the aviation fuel composition is becoming an objective.
SUMMARY OF THE INVENTION
It has been found that it is difficult to produce a high octane unleaded aviation fuel that meet most of the ASTM D910 specification for high octane aviation fuel. In addition to the MON of 99.6, it is also important to not negatively impact the flight range of the aircraft, vapor pressure, temperature profile and freeze points that meets the aircraft engine start up requirements and continuous operation at high altitude.
In accordance with certain of its aspects, in one embodiment of the present invention provides a an unleaded aviation fuel composition having a MON of at least 99.6, sulfur content of less than 0.05 wt %, CHN content of at least 97.2 wt %, less than 2.8 wt % of oxygen content, a T10 of at most 75° C., T40 of at least 75° C., a T50 of at most 105° C., a T90 of at most 135° C., a final boiling point of less than 190° C., an adjusted heat of combustion of at least 43.5 MJ/kg, a vapor pressure in the range of 38 to 49 kPa, comprising a blend comprising:

    
    
        from about 20 vol. % to about 35 vol. % of toluene having a MON of at least 107;
        from about 2 vol. % to about 10 vol. % of aniline;
        from above 30 vol. % to about 55 vol. % of at least one alkylate or alkylate blend having an initial boiling range of from about 32° C. to about 60° C. and a final boiling range of from about 105° C. to about 140° C., having T40 of less than 99° C., T50 of less than 100° C., T90 of less than 110° C., the alkylate or alkylate blend comprising isoparaffins from 4 to 9 carbon atoms, about 3-20 vol. % of C5 isoparaffins, about 3-15 vol. % of C7 isoparaffins, and about 60-90 vol. % of C8 isoparaffins, based on the alkylate or alkylate blend, and less than 1 vol. % of C10+, based on the alkylate or alkylate blend;
        from about 7 vol. % to about 14 vol. % of a branched alkyl acetate having branched chain alkyl group having 4 to 8 carbon atoms; and
        at least 8 vol. % of isopentane in an amount sufficient to reach a vapor pressure in the range of 38 to 49 kPa; and

wherein the fuel composition contains less than 1 vol. % of C8 aromatics.

    
    


The features and advantages of the invention will be apparent to those skilled in the art. While numerous changes may be made by those skilled in the art, such changes are within the spirit of the invention.



BRIEF DESCRIPTION OF THE DRAWINGS
This drawing illustrates certain aspects of some of the embodiments of the invention, and should not be used to limit or define the invention.
FIG. 1 shows the engine conditions for unleaded aviation fuel Example 1 at 2575 RPM at constant manifold pressure.
FIG. 2 shows the detonation data for unleaded aviation fuel Example 1 at 2575 RPM at constant manifold pressure.
FIG. 3 shows the engine conditions for unleaded aviation fuel Example 1 at 2400 RPM at constant manifold pressure.
FIG. 4 shows the detonation data for unleaded aviation fuel Example 1 at 2400 RPM at constant manifold pressure.
FIG. 5 shows the engine conditions for unleaded aviation fuel Example 1 at 2200 RPM at constant manifold pressure.
FIG. 6 shows the detonation data for unleaded aviation fuel Example 1 at 2200 RPM at constant manifold pressure.
FIG. 7 shows the engine conditions for unleaded aviation fuel Example 1 at 2757 RPM at constant power.
FIG. 8 shows the detonation data for unleaded aviation fuel Example 1 at 2757 RPM at constant power.
FIG. 9 shows the engine conditions for FBO sourced 100LL fuel at 2575 RPM at constant manifold pressure.
FIG. 10 shows the detonation data for FBO sourced 100LL fuel at 2575 RPM at constant manifold pressure.
FIG. 11 shows the engine conditions for FBO sourced 100LL fuel at 2400 RPM at constant manifold pressure.
FIG. 12 shows the detonation data for FBO sourced 100LL fuel at 2400 RPM at constant manifold pressure.
FIG. 13 shows the engine conditions for FBO sourced 100LL fuel at 2200 RPM at constant manifold pressure.
FIG. 14 shows the detonation data for FBO sourced 100LL fuel at 2200 RPM at constant manifold pressure.
FIG. 15 shows the engine conditions for FBO sourced 100LL fuel at 2757 RPM at constant power.
FIG. 16 shows the detonation data for FBO sourced 100LL fuel at 2757 RPM at constant power.



DETAILED DESCRIPTION OF THE INVENTION
We have found that a high octane low oxygen-content unleaded aviation fuel having an oxygen content of less than 2.8 wt % based on the unleaded aviation fuel blend that meets most of the ASTM D910 specification for 100 octane aviation fuel can be produced by a blend comprising from about 20 vol. % to about 35 vol. % of high MON toluene, from about 2 vol. % to about 10 vol. % of aniline; from about above 30 vol. % to about 55 vol. % of at least one alkylate cut or alkylate blend that have certain composition and properties and at least 8% vol. % of isopentane and from about 7 vol. % to about 14 vol. % of a branched alkyl acetate having branched chain alkyl group having 4 to 8 carbon atoms. Preferably, the combined amount of toluene and the branched alkyl acetate in the fuel composition is more than 30 vol. %, more than 31 vol. % more than 32 vol. %, or more than 33 vol. %. The high octane unleaded aviation fuel of the invention has a MON of greater than 99.6.
In one embodiment, an unleaded aviation fuel composition having a MON of at least 99.6, sulfur content of less than 0.05 wt %, CHN content of at least 97.2 wt %, less than 2.8 wt % of oxygen content, a T10 of at most 75° C., T40 of at least 75° C., a T50 of at most 105° C., a T90 of at most 135° C., a final boiling point of less than 190° C., an adjusted heat of combustion of at least 43.5 MJ/kg, a vapor pressure in the range of 38 to 49 kPa, comprising a blend comprising:

    
    
        from about 20 vol. % to about 35 vol. % of toluene having a MON of at least 107;
        from about 2 vol. % to about 10 vol. % of aniline;
        from above 30 vol. % to about 55 vol. % of at least one alkylate or alkylate blend having an initial boiling range of from about 32° C. to about 60° C. and a final boiling range of from about 105° C. to about 140° C., having T40 of less than 99° C., T50 of less than 100° C., T90 of less than 110° C., the alkylate or alkylate blend comprising isoparaffins from 4 to 9 carbon atoms, about 3-20 vol. % of C5 isoparaffins, about 3-15 vol. % of C7 isoparaffins, and about 60-90 vol. % of C8 isoparaffins, based on the alkylate or alkylate blend, and less than 1 vol. % of C10+, based on the alkylate or alkylate blend;
        from about 7 vol. % to about 14 vol. % of a branched alkyl acetate having branched chain alkyl group having 4 to 8 carbon atoms; and
        at least 8 vol. % of isopentane in an amount sufficient to reach a vapor pressure in the range of 38 to 49 kPa;

wherein the combined amount of toluene and the branched alkyl acetate in the fuel composition is more than 30 vol. %, preferably more than 33 vol. %; and wherein the fuel composition contains less than 1 vol. % of C8 aromatics.

    
    


Further the unleaded aviation fuel composition contains less than 1 vol. % of C8 aromatics. It has been found that C8 aromatics such as xylene may have materials compatibility issues, particularly in older aircraft. Further it has been found that unleaded aviation fuel containing C8 aromatics tend to have difficulties meeting the temperature profile of D910 specification. In one embodiment, the unleaded aviation fuel contains less than 0.2% vol. % of ethers. In another embodiment, the unleaded aviation fuel contains no straight chain alcohols and no noncyclic ethers. In one embodiment, the unleaded aviation fuel contains no alcohols having boiling point of less than 80° C. Further, the unleaded aviation fuel composition have a benzene content between 0 vol. % and 5 vol. %, preferably less than 1 vol. %.
Further, in some embodiments, the volume change of the unleaded aviation fuel tested for water reaction is within +/−2 mL as defined in ASTM D1094.
The high octane unleaded fuel will not contain lead and preferably not contain any other metallic octane boosting lead equivalents. The term “unleaded” is understood to contain less than 0.01 g/L of lead. The high octane unleaded aviation fuel will have a sulfur content of less than 0.05 wt %. In some embodiments, it is preferred to have ash content of less than 0.0132 g/L (0.05 g/gallon) (ASTM D-482).
According to current ASTM D910 specification, the NHC should be close to or above 43.5 mJ/kg. The Net Heat of Combustion value is based on a current low density aviation fuel and does not accurately measure the flight range for higher density aviation fuel. It has been found that for unleaded aviation gasoline that exhibit high densities, the heat of combustion may be adjusted for the higher density of the fuel to more accurately predict the flight range of an aircraft.
There are currently three approved ASTM test methods for the determination of the heat of combustion within the ASTM D910 specification. Only the ASTM D4809 method results in an actual determination of this value through combusting the fuel. The other methods (ASTM D4529 and ASTM D3338) are calculations using values from other physical properties. These methods have all been deemed equivalent within the ASTM D910 specification.
Currently the Net Heat of Combustion for Aviation Fuels (or Specific Energy) is expressed gravimetrically as MJ/kg. Current lead containing aviation gasoline has a relatively low density compared to many alternative unleaded formulations. Fuels of higher density have a lower gravimetric energy content but a higher volumetric energy content (MJ/L).
The higher volumetric energy content allows greater energy to be stored in a fixed volume. Space can be limited in general aviation aircraft and those that have limited fuel tank capacity, or prefer to fly with full tanks, can therefore achieve greater flight range. However, the more dense the fuel, then the greater the increase in weight of fuel carried. This could result in a potential offset of the non-fuel payload of the aircraft. Whilst the relationship of these variables is complex, the formulations in this embodiment have been designed to best meet the requirements of aviation gasoline. Since in part density effects aircraft range, it has been found that a more accurate aircraft range, normally gauged using Heat of Combustion, can be predicted by adjusting for the density of the avgas using the following equation:

HOC*=(HOCv/density)+(% range increase/% payload increase+1)

where HOC* is the adjusted Heat of Combustion (MJ/kg), HOCv is the volumetric energy density (MJ/L) obtained from actual Heat of Combustion measurement, density is the fuel density (g/L), % range increase is the percentage increase in aircraft range compared to 100 LL(HOCLL) calculated using HOCv and HOCLL for a fixed fuel volume, and % payload increase is the corresponding percentage increase in payload capacity due to the mass of the fuel.
The adjusted heat of combustion will be at least 43.5 MJ/kg, and have a vapor pressure in the range of 38 to 49 kPa. The high octane unleaded fuel composition will further have a freezing point of −58° C. or less. Further, the final boiling point of the high octane unleaded fuel composition should be less than 190° C., preferably at most 180° C. measured with greater than 98.5% recovery as measured using ASTM D-86. If the recovery level is low, the final boiling point may not be effectively measured for the composition (i.e., higher boiling residual still remaining rather than being measured). The high octane unleaded aviation fuel composition of the invention have a Carbon, Hydrogen, and Nitrogen content (CHN content) of at least 97.2 wt %, preferably at least 97.5 wt %, and less than 2.8 wt %, preferably 2.5 wt % of oxygen. Suitably, the unleaded aviation fuel have an aromatics content measured according to ASTM D5134 of greater than 15 wt % to about 35 wt %.
It has been found that the high octane low oxygen-content unleaded aviation fuel of the invention not only meets the MON value for 100 octane aviation fuel, but also meets the freeze point and the temperature profile of T10 of at most 75° C., T40 of at least 75° C., T50 at most 105° C., and T90 of at most 135° C., vapor pressure, adjusted heat of combustion, and freezing point. In addition to MON it is important to meet the vapor pressure, temperature profile, and minimum adjusted heat of combustion for aircraft engine start up and smooth operation of the plane at higher altitude. Preferably the potential gum value is less than 6 mg/100 mL.
It is difficult to meet the demanding specification for unleaded high octane aviation fuel. For example, US Patent Application Publication 2008/0244963, discloses a lead-free aviation fuel with a MON greater than 100, with major components of the fuel made from avgas and a minor component of at least two compounds from the group of esters of at least one mono- or poly-carboxylic acid and at least one mono- or polyol, anhydrides of at least one mono- or poly carboxylic acid. These oxygenates have a combined level of at least 15% v/v, typical examples of 30% v/v, to meet the MON value. However, these fuels do not meet many of the other specifications such as heat of combustion (measured or adjusted) at the same time, including even MON in many examples. Another example, U.S. Pat. No. 8,313,540 discloses a biogenic turbine fuel comprising mesitylene and at least one alkane with a MON greater than 100. However, these fuels also do not meet many of the other specifications such as heat of combustion (measured or adjusted), temperature profile, and vapor pressure at the same time.
Toluene
Toluene occurs naturally at low levels in crude oil and is usually produced in the processes of making gasoline via a catalytic reformer, in an ethylene cracker or making coke from coal. Final separation, either via distillation or solvent extraction, takes place in one of the many available processes for extraction of the BTX aromatics (benzene, toluene and xylene isomers). The toluene used in the invention must be a grade of toluene that have a MON of at least 107 and containing less than 1 vol. % of C8 aromatics. Further, the toluene component must have a benzene content between 0 vol. % and 5 vol. %, preferably less than 1 vol. %.
For example an aviation reformate is generally a hydrocarbon cut containing at least 70% by weight, ideally at least 85% by weight of toluene, and it also contains C8 aromatics (15 to 50% by weight ethylbenzene, xylenes) and C9 aromatics (5 to 25% by weight propyl benzene, methyl benzenes and trimethylbenzenes). Such reformate has a typical MON value in the range of 102-106, and it has been found not suitable for use in the present invention.
Toluene is preferably present in the blend in an amount from about 20 vol. %, preferably from about 25 vol. %, to at most about 40 vol. %, preferably to at most about 35 vol. %, more preferably to at most about 30 vol. %, based on the unleaded aviation fuel composition.
Aniline
Aniline (C6H5NH2) is mainly produced in industry in two steps from benzene. First, benzene is nitrated using a concentrated mixture of nitric acid and sulfuric acid at 50 to 60° C., which gives nitrobenzene. In the second step, the nitrobenzene is hydrogenated, typically at 200-300° C. in presence of various metal catalysts.
As an alternative, aniline is also prepared from phenol and ammonia, the phenol being derived from the cumene process.
In commerce, three brands of aniline are distinguished: aniline oil for blue, which is pure aniline; aniline oil for red, a mixture of equimolecular quantities of aniline and ortho- and para-toluidines; and aniline oil for safranine, which contains aniline and ortho-toluidine, and is obtained from the distillate (échappés) of the fuchsine fusion. Pure aniline, otherwise known as aniline oil for blue is desired for high octane unleaded avgas. Aniline is preferably present in the blend in an amount from about 2% v, preferably at least about 3% v, most preferably at least about 4% v to at most about 10% v, preferably to at most about 7%, more preferably to at most about 6%, based on the unleaded aviation fuel composition.
Alkylate and Alkyate Blend
The term alkylate typically refers to branched-chain paraffin. The branched-chain paraffin typically is derived from the reaction of isoparaffin with olefin. Various grades of branched chain isoparaffins and mixtures are available. The grade is identified by the range of the number of carbon atoms per molecule, the average molecular weight of the molecules, and the boiling point range of the alkylate. It has been found that a certain cut of alkylate stream and its blend with isoparaffins such as isooctane is desirable to obtain or provide the high octane unleaded aviation fuel of the invention. These alkylate or alkylate blend can be obtained by distilling or taking a cut of standard alkylates available in the industry. It is optionally blended with isooctane. The alkylate or alkylate blend have an initial boiling range of from about 32° C. to about 60° C. and a final boiling range of from about 105° C. to about 140° C., preferably to about 135° C., more preferably to about 130° C., most preferably to about 125° C., having T40 of less than 99° C., preferably at most 98° C., T50 of less than 100° C., T90 of less than 110° C., preferably at most 108° C., the alkylate or alkylate blend comprising isoparaffins from 4 to 9 carbon atoms, about 3-20 vol. % of C5 isoparaffins, based on the alkylate or alkylate blend, about 3-15 vol. % of C7 isoparaffins, based on the alkylate or alkylate blend, and about 60-90 vol. % of C8 isoparaffins, based on the alkylate or alkylate blend, and less than 1 vol. % of C10+, preferably less than 0.1 vol. %, based on the alkylate or alkylate blend. Alkylate or alkylate blend is preferably present in the blend in an amount from about above 30% v, preferably at least about 32% v, most preferably at least about 35% v to at most about 55% v, preferably to at most about 49% v, more preferably to at most about 47% v based on the unleaded aviation fuel composition.
Isopentane
Isopentane is present in an amount of at least 8 vol. % in an amount sufficient to reach a vapor pressure in the range of 38 to 49 kPa. The alkylate or alkylate blend also contains C5 isoparaffins so this amount will typically vary between 5 vol. % and 25 vol. % depending on the C5 content of the alkylate or alkylate blend. Isopentane should be present in an amount to reach a vapor pressure in the range of 38 to 49 kPa to meet aviation standard. The total isopentane content in the blend is typically in the range of 10% to 26 vol. % preferably in the range of 17% to 26 vol. %, preferably in the range of 12% to 18% by volume, based on the unleaded aviation fuel composition.
Co-Solvent
The unleaded aviation fuel may contain a branched alkyl acetate having branched chain alkyl group having 4 to 8 carbon atoms as a co-solvent. Suitable co-solvent may be, for example, t-butyl acetate, iso-butyl acetate, ethylhexylacetate, iso-amyl acetate, and t-butyl amyl acetate, or mixtures thereof. The unleaded aviation fuels containing aromatic amines tend to be significantly more polar in nature than traditional aviation gasoline base fuels. As a result, they have poor solubility in the fuels at low temperatures, which can dramatically increase the freeze points of the fuels. Consider for example an aviation gasoline base fuel comprising 10% v/v isopentane, 70% v/v light alkylate and 20% v/v toluene. This blend has a MON of around 90 to 93 and a freeze point (ASTM D2386) of less than −76° C. The addition of 6% w/w (approximately 4% v/v) of the aromatic amine aniline increases the MON to 96.4. At the same time, however, the freeze point of the resultant blend (again measured by ASTM D2386) increases to −12.4° C. The current standard specification for aviation gasoline, as defined in ASTM D910, stipulates a maximum freeze point of −58° C. Therefore, simply replacing TEL with a relatively large amount of an alternative aromatic octane booster would not be a viable solution for an unleaded aviation gasoline fuel. It has been found that branched chain alkyl acetates having an alkyl group of 4 to 8 carbon atoms dramatically decrease the freezing point of the unleaded aviation fuel to meet the current ASTM D910 standard for aviation fuel. The branched acetate is present in an amount from about 7 vol. % preferably from about 8 vol. %, to about 14 vol. %, preferably to about 10 vol. %, based on the unleaded aviation fuel composition.
Blending
For the preparation of the high octane unleaded aviation gasoline, the blending can be in any order as long as they are mixed sufficiently. It is preferable to blend the polar components into the toluene, then the non-polar components to complete the blend. For example the aromatic amine and co-solvent are blended into toluene, followed by isopentane and alkylate component (alkylate or alkylate blend).
In order to satisfy other requirements, the unleaded aviation fuel according to the invention may contain one or more additives which a person skilled in the art may choose to add from standard additives used in aviation fuel. There should be mentioned, but in non-limiting manner, additives such as antioxidants, anti-icing agents, antistatic additives, corrosion inhibitors, dyes and their mixtures.
According to another embodiment of the present invention a method for operating an aircraft engine, and/or an aircraft which is driven by such an engine is provided, which method involves introducing into a combustion region of the engine and the high octane unleaded aviation gasoline fuel formulation described herein. The aircraft engine is suitably a spark ignition piston-driven engine. A piston-driven aircraft engine may for example be of the inline, rotary, V-type, radial or horizontally-opposed type.
While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of examples herein described in detail. It should be understood, that the detailed description thereto are not intended to limit the invention to the particular form disclosed, but on the contrary, the intention is to cover all modifications, equivalents and alternatives falling within the spirit and scope of the present invention as defined by the appended claims. The present invention will be illustrated by the following illustrative embodiment, which is provided for illustration only and is not to be construed as limiting the claimed invention in any way.
ILLUSTRATIVE EMBODIMENT
Test Methods
The following test methods were used for the measurement of the aviation fuels.
Motor Octane Number: ASTM D2700
Tetraethyl Lead Content: ASTM D5059
Density: ASTM D4052
Distillation: ASTM D86
Vapor Pressure: ASTM D323
Freezing Point: ASTM D2386 and ASTM D5972
Sulfur: ASTM D2622
Net Heat of Combustion (NHC): ASTM D3338
Copper Corrosion: ASTM D130
Oxidation Stability—Potential Gum: ASTM D873
Oxidation Stability—Lead Precipitate: ASTM D873
Water Reaction—Volume change: ASTM D1094
Detail Hydrocarbon Analysis: ASTM 5134
Examples 1-9
The aviation fuel compositions of the invention were blended as follows. Toluene having 107 MON (from VP Racing Fuels Inc.) was mixed with Aniline (from Univar NV) while mixing.
Isooctane (from Univar NV) and Narrow Cut Alkylate having the properties shown in Table below (from Shell Nederland Chemie BV) were poured into the mixture in no particular order. Then, tert-butyl acetate or isobutyl acetate (from Univar NV) was added, followed by isopentane (from Matheson Tri-Gas, Inc.) to complete the blend.










TABLE 1







Narrow Cut Alkylate Properties 




















IBP (ASTM D86, ° C.)
39.1



FBP (ASTM D86, ° C.)
115.1



T40 (ASTM D86, ° C.)
94.1



T50 (ASTM D86, ° C.)
98



T90 (ASTM D86, ° C.)
105.5



Vol. % iso-C5
14.52



Vol. % iso-C7
7.14



Vol. % iso-C8
69.35



Vol. % C10+
0.1










Example 1


    
    
        isopentane 18% v
        Narrow range alkylate 23% v
        Isooctane 20% v
        High MON toluene 25% v
        aniline 5% v
        t-butyl acetate 9% v
    
    
















Property




















MON
102.5



RVP (kPa)
38.61



Freeze Point (deg C.)
<−65



Lead Content (g/gal)
<0.01



Density (g/mL)
0.760



Net Heat of Combustion (MJ/kg)
43.4



Adjusted Net Heat of
45.0



Combustion (MJ/kg)




Water Reaction (mL)
0



T10 (deg C.)
58.6



T40 (deg C.)
92.7



T50 (deg C.)
99.7



T90 (deg C.)
109.3



FBP (deg C.)
173.3










Example 2


    
    
        Isopentane 17% v
        narrow cut alkylate 24% v
        Isooctane 20% v
        Toluene 25% v
        Aniline 5% v
        tert-butyl acetate 9% v
    
    
















Property




















MON
102.5



RVP (kPa)
38.61



Freeze Point (deg C.)
<−66



Lead Content (g/gal)
<0.01



Density (g/mL)
0.751



Net Heat of Combustion (MJ/kg)
42.84



Adjusted Net Heat of
44.82



Combustion (MJ/kg)




T10 (deg C.)
74.4



T40 (deg C.)
99.2



T50 (deg C.)
101.1



T90 (deg C.)
110.8



FBP (deg C.)
182.9










Example 3


    
    
        isopentane 18% v
        Narrow range alkylate 23% v
        Isooctane 20% v
        High MON toluene 25% v
        aniline 5% v
        isobutyl acetate 9% v
    
    
















Property




















MON
101.1



RVP (kPa)
46.82



Freeze Point (deg C.)
−60



Lead Content (g/gal)
<0.01



Density (g/mL)
0.759



Net Heat of Combustion (MJ/kg)
43.43



Adjusted Net Heat of
45.32



Combustion (MJ/kg)




T10 (deg C.)
65.1



T40 (deg C.)
99.9



T50 (deg C.)
103.2



T90 (deg C.)
116.7



FBP (deg C.)
177.9










Example 4


    
    
        isopentane 18% v
        Narrow range alkylate 41% v
        High MON toluene 25% v
        aniline 6% v
        t-butyl acetate 10% v
    
    
















Property




















MON
103.2



RVP (kPa)
47.78



Freeze Point (deg C.)
−60



Lead Content (g/gal)
<0.01



Density (g/mL)
0.762



Net Heat of Combustion (MJ/kg)
43.35



Adjusted Net Heat of
45.22



Combustion (MJ/kg)




T10 (deg C.)
61.2



T40 (deg C.)
97.9



T50 (deg C.)
102.1



T90 (deg C.)
118.6



FBP (deg C.)
179.8










Example 5


    
    
        isopentane 16% v
        Narrow range alkylate 38% v
        High MON toluene 30% v
        aniline 6% v
        t-butyl acetate 10% v
    
    
















Property




















MON
102.2



RVP (kPa)
46.4



Freeze Point (deg C.)
<−65.5



Lead Content (g/gal)
<0.01



Density (g/mL)
0.774



Net Heat of Combustion (MJ/kg)
42.53



Adjusted Net Heat of
44.19



Combustion (MJ/kg)




T10 (deg C.)
65



T40 (deg C.)
99.7



T50 (deg C.)
102.9



T90 (deg C.)
115.3



FBP (deg C.)
179.4










Example 6


    
    
        isopentane 18% v
        Narrow range alkylate 32% v
        High MON toluene 35% v
        aniline 6% v
        t-butyl acetate 9% v
    
    
















Property




















MON
101.9



RVP (kPa)
48.26



Freeze Point (deg C.)
−60



Lead Content (g/gal)
<0.01



Density (g/mL)
0.779



Net Heat of Combustion (MJ/kg)
42.85



Adjusted Net Heat of
44.61



Combustion (MJ/kg)




T10 (deg C.)
62.4



T40 (deg C.)
100.6



T50 (deg C.)
103.9



T90 (deg C.)
114.3



FBP (deg C.)
177.9










Example 7


    
    
        isopentane 18% v
        Narrow range alkylate 38% v
        High MON toluene 30% v
        aniline 5% v
        t-butyl acetate 9% v
    
    
















Property




















MON
101.3



RVP (kPa)
48.54



Freeze Point (deg C.)
<−80



Lead Content (g/gal)
<0.01



Density (g/mL)
0.771



Net Heat of Combustion (MJ/kg)
42.8



Adjusted Net Heat of
44.2



Combustion (MJ/kg)




Water Reaction (mL)
1



T10 (deg C.)
62.8



T40 (deg C.)
100.4



T50 (deg C.)
103.8



T90 (deg C.)
114.2



FBP (deg C.)
179.6










Example 8


    
    
        isopentane 18% v
        Narrow range alkylate 24% v
        Isooctane 20% v
        High MON toluene 25% v
        aniline 4% v
        t-butyl acetate 9% v
    
    
















Property




















MON
101.2



RVP (kPa)
45.23



Freeze Point (deg C.)
<−79



Lead Content (g/gal)
<0.01



Density (g/mL)
0.759



Net Heat of Combustion (MJ/kg)
42.87



Adjusted Net Heat of
44.55



Combustion (MJ/kg)




Water Reaction (mL)
0



T10 (deg C.)
65



T40 (deg C.)
98.7



T50 (deg C.)
101.6



T90 (deg C.)
110.7



FBP (deg C.)
161.2










Example 9


    
    
        isopentane 18% v
        Narrow range alkylate 20% v
        Isooctane 20% v
        High MON toluene 30% v
        aniline 3% v
        t-butyl acetate 9% v
    
    
















Property




















MON
100.9



RVP (kPa)
38.2



Freeze Point (deg C.)
<−70



Lead Content (g/gal)
<0.01



Density (g/mL)
0.774



Net Heat of Combustion (MJ/kg)
42.38



Adjusted Net Heat of
43.99



Combustion (MJ/kg)




Water Reaction (mL)
0



T10 (deg C.)
71.2



T40 (deg C.)
100



T50 (deg C.)
102



T90 (deg C.)
109.6



FBP (deg C.)
158.8










Properties of an Alkylate Blend
Properties of an Alkyalte Blend containing 1⁄2 narrow cut alkylate (having properties as shown above) and 1⁄2 Isooctane is shown in Table 2 below.










TABLE 2







Alkylate Blend Properties




















IBP (ASTM D86, ° C.)
54.0



FBP (ASTM D86, ° C.)
117.5



T40 (ASTM D86, ° C.)
97.5



T50 (ASTM D86, ° C.)
99.0



T90 (ASTM D86, ° C.)
102.5



Vol. % iso-C5
5.17



Vol. % iso-C7
3.60



Vol. % iso-C8
86.83



Vol. % C10+
0.1










Combustion Properties
In addition to the physical characteristics, an aviation gasoline should perform well in a spark ignition reciprocating aviation engine. A comparison to the current leaded aviation gasoline found commercially is the simplest way to assess the combustion properties of a new aviation gasoline.
Table 3 below provides the measured operating parameters on a Lycoming TIO-540 J2BD engine for avgas Example 1 and a commercially purchased 100 LL avgas (FB 0100LL).














TABLE 3












Brake





Fuel

Turbine Inlet
Brake
Specific Fuel



Altitude

Consumption
CHTa, Cyl
Temperature
Horsepower
Consumption


Fuel
(ft)
RPM
(lbs/hr)
1 (° F.)
(° F.)
(Observed)
(lb./hp.-hr)






















FBO 100LL
3000
2575.09
212.35
472
1533
330.45
0.642


Example 1
3000
2575.01
202.7
450
1613
332.65
0.609


FBO 100LL
6000
2199.98
128.42
457
1615
256.54
0.495


Example 1
6000
2199.98
143.85
450
1603
263.15
0.547


FBO 100LL
8000
2575.16
221.27
464
1544
350.76
0.632


Example 1
8000
2574.93
219.22
454
1626
365.73
0.599


FBO 100LL
12000
2400.01
184.19
461
1520
297.77
0.618


Example 1
12000
2399.98
185.34
441
1577
301.05
0.616





aCHT = cylinder head temperature. Although testing was conducted on a six cylinder engine, the variation between 100LL and Example 1 results were similar over all six cylinders, so only cylinder 1 values are used for representation. Reference FIGS. 1, 3, 5, 7, 9, 11, 13, 15 for more complete data.






As can be seen from Table 3 that the avgas of the invention provides similar engine operating characteristics compared to the leaded reference fuel. The data provided in Table 3 was generated using a Lycoming TIO-540 J2BD six cylinder reciprocating spark ignition aviation piston engine mounted on an engine test dynamometer. Of particular note are the fuel consumption values. Given the higher density of the fuel, it would be expected that the test fuel would require significantly higher fuel consumption in order to provide the same power to the engine. It is clear from Table 3 that the observed fuel consumption values are very similar across all test conditions, further supporting the use of an adjusted heat of combustion (HOC*) to compensate for fuel density effects in the evaluation of a fuel's impact on the range of an aircraft.
In order to assure transparency with the existing leaded gasoline, the ability of an aviation engine to operate within its certified operating parameters when using an unleaded aviation fuel, such as cylinder head temperatures and turbine inlet temperatures over a range of air/fuel mixtures, was assessed using engine certification test normally submitted to FAA for a new engine. The test was run for unleaded aviation fuel Example 1 which results are shown in FIGS. 1 to 8 and for a commercial 100 LL fuel shown in FIGS. 9 to 16. The detonation data were obtained using the procedure specified in ASTM D6424. As can be seen in FIGS. 1, 3, 5 and 7 for the Example 1 test fuel and FIGS. 9, 11, 13 and 15 for the FBO sourced 100LL (101MON) reference fuel, the Lycoming IO 540 J2BD engine was able to operate over its entire certified operating range without issue using aviation fuel of Example 1 with no noticeable change in operating characteristics from operation with the 100LL reference fuel.
In order to fully evaluate the ability of an engine to operate correctly using a given fuel over its entire operating range, the resistance of the fuel to detonate must be included. Therefore, the fuel was evaluated for detonation against an FBO procured 100LL reference fuel (101 MON) at four conditions, 2575 RPM at constant manifold pressure (Example 1 FIG. 2, 100LL reference FIG. 10), 2400 RPM at constant manifold pressure (Example 1 FIG. 4, 100LL reference FIG. 12), 2200 RPM at constant manifold pressure (Example 1 FIG. 6, 100LL reference FIG. 14) and 2757 RPM at constant power (Example 1 FIG. 8, 100LL reference FIG. 16). These conditions provide the most detonation sensitive operating regions for this engine, and cover both lean and rich operation.
As can be seen from the detonation plots referenced-above, the unleaded aviation fuel or the invention performs comparably to the current 100LL leaded aviation fuel. Of particular importance is that the unleaded fuel experiences detonation at lower fuel flow than the comparable leaded fuel. Additionally, when detonation does occur, this observed intensity of this effect is typically smaller than that found for the leaded reference fuel.
Materials Compatibility
The Material (nitrile rubber in the wing bladder tanks of a Piper Saratoga: Part number 461-710) was soaked in 500 ml of aviation fuel in a screw-on-top glass jar and left at room temperature for 28 days.
The Material was tested with two fuels: Example 1 and an FBO procured 100LL aviation gasoline.
After the soaking period, the material was pulled out of the fuels, air dried and visually examined. Material showed no delaminating, swelling, shrinking, or any deterioration upon visual inspection.
It was, therefore, given a “Pass” grade.
Comparative Examples A-K
Comparative Examples A and B
A high octane unleaded aviation gasoline that use large amounts of oxygenated materials as described in US Patent Application Publication 2008/0244963 as Blend X4 and Blend X7 is provided. The reformate contained 14 vol. % benzene, 39 vol. % toluene and 47 vol. % xylene.
















Comparative A

Comparative B




Blend X4
Vol. %
Blend X7
Vol. %





















Isopentane
12.25
Isopentane
12.25



Aviation alkylate
43.5
Aviation alkylate
43.5



Reformate
14
Reformate
14



Diethyl carbonate
15
Diethyl carbonate 
8



m-toluidine
3
m-toluidine
2



MIBK
12.46
MIBK
10





phenatole
10

























Property
Blend X4
Blend X7




















MON
100.4
99.3



RVP (kPa)
35.6
40.3



Freeze Point (deg C.)
−51.0
−70.0



Lead Content (g/gal)
<0.01
<0.01



Density (g/mL)
0.778
0.781



Net Heat of Combustion
38.017
39.164



(MJ/kg)





Adjusted Net Heat of
38.47
39.98



Combustion (MJ/kg)





Oxygen Content (% m)
8.09
6.16



T10 (deg C.)
73.5
73



T40 (deg C.)
102.5
104



T50 (deg C.)
106
108



T90 (deg C.)
125.5
152.5



FBP (deg C.)
198
183










The difficulty in meeting many of the ASTM D-910 specifications is clear given these results. Such an approach to developing a high octane unleaded aviation gasoline generally results in unacceptable drops in the heat of combustion value (>10% below ASTM D910 specification) and final boiling point. Even after adjusting for the higher density of these fuels, the adjusted heat of combustion remains too low.
Comparative Examples C and D
A high octane unleaded aviation gasoline that use large amounts of mesitylene as described as Swift 702 in U.S. Pat. No. 8,313,540 is provided as Comparative Example C. A high octane unleaded gasoline as described in Example 4 of US Patent Application Publication Nos. US20080134571 and US20120080000 are provided as Comparative Example D.
















Comparative

Comparative




Example C
Vol. %
Example D
Vol. %





















Isopentane
17
Isopentane
3.5



mesitylene
83
Isooctane
45.5





Toluene
23





Xylenes
21





aniline
7


























Comparative 
Comparative 



Property
Example C
Example D




















MON
105
104



RVP (kPa)
35.16
17.79



Freeze Point (deg C.)
−20.5
−41.5



Lead Content (g/gal)
<0.01
<0.01



Density (g/mL)
0.830
0.794



Net Heat of Combustion
41.27
42.20



(MJ/kg)





Adjusted Net Heat of
42.87
43.86



Combustion (MJ/kg)





T10 (deg C.)
74.2
100.4



T40 (deg C.)
161.3
108.3



T50 (deg C.)
161.3
110.4



T90 (deg C.)
161.3
141.6



FBP (deg C.)
166.1
180.2










As can be seen from the properties, the Freeze Point is too high for both Comparative Examples C & D.
Comparative Examples E-K
Other comparative examples where the components were varied are provided below. As can been seem from the above and below examples, the variation in composition resulted in at least one of MON being too low, RVP being too high or low, Freeze Point being too high, or Heat of Combustion being too low.













Comparative

Comparative



Example E
Vol. %
Example F
Vol. %


















Isopentane
10
Isopentane
15


Aviation alkylate
60
isooctane
60


m-xylene
30
toluene
25

























Comparative 
Comparative 



Property
Example E
Example F




















MON
93.6
95.4



RVP (kPa)
40
36.2



Freeze Point (deg C.)
<−80
<−80



Lead Content (g/gal)
<0.01
<0.01



Density (g/mL)
0.738
0.730



Net Heat of Combustion
43.11
43.27



(MJ/kg)





Adjusted Net Heat of
44.70
44.83



Combustion (MJ/kg)





T10 (deg C.)
68.4
76.4



T40 (deg C.)
106.8
98.7



T50 (deg C.)
112
99.7



T90 (deg C.)
134.5
101.3



FBP (deg C.)
137.1
115.7























Comparative

Comparative



Example G
Vol. %
Example H
Vol. %


















Isopentane
15
Isopentane
10


Isooctane
75
Aviation alkylate
69


Toluene
10
toluene
15




m-toluidine
6

























Comparative 
Comparative 



Property
Example G
Example H




















MON
96
100.8



RVP (kPa)
36.9
44.8



Freeze Point (deg C.)
<−80
−28.5



Density (g/mL)
0.703
0.729



Lead Content (g/gal)
<0.01
<0.01



Net Heat of Combustion
44.01
43.53



(MJ/kg)





Adjusted Net Heat of
45.49
45.33



Combustion (MJ/kg)





T10 (deg C.)
75.3
65



T40 (deg C.)
97.1
96.3



T50 (deg C.)
98.4
100.6



T90 (deg C.)
99.1
112.9



FBP (deg C.)
111.3
197.4























Comparative

Comparative



Example I
Vol. %
Example J
Vol. %


















Isopentane
15
Isopentane
15


Narrow cut alkylate
24
Narrow cut alkylate
24


Isooctane
25
isooctane
25


Toluene
25
toluene
25


Aniline
6
Aniline
6


Isobutyl acetate
5
Tert-butyl acetate
5

























Comparative 
Comparative 



Property
Example I
Example J




















MON
100.8
100.7



RVP (kPa)
40.61
34.06



Freeze Point (deg C.)
−46
−29.5



Lead Content (g/gal)
<0.01
<0.01



Density (g/mL)
0.757
0.758



Net Heat of Combustion
42.85
42.81



(MJ/kg)





Adjusted Net Heat of
44.51
44.46



Combustion (MJ/kg)





T10 (deg C.)
69
78



T40 (deg C.)
99.5
100.5



T50 (deg C.)
102.5
101.5



T90 (deg C.)
115
113.5



FBP (deg C.)
184
180
























Comparative




Example K
Vol. %



















Isopentane
15



Narrow cut alkylate
24



Isooctane
25



Toluene
25



Aniline
6



2-ethyl hexanol
5

























Comparative 



Property
Example K



















MON
98.8



RVP (kPa)
40.26



Freeze Point (deg C.)
−27



Lead Content (g/gal)
<0.01



Density (g/mL)
0.756



Net Heat of Combustion
42.87



(MJ/kg)




Adjusted Net Heat of
44.53



Combustion (MJ/kg)




T10 (deg C.)
68



T40 (deg C.)
100



T50 (deg C.)
102.5



T90 (deg C.)
133.5



FBP (deg C.)
182.5

## Claims

1. An unleaded aviation fuel composition having a MON of at least 99.6, sulfur content of less than 0.05 wt %, CHN content of at least 97.2 wt %, less than 2.8 wt % of oxygen content, a T10 of at most 75° C., T40 of at least 75° C., a T50 of at most 105° C., a T90 of at most 135° C., a final boiling point of less than 190° C., an adjusted heat of combustion of at least 43.5 MJ/kg, a vapor pressure in the range of 38 to 49 kPa, comprising a blend comprising:
(a) from about 20 vol. % to about 35 vol. % of toluene having a MON of at least 107;
(b) from about 2 vol. % to about 10 vol. % of aniline;
(c) from above 30 vol. % to about 55 vol. % of at least one alkylate or alkylate blend having an initial boiling range of from about 32° C. to about 60° C. and a final boiling range of from about 105° C. to about 140° C., having T40 of less than 99° C., T50 of less than 100° C., T90 of less than 110° C., the alkylate or alkylate blend comprising isoparaffins from 4 to 9 carbon atoms, about 3-20 vol. % of C5 isoparaffins, about 3-15 vol. % of C7 isoparaffins, and about 60-90 vol. % of C8 isoparaffins, based on the alkylate or alkylate blend, and less than 1 vol. % of C10+, based on the alkylate or alkylate blend;
(d) from about 7 vol. % to about 14 vol. % of a branched alkyl acetate having branched chain alkyl group having 4 to 8 carbon atoms; and
(e) at least 8 vol. % of isopentane in an amount sufficient to reach a vapor pressure in the range of 38 to 49 kPa; and

wherein the fuel composition contains less than 1 vol. % of C8 aromatics.

2. The unleaded aviation fuel composition of claim 1 wherein the total isopentane content in the blend of 17% to 26 vol. % being in an amount sufficient to reach a vapor pressure in the range of 38 to 49 kPa.

3. The unleaded aviation fuel composition of claim 1 having a potential gum of less than 6 mg/100 mL.

4. The unleaded aviation fuel composition of claim 1 wherein less than 0.2 vol. % of alkanols and ethers are present.

5. The unleaded aviation fuel composition of claim 2 further comprising an aviation fuel additive.

6. The unleaded aviation fuel composition of claim 1 having a freezing point of less than −58° C.

7. The unleaded aviation fuel composition of claim 1 wherein no straight chain alcohol and no noncyclic ether are present.

8. The unleaded aviation fuel composition of claim 1 wherein the combined amount of toluene and the branched alkyl acetate in the fuel composition is more than 30 vol. %.

9. The unleaded aviation fuel composition of claim 1 wherein the combined amount of toluene and the branched alkyl acetate in the fuel composition is more than 31 vol. %.

10. The unleaded aviation fuel composition of claim 1 having water reaction within +/−2 mL as defined in ASTM D1094.

11. The unleaded aviation fuel composition of claim 1 wherein the combined amount of toluene and the branched alkyl acetate in the fuel composition is more than 33 vol. %.

12. The unleaded aviation fuel composition of claim 1 wherein the branched alkyl acetate is selected from the group consisting of t-butyl acetate, iso-butyl acetate, ethylhexylacetate, iso-amyl acetate, t-butyl amyl acetate, and mixtures thereof.

13. The unleaded aviation fuel composition of claim 1 having the final boiling point of at most 180° C.

14. The unleaded aviation fuel composition of claim 1 wherein the alkylate or alkylate blend have a C10+ content of less than 0.1 vol. % based on the alkylate or alkylate blend.

15. The unleaded aviation fuel composition of claim 8 having a benzene content between 0% v and 5% v.